AU773104B2 - Hydroxy-substituted N-alkoxy hindered amines - Google Patents

Description

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AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT n e *c Applicant(s): Ciba Specialty Chemicals Holding Inc.

Klybeckstrasse 141 CH-4057 Basel Switzerland DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Hydroxy-substituted N-alkoxy hindered amines Address for Service: Invention Title: The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 A-21979/A/22031/CGC 2020 HYDROXY-SUBSTITUTED N-ALKOXY HINDERED AMINES The instant invention pertains to hindered amine compounds which are substituted on the N-atom by N-alkoxy moieties containing one to three hydroxyl groups. These materials are particularly effective in stabilizing polyolefins, especially thermoplastic polyolefins, against the deleterious effects of oxidative, thermal and actinic radiation. The compounds are also effective in stabilizing acid catalyzed and ambient cured coatings systems.

Background of the Invention 4-Hydroxy-l -oxyl-2,2,6,6-tetramethylpiperidine and 4-oxo-1 -oxyl-2,2,6,6-tetramethylpiperidine are reported to have been used to trap carbon centered radicals formed from methanol, ethanol, isopropanol and sec-butanol by S. Nigam et al., J. Chem. Soc., Trans.

Faraday Soc. 1, 1976, 72, 2324 and by Asmus et al., Int. J. Radiat. Biol., 1976, 29, 211.

United States Patent No. 5,627,248 and European Patent Application No. 135,280 A2 describe, respectively, difunctional and monofunctional living free radical polymerization initiators, some of which contain hindered amine ethers substituted by hydroxy groups. These compounds differ substantially in structure and performance from the instant compounds.

European Patent Application No. 427,672 Al and United States Patent No. 4,972,009 mention, but do not exemplify, respectively, hydroxylamine and nitrone structures, some of which contain C1-C4 hydroxyalkoxy substituted 2,2,6,6-tetramethylpiperidine derivatives. Such structures are outside the scope of the instant invention.

United States Patent No. 5,204,473 describes N-hydrocarbyloxy hindered amine derivatives that are prepared exclusively from organic compounds containing only carbon and hydrogen atoms. Such compounds are structurally quite different from the instant compounds.

United States Patent No. 5,004,770 describes hindered amine compounds which are substituted on the N-atom by alkoxy moieties which alkoxy groups are themselves -2unsubstituted. These compounds are especially useful in polymers including polybutadiene, polystyrene, ABS, polyacetal, polyamide, polyester, polyurethane and polycarbonate.

United States Patent No. 5,096,950 also describes hindered amine compounds which are substituted on the N-atom by alkoxy moieties which alkoxy groups are themselves unsubstituted. These compounds are found to be useful in polyolefins.

The instant compounds are N-alkoxy substituted derivatives of 2,2,6,6-tetraalkylpiperidines where the alkoxy group is substituted by one to three hydroxy moieties. The instant compounds also comprise N-alkoxy bridged derivatives of the 2,2,6,6-tetraalkylpiperidines where the alkoxy moiety, which is substituted by one to three hydroxy groups, is shared by two hindered amine molecules. The free hydroxy moieties of these compounds may be reacted with carboxylic acids, acid chlorides or esters to form simple esters or polyesters, or with isocyanates to form urethanes or polyurethanes.

The instant compounds, because of their low bascity which is shared by the simple unsubstituted N-alkoxy compounds cited in the two patents mentioned above, are of particular value in the stabilization of polyolefins and automotive coating compositions where the activity of the more basic hindered amine stabilizes is significantly reduced because of interaction with the polymer substrate or acid catalytic system needed for curing such substrate.

Examples of polyolefin compositions in which the instant compounds are effective include flame retardant polyolefins where acidic residues from the decomposition of the halogenated flame retardants deactivate hindered amines not having the N-OR group, greenhouse films and agricultural mulch films where acidic residues from pesticides interfere with the activity of "normal" hindered amine stabilizers, and in thermoplastic polyolefins where pigment interactions with basic hindered amine stabilizers interfere with painting the substrate surfaces. Examples of coating compositions in which the instant compounds are effective include melamine crosslinked thermoset acrylic resins, which are cured using strong acids that interact with basic hindered amine stabilizers. The instant compounds are also effective in acrylic alkyd or polyester resins with isocyanate crosslinking agents, and in epoxy resins with carboxylic acid, anhydride, or amine crosslinking agents.

-3- Thus, current compounds are advantageously used in compositions also containing costabilizers, flame retardants tris(3-bromo-2,2-bis(bromomethyl)propyl)phosphate, decabromodiphenyl oxide, ethylene bis-(tetrabromophthalimide), or ethylene bis-(dibromonorbornanedicarboximide)), catalysts acids like toluene sulfonic acid, metal driers or amines), fillers, or in agricultural applications wherein pesticides come in contact with the stabilized polymer. Preferred is a composition wherein component is polypropylene, polyethylene, thermoplastic polyolefin (TPO), ABS or high impact polystyrene (HIPS), and component is an effective synergistic mixture of a compound of formula to and (ii) a flame retardant selected from the group consisting of the halogenated, phosphorus, boron, silicon and antimony compounds, metal hydroxides, metal hydrates, metal oxides and mixtures thereof.

While the unsubstituted N-OR compounds described in U.S. Patent Nos. 5,004,770 and 5,096,950 also perform well in the compositions described in the paragraph above, the instant compounds differ significantly in both structure and in performance from the prior art compounds by virtue of the presence of the one to three free hydroxy groups present on the Nalkoxy moiety. These hydroxyl groups in the instant compounds provide said compounds with superior antistatic properties, compatibility in more polar environments such as polyurethane based and in water-borne automotive coating systems, and in stabilizing painted automotive thermoplastic olefin structures.

The instant compounds are particularly suited for providing superior compatibility in polycarbonates and polycarbonate/ABS blends compared to the N-OE prior art compounds; and providing superior compatibility in polyesters and polyamides compared to the prior art N-OE compounds.

Objects of the Invention There are two objects to the instant invention which are: -4- 1. Novel compounds having on the 1-position of the hindered amine a moiety -O-E-OH where the OH group provides important properties; 2. compositions stabilized by the novel compounds described above; and 3. a process for the synthesis of the novel compounds.

Detailed Disclosure The instant invention pertains to novel compounds having 1-alkoxy substituted hindered amine derivatives where the alkoxy moiety is substituted by one to three hydroxy groups as described in formulas to or to novel compounds having 1-alkoxy bridged hindered amine derivatives where the alkoxy moiety, substituted by one to three hydroxy groups, is shared by two hindered amine molecules as described in formulas (16) to or to oligomeric or polymeric hindered amine molecules made from the reaction of dialkyl esters or isocyanates with hydroxy substituted N-alkoxy derivatives of 4-hydroxy-2,2,6,6-tetraalkylpiperidine as described in formula or to simple diester or urethane derivatives of hydroxy substituted Nalkoxy derivatives of 4-hydroxy-2,2,6,6-tetramethylpiperidine as described in formula

G

i

G

2 0 N-O-E- (OH)b G G (1) G G 2

HO

HO N-O-E- (OH) b N-0-E (OH) m Gj G 2 (3) G G 2 G G 2 (HO) bE0ON OKN0OE- (OH)b 0 0 1 2 GG 2 (4) *0 G G 2 R R 2 N( N-0E- (OH) b G G 2 R 0O 3. 1 N O E (OH)bj (OH) b

S

R N-0-E-(OH)bj (8) NR 70E(OG 2

N

N -R9-N-O-G

H)

S. S

SS

S.

*5*S

S

*SSS

R R

N-

R 9 N /Rl

(OH)

b GI G 2

N

E-O-N -N N 1 R2 N R

H

-N-(CH

2 -N-(CH 2

N\

N J N R 1

R

N N 'kNR 2 NG

N

G

G

E- OH) E- OH) bb E-(OH) b (11) i-(0) d SIH)2 R 9 G2 E- (OH) b (12) -8-

R

14 R 13 CH 2 Si-(0)hldi d (C H 2 (CH) -R 2 h 14 y E- (OH) b (13) 4 4 4

P.S.

*4*C 4.

0550..

5

S

0*55 45*

S

*4*S S. S S S 55 eSSI

S

Rio (CH CH) 0 H R 9 G 1 G 2 N G2 E-(OH) b (14) R 16

N

R 1 y E- (OH) b E- (OH) b Gj G 2 -L (OH) b 2 (16) (OH) b (17) (OH) Lb (18) N-0O L (IOH) b 0 G G 2 (19) 19 N-0- -L-(OH) Hb 1j G2 -2 (OH) b (OH)b (21) 21 1 2 R NN

H

G G 2 -L (OH) 2 (22) 11

R

2 4 (HO) -E-0 b (OH) b (23) L- (OH) b (24) G G 2 0 0 1 1 1 1 (HO) E-0-N -C-R -C b 126 G, G 2 (OH) b 2 R 7

N

N

R

N

(OH)

(26) 12

R

10

N-

N-

/Rl (OH)b Gj G 2 (27) R 13 R Si( O) (C2)-R1 14 2hd I14 (CH2) 0 1 -(OH )b (28)

-OR

28 (29) -13o 2 II II R29 C--O N-O-G-O-C-R 29 Gi

G

2

G

1 and G 2 are independently alkyl of 1 to 4 carbon atoms, or G 1 and G 2 together are pentamethylene; preferably G 1 and G 2 are each methyl; E is a straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl groups of 1 to 4 carbon atoms; b is 1, 2 or 3 with the proviso that b cannot exceed the number of carbon atoms in E or L, and when b is 2 or 3, each hydroxyl group is attached to a different carbon atom of E or L; the two hindered amine groups are generally, but not always, attached to two different carbon atoms of L; in each of the formulas to S* m is 0 or 1; R, is hydrogen, hydroxyl or hydroxymethyl;

R

2 is hydrogen, alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon atoms; n is 1 to 4; when n is 1, 14-

R

3 is alkyl of 1 to 18 carbon atoms, alkoxycarbonylalkylenecarbonyl of 4 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2- (hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkyl is interrupted by oxygen, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, or acyl radical of an aromatic acid containing 7 to 15 carbon atoms; when n is 2,

R

3 is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms; when n is 3, o

R

3 is a trivalent acyl radical of an aliphatic, unsaturated aliphatic, or cycloaliphatic tricarboxylic acid or tricarbamic acid containing 6-18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic or tricarbamic acid containing 9-18 carbon atoms, or R 3 is a trivalent acyl radical of a tris(alkylcarbamic acid) derivative of cyanuric acid containing 12-24 carbon atoms, such as 1,3,5-tris[6-carboxyaminohexyl]-2,4,6-trioxo-s-triazine; when n is 4,

R

3 is a tetravalent acyl radical of analiphatic or unsaturated aliphatic tetracarboxylic acid, especially 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4but-2-enetetracarboxylic acid, 1,2,3,5-pentanetetracarboxylic acid and 1,2,4,5pentanetetracarboxylic acid, or R 3 is a tetr.avalent acyl radical or an aromatic tetracarboxylic acid containing 10 to 18 carbon atoms; p is 1 to 3,

R

4 is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbon atoms; when p is 1, Rs is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, an acyl radical of an aromatic carboxylic acid containing 7 to 15 carbon atoms, or R 4 and Rs together are -(CH 2 5 CO-, phthaloyl or a divalent acyl radical of maleic acid; when p is 2,

R

5 is alkylene of 2 to 12 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms; when p is 3, R is a trivalent acyl radical of an aliphatic or unsaturated aliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9 to 15 carbon atoms; when n is 1, .*oo R 6 is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbon atoms, -NHalkyl of 1 to 18 carbon atoms or -N(alkyl) 2 of 2 to 36 carbon atoms, when n is 2,

R

6 is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of 2 to 18 carbon atoms, -NH-alkylene-NH- of 2 to 18 carbon atoms or -N(alkyl)-alkylene-N(alkyl)- of 2 to 18 carbon atoms, or R 6 is 4-methyl-1,3-phenylenediamino, when n is 3, -16-

R

6 is a trivalent alkoxy radical of a saturated or unsaturated aliphatic triol containing 3 to 18 carbon atoms, when n is 4,

R

6 is a tetravalent alkoxy radical of a saturated or unsaturated aliphatic tetraol containing 4 to 18 carbon atoms, R7 and R 8 are independently chlorine, alkoxy of 1 to 18 carbon atoms, -O-T 1 amino substituted by 2-hydroxyethyl, -NH(alkyl) of 1 to 18 carbon atoms, -N(alkyl)TI with alkyl of 1 to 18 carbon atoms, or -N(alkyl) 2 of 2 to 36 carbon atoms,

R

9 is a divalent oxygen atom, or R9 is a divalent nitrogen atom substituted by either hydrogen, alkyl of 1 to 12 carbon atoms or T 1 G

G

N-O-E- (OH) b

R

1 0 is hydrogen or methyl, q is 2 to 8,

R

11 and R 12 are independently hydrogen or the group T 2 -17-

T

2 0 o\ E- (OH) E- (OH) b b

SOS.

4* 'S eS. e 5555 S.

R

13 is hydrogen, phenyl, straight or branched alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, straight or branched alkyl of 1 to 4 carbon atoms substituted by phenyl, cycloalkyl of 5 to 8 carbon atoms, cycloalkenyl of 5 to 8 carbon atoms, alkenyl of 2 to 12 carbon atoms, glycidyl, allyloxy, straight or branched hydroxyalkyl of 1 to 4 carbon atoms, or silyl or silyloxy substituted three times independently by hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms.;,.

R

14 is hydrogen or silyl substituted three times independently by hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms; d is 0 or 1; h is 0 to 4; k is 0 to x is 3 to 6; y is 1 to z is an integer such that the compound has a molecular weight of 1000 to 4000 g/mol (=atomic units, amu), OS S

S

S os .55.

U S -18-

R

1 5 is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 8 carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms such as tert-octylamino, -N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms, or -N(alkyl) 2 of 2 to 16 carbon atoms,

R

1 6 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted once by chlorine and once by R 15 or s-triazinyl substituted twice by R 1 5 with the condition that the two R 15 substituents may be different;

R

1 7 is chlorine, amino substituted by alkyl of 1 to 8 carbon atoms or by T 1 -N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms, -N(alkyl) 2 of 2 to 16 carbon atoms, or the group T 3 S. T3 N- (CH N-Rs G G G G G2 G G

G

2 N 2 G 2 N 2 0^ 0 0 E- (OH) b E- (OH) b

R

18 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted twice by -N(alkyl) 2 of 2 to 16 carbon atoms or s-triazinyl substituted twice by -N(alkyl)Ti with alkyl of 1 to 8 carbon atoms; L is straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8 .i carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl of 1 to 4 carbon atoms, in formulas (16) to R 1

R

2

R

7

R

8

R

9 Rio, R 13

R

14 d,h, k, m, q, and T 1 have the same meanings as in formulas to

R

1 9 is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2-(hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms -19which alkyl is interrupted by oxygen, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, or acyl radical of an aromatic acid containing 7 to 15 carbon atoms;

R

20 is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

R

2 1 is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbon atoms;

R

22 is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, an acyl radical of an aromatic carboxylic acid containing 7 to 15 carbon atoms, or R 4 and Rs together are -(CH 2 5 CO-, phthaloyl or a divalent acyl radical of maleic acid;

R

23 is hydrogen, alkyl of 1 to 4 carbon atoms or acyl of 2 to 6 carbon atoms; i R 2 4 is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

R

25 is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbon atoms, -NHalkyl of 1 to 18 carbon atoms or -N(alkyl) 2 of 2 to 36 carbon atoms,

R

26 is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of 2 to 18 carbon atoms, NH-alkylene-NH- of 2 to 18 carbon atoms or -N(alkyl)-alkylene-N(alkyl)- of 3 to 18 carbon atoms, in formulas (29) and G is a carbon centered diradical derived from a primary, secondary or tertiary alcohol G-OH, where z is as defined above, and G is straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl of 1 to 4 carbon atoms, with the proviso that in formula (29) successive hindered amine moieties can be oriented in either a head to head or head to tail fashion;

T

4 is hydrogen or 0 0

T

4 is R271 O-R28

R

27 is a straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene or cycloalkenylene of 5 to 8 carbon atoms, phenylene or -NH-alkylene-NH- of 2 to 18 carbon atoms including 5-amino-l-aminomethyl-1,3,3-trimethylcyclohexane and -NH-xylylene-NH-; Gi G 2 G, G 2

R

28 is alkyl of 1 to 4 carbon atoms; N-O-G-OH or HO- N-O-G- G G 2 G, G 2

R

29 is a straight or branched chain alkyl or -NH-alkyl of 1 to 18 carbon atoms or -NHcycloalkyl of 5 to 8 carbon atoms; and with the further proviso that in formulas and when b is 1, E is not methyl, ethyl, 2-propyl or 2-methyl-2-propyl, and that in formula if G 1 and G 2 each are methyl, the moiety -E-(OH)b is not 1-phenyl-2-hydroxymethyl.

Preferably, G, and G 2 are each methyl.

-21 Preferably, in formulas to b is 1 or 2, most preferably 1.

Of special technical importance are compounds of formula and when b is 1 and E is methylene, ethylene, 2-propylene or 2-methyl-2-propylene.

When b is 1, E-OH and L-OH are respectively a carbon-centered radical or diradical formed preferably from 2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1 -propanol, 2-methyl-2butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol, 1dodecanol, 1 -octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1 -hexanol, cyclohexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or 1 -phenyl-1 -ethanol; most preferably E-OH and L-OH are formed from 2-methyl-2-propanol or cyclohexanol.

When b is 2, E-OH and L-OH are respectively a carbon-centered radical or diradical formed preferably from 1,2-ethanediol, 1,2-propanedial, 1,3-propanediol, 1,2-butanediol, 1,3butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3cyclohexanediol or 1,4-cyclohexanediol; most preferably E-OH and L-OH are formed from 1,4butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4cyclohexanediol.

When b is 3, E-OH and L-OH are respectively a carbon-centered radical or diradical formed from glycerol, 1,1,1-tris(hydroxymethyl)methane, 2-ethyl-2-(hydroxymethyl-1,3propanediol, 1,2,4-butanetriol or 1,2,6-hexanetriol; most preferably E-OH and L-OH are formed Sfrom glycerol, 1,1,1 -tris(hydroxymethyl)methane, 2-ethyl-2-(hydroxymethyl-1,3-propanediol.

Preferably in formulas (29) and is formed from ethanol, phenethyl alcohol, cyclohexanol or 2-methyl-2-propanol tert-butyl alcohol).

Preferably in formula m is 0, R 1 is hydrogen or hydroxymethyl, and R 2 is hydrogen; or m is 1, R 1 is hydroxy or hydroxymethyl, and R 2 is hydrogen, methyl or ethyl.

Preferably in formula R 2 is hydrogen or dodecyl.

-22- Preferably in formula n is 1-3, and when n is 1, R 3 is allyl, glycidyl, acryloyl, methacryloyl, octadecanoyl, hexadecanoyl, tetradecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl, methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; or when n is 2, R 3 is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl, cis- or trans-5-carbamoyl-1 (carbamoylmethyl)-1,3,3-trimethylcyclohexane or toluene-2,4-dicarbamoyl; or when n is 3, R 3 is 1,3,5-tris(6-carbamoylhexyl)-2,4,6-trioxo-s-triazine.

Preferably in formula p is 1 or 2, and when p is 1, R 4 is hydrogen and Rs is butyl; or

R

4 and Rs together are the divalent acyl radical of maleic acid; or when p is 2, R 4 is hydrogen or acetyl, and R 5 is 1,6-hexanediyl.

Preferably in formula n is 1 or 2, and when n is 1, R 6 is ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamino; or when n is 2, Re is 1,2-ethanedioxy, 1,4-butanedioxy, ethylenediamino, hexamethylenediamino, or 4-methyl-1,3-phenylenediamino.

Preferably in formula R 7 and R 8 are independently chlorine, octylamino, tert-octylamino or amino substituted by T 1 and ethyl, butyl or dodecyl; and R 9 is a divalent nitrogen atom substituted by ethyl, butyl or dodecyl.

Preferably in formula q is 2, 4 or 6, R 7 is chlorine, octylamino, octadecylamino or amino substituted by T 1 and ethyl, butyl or dodecyl; and Rio is hydrogen.

Preferably in formula n is 3, p is 2, R 2 is ethyl, butyl or dodecyl; and one of R 11 or

R

12 is T 2 and the other is hydrogen.

Preferably in formula k is 3, R 9 is a divalent oxygen atom or is a divalent nitrogen atom substituted by ethyl, butyl or dodecyl, R 13 is hydrogen or methyl, and when d is 0, x is 5 or 6, and when d is 1, x is 3 or 4.

Preferably in formula d is 0 or 1, h is 0-2, k is 0 or 3, y is 1-8, R 9 is a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, butyl or dodecyl, R 1 3 is hydrogen, methyl, ethyl, methoxy or ethoxy, and R 14 is hydrogen or trimethylsilyl.

-23- Preferably in formula R 9 is a divalent oxygen atom, Rio is hydrogen or methyl, m is 0 and z is an integer such that the molecular weight of the compound is 1500-3000 amu.

Preferably in formula (15) q is 6, y is 1-7, R 15 is tert-octylamino, morpholino, amino substituted by T 1 and butyl, which may also be designated as T 1 -butylamino, R 16 is hydrogen, acetyl, ethylcarbamoyl, 2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl, striazinyl substituted twice by T 1 -butylamino or s-triazinyl substituted once by diethylamino or dibutylamino and once by T 1 -butylamino, R 1 7 is dibutylamino, diethylamino, T 1 -butylamino or R 17 is T 3 where R 18 is acetyl or ethylcarbamoyl.

Preferably in formula m is 0, R 1 is hydrogen or hydroxymethyl, and R 2 is hydrogen; or m is 1, R 1 is hydroxy or hydroxymethyl, and R 2 is hydrogen or methyl.

Preferably in formula R 2 is hydrogen or dodecyl.

0: 0.

Preferably in formula R 1 9 is hydrogen, allyl, acryloyl, methacryloyl, octadecanoyl or hexadecanoyl.

Preferably in formula R 20 is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl, or cis- or trans-5-carbamoyl-1 -(carbamoylmethyl)-1,3,3-trimethylcyclohexane.

a.

Preferably in formula R 21 is hydrogen and R 22 is hydrogen or butyl; or R 2 1 and R 22 together are the divalent acyl radical of maleic acid.

Preferably in formula R 23 is hydrogen or acetyl, and R 24 is ethylene or hexamethylene.

Preferably in formula R 2 5 is ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamino.

Preferably in formula R 26 is. 1,2-ethanedioxy, 1-4-butanedioxy, ethylenediamino or hexamethylenediamino.

-24- Preferably in formula R 7 and R 8 are independently chlorine, octylamino, tert-octylamino, octadecylamino, T 1 -ethylamino, T 1 -butylamino or T 1 -dodecylamino, and R 9 is a divalent nitrogen atom substituted by ethyl, butyl or dodecyl.

Preferably in formula q is 2, 4 or 6, R 7 is chlorine, octylamino, octadecylamino, T 1 ethylamino, T 1 -butylamino or T 1 -dodecylamino, and Rio is hydrogen.

Preferably in formula d is 0 or 1, h is 0-2, k is 0 or 3, R 9 is a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, butyl or dodecyl, R 13 is hydrogen, methyl, ethyl, methoxy or ethoxy, and R 14 is hydrogen or trimethylsilyl.

Preferably in formula R 27 is ethylene, trimethylene, tetramethylene, octamethylene, 1,6-diaminohexane or 5-amino-1 -aminomethyl-1,3,3-trimethylcyclohexane; z is an integer such that the molecular weight of the compound is 1500-3000 amu, R 28 is methyl or ethyl, and G is ethylene, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, 1,4-cyclohexanediyl,

-CH(C

6

H

5

)CH

2 or -CH 2

C(CH

3 2 Preferably in formula R 29 is pentadecyl, heptadecyl, butylamino or cyclohexylamino.

Still more preferred embodiments of the instant invention are the compounds of formulas to (30) where E-OH, L-OH and G-O- are formed from 2-methyl-2-propanol tert-butyl alcohol) or cyclohexanol.

**Most preferably in formula when n is 1, R 3 is acryloyl, methacrloyl, glycidyl, .i octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl, methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; or when n is 2, R 3 is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl or cis- or trans-5-carbamoyl-1 -(carbamoylmethyl)-1,3,3trimethylcyclohexane or toluene-2,4-dicarbamoyl; or when n is 3, R 3 is 1,3,5-tris(6carbamoylhexyl)-2,4,6-trioxo-s-triazine.

Most preferably in formula p is 1 or 2, and when p is 1, R 4 is hydrogen and R 5 is hydrogen or butyl; or when p is 2, R 4 is hydrogen, and R 5 is 1,6-hexanediyl.

Most preferably in formula R 7 is chlorine, octylamino or T 1 -butylamino, R 8 is chlorine or T 1 -butylamino, and R 9 is a divalent nitrogen atom substituted by butyl.

Most preferably in formula q is 6, R 7 is T 1 -butylamino; and Rio is hydrogen.

Most preferably in formula n is 3, p is 2, and one of R 11 or R 12 is T 2 and the other is hydrogen.

Most preferably in formula k is 3, Rg is a divalent oxygen atom, R 1 3 is hydrogen or methyl, and d is 0, x is 5 or 6, and when d is 1, x is 3 or 4.

Most preferably in formula d is 0 or 1, h is 0-2, k is 0 or 3, y is 1-8, R 9 is a divalent oxygen atom, R 1 3 is hydrogen, methyl, ethyl, methoxy or ethoxy, and R 1 4 is hydrogen or trimethylsilyl.

Most preferably in formula (15) q is 6, y is 1-7, R 15 is T 1 -butylamino, R 16 is hydrogen, acetyl, ethylcarbamoyl, 2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl, striazinyl substituted twice by T 1 -butylamino or s-triazinyl substituted once by diethylamino or dibutylamino and once by T 1 -butylamino, R 17 is dibutylamino, diethylamino, T 1 -butylamino or R 1 7 *o is T 3 where R 1 8 is acetyl or ethylcarbamoyl.

Most preferably in formula R 19 is hydrogen, octadecanoyl or hexadecanoyl.

Most preferably in formula R 21 is hydrogen and R 22 is hydrogen or butyl.

Most preferably in formula R 23 is hydrogen, and R 24 is hexamethylene.

Most preferably in formula R 7 is chlorine, octylamino or T 1 -butylamino, R 8 is chlorine or T 1 -butylamino, and Rg is a divalent nitrogen atom substituted by butyl.

Most preferably in formula q is 6, R 7 is T-butylamino, and Rg is a divalent nitrogen atom substituted by butyl.

-26- Most preferably in formula R 27 is ethylene, trimethylene, tetramethylene or octamethylene, z is an integer such that the molecular weight of the compound is 1500 to 2000 amu, and R 28 is methyl.

Most preferably in formula R 29 is pentadecyl or heptadecyl.

Still more preferred embodiments of the instant invention are the compounds of formulas to (30) where E-OH, L-OH and are formed from 2-methyl-2-propanol tert-butyl alcohol).

Especially preferred compounds of formula are those where n is 1, R 3 is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl or methoxycarbonylbutyryl, or methoxycarbonylpentanoyl, and where n is 2, R 3 is succinyl, glutaryl, adipoyl or sebacoyl.

Especially preferred compounds of formula are those where R 4 is hydrogen, and when p is 1, Rs is hydrogen or butyl, or when p is 2, Rs is hexamethylene.

Especially preferred compounds of formula are those where R 7 is chlorine, octylamino or Ti-butylamino, R 8 is T 1 -butylamino, and R 9 is a divalent nitrogen atom substituted by butyl.

Especially preferred compounds of formula (10) are those where q is 6, R 7 is T 1 butylamino and Rio is hydrogen.

Especially preferred compounds of formula (11) are those where n is 3, p is 2, one of R 11 or R 1 2 is T 2 and the other is hydrogen.

Especially preferred compounds of formula (12) are those where d is 1, k is 3, x is 3 or 4,

R

9 is divalent oxygen atom, and R 13 is methyl.

Especially preferred compounds of formula (13) are those where k is 3, y is 4-8. R 9 is a divalent oxygen atom, R 1 3 is hydrogen or methyl, d and h are 0, R 14 is hydrogen, or d is 1 and h is 0, and R 14 is trimethylsilyl.

-27- Especially preferred compounds of formula (14) are those where m is 0, R 9 is a divalent oxygen atom, R 10 is hydrogen or methyl, and z is an integer such that the molecular weight of the compound is 1500-3000 amu.

Especially preferred compounds of formula (15) are those where q is 6, y is 1-7, R 5 i is Tl-butylamino, R 1 6 is hydrogen, acetyl, ethylcarbamoyl, 2,4-bis(dibutylamino)-s-triazinyl, 2,4bis(diethylamino)-s-triazinyl, s-triazinyl substituted twice by Ti-butylamino or s-triazinyl substituted once by diethylamino or dibutylamino and once by Ti-butylamino, R 17 is dibutylamino, diethylamino, or T 3 where R 1 8 is acetyl or ethylcarbamoyl.

Especially preferred compounds of formula (20) are those where R 1 9 is hydrogen, octadecanoyl or hexadecanoyl.

Especially preferred compounds of formula (21) are those where R 20 is succinyl, glutaryl, adipoyl or sebacoyl.

Especially preferred compound of formula (30) is that where R 29 is heptadecyl.

The instant invention also pertains to a polymer composition or a recording material (a) containing an effective stabilizing amount of one or more compounds selected from the compounds of formula to formula (30) as described above including compounds of formulae and when b is 1 and E is methyl, ethyl, 2-propyl or 2-methyl-2-propyl. In general, effective stabilizing amounts of a compound of the invention are from 0.01 to 10 especially from 0.05 to 5% by weight, based on component of the stabilizer of component Preferably, the organic material to be stabilized is a natural, semi-synthetic or synthetic polymer or a color photographic material, especially a thermoplastic polymer or a coating composition.

Most preferably, the polymer is a polyolefin, especially a thermoplastic polyolefin useful in automotive coatings and applications or a urethane based automotive coating.

-28- The compounds of this invention exhibit superior hydrolytic stability, handling and storage stability as well as good resistance to extractability when present in a stabilized composition.

In general, organic materials which can be stabilized include 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut- 1-ene, poly-4-methylpent-l-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerisation (normally under high pressure and at elevated temperature).

b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either n- or o-coordinated. These S" metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, Ila and/or Ilia of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups.

These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

-29- 2. Mixtures of the polymers mentioned under for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-l-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example Cs-Cg) including hydrogenated modifications thereof (e.g.

tackifiers) and mixtures of polyalkylenes and starch.

Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).

6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/ styrene.

7. Graft copolymers of styrene or ca-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and I brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl Schloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as Scopolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from a,(3-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.

-31 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from

S**

hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-mphenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block -32copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

S23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and S also halogen-containing modifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.

-33- 28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

29. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.

31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for example, in U.S.

Patent No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S. Patent No. 4,355,147.

32. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with I unsaturated acrylic resins. The unsaturated acrylic resins include the urethane acrylates, polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups and the acrylated melamines. The polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst.

33. Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.

34. Epoxymelamine resins such as light-stable epoxy resins crosslinked by an epoxy functional coetherified high solids melamine resin such as LSE-4103 (Monsanto).

In general, the compounds of the present invention are employed in from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular 34 substrate and application. An advantageous range is from about 0.05 to about and especially 0.05 to about 1 The stabilizers of the instant invention may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer. The resulting stabilized compositions of the invention may optionally also contain from about 0.01 to about preferably from about 0.025 to about and especially from about 0. 1 to about 1 by weight of various conventional additives, such as the materials listed below, or mixtures thereof.

1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-d i-tert-butyl -4-n -butyl phenol, 2,6-di-tert-butyl- 4-isobutylphenol, 2,6-d icyclopentyl-4-methyl phenol, 2-(cx-methylcyclohexyl)-4,6-dimethylphenol, *2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexyl phenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-d imethyl-6-(1 '-methyl undec- 1 phenol, 2,4-dimethyl-6-( 1'methylheptadec-1 '-yl)phenol, 2,4-dimethyl-6-(1 '-methyltridec-1 '-yl)phenol and mixtures thereof.

1 Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylth iom ethyl-6- methyl phenol, 2,4-d ioctylth io methyl -6-ethyl phenol, 2,6-di-dodecylthiomethyl-4nonylphenol.

1.3. Hvdroguinones and alkylated hydroguinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl hydroqui none, 2,5-d i-tert-b utyl-4-hyd roxyani sole, 4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxypheny stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

35 1 Tocooherols, for example c-tocopherol, r-tocopherol, y-tocopherol, 8-tocopherol and mixtures thereof (Vitamin E).

Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2methyiphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, for example methylenebis(6-tert-butyl-4-methylphenol), 2,2'methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), methylen ebis (4,6-di-tert-butyl phenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethyl ide nebis(6-te rt-butyl-4-isobutyl phenol), 2,2'-methylenebis[6-(cz-methylbenzyl)-4nonyiphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6d di-tert-butyl phenol), 4,4'-methylen ebis (6-te rt-butyl-2-methyl phenol), 1, 1 -bis(5-tert-butyl-4hydroxy-2-methylphenyl)butane, 2,6-b is(3-te rt-butyl -5-methyl-2-hyd roxybenzyl) -4-methyl phenol, 1, 1, 3-tri s(5-te rt-butyl -4-hyd roxy-2-methyl phe nyl) butane, 1,1 -bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'hydroxyphenyl)butyrate), bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3'tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1, 1 d imethyl-2- hyd roxyphenyl) butane, 2,2-bis-(3,5-d i-te rt-butyl -4-hyd roxyphenyl) propane, 2,2-bis-(5te rt-b utyl -4-hyd roxy2-methyl phenyl) n-dodecyl me rcapto butane, 1, 1,5,5-tetra-(5-tert-butyl-4hydroxy-2-methylphenyl)pentane.

1.7. N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyI ether, octadecyl-4-hydroxy-3, 5-di methylbenzylmercaptoacetate, trideoyl-4-hydroxy-3,5-di-tertbutylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3, 5-di-tert-butyl-4-hydroxybenzylmercaptoaoetate.

1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di- 36 dod ecyl me rcaptoethyl -2,2-bis- (3,5-d i-te rt-butyl -4-hyd roxybenl) mal onlate, bis[4-( 1 ,1,3,3-tetram ethyl butyl) ph enyl bi s(3,5-d i-te rt-butyl-4-hyd roxybenzyl) malonate.

1.9. Aromatic hydroxvbenzyl compounds, for example 1 ,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phelol.

1 .10. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)- 1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyalililo)-1 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris(3,5-di-tertbutyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanu rate, 1 ,3,5-tris(4-te rt-butyl-3-hyd roxy-2,6-di methylbenzyl)isocyanu rate, 2,4,6-trisi -tert-butyl-4- hyd roxyphe nyl ethyl) 1,3,5-triazi ne, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1 ,3,5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

0 0 1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphoflate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbelzylphosphoflate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl di-tert-butyl-4-hydroxyphenyl)carbamate.

1 .13. Esters of f-(35-di-tert-butvl-4-hydroxvphenl)rorionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1,9nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of 1-(5-tert-butl-4-hydroxy-3-methvlphellhrolionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1,9- 37 nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyihexanediol, trimethylalpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of 1-(3,5-dicvclohexyl-4-hydroxyvhenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanu rate, N, N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri methylol propane, 4-hydroxymethyl- 1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxvphenyI acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hyd roxyethyl) isocyan urate, N, N'-bis(hydroxyethyl)oxamide, 3thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1. 17. Amides of 1-(35-di-tert-butyl-4-hydroxyphenl)Propionic acid e.g. 4-hydroxyphenylpropionyl)hexamethylenediamide, N, N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N, N'-bis(3,5-di-tert-butyl-4-hydroxyphelylpropionyl)hydrazide, N,N bs2(-35d-et-uy--yrxpey~roinlx~ty~xmd (Naugard®XL-1 supplied by Uniroyal).

1. 18. Ascorbic acid (vitamin C) 1 .19. Aminic antioxidants, for example N ,N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butylp-phenylenediamine, N ,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1 -ethyl-3methylpentyl)-p-phenylenediamine, N,N'-bis(1 -methylheptyl)-p-phenylenediamine, N ,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N ,N'-bis(2-naphthyl)-pphenylenediamine, N -i sop ropyl -N'-phe nyl-p-phenyl ened iami ne, 1,3-dimethylbutyl)-N'-phenylp-phenylenediamine, N-(1 -methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'- 38 phenyl-p-phenlenediamine, 4-(p-toluenesulfamoyl)dipheflylamifle, N,N'-dimethyl-N,N'-di-secbutyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1 -naphthylamine, N-(4-tert-octylphenyl)-1 -naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-ootyldiphenylamine, 4-n-butylaminophenol, 4butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadlecanoylaminophenol, bis(4-methoxyphenyl)amine, 2 ,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenyl methane, 4,4'-d iami nodi phe nyl methane, N N'-tetramethyl-4,4'diaminodiphenylmethane, 1, 2-bis [(2-methyl phenyl) amino] ethane, 1 ,2-bi s(phenyl amino) propane, (o-tolyl)biguanide, bis[4-(1 ',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1 naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1 ,4- *benzothiazine, phenothiazine, a mixture of mono- und dialkylated tert-butyl/tertoctyiphenothiazines, a mixture of mono- und dialkylated tert-octyl-phenothiazines, Nallyiphenothiazin, N, N,N',N'-tetraphenyl-1 ,4-diaminobut-2-ene, N, N-bis(2,2,6,6-tetramethyl- *piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate, 2,2,6,6tetramethyl pipe ridi n-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilisers 2.1. 2-(2'-Hydroxyohenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)be nzotriazole, 2-(2'-hydroxy-5'-( 1,1 ,3,3-tetramethyibutyl)phenyl)benzotriazole, 2-(3',5'-di-tert- 2-(3'-tert-butyl- 2'-hydroxy-5'-methylphenyl)-5chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy- 4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis- (a,Qx-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2- 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hyd roxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2- 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyoxycarbony[ethyl) phenyl) benzotriazo Ie, 2-3-etbtl5-2(-tyhxyoycroyehl-'hdoy 39 phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzOtriazole, 2-(3'-tert-butyl-2'hyd roxy-5'- isooctyl oxyca rbonyl ethyl) phe nyl be nzotriazolIe, 2,2'-methylene-bis[4-( 1,1 ,3,3tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-butyl-5'- (2-methoxycarbonyl ethyl) -2'-hyd roxyphenyl] -2 H-be nzotriazole with polyethylene glycol 300;

CH

2 CH2- COO -CH 2

CH

2 where R 3'-tert-butyl-4'-hydroxy-5'-2H-berizotriazol-2ylphenyl, 2-[2'-hydroxy-3'-(ax,Q-dimethylbenzyl)-5'-( 1,1 ,3,3-tetramethylbutyl)-phenyl]benzotriazole; 2-[2'-hydroxy-3'-(l 1,3,3-tetramethylbuty)-5'-(,-dimethylbefly)-phelyl]belzotriazole.

2.2. 2-Hvdroxvbenzorhenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2' ,4'-trihydroxy and 2'-hydroxy-4 ,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butyiphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hyd roxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybeflzoate.

2.4. Acrlates, for example ethyl a-cyano-P3,f-diphenylacrylate, isooctyl cc-cyano-j3,1-diphenylacrylate, methyl oc-carbomethoxycinnamate, methyl (x-cyano-I3.methyl-p-methoxy-cinnamate, butyl ax-cyano-p3-methyl-p-methoxy-cinnamate, methyl cx-carbomethoxy-p-methoxycinnamate and N-(P-carbomethoxy-f3-cyanovinyl)-2-methylindoline.

Nickel compounds, for example nickel complexes of 2,2'-thio-bis-[4-(1 ,1 ,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as nbutylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tertbutylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1 -phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

40 2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2 ,2,6,6-tetramethyl-4-piperidyl)succinate, bis( 1,2,2 ,6,6-pentamethyl-4-piperidyl)sebacate, bis(l1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) nbutyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1 -(2-hydroxyethyl)-2,2,6,6tetramethyl-4-hydroxypiperidline and succinic acid, linear or cyclic condensates of N,N'bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro- 1 ,3,5-triazine, tri s(2,2,6,6-tetramethyl -4-pi pe ridyl) n itri lotri acetate, tetrakis(2,2,6,6-tetramethyl-4piperidyl)-1 ,2,3,4-butane-tetracarboxylate, 1,1 ,2-ethanediyl)-bis(3,3,5,5-tetramethyl pipe razi none), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1 ,2,2,6,6-pe ntamethyl pipe ridyl) n-butyl -2-(2-hyd roxy-3,5-d i-te rt-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5]decan-2,4-dione, bis(1 -octyloxy- 2,2,6,6-tetramethylpiperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cyclic condensates of N, N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1 ,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino- 2,2,6,6-tetramethylpiperidyl ,3,5-triazine and 1 ,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1 ,2,2,6,6-pentamethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis-(3-am inopropyl amino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-temethyl-1 ,3,8triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1 -(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5dione, 3-dodecyl-1 ,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethy pipe rid ine, a condensation product of N,N'bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro- 1 ,3,5-triazine, a condensation product of 1 ,2-bis(3-ami nopropylami no) ethane and 2,4,6trichloro- 1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.

[136504-96-6]); N -(2,2,6,6-tetramethyl -4-pi pe ridyl) n-dod ecylsucci ni mid, 1,2,2,6,6pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-7,7,9,9-tetramethyl-1 -oxa-3,8-diaza-4a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1 -oxa-3,8-diaza- 4-oxospiro [4,5]decane und epichlorohydrin, 1, 1 -bis(1 ,2,2,6,6-pentamethyl-4piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl- 4-piperidyl)hexamethylenediamine, diester of 4-methoxy-methylene-malonic acid with 1,2,2,6,6pentamethyl-4-hyd roxypi pe rid ine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4piperidyl)]siloxane, reaction product of maleic acid anhydride-cL-olefin-copolymer with 2,2,6,6tetramethyl-4-aminopiperidine or 1 ,2,2,6,6-pentamethyl-4-aminopiperidine.

41 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxaflilide, 2,2'-dioctyloxy-5,5'di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl -2'-ethoxanilide and its mixture with 2ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hvdroxyphenyl)-1 .3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphelyl)-1 ,3,5-triazine, 2-(2,4dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimlethylphelyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-trideoyloxyphenyl)-4,6-bis(2,4-dimethylphelyl)-1 ,3,5-triazine, 2-[2hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phelyl]-4,6-bis(2,4-dimethyl)-l ,3,5-triazine, 2-[2hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5-triazine, 2-[4- (dodecyloxy/tridecyloxy-2-hyd roxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphelyl)- 1,3,5triazine, 2-[2-hydroxy-4(2hydroxy-3-dodecyloxy-propoxy)phel]-4,6-bis(2,4-dimethyIphel)- 1 ,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphelyl-1 ,3,5-triazine, 2-(2-hydroxy-4methoxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1 ,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1 triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1 -oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4dimethylphenyl)-1,3,5-triazine.

3. Metal dleactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-b is(salicyloyl) hydrazine, N ,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropioflyl) hydrazine, 3salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilidle, isophthaloyl dihydrazide, sebacoyl bisphenyihydrazide, N,N'-diacetyladipoyl dihydrazide, N ,N'-bis(salioyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadlecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodlecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-ditert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodlecyloxypentaerythritol diphosphite, 42 bi s(2,4-d i-te rt-butyl -6-meth yl phe nyl) pe ntae ryth ritolI di phosphite, bis(2,4,6-tris (te rt-b utyl phenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8, 1 -tetra-tert-butyl-1 2H-dibenz[d,g]-1 ,3,2dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-tert-butyl-6methylphenyl) ethyl phosphite, 6-fluoro-2,4,8, 1 -tetra-tert-butyl-1 2-methyl-dibenz[d 1,3,2dioxaphosphocin, 2,2',2"-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl- 1 '-biphenyl-2,2'diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1 ,1 '-biphenyl-2,2'-diyl)phosphite, ethyl -2-(2,4,6-tri -te rt-butyl phenoxy) -1 ,3,2-d ioxaphosphirane.

Especially preferred are the following phosphites: Tris(2,4-di-tert-butylphenyl) phosphite (I rgafosO1 68, Ciba-Geigy), tris(nonylphenyl) phosphite, a. a

(CH

3 3 C C(CH 3 3

H

3 C-CH

/P-F

0 C (CH 3 3

(CH

3 3

C

a. a (CHA)C C(CHA) 0 P-0-CH 2 CH2- 0 (CHA)C

,C(CH

3 3 0

P--

2 CH(C H)CH CH 3

(C)

2 -N

(B)

3 (CH3)C

(CH

3 3

C

C(CH

3 3 43 0 0 (0H) 3 C CH 3 (H)C 0 0 (0)

O(CH

3 3

(CH

3 3 0 C(CH 3 3 (CH 3 3

C

0 0

H-

3 C O-F' \P-0 CH O 3 0 (E) o-O 0 o C(0H 3 3

(CH

3 3 0 OH 3 (F H -0P 0 P-0H 2 0H 3 (F 3C O PP-O-O 8H 3 (G) .9.*378/18 37 HC ODCO HOH 3

H

3 0 O'lc\C

H

3 2 3 2 Hydroxylamines, for example, N ,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N ,Ndioctyihydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, Noff* dihexadecyihydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-ootadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octylalpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradeoyl-alpha-tridcyl-nitrone, Nhexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadeCyl-nitrone, N-hexadecyl-alphaheptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-litrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. ThiosynerpiSts, for example, dilauryl thiodipropionate or distearyl thiodipropionate.

-44- 8. Peroxide scavengers, for example esters of 1-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(pdodecylmercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.

Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zink pyrocatecholate.

11. Nucleating agents, for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers). Especially preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol, und 1,3:2,4-di(benzylidene)sorbitol.

12. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, @o graphite, wood flour and flours or fibers of other natural products, synthetic fibers.

13. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-ditert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-ditert-butyl-benzofuran-2-one.

Amine oxides, for example amine oxide derivatives as disclosed in U.S. Patent Nos.

5,844,029 and 5,880,191, didecyl methyl amine oxide, tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amine oxide. U.S. Patent Nos. 5,844,029 and 5,880,191 disclose the use of saturated hydrocarbon amine oxides towards the stabilization of thermoplastic resins. It is disclosed that the thermoplastic compositions may further contain a stabilizer or mixture of stabilizers selected from phenolic antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, organic phosphorus compounds, alkaline metal salts of fatty acids and thiosynergists. The co-use of amine oxides with other stabilizers towards stabilizing polyolefins is not exemplified.

**The amine oxides costabilizers are of Formula (I)

E

1

(I)

E 2* wherein El and E 2 are independently a straight or branched chain alkyl of 6 to 36 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 36 carbon atoms, alkaryl of 7 to 36 carbon atoms, cycloalkyl of 5 to 36 carbon atoms, alkcycloalkyl of 6 to 36 carbon atoms or cycloalkylalkyl of 6 to 36 carbon atoms; -46-

E

3 is a straight or branched chain alkyl of 1 to 36 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 36 carbon atoms, alkaryl of 7 to 36 carbon atoms, cycloalkyl of 5 to 36 carbon atoms, alkcycloalkyl of 6 to 36 carbon atoms or cycloalkylalkyl of 6 to 36 carbon atoms; with the proviso that at least one of El, E 2 and E 3 contains a carbon-hydrogen bond; and wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups may be interrupted by one to sixteen -SO2-, -COO-, -OCO-, -NE 4

-CONE

4 and

-NE

4 CO- groups, or wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups may be substituted by one to sixteen groups selected from -OE 4

-SE

4

-COOE

4

-OCOE

4

-COE

4

-N(E

4 2

-CON(E

4 2

-NG

4

COE

4 and 5- and 6-membered rings containing the -C(CH 3

)(CH

2 Rx)NLi(CH 2 Rx)(CH3)C- group or wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups are both interuppted and substituted by the groups mentioned above; and wherein

E

4 is independently hydrogen or alkyl of 1 to 8 carbon atoms; Rx is hydrogen or methyl, preferably hydrogen; L, is a C1.30 straight or branched chain alkyl moiety, a -C(O)R 3 0 moiety wherein R 30 is a C1-30 straight or branched chain alkyl group, or a -OR 3 0 moiety wherein R 3 0 is a C1-30 straight or branched chain alkyl group; and wherein said aryl groups may be substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof.

A preferred structure of formula is where E 1 and E 2 are independently benzyl or substituted benzyl. It is also possible for each of E 1

E

2 and E 3 to be the same residue. E 1 and

E

2 are also preferably alkyl groups of 8 to 26 carbon atoms and most preferably alkyl groups of to 26 carbon atoms and E 3 is preferably an alkyl group of 1 to 22 carbon atoms and most preferably methyl or substituted methyl. Also, preferred amine oxides include those wherein El,

E

2 and E 3 are the same alkyl groups of 6 to 36 carbon atoms. Preferably, all of the -47aforementioned residues for E 2 and E 3 are saturated hydrocarbon residues or saturated hydrocarbon residues containing at least one of the aforementioned -SO-, -C02-, or -CON- moieties. Those skilled in the art will be able to envision other useful residues for each of El, E 2 and E 3 without detracting from the present invention.

The saturated amine oxides may also includes poly(amine oxides). By poly(amine oxide) is meant tertiary amine oxides containing at least two tertiary amine oxides per molecule.

Illustrative poly(amine oxides), also called "poly(tertiary amine oxides)", include the tertiary amine oxide analogues of aliphatic and alicyclic diamines such as, for example, 1,4diaminobutane; 1,6-diaminohexane; 1,10-diaminodecane; and 1,4-diaminocyclohexane, and aromatic based diamines such as, for example, diamino anthraquinones and diaminoanisoles.

Also included are tertiary amine oxides derived from oligomers and polymers of the aforementioned diamines. Useful amine oxides also include amine oxides attached to polymers, for example, polyolefins, polyacrylates, polyesters, polyamides, polystyrenes, and the like. When the amine oxide is attached to a polymer, the average number of amine oxides per polymer can vary widely as not all polymer chains need to contain an amine oxide. All of the aforementioned amine oxides may optionally contain at least one -CO2-, or -CONE 4 moiety. In a preferred embodiment, each tertiary amine oxide of the polymeric tertiary amine oxide contains a C, residue.

The groups El, E 2 and E 3 of formula may be attached to a molecule containing a hindered amine. Hindered amines are known in the art and the amine oxide of the present invention may be attached to the hindered amine in any manner and structural position of the hindered amine. Useful hindered amines when part of a compound of the amine oxide coadditive include those of the general formulas (II) and (III): -48- RxCH 2 CH, 3CH RxCH 2

H

3 L N N (III) R CH2

CH

e 3 wherein L 1 and Rx are as described above. Also included are amine oxides containing more than one hindered amine and more than one saturated amine oxide per molecule. The hindered amine may be attached to a poly(tertiary amine oxide) or attached to a polymeric substrate, as discussed above.

The co-stabilizers, with the exception of the benzofuranones listed under 11, are added for example in concentrations of 0.01 to 10%, relative to the total weight of the material to be stabilized.

I Further preferred compositions comprise, in addition to components and further additives, in particular phenolic antioxidants, light stabilizers or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 of the list), sterically hindered amines (item 2.6 of the list), phosphites and phosphonites (item 4 of the list) and peroxide-destroying compounds (item of the list.

49 Additional additives (stabilizers) which are also particularly preferred are benzofuran-2ones, such as described, for example, in US-A-4,325,863, US-A-4,338,244 or US-A-5,175,312.

The phenolic antioxidant of particular interest is selected from the group consisting of noctadecyl 3,5-di-tert-butyl-4-hydroxyhydroci nnamate, neopentanetetrayl tetrakis(3, 4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanu rate, thiodiethylene bis(3,5-di-tert-butyl-4hydroxyhydrocinnamate), 1, 3,5-tri methyl-2,4,6-tris(3,5-d i-te rt-b utyl-4-hyd roxy benzyl) benlzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-pcresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 1 ,3,5-tris(2,6-dimethyl-4-tert-butyl-3hyd roxybenzyl)isocynu rate, 1, 1,3,-tris(2-methyl-4-hyd roxy-5-te rt-butyl phe nyl) butane, 1 ,3,5-trisll2- 5-di-tert-butyl-4-hydroxyhyd rocinnamoyloxy)ethyllisocyanu r ate, 3,5-di-(3,5-di-tert-butyl-4hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1 di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyratel, octyl 4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyI)hydrazide, and A most preferred phenolic antioxidant is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1 ,3,5-tri methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybelzyl)belzefe, 1 ,3,5-tris(3,5-di-tert-butyl-4hyd roxybenzyl)isocyanu rate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis(4,6-di-tertbutylphenol).

The hindered amine compound of particular interest is selected from the group consisting of bis (2,2,6,6-tetram ethyl pi perid in -4-yl) sebacate, bis (1 2,2,6,6-pentamethyl pipe rid in-4-yl) sebacate, di( 1,2,2,6,6-pentamethylpiperidin-4-y) (3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, 4-benzoyl-2,2,6,6-tetramethyl pipe rid ine, 4-stearyloxy-2,2 ,6,6-tetramethyl piperidine, 3-n-octyl- 7,7,9,9-tetramethyl-1 ,3,8-triaza-spiro[4.5]decane-2,4-diofle, tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 50 1 ,2-bis(2 ,2,6,6-tetramethyl-3-oxopiperazin-4-yI)ethane, 2,2 ,4,4-tetramethyl-7-oxa-3,20-diaza-2 1- 1.11 heneicosane, polycondensation product of 2,4-dichloro-6-tert-octylamino-striazine and hexamethyl eneb is(am ino-2,2,6,6-tetramethyl p ipe rid ile), polycondensation product of 1 (2-hyd roxyethyl) -2,2,6,6-tetramethyl hyd roxypi pe rid ifle and succinic acid, polycondensation product of 4,4'-hexamethylenebis-(am ino-2,2,6,6-tetramethyl pipe rid ine) and 1 ,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-y) 1 ,2,3,4-butanetetracarboxylate, tetrakis( 1,2,2,6,6-pentamethylpiperidin-4-y) 1 ,2,3,4-butanetetracarboxylate, polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N, N',N",N"'-tetrakis[(4,6-bis(butyl- 1 ,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-y I-1,1 O-diamino-4,7-diazadecane, polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'hexamethylenebis(amino-1 ,2,2,6,6-pentamethylpiperidine), mixed [2,2,6,6-tetramethylpiperidin- 4-yI/P,3,fPj''-tetramethyI-3,9-(2,4,8 ,1 O-tetraoxaspiroll5.5]-undecane) diethyl] 1,2,3,4b utanetetracarboxyl ate, mixed 1, 2,2,6,6-pentamethyl pipe rid in-4-y/3, P, ',I'-tetramlethyI 10-tetraoxaspiro[l5.5]undecane)diethyl] 1 ,2,3,4-butanetetracarboxylate, octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate), 4,4'-ethylenebis(2,2,6,6-tetramethylpiperazifl-3-one), N-2,2,6,6-tetramethyl pipe rid in-4-yI -n dodecylsuccinimide, N-i ,2,2,6,6-pentamethyl piperidin-4-yI-n-dodecylsuccinimide, N-i -acetyl- S2,2,6,6-tetramethyl pipe rid in-4-yl n-dodecylsulcci nim ide, 1 -acetyl3-dodecyl-7,7,9,9-tetramethyl- 1 ,3,8-triazaspiro[4.5]decane-2,4-dione, d 1 -octyloxy-2,2 ,6,6-tetramethyl pipe rid in-4-yl) sebacate, di-( 1-cycloh exyloxy-2,2,6,6-tetra methyl pipe rid ifl-4-yI) succinate, 1 -octyloxy-2,2,6,6tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(l -cyclohexyloxy- 2,2,6,6-tetramethylpiperidin-4-y)imino-hexamethylele-[4-(1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yI)imino], 2,4,6-tris[N-(1 -cyclohexyloxy-2 ,2,6,6-tetramethyl piperidin-4-yI)-nbutylamino]-s-triazine, 2-(2-hydroxyethylamino)-4,6-bisN-[1 -(cyclohexyloxy)-2,2,6,6-tetramethylpi pe rid il-4-YIIbutylamino-s-triazine, oligomer of N -2,2,6,6-tetram ethyl pi peridi n-4-y) butylami no]-striazi n-4-y}-N N'-bi s(2,2,6,6-tetramethyl pipe rid in-4-y)-1, ,6-hexanediami ne terminated with 2,4bis(dibutylamino)-s-triazin-6-yi, N, N "-tris{2,4-bi s[ N-(1 ,2 ,2,6,6-pentamethyl pipe rid in -4-yl)butylam ino]-s-triazi n-6-yI}-3,3'-ethylened ii m inod ipropylai ne, N, N"'-tris{2,4-bis[N-(1 ,2,2,6,6- -51 pentamethyl pipe ridi n-4-y) butylamnino]-s-triazi n-6-yl 1-3,3'-ethyleflediiminod ipropylamifle and N,N',N",N"'-tetrakis2,4-bis[N-(1 ,2,2,6,6-pentamethylpiperidin-4-yl)butylamiol-s-triazin-6-y}- 3,3'-ethylenediiminodipropylamine; N,N',N"-tris{2,4-bis[N-(1 -cyclohexyloxy-2,2,6,6-tetramethylpipe ridi n-4-yI) butylamino]-s-triazin-6-yl}-3,3'-ethylelediimi nodipropylamine, N ,N"'-tris{2,4bis[N-(1 -cyclo hexyloxy-2,2,6,6-tetramethylpi perid i- 4 -yI) butylamino]-s-triazin-6-yI}-3,3'-ethylenediiminodipropylamine, N N"'-tetrakis{2,4-bisIN-(1 -cyclohexyloxy-2,2,6,6-tetramethylpipe rid in -4-yl) butylami noll-s-triazi n-6-yl}-3,3'-ethylefledii mi nodi propylamnine, oligomer of pro poxy-2,2,6,6-tetramethyl p ipe rid in-4-yl) butylam iflo]--tri azif--l4Y-N, N'bis(l -propoxy-2,2,6,6tetramnethyl pipe rid in-4-y) 6-hexanediamnine terminated with 2 ,4-bis(dibutylamino)-s-triazin-6-y, or the condensation product of 2-.morpholino-4,6-dichloro-s-triazifle with N,N'-bis(1 ,2,2,6,6pe ntamethylp ipe rid in-4-y) 1,6-hexaned iami ne.

A most preferred hindered amine compound is bi s(2,2,6,6-tetramethyl pipe rid in-4-yl) sebacate, bis(1 2,2,6,6-pe ntamethyl pipe rid in-4-yl) sebacate, di (1 ,2,2,6,6-pentamethylpiperidin- 4-yI) (3,5-di -te rt-butyl-4-hyd roxybenzyl) butyl maloflate, the polycondensation product of 1 hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6tetramethylpiperidine), N, N',N",N"'-tetrakis[(4,6-bis(butyl-( 1,2,2,6,6-pentamethylpiperidin-4- K2. yl)amino)- s-triazine-2-y]-1 ,1 O-diamino-4,7-diazadecane. di-(1 -octyloxy-2,2,6,6-tetramethyl *piperidin-4-yI) sebacate, di-( 1 -cyclohexyloxy-2,2,6,6-tetra methyl pipe rid in -4-yl) succinate, 1 octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-diy][ 2 cyc o h exyloxy-2,2,6,6-tetramethyl pipe rid in-4-yl) imi nohexamethylene-4 (11 -cyclohexyloxy- 2,2,6,6-tetramethyl pipe rid in-4-yl) imi no], or 2,4,6-tris[N-( 1 -cyclohexyloxy-2,2,6,6-tetramethyl piperidin-4-yl)-n-butylamino]-s-triazine.

The instant composition can additionally contain another UV absorber selected from the group consisting of the s-triazines, the oxanilides, the hydroxylbenzophenones, benzoates and the c-cyanoacrylates.

Particularly, the instant composition may additionally contain an effective stabilizing amount of at least one other 2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; or hindered amine or mixtures thereof.

52 Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from the group consisting of 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole; 2-[2-hydroxy-3,5-di(ccca-dimethylbenzyl)phenyl]-2H-benzotriazole; 2-[2-hydroxy-3-(ax,a-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole; hyd roxy-3-te rt-butyl (omega-hyd roxy-octa(ethyleneoxy) carbonyl) ethyl] phenyl- 2H-benzotriazole; and 2-{2-hyd roxy-3-te rt-b utyl -5-[2-(octyloxy)carbonyl) ethyl] phenyl}-2 H- benzotriazole.

Preferably the 2-hydroxyphenyl-2H-benzotriazole may also be selected from the group consisting of 5-trifluoromethyl-2-(2-hydroxy-3-ca-cumyl-5-tert-octylphenyI)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole; 2,2'-methylene-bi s[6-(5-trifl uoromethyl-2 H -benzotriazol-2-yl)-4-tert-ootyl phenol]; methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2'-[4-tert-octy-6-(5-trifluoromethyl-2H-benzotriazol-2-yl) phenol]; (f 5tiloo ehl2 -eztizl2y)--etbtl4hdoyyrcna i cd my 3-(5-trifl uoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxycnai cd hyrcin*ae meotyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate; ioc3-5-trifluoromethyl-2Hroy5(-benzoro2yl)p5-ertbyl]--hyd rioxhyrcinmte;looehl2[-yrx--3arlolxpoy~hnl-Hbnoraoe 5-trifluoromethyl-2-[2-hydroxy-5-(3-mhydrloxypropyl)phenyl]-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylyloxynpropyl)phenyl]-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloylamxypropyl)phenyl]-2H-benzoa-e triazole; 5-trifluoromethyl-2-(2-hydroxy-3-cx-cumyl-5-tert-butylphenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-ac-cumyl-5-nonylphenyl)-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-3-cc-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole; 53 5-trifluoromethyl-2-[2-hydroxy-3-L-cumyl-5-(3-hydroxypropyl)phelYl]-2H-belzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-amyl phenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butyl phenyl)-2H-benzotriazole; 5-trifluo romethyl-2-(2-hyd roxy-3-dodecyl -5-m ethyl phenyl)-2 H-benzotri azole; 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)pheflyl)-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phelylI-2H-belzotriazole; 5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-belzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3,5-di-cc-cumylphenyl)-2H-benzotriazole; 5-fluoro-2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzotriazole; 5-butylsulfonyl-2-(2-hydroxy-3,5-di-u-cumylphenyl)-2H-belzotriazole; (aa) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butyl phenyl)-2H-benzotriazole; (bb) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octyl phenyl)-2H-benzotriazole; and (cc) 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-belzotriazole.

Preferably, the other tris-aryl-s-triazine is selected from the group consisting of 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)--triazine; 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine; 2,4-bis(2,4-dimethylpheny)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s-triazine; and 2-(2-hydroxyethylamino)-4,6-bis[N-butyl-.N-(1 -cyclohexyl oxy-2,2,6,6-tetramethyl pipe rid in- 4-yl)amino]-s-triazine.

Other materials to be stabilized according to the invention are recording materials. By such materials are meant, for example, those described in Research Disclosure 1990, 31429 (pages 474-480) for photographic reproduction and other reprographic techniques.

The novel recording materials comprise, for example, those for pressure-sensitive copying systems, microcapsule photocopier systems, heat-sensitive copier systems, photographic material and ink-jet printing.

-54- The novel photographic material can be a black and white or a colour photographic material; colour photographic material is preferred. Further details on the structure of colour photographic material, and the components which can be employed in the novel material, can be found, inter alia, in US-A-5,538,840, column 27, line 25, to column 106, line 16, and in the publications cited therein; these passages of US-A-5,538,840 are hereby incorporated by reference. Application of the novel compounds is essentially as described for UV absorbers or hindered amine stabilizers in this reference. Further important components, especially couplers, are described in US- 5,578,437.

The acrylic resin lacquers which can be stabilized against light, moisture and oxygen in accordance to the instant invention are conventional acrylic resin stoving lacquers or thermosetting resins including acrylic/melamine systems which are described, for example, in H.

Kittel's "Lehrbuch and Beschichtungen", Vol. 1 Part 2 on pages 735 and 742 (Berlin 1972), "Lackkunstharze" (1977) by H. Wagner and H. F. Sarx on pages 229-238, and in S. Paul's "Surface Coatings: Science and Technology", (1985).

The polyester lacquers which can be stabilized against the action of light and moisture are conventional stoving lacquers described e.g. in H. Wagner and H. F. Sarx, op. cit., on pages 86-99.

The alkyd resin lacquers which can be stabilized against the action of light and moisture in accordance with the instant invention are the conventional stoving lacquers which are used in particular for coating automobiles (automobile finishing lacquers), for example lacquers based on alkyd/melamine resins and alkyd/acrylic/melamine resins (see H. Wagner and H. F. Sarx, **"Lackkunstharze" (1977), pages 99-123). Other crosslinking agents include glycoluril resins, blocked or unblocked isocyanates or epoxy resins. Other lacquers which can be stabilized include those with crosslinkable functionalities such as carbamate and siloxane.

The lacquers stabilized in accordance with the invention are suitable both for metal finish coatings and solid shade finishes, especially in the case of retouching finishes, as well as various coil coating applications. The lacquers stabilized in accordance with the invention are preferably applied in the conventional manner by two methods, either by the single-coat method or by the two-coat method. In the latter method, the pigment-containing base coat is applied first and then a covering coat of clear lacquer over it.

Although major emphasis in this application is directed to acid-catalyzed baked finishes, it is also to be noted that the compounds of the present invention are applicable for use in nonacid catalyzed thermoset resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicon, isocyanates or isocyanurates. The epoxy and epoxy-polyester resins are crosslinked with conventional crosslinkers such as acids, acid anhydrides, amines and the like. Correspondingly, the epoxide may be utilized as the crosslinking agent for various acrylic or polyester resin systems that have been modified by the presence of reactive groups on the backbone structure.

The amount of instant stabilizer compound used is 0.1 to 5% by weight, based on the solvent-free binder, preferably 0.5 to 2% by weight. The binders can be dissolved or dispersed S in customary organic solvents or in water or can be solvent-free.

oO° o When used in two-coat finishes, the compounds of the instant invention can be incorporated in the clear coat or both in the clear coat and in the pigmented base coat.

To attain maximum light stability, the concurrent use of other conventional light stabilizers can be advantageous. Examples are UV absorbers of the benzophenone, S° benzotriazole, acrylic acid derivatives, oxalanilide, aryl-s-triazine or metal-containing types (e.g.

organic nickel compounds). In two-coat systems, these additional light stabilizers can be added to the clear coat and/or the pigmented base coat.

S• •If such combinations of stabilizers are used, the sum of all light stabilizers is 0.2 to by weight, preferably 0.5 to 5% by weight, based on the film-forming resin.

When water-soluble, water miscible or water dispersible coating are desired ammonium salts of acid groups present in the resin are formed. Powder coating composition can be prepared by reacting glycidyl methacrylate with selected alcohol components.

-56- It is also contemplated that the instant compounds would find particular value when used with water-soluble inks and related polar oriented utilities where the presence of the OH moiety would provide for better compatibility and properties related to such aqueous environments.

The instant compounds are also useful in the stabilization of acid catalyzed thermoset resins which are disclosed in United States Patent No. 5,112,890, the relevant parts of which are incorporated herein by reference.

These resins are used in baked enamels or stoving lacquers. Hindered amine light stabilizaers are well known to be effective in stabilizing a host of organic substrates including polymers from the deleterious effects of oxygen and light. Such hindered amine light stabilizers have been used in the stabilization of hot-crosslinkable alkyd or acrylic metallic stoving lacquers (see U.S. Patent No. 4,426,472) and in stabilizing acid-catalyzed stoving lacquers based on hotcrosslinkable acrylic polyester or alkyl resins (see U.S. Patent Nos. 4,344,876 and 4,426,471).

None of the hindered amine light stabilizers of these patents possess structures having an Osubstituted hydroxyl group substituted directly on the N-atom of the hindered amine. The instant compounds have such substitution and additionally are even less basic than the NOR a..

compounds described in U.S. Patent No. 5,112,890 as is seen in instant working Example 114.

S.In their industrial uses, enamels with high solids content based on crosslinkable acrylic, polyester, urethane or alkyd resins are cured with an additional acid catalyst. Light stabilizers containing a basic nitrogen group are generally less than satisfactory in this application.

Formation of a salt between the acid catalyst and the light stabilizer leads to incompatibility or insolubility and recipitation of the salt and to a reduced level of cure and to reduced light protective action and poor resistance to moisture.

The acid catalyzed thermoset enamels must be stabilized in order to function acceptably in end-use applications. The stabilizers used are hindered amines, preferably those substituted on the N-atom by an inert blocking group in order to prevent precipitation of the basic amine with the acid catalyst with a concomitant retardation in cure, optionally in combination with UV absorbers as described above.

-57- The stabilizers are needed to impart greater retention of durability to the cured enamels (as measured by 200 gloss, distinction of image, cracking or chalking); the stabilizers must not retard cure (normal bake for auto finishes at 121 and low bake repair at 82'C) as measured by hardness, adhesion, solvent resistance and humidity resistance; the enamel should not yellow on curing and further color change on exposure to light should be minimized; the stabilizers should be soluble in the organic solvents normally used in coating applications, such as methyl amyl ketone, xylene, n-hexyl acetate, alcohol and the like.

The instant hindered amine light stabilizers on the N-atom by an 0-substituted moiety containing a free hydroxyl group fulfill each of these requirements and provide alone or in combination with a UV absorber outstanding light stabilization protection to the cured acid catalyzed thermoset enamels.

The instant invention also pertains to resin systems capable of being fully cured under ambient conditions. For example, applicable resins include alkyd, acrylic, polyester and epoxide resins as described in S. Paul's "Surface Coatings: Science and Technology" (1985), pages 310. Various acrylic and modified acrylic resins are described in H. Kittel's "Lehrbuch der Lacke .eve*: unde Beschichtungen", Vol. 1, Part 2, on pages 735 and 742 (Berlin 1972), and in "Lackkunstharze" (1977) by H. Wagner and H. F. Sarx, op. cit, on pages 229-238. Typical crosslinkable polyester resins which can be stabilized against the action of light and moisture ego* are described e.g. in H. Wagner and H. F. Sarx, op. cit., on pages 86-99. The unmodified and modified alkyd resins which can be stabilized are conventional resins which are used in trade sales, maintenance and automotive refinish coatings. For example, such coatings are based on alkyd resins, alkyd/acrylic resins and alkyd/silicon reins (see H. Wagner and H. F. Sarx, op. cit., pages 99-123) optionally crosslinked by isocyanates or epoxy resins.

In addition various acrylic lacquer coating compositions are disclosed in U.S. Patent No.

4,162,249. Other acrylic/alkyd resins with polyisocyanate additives are disclosed in U.S. Patent No. 4,471,083; and acrylic resins containing either pendant amino ester groups or glycidyl groups are described in U.S. Patent No. 4,525,521.

The ambient cured coatings stabilized by the instant compounds are suitable both for metal finish coatings and solid shade finishes, especially in the case of retouching finishes. The -58lacquers stabilized by the instant compounds are preferably applied in a conventional manner by two methods, either by the single-coat method or by the two-coat method. In the latter method, the pigment-containing base coat is applied first and a covering coat of clear lacquer applied over it. When used in two-coat finishes, the instant hindered amine compound can be incorporated in the clear coat or both in the clear coat and in the pigmented base coat.

The instant invention also pertains to abrasion-resistant coating compositions suitable for coating over polycarbonates. Such coatings as described in U.S. Patent No. 5,214,085 comprise a silyl acrylate, aqueous colloidal silica, a photoinitiator and optionally a polyfunctional acrylate as well as UV absorbers. Such coatings provide resistance after prolonged outdoor exposure to sunlight, moisture, thermal cycling causing yellowing, delamination and formation of microcracks and decreasing transparency.

0:00Related hindered amine stabilizers have been utilized individually and in combination with UV absorbers to improve the performance characteristics of ambient cured coating systems. Notwithstanding such improvements, there still exists a need to further retard the photooxidation and photodegradation of such ambient cured systems and thereby provide se**: increased effectiveness by maintaining the physical integrity of the coatings. Such effectiveness can be manifested by prevention of embrittlement, cracking, corrosion, erosion, loss of gloss, chalking and yellowing of the coating.

It has now been determined that the aforementioned improvements canbe achieved by substitution of the N-atom of the hindered amines with an -OR moiety and by the utilization of such derivatives in ambient cured coating systems as is taught in United States Patent No.

5,124,378, the relevant parts of which are incorporated herein by reference. The instant S. compounds are even less basic than the compounds of U.S. 5,124,378 and are particularly well suited for this task. In particular, the physical integrity of the coatings is maintained to a higher degree with significant reduction in loss of gloss and in yellowing. Accordingly, the instant invention relates to the use of the instant NOR compounds, where the R moiety is further substituted by a hydroxyl group, optionally together with further stabilizers, for stabilizing ambient cured coatings based on alkyd resins; thermoset acrylic resins; acrylic alkyds; acrylic alkyd or polyester resins optionally modified with silicon, isocyanates, isocyanurates, ketimines or oxazolidines; and epoxide resins crosslinked with carboxylic acids, anhydrides, polyamines -59or mercaptans; and acrylic and polyester resin systems modified with reactive groups in the backbone thereof and crosslinked with epoxides; against the degradative effects of light, moisture and oxygen.

The instant invention also relates to electrodeposited coatings applied to metal substrates where various top coats may be applied thereover. The inclusion of the instant compounds in the E-coat provides delamination resistance to said E-coats. The primary resins in said E-coats are acrylic or epoxy resins. These E-coats are described in European patent application EP 0 576 943 Al.

The instant invention also pertains to UV-cured coating systems using unsaturated acrylic resins, polyurethane acrylates, epoxy acrylates, polyester acrylates, unsaturated polyester/styrene resins and silyl acrylates.

Powder Coatinqs The instant invention also pertains to powder coating formulations which require resistance to photodegradation. Resin systems which would be applicable include glycidal methacrylate or acrylate-functional acrylic or acrylic hybrids, crosslinked with diacids or anhydrides; acid or anhydride functional acrylic or polyester resins crosslinked with TGIC; hydroxyl functional acrylic or polyester resins crosslinked with isocyanates. The stabilized coating may be a single layer applied to a substrate, or may be a clearcoat applied over a waterborne or solvent-borne basecoat.

The stabilized coating may also contain a UV absorber, consisting of one of the aforementioned compounds.

Radiation-Cured Systems The instant invention also pertains to radiation-cured coating systems. These systems would consist of a. Ethylenically unsaturated polymerizable comopounds b. At least one photoinitiator c. One or more of the instant stabilizing compounds The coating composition may also include a UV absorbing stabilizer, represented by one of the classes mentioned..

The coating may also include pigments or other colorants designed to provide opacity or aesthetic properties.

The ethylenically unsaturated polymerizable compounds can contain one or more than one olefinic double bond. They may be low molecular (monomeric) or high molecular (oligomeric) compounds.

Typical examples of monomers containing one double bond are alkyl or hydroxyalkyl acrylates or methacrylates, for example methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethyl acrylate, isobornyl acrylate, and methyl and ethyl methacrylate. Further examples of these monomers are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamides, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkylstyrenes, halostyrenes, N-vinylpyrrolidone, vinyl chloride and vinylidene chloride.

Examples of monomers containing more than one double bond are ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate and tetraacrylate, pentaerythritol divinyl *0i ether, vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris(2-acryloylethyl)isocyanurate. Examples of high molecular weight (oligomeric) polyunsaturated compounds are acrylated epoxy resins, acrylated polyethers, acrylated polyurethanes and acrylated polyesters. Further examples of unsaturated oligomers are unsaturated polyester resins, which are usually prepared from maleic acid, phthalic acid and one or more diols and which have molecular weights of greater than about 500. Unsaturated oligomers of this type are also known as prepolymers.

Typical examples of unsaturated compounds are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated -61 groups in the chain or in side groups, including unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth)acrylic groups in sidechains, as well as mixtures of one or more than one such polymer.

Illustrative examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, unsaturated fatty acids such as linolenic acid or oleic acid. Acrylic and methacrylic acid are preferred.

Suitable polyols are aromatic and, preferably, aliphatic and cycloaliphatic polyols.

Aromatic polyols are typically hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-bis(4hydroxyphenyl)propane, as well as novolacs and cresols. Polyepoxides include those based on the cited polyols, preferably on the aromatic polyols and epichlorohydrin. Further suitable polyols are polymers and copolymers which contain hydroxyl groups in the polymer chain or in side groups, for example polyvinyl alcohol and copolymers thereof or hydroxyalkyl S polymethacrylates or copolymers thereof. Other suitable polyols are oligoesters carrying S. hydroxyl end groups.

Illustrative examples of aliphatic and cycloaliphatic polyols are alkylenediols containing preferably 2 to 12 carbon atoms, including ethylene glycol, 1,2- or 1,3-propanediol, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having molecular weights of preferably 200 to 1500, 1,3cyclopentanediol, 1,3-or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris(P-hydroxyethyl)amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.

The polyols may be esterified partially or completely with one or with different unsaturated carboxylic acids, in which case the free hydroxyl groups of the partial esters may be modified, for example etherified, or esterified with other carboxylic acids.

Illustrative examples of esters are: Trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, -62pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentacrylate, dipentaerythritol hexacrylate, tripentaerythritol octacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol-modified triacrylate, sorbitol tetramethacrylate, sorbitol pentacrylate, sorbitol hexacrylate, oligoester acrylates and methacrylates, glycerol di- and-triacrylate, 1,4cyclohexanediacrylate, bisacrylates and bismethacrylates of polyethylene glycol having molecular weights of 200 to 1500, or mixtures thereof. Polyfunctional monomers and oligomers are available for example from UCB Chemicals, Smyrna, Georgia, and Sartomer, Exton, Pennsylvania.

Suitable ethylenically unsaturated polymerizable compounds are also the amides of identical or different unsaturated carboxylic acids of aromatic, cycloaliphatic and aliphatic polyamines containing preferably 2 to 6, more particularly 2 to 4, amino groups. Exemplary of such polyamines are ethylenediamine, 1,2- or 1 ,3-propylenediamine, 1,3-or 1,4butylenediamine, 1 ,5-pentylenediamine, 1 ,6-hexylenediamine, octylenediamine, *i dodecylenediamine, 1 ,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, bis(-aminoethyl) ether, diethylenetriamine, triethylenetetramine, bis(paminoethoxy)ethane or bis(-aminopropoxy)ethane. Other suitable polyamines are polymers and copolymers which may contain additional amino groups in the side-chain and oligoamides containing amino end groups.

Exemplary of such unsaturated amides are: Methylenebisacrylamide, 1,6hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane, P-methacrylamidoethylmethacrylate, hydroxyethoxy)ethyl]acrylamide.

Suitable unsaturated polyesters and polyamides are derived typically from maleic acid and diols or diamines. Maleic acid can be partially replaced by other dicarboxylic acids such as -63fumaric acid, itaconic acid, citraconic acid, mesaconic acid or chloromaleic acid. To control the reactivity of the polyester and to influence the crosslinking density and hence the product properties, it is possible to use in addition to the unsaturated dicarboxylic acids different amounts of saturated dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, succinic acid or adipic acid. The unsaturated polyesters can be used together with ethylenically unsaturated comonomers such as styrene. The polyesters and polyamides can also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from those with long chains containing typically from 6 to 20 carbon atoms.

Polyurethanes are typically those derived from saturated or unsaturated diisocyanates and unsaturated and saturated diols.

Suitable polyester acrylates or acrylated polyesters are obtained by reacting oligomers, typically epoxides, urethanes, polyethers or polyesters, with acrylates such as hydroxyethyl acrylate or hydroxypropyl acrylate.

Polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomers include olefins such as ethylene, propene, butene, hexene, (meth)acrylates, acrylonitrile, styrene or vinyl chloride. Polymers containing (meth)acrylate groups in the side-chain are also known. They may typically be reaction products of epoxy resins based on novolak with (meth)acrylic acid, homo- or copolymers of polyvinyl alcohol or their hydroxyalkyl derivatives which are esterified with (meth)acrylic acid or homo- and copolymers of (meth)acrylates which are esterified with hydroxyalkyl(meth)acrylates.

Preferred monomers are typically alkyl- or hydroxyalkyl acrylates or methacrylates, styrene, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate or bisphenol A diacrylate, 4,4'-bis(2acryloyloxyethoxy)diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, preferably acrylates, styrene, hexamethylene glycol or bisphenol A diacrylate, 4,4'bis(2-acryloyloxyethoxy)diphenylpropane or trimethylolpropane triacrylate.

Particularly preferred (oligomeric) polyunsaturated compounds are polyester acrylates or unsaturated polyester resins which are prepared from maleic acid, fumaric acid, phthalic acid -64and one or more than one diol, and which typically have molecular weights from about 500 to 3000.

Preferred unsaturated carboxylic acids are acrylic acid and methacrylic acid.

The photopolymerizable compounds are used by themselves or in any desired mixtures. It is preferred to use mixtures of polyol(meth)acrylates.

Binders may also be added to the unsaturated photopolymerizable compounds. The addition of binders is particularly useful if the photopolymerizable compounds are liquid or viscous substances. The amount of binder may be from 5-95, preferably 10-90 and, most preferably, 40-90, percent by weight, based on the entire composition. The choice of binder will depend on the field of use and the desired properties therefore, such as the ability of the compositions to be developed in aqueous and organic solvent systems, adhesion to substrates and susceptibility to oxygen.

Suitable binders are typically polymers having a molecular weight of about 5,000 to 2,000,000, preferably 10,000 to 1,000,000. Illustrative examples are: Homo- and copolymers of acrylates and methacrylates, including copolymers of methyl methacrylate/ethyl acrylate/methacrylic acid, poly(alkylmethacrylates), poly(alkylacrylates); cellulose esters and ethers such as cellulose acetate, cellulose acetobutyrate, methyl cellulose, ethyl cellulose; polyvinyl butyral, polyvinyl formal, cyclized rubber, polyethers such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran; polystyrene, polycarbonate, polyurethane, chlorinated polyolefins, polyvinyl chloride, copolymers of vinyl chloride/vinylidene chloride, copolymers of ,J vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, copoly(ethylene/vinyl acetate), polymers such as polycaprolactam and poly(hexamethylene adipamide), polyesters such as poly(ethylene glycol terephthalate) and poly(hexamethylene glycol succinate).

The unsaturated compounds can also be used in admixture with non-photopolymerizable film-forming components. These components may be physically drying polymers or solutions thereof in organic solvents, for example nitrocellulose or cellulose acetobutyrate. The photopolymerizable unsaturated monomers may be a component of a free radical-ionic curable blend, such as a free radical-cationic curable blend. Also of importance are systems that undergo both thermal and photo-induced curing cycles, such as are used in powder coatings, laminates, certain adhesives and conformal coatings.

Mixtures of a prepolymer with polyunsaturated monomers which, additionally contain a further unsaturated monomer are frequently used in paint systems. The prepolymer in this instance primarily determines the properties of the paint film and, by varying it, the skilled person can influence the properties of the cured film. The polyunsaturated monomer acts as crosslinking agent that renders the paint film insoluble. The mono-unsaturated monomer acts as reactive diluent with the aid of which the viscosity is lowered without having to use a solvent.

Moreover, properties of the cured composition such as curing rate, crosslinking density and surface properties are dependent on the choice of monomer.

Unsaturated polyester resins are usually used in two-component systems, together with a mono-unsaturated monomer, preferably with styrene.

Binary electron-rich/electron-poor monomer systems are often employed in thick pigmented coatings. For example, vinyl ether/unsaturated polyester systems are employed in powder coatings and styrene/unsaturated polyester systems are used in gel coats.

A preferred process is that wherein the ethylenically unsaturated polymerizable S compounds are a mixture of at least one oligomeric compound and (ii) at least one monomer.

An interesting process is that wherein the ethylenically unsaturated polymerizable compounds are a mixture of unsaturated polyesters, especially those that are prepared from maleic acid, fumaric acid and/or phthalic acid and one or more than one diol, and which have molecular weights of 500 to 3,000, and (ii) acrylates, methacrylates or styrene or combinations thereof.

An important process is also that wherein the ethylenically unsaturated polymerizable compounds are a mixture of unsaturated polyesters and (ii) acrylates or methacrylates or combinations thereof.

-66- Another interesting process is that wherein the ethylenically unsaturated polymerizable compounds are a mixture of unsaturated polyester acrylates and (ii) acrylates or methacrylates or combinations thereof.

Synthesis of Compounds The instant compounds may be prepared by the reaction of tributyltin hydride and a halogen substituted alcohol to produce carbon centered radicals that are trapped by nitroxyl compounds.

The instant compounds may also be prepared by coupling an N-oxyl hindered amine with a carbon centered radical generated by the photochemical or thermal decomposition of a perester or dialkyl peroxide in the presence of an alcohol. The bridge compounds described above can be formed when two nitroxyl radicals couple with the same solvent molecule, especially when the amount of solvent is reduced.

The preferredTmithod of preparation of the instant compounds is to react an N-oxyl hindered amine with a carbon centered radical generated by mixing an aqueous or alcoholic solution of a metal ion such as Fe2+, Fe 3 Cu 2 or Cu' and a peroxide such as tert-butyl hydroperoxide or hydrogen peroxide in the presence of an alcohol solvent at a temperature of 20-800C. Especially effective is the combination of ferrous chloride, ferric chloride or ferrous sulfate, particularly ferrous chloride, or ferric chloride, and hydrogen peroxide. Water may be added to the alcohol at the beginning of the reaction to improve solubility of the metal salt or to dissolve an alcohol which is solid at the reaction temperature. A ligand such as 2,2'-dipyridyl, 2,2':6',2"-terpyridyl, may be added to the reaction mixture. Two nitroxyl radicals can sometimes couple with the same solvent molecule to produce bridged compoundsdescribed in some formulas listed earlier. The formation of bridge compounds is more favored when the amount of solvent is reduced.

Some of the instant hydroxy-substituted N-alkoxy compounds may be reacted with monofunctional or difunctional esters, acids or acid chlorides or isocyanates to form polymeric ester or urethane derivatives.

-67- Thus, another object of the invention is a process for the synthesis of the N- (hydroxyalkoxy) substituted hindered amines of formula IV G G 2 T N-O-E-(OH) (IV) GQ G2 wherein G1 and G 2 are independently alkyl of 1 to 4 carbon atoms, or G, and G2 together are pentamethylene; T is a divalent organic radical required to complete a five- or six-membered ring containing the hindered amine nitrogen atom and two quaternary carbon atoms substituted by G1 and G2; o E is a (b 1) valent alkylene radical of 2 to 18 carbon atoms, an alkenylene radical of 3 to 19 carbon atoms, a cycloalkylene radical of 5 to 12 carbon atoms, a cycloalkenylene radical of 5 to 12 carbon atoms or an alkylene radical of 2 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl of 1 to 4 carbon atoms; and b is 1, 2 or 3; with the proviso that b cannot exceed the number of saturated carbon atoms in E, and when b is 2 or 3, each hydroxyl group is bonded to a different carbon atom in E; which process comprises reacting a N-oxyl hindered amine of formula V /G 'G2 T N-O (V) G1 G2 with an alcohol of formula VI E-(OH)b (VI) in the presence of a peroxide or organic hydroperoxide and a catalytic amount of a metal salt or metal-ligand complex.

-68- The N-oxyl compounds of formula V may be prepared by the reaction of the corresponding N-H hindered amine with hydrogen peroxide and sodium tungstate as described by E. G. Rozantsev et al., in Synthesis, 1971, 192; or with tert-butyl hydroperoxide and molybdenum (VI) as taught in United States Patent No. 4,691,015.

More specifically, the instant process involves the reaction of a mixture of to 100 moles of the alcohol of formula VI, 1 to 15 moles of hydrogen peroxide or organic hydroperoxide, and 0.001 to 0.5 moles of metal salt or metal-ligand complex per mole of N-oxyl compound of formula V. The reaction is preferably carried out at a temperature in the range of 200 to 100 0

C.

The alcohol may serve two functions both as reactant and as solvent for the reaction. A mixture of products may result if the alcohol contains non-equivalent carbon-hydrogen bonds which are reactive in the instant process. For example, tertbutyl alcohol can give only one product whereas tert-amyl alcohol can give three distinct reaction products. A cosolvent may be used if the alcohol is a solid at the temperature of the reaction or if the metal salt or metal-ligand complex is not very soluble in the alcohol. Typical cosolvents are water, methanol and ethylene glycol.

The instant process mainly uses a less than stoichiometric amount, based on peroxide, of a transition metal salt or a metal-ligand complex with the metal chosen from groups IVA, VA, VIIA, VIllA or IB (transition metals, metals of lowest weight in these groups being Ti, V, Mn, Fe, Co, Ni, Cu) of the periodic table. Iron(ll), iron(lll), copper(l) and copper(ll) are the most effective catalysts. The metal may be in S: the form of a simple salt such as a metal chloride or sulfate, a metal salt of an organic acid such as acetic acid, or a metal oxide which may also contain a cation from group IA or IIA of the periodic table, such as sodium metavanadate. The metal may also be complexed with a ligand such as 2,2'-dipyridyl, ethylenediaminetetraacetic acid or its disodium salt, triphenylphosphine oxide, or the anion of acetylacetone. These metal ligand complexes are items of commerce or may be formed in situ by mixing a metal salt with the ligand. The amount of ligand may be less than the amount required to completely complex the metal based on its oxidation state. The metal salt or metalligand complex may be bound to a solid support such as silica gel so that it can be -69recovered and reused.

A mineral acid or sulfonic acid may be added to the reaction mixture in an amount corresponding to up to one mole per mole of nitroxyl moiety.

The instant process can be run in air or in an inert atmosphere such a nitrogen or argon.

There are several variations of the instant process. One variation involves the addition of a solution of aqueous hydrogen peroxide or organic hydroperoxide to a mixture of the N-oxyl hindered amine, the alcohol and cosolvent (if used) and acid (if used), and metal salt or metal-ligand complex which has been brought to the desired temperature for reaction. The proper temperature is maintained by controlling the rate of peroxide addition and/or by using a heating or cooling bath. After the peroxide is o added, the reaction mixture is stirred till the starting N-oxyl compound of formula V has disappeared or is no longer being converted to the compound of formula IV. The reaction is best monitored by thin layer chromatography, gas chromatography or liquid chromatography. Additional portions of metal salt or metal-ligand complex can be added while the reaction is in progress. After the initial peroxide charge has been added to the reaction mixture, more peroxide can be added dropwise to bring the reaction to completion.

A second variation of the instant process is to simultaneously add separate solutions of the peroxide and the nitroxyl compound to a mixture of the alcohol, S 0 cosolvent (if used), acid (if used) and metal salt or metal-ligand complex. The nitroxyl i S• compound may be dissolved in water or the alcohol solvent used in the reaction.

Some of the nitroxyl compound may be introduced into the reaction mixture prior to starting the peroxide addition, and all of the nitroxyl compound should be added prior to completing the peroxide addition.

Another variation of the instant process involves the simultaneous addition of separate solutions of the peroxide and of the aqueous or alcohol solution of the metal salt or metal-ligand complex to a mixture of the nitroxyl compound, alcohol, cosolvent (if used), and acid (if used). Some of the metal may be introduced into the reaction mixture prior to starting the peroxide addition.

Still another variation of the instant process is the simultaneous addition of separate solutions of the peroxide, of the aqueous or alcohol solution of the nitroxyl compound, and of an aqueous or alcohol solution of the metal salt or metal-ligand complex to the alcohol, cosolvent (if used) and acid (if used). A portion of the nitroxyl compound and/or metal salt or metal-ligand complex may be introduced into the reaction mixture prior to starting the peroxide addition. All of the nitroxyl compound should be added prior to completing the peroxide addition.

If acid is used in the reaction, the acid may be added in one portion at the beginning of the reaction, or a portion of acid may be added at the beginning of the reaction and the remainder added while the reaction is in progress; or all of the acid may be added while the reaction is in progress. Some or all of the acid may be mixed with the metal salt if the metal salt is added as a solution while the reaction is in progress.

If a metal-ligand complex is prepared in situ, the metal salt and ligand are most effectively mixed prior to contact with the nitroxyl compound.

At the end of the reaction, the residual peroxide should be carefully decomposed prior to the isolation of any products.

Preferred Processes

G

1 and G 2 in formula (IV) and are preferably methyl. T is preferably 2hydroxy-1,3-propanediyl or 2-oxo-1,3-propanediyl.

When b is 1, is a carbon centered radical formed preferably from 2methyl-2-propanol tert-butyl alcohol), 2-propanol, 2,2-dimethyl-1-propanol, 2methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1-hexanol, 2octanol, cyclohexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or 1-phenyl-1- -71 ethanol; and is most preferably formed from 2-methyl-2-propanol tert-butyl alcohol) or cyclohexanol.

When b is 2, -E-(OH) 2 is a carbon centered radical formed preferably from 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol; and -E-(OH) 2 is formed most preferably from 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol.

When b is 3, -E-(OH) 3 is a carbon centered radical formed preferably from 1,1,1 -tris(hydroxymethyl)ethane, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 1,2,4butanetriol or 1,2,6-hexanetriol; and -E-(OH) 3 is formed most preferably from 1,1,1tris(hydroxymethyl)ethane or 2-ethyl-2-(hydroxymethyl)-1,3-propanediol.

b is preferably 1 or 2; most preferably 1.

Preferred products of the instant process are the compounds of formulae (1) to (30) described above.

Preferably the peroxides are hydrogen peroxide, the addition compound of urea and hydrogen peroxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide and S. cumene hydroperoxide. More perferably the peroxides are hydrogen peroxide and the addition compound of urea and hydrogen peroxide; and most perferably hydrogen peroxide.

The hydrogen peroxide may be 15 to 50% by weight solution in water, *preferably 30 to 50% by weight solution in water.

Preferably, the metals are chosen from the groups IVA, VA, VIIA, VIIIA and IB of the periodic table. More preferred are iron(ll), iron(lll), copper(I), copper(ll), cobalt(ll), cobalt(lll), manganese(ll), manganese(lll), vanadium(ll), vanadium(llI), cerium(lll) and titanium(lll). Most preferred are iron(ll), iron(llI), copper(l) and copper(ll).

Preferably the counterions for the above metals are chloride, sulfate, acetyl- -72acetonate (acac), acetate, citrate, oxalate, nitrate, perchlorate, cyanide, hydroxide, phosphate, pyrophosphate and oxide.

Preferably the ligands for the above metals are 2,2'dipyridyl, terpyridyl, 1,10-phenanthroline, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, pyridine, picolinic acid, 2-pyrazinecarboxylic acid, aromatic diimines formed from the reaction of aniline or substituted anilines with 1,2diketones such as 2,3-butanedione, and triphenylphosphine oxide.

Preferably the metal salts are ferrous chloride, ferric chloride, ferric acetylacetonate, ferric phosphate, ferric pyrophosphate, ferrous phosphate, ferrous sulfate, ferric sulfate, ferrous acetate, ferric citrate, ferrous oxalate, ferric oxalate, ferric nitrate, ferrous perchlorate, ferric perchlorate, cuprous chloride, cupric chloride, cuprous sulfate, manganous chloride, sodium metavanadate, titanous chloride, vandium(ll) chloride and vanadium(lll) chloride. Most preferred metal salts are ferrous chloride, ferric chloride, ferric acetylacetonate, ferric phosphate, ferric pyrophosphate, ferrous phosphate, ferrous sulfate, ferric sulfate and-cupric sulfate.

Preferably the metal-ligand complexes are those from iron(ll), iron(lll), copper(l) or copper(ll) salts and 2,2'-dipyridyl, triphenylphosphine oxide, ethylenediaminetetraacetic acid or ethylenediaminetetraacetic acid disodium salt. Most 9. preferably, the metal-ligand complex are those from ferrous chloride or ferric chloride and 2,2'-dipyridyl.

o Preferably the acids are hydrochloric acid, sulfuric acid, methanesulfonic acid, oxalic acid, trifluoroacetic acid, polyphosphoric acid and phosphoric acid; most preferably, the acid is methanesulfonic acid, polyphosphoric acid or phosphoric acid.

The preferred amount of alcohol solvent for the instant process depends to some extent on the relative number of reactive hydrogens on the alcohol reactant and the hindered amine nitroxyl compound. The reaction is typically carried out with a ratio of 5 to 100 moles of solvent per mole of nitroxyl moiety with the preferred ratio being 10 to 50 moles per mole of nitroxyl moiety, and the most preferred ratio being -73to 30 moles of solvent per mole of nitroxyl moiety. A cosolvent may be present, which is preferably selected from water, methanol, ethylene glycol, or mixtures thereof.

The preferred amount of hydrogen or organic hydroperoxide is 1 to 20 moles per mole of nitroxyl moiety, with the more preferred amount being 1 to 5 moles of peroxide per mole of nitroxyl moiety and the most preferred amount being 1 to 3 moles of peroxide per mole of nitroxyl moiety.

The preferred amount of metal salt or metal-ligand complex is 0.001 to molar equivalent per mole of nitroxyl moiety, with a ratio of 0.001 to 0.05 moles of metal salt or metal-ligand complex per mole of nitroxyl moiety being the most preferred.

:o If an acid is used in the instant process, the preferred amount of acid is 0.01 to 1 molar equivalent per mole of nitroxyl moiety, with a ratio of 0.01 to 0.5 molar equivalents of acid per mole of nitroxyl moiety being most preferred.

The reaction is usually run at 200 to 1000C; preferably at 600 to 1000C.

The following examples are for illustrative purposes only and are not to be construed to limit the instant invention in any manner whatsoever. Room temperature depicts a temperature in the range 20-25oC.

Abbreviations: v parts by volume w parts by weight 'Hnmr nuclear magnetic resonance (NMR) of 1

H

m/z mass spectrometry (atomic units) amu molecular weight in g/mol atomic units).

Examples P1-P illustrate the novel process for preparing the compounds of the invention.

Example P1 illustrates the use of ferric chloride in the instant process.

-74- Example P1 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 9.4 g (140 mmol) of 50% aqueous hydrogen peroxide mixed with 20 mL of tert-butyl alcohol is added over four hours at 45-50 0 C to a mixture of 3.44 g (20.0 mmol) of 4hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 0.125 g (0.77 mmol) of anhydrous ferric chloride, mL of tert-butyl alcohol and 10 mL of water. The temperature is then maintained at 45-500C for 19 hours. Analysis by gas chromatography shows less than 1% of the starting nitroxyl compound is present.

Example P2 shows recycling a metal catalyst on a solid support.

Example P2 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine 2,2'-Dipyridyl (0.16 g, 1.0 mmol) and 2.54 g (0.80 mmol) of 5% ferric chloride on silica gel are stirred togetherin 30 mL of tert-butyl alcohol which is heated to 450C. To the mixture are added 3.44 g (20.0 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 10 mL of water.

S A solution of 9.4 g (138 mmol) of 50% aqueous hydrogen peroxide mixed with 20 mL of tertbutyl alcohol is added over four hours at 45-500C to the reaction mixture. The temperature is maintained at 45-500C for 30 minutes. Analysis by gas chromatography shows that the starting nitroxyl compound is completely reacted to form greater than 90% of the title compound.

The silica gel is separated by filtration and the above experiment is repeated using the recovered silica gel. After nearly all the peroxide is added to the reaction mixture in 4.5 hours, gas chromatography shows 36% of the starting nitroxyl compound is still present. After the reaction mixture is heated for an additional 19 hours at 45-500C, only 5% of the starting nitroxyl compound still remains.

Example P3 Reaction of 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with Isopropyl Alcohol 2,2'-Dipyridyl (0.156 g, 1 mmol) is added to a mixture of 0.20 g (1 mmol) of ferrous chloride tetrahydrate in 30 mL of isopropyl alcohol at 400C. To this mixture are added 3.44 g mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 10 mL of water. A solution of 9.4 g (138 mmol) of 50% aqueous hydrogen peroxide in 20 mL of isopropyl alcohol is added over seven hours at 40-450C to the above mixture. The crude reaction mixture is cooled and reacted with 0.5 g of sodium borohydride. Gas chromatography/mass spectrometry analyses indicate the major component of the reaction mixture is 4-hydroxy-1 -(2-hydroxypropoxy)-2,2,6,6-tetramethylpiperidine (m/z 231).

Example P4 Reaction of 1-Oxyl-2,2,6,6-tetramethyl piperidin-4-one with tert-Amyl Alcohol 2,2'-Dipyridyl (0.078 g, 0.50 mmol) is added to a mixture of 0.99 g (5.0 mmol) of ferrous chloride tetrahydrate is 150 mL of tert-amyl alcohol at 250C. To this mixture is added 0.2 g of tetrabutylammonium chloride and 17.2 g (101 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4one. A solution of 29.5 g (434 mmol) of 50% aqueous hydrogen peroxide is added over three hours at 25-300C to the above mixture. Aqueous sodium sulfite solution is added to decompose peroxides. The reaction mixture is thoroughly extracted with ethyl acetate to afford 23.4 g of an orange oil. Gas chromatography/mass spectrometry analyses indicate that the oil contains three major reaction products in a nearly 2:2:1 ratio (area percent). The three products are consistent with the reaction of the starting nitroxyl compound with each of the possible carbon radicals formed from tert-amyl alcohol.

Example Reaction of 1-Oxyl-2,2,6,6-tetramethyl piperidin-4-one with 1-Butanol The procedure of Example P4 is repeated with 150 mL of n-butyl alcohol in place of S. tert-amyl alcohol. Work-up of the reaction mixture yields 19.2 g of an orange oil. Gas chromatography/mass spectrometry analyses indicate that three of the components of the product mixture correspond to the reaction of the starting nitroxyl compound with radicals formed by hydrogen abstraction from 1-butanol.

Example P6 Reaction of 1-Oxyl-2,2,6,6-tetramethyl piperidin-4-one with Neopentyl Glycol -76- The procedure of Example P4 is repeated with a mixture of 400 mL of 2,2-dimethyl-1,3propanediol neopentyl glycol) and 55 mL of water in place of tert-amyl alcohol. Work-up of the reaction mixture yields 14.0 g of a brown oil.

Example P7 Reaction of 1-Oxyl-2,2,6,6-tetramethyl piperidin-4-one with 2-Octanol The procedure of Example P4 is repeated with a mixture of 150 mL of 2-octanol in place of tert-amyl alcohol. The peroxide is added over a period of six hours at 25-300C and the reaction mixture is stirred overnight at room temperature. Work-up of the reaction mixture gives 19.4 g of an orange oil. Gas chromatography/mass spectrometry analyses indicate that five of the components of the product mixture correspond to the reaction of the starting nitroxyl compound with radicals formed by hydrogen abstraction from 2-octanol.

Examples P8-P12 indicate the use of mineral acid with various iron salts in the instant S: process.

i• Example P8 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 40 mL of water and three-fourths of a solution of 25.0 g (0.37 mol) of 50% aqueous hydrogen peroxide are added simultaneously over three hours at 40 0 C to a mixture of 1.12 g mmol) of ferrous sulfate heptahydrate, 25 mL of water, 0.5 mL of 98% sulfuric acid and 200 mL of tert-butyl alcohol. At the conclusion of the nitroxyl addition, 0.145 g (0.5 mmol) of ferrous sulfate heptahydrate, 0.1 mL of 98% sulfuric acid, and 1-2 mL of water are added to the reaction mixture. The remainding one-fourth of the peroxide solution is added over one hour at 40 0

C.

One hour later, a solution of 2.9 g. (40 mmol) of 50% aqueous hydrogen peroxide is added dropwise to the reaction mixture. After another 1.3 hours, a solution of 0.14 g (0.5 mmol) of ferrous sulfate heptahydrate, 0.15 mL of 98% sulfuric acid and 1-2 mL of water are added in one portion. The reaction mixture is stirred an additional 40 minutes at 400C. After the peroxides are decomposed with sodium sulfite, the reaction mixture is treated with sodium hydroxide and sodium borohydride and concentrated. The residue is dissolved in ethyl acetate and passed -77through silica gel to afford 20.5 g (84% yield) of the title compound as a white solid.

Example P9 4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 75 mL of water and a solution of 49.5 g (0.73 mol) of 50% aqueous hydrogen peroxide are added simultaneously over seven hours at 400C to a mixture of 1.61 g (8.1 mmol) of ferrous chloride tetrahydrate, 50 mL of water, 1.6 mL of 37% hydrochloric acid and 390 mL of tert-butyl alcohol. About four hours into the addition, a solution of 0.22 g (1.1 mmol) of ferrous chloride tetrahydrate, 0.2 mL of 37% hydrochloric acid and 1-2 mL of water are added to the reaction mixture. The reaction mixture is stirred overnight at room temperature. The reaction is then completed by adding a solution of 0.11 g (0.55 mmol) of ferrous chloride tetrahydrate, 0.1 mL of 37% hydrochloric acid and 1-2 mL of water and a solution of 5.8 g (85 mmol) of aqueous hydrogen peroxide while heating the reaction mixture at 400C. The reaction mixture is filtered to remove solids, quenched with sodium sulfite, treated with sodium hydroxide and sodium borohydride and concentrated. The residue is dissolved in ethyl acetate and passed through silica gel to afford 42.6 g (87% yield) of the title compound as a white solid.

Example 4-Hydroxy-l -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine o A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 50 mL of water and a solution of 25.3 g (0.37 mol) of 50% aqueous hydrogen peroxide are added simultaneously over 3-3.5 hours at 400C to a mixture of 0.27 g (1.0 mmol) of .ferric chloride hexahydrate, 25 mL of water, 1.1 mL of 37% hydrochloric acid and 200 mL of tertbutyl alcohol. About two hours into the addition, 0.5 mL of 37% hydrochloric acid is added to the reaction mixture. After the peroxide addition is complete, 1.2 mL of 37% hydrochloric acid is added and the reaction mixture is heated at 40-500C for 3.5 hours. The reaction mixture is stirred overnight at room temperature. The reaction is completed by adding two portions of 0.3 mL of 37% hydrochloric acid while heating the reaction mixture at 450C for 5.5 hours. Work-up is done as in Example P9 and affords 21.5 g (88% yield) of the title compound as a white solid.

Gas chromatography shows the product has a purity greater than 96%.

-78- Example P11 4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 40 mL of water and three-fourths of a solution of 25.0 g (0.37 mol) of 50% aqueous hydrogen peroxide are added simultaneously over 2.5 hours to 400C to a mixture of 1.46 g (4.1 mmol) of ferric acetylacetonate, 25 mL of water, 0.5 mL of 98% sulfuric acid and 200 mL of tertbutyl alcohol. At the conclusion of the nitroxyl addition, 0.18 g (0.5 mmol) of ferric acetylacetonate is added to the reaction mixture. The remaining one-fourth of the peroxide solution is added over one hour at 400C. After heating for two hours, gas chromatography shows less than nitroxyl compound remaining in the reaction mixture. Sulfuric acid (0.3 mL) and a solution of 4.9 g (72 mmol) of 50% aqueous hydrogen peroxide are added to the reaction mixture at 400C, and the reaction mixture is stirred overnight at room temperature. Work-up as in Example P9 affords 18.1 g (74% yield) of the title compound as a white solid.

Example P12 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine When the procedure of Example P11 is repeated without the addition of sulfuric acid, 69% of the starting nitroxyl compound remains present 1.5 hours after the peroxide addition is completed. This compares with only 10% nitroxyl compound remaining at a comparable time as seen in Example P11.

Example P13 1 -(2-Hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-one A solution of 23.6 g (347 mmol) of 50% aqueous hydrogen peroxide is added over hours to a mixture of 17.0 g (100 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 0.994 g mmol) of ferrous chloride tetrahydrate, 1 mL of 37% hydrochloric acid, 360 mL of tert-butyl alcohol, and 120 mL of water. The reaction is saturated with potassium chloride and the aqueous layer is extracted with tert-butyl alcohol. The combined organic layers are concentrated to an orange oil. The oil is dissolved in methylene chloride and purified by flash chromatography -79on silica gel with 4:1 hexane:ethyl acetate. The resulting yellow oil is crystallized to afford 8.3 g of a white solid melting at 57-600C. The isolated product is injected into a gas chromatograph and has the same retention time as an authenic sample of the title compound.

Examples P14, P15 and P16 illustrate the effect of various ligands of formula (IV) X X

(IV)

N

N

H

3 C CH 3 on the formation of the compound of Example P13.

Example P14 1 -(2-Hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-one To a mixture of 0.994 g (5 mmol) of ferrous chloride tetrahydrate and 150 mL of tertbutyl alcohol at 350C are added, sequentially, 1.18 g (5.0 mmol) of N,N'-(1,2-dimethyl-1,2ethanediylidene)bis(benzenamine), where in formula IV, X is hydrogen, and 17.0 g (100 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one. A solution of 47.5 g (700 mmol) of 50% aqueous hydrogen peroxide mixed with 60 mL of tert-butyl alcohol is added over eight hours at 35-400C to the above mixture. The reaction is stirred an additional 16 hours at 400C. Analysis by gas chromatography shows less than 4% starting nitroxyl present. Solids are removed by filtration, and the filtrate is reacted with aqueous sodium sulfite to decompose excess peroxide. The reaction mixture is thoroughly extracted with ethyl acetate to afford, after concentration, 21.4 g of crude product containing greater than 93% of the title compound as based on gas chromatography.

Example 1 -(2-Hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-one Example P14 is repeated using 1.48 g (5 mmol) of N,N'-(1,2-dimethyl-1,2-ethanediylidene)bis(4-methoxybenzenamine), where in formula IV, X is methoxy, in place of dimethyl-1,2-ethanediylidene)bis(benzenamine), where in formula IV, X is hydrogen. Analysis by gas chromatography shows 3% starting nitroxyl compound present at the end of the reaction time. After work-up, the reaction mixture affords 17.7 g of an orange material which contains 97% of the title compound as seen by gas chromatography.

Example P16 1-(2-Hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-one Example P14 is repeated using 5.0 mmol of N,N'-(1,2-dimethyl-1,2-ethanediylidene)bis(4-chlorobenzenamine), where in formula IV, X is chlorine, in place of N,N'-(1,2-dimethyl-1,2ethanediylidene)bis(benzenamine), where in formula IV, X is hydrogen.

o* Example P17 4-Benzoyloxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 18.4 g (0.27 mol) of 50% aqueous hydrogen peroxide mixed with 50 mL of tert-butyl alcohol is added over two hours to a mixture of 24.9 g (0.090 mol) of 4-benzoyloxy-1oxyl-2,2,6,6-tetramethylpiperidine, 7.13 g (0.036 mol) of ferrous chloride tetrahydrate, 3.7 g (0.030 mol) of picolinic acid, and 150 mL of tert-butyl alcohol at 600C. The reaction temperature is maintained at 60°C for five hours after the peroxide addition is complete. The reaction mixture is filtered to remove solids, and the filtrate is stirred for 30 minutes with 1 liter of 10% aqueous sodium sulfite solution to decompose excess peroxide. The aqueous solution is extracted three times with methylene chloride, and the combined organic layers are dried over anhydrous magnesium sulfate and finally concentrated to an orange oil. Purification by flash chromatography on silica gel with 4:1 hexane:ethyl acetate affords 12.0 g of an amber oil.

The product is confirmed to be the title compound by nmr and mass spectrometry analyses.

Example P18 shows the effect of omitting the picolinic acid from Example P17.

Example P18 4-Benzoyloxy-1 -(2-hydroxy-2-methylpropoxy)- -81 2,2,6,6-tetramethylpiperidine A solution of 20.4 g (0.30 mol) of 50% aqueous hydrogen peroxide mixed with 25 mL of tert-butyl alcohol is added over three hours to a mixture of 27.6 g (0.10 mol) of 4-benzoyloxy-1oxyl-2,2,6,6-tetramethylpiperidine, 7.13 g (0.036 mol) of ferrous choride tetrahydrate and 115 mL of tert-butyl alcohol at 400C. The reaction temperature is maintained at 40 0 C for twenty hours after the peroxide addition is complete. The crude reaction mixture is purified by flash chromatography on silica gel to afford 16.2 g of the title compound.

Example P19 Reaction of Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate with Neopentyl alcohol Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and ferrous chloride in neopentyl alcohol according to the procedure of Example P18.

Example °Reaction of 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with Neopentyl Glycol Aqueous hydrogen peroxide is added to a mixture of 4-hydroxy-l-oxyl- 2,2,6,6-tetramethylpiperidine and ferrous chloride in neopentyl glycol according to the procedure of Example P18.

Example P21 Reaction of 4-Octadecanoyloxy-l -oxyl-2,2,6,6piperidine with tert-Amyl Alcohol Aqueous hydrogen peroxide is added to a mixture of 4-octadecanoyloxy-1oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride in tert-amyl alcohol according to the procedure of Example P18.

Example P22 Reaction of 4-Octadecanoyloxy-l-oxyl-2,2,6,6piperidine with tert-Butyl Alcohol Aqueous hydrogen peroxide is added to a mixture of 4-octadecanoyloxy-1- -82oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride in tert-butyl alcohol according to the procedure of Example P18.

Example P23 Reaction of 4-Benzoyloxy-1-oxyl-2,2,6,6tetramethylpiperidine with Propylene Glycol Aqueous hydrogen peroxide is added to a mixture of 4-benzoyloxy-l -oxyl- 2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in propylene glycol according to the procedure of Example P18.

Example P24 Reaction of 1-Oxyl-2,2,6,6-tetramethyl piperidin-4-one with Trimethylene Glycol Aqueous hydrogen peroxide is added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidine-4-one and ferrous chloride tetrahydrate in trimethylene glycol according to the procedure of Example P18.

Example Reaction of Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate with 2-Propanol Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and ferrous chloride tetrahydrate in 2-propanol according to the procedure of Example P18.

Example P26 Reaction of 4-Benzoyloxy-l-oxyl-2,2,6,6-tetramethylpiperidine with 1,4-Butanediol Aqueous hydrogen peroxide is added to a mixture of 4-benzoyloxy-1-oxyl- 2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in 1,4-butanediol according to the procedure of Example P18.

Example P27 Reaction of 4-Hexyloxy-1-oxyl-2,2,6,6-tetramethyl- -83piperidine with Pinacol Aqueous hydrogen peroxide is added to a mixture of 4-hexyloxy-l-oxyl- 2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in pinacol according to the procedure of Example P18.

Example P28 Reaction of 4-Hydroxy-l-oxyl-2,2,6,6-tetramethylpiperidine with 2-Ethyl-1-hexanol Aqueous hydrogen peroxide is added to a mixture of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in 2-ethyl-1-hexanol according to the procedure of Example P18.

Examples P38-P47 show the effectiveness of various metals in the instant process.

Example P38 4-Hydroxy-l-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 50% aqueous hydrogen peroxide is added at a rate of approximately 100 mmol per hour and, simultaneously, a solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 40-45 mL of water is added at a rate of 35-50 mmol per hour to a mixture of metal salt, acid if used, 25 mL of water and 200 mL of tert-butyl alcohol maintained at 35-450C. The reaction mixture is maintained at 35-450C after all reactants are added, and in some cases the reaction mixture is stirred overnight at room temperature. The reaction is monitored by gas chromatography. Results are tabulated below.

Table I Formation of 4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine Using Hydrogen Peroxide and Various Metals mol metala mol acida moles HZO2 yieldc 4% CoCl2 10% HCI 2.9 3% -84- 11%MnCI 2 10% HCI 3.6 16% 4% NaV0 3 none 1.5 <1% 4% CeCI 3 none 1.5 <1% 4% TiCI 3 60% HCI 3.5 2% 4% VCl 2 10% HCI 2.2 1% 4% VCl 3 10% HCI 3.6 6% moles per mole of nitroxyl starting material; moles of peroxide added to reaction per mole of nitroxyl starting material; and gas chromatographic yields based on integrated area of title compound with respect to total area of all hindered amine components present in the reaction mixture.

Example P39 1 -(2-Hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-one A solution of 1.0 g (15 mmol) of 50% aqueous hydrogen peroxide in 5 mL of tert-butyl alcohol is added over 30 minutes at 600C to a mixture of 0.5 g (2.9 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 0.1 g (0.16 mmol) of butylsalicylidene)-1,2-cyclohexanediaminomanganese(ll) chloride (Jacobsen's catalyst), and 10 mL of tert-butyl alcohol. The reaction is stirred overnight at 600C.

Gas chromatography shows 2.5% of the title compound is present in the reaction mixture.

Example 1-(2-Hydroxy-2-methylpropoxy)- T e 2,2,6,6-tetramethylpiperidin-4-one The procedure of Example P39 is repeated using 0.25 g (1.05 mmol) of cobalt(ll) chloride hexahydrate in place of the Jacobsen's catalyst. Gas chromatography shows 9% of the title compound is present in the reaction mixture.

Example P41 4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 0.25 g (1.0 mmol) of copper(ll) sulfate pentahydrate in 5 mL of water is added to a solution of 0.16 g (1.0 mmol) of 2,2'-dipyridyl in 120 mL of tertbutyl alcohol. To this solution is added 8.6 g (50 mmol) of 4-hydroxy-1-oxyl-2,2,6,6tetramethylpiperidine. A solution of 13.6 g (200 mmol) of 50% aqueous hydrogen peroxide mixed with 13 mL of tert-butyl alcohol is added dropwise to the reaction mixture at 23-40 0 C over three hours. The mixture is then stirred at ambient temperature for 72 hours. Gas chromatography shows 9% of the title compound is present in the reaction mixture.

Example P42 4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 75 mL of water and a solution of 48.1 g (0.71 mol) of aqueous hydrogen peroxide are added simultaneously over six hours at 35-450C to a mixture of 0.79 g (8.0 mmol) of copper(l) chloride, 50 mL of water, 1.6 mL of 37% hydrochloric acid, and 400 mL of tert-butyl alcohol. The reaction mixture is stirred overnight at room temperature. The reaction mixture is heated to 40-450C and treated with a total of 1.78 g of copper(l) chloride, 4.4 mL of 37% hydrochloric acid, and 85 g (1.25 mol) of 50% aqueous hydrogen peroxide to react completely the remaining nitroxyl compound. Work-up according to the procedure of Example P9 affords 38.6 g of a tan solid containing 88% of the title compound based on gas chromatographic analysis.

4e Example P43 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 50 mL of water and a solution of 31.5 g (0.46 mol) of aqueous hydrogen peroxide are added simultaneously over three and 4.5 hours respectively to a mixture of 0.69 g (4.0 mmol) of copper(ll) chloride dihydrate, 25 mL of water, 0.8 mL of 37% hydrochloric acid, and 200 mL of tert-butyl alcohol at 0 C. The reaction mixture is maintained at 45-50 0 C and treated with a total of 0.32 g -86of copper(ll) chloride dihydrate, 0.6 mL of 37% hydrochloric acid, and 35.5 g (0.52 mol) of 50% aqueous hydrogen peroxide to react completely the remaining nitroxyl compound. Work-up according to the method of Example P9 affords 17.1 g of an offwhite solid containing 90% of the title compound based on gas chromatographic analysis.

Example P44 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 50 mL of water and a solution of 29.3 g (0.43 mol) of aqueous hydrogen peroxide are added simultaneously over three and 4.25 hours respectively to a mixture of 1.0 g (4.0 mmol) of copper(ll) sulfate pentahydrate, 25 mL of water, 0.6 mL of 98% sulfuric acid, and 200 mL of tert-butyl alcohol at 35-50 0

C.

The reaction mixture is maintained at 45-500C and treated with a total of 0.44 g of copper(ll) sulfate pentahydrate, 0.4 mL of 98% sulfuric acid, and 6.7 g (98 mmol) of 50% aqueous hydrogen peroxide to react completely the remaining nitroxyl compound. Work-up according to the method of Example P9 affords 19.1 g of a white solid containing 95% of the title compound based on gas chromatographic analysis.

Example 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 7.4 g (109 mmol) of 50% aqueous hydrogen peroxide in 10 mL of water is added dropwise over five hours at 43-60°C to a mixture prepared by the sequential addition of 5 mL of water, 0.5 mL of glacial acetic acid, 60 mL of tert-butyl alcohol and a solution of 5.4 g (31.4 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 5 mL of water to 0.166 g (0.95 mmol) of ferrous acetate. A fresh solution of 4.4 g (65 mmol) of 50% aqueous hydrogen peroxide and 4 mL of water is then added to the reaction mixture at 600C. The mixture is stirred overnight at room temperature.

Analysis by gas chromatography shows that the reaction mixture contains 52% of the title compound and 41% unreacted starting material based on the original -87nitroxyl content.

Example P46 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine The procedure of Example P9 is repeated using a mixture of ferrous chloride and ferric chloride.

Example P47 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine The procedure of Example P9 is repeated using a mixture of ferric chloride and iron powder in place of ferrous chloride.

Examples P48 and P49 show the reaction where tert-butyl hydroperoxide is used in place of hydrogen peroxide.

Example P48 4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 5.2 g (30 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl- .i piperidine dissolved in 20 mL of water and a solution of 7.8 g (61 mmol) of aqueous tert-butyl hydroxperoxide are added simultaneously over one hour at 500C to a mixture of 0.33 g (1.2 mmol) of ferric chloride hexahydrate, 8 mL of water, 0.2 mL of 37% hydrochloric acid, and 60 mL of tert-butyl alcohol. The reaction mixture is maintained at 450C for one hour after the addition and is then stirred at room temperature for three days. Gas chromatography shows 3% of the title compound is present in the reaction mixture.

Example P49 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine The procedure of Example P48 is repeated using ferrous chloride in place of -88ferric chloride.

Example 4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine This example uses the addition compound formed from urea and hydrogen peroxide in place of 50% aqueous hydrogen peroxide.

A solution of 52.2 g (555 mmol) of urea-hydrogen peroxide addition compound dissolved in 75 mL of water and a solution of 3 mL of concentrated sulfuric acid dissolved in 29 mL of water are prepared. Portions of both solutions are added simultaneously over two hours at a temperature of 400C to a mixture of 0.17 g (61 mmol) of ferrous sulfate heptahydrate, 34.75 g (202 mmol) of 4-hydroxy-l-oxyl- 2,2,6,6-tetramethylpiperidine, 410 mL of tert-butyl alcohol and 70 mL of water. A fresh portion of 0.485 g of ferrous sulfate heptahydrate is added and the reaction mixture is stirred overnight at 450C for 16 hours. The remaining peroxide and acid solutions are added simultaneously to the reaction mixture over seven hours at 450C. Concentrated sulfuric acid (1.8 mL) is added and the mixture is stirred at room temperature for 64 hours. After the reaction mixture is heated at 45-50°C for 6.5 hours, 1.8 mL of concentrated sulfuric acid and 0.101 g of ferrous sulfate heptahydrate are added. The reaction mixture is then heated at 450C for 16 hours to bring the nitroxyl concentration to less than 1% of its original value. The reaction mixture is worked up following the procedure similar to that described in Example 20 to afford 38.1 g (77% yield) of product as a white solid.

Anaylsis by gas chromatography shows the reaction product contains approximately 94% of the title compound.

Example P51 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine Examples 51-54 show the effect of different acids on the instant process.

A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 35 mL of water and a solution of 23.3 g (342 mmol) of 50% aqueous hydrogen peroxide are added simultaneously over 2.5 hours and 6.5 hours, -89respectively, to a mixture of 0.527 g (3.0 mmol) ferrous acetate, 20 mL of water, 2.3 g of trifluoroacetic acid, and 200 mL of tert-butyl alcohol which is maintained at 430C.

Near the end of the peroxide addition, a solution of 0.347 g (2.0 mmol) of ferrous acetate and 1.25 g of trifluoroacetic acid in 5 mL of water is added to the mixture. A fresh portion of 5.1 g (75 mmol) of 50% aqueous hydrogen peroxide is then added over 90 minutes, and the reaction mixture is stirred for 15 hours at 42-450C. The reaction mixture is worked up following a procedure similar to that described in Example P9 to afford 17.5 g (71% yield) of product as a white solid.

Analysis by gas chromatography shows the reaction product contains approximately 92% of the title compound.

Example P52 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 35 mL of water and a solution of 31.6 g (464 mmol) of 50% aqueous hydrogen peroxide are added simultanedisly over 2.5 hours and 15 hours, respectively, to a mixture of 0.561 g (3.1 mmol) of ferrous oxalate dihydrate, 20 mL of water, 1.26 g of oxalic acid dihydrate, and 200 mL of tert-butyl alcohol which is maintained at 43-650C. After the peroxide is added, the reaction mixture is stirred for seven hours at 50-600C. Oxalic acid dihydrate (1.26 g) and 0.380 g (2.2 mmol) of ferrous oxalate dihydrate are added to the reaction mixture and stirring is continued at 65-800C for seven hours.

Analysis by gas chromatography shows the reaction mixture comprises approximately 86% of the title compound and less than 4% of the starting material based on hindered amine content.

Example P53 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 35 mL of water and a solution of 23.4 g (344 mmol) of 50% aqueous hydrogen peroxide are added simultaneously over 2.5 hours and 6 hours, respectively, to a mixture of 0.563 g (2.0 mmol) ferrous sulfate heptahydrate, 10 mL of water, 1.3 mL of methanesulfonic acid, and 200 mL of tert-butyl alcohol which is maintained at 450C. The reaction mixture is stirred at 45 0 C for two hours after the completion of the peroxide addition.

Analysis by gas chromatography shows the reaction mixture comprises of the title compound and less than 2% of the starting material based on hindered amine content.

Example P54 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 46.5 g (270 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 120.5 g of tert-butyl alcohol and 108 mL of water and a solution of 37.4 g (550 mmol) of 50% aqueous hydrogen peroxide are added simultaneously over 3 hours and 11.5 hours, respectively, to a mixture of 3.5 g (12.9 mmol) ferric chloride heptahydrate, 32 mL of water, 1.3 g of 85% phosphoric acid, and 292 mL of tert-butyl alcohol which is maintained at 800C. The reaction mixture is maintained at 800C for minutes after completion of the peroxide addition.

Analysis by gas chromatography shows less than 1% of the starting nitroxyl compound remains. Excess peroxide is destroyed by sodium sulfite and the crude product is filtered and treated with sodium borohydride in 14 molar aqueous sodium hydroxide to afford 71% yield of the title compound as analyzed by gas chromatography.

Example 4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine This example shows that a solution of the metal salt can be added dropwise to the reaction mixture throughout the course of the reaction.

A solution of 1.62 g (8.1 mmol) of ferrous chloride tetrahydrate, 2 mL of 37% hydrochloric acid, and 50 mL of water and a solution of 35.7 g (525 mmol) of aqueous hydrogen peroxide are added simultaneously over 13 hours and 16 hours, respectively, to a mixture of 34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetra- -91 methylpiperidine in 100 mL of water and 400 mL of tert-butyl alcohol which is maintained at a temperature of 38-450C. The reaction mixture is heated at 40-450C for eight hours after completion of the peroxide addition.

Analysis by gas chromatography shows that the reaction mixture contains 86% of the title compound and less than 5% of the starting nitroxyl compound.

Example P56 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine Examples 56-57 show the effect of increasing the reaction temperature.

A solution of 2 mL of 98% sulfuric acid in 30 mL of water and a solution of 27.1 g (398 mmol) of 50% aqueous hydrogen peroxide are added simultaneously over 5.5 hours to a solution of 0.119 g (0.43 mmol) of ferrous sulfate heptahydrate, mL of water, 34.6 g (201 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 410 mL of tert-butyl alcohol which is maintained at a temperature of 43-450C. The reaction mixture is heated at 450C for 20 hours after completion of the peroxide addition.

*Analysis by gas chromatography shows that the reaction mixture contains 73% of the title compound and 18% of the starting nitroxyl compound.

Example P57 S. 4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 27.7 g (407 mmol) of 50% aqueous hydrogen peroxide and :90% of a solution of 2.2 mL of 98% sulfuric acid in 30 mL of water are added simultaneously over 5.25 hours and 6.5 hours, respectively, to a solution of 0.115 g (0.41 mmol) of ferrous sulfate heptahydrate, 70 mL of water, 34.6 g (201 mmol) of 4hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 410 mL of tert-butyl alcohol which is maintained at a temperature of 63-680C. All of the peroxide is consumed after hours.

Analysis by gas chromatography shows that the reaction mixture contains 76% of the title compound and 12% of the starting nitroxyl compound.

-92- Example P58 4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 10.0 g (58.1 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 20 mL of water and a solution of 15 g (220 mmol) of 50% aqueous hydrogen peroxide are added simultaneously over 1.5 hours and 7 hours, respectively, to a solution of 0.394 g (1.77 mmol) of ferric phosphate tetrahydrate, 13 mL of water, and 120 mL of tert-butyl alcohol which is maintained at a temperature of 63-810C. The reaction mixture is stirred overnight at room temperature. A fresh portion of 1.0 g (15 mmol) of 50% aqueous hydrogen peroxide is added, and the reaction mixture is stirred for 24 hours at 800C to bring the amount of the nitroxyl compound to less than 1.5% of the original amount. Excess peroxide is decomposed with sodium sulfite.

Analysis by gas chromatography shows the reaction mixture contains approximately 89% of the title compound based on total hindered amine content.

oo Example P59 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 10.1 g (58.7 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 30 mL of water and a solution of 16.3 g (240 mmol) of 50% aqueous hydrogen peroxide are added simultaneously over 2 hours and 6 hours, respectively, to a solution of 1.31 g (1.76 mmol) of ferric pyrophosphate, 20 mL of water, and 120 mL of tert-butyl alcohol which is maintained at a temperature of 60-79°C. The reaction mixture is stirred overnight at room temperature. To the reaction mixture are added a solution of 15 mL of tert-butyl alcohol, 0.34 g (0.46 mmol) of ferric pyrophosphate, and 3.8 g (56 mmol) of 50% aqueous hydrogen peroxide. The mixture is then heated for ten hours at 75-800C. Excess peroxide is decomposed with sodium sulfite. The reaction mixture is worked up in a procedure similar to that described in Example P9 to afford 10.2 g (71% yield) of product as a white solid which is consistent with the title compound according to gas chromatography analysis.

Example -93- 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine This example illustrates the effect of combining two different metal salts in the instant process.

A solution of 0.13 g (0.52 mmol) of cupric sulfate pentahydrate, 1 mL of 98% sulfuric acid, and 15 mL of water and a solution of 13.6 g (200 mmol) of 50% aqueous hydrogen peroxide are added simultaneously over 3.5 hours and 4.25 hours, respectively, to a solution prepared by the addition of 17.4 g (101 mmol) of 4-hydroxy- 1-oxyl-2,2,6,6-tetramethylpiperidine in 50 mL of water to a mixture of 0.14 g (0.50 mmol) of ferrous sulfate heptahydrate, 10 mL of water and 200 mL of tert-butyl alcohol. The reaction mixture is kept at 40-450C during the addition, and then stirred overnight at room temperature.

Analysis by gas chromatography shows that 77% of the starting compound is converted to the title compound.

Example P61 S-Mixture of Bis[1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-yl] Adipate and Bis[1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-yl] Glutarate A solution of 159 g (2.34 mol) of 50% aqueous hydrogen peroxide is added dropwise to a mixture of 168.4 g of a mixture of bis[1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl] adipate and bis[1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] glutarate prepared from DBE-3® (dibasic ester, DuPont having approximately 9:1 dimethyl adipate:dimethyl glutarate), 2.03 g (7.5 mmol) of ferric chloride hexahydrate, 1.5 mL of 37% hydrochloric acid, 1.9 mL of tert-butyl alcohol and 262 mL of water at a temperature of 400C. After a total reaction time of 30 hours, the temperature is increased to 700C and a solution of 71 g (1.04 mol) of 50% aqueous hydrogen peroxide is added to the mixture over six hours. After the mixture is stirred for 13 hours at 650C, another 71 g portion of 50% aqueous hydrogen peroxide is added over six hours, and the mixture is stirred at 650C for 17 hours. Excess peroxide is decomposed with sodium sulfite. The mixture is filtered to remove solids, and most of the tert-butyl alcohol and water are removed by co-distillation with heptane. The -94residue is extracted with ethyl acetate, and the solution is washed with saturated sodium chloride solution. Solvent is evaporated, and the residue is purified by flash chromatography on silica gel with hexane/ethyl acetate to afford 84.1 g of a white solid melting at 131.5-1330C. A second crop of 16.3 g of a white solid melting at 128- 1300C is also obtained.

NMR analysis shows the structure of the white solid to be consistent with the expected adipate/glutarate reaction product.

Example P62 Mixture of Bis[1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-yl] Adipate and Bis[1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-yl] Glutarate The procedure outlined in Example P61 is repeated using a mixture of bis[1oxyl-2,2,6,6-tetramethylpiperidin-4-yl] adipate and bis[1-oxyl-2,2,6,6-tetramethyl- S piperidin-4-yl] glutarate prepared from DBE-2® (dibasic ester, DuPont having approximately 3:7 dimethyl adipate:dimethyl glutarate) in place of bis[1-oxyl-2,2,6,6tetramethylpiperidin-4-yl] adipate and bis[1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] glutarate prepared from DBE-3® described in Example P61.

Example P63 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 34.6 g (201 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 50 mL of water and a solution of 25.2 g (370 mmol) of 50% aqueous hydrogen peroxide are added simultaneously over four hours and eight hours, respectively, to a mixture of 1.12 g (4.0 mmol) of ferrous sulfate heptahydrate, 20 mL of water and 1 mL of methanesulfonic acid and 400 mL of tert-butyl alcohol which is maintained at 80-850C. A solution of 0.506 g (1.8 mmol) of ferrous sulfate heptahydrate and 0.3 mL of methanesulfonic acid in 2 mL of water is added to the reaction mixture during the peroxide addition. The mixture is stirred at 80-850C for minutes after the peroxide is added. Gas chromatography shows that less than 1% of the starting nitroxyl remains. The reaction is worked up following a procedure similar to that of Example P9 to afford 40.8 g of a white solid which contains 98% of the title compound by gas chromatography analysis.

Further examples illustrating the novel compounds are the following: Example 1 Reaction of 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-one with Cyclohexanol A solution of 55 g (0.49 mol) of 30% aqueous hydrogen peroxide is added dropwise over a 4.25 hour period to a mixture of 23.5 g (0.14 mol) of 1-oxyl-2,2,6,6-tetramethyl-piperidin-4-one and 4.0 g (0.020 mol) of ferrous chloride tetrahydrate in 14 g (0.14 mol) of cyclohexanol and 150 g of cyclohexane. The reaction temperature is maintained at approximately 40 0 C throughout the addition. The reaction mixture is stirred at 400C for three hours after the peroxide addition is complete. A second portion of 30% aqueous hydrogen peroxide (10 g, 0.09 mol) is added and the reaction mixture is heated at 400C for seven hours. After the mixture is cooled to room o oo temperature, sodium sulfite (5 g) is added. The reaction temperature is carefully brought to 600C for one hour to decompose excess peroxide. Upon cooling, the organic layer is separated, dried over anhydrous magnesium sulfate, and concentrated to give 22.6 g of a brown oil. The oil is dissolved in cyclohexane and passed through silica gel with cyclohexane and then 1:2 (v/v) ethanol/cyclohexane to afford 16.5 g of a yellow oil.

Analysis by gass chromatography and mass spectrometry shows the product to be a mixture which contains at least four isomers of 1-(hydroxycyclohexyloxy)-2,2,6,6-tetramethyl- .i piperidin-4-one.

Example 2 Bis[1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-yl)] Sebacate -96- A solution of 73 g (0.64 mol) of 30% aqueous hydrogen peroxide is added dropwise over a 3.5 hour period to a mixture of 30.0 g (0.059 mol) of bis(1 -oxyl-2,2,6,6-tetramethylpiperidin-yl) sebacate and 4.7 g (0.024 mol) of ferrous chloride tetrahydrate in 150 g of tert-butyl alcohol and 6 g of water. The reaction temperature is kept at approximately 400C throughout the peroxide addition. The reaction mixture is stirred at 400C for four hours after the addition is complete. The reaction mixture is diluted with 150 g of ethyl acetate. A colution of 100 g of 20% aqueous sodium sulfite solution is added and the reaction mixture is stirred for 1.5 hours at 45-600C to decompose excess peroxide. The aqueous layer is extracted with 100 g of ethyl acetate, and the combined organic layers are washed with 200 g of 5% sulfuric acid. Solvent is evaporated to obtain 39.4 g of a pale yellow liquid which is purified by flash chromatography on silica gel with a 4:1:5 part mixture (by volume) of ethyl acetate:isopropanol:hexane to afford 19.1 g (49% yield) of the title compound as a pale yellow oil.

1 Hnmr (CDCI): 8 3.65 ppm (4H, -NOCH 2 Example 3 Reaction of Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate with Cyclohexanol A solution of 70 g (0.62 mol) of 30% aqueous hydrogen peroxide is added dropwise over 2.75 hours to a mixture of 32.4 g (0.063 mol) of bis(1-oxyl-2,2,6,6-tetramethylpiperidin-yl) oo. sebacate and 5.0 g (0.025 mol) of ferrrous chloride tetrahydrate in 100 g of cyclohexanol. The reaction temperature is maintained at 40-450C during the addition. The reaction mixture is then stirred at 400C for five hours and during this time, fresh 50% aqueous hydrogen peroxide (5.0 g, 0.074 mol) is added to the reaction mixture in two equal portions. The following day, the reaction mixture is heated to 400C, another portion of 50% aqueous hydrogen peroxide (2.5 g, 0.037 mol) is added, and the mixture is maintained at 400C for another five hours. A solution of 100 g of 20% aqueous sodium sulfite is added to the mixture and the reaction temperature is maintained at 700C for 45 minutes to decompose excess hydrogen peroxide. The combined organic layers are concentrated to give 151 g of crude product. Water is added, and residual cyclohexanol is removed by steam distillation. The remaining 50 g of crude product is purified by -97flash chromatography on silica gel with a 10:1:10 part mixture of ethyl acetate:ethanol:hexane to afford 32.9 g of an oil.

NMR analysis shows that the oil contains bis[1-(trans-2-hydroxycyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-yl] sebacate in addition to other structural isomers of said sebacate compound.

Example 4 Reaction of 4-Hydroxy-l-oxyl-2,2,6,6tetramethylpiperidine with Cyclohexanol A solution of 50 g (0.74 mol) of 50% aqueous hydrogen peroxide is added dropwise over a 1.75 hour period to a mixture of 35.0 g (0.20 mol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 10.0 gr (0.050 mol) of ferrous chloride tetrahydrate in 100 g of cyclohexanol. The reaction temperature is maintained at approximately 40-450C throughout the addition. After the peroxide addition is complete, the reaction mixture is stirred at 400C for five hours. The mixture of**: is cooled to room temperature and a solution of 100 g of 20% aqueous sodium sulfite is added.

The reaction mixture is carefully heated at 600C for one hour to decompose excess peroxide.

After acetone is added to the organic layer, the crude product mixture is filtered to remove solids and the filtrate is concentrated. Water is added and residual cyclohexanol is removed by steam distillation. The crude product is purified by flash chromatography on silica gel with 2:1 (v/v) hexane/ethyl acetate to afford 36.3 g of a yellow oil.

Analysis by mass spectrometry shows the oil to be a mixture of isomers of 1-(hydroxycyclohexyloxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine and 1-(dihydroxycyclohexyloxy)-4-hydroxy- 2,2,6,6-tetramethylpiperidine.

-98- Example Reaction of 2,4-Bis[N-(1-oxyl-2,2,6,6-tetramethyl piperidin-4-yl)butylamino-6-chloro-s-triazine with Cyclohexanol A solution of 30 g (0.44 mol) of 50% aqueous hydrogen peroxide is added over a 2 hour period to a mixture of 39.4 g (0.070 mol) of 2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)butylamino-6-chloro-s-triazine and 7.0 g (0.035 mol) of ferrous chloride tetrahydrate in 150 g of cyclohexanol at a temperature of 40-450C. The reaction mixture is stirred at 400C for ten hours after the peroxide addition is complete, and during this time, another 19 g (0.28 mol) portion of aqeuous hydrogen peroxide is added. Another portion of 50% aqueous hydrogen peroxide g, 0.37 mol) is added while the reaction mixture is heated at 50-650C for four hours. The reaction mixture is treated with a solution of 100 g of 20% aqueous sodium sulfite at 600C for one hour to decompose residual peroxide. The organic layer is concentrated to a brown oil which is extracted thrice with cyclohexane and once with ethyl acetate. The combined extracts are concentrated to afford 43.4 g of a yellow solid.

Example 2,4-Bis{N-[1 -(trans-2-hydroxycyclohexyloxy)- 2,2,6,6-tetramethylpiperidin-4-yl]butylamino}- 6-(2-hydroxyethyl)amino-s-triazine The product obtained in Example 5 is reacted with ethanolamine and sodium hydroxide solution. The crude reaction mixture is duluted with ethyl acetate and washed with water. The aqueous layer is extracted with ethyl acetate, and the combined organic layers are concentrated. The residue is dissolved in ethyl acetate and cyclohexane is added. A brown oil is removed. The remaining solution is concentrated to give 13.7 g of crude product. The crude product is purified by flash chromatography on silica gel with 2:1 ethyl acetate/hexane and then 8:1 ethyl acetate/methanol to afford 6.4 g of a yellow oil. The oil is dissolved in ethanol and treated with decolorizing carbon at 600C for one hour. Solids are removed by filtration and the solvent is evaporated to give 6.5 g of an off-white solid, melting at 67-800C.

-99- NMR analysis shows the solid contains the title compound in addition to a mixture of hydroxycyclohexyloxy and dihydroxycyclohexyloxy structural isomers.

Example 6 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 50.7 g (0.75 mol) of 50% aqueous hydrogen peroxide mixed with 25 mL of tert-butyl alcohol is added over two hours to a mixture of 25.8 g (0.15 mol) of 4-hydroxy-1-oxyl- 2,2,6,6-tetramethylpiperidine, 8.95 g (0.045 mol) of ferrous chloride tetrahydrate and 110 mL of tert-butyl alcohol at 500C. The reaction mixture is then maintained at 500C for six hours and monitored by gas chromatography. Another 17.7 g (0.26 mol) of 50% hydrogen peroxide is added and the reaction mixture is heated at 500C for two more hours to bring about complete reaction of the starting nitroxyl compound. The reaction mixture is filtered to remove solids, and the filtrate is diluted with water. The tert-butyl alcohol-water solution is extracted three times with methylene chloride and the aqueous layer is thoroughly extracted with ethyl acetate to afford 7.4 g of the title compound. The combined organic layers are washed once with saturated sodium chloride, dried over anhydrous magnesium sulfate and concentrated to give 21.7 g of an orange oil. The orange oil is purified by flash chromatography on silica gel with 3:2 heptane:ethyl acetate to afford another 12.4 g of the title compound and 4.2 g of a compound which has the same retention time by gas chromatography as an authenic sample of 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-one.

Examples 6A to 6D illustrate the effect of adding a ligand to the procedure described in Example 6.

Example 6A 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine Ferrous chloride tetrahydrate (0.99 g, 5.0 mmol) is added to 400 mL of tert-butyl alcohol which is heated to 400C. The mixture is stirred for 15 minutes and 0.78 g (5.0 mmol) of 2,2'-dipyridyl is added to the tert-butyl alcohol solution. The solution is then stirred for five minutes and 17.2 g (100 mmol) of 4-hydroxy-l-oxyl-2,2,6,6-tetramethylpiperidine is added. A solution of 49 g (0.72 mol) of 50% aqueous hydrogen peroxide mixed with 100 mL of tert-butyl -100alcohol is added to the reaction mixture over a 10-hour period at 40-45°C. Another 6 g (0.088 mol) of 50% aqueous hydrogen peroxide is then added while the reaction mixture is heated at 450C for four hours until the starting nitroxyl compound is reacted. Analysis by gas chromatography shows the reaction mixture contains 6 area of 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-one compared to 22 area in Example 6. Solids are removed by filtration, and after 1.5 g of sodium borohydride is added, the filtrate is stirred for one hour. The filtrate is diluted with water, and the mixture is thoroughly extracted with ethyl acetate. The extract is concentrated to afford 24.2 g of a light tan crystalline solid which has the same gas chromatography retention time as an authenic sample of the title compound. In a similar experiment, the final product is recrystallized several times from heptane to obtain 16.9 g (69% yield) of the title compound, melting at 127-1310C.

Example 6B 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 32.3 g (475 mmol) of 50% aqueous hydrogen peroxide mixed with 35 mL of tert-butyl alcohol is added over six hours at 45-500C to a mixture prepared by adding sequentially 0.362 g (1.2 mmol) of ethylenediaminetetraacetic acid, 55 mL of tert-butyl alcohol and 17.2 g (100 mmol) of 4-hydroxy-l -oxyl-2,2,6,6-tetramethylpiperidine to a solution of 0.80 g (4 mmol) of ferrous chloride dissolved in 5 mL of water. Analysis by gas chromatography shows 15% starting nitroxyl compound remains at the end of the peroxide addition. The reaction mixture is stirred for one hour at 45-500C and then for 72 hours at 250C to complete the reaction. Analysis by gas chromatography shows the reaction mixture contains a ratio of 7 parts of the title compound to 1 part of 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4one.

S'.i Example 6C 4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine The procedure of Example 6B is repeated using triphenylphosphine oxide in place of the ethylenediaminetetraacetic acid.

Example 6D 101 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine The procedure of Example 6B is repeated using ethylenediaminetetraacetic acid disodium salt in place of ethylenediaminetetraacetic acid.

Example 7 Bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl] Adipate Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-tetramethylpieridin-4-yl) adipate and ferrous chloride tetrahydrate in tert-butyl alcohol at 30-500C. Excess peroxide is decomposed with aqeuous sodium sulfite solution. The organic layer is concentrated and the crude product is purified by flash chromatography on silica gel to afford the title compound.

Example 8 Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl] Glutarate Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-tetramethylpieridin-4-yl) glutarate and ferrous chloride tetrahydrate in tert-butyl alcohol at 30-50°C. Excess peroxide is decomposed with aqeuous sodium sulfite solution. The organic layer is concentrated and the crude product is purified by flash chromatography on silica gel to afford the title compound.

102- Example 9 Bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl] Succinate Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-tetramethylpieridin-4-yl) succinate and ferrous chloride tetrahydrate in tert-butyl alcohol at 30-500C. Excess peroxide is decomposed with aqeuous sodium sulfite solution. The organic layer is concentrated and the crude product is purified by flash chromatography on silica gel to afford the title compound.

Example Bis[1 -(2-hydroxy-1 -phenethoxy)-2,2,6,6tetramethylpiperidin-4-yl] Sebacate Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-tetramethyl- S pieridin-4-yl) sebacate and ferrous chloride tetrahydrate in phenethyl alcohol at 30-500C. Excess S peroxide is decomposed with aqeuous sodium sulfite solution. The organic layer is concentrated and the crude product is purified by flash chromatography on silica gel to afford the title compound.

Example 11 2,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-yl]butylamino}- 6-chloro-s-triazine A total of 40 g (0.59 mol) of 50% aqueous hydrogen peroxide is added in two portions over five hours to a mixture of 43.2 g (0.076 mol) of 2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)butylamino-6-chloro-s-triazine and 7.0 g (0.035 mol) of ferrous chloride tetrahydrate in 150 g of tert-butyl alcohol and 15 g of water. Another portion of 50% aqueous hydrogen peroxide (3 g, 0.044 mol) is added to the reaction mixture while the temperature is -103maintained at 40-450C for 2.25 hours. The reaction mixture is diluted with 100 g of ethyl acetate.

A solution of 100 g of 20% aqueous sodium sulfite is added and the reaction mixture is heated at 600C for one hour to decompose residual peroxide. The aqueous layer is extracted with ethyl acetate, and the combined organic layers are concentrated. The crude product is purified by flash chromatography on silica gel with 1:1 hexane/ethyl acetate to afford 54.1 g of the title compound.

Example 12 2,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-yl]butylamino}- 6-(2-hydroxyethyl)amino-s-triazine The title compound is prepared by the reaction of the intermediate prepared in Example 11 with ethanolamine and sodium hydroxide. The aqueous layer is removed, and the remaining layer is extracted with cyclohexane. Solvent is evaporated at reduced pressure, and the crude product is purified by flash chromatography on silica gel with 1:2 hexane/ethyl acetate to afford 4.1 g of the title compound as a white solid, melting at 110-1200C.

'Hnmr (CDC1 3 5 3.54 ppm (q,2H, NCH 2 3.59 ppm (s,4H, NOCH 2 Example 13 Reaction of the Product of Example 11 with N,N'-Bis(3-aminopropyl)ethylenediamine The product prepared in Example 11 is reacted with N,N'-bis(3-aminopropyl)ethylenediamine in a 3:1 molar ratio. The product mixture includes N,N',N"-tris{2,4-bis[N-[1-(2-hydroxy-2methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine and N,N',N"'-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine.

Example 14 -104 2,4-Bis{N-[1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetram ethyl p iperid in-4-yl] butylami no}- 6-octylami no-s-triazine The reaction of the compound prepared in Example 11 with excess octylamine yields the title compound as an off-white glass melting at 68-86 0

C.

Example N,N'-Bis{4,6-bis{N-[1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-yl]butylamino}s-triazin-2-yl}-1 ,6-diaminohexane The title compound is prepared by the reaction of the compound prepared in Example 11 with hexamethylenediamine.

Example 1 6A Reaction of 4-Hydroxy-1 -oxyl-2,2,6,6tetramethylpiperidine with tert-Butyl Alcohol :A solution of 50% aqueous hydrogen peroxide is added to a mixture of 4-hydroxy-1 -oxyl- 2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in tert-butyl alcohol at 30-60'C.

Excess peroxide is decomposed with aqeuous sodium sulfite. The organic layer is concentrated and the crude product is purified by flash chromatography on silica gel to afford a sample of 4hydroxy-1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine.

-105- Example 16B 1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl Methacrylate The title compound is prepared by reaction of the compound prepared in Example 16A with methyl methacrylate.

Example 17 4-Allyloxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A suspension of 8.4 g (0.21 mol) of 60% sodium hydride in mineral oil is added in portions at 500 C to a solution of 49.1 g (0.20 mol) of the compound obtained in Example 16A in 500 ml of anhydrous diglyme. Allyl bromide (20.8 ml, 29.1 g, 0.24 mol) is then added to the reaction mixture over several hours, and the mixture is stirred at 500 C for 7 Iours. The reaction is cooled and quenched with 2N hydrochloric acid solution. After the addition of a saturated solution of sodium bicarbonate to neutralize excess acid, the organic layer is concentrated to afford 47.5 g (83% yield) of the title compound, which is a yellow oil.

Example 18 4-(2,3-Epoxypropoxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine The title compound is prepared by the reaction of the compound prepared in Example 16A with epichlorohydrin.

106 Example 19 1 -(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl -(2-hyd roxy-2-m ethyl propoxy) 2,2,6,6-tetramethyl pipe rid in-4-yloxy]carbonyl]amino] methyl}-3,5,5-trimethylcyclohexylcarbamate The title compound is prepared by the reaction of the compound prepared in Example 1 6A with 5-isocyanato-1 -(isocyanatomethyl)-1 ,3,3-trimethylcyclohexane isophorone diisocyanate).

Example Bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-y] 1 ,6-Hexanedicarbamate The title compound is prepared by the reaction of the compound prepared in Example 16A with hexamethylene diisocyanate.

Example Bisil hyd roxy-2-methyl propoxy)-2,2,6,6-tetramethyl pipe rid in-4-ylI toluene-2,4- :dicarbamate The title compound is prepared from the reaction of the compound obtained in Example 16A with toluene-2,4-diisocyanate.

-107- Example 1,3,5-tris{[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4yloxy]carbonylaminohexyl}-2,4,6-trioxo-s-triazine The title compound is prepared from the reaction of the compound obtained in Example 16A with 1,3,5-tris[6-isocyanatohexyl]-2,4,6-trioxo-s-triazine (DESMODUR® N-3390).

Example 21 1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl Acrylate The title compound is prepared by the reaction of the compound prepared in Example 16A with methyl acrylate.

Example 22 2,4,6-Tris{N-[1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-yl]butylamino}s-triazine A solution of 40 g (0.35 mol) of 30% aqueous hydrogen peroxide is added over 1.25 Shours to a mixture of 11.7 g (0.011 mol) of 2,4,6-tris[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-s-triazine and 3.0 g (0.015 mol) of ferrous chloride tetrahydrate in 100 g of tert-butyl alcohol and 9 g of water. The reaction temperature is maintained at 60-650C during the peroxide addition. Two equal portions (2 g, 0.29 mol) of 50% aqueous hydrogen peroxide are added to the reaction mixture while the temperature is maintained at 60 0 C for 9.5 hours. After the reaction mixture is diluted with ethyl acetate and cooled to room temperature, a solution of 100 g of aqueous sodium sulfite is added. The reaction mixture is heated at 600C for one hour to decompose the excess peroxide. The aqueous layer is extracted with ethyl acetate, and the combined organic layers are concentrated. The crude product is purified by flash chromatography on silica gel with 2:1 cyclohexane/ethyl acetate to afford a material which 108is triturated with 1:1 cyclohexane/acetone to give 4.0 g of the title compound as a white solid, melting at 172-1760C.

Example 23A Reaction of 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-one with tert-Butyl Alcohol Aqueous hydrogen peroxide is added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin- 4-one and ferrous chloride in tert-butyl alcohol at 30-600C. Excess peroxide is decomposed with aqueous sodium sulfite. The organic layer is concentrated and the residue is purified by flash chromatography to afford the desired 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-one.

Example 23B :i 4-Butylamino-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A mixture of butylamine, the compound prepared in Example 23A and a catalytic amount of 5% platinum on carbon is hydrogenated at 3 atmospheres using a Parr apparatus. The catalyst is removed by filtration, and the solvent is evaporated to afford the title compound.

Example 24 4-Trimethylsilyloxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine Chlorotrimethylsilane (6.4 ml, 0.050 mol) is added over 15 minutes at 600 C to a mixture of 12.25 g (0.050 mol) of the compound obtained in Example 16A, 8.5 ml of triethylamine and 125 ml of anhydrous tetrahydrofuran. The reaction mixture is stirred at 600 C for 2 hours, then stirred at room temperature for 1 hour. Solvent is evaporated, and the residue is partitioned 109between water and dichloromethane. The organic layer is dried over magnesium sulfate and concentrated to obtain 14.6 g (92% yield) of the title compound as a yellow oil.

Example 4-Benzoyloxy-1-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine A solution of 50% aqueous hydrogen peroxide is added slowly to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in tert-butyl alcohol at 30-60 0 C. Excess peroxide is decomposed by aqueous sodium sulfite solution. The organic layer is concentrated and the residue is purified by flash chromatography to afford the title compound.

Example 26 1-(2-Hydroxy-2-methylpropoxy)-4-[3-(trimethylsilyl)propoxy]-2,2,6,6-tetramethylpiperidine The title compound is prepared by reacting the compound prepared in Example 17 with trimethylsilane and hydrogen hexachloroplatinate(IV) in isopropyl alcohol.

Example 26A 1 -(2-Hydroxy-2-methylpropoxy)-4-[3-(diethylmethylsilyl)propoxy]-2,2,6,6-tetramethylpiperidine A mixture of 28.5 g (0.10 mol) of the compound obtained in Example 17, 14.5 ml (0.10 mol) of diethylmethylsilane, and 1 ml of a solution of 2% hydrogen hexachloroplatinate(IV) in isopropyl alcohol is heated at reflux for 4 hours. The reaction mixture is distilled under vacuum to obtain a viscous, pale yellow oil. Mass spectroscopy reveals that the reaction product has a molecular ion of 387, which is consistent with formation of the title compound.

Example 27 -110- Tetrakis{3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yloxy]propyl}- 1,3,5,7-tetramethylcyclotetrasiloxane The title compound is prepared by heating a mixture of 30.3 g (0.106 mol) of the compound obtained in Example 17, 6.3 ml (0.026 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane, and 1 ml of a 2% solution of hydrogen hexachloroplatinate(IV) in isopropyl alcohol at 1000 C for 4 hours. The reaction mixture is cooled and partitioned between dichloromethane and water.

The organic layer is filtered and concentrated at reduced pressure to obtain 31.7 g (98% yield) of the title compound as a viscous orange oil.

Example 28 Poly{[3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yloxy]propyl]methyl}silane The title compound is prepared by the reaction of the compound prepared in Example 17 with poly(methylsilane) and hydrogen hexachloroplatinate(IV) in isopropyl alcohol.

Example 29 Poly{[3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4yloxy]propyl]methyl}siloxane, terminated with trimethylsiloxy The title compound is prepared by heating a mixture of 29.6 g (0.104 mol) of the compound obtained in Example 17, 6.8 g (0.004 mol) of poly(methylhydrosiloxane), terminated Swith trimethylsiloxy, average molecular weight 1700, and 1 ml of a 1% solution of hydrogen hexachloroplatinate(IV) in isopropyl alcohol at 1000 C for 1 hour. The resulting polymeric mass is partially dissolved in hot dichloromethane, and the suspension is extracted with hot water.

The organic layer is concentrated to obtain 34.7 g of the title compound as a white, rubbery solid.

Anal. Calcd. for C 439 .5H 9 10

N

25 5 0 1 03 Si27.

5 (n=25.5 in starting material): C, 58.82; H, 10.21; N, 3.97 -111 Found C, 59.62; H 10.11, N 3.08 Example Mixture of Bis[l -(2-Hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl] Glutarate and Bis(1[l-(2-Hydroxy- 2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl] Adipate A mixture of the compound prepared in Example 16A, DBE-2 dimethyl ester mixture (DuPont), and lithium amide is heated at reflux in xylene. Methanol is distilled from the reaction mixture. The reaction mixture is quenched with dilute mineral acid, and the organic layer is washed with water and dried over anhydrous magnesium sulfate. The xylene solution is evaporated at reduced pressure to afford the title compound mixture.

Example 0 *Mixture of bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-y)] adipate and bis[l -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yi)I glutarate A solution of aqueous 50% hydrogen peroxide is added dropwise to a mixture of ferric chloride, aqueous hydrochloric acid, water, t-butyl alcohol, and bis(1 -oxyl-2,2,6,6tetramethylpiperidin-4-yl) adipate and bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) glutarate, prepared from DBE-3 dibasic ester (DuPontr). Excess peroxide is decomposed with aqueous S. sodium sulfite solution. The reaction mixture is filtered and solvents are evaporated. The S residue is purified by flash chromatography on silica gel with hexane/ethyl acetate to afford the title compound as a white solid, mp 131.5-133.

S...i Example Mixture of bisll-(2-hydroxy-2-methyl-propoxy)-2,2,6,6-tetramethylpiperidin- 4-yl] glutarate and bis[1-(2-hydroxy-2-methyl-propoxy)-2,2,6,6-tetramethylpiperidin-4-yl] succinate When the procedure of Example 30 is repeated with DBE-9 a dimethyl ester mixture (DuPont), the title mixture is prepared.

Example 31 Reaction of Bis(l -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate with Neopentyl alcohol -112- Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and ferrous chloride in neopentyl alcohol according to the procedure of Example Example 32 Reaction of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one with Neopentyl Glycol Aqueous hydrogen peroxide is added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin- 4-one and ferrous chloride in neopentyl glycol according to the procedure of Example Example 33 Reaction of 4-Octadecanoyloxy-1 -oxyl-2,2,6,6piperidine with tert-Amyl Alcohol Aqueous hydrogen peroxide is added to a mixture of 4-octadecanoyloxy-l-oxyl-2,2,6,6tetramethylpiperidine and ferrous chloride in tert-amyl alcohol according to the procedure of Example Example 33A SReaction of 4-hydroxy-1 -oxyl-2,2,6,6-tetramethylpiperidine with 2-methyl-2-butanol A solution of 34.5 g (0.20 mol) of 4-hydroxy-1 -oxyl-2,2,6,6-tetramethylpiperidine in 50 ml of water and a solution of 22.5 g of 50% aqueous hydrogen peroxide are added at 90-950 C to a mixture containing a total of 1.88 g of ferrous sulfate heptahydrate, 2.05 g of methanesulfonic acid, 20 ml of water, and 450 ml of 2-methyl-2-butanol (t-amyl alcohol). The reaction is completed in 6 hours. The reaction mixture is filtered to remove solids, and the filtrate is stirred with sodium sulfite followed by basic sodium borohydride. The aqueous layer is removed, and the organic layer is concentrated and purified by flash chromatography on silica gel with hexane/ethyl acetate to afford 46.3 g of a yellow oil. Analysis by gas chromatography-mass -113spectroscopy reveals that the product is a mixture of 3 major components, all with molecular weight 259, which correspond to the addition of t-amyl alcohol to the starting nitroxyl compound.

Example 33B Transesterification of the reaction product of Example 33A with methyl stearate A mixture of 44.8 g (0.173 mol) of the reaction product obtained in Example 33A, 47.1 g (0.158 mol) of methyl stearate, 0.223 g of lithium amide, and toluene is heated at reflux.

Methanol is distilled from the reaction mixture along with some of the toluene. The reaction mixture is quenched with dilute acetic acid, and washed successively with water, dilute aqueous sodium bicarbonate solution, and saturated sodium chloride solution. The toluene solution is dried over magnesium sulfate, filtered, and concentrated to obtain a solid. Purification by flash chromatography on silica gel with hexane/ethyl acetate affords 70.0 g of an off white solid product, mp 38-43.

Example 34 4-Benzoyloxy-1 -(2-hydroxycyclohexyloxy)- 2,2,6,6-tetramethylpiperidine Tributyltin hydride is added dropwise to a solution of 2-bromocyclohexanol and excess 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. The mixture is heated to facilitate reaction. The crude reaction mixture is passed through silica gel with heptane and then heptane/ethyl acetate to afford the title compound as a mixture os cis/trans isomers.

-114- Example 4-Hydroxy-1 -(2-hydroxycyclohexyloxy)- 2,2,6,6-tetramethylpiperidine The title compound is prepared by heating the compound prepared in Example 34 in a solution of potassium hydroxide in methanol.

Example 36 Reaction of 4-Benzoyloxy-1-oxyl-2,2,6,6tetramethylpiperidine with Propylene Glycol Aqueous hydrogen peroxide is added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in propylene glycol according to the S procedure of Example Example 37 S. Reaction of 4-Benzoyloxy-1-oxyl-2,2,6,6tetramethylpiperidine with Trimethylene Glycol Aqueous hydrogen peroxide is added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in trimethylene glycol according to the procedure of Example Example 38 Bis[1 -(2-hydroxyethoxy)-2,2,6,6tetramethylpiperidin-4-yl] Sebacate Tributyltin hydride is added dropwise to a solution of 2-iodoethanol and excess bis(1oxyl-_2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. The crude reaction mixture -115is passed through silica gel with heptane and then heptane/ethyl acetate to afford the title compound.

Example 39 Reaction of Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate with Isopropanol Aqueous hydrogen peroxide is added to a mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and ferrous chloride tetrahydrate in isopropanol according to the procedure of Example Example Reaction of 4-Benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 1,4-Butanediol Aqueous hydrogen peroxide is added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in 1,4-butanediol according to the procedure of Example Example 41 Reaction of 4-Hexyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with Pinacol Aqueous hydrogen peroxide is added to a mixture of 4-hexyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in pinacol according to the procedure of Example -116- Example 42 Reaction of 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-one with Glycerol Aqueous hydrogen peroxide is added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin- 4-one and ferrous chloride tetrahydrate in glycerol according to the procedure of Example Example 43 Reaction of 4-Hydroxy-l-oxyl-2,2,6,6-tetramethylpiperidine with 2-Ethyl-l-hexanol Aqueous hydrogen peroxide is added to a mixture of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in 2-ethyl-l-hexanol according to the procedure of Example Example 44 1 -(2-Hydroxy-2-methylpropoxy)-4-hexadecanoyloxy- 2,2,6,6-tetramethylpiperidine A mixture of 12.11 g (49.4 mmol) of the compound obtained in Example 16A, 12.11 g (44.8 mmol) of methyl hexadecanoate (methyl palmitate), 0.76 g of lithium amide, and toluene is heated at reflux. Methanol is distilled from the reaction mixture along with some of the toluene.

The reaction mixture is quenched with dilute acetic acid, and washed successively with aqueous methanol, dilute aqueous sodium bicarbonate solution, and saturated sodium chloride solution. The toluene solution is dried over magnesium sulfate, filtered, and concentrated to obtain a solid. Purification by flash chromatography on silica gel with hexane/ethyl acetate affords 18 g of a solid. Recrystallization from methanol yields 10.7 g of the title compound as a white solid, mp 60-64.

-117- Example 44A 1-(2-hydroxy-2-methylpropoxy)-4-eicosanoyloxy-2,2,6,6-tetramethylpiperidine A mixture of 8.40 g (34.2 mmol) of the compound obtained in Example 16A, 10.17 g (31.1 mmol) of methyl eicosanoate, 0.35 g of lithium amide, and toluene is heated at reflux. The reaction mixture is quenched with dilute acetic acid, and washed successively with aqueous methanol, dilute aqueous sodium bicarbonate solution, and saturated sodium chloride solution.

The toluene solution is dried over magnesium sulfate, filtered, and concentrated to obtain a solid which is purified by flash chromatography on silica gel with hexane/ethyl acetate to afford 9.9 g of the title compound as a white solid, mp 69-73.

Example 44B 1-(2-hydroxy-2-methylpropoxy)-4-(2-ethylhexanoyloxy)-2,2,6,6-tetramethylpiperidine A mixture of 51.6 g (0.210 mol) of the compound obtained in Example 16A, 30.6 g (0.193 mol) of methyl 2-ethylhexanoate, 1.26 g of lithium amide, and toluene is heated at reflux.

Methanol is distilled from the reaction mixture along with some of the toluene. The reaction mixture is quenched with dilute acetic acid, and washed successively with aqueous methanol, dilute aqueous sodium bicarbonate solution, and saturated sodium chloride solution. The toluene solution is dried over magnesium sulfate, filtered, and concentrated to obtain a yellow liquid. Purification by flash chromatography on silica gel with hexane/ethyl acetate affords 51.0 g of the title compound as a pale yellow oil.

Example 44C 1-(2-hydroxy-2-methylpropoxy)-4-dodecanoyloxy-2,2,6,6-tetramethylpiperidine A mixture of 72.7 g (0.297 mol) of the compound obtained in Example 16A, 51.9 g (0.242 mol) of methyl dodecanoate (methyl laurate), 0.43 g of lithium amide, and toluene is heated at reflux. Methanol is distilled from the reaction mixture along with some of the toluene.

The reaction mixture is quenched with dilute acetic acid, and washed successively with -118aqueous methanol, dilute aqueous sodium bicarbonate solution, and saturated sodium chloride solution. The toluene solution is dried over magnesium sulfate, filtered, and concentrated to obtain a solid. Purification by flash chromatography on silica gel with hexane/ethyl acetate affords 96.7 g of the title compound as a white solid, mp 46-8.

Example Reaction of N,N',N",N"'-Tetrakis{2,4-bis[N-(1-oxyl- 2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin- 6-yl}-3,3'-ethylenediiminodipropylamine with Cyclohexanol A mixture of N,N',N",N"'-tetrakis{2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine in cyclohexanol is reacted with aqueous hydrogen peroxide and ferrous chloride tetrahydrate according to the method of Example 4. A white solid melting at 133-1750C is obtained.

Example 46 Reaction of 2,4,6-Tris[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-s-triazine with Cyclohexanol A mixture of 2,4,6-tris[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-s-triazine and cyclohexanol is reacted with aqueous hydrogen peroxide and ferrous chloride tetrahydrate according to the procedure of Example 4. A light brown oil is obtained.

-119- Example 47 Bis[l -(3-hydroxypropoxy)-2,2,6,6-tetramethylpiperidin-4-yl] Sebacate Tributyltin hydride is added dropwise to a solution of 3-bromo-1 -propanol and excess bis(1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. The mixture is heated to facilitate reaction. The crude reaction mixture is passed through silica gel with heptane and then heptane/ethyl acetate to afford the title compound.

Example 48 Bis[l1-(12-hydroxy-1 -dodecyloxy)-2,2,6,6tetramethylpiperidin-4-yl] Sebacate Tributyltin hydride is added dropwise to a solution of 12-bromo-1-dodecanol and excess bis(l -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. The mixture is heated to facilitate reaction. The crude reaction mixture is passed through silica gel with heptane and then heptane/ethyl acetate to afford the title compound.

Example 49 Bis[1 -(2-hydroxypropoxy)-2,2,6,6-tetramethylpiperidin-4-yl] Sebacate Tributyltin hydride is added dropwise to a solution of 1-bromo-2-propanol and excess *bis(l -oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. The mixture is heated to facilitate reaction. The crude reaction mixture is passed through silica gel with heptane and then heptane/ethyl acetate to afford the title compound.

120 Example Reaction of the Product of Example 11 with N ,N'-Bis(3-aminopropyl)ethylenediamine N,N'-Bis(3-aminopropyl)ethylenediamine and the product prepared in Example 11 are reacted in a 1:3.0 to 1:3.5 molar ratio. The product mixture includes N,N',N"-tris{2,4-bis[N-[l hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidi n-4-yl] butyl ami nol-s-triazin-6-yl}-3,3'ethylenediiminodipropylamine, N ,N',N"'-tris{2,4-bis[N-[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethyl pipe rid in-4y] butylami no]-s-triazin-6-yl}-3,3'-ethylened i ihinod ipropylami ne, and N, N"'-tetrakis{2,4-bis[N-[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4yl] butylam ino]-s-triazi n-6-yl}-3,3'-ethylenedii mi nod ipropylami ne.

Example 51 N"'-Tetrakis{2,4-bis[N-[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidil-4-yIbutylaino]s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine title compound is prepared by the addition of aqueous hydrogen peroxide to a ~mixture of N, ,N"'-tetrakis{2,4-bis[N-(1 -oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-stri azi n-6-yl}-3,3'-ethylen edi im inod ipropyl amine, ferrous chloride and tert-butyl alcohol according to the procedure of Example 7.

Example 51 A N, N -Tris{2,4-bi s[N 1 -(2-hyd roxy-2- methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]s-triazi n-6-yl}-3,3'-ethyle ned i im inod ipropylam i ne The title compound is prepared by the addition of aqueous hydrogen peroxide to a mixture of N, N"'-tris{2,4-bis[N-(1 -oxyl-2,2,6,6-tetramethylpiperidin-4yl)butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine, ferrous chloride and tert-butyl alcohol according to the procedure of Example 7.

121 Example 51 B N N"-Tris{2,4-bis[N-[1 -(2-hydroxy-2-methylp ropoxy) -2,2,6,6-tetramethyl pipe rid in-4-yl] butylamino]s-tri azi n-6-yI}-3,3'-ethylened i imi nod ipropylamifle The title compound is prepared by the addition of aqueous hydrogen peroxide to a mixture of N, N',N"-tris{2,4-bis[N-(1 -oxyl-2,2,6,6-tetramethylpiperidin-4yI)butylamino]-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamine, ferrous chloride and tert-butyl alcohol according to the procedure of Example 7.

Example 52 Reaction of the Product of Example 11 with N ,N'-Bis(3-aminopropyl)ethylenediamine N,N'-Bis(3-aminopropyl)ethylenediamine and the product prepared in Example 11 are reacted in a 1:4.0 molar ratio. The product mixture includes N,N',N"-tris{2,4-bis[N-[l-(2-hydroxydiiminodipropylamine, N, N"'-tris{2,4-bis[N-[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramehy pierdi 4y]btla o--rain6yl33-tyeeiir o poya e and N, N"'-tetrakis{2,4-bis[N-[1 -(2-hydroxy2-methylpropoxy)-2,2,6,6-tetramethylpiperidin- 4 butylam ino] -s-triazi n-6-yl}-3,3'-ethyl enedi imi nod ipropylam ine.

Example 53A -(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-4,6-dichloro-s-triazine The compound prepared in Example 23B is reacted with an equimolar amount of cyanuric chloride and sodium bicarbonate at 0 0 C to give the title compound.

Example 53B N, N'-Bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6- 122tetramethylpiperidin-4-yl]- 1,6-hexanediamine The title compound is prepared by the hydrogenation at 50 psi of the compound obtained in Example 23A, hexamethylenediamine, methanol and a catalytic amount of platinum on carbon.

Example 53C N,N'-Bis{2-[N-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-4-chloro-s-triazin- 6 -yl}- N,N'-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl]-1,6-hexanediamine The title compound is prepared by reaction of the two compounds prepared in Examples 53A and 53B in a 2:1 molar ratio in xylene at 60-800C with sodium hydroxide as the acid acceptor.

Example 53D Oligomer of -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-4-yl}- N,N'-bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6, 6 tetramethylpiperidin-4-yl]-1,6-hexanediamine terminated with 2,4-bis(dibutylamino)-s-triazin-6-yl The compounds prepared in Examples 53B and 53C are mixed together in a 2:1 molar ratio in xylene solution at 100-1600C with sodium hydroxide as the acid acceptor. The reaction mixture is then treated with 2,4-bis(dibutylamino)-6-chloro-s-triazine under the same conditions to give an oligomeric product having a low number 4, 6, 8) of repeating units terminated by the 2,4-bis(dibutylamino)-s-triazin-6-yl moieties as seen in the structure below.

123-

C

4 H9 caH 6 H N N~

NCH

2 CH)/4N9-(

C

4

H

9 NY.N Ny N N -N C 4

H

9 N N-C4H

N

N N N C 4H; CMH 9 I C 4 H CH 9 0 0 0 0 HO HO0 HO HO

HO

-2,4,6 Example 54 Oligomer of -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-4-yl}- N,N'-bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethyl pipe ridi ,6-hexanediami ne terminated with 2,4-bis(dibutylamino)-s-triazin-6-yI N, N'-Bis (2,2,6,6-tetramethyl pipe rid in-4-yl) 6-hexaned iami ne and N,N'-bis{2-[N-(2,2,6,6tetramethyl piperidi n-4-yl) butylamino]-4-chloro-s-triazin-6-yl-N, N'-bis(2,2,6,6-tetramethylpiperidin-4-y)-1 ,6-hexanediamine are mixed together in a 2:1 molar ratio in xylene at 100-1 60 0

C

with sodium hydroxide as the acid acceptor. The reaction mixture is then treated with 2,4bis(dibutylamino)-6-chloro-s-triazine under the same conditions. The resulting mixture of oligomers is heated with tert-butyl hydroperoxide and a catalytic amount of molybdenum trioxide in an inert solvent such as 1 ,2-dichloroethane to form the corresponding N-oxyl compounds.

Aqueous hydrogen peroxide in then added to the mixture of the N-oxyl compounds and ferrous chloride tetrahydrate in tert-butyl alcohol according to the procedure of Example 7. The final products is a mixture of oligomers as in Example 530 although the ratios of the individual components may not be the same as in Example 53D.

-124- Example Oligomer of -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl pipe rid in-4-yl] butylami no] -s-tri azi n-4-yl}- N,N'-bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethyl pipe rid in-4-yl]-1, ,6-hexaned iami ne terminated with 2-butylamino-4-{N-[1 -(2-hydroxy- 2-methyl propoxy)-2,2,6,6-tetramethyl pipe rid il-4-ylIbutylamino-s-triazin-6-yi The title compound is prepared by heating a mixture of the compounds prepared in Examples 53A and 53B3, in a 1.33 to 1.0 molar ratio in xylene at 100-1600C using sodium hydroxide as the acid acceptor. Dibutylamine is then added to the reaction mixture under the same conditions to complete the reaction. The product is a mixture of oligomers that include 1-4 repeating units as seen in the structure below.

.RC.HA9\ C 4H9 N- (CH 2

C

4

H

9 N~ N N N C 4

H

9 C4H 9 N NC 4 H 9 0 0

N

HO HO 0 HO HO -1-4 125 Example 56 Oligomer of N-{2-IIN-[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl pipe rid in-4-yl] butylami no-s-triazil-4-yl}- N ,N'-bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethyl pipe rid in-4-yl- 1, ,6-hexanediam ine terminated with 2-butylamino-4-{N-[1 -(2-hydroxy- 2-methylpropoxy) -2,2,6,6-tetramethylpi perid il-4-yl]butylamino-s-triazin-6-yl The title compound is prepared by heating a mixture of the compounds prepared in Examples 53B and 530, in a 0.5:1 molar ratio in xylene at 100-1600C using sodium hydroxide as the acid acceptor. Dibutylamine is then added to the reaction mixture under the same 0:109 conditions to complete the reaction. The product is a mixture of oligomers that include 1, 3, :00% and 7 repeating units as seen in the structure below.

be 0Q C 4 H 9\C H9 N N- (CH 2 -N

N\

0*0 4 9 NN N NN., N C 4 H 9 0*00 C H 9 N

N-CH

49N N 4 00 0 N

NO

0:0 0 *00HOH .00. 0 s 1,3,5,7 126- Example 57 Oligomer of -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-4-yl}- N,N'-bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl]-1,6-hexanediamine terminated with 2-butylamino-4-{N-[1-(2-hydroxy- 2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino-s-triazin-6-yl N,N'-Bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamine and N,N'-bis{2-[N-(2,2,6,6tetramethylpiperidin-4-yl)butylamino]-4-chloro-s-triazin-6-yl}-N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamine are mixed together in a 0.5:1 molar ratio in xylene at 100- 1600C with sodium hydroxide as the acid acceptor. The reaction mixture is then treated with dibutylamine under the same conditions. The resulting mixture of oligomers is treated with terti butyl hydroperoxide and a catalytic amount of molybdenum trioxide in an inert solvent such as 1,2-dichloroethane to form the corresponding N-oxyl compounds. Aqueous hydrogen peroxide in then added to a mixture of the N-oxyl compounds and ferrous chloride tetrahydrate in tertbutyl alcohol according to the procedure of Example 7. The final product is a mixture of oligomers such as prepared in Example 56 although the ratios of the individual components may not be the same as those in the product of Example 56.

*0 -127- Example 58 Oligomer of N-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethypiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N'-bis[1-(2-hydroxy-2methylpropoxy)-2,2,6,6-tetramethypiperidin-4-yl]-1,6-hexanediamine, terminated with acetyl The compounds prepared in Examples 53B and C are mixed together in a 2:1 molar ratio in xylene solution at 100-160° C with sodium hydroxide as the acid acceptor. After the reaction is complete, the reaction mixture is concentrated at reduced pressure. Acetic anhydride is added to the reaction mixture at room temperature, and the mixture is then heated at 130° C. The crude mixture is cooled and neutralized with potassium carbonate. The reaction mixture is concentrated at reduced pressure. The product is a mixture of oligomers that include 2, 4, and 6 repeating units as seen in the structure below.

O o H 3..C3 N- (CH 2 N CH 2 N CH3 SN N 49 N N n o 2,4,6 128- Example 59 Oligomer of -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-4-yl}- N,N'-bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl]-1,6-hexanediamine terminated with Acetyl Example 54 is repeated except that acetic anhydride is used in place of 2,4-bis(dibutylamino)-6-chloro-s-triazine according to the procedure of Example 58. The final product is a mixture of oligomers as described in Example 58 although the ratios of the components may not be identical to those of the product prepared in Example 58.

Example Poly[1l-(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-yl Methacrylate The title compound is prepared from the free radical polymerization of the compound obtained in Example 16B. The average molecular weight of the polymer is 1500-3000 amu.

Example 61 Poly[1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidin-4-yl Acrylate The title compound is prepared from the free radical polymerization of the compound obtained in Example 21. The average molecular weight of the polymer is 1500-3000 amu.

129- Example 62 1,4-Bis(4-hydroxy-2,2,6,6-tetramethyl piperidin-1 -yloxy)-2-butanol Tributyltin hydride is added dropwise to a solution of 1,4-dibromo-2-propanol and excess 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. The mixture is heated to facilitate the reaction. The crude reaction mixture is passed through silica gel with heptane and then heptane/ethyl acetate to afford the title compound.

Example 63 1,3-Bis(4-hydroxy-2,2,6,6-tetramethyl piperidin-1 -yloxy)-2-propanol Tributyltin hydride is added dropwise to a solution of 1,3-dibromo-2-propanol and excess 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. The mixture is heated to facilitate the reaction. The crude reaction mixture is passed through silica gel with heptane and then heptane/ethyl acetate to afford the title compound.

Example 64 2-Hydroxy-2-methylpropane-1,3-diyl bis{[1-(2-hydroxy- 2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl] (1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate The title compound is isolated by high pressure liquid chromatography from the crude reaction product obtained in Example 2.

-130- Example 1,3-Bis(4-octadecanoyloxy-2,2,6,6-tetramethyl piperidin-1 -yloxy)-2-methyl-2-propanol Aqueous hydrogen peroxide is added to a mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6tetramethylpiperidine and ferrous chloride tetrahydrate in tert-butyl alcohol at 30-500C. Excess peroxide is decomposed with aqueous sodium sulfite solution. The organic layer is concentrated to obtain a mixture which includes 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6tetramethylpiperidine and the title compound. The title compound is separated from the mixture by high pressure liquid chromatography.

Example 66 1,3-Bis(4-hydroxy-2,2,6,6-tetramethyl piperidin-1 -yloxy)-2-methyl-2-propanol The title compound is isolated by high pressure liquid chromatography from the crude reaction product obtained in Example 16A.

Example 67 1,3-Bis(4-oxo-2,2,6,6-tetramethyl piperidin-1 -yloxy)-2-methyl-2-propanol The title compound is isolated by high pressure liquid chromatography from the crude reaction product obtained in Example 23A.

131 Example 68 1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl Hexanoate The title compound is prepared by heating a mixture of methyl hexanoate, the compound prepared in Example 16A, lithium amide and xylene at reflux while methanol is removed by distillation.

Example 69 4-Benzoyloxy-1-(2-hydroxyethoxy)- 2,2,6,6-tetramethylpiperidine Tributyltin hydride is added dropwise to a solution of 2-iodoethanol and 4-benzoyloxy-1 oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. The crude reaction mixtuire is passed through silica gel with heptane and then heptane/ethyl acetate to afford the title compound.

Example 4-Hydroxy-1 -(2-hydroxyethoxy)- 2,2,6,6-tetramethylpiperidine The title compound is prepared by heating a methanolic solution of the compound obtained in Example 69 with potassium hydroxide.

132- Example 71 Poly[4-hydroxy-1 -(2-hydroxyethoxy)- 2,2,6,6-tetramethylpiperidin-4-yl succinate] The title compound is prepared by the reaction of approximately equimolar amounts of dimethyl succinate and the compound prepared in Example Example 72 Poly[4-hydroxy-1 -(2-hydroxycyclohexyloxy)- 2,2,6,6-tetramethylpiperidin-4-yl succinate] The title compound is prepared by the reaction of approximately equimolar amounts of dimethyl succinate and the compound prepared in Example Example 73 1-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy- 2,2,6,6-tetramethylpiperidine A mixture of methyl stearate, the compound prepared in Example 16A and a catalytic S amount of lithium amide is heated at reflux in xylene. Methanol is distilled from the reaction mixture. The reaction is quenched with dilute acid. The organic layer is concentrated and the crude product is purified by flash chromatography on silica gel to afford the title compound as a white solid melting at 51-560C.

-133- Example 73A 1-(4-Octadecanoyloxy-2,2,6,6-tetramethyl piperidin-1 -yloxy)-2-octadecanoyloxy-2-methylpropane The title compound is prepared by the reaction of the compound prepared in Example 16A with excess methyl stearate and a catalytic amount of lithium amide in xylene.

Example 74 4-Hydroxy-1 -(2-hydroxy- 1 -phenethoxy)- 2,2,6,6-tetramethylpiperidine The title compound is prepared by heating a methanolic solution of the compound obtained in Example 10 with potassium hydroxide.

Example S* Poly[4-hydroxy-1 -(2-hydroxy-1 -phenylethoxy)- 2,2,6,6-tetramethylpiperidin-4-yl succinate] The title compound is prepared by the reaction of approximately equimolar amounts of dimethyl succinate and the compound obtained in Example 74.

Example 76 Stabilization of Thermoplastic Olefins Molded test specimens are prepared by injection molding thermoplastic olefin (TPO) pellets containing pigments, a phosphite, a phenolic antioxidant or hydroxylamine, a metal stearate, ultraviolet light absorbers or a hindered amine stabilizer or a mixture of UV absorber and hindered amine stabilizer.

-134- Pigmented TPO pellets are prepared from pure pigment or pigment concentrate, coadditives and commercially available TPO by mixing the components in a Superior/MPM 1" single screw extruder with a general all-purpose screw (24:1 LD) at 400 0 F (2000C), cooled in a water bath and pelletized. The resulting pellets are molded into 60 mil (0.006 inch), 2"x2" plaques at about 375 0 F (1900C) on a BOY 30M Injection Molding Machine.

Pigmented TPO formulation composed of polypropylene blended with a rubber modifier where the rubber modifier is an in-situ reacted copolymer or blended product containing copolymers of propylene and ethylene with or without a ternary component such as ethylidene norbornene are stabilized with a base stabilization system consisting of an N,N-dialkyl hydroxylamine or a hindered phenolic antioxidant with or without an organophosphorus compound.

All additive and pigment concentrations in the final formulation are expressed as weight o percent based on the resin.

Formulation contained thermoplastic olefin pellets and one or more of the following components: 0.0 to 2.0% pigment, 0.0 to 50.0% talc, 0.0 to 0.1% phosphite, 0.0 to 1.25% phenolic antioxidant, 0.0 to 0.1% hydroxylamine 0.05 to 0.10 calcium stearate, 0.0 to 1.25% UV absorber 0.0 to 1.25% hindered amine stabilizer.

The components are dry-blended in a tumble dryer prior to extrusion and molding.

Test plaques are mounted in metal frames and exposed in an Atlas Ci65 Xenon Arc Weather-Ometer at 700C black panel temperature, 0.55 W/m 2 at 340 nonometers and relative humidity with intermittent light/dark cycles and water spray (Society of Automotive Engineers SAE J 1960 Test Procedure). Specimens are tested at approximately 625 kilojoule -135intervals by performing color measurements on an Applied Color Systems spectrophotometer by reflectance mode according to ASTM D 2244-79. Data collected include delta E, a* and b* values. Gloss measurements are conducted on a BYK-Gardner Haze/Gloss Meter at 600 according to ASTM D 523.

UV Exposure Testing Test speciments exposed to UV radiation exhibit exceptional resistance to photodegration when stabilized with light stabilizer systems comprising a combination of 2-(2hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole (TINUVIN®328, Ciba the compound of Example 73 and N,N',N",N'"-tetrakis[4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-striazin-2-yl]-1,10-diamino-4,7-diazadecane (CHIMASSORB® 119, Ciba). The control sample consists of a stabilizer formulation commonly used in the industry to impart UV stability. All of the samples contain a pigment, Pigment Red 177, and talc.

The test plaques described earlier contain the following (all concentrations are weight percent based on resin): Polymer substrate is commercially available polyolefin blend POLYTROPE® TPP 518-01 supplied by A. Schulman Inc. Akron, Ohio) Color package is 0.025% Red 3B -Pigment Red 177, C.I. #65300.

Each plaque contains: 0.2% TINUVIN® 328; 0.1% calcium stearate; and talc.

The Control plaques additionally contain 136 0.1% IRGANOX® B225 (50:50 blend of IRGANOX® 1010, Ciba (neopentanetetrayl tetrakis(4-hydroxy-3,5-di-tert-butyl hydrocinnamate) and IRGAFOS® 168, Ciba (tris-(2,4-di-tertbutylphenyl) phosphite; 0.2% TI NUVIN® 770, Ciba [bis(2,2,6,6-tetram ethyl pi perid in-4-yl) sebacate]; 0.2% CHIMASSORB 944, Ciba [polycondensation product of 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazinel.

The two test plaques (NOR-i and NOR-2) each contain 0.05% N,N,-dialkylhydroxylamine; NOR-i additionally contains 0.2% of CHIMASSORB® 119; and 0.2% of TI NUVI No 123, Ciba, [bis(1 -octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate].

NOR-2 additionally contains 0.2% of CHIMASSORB® 119; and 0.2% of the compound of Example 73.

The results of the UV testing are given in the table below.

a. a a a a.

a a. a a a Sample control NOR-i NOR-2

DE*

0 3000 L/ M 2 KiLM! 0.0 4.7 0.0 4.0 Gloss Value 0 3000

K/

2 K/m 66.6 5.4 65.5 16.9 Gloss Value 0 3000 .Kim n&/ 100 8.1 100 25.8 100 69.8 0.0 3.8 64.9 45.3 -137- The compound of Example 73 present in test plaques NOR-2 specifically shows greatly improved gloss retention compared to the less effective control system and in fact is also more effective that a related hindered amine compound (TINUVIN® 123) present in test plaques NOR- 1. Resistance to color change upon UV exposure is also enhanced.

Polymer blends containing an unsaturated ternary component, such as EPDM blends, are especially benefited with the more efficient instant light stabilizer systems described above.

In all cases, the light stabilized formulations show much greated resistance to photodegradation than unstabilized specimens which fail quickly under the UV exposure conditions outlined above.

Example 77 Paintable TPO Molded test specimens are prepared by injection molding thermoplastic olefin (TPO) pellets containing the instant compounds, pigments and other coadditives as described in Example 76.

The light stable formulations are painted with one-pack paint systems and tested for TPO/paint interactions. Before painting, the test specimens are first washed in accordance with GM998-4801 and dried for 15 minutes at 200 0 F (940C). Adhesion promoter is applied to the dry film thickness of 0.2-0.4 mils. The samples are dried for five minutes before a 1K basecoat is applied to a film thickness of 1.2-1.4 mils. The painted panels are dried for three minutes, a :clearcoat is then applied to a dry film thickness of 1.2-1.5 mils followed by ten minutes flash drying and a 30 minute oven bake at 250 0 F (1210C).

Paint adhesion is measured by Aggressive Adhesion Testing (proprietary test procedure conducted at Technical Finishing, Inc.) and Taber Scuff. Painted panels which retain greater than 80% of the paint finish are considered acceptable. After Aggressive Adhesion Testing, samples with less than 5% paint loss are deemed acceptable.

-138- Samples are tested to evaluate the TPO/paint interactions as follows: Aggresive HALS Formulation* Taber Scuff Test Adhesion Test PKa A 100% removed 6% Loss (fail) 9.1 B 0% removed 4% Loss (pass) 4.6 C 0% removed 3% Loss (pass) Formulation A contains 0.2% CHIMASSORB® 944, 0.2% TINUVIN® 328, 500 ppm calcium stearate and 750 ppm N,N-dialkylhydroxylamine in reactor-grade TPO.

o A also contains 0.2% of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN® 770, pKa of 9.1).

S Formulations B and C contain 0.2% CHIMASSORB® 119, 0.2% TINUVIN®328, 500 ppm calcium stearate and 750 ppm N,N-dialkylhydroxylamine in reactor-grade TPO.

B also contains 0.2% of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN® 123, pKa of 4.6).

C also contains 0.2% of 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine (compound of Example 73, pKa of The data in the table indicate that, although formulation A failed in both the Taber Scuff and Aggressive Adhesion Tests, both formulations B and C passed both paint adhesion tests.

However, as inspection of the pKa values attests, the lower the pKa value (less basic) for the test hindered amine compound the less paint loss results in this Aggressive Adhesion Test. The instant compound of Example 73 having the hydroxyl moiety present has the lowest pKa value and also the least paint loss even better than the close prior art compound where no hydroxyl moiety is present.

-139- Example 78 Stabilization of Polypropylene Molded Articles Molded test specimens are prepared by injection molding polypropylene pellets containing pigments, a phosphite, a phenolic antioxidant or hydroxylamine, a metal stearate, ultraviolet light absorbers or a hindered amine stabilizers or a mixture of UV absorbers and hindered amine stabilizers.

Pigmented polypropylene pellets are prepared from pure pigment or pigment concentrates, stabilizers, co-additives and commercially available polypropylene by mixing the components in a Superior/MPM 1" single screw extruder with a general all-purpose screw (24:1 L/D) at 475 0 F (2500C), cooled in a water bath and pelletized. The resulting pellets are molded into 60 mil (0.06 inch thick) 2"x2" plaques at about 4750F (2500C) on a BOY 30M Injection Molding Machine.

Pigmented polypropylene formulations composed of polypropylene homopolymer or polypropylene copolymer are stabilized with a base stabilization system consisting of an N,Ndialkylhydroxylamine or a hindered phenolic antioxidant with or without an organophosphorous compound.

t** All additive and pigment concentrations in the final formulations are expressed as weight percent based on the resin.

Formulations contained polypropylene pellets and one or more of the following components; 0.0% 2.0% pigment, 0.0% 50.0% talc, 0.0% 50.0% calcium carbonate, 0.0% 0.1% phosphite, 0.0% 1.25% phenolic antioxidant, 0.0% 0.1% hydroxylamine, 0.05% 0.10% calcium stearate, I 140- 0.0% 1.25% UV absorber, 0.0% -1.25% hindered amine stabilizer.

The components are dry blended in a tumble dryer prior to extrusion and molding.

Test plaques are mounted in metal frames and exposed in an Atlas Ci65 Xenon Arc Weather-o-meter at 70°C black panel temperature, 0.55 W/m 2 at 340 nanometers and relative humidity with intermittent light/dark cycles and water spray (Society of Automotive Engineers SAE J 1960 Test Procedure). Specimens are tested at approximately 625 kilojoule intervals by performing color measurements on an Applied Color Systems spectrophotometer by reflectance mode according to ASTM D 2244-79. Data collected included delta E, a* and b* values. Gloss measurements are conducted on a BYK-GARDNER Haze/Gloss Meter at 600 according to ASTM D523.

UV Exposure Testing 0 Test specimens exposed to UV radiation exhibit exceptional resistance to photodegradation when stabilized with light stabilizer systems comprised of a combination of Tinuvin 328, the compound of Example 73 and CGL 2020. CGL 2020 is oligomer of 2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N'-bis(2,2,6,6-tetramethylpiperidin- 4-yl)-1,6-hexanediamine terminated with 2,4-bis(dibutylamino)-s-triazin-6-yl. The Control sample consists of a stabilizer formulation commonly used in the industry to impart UV stability.

All of the samples contain Pigment Red 177.

*0 DE* Gloss Values Gloss Retention Red 3B Formulations 0 Kj/m 3000 0 Kj/m 2 3000 0 Kj/m 2 3000 Kj/m 2 Kj/m 2 Kj/m 2 Comn. 1 Como. 2 Como. 3 141 DE* Gloss Values Gloss _Retention Red 3B Formulations 0 Kj/m 2 3000 0 3000 0 Kj/m 2 3000 Kj/m 2 Kj/m 2 Kj/m 2 Kj/m 2 Comp. 1 Comp. 2 Comp. 3 Ex. 73 0.10% Ex. 0.10% 0.1% Tin. 0 0.6 88% 77% 100% 88% 73 CGL 2020 328 NOR 2 0.10% 0.10% 0.1% Tin. 0 8.2 87% 13% 100% 14% NOR 2 CGL 2020 328 All formulations are base stabilized with 0.05% dialklyhydroxylamine in the final resin formulation.

Polymer substrate is a commercially available polypropylene homopolymer Profax 6501 (commercial supplier Montell Polyolefins).

Color package is 0.25% Red 3B Pigment Red 177, C.I. 65300 in the final resin formulation.

Each formulation contains a hydroxyphenyl benzotriazole UV absorber Tinuvin 328, 2-(2hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole.

NOR 2 is bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate.

Each formulation contains 0.1% calcium stearate.

Samples are 60 mil thick 2" x 2" injection molded plaques.

UV exposures conducted under SAE J 1960 Exterior Automotive conditions.

All additive and pigment concentrations in the final formulations are expressed as weight percent on the resin.

The formulation containing the subject compound of Example 73 specifically shows greatly improved gloss retention compared to the less effective Control stabilizer system even at a lower total concentration. Resistance to color change upon UV exposure is also significantly enhanced. The subject compound of Example 73 is also significantly more effective in maintaining appearance when compared with another solid N-O-R HALS (NOR 2) of similar molecular at equal concentrations.

In all cases, the light stabilized formulations show much greater resistance to photodegradation than unstabilized specimens which fail quickly under the UV exposure conditions outlined above.

-142- Example 79 Polypropylene Fiber Fiber samples are prepared by extruding fiber-grade polypropylene with the instant compounds, coadditives and pigments. Typical formulations contain the instant compounds at levels from 0.05 to a metal stearate such as calcium stearate at 0.05 to pigments from 0 to UV absorbers at levels of 0.05 to phosphites at 0 to phenolic antioxidants at 0 to 1.25%, N,N-dialkylhydroxylamines at 0 to 0.1% and optionally other hindered amines at levels of 0 to All additive and pigment concentrations in the final formulations are given as weight percent based on the resin.

Pigment concentrates are prepared from pure pigment and polypropylene (PROFAX®, Hercules) by mixing the two components in a high shear mixer in a ratio of 25% pigment and 75% resin, pressing the resulting resin/pigment mixture on a Wabash Compression molder (Model 30-1515-4T3) into a thin sheet and dividing the sheet into fine chips for dispersion in polypropylene at reduced concentrations. Alternatively, pigment concentrates areobtained as pigment dispersions in a suitable carrier resin for subsequent blending in fiber at reduced concentrations.

Formulations containing polypropylene, 0.05-0.1% phosphite, 0-1.25% phenolic antioxidant, 0-0.1% dialkylhydroxylamine, 0.05-0.1% calcium stearate, 0-1.25% UV absorber, 0- 1.25% hindered amine are dry blended in a tumble dryer, extruded on a Superior/MPM 1" single screw extruder with a general all-purpose screw (24:1 UD) at 475 0 F (2460C), cooled in a water bath and pelletized. The resulting pellets are spun into fiber at about 475 0 F (2460C) on a HILLS Research Fiber Extruder (Model REM-3P-24) fitted with a 41 hole, delta configuation spinneret. The spun tow is stretched at a draw ratio of 3.2:1 producing a final denier of 615/41.

Fiber samples are knitted into socks on a Lawson-HemphillFiber Analysis Knitter, cut into appropriate lengths and exposed in an Atlas Ci65 Xenon Arc Weather-O-meter at 89°C black panel temperature, 0.55 W/m 2 at 340 nanometers and 50% relative humidity (Society of Automotive Engineers SAE J 1885 Test Procedure).

-143- Fiber samples are tested by performing color measurements on an Applied Color Systems spectrophotometer by reflectance mode according to ASTM D 2244-79. Identical, but separate, fiber samples are examined for catastrophic failure and the time to failure is recorded.

The samples containing the instant compounds exhibit good stabilization performance against the deleterious effects of UV light.

Example Other socks of propylene fiber as prepared in Example 79 are exposed in a Blue M forced draft oven at 1200C. Failure is determined by the criterion set forth in Example 79. The longer it takes for the catastrophic failure to occur, the more effective is the stabilizing system.

The socks containing the instant compounds exhibit good thermal stabilization efficacy.

S°Example 81 Film grade polyethylene is dry blended with approximately 10% by weight of the test additives, such as the compound of Example 51, and then melt compounded at 2000C into "Masterbatch" pellets. The fully formulated "Masterbatch" pellets are dry blended with polyethylene resin to get the desired final stabilizer concentrations. Typical formulations contain the instant compounds at levels from 0.05% to a metal stearate such as calcium stearate at 0.05% to a phosphite at 0% to a phenolic antioxidant at 0% to 1.25%, an N,Ndialkylhydroxylamine at 0% to 0.1% and optionally a hindered amine at 0% to The This stabilized fully formulated resin is then blown at 2000C into a 150 micron thick film on a DOLCI Sfilm line.

The blown films are exposed in an Atlas Xenon-Arc WeatherOmeter according to ASTM G26 at 630C bpt, 0.35 W/m 2 at 340 nm with no spray cycle. Films are tested periodically for any change in elongation using an Instron 112 tensile tester. Failure in this test is determined by observation of the loss of elongation in the film. The longer it takes for this loss to occur, th more effective is the stabilizer system.

-144- The films containing the instant compound mixture show good light stabilizing efficacy.

Example 82 Film grade polyethylene is dry blended with 10% loading of the test additives, such as the compound of Example 51, as described in Example 81, and then melt compounded at 2000C into fully formulated master batch pellets. The master batch pellets are dry blended with the polyethylene resin to get the final stabilizer concentration. The fully formulated resin is then blown at 2000C into a 150 micron thick film using a DOLCI film line.

The resulting films are exposed on a greenhouse on galvanized iron backing. Treatment includes applications of pesticides on a regular basis sodium N-methyldithiocarbamate, VAPAM' every six months and SESMETRIN' every month). Performance is measured by monitoring the percent residual elongation. Failure is defined as the time to a 50% loss of original elongation.

S°The films containing the instant compounds show good resistance to pesticides.

Example 83 Master batch pellets prepared as described in Example 81 are dry blended into polyethylene resin to get the final stabilizer cocentration. The fully formulated resin is then blown at 2000C into a 25 micron thick film using a DOLCI film line.

The resulting films are exposed on a soil to simulate agricultural mulch film conditions.

Treatment includes exposure to methyl bromide fumigant for three days at 60 g/m 3 Performance is measured by monitoring the time to physical embrittlement.

The films containing the instant compounds show good resistance to fumigants.

Example 84 -145- Greenhouse film samples are prepared as described in Example 81, but in addition to the instant compounds also contain a metal stearate or a metal oxide. Typical formulations contain from 0.05 to 2% by weight of the instant hindered amines, 0.05 to 0.5% of a metal stearate such as calcium oxide, and 0.05 to 0.5% of a metal oxide such as zinc oxide or magnesium oxide.

Effectiveness is monitored as described in Example 82. The films containing the instant compounds exhibit good light stability.

Example Polypropylene fiber is prepared as described in Example 79. In addition to the instant compounds, selected halogenated flame retardants are also included in the formulation. The flame retardants are tris(3-bromo-2,2-bis(bromomethyl)propyl)phosphate, decabromodiphenyl oxide, ethylene bis-(tetrabromophthalimide), or ethylene bis-(dibromo-norbornanedicarboximide).

Using the criterion for light stabilization described in Example 79, the socks knitted from the polypropylene fiber containing the instant compounds exhibit good light stability.

Example 86 Molding grade polypropylene is dry blended with test additives and then melt compounded into pellets. In addition to the instant compounds, selected flame retardants are also included. The flame retardants are tris(3-bromo-2,2-bis(bromomethyl)propyl)phosphate, decabromodiphenyl oxide, ethylene bis-(tetrabromophthalimide), or ethylene bis-(dibromonorbornanedicarboximide). The pelletized fully formulated resin is then injection molded into test specimens using a Boy 50M laboratory model injection molder.

Test plaques are mounted in metal frames and exposed in an Atlas Ci65 Xenon Arc Weather-Ometer with intermittent light/dark cycles and water spray following the ASTM G26 test procedure. Specimens are tested at periodic intervals for changes in tensile properties. Failure 146in this test is determined by the observation of the loss of tensile properties. The longer it takes for the loss in properties to occur, the more effective is the stabilizer system.

The test samples containing the instant compounds exhibit good light stabilization properties.

Example 87 Molded test specimens are prepared by injection molding thermoplastic olefin (TPO) pellets as described in Example 76. In addition to the instant compounds, selected flame retardants are also included in the test specimens. The flame retardants are tris(3-bromo-2,2bis(bromomethyl)propyl) phosphate, decabromodiphenyl oxide, ethylene bis-(tetrabromophthalimide), or ethylene bis-(dibromo-norbornanedicarboximide).

•The samples including the instant hindered amines exhibit good light stabilizing activity.

Example 88 Film grade polyethylene is compounded and blown into film at 2000C as described in Example 82 using a DOLCI film line. In addition to the instant compounds, selected flame retardants are included in the formulation. The flame retardants are tris(3-bromo-2,2-bis(bromomethyl)propyl) phosphate, decabromodiphenyl oxide, ethylene bis-(tetrabromophthalimide), or ethylene bis-(dibromo-norbornanedicarboximide).

When tested for light stabilizing activity as described in Example 82, the films containing the instant compounds exhibit good stabilization.

Example 89 Molded test specimens are prepared by injection molding thermoplastic olefin (TPO) pellets containing the instant compounds, pigments and other coadditives as described in Example 77.

147- The test specimens are painted with one-pack paint systems and tested for TPO/paint interactions. Before painting, the test specimens are first wiped with isopropanol and air blasted to remove any dust. After a five minute flash, these specimens are coated with the adhesion promoter, then the base coat, and then optionally a clear coat. Typical film thickness of these various coatings are 0.1-0.3 mils for the adhesion promoter, 0.6-0.8 mils for the base coat, and 1.2-1.5 mils for the clear coat. After painting, the specimens are cured in an over at 1200C for minutes.

Samples are tested to evaluate the TPO/paint interactions as follows: In the initial adhesion test, a clear cellophane adhesive tape is used to pull on a 3 mm cross hatched paint surface or; in the humidity test, the painted plaques are exposed for 240 hours at 380C in an atmosphere having 98% relative humidity. The blister rating is tested by visual observation according to ASTM D 714.

The samples containing the instant compounds exhibit good TPO/paint interaction properties as determined by the criteria above.

Example Thermoplastic Elastomers Resin materials of the general class known as thermoplastic elastomers, examples of which include, copolymers of styrene with butadiene or isoprene and/or ethylene-cobutylene such as SBS, SEBS and SIS, are dry blended with the instant compounds and melt compounded into pellets. Typical formulations contain the instant compounds at levels from 0.05% to a metal stearate such as calcium stearate at 0.05% to pigments from 0% to UV absorbers at levels of 0.05% to phosphites at 0.0% phenolic antioxidants at 0.0% 1.25%, N,N-dialkylhydroxylamine at 0.0% and optionally other hindered amine stabilizers at levels of 0.0% to The pelletized fully formulated resin is then processed into a useful article such as blown or cast extrusion into film; injection molded into a molded article; thermoformed into molded articles; extruded into wire and cable housing; or rotational molded into hollow articles.

-148- The materials containing the instant compounds exhibit stability against deleterious effects of UV light and thermal exposure.

Example 91 Articles prepared according to Example 90 which additionally contain selected organic pigments as well as the instant compounds also exhibit stability against the deleterious effects of actinic light and thermal exposure.

Example 92 Articles prepared according to Example 90 which additionally contain a hindered phenolic antioxidant selected from the group consisting of neopentanetetrayl butyl-4-hydroxyhydrocinnamate, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5trimethyl-2,4,6-tris(3,5,-di-tert-butyl-4-hydroxybenzyl)benzene, 1,2-bis(3,5-di-tert-butyl-4hydroxyhydrocinnamoyl)hydrazine, calcium [bis(monoethyl 3,5-ditert-butyl-4-hydroxybenzyl)phosphonate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 1,3,5-tris(3hydroxy-4-tert-butyl-2,6-dimethylbenzyl) isocyanurate, as well as the instant compounds also exhibit stability against the deleterious effects of actinic light and thermal exposure.

Example 93 Articles prepared according to Example 90 which additionally contain an organophosphorus stabilizer selected from the group consisting of tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2',2"-nitrilo[triethyl-tris- (3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], tetrakis(2,4-di-butylphenyl) 4,4'biphenylenediphosphonite, tris(nonylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, 2,2'-ethylidenebis(2,4-di-tert-butylphenyl) fluorophosphite and 2-butyl-2-ethylpropan-1,3-diyl 2,4,6-tri-tert-butylphenyl phosphite as well as the instant compounds of also exhibit stability against the deleterious effects of actinic light and thermal exposure.

-149- Example 94 Articles prepared according to Example 90 which additionally contain a benzofuranone stabilizer which is 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-2H-benzofuran-2-one, as well as the instant compounds also exhibit stability against the deleterious effects of UV light and thermal exposure.

Example Articles prepared according to Example 90 which additionally contain a dialkylhydroxylamine stabilizer which is N,N-dialkylhydroxylamine made by the direct oxidation of N,Ndi(hydrogenated tallow)amine as well as the instant compounds also exhibit stability against the deleterious effects of actinic light and thermal exposure.

Example 96 Articles prepared according to Example 90 which additionally contain other hindered amine stabilizers selected from the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N.N',N",N"'-tetrakis[4,6-bis(butyl-1 ,2,2,6,6-pentamethylpiperidin-4yl)amino-s-triazin-2-yl]-1 ,1 0-diamino-4,7-diazadecane, the polycondensation product of 4,4'hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-striazine, the polycondensation product of 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethyl- S piperidine) and 2,4-dichloro-6-morpholino-s-triazine, 2,2,6,6-tetramethylpiperidin-4-yl octadecanoate, 3-dodecyl-1-(1 -acetyl-2,2,6,6-tetramethylpiperidin-4-yl)-pyrrolidin-2,5-dione, :1,3,5-tris(N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)ethyl]amino-s-triazine, poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane, the polycondensation product of 2,4-dichloro-6-(2,2,6,6-tetramethylpiperidin-4-yl)butylamino)-s-triazine and 2,2'ethylene-bis{[2,4-(2,2,6,6-tetramethypiperidin-4-yl)butylamino-s-triazin-6-yl]aminotrimethyleneamino} as well as the instant compounds also exhibit stability against the deleterious effects of actinic light and thermal exposure.

-150- Example 97 Articles prepared according to Example 90 which additionally contain other N-hydrocarbyloxy substituted hindered amines selected from the group consisting of bis(l -octyloxy- 2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(l -octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1 -cyclohexyloxy- 2,2,6,6-tetramethylpiperidin-4-yl) sebacate, and 1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4yl octadecanoate as well as the instant compounds also exhibit stability against the deleterious effects of actinic light and thermal exposure.

Example 98 Articles prepared according to Example 90 which additionally contain a o-hydroxyphenyl- 2H-benzotriazole, a hydroxyphenyl benzophenone or a o-hydroxyphenyl-s-triazine UV absorber selected from the group consisting of 2-(2-hydroxy-3,5-di-cx-cumylphenyl)-2H-benzotriazole, 2- (2-hydroxy-5-methylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2Hbenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-a-cumyl- 5-tert-octylphenyl)-2H-benzotriazole, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl4-hydroxybenzoate, 2-hydroxy-4-n-octyloxybenzophenone and 2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine as well as the instant compounds also exhibit stability against the deleterious effects of UV light and thermal exposure.

Example 99 The hindered amine test stabilizers are incorporated into a two-component polyester urethane coating based on a commercially available polyester polyol (DESMOPHEN® 670-80) and commercially available isocyanurate (DESMODUR" N-3390) at a level of 2% by weight based on total resin solids. The coating system is catalyzed with 0.015% dibutyl tin dilaurate based on total resin solids.

Each coating formulation is applied by drawdown onto transparent glass slides approximately 4" x 6" to a film thickness of about 2 mils (0.002") in triplicate.

-151 These triplicate glass plates are processed as seen below: Plate 1 bake for 30 minutes at 180F (820C); age at room temperature; and observe daily.

Plate 2 allow to air dry (ambient cure); age at room temperature; and observe daily.

Plate 3 allow to air dry for one day; age in a 120 0 F (490C) oven; observe daily and continue aging at 120 0 F (490C).

Starting at time zero, all plates are evaluated for visual appearance, noting the development of any cloudiness within the coating and any exudate on the surface of the coating. The results of four days of observation are noted below.

Plate 1 0 Sample* 0 Day 1 Day 2 Day 3 Day 4 18 months A cl cl cl cl cl clear B sl h haze haze haze haze haze C cl cl cl cl cl clear

*C

-152- Plate 2 Sample* 0 Day Day 2 a3 Day 4 A cl cl cl cl cl B sl h haze haze haze haze C cl cl cl cl cl 18 months clear haze clear Plate 3 Sample* 0 Dav1 Day2 Dav3 Dav4 18 months 0 0 0 0* *0 0 A cl cl cl cl cl B sl h haze haze haze haze C cl cl cl cl cl clear haze clear *A is unstabilized.

B contains 2% by weight of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN® 123).

C contains 2% by weight of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl] sebacate, compound of Example 2.

These data show that the instant compound having a hydroxy moiety present on the group attached to the 1-position of the hindered amine provides excellent solubility and compatibility for the polyester urethane coating that cannot be achieved with the closest prior art compound where said hydroxy moiety is absent.

Experience teaches that, if the instant compounds are soluble and compatible in this particular clearcoat, they will certainly be compatible and soluble in other resin systems.

-153- Example 100 Approximately 50 mL of the same stabilized formulated two-component clear coatings described in Example 99 are alllowed to gel in a sealed 4 ounce jar. The solidified coatings are visually observed for clarity after solidification. The development of opacity or cloudiness is indicative of an incompatibility between the hindered amine stabilizer and the formulated coating.

Solidified coating in jar Sample* 0 Day 1 Day 2 18 months A clear clear clear clear B clear cloudy cloudy cloudy C clear clear clear clear *A is unstabilized.

B contains 2% by weight of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN® 123).

C contains 2% by weight of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl] sebacate, compound of Example 2.

These data show that the instant compound having a hydroxy moiety present on the group attached to the 1-position of the hindered amine provides excellent solubility and compatibility for the polyester urethane coating that cannot be achieved with the closest prior art compound where said hydroxy moiety is absent.

154 Example 10 1 1 -(2-Hydroxy-2-methylpropoxy)-4-[9-(methoxycarbonyl) nonanoyloxy]-2,2,6,6-tetramethy pipe rid ine, The title compound is prepared by the reaction of the compound prepared in Example 1 6A with one equivalent or more of dimethyl sebacate and a catalytic amount of lithium amide in xylene.

Example 102 1 -(2-Hydroxy-2-methylpropoxy)-4-[5-(methoxycarbonyl) pe ntanoyloxy]-2,2,6,6-tetramethyl pipe rid ine 11:09The title compound is made by the procedure of Example 101 where dimethyl sebacate .00% is replaced by an equivalent amount of dimethyl adipate.

Example 103 1 -(2-Hydroxy-2-methylpropoxy)-4-[3-(methoxycarbonyl)propionyloxy]-2,2,6,6-tetramethylpiperidine The title compound is made by the procedure of Example 101 where dimethyl sebacate is replaced by an equivalent amount of dimethyl. succinate.

Example 104 1 -(2-Hydroxy-2-methylpropoxy)-4-[4-(methoxycarbonyl)butyryloxy]-2,2,6,6-tetramethylpiperidine The title compound is made the procedure of Example 101 where dimethyl sebacate is replaced by an equivalent amount of dimethyl glutarate.

155 Example 1 04A Mixture of 1 -(2-Hydroxy-2-methylpropoxy)-4-[5-methoxy-carbonyl)petaoyIoxy]-2,2,6,6tetramethylpiperidine and 1 -(2-Hydroxy-2-methylpropoxy)-4-[4-methoxy-carbonyl)butyryloxy- 2,2,6,6-tetramethylpiperidine Example 101 is repeated with an equivalent amount of DBE-2 dibasic ester (DuPont®) in place of dimethyl sebacate.

Example 104B Mixture of 1 -(2-Hydroxy-2-methylpropoxy)-4-[5-methoxy-carbonyl)pentanoyoxy]-2, 2 6 6 tetramethylpiperidine and 1 -(2-Hydroxy-2-methylpropoxy)-4-[4-methoxy-carbonyl)butyryloxY]- 2,2,6,6-tetramethylpiperidine S00% Example 101 is repeated with an equivalent amount of DBE-3 dibasic ester (DuPonte) in place of dimethyl sebacate.

00

S

S Example 105 8505Condensation Product of 4-Hydroxy-1 -(2-hydroxy-2-methylpropoxy)- 2,2,6,6-tetramethylpiperidine with Hexamethylene Diisocyanate, and Terminated with Methoxy The title compound is prepared from the reaction of approximately equimolar amounts of the compound prepared in Example 16A with hexamethylene diisocyanate followed by reaction with excess methanol.

156- Example 106 Condensation Product of 4-Hydroxy-1 -(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine with Hexamethylene Diisocyanate, and Terminated with Methoxy The title compound is prepared from the reaction of approximately equimolar amounts of the compound prepared in Example 70 with hexamethylene diisocyanate, followed by reaction with excess methanol.

Example 107 Condensation Product of 4-Hydroxy-1-(2-hydroxy-1-phenethoxy)- 2,2,6,6-tetramethylpiperidine with Hexamethylene S* Diisocyanate, and Terminated with Methoxy The title compound is prepared from the reaction of approximately equimolar amounts of the compound prepared in Example 74 with hexamethylene diisocyanate, followed by reaction with excess methanol.

Example 108 Stabilization of a Two-Component Acrylic Urethane Clearcoat The hindered amine test stabilizers are incorporated into a two-component acrylic urethane coating as described om Example 99. The system is catalyzed with 0.02% by weight of dibutyltin dilaurate based on the total resin solids. The stabilizers are added at the appropriate level to the acrylic polyol portion of the two-component coating which is then combined with the isocyanate component immediately prior to application.

-157- Steel panels 3" x 4" primed with an electrocoat primer are then coated with a light blue metallic basecoat, then with the stabilized clearcoat. The basecoat is spray applied to a thickness of 1.0 mil (25 microns) dry film thickness and the stabilized clearcoat is then applied to a thickness of 2.0 mils (50 microns) dry film thickness. The coating is air-dried and aged for two weeks. The panels are then exposed in a Xenon-Arc Weather-Ometer under the following conditions: Cam 180 cycle: 40 minutes light only; 20 minutes light and front spray; 60 minutes light only; 60 minutes dark and rear spray condensate.

Lamp filters are: quartz inner/borosilicate S outer.

Irradiance: 0.45 watts per square meter.

200 Gloss is measured before exposure and at 500 hour intervals during exposure.

Higher gloss retention is desirable.

Sample*

A

B

C

D

E

F

G

Percent Retention of 200 Gloss 4500 hours 8500 hours 17 12000 hours *A is unstabilized.

B contains 1% by weight of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN® 123).

-158- C contains 0.9% by weight of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4yl] sebacate, compound of Example 2.

D contains 1.04% by weight of 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-Nbutylamino]-6-(2-hydroxyethylamino)-s-triazine.

E contains 1.01% by weight of the compound of Example 12.

F contains 2% by weight of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN®123).

G contains 1.8% by weight of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4yl] sebacate, compound of Example 2.

These data show that the instant hydroxy substituted compounds give comparable 200 Gloss Retention values to NOR compounds at equivalent molar concentrations.

Example 109 Stabilization of a Two-Component Acrylic Urethane Clearcoat A clearcoat as prepared in Example 108 is applied by spin-coating to 1" silicon disks to a dry film thickness of approximately 25 microns. The initial optical film thickness of each disk is measured using a Zeiss interferometer. The disks are then exposed in a Xenon-Arc Weather- Ometer under the following conditions: Cam 180 cycle: 40 minutes light only; 20 minutes light and front spray; 60 minutes light only; 60 minutes dark and rear spray condensate.

Lamp filters are: quartz inner/quartz outer.

Irradiance: 0.55 watts per square meter.

Optical film thickness is remeasured every 250 hours and film loss is determined for each formulation. The film loss caused by weathering after 3972 and 5561 hours is tabulated in the table below. A lower value for film loss is desirable.

-159- Sample*

A

B

C

D

E

Film Loss (in microns) 3972 hours 23.3 6.9 6.7 6.3 5.9 5561 hours complete erosion 16.3 17.8 14.3 12.4 16.1 16.7 p. *A is unstabilized.

B contains 1% by weight of bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN® 123).

C contains 0.9% by weight of bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4yl] sebacate, compound of Example 2.

D contains 1.04% by weight of 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-Nbutylamino]-6-(2-hydroxyethylamino)-s-triazine.

E contains 1.01 by weight of the compound of Example 12.

F contains 0.78% by weight of 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine.

G contains 0.56% by weight of 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidine, compound of Example 16A.

These data show that the instant hydroxy substituted compounds give comparable resistance to erosion as the closest NOR compounds at equivalent molar concentrations.

Example 110 Coatings over Plastic Substrates -160- A major application for non-basic hindered amines is in the protection of automotive topcoats applied over plastic substrates. However, many low molecular weight, non-reactable light stabilizers migrate into the plastic substrate during drying and cure. As a consequence, a significant portion of the light stabilizer may be lost from the topcoat into the substrate and hence be ineffective in protecting said topcoat.

The extent of migration of hindered amine stabilizers during application and cure of the coating is determined by comparing the concentration of hindered amine in the cured clearcoat applied over a plastic substrate versus the same clearcoat applied over a non-permeable substrate such as glass or steel.

Hindered amine stabilizers under test are incorporated into a flexible thermoset acrylic/melamine clear coating appropriate for use on automotive plastic substrates. The hindered amine is incorporated at a level of 1.5% by weight based on total resins solids.

Each coating formulation is applied by an automatic spray appratus onto automotive grade RIM (Reacting Injection Molded) substrate and TPO (thermoplastic polyolefin). Both substrates are in form of 4" x 12" plaques. Each coating is applied to achieve a dry film thickness of approximately 2.0 mils (50 microns). The coatings are cured by baking at 250 0

F

(121C) for 20 minutes.

*o Sgo Triplicate samples of each cured coating formulation are removed from each substrate and cryoground to a fine powder. A known amount of each sample is extracted in refluxing toluene overnight. The hindered amine present is analyzed quantitatively by dilution to a known volume and analyzed by HPLC or SFC chromatography. Calibration curves for each test stabilizer compound are developed. The hindered amine content of each extracted coating is determined by this method.

When the instant hindered amine compounds substituted on the N-atom with an -O-E- OH moiety are compared to the corresponding -NOR compounds lacking such a hydroxyl moiety, a higher percent recovery of the instant hindered amine compound from the clearcoat over a plastic substrate is found indicating that much less of the instant hindered amine 161 stabilizer migrates into the plastic substrate allowing for better stabilization of the clear topcoat over such plastic substrates.

Example 111 Stabilization of Waterborne Wood Varnish Waterborne coating comprise a significant and increasing proportion of the coating in use for a wide variety of applications including automotive basecoats, industrial coatings and trade sale coatings. These coatings may be pigmented or transparent. The trends are also towards higher solids formulation which in general depend on light stabilizers to maintain properties on exterior exposure, and towards lower levels of cosolvents. This requires higher solubility of stabilizers in such cosolvents (primarily water) or actual solubility in water.

The test stabilizers are incorporated into a waterborne dispersion by predissolution in a cosolvent blend. The waterborne dispersion is a commercially available acrylic/urethane hydrid resin. The cosolvent blend is a 1:1 mixture of TEXANOL® (2,2,4-trimethyl-1,3-pentanediol, Texaco) and ARCOSOLVE® TPM (tripropylene glycol methyl ether, AtlanticRichfield).

0.45 gram of the test stabilizer is predissolved in 10 g of the cosolvent blend which is then incorporated into the following composition: FLEXTHANE® 630 (Air Products) 100.0 Foamaster VF 0.1 Water 10.0 TEXANOLARCOSOLVE/hindered amine 10.5 UV absorber (TINUVIN® 1130, Ciba) 1.2 BYK 346 MICHEMLUBE® 162 -162- Each coating is brush applied onto 6" x 6" sections of cedar and pine boards. The weight of the coating applied is regulated by weighing the coating and brush before and after application and ensuring that the same weight of coating is applied to each section.

The coated board sections are allowed to dry at ambient temperature for two weeks, then evaluated for visual appearance, gloss and Hunter a* and b* color. The sections are exposed on racks at a 450 angle in South Florida for six months before being returned and evaluated for visual appearance, gloss, color change and any other signs of degradation or delamination.

The instant hindered amine compounds substituted on the N-atom with an -O-E-OH moiety provide better stabilization efficacy to the sections in respect to visual appearance, gloss retention, resistance to color change and to delamination than do the corresponding -NOR compounds lacking such a hydroxyl moiety.

Example 112 Stabilization of Pigmented Automotive OEM Basecoat A basecoat pigmented with a mixture of Pigment Red 177 and mica is stabilized with 1% by weight of a hindered amine stabilizer based on the total basecoat solids (pigment plus resin).

oo The basecoat is spray applied at a dry film thickness of 1 mil (25 microns) to primed 4" x 12" steel panels, then topcoated with a high solids commercially available automotive clearcoat.

The coated panels are cured in an over at 250 0 F (1210C) for 30 minutes. The panels are then exposed in a Xenon-Arc Weather-Ometer under the following conditions: Cam 180 cycle: 40 minutes light only; 20 minutes light and front spray; 60 minutes light only; 60 minutes dark and rear spray condensate.

Lamp filters are: quartz inner/borosilicate S outer.

Irradiance: 0.55 watts per square meter.

163- 200 Gloss, Distinctness of Image, Hunter Color Space Values b* and AE) are measured before exposure and after 3000 hours of exposure.

The instant hindered amine compounds substituted on the N-atom with an -O-E-OH moiety provide better stabilization efficacy to the panels in respect to distinctness of image, gloss retention and resistance to color change than do the corresponding -NOR compounds lacking such a hydroxyl moiety.

Example 113 ABS Molding Applications Thermoplastic materials composed of mixtures of copolymers derived from the copolymerization of styrene monomer with acrylonitrile and the copolymerization of stryrene monomer with butadiene, generally referred to as ABS, are dry blended with the instant compounds and melt compounded into pellets. Typical formulations contain the instant compounds at levels from 0.05% to a metal stearate such as calcium stearate at 0.05% to pigments from 0% to UV absorbers at levels of 0.05% to phosphites at 0.0% S. phenolic antioxidants at 0.0% 1.25%, N,N-dialkylhydroxylamine at 0.0% and optionally other hindered amine stabilizers at levels of 0.0% to The pelletized fully formulated resin is then processed into a useful article such as extrusion into sheet, film, profile and pipe molded into bottles; injection molded into a molded article; thermoformed into molded articles; or rotational molded into hollow articles.

The materials containing the instant compounds exhibit stability against deleterious effects of UV light and thermal exposure.

Example 114 164pKa Values In order to determine the pKa values of water insoluble materials, organic references with known pKa values in water are titrated non-aqueously. A plot of the half neutralization potential (HNP) versus the known aqueous pKa value of the reference material is establed. The HNP of the test material is determined and extrapolated to find the corresponding pKa value of the test material. Such organic reference materials include 2,2,6,6-tetramethylpiperidine; 4hydroxy-2,2,6,6-tetramethylpiperidine; 1-hydroxyethyl-4-hydroxy-2,2,6,6-tetramethylpiperidine; triacetoneamine and N-methylaniline.

The reference materials, which are structurally at least peripherally related to the instant test materials and are soluble in both water and 1:1 acetonitrile:chloroform, are used to make a calibration plot in the non-aqueous titration (1:1 acetonitrile:chloroform solvent and 0.1N perchloric acid/dioxane titrant) system. Approximately 0.5 milliequivalents of test material is weighed into a titration beaker. Thirty mL of acetonitrile is added to dissolve the sample. Prior to titration, 30 mL of chloroform is added. Titration is carried out and the HNP is determined. The electrolyte for the reference electrode is 2-(aminomethylpyridine. The electrode is allowed to stand in the solvent system for two hours after filling with the electrolyte to achieve equilibration.

All samples are run in duplicate. The pKa values are seen in the table below.

Sample* HPN (my) Calculated pK, I 523 3.9 II 436 4.9 III 513 3.8 IV 4.6 V 3.8 VI 4.8 *1 is the compound of Example 73.

II is 1 -cyclohexyloxy-4-ocatadecanoyloxy-2,2,6,6-tetramethylpiperidine.

165- Ill is the compound of Example 2.

IV is bis(1 -octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

V is the compound of Example VI is the reaction product of 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino] -6-chloro-s-triazine with N,N'-bis(3-aminopropyl)ethylenediamine.

As can be seen from each of the above pairs of related compounds where the individual compounds differ from the other only by whether the 1-position of the piperidine ring is substituted by an -O-R group or by an -O-E-OH, the instant -O-E-OH compounds consisting have a significantly lower pKa value meaning that said instant compounds are distinguished by consistently lower basicity than the prior art N-OR compounds.

Inspection of the results given in Example 77 shows that this lower basicity and lower pKa values can be translated into superior performance for the instant compounds compared to the closely related prior art N-OR compounds in preventing paint loss on paintable thermoplastic polyolefins (TPO).

Example 115 Flame Retardancy Fiber grade polypropylene, is dry blended with the test additives and then melt compounded at 2340C (450 0 F) into pellets. All formulations additionally contain melt processing stabilizer system. The pelletized fully formulated resin is then spun at 2460C (475 0 F) into fiber using a Hills laboratory model fiber extruder. The spun tow of 41 filaments is stretch at a ratio of 1:3.2 to give a final denier of 615/41.

The fibers are then knitted into socks and on a Lawson-Hemphill Analysis Knitter. Ten replicates of each sample are tested under NFPA701-1996 Vertical burn procedure. The time in seconds for the knitted sock to extinguish after the insult flame is removed is reported as "After Flame". Efficacy as a flame retardant is demonstrated when low After Flame times are observed relative to a blank sample containing no flame retardant. The burning time of the drips 166from the material and the weight loss are also recorded. The data demonstrates that the instant NOR HALS are effective as flame retardants.

Additive After flame Drip Burn Weight loss BLANK, no FR 32 >50 63 Compound of 0.5 12.5 36 Example 73, Example 116 Flame Retardancy of Polypropylene Thick Sections Molding grade polypropylene is dry blended with test additives and then melt compounded into pellets. In addition to the instant compound, halogenated flame retardants are included in the formulation. Typical formulations contain the instant compound and a flame retardants such as: tris(3-bromo-2,2 bis (bromomethyl)propyl) phosphate (FMC PB370); bis(2,3dibromopropyl ether) of bisphenol A (PE68); decabromodiphenyloxide (DBDPO); ethylene bistetrabromophthalimide (SATEX BT-93); ethylene bis-dibromonorbornanedi-carboximide

(SATEX

BN-451). Other formulations may contain Sb20 3 in addition to the brominated flame retardants.

Other formulations may contain phosphorous based flame retardants such as ethylene diamine diphosphate (EDAP). The pelletized fully formulated resin is then compression molded into test specimens using a Wabash Compression Molder.

Test plaques are tested under UL-94 Vertical burn conditions. A minimum of three replicates are tested. The average time in seconds for the test sample to extinguish after a first and second insult flame is removed is reported. Efficacy as a flame retardant is demonstrated when low Flame times are observed. The instant compounds enhance the flame retardancy of a halogenated or phosphate flame retardant tested alone.

-167- Example 117 Flame Retardancy in TPO Thick Sections Molded test specimens were prepared by injection molding thermoplastic olefin (TPO) pellets containing the instant compounds. The TPO formulations may also contain pigments, a phenolic antioxidant, phosphite or hydroxylamine, a metal stearate, ultraviolet light absorbers (UVA) or a hindered amine stabilizers (HALS) or a mixture of UV absorbers and hindered amine stabilizers.

In addition to the instant compound, halogenated flame retardants are included in the formulation. Typical formulations contain the instant compound and a flame retardants such as: tris(3-bromo-2,2 bis (bromomethyl)propyl) phosphate (FMC PB370); bis(2,3-dibromopropyl ether) of bisphenol A (PE68); decabromodiphenyloxide (DBDPO); ethylene bistetrabromophthalimide (SATEX BT-93); ethylene bis-dibromonorbornanedi-carboximide

(SATEX

BN-451). Other formulations may contain Sb20 3 in addition to the brominated flame retardants.

Other formulations may contain phosphorous based flame retardants such as ethylene diamine diphosphate (EDAP).

Test plaques are tested under UL-94 Vertical burn conditions. A minimum of three replicates are tested. The average time in seconds for the test sample to extinguish after a first and second insult flame is removed is reported. The instant compounds enhance the flame retardancy of a halogenated or phosphate flame retardant tested alone.

Example 118 Light Stability in Flame Retardant ABS Molding Applications Molding grade ABS is dry blended with test additives and then melt compounded into pellets. In addition to the instant compounds, selected flame retardants are also included. The flame retardants are tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate, decabromodiphenyl oxide, ethylene bis(tetrabromophthalimide) and ethylene bis(dibromonorbornanedicarboximide).

The pelletized fully formulated resin is then injection molded into test specimens using a BOY 168laboratory model injection molder. Other formulations may contain antimony trioxide (Sb 2 0 3 in addition to the brominated flame retardants. Other formulation may contain phosphorus based flame retardants such as ethylenediamine diphophate (EDAP).

Test plaques are mounted in metal frame and exposed in an Atlas Ci65 Xenon Arc Weather-O-meter with intermittent light/dark cycles and water spray following the ASTM G26 test procedure. Specimens are tested at periodic intervales for changes in tensile properties and for changes in color. The longer it takes for the loss in properties to occur and the less the color change as measured by AE, the more effective is the stabilizer system.

The test samples containing the instant compounds exhibit good retention of tensile properties and minimal color change during the accelerated weathering.

Example 119 Light Stability in Flame Retardant HIPS Molding Applications Molding grade high impact polystyrene is dry blended with test additives and then melt compounded into pellets. In addition to the instant compounds, selected flame retardants are also included. The flame retardants are tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate, decabromodiphenyl oxide, ethylene bis(tetrabromophthalimide) and ethylene bis(dibromonorbornanedicarboximide). The pelletized fully formulated resin is then injection molded into test specimens using a BOY 50M laboratory model injection molder. Other formulations may contain antimony trioxide (Sb 2 0 3 in addition to the brominated flame retardants. Other formulation may Scontain phosphorus based flame retardants such as ethylenediamine diphophate (EDAP).

Test plaques are mounted in metal frame and exposed in an Atlas Ci65 Xenon Arc Weather-O-meter with intermittent light/dark cycles and water spray following the ASTM G26 test procedure. Specimens are tested at periodic intervales for changes in tensile properties and for changes in color. The longer it takes for the loss in properties to occur and the less the color change as measured by AE, the more effective is the stabilizer system.

-169- The test samples containing the instant compounds exhibit good retention of tensile properties and minimal color change during the accelerated weathering.

Example 120 Stabilization of High Solids Acid-catalyzed Thermoset Acrylic Resin Enamel A high solids (50% by weight) thermoset acrylic resin enamel, catalyzed by 0.8% by weight of dodecylbenzenesulfonic acid, based on the film-forming resin is stabilized by the addition of various instant compounds. The high solids thermoset acrylic resin enamel formulation (Acryloid AT 400 from Rohm and Haas) is based on hydroxyethyl methacrylate, methyl methacrylate, styrene, butyl acrylate and butyl methacrylate and a melamine curing agent.

Pieces of steel sheeting 4" x 12" (9.16 cm x 30.48 cm), coated with a primer based on polyester/epoxy resin, are then coated with a TiO 2 -pigmented base coat based on a binder of of monomers such as hydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid with 30% of a melamine resin and an acid catalyst and finally with a clear finishing enamel.

The base coat is sprayed onto the sheet to a thickness of about 0.8 mil (0.0203 mm) and air dried for three minutes. The clear finishing enamel is then sprayed onto the sheet to a thickness S* of about 2.0 mil. After 15 minutes air-drying, the coated sheets are baked for 30 minutes at 1210C.

The stabilizers under test are added to the thermoset acrylic resin finishing enamel in a concentration of 1% by weight before the enamel is coated onto the base coat.

The coated sheets, after storage for three weeks in an air-conditioned room (230C/50% relative humidity), are subjected to weathering for 2000 hours according to SAE J1920 in a Xenon arc Weather-Ometer. In this apparatus, samples are subjected to weathering in repeated cycles of 180 minutes. The effectiveness of the stabilization is measured by the retention of 200 gloss after weathering.

-170- The sheets stabilized by the instant compounds exhibit good retention of 200 gloss after weathering under extreme weather conditions.

Example 121 The samples prepared in Example 120 are also evaluated on the basis of Knoop Hardness (ASTM D-1474-68) on baked and overbaked samples; on the distinction of image (DOI); on Hunter Associates Apparatus; on 200 gloss (ASTM D-523-80); and on cracking based on visual observation.

The samples stabilized by the instant compounds exhibit a pattern of greater retention of 200 gloss and DOI, and a longer absence of severe cracking after exposure.

Example 122 The thermoset acrylic enamel of Example 120 is formulated to include 3% by weight of a benzotriazole UV absorber and 1.5% by weight of an instant hindered amine test compound.

The enamel is coated over a white base coat or over a silver metallic base coat. Baking is conducted at 121 0 C normal bake or at 820C automotive low bake repair temperature.

The coated panels are exposed in a Xenon arc exposure apparatus and 200 gloss and distinction of image (DOI) values are determined.

The samples stabilized by the instant compounds exhibit a pattern of greater retention of 200 gloss and DOI.

Example 123 Two thermoset acrylic enamles are formulated to include 3% by weight of a benzotriazole UV absorber and 1% by weight of an instant hindered amine test stabilizer.

The thermoset acrylic enamels are based on a binder of 70% of monomers such as hydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid with 30% of a 171 melamine resin and an acid catalyst such as p-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid or phenyl acid phosphate.

Pieces of steel sheeting 4" x 12" (9.16 cm x 30.48 cm), coated with a primer based on polyester/epoxy resin, are then coated with a base coat and finally with a clear finishing enamel.

The base coat is sprayed onto the sheet to a thickness of about 0.8 mil (0.0203 mm) and air dried for three minutes. The clear finishing enamel is then sprayed onto the sheet to a thickness of about 2.0 mil. After 15 minutes air-drying, the coated sheets are baked for 30 minutes at 1210C.

The coated panels are exposed in a Xenon arc exposure apparatus and 200 gloss and distinction of image (DOI) values are determined.

The samples stabilized by the instant compounds exhibit a pattern of greater retention of 200 gloss and DOI.

Example 124 A white polyester/melamine based oil-free alkyl coil coating is utilized in this example.

The fully formulated paint is applied over a primed steel sheet using a wire wound rod to give 0.6-0.8 mil dry film. The panels are baked for about 90 seconds at 2200C, removed from the oven and immediately quenched in water. The coated panels are exposed in a Xenon Arc Weather-Ometer, and in South Florida at an angle of 450 S to the sun. 200 gloss values are determined.

The samples stabilized by the instant compounds exhibit a pattern of greater retention of 200 gloss.

Example 125 The thermoset acrylic enamel of Example 124 including 0.8% dodecylbenzenesulfonic acid is formulated to include varying concentrations of benzotriazole or s-triazine UV absorbers and the instant hindered amine test compounds. The enamel is coated over a silver metallic -172base coat pursuant to the procedure of Example 124 and baking is conducted for 30 minutes at 121°C the normal backe temperature.

The coated panels are exposed in a Xenon arc Weather-Ometer and the time to the loss of 200 gloss is determined.

The samples stabilized by the instant compounds and a UV absorber exhibit an excellent retention of 200 gloss and a much longer time till 50% loss in 20° gloss is observed.

o *o *oo oo* go 173- Example 126 A thermoset acrylic enamel based on a binder of 70% of monomers such as hydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid with 30% of a melamine resin and an acid catalyst such as p-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid or dodecylbenzenesulfonic acid is formulated. Commercially available 9.16 cm x 30.48 cm Uniprime panels are used as the substrate. The panels are coated with a silver metallic base coat and then with a clear finishing enamel. The base coat is stabilized with 1% of a benzotriazole UV absorber and 1% of an instant hindered amine test compound (based on solid resin) and is sprayed onto the panel to a thickness of about 0.6-0.8 mil and air dried for three minutes. The clear coat including the above-noted stabilizers is then sprayed to a thickness of 1.7-2.0 mils and after 10 minutes of air drying, the coated panels are baked for 30 minutes at 1210C. The coated panels are then exposed in a Xenon arc apparatus and the 200 gloss values are determined.

The samples stabilized by the instant compounds and a UV absorber exhibit excellent S retention of 200 gloss.

Example 127: A water-borne acrylic melamine enamel is formulated as seen below: Parts Resin Solids Synthacryl VSW 6483 (acrylic dispersion from Hoechst) Synthacryl VSW 6484 42 (50% acrylic resin in butyl diglycol, Hoechst) Maprenal MF 915 melamine resin in isobutanol) Maprenal MF 927 3 (melamine resin) 100 A water-based base coat/clear coat enamel is prepared by spray applying a 0.6-0.8 mil thick film of commercial silver metallic waterborne base coat (from BASF) over an epoxy primed -174coil coated aluminum panel. This material is baked at 80 0 C for five minutes and then clear coated with 1.6-1.8 mil of the waterborne enamel. The system is baked at 800C for ten minutes and then at 140 0 C for a further 30 minutes. Prior to application of the clear coating, instant test and light stabilizers dissolved in a minumum amount of butyl glycol acetate are added to the paint. The coated panels are exposed in a Xenon arc apparatus for 975 hours. The distinction of image (DOI) retention of the panels is measured.

The samples stabilized by the instant compounds exhibit greater retention of DOI values.

Example 128 Stabilization of Tung Oil Phenolic Varnish Pieces of 1.27 cm x 20.32 cm x 30.48 cm western red cedar panels having a fine radial cut are used to test a commercially available tung oil phenolic varish (supplied by McCloskey).

One half of each panel is coated with two coats of unstabilized varnish. An equal amount of varnish containing 5% by weight (based on resin solids) of test stabilizers is applied to the other half of the panel in two coats. After storage for two weeks at ambient temperature, the wood panels are exposed outdoors at an angle of 450 S for a period of eight months. The 60' gloss of each half of the panel is measured at the top, middle and bottom portion of the panel and averaged according to ASTM D 523. Due to the lack of homogeneity of wood substrates, the gloss retention of the same varnish tends to differ slightly from panel to panel. Thus, the application of an unstabilized control varnish to every panel allows for a more meaningful measurement of the improvement in gloss due to the presence of the instant test compound.

e The panels stabilized by the instant compounds show excellent gloss retention after long exposure.

175- Example 129 Stabilization of an Aromatic Urethane Varnish A sample of commercial aromatic urethane varnish (Flecto-Varathane #90) is tested by the same method described in Example 128. After outdoor exposure at an angle of 450 S for a period of five months, the 600 gloss retention values of unstabilized and stabilized portions of the panels are determined.

The panels stabilized by the instant compounds show excellent gloss retention.

Example 130 Stabilization of a White Two-Component Polyester Urethane Gloss Enamel A white polyester is formulated as shown below: Parts Component I Desmophen 670-90 (polyester glycol, Mobay) Titanium Dioxide Cellosolve Acetate 132.4 198.6 98.9 Sand Mill Desmophen 670-90 Flow Aid Tertiary Amine Cellosolve Acetate 94.98 0.28 0.015 332.6 Component II -176 Desmodur N-100 (polyisocyanate, Mobay) 93.9 Cellosolve Acetate 58.7 This material is spray applied at a dry film thickness of 1.5-2.0 mil onto Bonderite 40 cold rolled steel panels that have been previously primed with a commerical epoxy polyamide maintenance primer (Sherwin-Williams Tile Clad II). Prior to application, the instant test compounds are added to the paint. After ambient storage for two weeks, three panels of each formulation are exposed outdoors at an angle of 450 S for a period of nine moriths. Thereafter, 200 gloss retention is determined by ASTM D 523-80 at the top, middle and bottom portions of each panel. Thus, the average values for nine gloss retention measurements for each triplicate set of panels are obtained.

The panels stabilized by the instant compounds show excellent gloss retention.

Example 131 0 Stabilization of Acrylic Alkyd Refinish Enamel A commercially available acrylic alkyd enamel pigments with non-leafing aluminum pigment and tinted a light blue is stabilized with a benzotriazole UV absorber and an instant hindered amine test compound and is then spray applied onto Bonderite 40 panels primed with an alkyd primer. After the coating is allowed to cure at room temperature for 14 days, the panels are exposed outdoors at an angle of 450 S for a period of eight months. The 200 gloss of the exposed panels is measured.

The panels stabilized by the instant compounds show excellent gloss retention.

-177- Example 132 Stabilization of a Medium Oil Alkyd Enamel A medium oil alkyd enamel pigmented with a non-leafing aluminum pigment and tinted light blue is stabilized with a benzotriazole UV absorber and an instant hindered amine test compound and is then sprayed applied onto cold rolled steel panels primed with an epoxy primer. After the coating is allowed to cure at room temperature for two weeks, the panels are exposed for accelerated weathering in a Xenon Arc Weather-Ometer for 840 hours. The 200 gloss values of the panels are determined before and after exposure.

The panels stabilized by the instant compounds show excellent gloss retention.

Example 133 Electrocoat Composition A typical E-coat composition is prepared by adding the diglyicidyl ether of bisphenol A, polyethylene oxide diol, bisphenol A and xylene to a flask and heating to 1350C. The catalyst dimethylbenzylamine in xylene is added and the temperature maintained at 1430C for two hours.

The weight per epoxy (WPE) is measured and a previously prepared crosslinker composed of *o 2,4-toluenediisocyanate, trimethylolpropane blocked with an alcohol is then added and temperature reduced to 100C. The remaining epoxy groups are then capped with two different secondary amines, namely diketimine of diethylenetriamine and methylethanolamine, in phenyl cellosolve. The temperature is maintained for one hour at 1100C and the crosslinker hexamethylenediisocyanate blocked with an alcohol is added. The temperature is maintained near 1000C for 30 minutes and the resin mixture is added to deionized water, surfactant and lactic acid to give a resin emulsion.

To this resin emulsion is added the instant hindered amine compound, additional epoxy resin, carbon black, dibutyltin oxide catalyst, titanium dioxide, lead silicate, water and UV 178absorber. After dispersion using a sand mill to achieve proper fineness, the mixture is incorporated into an electrocoat bath with water for electrocoating onto a metal substrate.

The steel coating electrocoated with the above E-coat resin composition to a thickness of 23-30 lam and cured for 20 minutes at a temperature of 176-201 C. A pigmented resin layer is coated thereover at a thickness of 20-51 lam using an acrylic coating composition in an organic solver, pigments and a UV absorber. The coated panels are then baked at 121-1290C to cure the pigmented layer.

The panels are then exposed outdoors for four months. The panels containing the instant hindered amine compound, particularly when used with a UV absorber, provided excellent resistance to delamination of the E-coat layer from the metal substrate.

Example 134 Abrasion-Resistant Coating Compositions A solution in isopropanol of 50% (by weight) of 1,6-hexanediol, 10% 3-methacryloyloxypropyltrimethoxysilane and 40% colodial silica (in form of a 34% aqueous dispersion) is vacuum stripped to remove volatiles and combined with an instant hindered amine compound, a benzotriazole UV absorber and 2,4,6-trimethylbenzoyldiphenylphosphine photoinitiator. These compositions show no gelation on storage.

The compositions above are applied by roller coating to a 15 mil film of bisphenol A polycarbonate and the coated films are passed under a mercury lamp at 430C at a line speed of 610 cm/min. The compositions are cured to a colorless and optically clear coatings over the polycarbonate substrate.

The coatings as measured by the Taber Abrasion Test (ASTM D1044) are abrasion resistant.

-179- The test specimens are also subjected to accelerated aging tests using an Atlas Xenon Arc Weather-Ometer. The results show that the coatings containing the instant hindered amine compound exhibit excellent resistance to yellowness and haze formation.

Example 135 Coating over Polycarbonate A two-component polyester urethane coating is stabilized by the addition of an instant hindered amine compound. The high-solids polyester polyol (Desmophen 670-80, Bayer) is crosslinked with an isocyanate based resin (Desmodue N-3390, Bayer). The coating is catalyzed with 0.015% by weight of dibutyltin dilaurate catalyst.

Plaques of polycarbonate-based plastic substrate (Xenoy) 4" x 6" are coated with the formulated clear coat at a thickness of approximately 1.5 mils. The coating is spray applied to the substrate and then baked at 820C for 20 minutes.

After storage for one week at room temperature, each plaque is cut into 2" x 3" strips with five replicates being made for each formulation. Each strip is placed into a 8-oz jar along with 2 mL of distilled water and sealed. All samples are placed in an over at 540C. A crosshatch adhesion test is performed once a week on at least two of the replicate samples until the sample failed adhesion loss) or until 40 days elapses.

The samples containing the instant hindered amine compounds exhibit excellent resistance to delamination.

Example 136 Chromogenic photographic layers are prepared by hand-coating a gelatine emulsion containing silver bromide, yellow coupler and an additive on a polyethylene-coated paper.

The composition of the layer is as given in following table, amounts are in mg/m2: 180- Component Amount in the layer Gelatine 5150 AgBr 520 Yellow coupler 1.07 mmol/m' Coupler solvent solv1 33% of the coupler weight/m 2 Additive (cf table 4) 30% of the coupler weight/m 2 Hardener hal 300 Surfactant sul 340 The layers are dried for 7 days in a ventilated cabinet.

The dried samples are exposed to white light through a stepwedge of 0.3 logE exposure steps. They are developed with the P94 process for negative colour paper from Agfa-Gevaert, following the manufacturers' recommendations.

After exposure and processing, the remission density of the yellow dye is measured in the blue channel. The samples are then exposed in an Atlas WeatherOmeter behind a separate UV filter so as to receive 60kJ/cm 2 light energy. The UV filter consists of an emulsion coated onto a polyester transparent support, such that the layer contains lg/m 2 Tinuvin B976®. The temperature is 43 0 C and the relative humidity 50%. The density loss starting from a blue-density of 1 is determined. Low AD number are desired.

Table 1 Coupler Additive -AD(60kJ/cm 2 from OD=1) CoupY1 none 63 CoupY1 X 181 CoupY1 B Y 59 CoupY2 none CoupY2 AX CoupY3 none 24 CoupY3 AX CoupY3 BY 22 CoupY4 none 36 CoupY4 AX 23 These results show that additives of the present invention improve the light stability of yellow photographic layers.

Example 137 Chromogenic photographic layers are prepared by hand-coating a gelatine emulsion containing silver bromide, yellow coupler and an additive on a polyethylene-coated paper.

The composition of the layer is as given in following table, amounts are in mg/m2: Component Amount in the layer Gelatine 5150 AgBr 520 Yellow coupler 1.07 mmol/m 2 Coupler solvent solv1 33% of the coupler weight/m 2 Additive (cf table 4) 30% of the coupler weight/m 2 Hardener hal 300 Surfactant sul 340 The layers are dried for 7 days in a ventilated cabinet.

182- The dried samples are exposed to white light through a stepwedge of 0.3 logE exposure steps. They are developed with the P94 process for negative colour paper from Agfa-Gevaert, following the manufacturers recommendations.

After exposure and processing, the remission density of the yellow dye is measured in the blue channel. The samples are then subjected to storage in a Weiss climatic cabinet for 28 days. The density loss starting from a blue-density of 1 is determined. Low AD numbers are desired.

Table 1 Coupler Additive -AD(28d at 80°C and from OD=1) in CoupY1 none 22 CoupY1 X 16 CoupY1 Y CoupY2 none 18 CoupY2 X CoupY2 Y CoupY2 Z These previous results show that additives of the present invention also improved the dark stability of yellow photographic layers.

Components used in Examples 136 and 137: CoupY1 CoupY2 CoupY3 -183 0 0.

X is the compound of Example Y istecmon*o xml 3 Y is the compound of Example 73.

184- Example 138 Stabilization of Thermoplastic Polyolefins Molded test specimens are prepared and tested as in Example 76 replacing N,Ndialkylhydroxylamine base stabilizer in Sample NOR-2 with the amine oxide, Genox" EP. Light stabilizer formulations comprising a mixture of components outlined in Example 76, an amine oxide and the instant compounds exhibit good stabilization performance against deleterious effects of UV light.

Example 139 Paintable Thermoplastic Polyolefins Molded test specimens are prepared as in Example 77 replacing N,Ndialkylhydroxylamine base stabilizer in Sample NOR-2 with the amine oxide, Genox" EP.

Formulations comprising a mixture of components outlined in Example 77, an amine oxide and the instant compounds exhibit good paint adhesion compared with a formulation substituting the close prior art compound where no hydroxyl moiety is present for the instant compounds.

Example 140 Stabilization of Polypropylene Fiber Fiber specimens are prepared and tested as in Example 79 replacing N,Ndialkylhydroxylamine base stabilizer in Sample NOR-2 with the amine oxide, Genox" EP. Light stabilizer formulations comprising a mixture of components outlined in Example 79, an amine oxide and the instant compounds exhibit good stabilization performance against deleterious effects of UV light.

185- Example 141 Stabilization of a Glycidyl Methacrylate-based Powder Clearcoat One of the major new coating technologies which can be used to meet increasingly stringent VOC solvent emission requirements is the use of powder coatings. Applications requiring the use of light stabilizers include clearcoats for finishing of automotive topcoats, finishing of garden implements, protection of automotive wheel covers. For optimum incorporation and shelf stability, stabilizers used in a powder coating should be moderatemelting (-1000 C) solids, nonvolatile, and heat stable at typical powder coating baking temperatures (140-1800 C).

Prior to incorporation of the Hindered Amine Light Stabilizers under test, a premix of commercially available GMA-based powder coating resin, UV absorber, and flow aids is made by extruding together at 1450 C. The Hindered Amine Light Stabilizers under test are then incorporated into portions of this premix, along with a commercially available 1,12 dodecanoic acid crosslinking resin. The final mix is extruded at 1000 C, then the extrudate is milled on an ultracentrifugal mill and powder cyclone, and sieved. The powders are electrostatically sprayed onto a basecoat to a film thickness of 60 microns. The coatings are cured for 30 minutes at 1600 C.

The panels are weathered in a Xenon WeatherOmeter, and in Florida at 50 South angle.

Gloss and color are measured.

The panels stabilized by the instant compounds show excellent gloss retention.

Example 142 Stabilization of an Oil Modified Urethane Alkyd for Wood Application The Hindered Amine Light Stabilizers under test are incorporated into a commercially available solvent-borne urethane alkyd McWhorter 43-4355. A 2-hydroxy benzotriazole UV -186absorber is also incoporated into all formulations. The Hindered Amine light stabilizers are added at equivalent piperidine levels. After mixing, the clear coatings are applied by brushing to white pine boards. Each board is divided into 8 sections separated by a groove 1/8" deep, which is sealed with a film-forming clear varnish and the back and sides are coated with a white chlorinated pool paint. The stabilized coatings are applied in triplicate in three coats to sections of the boards in such a way as to ensure that a control formulation is present on each of the boards for comparison. The wood samples are allowed to dry for 1 week, then placed on exposure in Florida, Australia, and New York.

The panels stabilized by the instant compounds show good color retention, cracking resistance, and visual gloss retention.

Example 143 Performed Films for Lamination to plastic parts oo The instant invention also pertains to protective and decorative films which are performed, then applied to a substrate via a dry paint transfer process. These films consist of a single decorative layer which is applied to a carrier sheet, then laminated to a self-supporting, thermoformable backing sheet. The carrier sheet is then removed from the opposite side of the film, exposing the decorative layer. The composite film/backing sheet then is thermoformed to a three-dimensional shape. Additionally, these films may also consist of multiple layers, where, for example, a thermoplastic, thermoformable clearcoat is applied to the carrier sheet, then hardened to form an optically clear film. A color coat is then applied to the exposed face of the clearcoat, and hardened, resulting in a clear coat/color coat paint film supported by the carrier.

i This composite is then laminated to a thermoformable backing sheet, as above. The carrier sheet is removed, as above, and the composite clearcoat/colorcoat/backing is then thermoformed, as above.

The polymeric resins for the above application must be thermoplastic, and may be fluoropolymer/acrylic blends.

Claims (2)

1. A 1-alkoxy substituted hindered amine where the alkoxy moiety is substituted by one to three hydroxy groups as described in formulas to or a derivative thereof of formula (29) or Gi G 2 0 N-O-E- (OH) b (OH)b b (OH) 188 (HO) -E-0N N0OE- (OH) b O- -b G G 2G G 2 (4) O G G 2 N( N0OE(OH) b O G G 2 G. G 1 G 2 GG2 -E (OH)bj (6) Gi G ->qNOE- (OH) b H G, 2 189 RC N0OE (OH)j (8) R 7 G G 2 N (9) N- CH 2 )-N NI- R 9 N N~ R 9 N 7 (HO) b H CH 2 (CH2)- N N "kNR 2 N Gi N LG I OH) E- OH) b b E- (OH) b (11) 190 R____13 (CIH 2 k E- (OH) b (12) R 1 R 13 (CH 2 Si(O) (C H2)k H X 9 G 2 N 2 E b (CH 2 h R 14 (13) 191 (CH CH)- 2 2m 0 E- (OH) b z (14) N N N R 1 E-(OH) b E- (OH) b r-o- -L (OH) b (16)

192- (OH) b -s 2 (17) (OH) E b b S* S. S S S a 55 55 *5 (18) (19) OH) b (OH) b (va) (HO) -rI- I I 0 (ue) 9. .9 @0o 0**S 0**e 9. 9 94 0990 4 0000 9 0 04 0 90@9 9eS* 0 9.. .9 9* 0 0090 S q (OH) 11 (33) q (HO) -i. (Le) q (HO) C6 L 194 0 0 1 1 1 (HO) b (OH) b -0t--L (OH) a. S 0 S 0 @005 0e 55 (26) 5 @005 S 0005 OS S S. *5 S *505 R 10 N- (CH 2 R N N /Rl (HO) -E-0-1 b (OH) b (27) 0065 5* 0 S OS 5 195 R (CH 14 2h R 13 14 d I d Ch 2 (CH2) (OH) b (28) (29) 0 11 -2 0 11 I-O-G-0-C-R 2 9 wherein G, and G 2 are independently alkyl of 1 to 4 carbon atoms, or G, and G 2 together are pentamnethylene; -196- E is a straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl groups of 1 to 4 carbon atoms; b is 1, 2 or 3 with the proviso that b cannot exceed the number of carbon atoms in E or L, and when b is 2 or 3, each hydroxyl group is attached to a different carbon atoms of E or L; the two hindered amine groups are generally, but not always, attached to two different carbon atoms of L; in each of the formulas to m is 0or 1; R 1 is hydrogen, hydroxyl or hydroxymethyl; R 2 is hydrogen, alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon atoms; *n is 1 to 4; when n is 1, R 3 is alkyl of 1 to 18 carbon atoms, alkoxycarbonylalkylenecarbonyl of 4 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2- (hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkyl is interrupted by oxygen, *0 an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, or acyl radical of an aromatic acid containing 7 to 15 carbon atoms; when n is 2, R 3 is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, a divalent -197- acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms; when n is 3, R 3 is a trivalent acyl radical of an aliphatic, unsaturated aliphatic, or cycloaliphatic tricarboxylic acid or tricarbamic acid containing 6-18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic or tricarbamic acid containing 9-18 carbon atoms, or R 3 is a trivalent acyl radical of a tris(alkylcarbamic acid) derivative of cyanuric acid containing 12-24 carbon atoms, when n is 4, R 3 is a tetravalent acyl radical of an aliphatic or unsaturated aliphatic tetracarboxylic acid, or R 3 is a tetravalent acyl radical of an aromatic S tetracarboxylic acid containing 10 to 18 carbon atoms; p is 1 to 3, R 4 is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbon atoms; when pis 1, when p is 2, Rs is alkylene of 2 to 12 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoris, a divalent -198- acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms; when p is 3, Rs is a trivalent acyl radical of an aliphatic or unsaturated aliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9 to 15 carbon atoms; when n is 1, Re is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbon atoms, -NHalkyl of 1 to 18 carbon atoms or -N(alkyl) 2 of 2 to 36 carbon atoms, *o when n is 2, R 6 is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of 2 to 18 carbon atoms, -NH-alkylene-NH- of 2 to 18 carbon atoms or -N(alkyl)-alkylene-N(alkyl)- of 2 to 18 carbon atoms, or Re is 4-methyl-1,3-phenylenediamino, when n is 3, R 6 is a trivalent alkoxy radical of a saturated or unsaturated aliphatic triol containing 3 to 18 carbon atoms, when n is 4, Re is a tetravalent alkoxy radical of a saturated or unsaturated aliphatic tetraol containing 4 to 18 carbon atoms, R 7 and R 8 are independently chlorine, alkoxy of 1 to 18 carbon atoms, -O-T 1 amino substituted by 2-hydroxyethyl, -NH(alkyl) of 1 to 18 carbon atoms, -N(alkyl)T 1 with alkyl of 1 to 18 carbon atoms, or -N(alkyl) 2 of 2 to 36 carbon atoms, -199- R 9 is a divalent oxygen atom, or R 9 is a divalent nitrogen atom substituted by either hydrogen, alkyl of 1 to 12 carbon atoms or T 1 G G 2 T, N-O-E- (OH)b G G 2 Rio is hydrogen or methyl, q is 2 to 8, R 11 and R 12 are independently hydrogen or the group T 2 r T2= 0\ 0\ SE- (OH) E- (OH) b b R 1 3 is hydrogen, phenyl, straight or branched alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, straight or branched alkyl of 1 to 4 carbon atoms substituted by phenyl, cycloalkyl of 5 to 8 carbon atoms, cycloalkenyl of 5 to 8 carbon atoms, alkenyl of 2 to 12 carbon atoms, glycidyl, allyloxy, straight or branched hydroxyalkyl of 1 to 4 carbon atoms, or silyl or silyloxy substituted three times independently by hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms; -200- R 14 is hydrogen or silyl substituted three times independently by hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms; d is 0 or 1; h is 0 to 4; k is 0 to x is 3 to 6; y is 1 to z is an integer such that the compound has a molecular weight of 1000 to 4000 amu, R 15 is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 8 carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms such as tert-octylamino, -N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms substituted by T, or -N(alkyl) 2 of 2 to 16 carbon atoms, R 16 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted once by chlorine and once by R 15 or s-triazinyl substituted twice by R 15 with the condition that the two R 15 substituents may be different; R 1 7 is chlorine, amino substituted by alkyl of 1 to 8 carbon atoms or by T 1 -N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms, -N(alkyl) 2 of 2 to 16 carbon atoms, or the group T 3 T 3 N-R E- (OH) b E- (OH) b -201 R 18 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted twice by -N(alkyl) 2 of 2 to 16 carbon atoms or s-triazinyl substituted twice by -N(alkyl)Ti with alkyl of 1 to 8 carbon atoms; L is straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl of 1 to 4 carbon atoms, in formulas (16) to R 1 R 2 R 7 Rs, Rg, Rio, R 1 3 R 14 d,h, k, m, q, and T 1 have the same meanings as in formulas to R 19 is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2-(hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkyl is interrupted by oxygen, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, or acyl radical of an aromatic acid containing 7 to 15 carbon atoms; R 20 is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms; R 21 is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbon atoms; R 22 is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, an acyl radical of an aromatic carboxylic acid containing 7 to 15 carbon atoms, or R 4 and Rs together are -(CH 2 5 CO-, phthaloyl or a divalent acyl radical of maleic acid; -202- R 2 3 is hydrogen, alkyl of 1 to 4 carbon atoms or acyl of 2 to 6 carbon atoms; R 24 is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms; R 25 is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbon atoms, -NHalkyl of 1 to 18 carbon atoms or -N(alkyl) 2 of 2 to 36 carbon atoms, R 26 is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of 2 to 18 carbon atoms, NH-alkylene-NH- of 2 to 18 carbon atoms or -N(alkyl)-alkylene-N(alkyl)- of 3 to 18 carbon atoms, in formulas (29) and G is a carbon centered diradical derived from a primary, secondary or tertiary alcohol G-OH, where z is as defined above, and G is straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl of 1 to 4 carbon atoms, with the proviso that in formula (29) successive hindered amine moieties can be oriented in either a head to head or head to tail fashion; T 4 is hydrogen or O 0 T 4 is O-R28 T4 is -203- R 27 is a straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene or cycloalkenylene of 5 to 8 carbon atoms, phenylene or -NH-alkylene-NH- of 2 to 18 carbon atoms including 5-amino- -aminomethyl-1,3,3-trimethylcyclohexane and -NH-xylylene-NH-; G G2 Gi G 1 2 G- R 28 is alkyl of 1 to 4 carbon atoms; N-O-G-OH or HO N-O-G- G G,2 G, G2 R 2 9 is a straight or branched chain alkyl or -NH-alkyl of 1 to 18 carbon atoms or -NH- cycloalkyl of 5 to 8 carbon atoms; and with the further proviso that in formulas and when b is 1, E is not methyl, ethyl, 2-propyl or 2-methyl-2-propyl and that in formula if G and G2 each are methyl, the moiety -E-(OH)6 is not 1-phenyl-2-hydroxymethyl. 2. A compound according to claim 1 where in formulas to G1 and G2 are each methyl; and in formulas to b is 1 or 2, when b is 1, E-OH and L-OH are respectively a carbon-centered radical or diradical formed preferably from 2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1 -propanol, 2-methyl-2- butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol, 1- dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, Sallyl alcohol, phenethyl alcohol or 1 -phenyl-1 -ethanol; most preferably E-OH and L-OH are formed from 2-methyl-2-propanol or cyclohexanol, when b is 2, E-OH and L-OH are respectively a carbon-centered radical or diradical formed preferably from 1,2-ethanediol, 1,2-propanedial, 1,3-propanediol, 1,2-butanediol, 1,3- butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3- cyclohexanediol or 1,4-cyclohexanediol; when b is 3, E-OH and L-OH are respectively a carbon-centered radical or diradical formed from glycerol, 1,1,1-tris(hydroxymethyl)methane, 2-ethyl-2-(hydroxymethyl-1,3- propanediol, 1,2,4-butanetriol or 1,2,6-hexanetriol; -204- in formulas (29) and is formed from ethanol, phenethyl alcohol, cyclohexanol or 2-methyl-2-propanol tert-butyl alcohol); in formula m is 0, R, is hydrogen or hydroxymethyl, and R 2 is hydrogen; or m is 1, R 1 is hydroxy or hydroxymethyl, and R 2 is hydrogen, methyl or ethyl; in formula R 2 is hydrogen or dodecyl; in formula n is 1-3, and when n is 1, R 3 is allyl, glycidyl, acryloyl, methacryloyl, octadecanoyl, hexadecanoyl, tetradecanoyl, methoxycarbonylpropionyl, methoxycarbonyl- butyryl, methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; or when n is 2, R 3 is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl, cis- or trans-5-carbamoyl-1 -(carbamoyl- **CE methyl)-1 ,3,3-trimethylcyclohexane or toluene-2,4-dicarbamoyl; or when n is 3, R 3 is 1,3,5-tris(6- carbamoylhexyl)-2,4,6-trioxo-s-triazine; in formula p is 1 or 2, and when p is 1, R 4 is hydrogen and R 5 is butyl; or R 4 and R together are the divalent acyl radical of maleic acid; or when p is 2, R 4 is hydrogen or acetyl, and R 5 is 1,6-hexanediyl; in formula n is 1 or 2, and when n is 1, R 6 is ethoxy, 6-methyl-i -heptyloxy, ethylamino, butylamino or octylamino; or when n is 2, R 6 is 1,2-ethanedioxy, 1,4-butanedioxy, ethylenediamino, hexamethylenediamino or 4-methyl-i ,3-phenylenediamino; :i in formula R 7 and R 8 are independently chlorine, octylamino, tert-octylamino or amino substituted by T 1 and ethyl, butyl or dodecyl; and R 9 is a divalent nitrogen atom substituted by ethyl, butyl or dodecyl; in formula q is 2, 4 or 6, R 7 is chlorine, octylamino, octadecylamino or amino substituted by T 1 and ethyl, butyl or dodecyl; and Rio is hydrogen; in formula n is 3, p is 2, R 2 is ethyl, butyl or dodecyl; and one of R 11 or R 1 2 is T 2 and the other is hydrogen; -205- in formula k is 3, R 9 is a divalent oxygen atom or is a divalent nitrogen atom substituted by ethyl, butyl or dodecyl, R 13 is hydrogen or methyl, and when d is 0, x is 5 or 6, and when d is 1, x is 3 or 4; in formula d is 0 or 1, h is 0-2, k is 0 or 3, y is 1-8, R 9 is a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, butyl or dodecyl, R 13 is hydrogen, methyl, ethyl, methoxy or ethoxy, and R 14 is hydrogen or trimethylsilyl; in formula Rg is a divalent oxygen atom, Ro 1 is hydrogen or methyl, m is 0 and z is an integer such that the molecular weight of the compound is 1500-3000 amu; in formula (15) q is 6, y is 1-7, R 15 is tert-octylamino, morpholino, amino substituted by Ti and butyl, which may also be designated as T 1 -butylamino, R 16 is hydrogen, acetyl, ethyl- carbamoyl, 2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl, s-triazinyl substituted twice by T 1 -butylamino or s-triazinyl substituted once by diethylamino or dibutyl- amino and once by T 1 -butylamino, R 17 is dibutylamino, diethylamino, T 1 -butylamino or R 1 7 is T 3 0*00. where R 1 8 is acetyl or ethylcarbamoyl; in formula m is 0, R 1 is hydrogen or hydroxymethyl, and R 2 is hydrogen; or m is 1, R 1 is hydroxy or hydroxymethyl, and R 2 is hydrogen or methyl; in formula R 2 is hydrogen or dodecyl; in formula R 19 is hydrogen, allyl, acryloyl, methacryloyl, octadecanoyl or hexadecanoyl; in formula R 20 is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl, or cis- or trans-5-carbamoyl-1 -(carbamoylmethyl)-1,3,3-trimethylcyclohexane; in formula R 21 is hydrogen and R 22 is hydrogen or butyl; or R 2 1 and R 22 together are the divalent acyl radical of maleic acid; -206- in formula R 2 3 is hydrogen or acetyl, and R 24 is ethylene or hexamethylene; in formula R 25 is ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octyl- amino; in formula R 26 is 1,2-ethanedioxy, 1-4-butanedioxy, ethylenediamino or hexamethylenediamino; in formula R 7 and R 8 are independently chlorine, octylamino, tert-octylamino, octadecylamino, T 1 -ethylamino, T 1 -butylamino or T 1 -dodecylamino, and R 9 is a divalent nitrogen atom substituted by ethyl, butyl or dodecyl; in formula q is 2, 4 or 6, R 7 is chlorine, octylamino, octadecylamino, T 1 -ethylamino, Ti-butylamino or T 1 -dodecylamino, and Rjo is hydrogen; in formula d is 0 or 1, h is 0-2, k is 0 or 3, R 9 is a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, butyl or dodecyl, R 13 is hydrogen, methyl, ethyl, methoxy or ethoxy, and R 14 is hydrogen or trimethylsilyl; in formula R 27 is ethylene, trimethylene, tetramethylene, octamethylene, 1,6- diaminohexane or 5-amino-1 -aminomethyl-1,3,3-trimethylcyclohexane; z is an integer such that the molecular weight of the compound is 1500-3000 amu, R 28 is methyl or ethyl, and G is ethylene, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, 1,4-cyclohexanediyl, -CH(C 6 H 5 )CH 2 or S -CH 2 C(CH 3 2 and in formula R 29 is pentadecyl, heptadecyl, butylamino or cyclohexylamino. A compound according to claim 1 where in formula when n is 1, R 3 is acryloyl, methacrloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl, methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; or when n is 2, R 3 is succinyl, glutaryl, adipoyl, sebacoyl, 1,6- hexanedicarbamoyl or cis- or trans-5-carbamoyl-1 -(carbamoylmethyl)-1,3,3-trimethylcyclo- -207- hexane or toluene-2,4-dicarbamoyl; or when n is 3, R 3 is 1,3,5-tris(6-carbamoyhexyl)-2,4,6- trioxo-s-triazine; in formula p is 1 or 2, and when p is 1, R 4 is hydrogen and Rs is hydrogen or butyl; or when p is 2, R 4 is hydrogen, and Rs is 1,6-hexanediyl; in formula R 7 is chlorine, octylamino or T 1 -butylamino, Re is chlorine or T,- butylamino, and R 9 is a divalent nitrogen atom substituted by butyl; in formula q is 6, R 7 is T 1 -butylamino; and Ro 1 is hydrogen; in formula n is 3, p is 2, and one of R 11 or R 12 is T 2 and the other is hydrogen; in formula k is 3, R 9 is a divalent oxygen atom, Ri 3 is hydrogen or methyl, and d is 0, x is 5 or 6, and when d is 1, x is 3 or 4; in formula d is 0 or 1, h is 0-2, k is 0 or 3, y is 1-8, R 9 is a divalent oxygen atom, R 13 is hydrogen, methyl, ethyl, methoxy or ethoxy, and R 1 4 is hydrogen or trimethylsilyl; in formula (15) q is 6, y is 1-7, R 1 i is T 1 -butylamino, R 16 is hydrogen, acetyl, ethyl- carbamoyl, 2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl, s-triazinyl substituted twice by T 1 -butylamino or s-triazinyl substituted once by diethylamino or dibutyl- amino and once by T 1 -butylamino, R 17 is dibutylamino, diethylamino, T 1 -butylamino or R 17 is T 3 where R 18 is acetyl or ethylcarbamoyl; in formula R 1 9 is hydrogen, octadecanoyl or hexadecanoyl; in formula R 2 1 is hydrogen and R 22 is hydrogen or butyl; in formula R 23 is hydrogen, and R 24 is hexamethylene; in formula R 7 is chlorine, octylamino or T 1 -butylamino, Re is chlorine or T 1 butylamino, and R 9 is a divalent nitrogen atom substituted by butyl; in formula q is 6, R 7 is T 1 -butylamino, and R 9 is a divalent nitrogen atom substituted by butyl; in formula R 27 is ethylene, trimethylene, tetramethylene or octamethylene, z is an integer such that the molecular weight of the compound is 1500 to 2000 g/mol, and R 28 is methyl; and in formula R 29 is pentadecyl or heptadecyl. 4. A compound according to claim 1 wherein G 1 and G 2 are each methyl E-OH, L-OH and in compounds of formulas to (30) are formed from 2-methyl-2-propanol or cyclohexanol. 208 A compound according to claim 1 where in formula when n is 1, R 3 is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonyl pro pionyl or methoxycarbonylbutyryl, or methoxycarbonyl- pentanoyl, and when is is 2, R 3 is succinyl, glutaryl, adipoy. or sobacoyl; in formula where R 4 is hydrogen, and when p is 1, R 5 is hydrogen or butyl, or when p is 2, R 5 is hexamethylene; in formula where R 7 is chlorine, octylamino or T,-butylamino, R 8 is T 1 -butylamino, and R 9 is a divalent nitrogen atom substituted by butyl; in formula (10) where q is 6, R 7 is Tl-butylamino and RIO is hydrogen; in formula (111) where n is 3, p is 2, one of R 11 or R 12 is T 2 and the other is hydrogen; in formula (12) where d is 1, k is 3, x is 3 or 4, R 9 is divalent oxygen atom, and R 13 is methyl; in formula (13) where k is 3, y is 4-8. R 9 is a divalent oxygen atom, R 1 3 is hydrogen or ~.:~:methyl, d and h are 0, R 1 4 is hydrogen, or d is 1 and h isO0, and R 14 is trimethylsilyl; in formula (14) where m is 0, R 9 is a divalent oxygen atom, Rio is hydrogen or methyl, and z is an integer such that the molecular weight of the compound is 1500-3000 amu; in formula (15) where q is 6, y is 1-7, R 15 is TI-butylamino, R 16 is hydrogen, acetyl, ethyl- carbamoyl, 2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(di ethyl amino) -s-triazi nyl, s-triazinyl substituted twice by T 1 -butylamino or s-triazinyl substituted once by diethylamino or dlibutyl- amino and once by Tl-butylamino, R 17 is dibutylamino, diethylamino, or T 3 where R 18 is acetyl or ethylcarbamoyl; in formula (20) where R 19 is hydrogen, octadecanoyl or hexadecanoyl; and in formula (21) where R 20 is succinyl, glutaryl, adipoyl or sebacoyl; and in formula (30) where R 29 is heptadlecyl. 6. 'A compound according to claim 1 which is bisf 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)] sebacate; a mixture of bis[1 .(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl] glutarate and bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetranethylpiperidin-4-y] adipate; 1 -(2-hyd roxy-2-methylpropoxy)-4-octadecanoyloxy-2 ,2,6,6-tetramethyl pipe ridi ne; b isil -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl adipate; bisf 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra methylpiperidin-4-y] glutarate; bis(1 -(2-hydroxy-2-methyl propoxy)-2,2,6,6-tetramethylpiperidin-4-y] succinate; 209 a mixture of bis[1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetraethylpiperidil- 4 -yI] glutarate and bis[1 -(2-hydroxy-2-methylpropoxy)-2,2 ,6,6-tetramethylpiperidin-4-y] succinate; 1 -(4-octadecanoyloxy-2 ,2,6,6-tetramethylpiperidin-1 -yloxy)-2-octadecanoyloxy-2- methyipropane; 1 -(2-hydroxy-2-methylpropoxy)-4-[9-(methoxy-carbol)flonanoyloxy]- 2 ,2,6,6-tetra- methylpiperidine; 1 -(2-hydroxy-2-methylpropoxy)-4-[5-(methoxy-carbofl)peltaloyI- 2 2 ,6,6-tetra- methylpiperidine; 1 (-yrx--ehlrpx)4[-mtox-abnlpoinlx]2266tta methylpiperidine; 1 -(2-hydroxy-2-methylpropoxy)-4-4-(methoxy-carbofl)butyryIoxy- 2 ,2,6,6-tetra- methylpiperidine; (in) condensation product of 4-hydroxy-1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra- methylpiperidine with hexamethylene diisocyanate and terminated with methoxy; condensation product of 4-hydroxy-1 -(2-hydroxy-ethoxy)-2,2,6,6-tetranethyl- piperidine with hexamethylene diisocyanate and terminated with methoxy; condensation product of 4-hydroxy-1 -(2-hydroxy- 1 -phenethoxy)-2,2,6,6-tetramethyl- piperidine with hexamethylene diisocyanate and terminated with methoxy; 1 (2-hyd roxy-2-methyl propoxy) -4-hexadecanoyl oxy- 2 ,2,6,6-tetramethyl pipe rid i ne; 1 -(4-hexadecanoyloxy-2,2,6,6-tetramlethylpiperidin-l -yloxy)-2-hexadecanoyloxy-2- methyl propane; 1 (-yrx--ehlrpx)4[-mtox-abnlpnaolx]2266tta methylpiperidine, 1 (-yrx--ehlrpx)4[-mehx-abnlbtrlx]2266 tetramethylpiperidine; 1 ,3,5-tris{[1- (2-hyd roxy2methy propoxy)-2,2,6,6-tetrainethyl pipe ridi n- 4 yloxy]carbonylaminohexyl-2,4,6-trioxo-s-triazine; reaction of 4-hydroxy-1 -oxyl-2,2,6,6-tetramethylpiperidine with 2-methyl-2-butanol; transesterification of the reaction product of 4-hydroxy-1 -oxyl-2,2,6,6- tetramethylpiperidi ne with 2-methyl-2-butanol with methyl stearate or mixture of 1 -(2-hydroxy-2-methylpropoxy)-4-[5-methoxy-carbonyI) pentanoyloxyl- 2,2,6,6-tetramethylpiperidine and 1 -(2-Hydroxy-2-methylpropoxy)-4-[4-nethoxy- carbo nyl) butyryloxy]-2,2,6,6-tetranlethyl piperid ine. -210- 7. A composition which comprises an organic polymer or recording material subject to the adverse effects of heat, oxygen and light, and an effective stabilizing amount of one or more compounds selected from the compounds of formula to formula (30) according to claim 1. 8. A composition according to claim 7 wherein component is a thermoplastic organic polymer, a coating binder, a color photographic material or a printing ink. 9. A composition according to claim 7 comprising a further component selected from solvents, pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, further light stabilizers, metal passivators, metal oxides, organophosphorus compounds, hydroxylamines, UV absorbers, sterically hindered amines, flame retardants and mixtures thereof. A composition according to claim 9 which is a polyolefin composition comprising, as further component, a halogenated flame retardant. 11. A composition according to claim 10, wherein the halogenated flame retardant is selected from tris-(3-bromo-2,2-bis(bromoethyl)propyl)phosphate, decarbromodiphenyl oxide, ethylene bis-(tetrabromophthalimide), and ethylene bis-(dibromo-norbornanedicarboximide),, 12. A composition according to claim 9 containing a UV absorber selected from the classes of the 2-(2-hydroxyphenyl)-2H-benzotriazoles, 4-hydroxybenzoates, 2-hydroxy-benzo- phenones, oxalanilides, 2-hydroxyphenyl-s-triazines, or mixtures thereof. 13. A composition according to claim 7 comprising from 0.01 to 10 by weight, based on component of the stabilizer of component 14. A process for stabilizing an organic polymer or recording material against damage by light, oxygen and/or heat, which comprises adding to or applying to said material at least one compound of the formulas to (30) according to claim 1. 15. Use of a compound of the formulas to (30) according to claim 1 for stabilizing an organic polymer or recording material against damage by light, oxygen and/or heat. 16. A process for preparing a compound of formula IV 16. A process for preparing a compound of formula IV -211- G 1 G2 T 'N-O-E-(OH)b (IV) wherein G 1 and G 2 are independently alkyl of 1 to 4 carbon atoms, or G, and G 2 together are pentamethylene; T is a divalent organic radical required to complete a five- or six-membered ring containing the hindered amine nitrogen atom and two quaternary carbon atoms substituted by G 1 and G 2 E is a (b 1) valent alkylene radical of 2 to 18 carbon atoms, an alkenylene radical of 3 to 19 carbon atoms, a cycloalkylene radical of 5 to 12 carbon atoms, a cycloalkenylene radical of 5 to 12 carbon atoms or an alkylene radical of 2 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl of 1 to 4 carbon atoms; and b is 1, 2 or 3; with the proviso that b cannot exceed the number of saturated carbon atoms in E, and when b is 2 or 3, each hydroxyl group is bonded to a different carbon atom in E; which process comprises reacting a N-oxyl hindered amine of formula V ,.Gi G 2 T N-O0 (V) G G with an alcohol of formula VI E-(OH)b (VI) in the presence of a peroxide or organic hydroperoxide and a catalytic amount of a metal salt or metal-ligand complex. S' 17.A process according to claim 16 where the compound of formula IV Scorresponds to formulae to (28) according to claim 1. S *o -212- 18. A process according to claim 16 where G 1 and G 2 are each methyl, and T is 2-hydroxy-1,3-propanediyl or 2-oxo-1,3-propanediyl. 19. A process according to claim 16 wherein the compound E-(OH)b of formula VI, when b is 1, is 2-methyl-2-propanol or cyclohexanol, and when b is 2, is 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3- propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol, and when b is 3, is 1,1,1 -tris(hydroxymethyl)ethane, 2-ethyl-2- (hydroxymethyl)-1,3-propanediol, 1,2,4-butanetriol or 1,2,6-hexanetriol. A process according to claim 16 wherein the peroxide is hydrogen peroxide, or the addition compound of urea and hydrogen peroxide. 21. A process according to claim 16 wherein the metal is a transition metal chosen from the group IVA, VA, VIIA, VIIIA and IB of the periodic table, especially iron(ll), iron(III), copper(l), copper(ll), cobalt(lI), cobalt(lll), manganese(ll), manganese(III), vanadium(II), vanadium(lll), cerium(ll) or titanium(lll). 22. A process according to claim 21 wherein the counterion for the transition metal is chloride, siuliate, acetylacetonate, acetate, citrate, oxalate, nitrate, perchlorate, cyanide, hydroxide, phosphate, pyrophosphate or oxide, and an organic ligand may be present selected from 2,2'dipyridyl, 2,2':6,2"-terpyridyl, 1,10- S phenanthroline, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, pyridine, picolinic acid, 2-pyrazinecarboxylic acid, aromatic diimines formed from the reaction of aniline or substituted anilines with 1,2-diketones such as 2,3-butanedione, or triphenylphosphine oxide. 23. A process according to claim 16 wherein the compound of formula VI is used as a solvent in the ratio of 5 to 100 moles per mole of nitroxyl moiety in formula S V, s. wherein the amount of peroxide or organic hydroperoxide is 1 to 20 moles per mole of nitroxyl moiety in formula V, S 0000 S.as SI Docll.ent2-24I)2/() -213- wherein the amount of metal salt or metal-ligand complex is 0.001 to 0.5 molar equivalent per mole of nitroxyl moiety in formula V, where no acid is used, or an acid is used in an amount up to 1 molar equivalent per mole of nitroxyl moiety in formula V, and wherein the process is run at a temperature of 20° to 100 0 C. 24. 1-alkoxy substituted hindered amines substantially as hereinbefore described and processes for preparing the same, substantially as hereinbefore described with reference to the Examples. DATED this 31st day of January, 2003 CIBA SPECIALTY CHEMICALS HOLDING INC. By its Patent Attorneys DAVIES COLLISON CAVE 0* 000 0*0* 6000 .00. 0 0 0 0 0 00 **o