GB2266531A - Novel piperidine-triazine co-oligomers for use as stabilisers for organic materials - Google Patents

Abstract

Novel piperidine-triazine compounds comprising recurring units of the formulae (Ia) and (Ib> <IMAGE> having a number-average molecular weight from 1,000 to 20,000 and a (Ia):(Ib) ratio from 4:1 to 1:4, in which R1 is e.g. an alkylamino group, R2 is e.g. 1,2,2,6,6-pentamethyl-4-piperidyl and R3 and R4 are e.g. C2-C12alkylene. These compounds are useful as light-stabilisers, heat-stabilisers and oxidation-stabilisers for organic materials. In particular, the compounds of the present invention exert a surprising light stabilising action in polypropylene fibres. <IMAGE>

Description

9 ^ 122660%51 Novel piperidine-triazine co-oliggomers for use as

stabilisers for organic materials The present invention relates to novel piperidine-triazine co-oligomers, to the use thereof as light-stabilisers, heat-stabilisers and oxidation- stabilisers for organic materials, in particular synthetic polymers, and to organic materials thus stabilised.

The stabilisation of synthetic polymers by triazine-oligomers and -cooligomers comprising 2,2,6,6-tetramethylpiperidine groups has been described in numerous patents, in particular in US-A-4 086 204, US-A-4 315 859, US-A-4 331586, US-A-4 335 242, US-A-4 412 020, US-A-4 459 395, US-A-4 477 615, US-A-4 547 548, EP-A-1 17 229 and EP-A-217 149 and P-A- Sho 63-196 654.

The present invention relates to novel piperidine-triazine co-oligomers comprising recurring units of the formulae (Ia) and (1b) R3-N- R4--- N R3N 1 X2 K2 CHj ICH3 CH3 CH3 R1 N 11CH3 CH3 N CH3 CH3 1 1 CH3 (Ia) Ut'3 (Ib) having a number-average molecular weight from 1,000 to 20,000 and a (Ia):(Ib) ratio from 4:1 to 1A, in which R, is a group -ORS, -SR5 or - N R7, where RS, R6 and R7 which 1 R6 can be identical or different are hydrogen, Cl-C18alkyl, CS- CUCYCloalkyl which is unsubstituted or mono-, di- or tri-substituted by Cl-C4alkyl; C3-C18alkenyl, phenyl which is unsubstituted or mono-, di- or tri-substituted by Cl-C4alkyl or Cl-C4alkoxy; C7-C9phenylalkyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by Cl-COR71; tetrahydrofurfuryl, 1,2,2,6,6-pentainethyl-4-piperidyl or C2-C4alkyl substituted in the 2-, 3or 4-position by Cl-C8alkoxy, by di(CI- C4alkyl)amino or by a group of the formula (H) A N - (jj) where A is a direct bond, -0-, -CH2-, -CH2CH27 or >N-CH3, or R, is a group of the formula (II) or one of the groups of the formulae (HIa)-(HIc) CH3 CH3 / - \ - (HIa) CH3 -N N (CH2) - N in 1 C t n CH3 CH3 CH3 CH3 CH3 -N X -(CH2) N (Mb) m 1 0- R9 CH3 CH3 CH3 CH3 CH3 -NoNO-CH2-N- (HIC) CH3 CH3 CH3 CH3 CH3 i N CH3 U113 in which R8 is Cl-C18alkyl, CS-C12cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by Cl-C4alkyl; GrC9phenylalkyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by Cl- C4alkyl; or 1,2,2,6,6-pentamethyl-4-piperidyl, m is an integer from 2 to 6, n is zero or 1, X is -0- or >N-CH3 and R9 is as defined above for Rg or is hydrogen, R2 is as defined for R8 or is hydrogen, R3 is C2- C12alkylene, C4-C12alkylene interrupted by 1, 2 or 3 oxygen atoms or by a group >N-CH3; CS-C7Cycloalkylene, C-5-C7cycloalkylenedi(C1-C4aHqlene), ClC4alkylenedi(C5-C7cycloalkylene), C2-C4alkylidenedi(C.5-C7cycloalkylene) or phenylenedimethylene, and R4 is C2-CI2alkylene, C4-C12alkylene interrupted by 1, 2 or 3 oxygen atoms; 2- hydroxytrimethylene, phenylenedimethylene, carbonyl, C2-Clsdiacyl, C4- C15dicarbarnoyl, a group -(CH2)p-CO- where p is an integer from 1 to 10, or a group -COO-Rlo-OOCwhere R10 is as defined for R3.

The co-oligomers according to the invention can have different end groups, depending on the type and molar ratios of the reagents used in the preparation.

In particular, the end group bound to the triazine ring of formula (Ia) in the following indicated as X, - is, for example, Cl, OH, ONa, OK or a group R, or a group -N-R3-N-CH3 1 ' and the end group bound to the nitrogen atom of the K2 CH3 1CH3 CH3 N CH3 1 CH3 formula (Ia) or (Ib) is, for example, methyl or a group X,-f.'( with X, being N N R1 as defined above, or a group -R40H.

In the individual respective groups of the formulae (Ia) and (Ib), the groups Rp R2, R3 and R4 can in each case be identical or different Examples of alkyl having not more than 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

Examples Of C2-C4alkyl substituted by Cl-Csalkoxy, preferably by ClC4alkoxy, in particular methoxy or ethoxy, are 2-methoxyethyl, 2ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3octoxypropyl and 4-methoxybutyl.

Examples Of C2-C4alkyl substituted by di(CI-C4alkyl)arnino, preferably by dimethylamino or diethylamino, are 2-dimethylaminoethyl, 2-diethylarninoethyl, 3- dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and 4- diethylaminobutyl.

A representative example of C2-C4OV1 substituted by a group of the formula (II) is the group of the formula A N - (CH2)2--4--. 0 N- (CH2)23- is preferred.

\-i \-j Examples of unsubstituted or substituted C.5-CI2cycloalkyl are cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tbutylcyclohexyl, cyclooctyl, cyclodecyl and cyclododecyl. Unsubstituted or Cl-C4alkyl-substituted cyclohexyl is preferred.

Examples of C3-C18alkenyl are allyl, 2-methylallyl, butenyl, hexenyl, decenyl, undecenyl and oleyl. Allyl is preferred. The carbon atom in position 1 is preferably saturated.

Examples of substituted phenyl are methylphenyl, dimethylphenyl, trimethylphenyl, t-butylphenyl, di-t-butylphenyl, 3,5-di-t-butyl-4methylphenyl, methoxyphenyl and ethoxyphenyl.

Examples of phenylalkyl which is unsubstituted or substituted on the phenyl are benzyl, methylbenzyI, dimethylbenzyI, trimethylbenzyI, tbutylbenzyl and 2-phenylethyl. Benzyl is preferred.

Examples Of C2-C12alkylene are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene, decamethylene and dodecamethylene.

Examples of C4-C12alkylene interrupted by 1, 2 or 3 oxygen atoms m 3oxapentane-1,5-diyl, 4-oxaheptane-1,7-diyl, 3,6-dioxaoctane-1,8-diyl, 4,7dioxadecane-1,10-diyl, 4,9-dioxadodecane-1,12-diyl and 3,6,9trioxaundecane-1,11-diyl.

A representative example of C4-C12alkylene R3 and R10 interrupted by a group >N-CH3 is the group - (CH2)2-6 - N - (CH2)2-6 CH3 Representative examples of groups having 1 or 2 CS-C7cycloalkylene groups are cyclohexylene, methylcyclohexylene, cyclohexylenedimethylene, methylenedicyclohexylene and isopropylidenedicyclohexylene.

Representative examples of C2-Clsdiacyl R4 are oxalyl, malonile, ethyImalonile, butyImalonile, benzyImalonile, succinyl, glutaryl, adipoyl, trimethyladipoyl, sebacoyl, oxydiacetyl, cyclohexanedicarbonyl, phthaloyl, isophthaloyl and terephthaloyl. C2-C,5alkanedioyl unsubstituted or substituted by benzyl; CrClsalkanedioyl wherein the alkane residue is interrupted by oxygen; (C.5-C7cycloaUme)dicarbonyl, phthaloyl, isophthaloyl and terephthaloyl are preferred.

Representative examples of C4--Clsdicarbamoyl R4 are hexamethylenedicarbamoyl, trimethylhexamethylenedicarbamoyl, cyclohexylenedicarbamoyl, phenylenedicarbamoyl, CH3 C H32 toluylenedicarbamoyl or a group -CONH or CH3 CH2NWO- CH2 NHC (C2-C13alkylene)dicarbamoyl, 2 (CS-C7cycloalkylene)dicarbamoyl, phenylenedicarbamoyl, toluylenedicarbamoyl and the CH3 CI-13 groups -CONH and CH2 0 MC are preferred.

2 CH3 CH2NHCO- Those co-oligomers are preferred which comprise recurring units of the formulae (Ia) and (Ib) having a number-average molecular weight from 1, 000 to 10,000 and a (Ia): (Ib) ratio from 3:1 to L3, in which R, is a group -OR5, -SRS or - N - R7 where R5, R6 and R7 1 R6 which can be identical or different are hydrogen, Cl-CMalkyl, CS- C8cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by Cl-C4alkyl; C3-C12alkenyl, phenyl which is unsubstituted or mono-, di- or tri-substituted by Cl-C4alkyl or Cl-C4alkoxy; benZY1 which is unsubstituted or mono-, di- or tri-substituted on the phenyl by ClC4alkyl; tetrahydrofurfuryl, 1,2,2,6,6-pcntametliyl-4-piperidyl or C2C3alkyl substituted in the 2- or 3-position by Cl-C4alkoxy, by di(C1C4alkyl)amino or by a group of the formula (11) in which A is a direct bond, -0-, -CH2- or -CH2CH2-, or R, is a group of the formula (II) or one of the groups of the formulae (IIIa)-(HIc) in which RS is Cl-C12alkyl, CSCScycloalkyl which is unsubstituted or mono-, di- or tri-substituted by Cl-C4alkyl; benzyl which is unsubstituted or mono-, di- or trisubstituted on the phenyl by Cl-C4alkyl; or 1,2,2,6,6-pentamethyl-4piperidyl, m is 2, 3 or 4, n is zero or 1, X is -0- or >N-CH3 and R9 is as defined above for R8 or is hydrogen, R2 is as defined above for R8 or is hydrogen, R3 is C2-Cloalkylene, C4-Cllene interrupted by 1, 2 or 3 oxygen atoms or by an >N-CH3 group; cyclohexylene, cyclohexylenedimethylene, methylenedicyclohexylene, isopropylidenedicyclohexylene or phenylenedimethylene, and R4 is C2- Cllene, C47-Cloalkylene interrupted by 1, 2 or 3 oxgyen atoms; 2- hydroxytrimethylene, phenylenedimethylene, carbonyl, Ci-Clodiacyl, C4- C12dicarbamoyl, a group -(CH2)pCOwhere p is an integer from 1 to 5, or a group -COO-Rlo-OOC- where R10 is as defined for R3.

Those co-oligomers are particularly preferred which comprise recurring units of the tP formulae (Ia) and (1b) having a number-average molecular weight from 1, 000 to 8,000 and a (Ia):(Ib) ratio from 2:1 to L3, in which R, is a group -ORS, -SR5 or -N- R7 where 1 R6 R5 is Cl-CUalkyl, cyclohexyl which is unsubstituted or mono-, di- or tri-substituted by Cl-C4alkyl; allyl, undecenyl, phenyl, benzyl, tetrahydrofurfuryl or 1,2,2,6,6-pentamethyl-4-piperidyl, R,6 and R7 which can be identical or different are as defined above for R5 or are hydrogen or C2-C3alkyl substituted in the 2- or 3-position by Cl-C4alkoxy, by dimethylainino, by diethylainino or by a 4-morpholinyl group, or R, is 4- morpholinyl or one of the groups of the formulae (IIIa)-(HIc) in which R8 is Cl-C8alkyl, cyclohexyl which is unsubstituted or mono-, di- or tri- substituted by Cl-C4alkyl; benZY1 or 1,2,2,6,6-pentamethyl-4-piperidyl, m is 2 or 3, n is zero or 1, X is -0- or >N-CH3 and R9 is as defined above for R8 or is hydrogen, R2 is as defined for Rg or is hydrogen, R3 'S C2-C8alkylene, C6-Cloalkylene interrupted by 2 or 3 oxygen atoms; cyclohexylenedimethylene, methylenedicyclohexylene or phenylenedimethylene, and R4 is C2-C8alkylene, C47C8alkylene interrupted by 1 or 2 oxygen atoms; 2-hydroxytrimethylene, phenylenedimethylene, carbonyl, C2-C8diacyl, C4-Clodicarbamoyl, a group -(CH2)pCO- where p is 1, 2 or 3, or a group -COO-Rlo-OOCwhere Rio is as defined for R3.

Those co-oligomers are of special interest which comprise recurring units of the formulae (Ia) and (Ib) having a number-average molecular weight from 1,500 to 6,000 and a (1a):(Ib) ratio from 2:1 to L2, in which R, is a group -ORS or -N- R7 where R-5 is 1 R6 Cl-C8alkyl, cyclohexyl, allyl, benzyl, tetrahydrofurfuryl or 1,2,2,6,6- pentainethyl-4-piperidyl, R6 and R7 which can be identical or different are as defined above for R5 or are hydrogen, or R, is 4-morpholinyl or one of the groups of the formulae (H1a)-(J11c) in which R8 is 1,2,2,6,6- pentamethyl-4-piperidyl, m is 2, n is zero or 1, X is -0- or >N-CH3 and R9 is hydrogen or 1,2,2,6,6-pentarnethyl-4-piperidyl, R2 is hydrogen, methyl or 1,2,2,6,6-pentamethyl-4-piperidyl, R3 'S C2-C6alkylene, C6- Cloalkylene interrupted by 2 or 3 oxygen atoms; cyclohexylenedimethylene, methylenedicyclohexylene or phenylenedimethylene, and R4 is C2-C6alkylene, 2-hydroxytdmethylene, phenylenedimethylene, C2-C6diacyl, -CH2CO- or a group -COO-Rlo-OOC- where Rjo is C4-C6alkylene.

Those co-oligomers are of particular interest which comprise recurring units of the formulae (Ia) and (Ib) having a number-average molecular weight from 2,000 to 5,000 and a (Ia): (Ib) ratio from 1: 1 to L2, in which R, is a group -ORS or - N - R7 where RS is 1 R6 Cl-C4alkyl or tetrahydrofurfuryl, R6 and R7 which can be identical or different are Cl-C8alkyl, cyclohexyl or 1,2,2,6,6-pentamethyl-4-piperidyl or R6 can also be hydrogen, or R, is 4-morpholinyl or a group of the formula (II1a) where n is zero, R2 is 1,2,2,6,6-pentamethyl-4-piperidyl, R3 is a group -(CH2)2-6- or -(CH2)3-0-(CH2)2-4-0-(CH2)3- and R4 is 2hydroxytrimethylene.

The compounds of the present invention can be prepared by processes known per se, e.g.

by N-methylation of the corresponding co-oligomeric compounds comprising 2,2,6,6-tetramethylpiperidine groups, using any of the known Nmethylation processes, for example by reacting the 2,2,6,6tetramethylpiperidine compounds with formaldehyde and formic acid, operating in water or in an aromatic hydrocarbon solvent, or by reacting them with formaldehyde and hydrogen in the presence of a hydrogenation catalyst such as Pt, Pd, or Ni, as described in US-A-4 459 395, EP-A-319 480 and EP-A-365 469.

The co-oligomers not methylated in the 1-position of the 2,2,6,6tetramethylpiperidine groups can be prepared by known processes, for example as described in US-A-4 547 548.

The co-oligomers of the present invention are highly efficacious in improving the light-stability, heat-stability and oxidation-stability of organic materials, especially synthetic polymers, for example the polyolefins.

In particular, the remarkable light-stabilising action in polypropylene, especially in the form of fibres, is surprising.

Examples of organic materials which can be stabilised are:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-l-ene, poly-4-methylpent-l-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

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 M, Vb, VIb or VHI 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 cy-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) 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 beeing elements of groups Ia, Ha andlor IlIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst stystems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/WPE, PP/WPE) and mixtures of different types of polyethylene (for example LDPE/HWE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylenelpropylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylenelbut1-ene copolymers, propylenelisobutylene copolymers, ethylenelbut-l-ene copolymers, ethylenelhexene copolymers, ethylenelmethylpentene copolymers, ethylene/heptene copolymers, ethyleneloctene copolymers, propylenelbutadiene copolymers, isobutylenelisoprene copolymers, ethylene/alkyl acrylate copolymers, ethylenelalkyl methacrylate copolymers, ethylenelvinyl 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-norbomene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylenelethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylenelcarbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example C,5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.

5. Polystyrene, poly(p-methylstyrene), poly((X-methylstyrene).

6. Copolymers of styrene or oc-methylstyrene with dienes or acrylic derivatives, for example styrenelbutadiene, styrenelacrylonitrile, styrene/alkyl methacrylate, styrene/butadienelalkyl acrylate, styrenelbutadienelalkyl methacrylate, styrenelmaleic anhydride, styrenelacrylonitrilelmethyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propyleneldiene terpolymer; and block copolymers of styrene such as styrenelbutadienelstyrene, styrenelisoprenelstyrene, styrenelethylenelbutylenelstyrene or styrenelethylenelpropylene/ styrene.

7. Graft copolymers of styrene or a-methylstyrene, for example styrene on polybutadiene, styrene, on polybutadiene-styrene or polybutadieneacrylonitrile 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 acrylatelbutadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloridelvinylidene chloride, vinyl chloridelvinyl acetate or vinylidene chloridelvinyl acetate copolymers.

9. Polymers derived from (x,p-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 acrylonitrilel butadiene copolymers, acrylonitrilelalkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrilelvinyl halide copolymers or acrylonitrilel 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.

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.

15. 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 andlor from aminocarboxylic acids or the corresponding lactains, for example polyamide 4, polyamide 6, polyamide 616, 6110, 619, 6112, 416, 12112, polyamide 11, polyamide 12, aromatic polyamides starting from mxylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic orland terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,trimethylhexamethylene terephthalamide or poly-m-phenylene 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 and polybenzimidazoles.

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

19. Polycarbonates and polyester carbonates.

20. 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 phenoYformaldehyde resins, urealforinaldehyde resins and melaminelforinaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and 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, polylsocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides.

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.

28. Blends of the aforementioned polymers (polyblends), for example PP/EMM, Polyamide/EPDM or ABS, PVCIEVA, PVCIABS, PVCIMBS, PC/ABS, PBTPIABS, PC/ASA, PC/PBT, PVC/CPE, PVClacrylates, POMIthermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.

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 (e.g. 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 styrenelbutadiene copolymers.

The compounds of the present invention can be used in mixtures with organic materials in various proportions depending on the nature of the material to be stabilised, on the end use and on the presence of other additives.

In general, it is appropriate to use, for example, 0.0 1 to 5 % by weight of the compounds of the present invention, relative to the weight of the material to be.stabilised, preferably between 0.05 and 1 %.

In general, the compounds of the present invention can be added to the polymeric materials before, during or after the polymerisation or crosslinking of the said materials.

The compounds of the present invention can be incorporated in the polymeric materials, for example, in the pure form or encapsulated in waxes, oils or polymers.

The compounds of the present invention can be incorporated in the polymeric materials by various processes, such as dry mixing in the form of powder, or wet mixing in the form of solutions or suspensions or also in the form of a masterbatch; in such operations, the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.

The materials stabilised with the products of the present invention can be used for the production of mouldings, films, tapes, monofilaments, fibres, surface coatings and the like.

If desired, other conventional additives for synthetic polymers, such as antioxidants, UV absorbers, nickel stabilisers, pigments, fillers, plasticisers, antistatic agents, flameproofing agents, lubricants, corrosion inhibitors and metal deactivators, can be added to the mixtures of the compounds of the present invention with the organic materials.

Particular examples of additives which can be used in admixture with the compounds of the formula (1) are:

1. Antioxidants 1. 1. AlkLIated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di- tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6- dicyclopentyl-4-methylphenol, 2-((x-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tertbutyl-4-methoxymethylphenol, 2,6-di-nonyl-4methylphenol, 2,4-dimethyl6(1'-methylundec-l'-yl)phenol, 2,4-diinethyl-6-(1'-methylheptadec-l'yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-;1!-yl)phenoI and mixtures thereof.

1.2. Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tertbutylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroguinones and glkLIated hydroquinones, for example 2,6-di-tertbutyl-4methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tertamylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tertbutylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-dite.rt-butyl-4-hydroxyphenyl) adipate.

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

1.5. ALkylidenebisl)henols, for example 2,2-methylenebis(6-tert-butyl-4methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'methylenebis[4-methyl-6-(a-methyl- cyclohexyl)phenoll, 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tertbutylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-((xmethylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(oc,(x-dimethylbenzyl)4nonylphenoll, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'methylenebis(6-tertbutyl-2-methylphenol), 1,1-bis(S-tert-butyl-4-hydroxy2-methylphenyl)butane, 2,6-bis(3tert-butyl-5-methyl-2-hydroxybenzyl)-4methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy2-methylphenyl)butane, 1,1bis(S-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyratel, bis(3tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3'tert-butyl-2'-hydroxy5'-methylbenzyl)-6-tert-butyl-4-methylphenyllterephthalate, 1,1-bis-(3,5-dimethyl-2hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5tert-butyl4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5tertbutyl4-hydroxy2-methylphenyl)pentane.

1.6. 0-, N- and S-benzyl compounds for example 3,5,3',5'-tetra-tert-butyl4,4-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5dimethylbenzylmercaptoacetate, tris-(3,5-di-tertbutyl-4hydroxybenzyl)arnine, bis(4-tert-butyl-3-hydroxy-2,6dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4hydroxybenzyl)sulfide, isooctyl-3,5di-tert-butyl4hydroxybenzyImercaptoacetate.

1.7. Hydroxybenzylated malonates. for example dioctadecyl-2,2-bis-(3,5-ditert-butyl-2hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4hydroxy-5-methylbenzyl)-malonate, di-dodecylmercaptoethyl-2,2-bis-(3,5-ditert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3tetrainethylbutyl)phenyll-2,2-bis(3,5-di-tert-butyl-4-hydroxy benzy1)malonate.

1.8. Aromatic hydroxybenzyi compounds, for example 1,3,5-tris-(3,5-ditert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tertbutyl-4-hydroxybenzyl)-2,3,5,6tetramethylbenzene, 2,4,6-tris(3,5-di-tertbutyl-4-hydroxybenzyl)phenol.

1.9. Triazine Compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tertbutyl-4hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-ditert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5di-tert-butyl-4-hydroxyphenoxy)1,3,5-triazine,.2,4,6-tris(3,5-di-tertbutyl-4-hydroxyphenoxy)-1,2,3-triazin e, 1,3,5-tris(3,5-di-tert-butyl-4hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4hydroxyphenylethyl)-1,3,5-tri- azine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-l, 3,5-triaz ine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1. 10. BenUlphosphonates. for example dimethyl-2,5-di-tert-butyl4hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4hydroxybenzylphosphonate, dioctadecyl3,5-di-tertbutyl-4hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy3methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5di-tert-butyl-4-hydroxybenzylphosphonic acid.

1. 11. Acylaminophenols, for example 4-hydroxylauranilide, 4hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4hydroxyphenyl)carbainate.

1. 12. Esters of P-(3,5-di-tert-buylhydroxyi)hl propionic acid with monoor polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6hexanediol, 1,9"-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tds(hydroxyethyl) isocyanurate, N,Wbis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- 1-phospha-2,6,7trioxabicyclo[2.2.21 octane.

1. 13. Esters of 5-(5-tert-buyl-4-hvdroxy-3-methylphenyl)T)ropionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,Wbis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- 1-phospha-2,6,7trioxabicyclo[2.2.21 octane.

1. 14 Esters of @-(3,5-dicyclohexvl-4-hydroxyphenyI ropionic acid w! monoor poly )v th hydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, NNbis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- 1-phospha-2,6,7trioxabicyclo[2.2.21 octane.

1. 15 Esters of 3,5-di-terL-butyl-4_-hydronpheLiyl acetic acid with monoor polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,Mbis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7trioxabicyclo[2.2.2]octane.

1. 16. Amides of P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N, -bis(3,5-ditert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,M-bis(3,5-di-tert-butyl- 4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl- 4-hydroxyphenylpropionyl)hydrazine.

2. UV absorbers and light stabilisers 2.1. 2-(2'-HydronpheLiyl)benzotriazoles, for example 2-(2'-hy.droxy-5'methylphenyl)benzotriazole, 2(3',5'-di-tert-butyl-2hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl2'hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5'-(1,1,3,3tetrainethylbutyl)pheny1)benzotriazole, 2-(3,5'-di-tert-butyl-2'hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl2'-hydroxy-5'methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'octyloxyphenyl)benzotriazole, 2-(T'Sl_ di-tert-ainyl-2'hydroxyphenyl)benzotriazole, 2-(3',5'-bis-((x,(x-dimethylbenzyl)-2'hydroxyphenyl)benzotriazole, mixture of 2-(3'-tert-butyl-2'-hydroxy-5-(2octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-S'(2methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl2'-hydroxy-5'-(2methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tertbutyl-2'-hydroxy-5'-(2-octyl- oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2- ethylhexyloxy)carbonylethyl] -2'-hydroxyphenyl)benzotriazole, 2-(3'dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-(3'-tert-butyl-2'hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenoll; the transesterification product of 2-[3'-tert-butyl-5'-(2methoxycarbonylethyl)-2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)3J1-, where R = 3'-tert-butyl4-hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and Thydroxy-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(4tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4- di-tertbutylphenyl 3,5-di-tert-butyl4-hydroxybenzoate, hexadecyl 3,5-di- tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tertbutyl-4- hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4- hydroxybenzoate.

2.4. Acrylates, for example ethyl (x-cyano-p,p-diphenylacrylate, isooetyl (X-cyano-P,P-diphenylacrylate, methyl (x-carbomethoxycinnainate, methyl (x-cyano-p-methyl-p-methoxycinnamate, butyl (x-cyano-p-methyl-p-methoxycinnamate, methyl ot-carbomethoxy-pmethoxycinnamate and N-(0-carbomethoxyo-cyanovinyl)-2-methylindoline.

2.5. 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 n-butylamine, triethanolamine or Ncyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4hydroxy-3,5-ditert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1 -phenyl-41auroyl-5hydroxypyrazole, with or without additional ligands.

2.6. Stericgk hindered amines, for example bis(2,2,6,6-tetramethylpiperidyl)sebacate, bis(2,2,6,6-tetramethyl-piperidyl)succinate, bis(1,2, 2,6,6pentamethylpiperidyl)sebacate, bis(1,2,2,6,6-pentamethylpiperidy1) nbutyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4piperidyl)hexamethylenediarnine and 4-tert-octylamino-2,6-dichloro-1,3,5triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4- piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)bis(3,3,5,5tetramethylpiperazinone), 4-benzoyl-2,2,6,6tetramethylpiperidine, 4stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butyl benzyl)malonate, 3-n-octyl7,7,9,9-tetramethyl-1,3,8-triazasprio[4.5]decan2,4-dion, bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(loctyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate of N,N'bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6bis(4-n-butylainino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-nbutylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3aininopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-l-(2,2,6,6tetramethyl-4piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-l-(1,2,2,6,6pentamethyl-4-piperidyl)pyrrolidine-2,5-dione.

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

2.8. 2-(2-Hydroxvphenyl)-1,3,5-triazines, for example 2,4,6-tris(2hydroxy-4-octyloxyphenyl)- 1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)4,6-bis(2,4-dimethylphenyl)1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6bis(2,4-diinethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, -[2-hydroxy4-(2hydroxy3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5triazine, 2-[2-hydroxy-4-(2hydroxy-3-octyloxy-propyloxy)phenyll-4,6-bis(2,4dimethyl)-1,3,5-triazine.

3. Metal deactivators. for example N,W-diphenyloxamide, Nsalicylal-N'salicyloyl hydrazine, N,N'-bis(salicyloyl) hydrazine, NN'-bis(3,5-di-tertbutyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,M-diacetyladipoyl dihydrazide, N,M-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Further phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritoldiphosphite,bis(2,4-di-tert-butylphenyl) pentacrythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaeryt hritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,.bis(2,4, 6-tris(tert-butylphenyl)pentaerythritoI diphsophite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3, 2-dioxaphosphocin, 6-fluoro2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tertbutyl-6-methylphenyl)methylphosphite, bis(2,4-di-tertbutyl-6-methylphenyl)ethylphosphite.

5. Peroxide scavengers, for example esters of P-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.

6. Polyamide stabilisers, for example, copper salts in combination with iodides andlor phosphorus compounds and salts of divalent manganese.

7. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, 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 tin pyrocatecholate.

8. Nucleating agents,, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

9. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxydes, carbon black, graphite.

10. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

11. Benzofuranones and indolinones for example those disclosed in US-A-4 325 863 or US-A-4 338 244.

The compounds of the invention can also be used as stabilisers, especially as light-stabilisers, for almost all materials known in the art of photographic reproduction and other reproduction techniques as e.g. described in Research Disclosure 1990, 31429 (pages 474 to 480).

21 - Several examples of the preparation and use of the co-oligomers comprising recurring units of the formula (Ia) and (1b) are reported for more detailed illustration of the present invention; these examples are given solely for illustrative purposes and do not imply any restriction.

The compounds described in Examples 1, 3, 4, 7 and 8 relate to a particularly preferred embodiment of the present invention.

Example 1: 20.8 g (0.1 mol) of 2,4-dichloro-6-isopropoxy-1,3,5-triazine, 9.3 g (0.1 mol) of epichlorohydrin, 82.9 g (0.21 mol) of N,N'-bis(2,2,6,6tetramethyl-4-piperidyl)-1,6-hexanediatnine and 100 mI of. 4-methyl-2pentanol are heated for one hour at 800C and for 8 hours under rflux, 12 g (0.3 mol) of NaOH being added slowly during the last 6 hours of the reaction.

After the completion of the addition of NaOH, the reaction mixture is heated under reflux for a further 2 hours. The water of reaction and a major part of the 4-methyl-2-pentanol then distill off, 400 mI of xylene are added, and 100 mI of solvent are slowly distilled off to complete the removal of the 4-methyl-2-pentanol.

A mixture containing 21.2 g (0.46 mol) of formic acid and 14.4 g (0.48 mol) of methanol-free 30 % formaldehyde is added in 3 hours to the xylene solution thus obtained, heated to 1 101C, with simultaneous azeotropic removal of the water added and of the water of reaction.

The mixture is cooled to 7TC, a solution of 3 g of NaOH in 60 mI of water is added, and stirring is carried out for 30 minutes. The aqueous layer is separated off, and the organic phase is washed with water, dried over Na2S04 and evaporated under reduced pressure.

This gives a product melting at 77850C and having a number-average molecular weight of Mn = 2800.

Example 2: Following the procedure described in Example 1, a compound melting at 78-88'C and having a number-average molecular weight of Mn = 3800 is obtained by reaction of 22.2 g (0. 1 mol) of 2-butoxy-4,6-dichloro- 1,3,5- triazine, 9.3 g (0. 1 mol) of epichlorohydrin and 78.9 (0.2 mol) of N,N'bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine in 100 mI of 4methyl-2-pentanol and subsequent methylation in xylene with the formic acid/formaldehyde mixture indicated in Example 1.

Example 3: Following the procedure described in Example 1, a compound melting at 103-1120C and having a number-average molecular weight of Mn = 3500 is obtained by reaction of 22.1 g (0.1 mol) of 2,4-dichloro-6-diethylamino-1, 3,5-triazine, 9.3 g (0.1 mol) of epichlorohydrin and 78.9 g (0.2 mol) of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine in 100 mI, of 4-methyl-2-pentanol and subsequent methylation in xylene with the formic acid/formaldehyde mixture indicated in Example 1.

Example 4: Following the procedure described in Example 1, a compound melting at 110-1 170C and having a number-average molecular weight of Mn = 4000 is obtained by reaction of 27.7 g (0. 1 mol) of 2,4-dichloro-6-t-octylamino- 1,3,5-triazine, 9.3 g (0. 1 mol) of epichlorohydrin and 78.9 g (0.2 mol) of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine in 100 mI of 4-methyl-2-pentanol and subsequent methylation in xylene with the formic acid/formaldehyde mixture indicated in Example 1.

Example 5: Following the procedure described in Example 1, a compound melting at 94-1020C and havino, a number-average molecular weight of Mn = 4100 is obtained by reaction of 24.7 g (0.1 mol) of 2,4-dichloro-6cyclohexylamino-1,3,5-triazine, 18.5 g (0.2 mol) of epichlorohydrin and 118.4 g (0.3 mol) of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6hexanediamine in 150 mI of 4-methyl-2-pentanol and subsequent methylation in xylene with a mixture comprising 31.8 g (0.69 mol) of formic acid and 72.1 g (0.72 mol) of methanol-free 30 % formaldehyde.

Example 6: Following the procedure described in Example 1, a compound melting at 75-84'C and having a number-averagge molecular weight of Mn = 2200 is obtained by reaction of 25 g (0.1 mol.) of 2,4-dichloro-6-tetrahydrofurfuryloxy-1,3,5- triazine, 9.3 g (0. 1 mol) of epichlorohydrin and 88.8 g (0.225 mol.) of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediainine in 110 mI of 4-methyl-2-pentanol and subsequent methylation in xylene with the formic acid/formaldehyde mixture indicated in Example 1.

Examffle 7: Following the procedure described in Example 1, a compound melting at 100- 103 OC and having a number-average molecular weight of 1WE = 2000 is obtained by reaction of 18.7 g (0.05 mol.) of 2,4-dichloro6-[N-(2,2,6,6-tetramethyl4-piperidyl)piperazinol-1,3,5-triazine, 4.6 g (0. 05 mol) of epichlorohydrin and 41.4 g (0.105 mol) of N,W-bis (2,2,6,6tetramethyl-4-piperidyl)-1,6-hexanediamine in 75 mI of 4-methyl-2pentanol and subsequent methylation in xylene with the formic acid/formaldehyde mixture indicated in Example 1.

Example 8: Following the procedure described in Example 1, a compound melting at 105-109'C and having a number-average molecular weight of 1M = 3150 is obtained by reaction of 11.7 g (0.05 mol) of 2,4-dichloro-6morpholino-1,3,5-triazine, 4.6 g (0.05 mol) of epichlorohydrin and 41.4 g (0.105 mol) of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)1,6-hexanediamine in 75 mI of 4-methyl-2-pentanol and subsequent methylation in xylene with the formic acid/formaldehyde mixture indicated in Example 1.

In the examples, the number-average molecular weight was determined by means of a vapour pressure osmometer (OGonotec) as described in EP-A-255 990.

Example 9: (Light-stabilising action in polypropylene fibres) 2.5 g of each of the products indicated in Table 1, 1 g of tris(2,4-di-tbutylphenyl) phosphite, 0.5 g of calcium monoethyl 3,5-di-t-butyl-4hydroxybenzylphosphonate, 1 g of calcium stearate and 2.5 g of titanium dioxide are mixed in a slow mixer with 1000 g of polypropylene powder of melt index = 12 g/10 minutes (measured at 2301C and 2.16 kg).

The mixtures are extruded at 200-2301C to give polymer granules which are then converted into fibres, using a pilot-type apparatus (OLeonardSumirago(VA) Italy) operating under the following conditions:

extruder temperature 200-230C head temperature 255-2600C stretch ratio 1: 3.5 count 11 dtex per filainent The fibres thus prepared are exposed, mounted on a white card, in a model 65 WR Weather-0-Meter (ASTM D2565-85) with a black panel temperature of 63'C.

The residual tenacity is measured on samples taken after various times of exposure to light by means of a constant-speed tensometer, and the exposure time in hours (T50) needed to halve the initial tenacity is then calculated.

Fibres prepared under the same conditions as indicated above, but without addition of the stabilisers of the invention, are exposed for comparison.

The results obtained are shown in Table 1.

TABLE 1

Stabiliser T50ALOP-r-81 None 190 Compound from Example 1 2080 Compound from Example 2 1980 Compound from Example 3 2050 Compound from Example 4 2000 Compound from Example 5 1970 Compound from Example 6 2010

Claims (13)

WHAT IS CLAIMED IS:

1. A co-oligomer comprising recurring units of the formulae (Ia) and (1b) N R4-N R3- N 1"6'"1--N-R3-N- 1 1 R2 K2 CH.3 CH3 CH3 ICH3 R1 CH3 N CH3 CH3 N CH3 1 1 CH3 (Ia) kjt3 (Ib) having a number-average molecular weight from 1,000 to 20,000 and a (Ia):(Ib) ratio from 4:1 to 1A, in which R, is. a group -OR5, -SRS or - N - R7, where R5, R6 and R7 which 1 R6 can be identical or different are hydrogen, Cl-C18alkyl, C5-CI2cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by Cl-C4alkyl; C3C18alkenyl, phenyl which is unsubstituted or mono-, di- or trisubstituted by Cl-C4alkyl or Cl-C4alkoxy; C7-C-9phenylallcyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by ClC4alkyl; tetrahydrofurfuryl, 1,2,2,6,6-pentamethyl-4-piperidyI or C2C4alIVI. substituted in the 2-, 3- or 4-position by Cl-C8alkoxy, by di(C1- C4alkyl)ainino or by a group of the formula (H) A N - (jj) \-i where A is a direct bond, -0-, -CH2-, -CH2CH27 or >N-CH3, or R, is a group of the formula (R) or one of the groups of the formulae (HIa)-(IIIc) CH3 CH3 (H1a) CH3 -N N N - -(CH2) - N m 1 X8 CH3 CH3 CH3 CH3 CH3 -N -X-(CH2) -N (HIb) rn 1 } R9 CH3 CH3 CH3 CH3 CH3 -No- ND-CH27-N- (HIC) CH3 CH3 Cl-13 CH3 CH3 N CH3 1 CH3 in which Rg is Cl-CIgalkyl, CS-C12cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by Cl-C4alkyl; C7-C9phenfialkyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by Cl- C4alkyl; or 1,2,2,6,6-pentamethyl-4-piperidyl, m is an integer from 2 to 6, n is zero or 1, X is -0- or >N-CH3 and R9 is as defined above for R8 or is hydrogen, R2 is as defined for Rg or is hydrogen, R3 is C2- C12alkylene, C4-C12alkylene interrupted by 1, 2 or 3 oxygen atoms or by a group >N-CH3; C5-C7eycloalkylene, CS-C7cycloalkylenedi(C1-C4alkylene), Cl- C4alkylenedi(C5-C7cycloalkylene), C27C4alkylidenedi(C5-C7cyclodkylene) or phenylenedimethylene, and R4 is C2-C12a.kylene, C47C12alkylene interrupted by 1, 2 or 3 oxygen atoms; 2-hydroxytrimethylene, phenylenedimethylene, carbonyl, C27C15diacyl, C47C15dicarbarnoyl, a group -(CH2)p-CO- whefe p is an integer from 1 to 10, or a group -COO-Rlo-OOC- where R10 is as defined for R3.

2. A co-oligomer comprising recurring units of the fonnulae (1a) and (Ib) according to claim 1, having a number- average molecular weight from 1,000 to 10,000 and a (1a):(1b) ratio from 3:1 to L3, in which R, is a group -ORS, -SR_5 or -N - R7 where RS, R.6 and 1 R6 R7 which can be identical or different are hydrogen, Cl-CMalkYL CS- C8CYCI0alkyl which is unsubstituted or mono-, di- or tri-substituted by Cl-C4alkyl; C3-CI2alkenyl, phenyl which is unsubstituted or mono-, di or td-substituted by Cl-C4alkyl or Cl-C4alkoxy; benzyl which is unsubstituted or mono-, di- or tri-substituted on the phenyl by Cl- C4alkyl; tetrahydrofurfuryl, 1,2,2,6,6-pentamethyl-4-piperidyl or C2-C3alkyl substituted in the 2- or 3-position by Cl-C4alkoxy, by di(CI- C4alkyl)amino or by a group of the formula (H) in which A is a direct bond, -0-, -CH2- or -CH2CH2-, or R, is a group of the formula (II) or one of the groups of the formulae (IIIa)-(11Ic) in which R8 is Cl-CUalkyl, CS- C8cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by Cl-C4alkyl; benzyl which is unsubstituted or mono-, di- or tri- substituted on the phenyl by Cl-C4alkyl; or 1,2,2,6,6-pentamethyl-4- piperidyl, m is 2, 3 or 4, n is zero or 1, X is -0- or >N-CH3 and R9 is as defined above for R8 or is hydrogen, R2 is as defined above for R8 or is hydrogen, R3 'S C2-Cloalkylene, C4-Cloalkylene interrupted by 1, 2 or 3 oxygen atoms or by an >N-CH3 group; cyclohexylene, cyclohexylenedimethylene, methylenedicyclohexylene, isopropylidenedicyclohexylene or phenylenedimethylene, and R4 is C2- CloaUcylene, C4-Cloalkylene interrupted by 1, 2 or 3 oxe, en atoms; 2- hydroxytrimethylene, tly phenylenedimethylene, carbonyl, C2-Clodiacyl, C4-CUdicarbamoyl, a group (CH2)pCOwhere p is an integer from 1 to 5, or a group -COO-Rlo-OOC- where R10 is as defined for R3.

3. A co-oligomer comprising recurring units of the formulae (Ia) and (Ib) according to claim 1, having a number-average molecular weight from 1,000 to 8,000 and a (Ia):(Ib) ratio from 2:1 to L3, in which R, is a group ORS, -SR5 or - N R7 where R5 is 1 R6 Cl-CUalkyl, cyclohexyl which is unsubstituted or mono, di- or tri- substituted by ClC4alkyl; allyl, undecenyl, phenyl, benzyl, tetrahydrofurfuryl or 1,2,2,6,6-pentamethyl-4-piperidyl, R6 and R7 which can be identical or different are as defined above for R.5 or are hydrogen or C2C3alkyl substituted in the 2- or 3-position by Cl-C4alkoxy, by dimethylamino, by diethylamino or by a 4-morpholinyl group, or R, is 4- morpholinyl or one of the groups of the formulae (1Ha)-(nlc) in which R8 is Cl-C8alkyl, cyclohexyl which is unsubstituted or mono-, di- or tri- substituted by Cl-C4alkyl; benzyl or 1,2,2,6,6-pentamethyl-4-piperidyl, m is 2 or 3, n is zero or 1, X is -0- or >N-CH3 and R9 is as defined above for R8 or is hydrogen, R2 is as defined for Rg or is hydrogen, R3 is C2- C8alkylene, C6-Cloalkylene interrupted by 2 or 3 oxygen atoms; cyclohexylenedimethylene, methylenedicyclohexylene or phenylenedimethylene, and R4 'S C2-Cgalkylene, C4-C8alkylene interrupted by 1 or 2 oxygen atoms; 2-hydroxytrimethylene, phenylenedimethylene, carbonyl, C2-C8diacyl, C4-Clodicarbamoyl, a group -(CH2)pCO- where p is 1, 2 or 3, or a group -COO-Rlo-OOCwhere R10 is as defined for R3.

4. A co-oli. th rm accordina to gomer comprising recurring units of a fo ulae (Ia) and (Ib) 1- claim 1, having a number-average molecular weight from 1,500 to 6,000 and a Qa):(Ib) ratio from 2:1 to 12, in which R, is a group -OR.5 or -N- R7 where R_5 is Cl-Qgalkyl, R6 cyclohexyl, allyl, benzyl, tetrahydrofurfuryl or 1,2,2,6,6-pentamethyl- 4-piperidyl, Rc, and R7 which can be identical or different are as defined above for R5 or are hydrogen, or R, is 4-morpholinyl or one of the groups of the formulae (IIIa)-(IIIc) in which R8 is 1,2,2,6,6- pentamethyl-4-piperidyl, m is 2, n is zero or 1, X is -0- or >N-CH3 and E 9 is hydrogen or 1,2,2,6,6-pentamethyl-4-piperidyl, R2 is hydrogen, methyl or 1,2,2,6,6-pentamethyl-4-piperidyl, R3 is C27C6alkylene, C6- Cloalkylene interrupted by 2 or 3 oxygen atoms; cyclohexylenedimethylene, methylenedicyclohexylene or phenylenedimethylene, and R4 is C2-C6alkylene, 2-hydroxytrimethylene, phenylenedimethylene, C2-C6diacyl, -CH2CO- or a group -COORIO-OOC- where RIO is C4-C6alkylene.

5. A co-oliggomer comprising recurring units of the formulae (Ia) and (Ib) according to claim 1, having a number-average molecular weight from 2,000 to 5,000 and a (Ia):(Ib) Z ratio from 1: 1 to L2, in which R, is a group -ORS or -N - R7 where R.5 is Cl-C4alkyl 1 R6 or tetrahydrofurfuryl, R6 and R7 which can be identical or different are Cl-C8alkyl, cyclohexyl or 1,2,2,6,6-pentamethyI-4-piperidy1 or IZ6 can also be hydrogen, or R, is 4-morpholinyl or a group of the formula (HIa) where n is zero, R2 is 1,2,2,6,6-pentametliyl-4-piperidyl, R3 is a group -(CH2)2-6- or -(CH2)3-0-(CH2)2-4-0-(CH2)3- and R4 is 2- hydroxytrimethylene.

6. A composition comprising an organic material susceptible to degradation induced by light, heat and oxidation and at least one co- oligomer comprising recurring units of the formulae (k) and (Ib) according to any one of claims 1 to 5.

C

7. A composition according to claim 6, wherein the organic material is a synthetic polymer.

8. A composition according to claim 7, comprising other conventional additives for 4t) ZZ synthetic polymers, in addition to the co-oligomers comprising recurring units of the formulae (1a) and (1b).

9. A composition according to claim 6, wherein the organic material is a polyolefm.

10. A composition according to claim 6, wherein the organic material is polyethylene or polypropylene.

11. Ile use of a co-oligomer comprising recurring units of the formulae (1a) and (Ib) according to claim 1 for stabilising an organic material against-degradation induced by light, heat and oxidation.

12. A co-oligomer according to claim 1 substantially as hereinbefore described with reference to any one of Examples 1 to 8.

13. A composition according to claim 6 substantially as tereinbefore described with reference to Example 9.