DE2648701A1 - FLAME RETARDANT CHLORINE-BASED ALIPHATIC POLYMERS - Google Patents

Description

ClSA-GEiGY AG, Essel, Switzerland Case 5-

/ 3VLA 1652/1 + 2

Germany

26Α8701

DR.RRLEND DINNi PATKNTANVv ¹ ALT 2 8 BREMEN

UHLANDbTRASSE

Flame retardant ^ chlorine-containing aliphatic polymeric masses

0 9 8 1 8/1 IU

26A8701 J *

The present invention relates to novel flame retardants Compounds based on aliphatic polymers containing chlorine. In particular, it relates to polymers and Copolymers based on vinyl chloride.

Usually, the flame retardancy is plasticized PVC * s by adding phosphorus, halogen, antimony, boron or aluminum-containing compounds are improved. For example, phosphate esters or antimony oxide are used for this.

It has now surprisingly been found that the flame retardancy of PVC and in particular of plasticized PVC can be largely improved by novel flame-retardant compounds.

In particular, the flame-relieving effect can be determined Phosphoric acid esters or other aromatic esters significantly improved through the use of certain other additives will. This allows either better flame resistance without increasing the phosphorus content or the same Achieve flame resistance with lower phosphorus content. Furthermore, in some cases where flame retardant ingredients are used are present by the inventive compositions achievable flame retardancy better than would be expected based on the total content of the flame retardant components.

This invention therefore relates to compositions based on a chlorine-containing aliphatic polymer, which are characterized by the fact that they

a) an ester of a phosphorus acid, an aromatic one Carboxylic acid esters, sulfonic acid esters or carbonic acid esters or

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a mixture of these, and

b) a compound of formula I.

R (CH ₂ X) _n (I)

in which R denotes an aromatic carbon radical or heterocyclic radical, η an integer of at least 2 and the X are the same or different and each represent a leaving group.

The chlorine-containing aliphatic polymer is preferably a thermoplastic.

In the compounds of the formula I, each aromatic or heterocyclic ring can contain 0 to 6, preferably 1 to 3 and particularly preferably 1, -CHpX groups, provided that at least 2 -CHpX groups are present in the molecule.

Thus, η can be from 2 to 12, preferably from 2 to 6 and particularly preferably from 2 to 4.

The aromatic nucleus preferably has a free ortho position adjacent to the -CHpX group, and the The position of the latter is preferably such that intramolecular ring closure is prevented.

The leaving group X in formula I is halogen, -OH, -SH, -NH ₂ , -CO ₂ H, -PO ₃ H ₂ , OB (OH) ₂ and their derivatives, e.g. ^{-OR 1 , -SR 1} , - NHR ¹ , -NR ¹ R ² or -OB (OR ¹ J (OR ² ). Examples of such derivatives and other X groups can be given by the general formulas, without restricting the invention thereto

/ ^y1r1 Ϊ

-.γ-C-Z _ γ _ ρ 'YS

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1 2
in which Y, Y and "Y independently of one another -O-, -NH-,

-N- or -S- are or absent, but preferably -0-

or -S-, ZH, R ¹ , OR ¹ , -SR ¹ , NH ₂ , HHR ¹ or IiR ¹ R ² or a direct back connection of. C to R or to a with R

linked CHp, but is preferably H or R, W 0, S, NH or NR, but is preferably 0 or S, L is 0 or S or is absent, but is preferably 0, M is 0 or absent, but preferably 0, and R is straight-chain or branched alkyl 1 to 12, preferably 1 to 4, and particularly preferably 1, carbon atom (s), alkenyl or alkynyl with 2 to 12, preferably 2 to 4 carbon atoms, cycloalkyl or cycloalkenyl with 5 to 12, preferably 6, carbon atoms, aralkyl, Aralkenyl or alkaryl with 7 to 12 carbon atoms, preferably benzyl or naphthylmethyl, or aryl with β to 15, preferably 6 to 12 carbon atoms, and particularly preferably phenyl or naphthyl, can be represented. R can optionally be replaced by one or more halogen, hydroxyl, epoxy, nitrile, amine, amide, ether, carboxyl

or ester groups or their combinations

but is preferably unsubstituted. R corresponds to the same definition as R 'and can be the same as R or be different from R. The leaving group can also be a salt of an acidic or basic X group. Of the examples that do not limit the invention

> However, compounds of the formula I in which X = OH

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or a derivative of this group is preferred.

The aromatic radical R can be monocyclic or dicyclic or polycyclic, fused or non-fused and can also be selected from fused and non-fused at the same time Groups exist. If R contains more than one independent aromatic radical, such radicals can be used directly or via carbon-containing or heteroatom-containing groups or groups containing both carbon atoms and heteroatoms, be linked. These linking groups can also be selected in such a way that they consist of recurring aryl groups or consist of heterocyclic groups, the linkage or linkages being made or being established by -CH ^ X groups, in which X contains R and / or R, at least one of which is an R or -CHpR group. So can the R group be an oligomeric group containing the above-mentioned aromatic hydrocarbon radicals and heterocyclic radicals, and arises through addition or condensation reactions. Such linking groups are present but are preferred other, non-linking CHpX groups can also be found in the overall system at the same time.

The links are preferably short-chain groups, preferably with no more than 3 carbon atoms. Particularly the linkages preferably contain no neighboring carbon atoms. The R group can be unsubstituted or otherwise by one or more halogen atoms or alkyl groups with 1 to 12, preferably 1 to 4, carbon atoms, alkenyl » or alkynyl groups with 2 to 12, preferably 2 to

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26A8701

4, carbon atoms, cycloalkyl groups with 5 to 12 carbon atoms, Hydroxyl groups, alkoxy groups with 1 to 12, preferably 1 to 4, carbon atoms (which optionally contain a Contain epoxy group), cycloalkoxy groups with 5 to 12 Carbon atoms, acyloxy groups with 1 to 12, preferably 1 to 4 carbon atoms, carboxyl groups or carboalkoxy groups with 2 to 12, preferably 2 to 4, carbon atoms, or their mixtures, may be substituted. Preferably, however, R is an otherwise unsubstituted or alkyl-subs-substituted, preferably methyl-substituted, di-, tri- or tetracyclic radical. R is very particularly preferably a otherwise unsubstituted di-, tri- or tetracyclic aromatic radical.

The X group is preferably an OH, OR, OCOH or OCOR group, in which R has the meaning given above, but X is particularly preferably methyl, phenyl or benzyl.

Examples of the radical R of the formula I, without restricting the invention thereto, include the radicals derived from the following systems:
R = a monocyclic residue

1 benzene

2 toluene

3 xylenes

4 ethylbenzene

5 mesitylene

6 durol

7 isodurol

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8 V-cymene or cymene

9 Aaisol

10 phenyl acetate

11 chlorobenzene

12 bromobenzene

13 pyridine

14 triazine

15 pyrimidine

16 pyrazine

17 p-t-butylphenol

R is preferably derived from compounds 1-10 and 1? away. R = a non-fused bicyclic radical

1 biphenyl

2 diphenylmethane

3 1,1-diphenylethane

4 1,2-diphenyl ethane

5 2,2-diphenyl propane

6 diphenylcarbinol

7 benzophenone

8 phenyl benzoate

9 diphenylacetic acid (and its esters)

10 * diphenyl ether

11 diphenylacetonitrile

12 diphenyl sulfide

13 diphenyl disulfide

14 diphenyl sulfoxide

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So

15 diphenyl sulfone

16 diphenylamine

17 N, N-diphenylmethylamine

18 diphenylmethylphosphine

19 Diphenylmethylphosphoric oxide

20 diphenyl octyl phosphate

21 ■ dipyridyl

22 3.3 ¹ ~ dimethyl mphenyl

23 2.2 ^1- dimethyl mphenyl

24 4.4 ¹ ~ dimethylbiphenyl

25 2,2-Diphenyldicarboxylic acid

26 stilbene

27 benzoin

28 benzil

29 benzilic acid

30 dibenzyl sulfate

31 dibenzyl oxalate

32 dibenzyl succinate

33 diphenyl carbonate

34 Octyl distyryl phosphinate

35 ferrozenes

36 Diphenyl succinate

37 ethylenedioxydiphenyl

Among these, groups derived from Nos. 1, 2, 10 and 15 are preferred. R = a fused bicyclic radical

1 Naphtaiiii

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2 methylnaphthalene

3 methoxynaphthalene

4 tetralin

5 quinoline

6 isoquinoline

7 quinoxaline

8 quinazoline

9 phthalazine

10 phthalimide

11 indole

12 benzofuran

13 benzimidazole

14 benzothiazole

15 benzotriazole

Among these, naphthalene and methyl naphthalene are preferred. R = a non-fused tricyclic radical

1 terphenyl

2 triphenylmethane

3 dibenzylbenzene

4 0, O-diphenylhydroquinone

5 O, O-diphenylresorcinol

6 triphenylamine

7 'triphenylphosphine

8 triphenylphosphine oxide

9 triphenyl phosphate

10 tricresyl phosphate

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11 trixylyl phosphate

12 an isopropylphenyl / phenylphosphate mixture (e.g. commercially available under the trademarks Reofos 50, 65 and 95 and as described in G.B. Patent No.

1 146 173 manufactured)

13 triphenylantimony

14 tribenzyl phosphate

15 diphenyl styryl phosphonate

16 triphenyl ortho-formate

Among the aforementioned groups, those derived from Nos. 1, 2, 3, 5, 6, 8, 9, 10, 11 and 12 are preferred. R = a fused tricyclic radical

1 anthracene

2 phenanthrene

3 phenylnaphthalene

4 azenaphtes

5 azenaphthylene

6 dihydroanthracene

7 anthrene

8 xanthene

9 xanthone

10 fluorene

11 Fluorenoii

12 acridine

13 phenanthridine

14 phenazine

15 benzcinnoline

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16 carbazole

17 Dibenzfuran

18 dibenzthiophene

19 phenothiazine

20 phenoxazine

21 Dimer α-methylstyrene

22 dimer styrene

23 biphenylene

24 1-methylanthracene

Among the aforementioned residues are those of Nm. 1, 2,

3, 4, 5, 10, 16, 17, 21, 22 and 24 derived preferred. R = a non-fused tetracyclic residue

1 quaterphenyl

2 tetraphenylmethane

3 triphenylbenzene

4 2,4,6-triphenyltriazine

5 N, N ¹ N ¹¹ ^ -triphenylmelamine

6 N, N N -triphenyl isocyanuric acid

7 tin tetraphenyl

8 lead tetraphenyl

9 tetraphenylethane

10 tetrabenzyl orthosilicate

11 2,4,6-triphenoxytriazine

12 tetraphenyl silicate

Among the aforementioned remains are those of nos. 2, 4,

55 6 and 11 derived preferred.

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R = a fused tetracyclic residue

1 Dinaphthyl 2 Phenylanthrazene 3 Phenylphenanthrene 4th N ~ phenylacridone 5 N-phenylcarbazole 6th N-phenylphenothiazine • 7 N-phenylplienoxazine 8th 9-Piienyla cridin 9 2,3-diphenylquinoxaline 10 Triphenylene 11 Azeanthrones 12th Pyrene 13th Naphtacene 14th Fluoranthene 15th Chryses 16 Dinaphthyl methane Among the aforementioned residues are those of Dinaphtyl and N-phenylcarbazole-derived preferred. R = a polycyclic (more than tetracyclic) residue

1 9,10-diphenylanthracene

2 sexiphenyl

3 rubrics

4 9,9-diphenylxanthene

5 9,9-diphenylacridane

6 hexacene

7 hexaphs

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8 pyranthrene

9 hexaphenyl melamine

R = an oligomeric radical

1 polyphenyl

2 poly (methylene phenylene)

3 polyxylylene

4 polystyrenes

5 polynaphthylenes

6 polybenzyl ether

7 polybenzyl esters

8 polyphenyl ethers

9 polyphenyl esters

Examples of the X group of the formula I that do not limit the invention are:

-Cl, -Br, -OH, -OCH ₃ , -OC ₂ H ₅ , -OC ₄ H ₉ , OCH ₂ CH = CH ₂ , OCH = CH ₂

-OH

, -0COC "IIC-OCO-: 0 S ^V

Il .. Il

I!

i -OCJI »-OCCII>

-OCNHCH ₃ , -OCN (CH ₃ ) ₂ , -OCNHCH ₃ , -OCN (CH ₃ ) ₂ , 0

Il,

-OCKH-Λ /> »-OSO

\ J:

-0 C) I ₂ CII - CII,

-0 BhO

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IQO XJ C! Γ * Γ * ΧΤ

■ ζ) - ^ Upiii-, -D-uon ,,

Q / -ITT QO XJ C! Γ * Γ * ΧΤ Q O OXT

SS S

11 Il Il,,

-SCOCH ₃ , -SC-OC ₂ H ₅ , -SCN (CH ₃ ) ₂ ,

O O

, _Ν Il Il

-NHCH ^, -N (CH,) p, NHC-CH ,, -NHC-NHp, NH

-NHC-OC ₀ Hc-, -InTHC-NH ^, -NHC-NH-C-NH ₀ ,

²⁵ Il * ' Il Il ^2>

NH NH NH

0 0 0 -, -P (OH) ₂ , -P (OCH ₃ ) _2l

Examples of salts include the alkali,

Ammonium or amine salts of acidic compounds and inorganic, organic or quaternary salts of basic compounds, e.g.

0 '0
- CONa, - P (0NH ₄ ) ₂ , - N ^ CH ^ Cl " _e in.

The following compounds of constitution 1 may be mentioned in detail without restricting the invention thereto:
R = a monocyclic radical

1,4-bis (carboxymethyl) benzene, 1,4-bis (methoxycarbonylmethyl) benzene, 1,4-bis-hydroxymethylbenzene, 1,4-bismethoxymethylbenzene, 1,4-r-bisbenzoxymethylbenzene, 1,4-bischlorinethylbenzene, 1,4-bisacetyloxymethylbenzene, 2,4,6-trischloromethylmesitylene, 3j6-Bismethoxymethylduren, 2,4,6-Trisacetoxymethylacetat, 2,6-bishydroxymethylpyridine, 2,6-bishydroxymethyl-

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ä »

4-t-butylphenol, l, 3> 5-tris-hydroxyinethyrbenzene and 1,4-bis--

hydroxymethyl-2, 3 ₅ 5,6-tetrachlorobenzene.

R = a non-fused bicyclic radical

4,4 bis (chloromethyl) biphenyl, 4,4 bis (bromethyl) biphenyl, 4,4 -Bis (carboxymethyl) biphenyl, 4,4 -Bis (methoxy-

η. '

carbonylmethyl) biphenyl, 4,4-bis (hydroxymethyl) biphenyl,

1 1

4,4 bis (methoxymethyl) biphenyl, 4,4 bis (phenyloxymethyl) biphenyl, 4,4 -Bis (benzyloxymethyl) biphenyl, 4,4 -Bis- (acetyloxymethyl) biphenyl, 4,4 -Bis (formyloxymethyl) biphenyl, α, α -Bitolyldiphosphonsaures disodium salt, 4-hydroxymethyl-4 ~ -methoxymethylbiphenyl, 4-hydroxymethyl-4-acetoxymethylbiphenyl, 4,4 -bis (dimethylaminomethyl) biphenyl, 4,4 "-bis- (methylcarbamoyloxymethyl) biphenyl, 4,4 bis (trimethylaminomethyl) biphenyl dichloride, 2,4-bis (acetoxymethyl) -6-phenylphenol acetate, 4,4 bis (hydroxymethyl) diphenyl methane, 4,4 bis (methoxymethyl) diphenyl methane, 4,4 bis (benzyloxymethyl) diphenyl methane, 4,4 bis (formyloxymethyl) diphenyl methane, 4,4 bis (carbamoyloxymethyl) diphenyl methane, 3,3'-bis (acetoxymethyl) -4,4'-bis-acetoxydiphenylmethane, 4,4 ^ -BiS (hydroxymethyl) benzophenone, 4,4 bis (hydroxymethyl) diphenyl ether, 4,4 bis (methoxymethyl) diphenyl ether, 4,4 bis (acetyloxymethyl) diphenyl ether, 4,4-bis (hydroxymethyl) diphenylsulfone, 3,3'-bis (acetoxymethyl ) -4,4'-bisacetoxydiphenyl sulfone, N, N-bis (4-hydroxymethylphenyl ) methylamine, bis (4-hydroxymethylphenyl) octyl phosphate, 4,4-bis (methoxymethyl) -3,3 -dimethyldiphenyl, 2,2-bis- (3'-acetoxymethyl-4'-acetoxyphenyl) -propane and 1,4-butanediol bis (3- (2 -hydroxymethylphenoxy) -2-hydroxypropyl) ether.

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le

R = a fused bicyclic res t

1,4-bis (chloromethyl) naphthalene, 1,4-bis (hydroxymethyl) naphthalene, 1,4-bis (methoxymethyl) naphthalene, 1,4-bis (naphthalene) diacetic acid, 2,3-bis (hydroxymethyl) naphthalene , 1,5-bis (chloromethyl) naphthalene, 2,6-bis (hydroxymethyl) naphthalene, 1,4-bis (hydroxymethyl) naphthalene, 1,5-bis (hydroxyraethyl) naphthalene, 1,5-bis (methoxymethyl) naphthalene, 1,5-bis (formyloxyine thyl) naphthalene, 1,5-bis (ace toxymethyl) naphthalene, 1-methylbis (chloromethyl) naphthalene, 2-methyl-bis (chloromethyl) naphthalene, 1-methyl bis (hydroxymethyl) naphthalene, 2-methyl-bishydroxymethyl) naphthalene, 1-methyl-bis (methoxymethyl) naphthalene, 2-methyl-bis (methoxymethyl) naphthalene, 5,8-bis (chloromethyl) tetralin. 5,8-bis (hydroxymethyl) tetralin, 5,8-bis (methoxymethyl) tetralin, 4,8-bis (chloromethyl) quinoline, 5,8-bis (hydroxymethyl) quinoline, 4,8-bis (methoxymethyl) quinoline , 4,8-bis (hydroxymethyl) isoquinoline, 4,8-bis (acetoxymethyl) -isoquinoline, 5,8-bis (chloromethyl) quinoxaline, 5,8-bis (hydroxymethyl) quinoxaline, 5,8-bis (formyloxymethyl ) quinoxaline, 5,8-bis (chloromethyl) phthalazine, 3, 6-bis (chloromethyl) phthalimide, 4,7-bis (hydroxymethyl) indole, 4,7-bis (methoxymethyl) indole, 4,7-bis (hydroxymethyl ) benzofuran, 4,7-bis (methoxymethyl) benzofuran, 4,7-bis (chloromethyl) benzofuran, 4,7-bis (hydroxymethyl) benzotriazole, and 4,7-bis (formyloxymethyl) benzotriazole. R = a non-fused tricyclic radical

1,4-di (4 ~ -chloromethylphenyl) benzene, 1,4-di (4 hydroxymethylphenyl) benzene, 1,4-di (4-formyloxymethylphenyl) benzene, Tri (4-methoxymethylphenyl) methane, tri (4-hydroxymethyl-

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26A8701

te

phenyl) methane, tri (4-chloromethylphenyl) methane, 1,4-di (4-methoxymethylbenzyl) benzene, 1,4-di (4-hydroxymethylbenzyl) benzene, 1,4-di (4 -formyloxymethylbenzyl) benzene, 1, 4-di- (4-chloromethylbenzyl) benzene, 1,4-di (4 -acetoxymethylbenzyl) benzene, 0,0 -di (4-chloromethylphenyl) hydroquinone, 0,0 -di (4-methoxymethylphenyl) hydroquinone, 0,0 -Di (4-benzoyloxymethylphenyl) hydroquinone, 0,0 -Di (4-dimethylaminomethylphenyl) -resorzin, tri (4-hydroxymethylphenyl) amine, tri (4-methoxymethylphenyl) amine, tri (4-formyloxymethylphenyl) phosphine, tri (4-benzoyloxymethylphenyl) phosphine, tri (4-carbamoyloxymethylphenyl) phosphine, tri (4-dimethylaminomethylphenyl) phosphine oxide, tri (4-bromomethylphenyl) phosphine oxide, tri (4-benzoyloxymethylphenyl) phosphine oxide, tri (4-chlorme ethylphenyl) phosphate »Tri (4-methoxymethylphenyl) phosphate, di (4-hydroxymethylphenyl) mono (p-methoxymethylphenyl) phosphate, tri (4-methoxymethylmeta-cr e syl) phosphate, monophenyl-di (4- £ ie thoxymethylphenyl) phosphate, monophenyl-mono (4-hydrox methylphenyl) mono (pmethoxymethylphenyl) phosphate, di (methoxymethylphenyl) mono- (2-isopropylphenyl) phosphate, di (hydroxymethylphenyl) mono- (4-isopropy! phenyl) phosphate and tris (2,4-di-butoxymethyl-6 -phenyl-phenyl) -boros acid esters.
R = a fused tricyclic radical

1,4-dihydroxymethylanthracene, 5-hydroxymethyl-1,4-di (methoxymethyl) anthracene, 1,4-di (hydroxymethyl ) -5, & - di (methoxymethyl) anthracene, 2,7-di (acetoxymethyl) anthracene, 1,4,7-tris (acetoxymethyl) azenaphthylene, 1,4,7-tris (dimethylaminome thy!) Azenaphthylene, 1,4,5,8-tetra (hydroxymethyl) -

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26487Q1 30

fluorene, 1,4,5,8-tetra (acetoxymethyl) xanthene, 1,4,5-tri- (brominethyl) xanthene, 1,4,5,8-tetra (dimethylaminomethyl) carbazole, 1,4,5, 8-tetra (carbamoyloxymethyl) acridine, 1,4,6,9-tetra (benzoyloxymethyl) phenazine, 2,7,10-tris (chlorine thyl) phenanthridine, 1,4,6,9-tetra (methoxymethyl) phenoxazine, 1,4,6,9-tetra (hydroxymethyl) phenothiazine and 1,3,3-trimethyll-phenyl-4,7-di (methoxymethyl) indane.
R = a non-fused tetracyclic residue

Tetra (3j5-dihydroxymethylphenyl) methane, tetra (4 ~methoxymethylphenyl) methane, tetra (4-formyloxymethylphenyl) methane, tetra (4-dimethylaminomethylphenyl) methane, 1,3,5-tri- (3j5-dichloromethylphenyl) benzene , 1,3 »5-tri (4-methoxymethylphenyl) benzene, 1,3,5-tri (4-carbamoyloxymethylphenyl) benzene, 1,3,5-tri (4-benzoyloxymethylphenyl) benzene, N, N, N -Tri (3,5-dihydroxymethylphenyl) melamine, N, N, N -Tri (3j5-diformyloxymethylphenyl) melamine, N, N, N -Tri (4-methoxymethylphenyl) melamine, 2,4,6-tri (3,5-dichloromethylphenyl) triazine, 2,4,6-tri (3,5-dicarbamoyloxymethylphenyl) triazine, 2,4,6-tri (4-acetoxymethylphenyl) triazine, N, N, N -tri (3,5 -dihydroxymethylphenyl) isocyanuric acid ester, tin tetra (3,5-diformyloxymethylphenyl), tin tetra (4-hydroxymethylphenyl), tin tetra (4-chloromethylphenyl), lead tetra (4-acetoxymethylphenyl), lead tetra (4-bromomethylphenyl) , Lead tetra (4-methoxymethylphenyl) and tetrakis (2-butoxymethylphenyl) silicate. R = a fused tetracyclic residue

2-phenyl-5,8-dibromomethylanthracene, 2-phenyl-5,8-dihydroxymethylanthracene, 2-phenyl ~ 5,8-diformyloxymethyl-

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anthracene, 3-phenyl-3} 6-dimethoxymethylphenanthrene, 3-phenyl-3,6-diacetoxymethylphenanthrene, 3-phenyl-3,6-dihydroxymethylphenanthrene, N-phenyl-2, δ-dichloromethylcarbazole, N-phenyl-2,6- dicarbamoyloxyniethylcarbazole, N-phenyl-2,7-dimethoxymethylphenothiazine, N-phenyl-2,4,6-tribromomethylphenothiazine, N-phenyl-2,4,6-triacetoxymethylphenoxazine, 2,3-diphenyl-5,8-diforinyloxymethylquinoxaline and 2, 3-diphenyl-5,8-dihydroxymethylquinoxaline.
R = a polycyclic (higher than tetracyclic) residue

2,6 ~ -Dimethoxymethyl-9 , 10-diphenylanthracene, 2,8-dichloromethylrubrene, 2,6-dihydroxymethyl-9,9-diphenylxanthene, 2,6-diacetoxymethyl-9,9-diphenylxanthene, 2,6-dicarbamoyloxymethyl 1-9 , 9-diphenylxanthene, 1,4,6,9 _} 12,15-hexamethoxymethylhexazene, poly (4,4 ^t -dibenzyl) phthalic acid ester, polyethylene dioxy (4,4'-dibenzyl), chloromethylated polystyrene, the polyester from 4,4 -Bis (hydroxymethyl) biphenyl and phthalic anhydride, the polyester from 4,4'-bis (hydroxymethyl) biphenyl and succinic anhydride, the polyurethane from 1,5-bis (hydroxyinethyl) naphthalene and toluene diisocyanate, the polyether from 1,5-bis (hydroxymethyl ) naphthalene and ethylene glycol and the polybenzyl ether obtainable from 4,4'-bis (chlorinethyl) biphenyl by hydrolysis.

The phosphoric acids include derivatives of phosphoric acid, phosphonic acid, phosphinic acid and phosphorous Acid and its dehydration products. Although one can also use "partial ester" salts, the fully esterified ones are Products preferable. In particular, the

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Phosphorus acid esters are preferred.

The following compounds may be mentioned as examples of the phosphoric acid-based phosphorous-containing esters, without to restrict the invention to:

1 triphenyl phosphate

2 cresyl diphenyl phosphate

3 phenyl xylyl phosphate

4 trityl phosphate

5 trixylyl phosphate

6 phenyl / isopropylphenyl phosphate (e.g. those under the Trademarks Reofos 95, 65 and 50 are commercially available

and as described in GB Patent No. 1 "146 173, getting produced).

7 phenyl / sec-butylphenyl-phosphate

8 phenyl / ρ-t-butylpheny1-phosphate

9 di (2-quynylphenyl) phenylphosphate

10 di (4-benzylphenyl) phenyl phosphate.

11 Tri (4-t-buty! Phenyl) pho sphat

12 Tri (4-nony! Phenyl) phosphate

13 Tri (4-t-aemylphenyl) phosphate

14 tri (4-chlorophenyl) phosphate

15 tri [4- (bromoisopropyl) phenyl] phosphate

16 Tri [4- (chloroisopropyl) phenyl! Phosphate

17 Diphenyl (2-bromoethyl) phosphate

18 diphenyl (2-chloroethyl) phosphate

19 Diphenyl (2,3-dibromopropyl) phosphate

20 Diphenyl (2,3-dichloropropyl) phosphate

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21 diphenyl n-octyl phosphate

22 Diphenyl-n-decy! Phosphate

23 phenyldi (2-tiromethyl) phosphate

24 phenyldi (2-chloroethyl) phosphate

25 phenyldi (2,3-dichloropropyl) phosphate

26 phenyldi (2,3-dibromopropyl) phosphate

27 phenyl di-n-octyl phosphate

28 phenyl di-n-decyl phosphate

29 tri (2-chloroethyl) phosphate

30 tri (2-brömäthyl) pho sphat

31 Tri (2,3-dibromopropyl) phosphate

32 tri (2,3-dichloropropyl) phosphate

33 triosyl phosphate

34 tridecyl phosphate

35 triallyl phosphate

f Γ ² ° ^{1 (} \\ /

ClCII CII O-POCH., CClI ₀ OP. 3d ^ ^ ι a. . .2 \

ClCH ₂ CII ₀ O CII ₉ Cl

37 Tri (meta-ethylphenyl) phosphate

38 Phosphoric acid diphenyl ester calcium salt

The following compounds may be mentioned as examples of esters based on phosphonic acids, without restricting the invention thereto:

39 Diphenyl phenyl phosphonate

40 di (4-bromophenyl) phenylphosphonate

41 di (4-t-buty! Phenyl) phenyl phosphonate

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42 di (2-isopropylphenyl) phenylphosphonate

43 Di (4-benzylphenyl) phenylphosphonate

44 diphenyl styryl phosphonate

45 diphenyl- (1,2-dibromo-2-phenylethyl) phosphonate

46 diphenyl n-octyl phosphonate

47 diphenyl n-decyl phosphonate

48 di (4-chlorophenyl) -n-butylphosphonate

49 di (4-bromophenyl) -n-hexylphosphonate

50 di (2-isopropylphenyi) -n-o ctyIphosphonate

51 Phenyl-n-o ctyl-n-hexylphosphonate

52 bis-2,3-dibromopropyl-2,3-dibromopropylphosphonate

53 diethyl phenyl phosphonate

54 Diethyl diethanolaminomethyl phosphonate

The following compounds may be mentioned as examples of the esters based on the phosphinic acids, without restricting the invention thereto:

55 n-octyl distyryl phosphinate

56 n-Octyl-di (1,2-dibromo-2-phenylethyl) phosphinate

57 phenyl distyryl phosphinate

58 n-Oc.tyl-distyrylphosphinate

The following compounds may be mentioned as examples of esters based on phosphorous acid, without restricting the invention thereto:

59 triphenyl phosphite

60 trioctylphosph.ite

61 'tri-4-nonylphenyl phosphite

62 tri-2,3-dibromopropylphosphite

63 Acid diphenyl phosphite

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- 22 -

26A8701 3S "

64 Acid dioctyl phosphite

Preferred compounds include the esters of pentavalent phosphorus and particularly preferably the triaryl phosphates and trihaloalkyl phosphates, e.g. B. the connections 1 to 10 and 29 to 32 and mixtures of these compounds, or mixed aryl phosphates, haloalkyl phosphates and aryl haloalkyl phosphates.

It should be noted that if an ester of a phosphorus-containing acid optionally also _{corresponds to the formula R (CH 2} X) _n , the ester is then to be regarded as a compound of the formula R (CHpX) _n and in connection with another ester of a phosphorus-containing acid Acid which does not correspond to the formula R (CH ₂ X) _n is to be used. . Only in the case of the presence of another component of the formula R (CH ₂ X) _n can "the ester of the phosphorus acid of the formula R (CH ₂ X) _{n be} regarded as the ester component.

Various types of carboxylic acid esters with aromatic groups can be used, e.g. the esters of Phthalic acid, benzoic acid and mellitic acid.

The carboxylic acid esters include the di-n-butyl, dilsobutyl, di-2-ethylbutyl, isobutylnonyl, di-n-heptyl, Di-2-ethylhexyl, diisooctyl, dicapryl, di-n-o.ctyl, isooctylisodecyl, Linevol-7.9-, Linevol-9.11- (Linevol-7.9 and Linevol-9,11 are mixtures of mainly straight-chain alcohols with 7 and 9, or 9 and 11, carbon atoms), di-2-phenylethyl-, Ditridecyl, butyllybenzyl and dimethyl glycol esters of phthalic acid, the triisooctyl ester of mellitic acid,

709818/1 1 U

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the butyl ester of Butylphthalylglykolsäure, the Trio.ctylester of mellitic acid, the dibenzyl, diphenyl and di-2-phenoxyethyl ester of phthalic acid, the Triphenylester of mellitic acid, pyromellitic acid etraphenylester the ^T, the ethyl ester of benzoylbenzoic acid, the ester and dipropylene glycol Benzyl esters of benzoic acid, the diphenoxyethyl and bis (phenylpolyethylene glycol) esters of diglycolic acid, the phenoxyethyl esters of lauric acid and oleic acid, the diphenyl, dibenzyl, benzylyo ctyl, O.cty ^ phenyl and butybenzyl esters of adipic acid Dibenzyl ester of sebacic acid, the di (2-phenoxyethyl) ester of adipic acid, the butyl / benzyl ester of sebacic acid, the n-octyl-n-decyl ester of phthalic acid and succinic acid, the phenyl diglycol, cresyl diglycol and bis (dimethylbenzyl) esters carbonic acid and the diethylene glycol diester of benzoic acid.

Various polyesters can also be used, e.g. B. of phthalic anhydride and one or more Gly-kolen derived polyesters, the end groups optionally reacted with an alcohol or a monobasic acid have been; polyester derived from a phthalic acid / adipic acid mixture and a glycol, with the end groups have optionally been reacted with an alcohol or a monobasic acid and a mixture of phthalic acid and AGS acids (a commercial mixture of adipic acid, glutaric acid and succinic acid) and a glycol Polyester, the end groups optionally having been reacted with an alcohol or a monohydric acid.

709818 / 11U

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In addition, lactone-modified, e.g. ε-caprolactone-modified, Use polyesters of the above three types.

Other useful compounds of type a include the diethylene glycol diester of benzoic acid, the tribenzyl ester of citric acid, alkyl sulfenic acid esters of phenols, e.g. those commercially available under the brand name "Mesamoll" Products, the o-cresyl ester of p-toluenesulfonic acid, the Triphenyl ester of orthoformic acid and the diphenyl ester of carboxylic acid.

Preferred aromatic esters are those conventionally used as plasticizers for vinyl chloride polymers Esters, and particularly preferably the esters derived from phenols.

Further preferred aromatic esters are those with a non-deactivated benzene nucleus, e.g. the butylene / benzyl and bisphenoxyethyl esters of phthalic acid.

In the compositions according to the invention, the compounds (a) and (b) must be present in any ratio. Particularly useful proportions of the phosphorus-containing ester (a) Per hundred parts of the chlorine-containing aliphatic polymer are in the range from 0.1 to 150 parts, preferably 1 to 150 parts, particularly preferably 2 to 100 parts and very advantageously 5 to 80 parts. Particularly useful proportions of compound (b) per hundred parts of the chlorine-containing aliphatic Polymer are in the range from 1 to 50 parts, preferably 1 to 35 parts, particularly preferably 2 to 25 parts

709818 / 11U - 25 -

and "particularly preferably 2 to 15 parts. Particularly useful Proportions of the aromatic ester (a) per hundred parts of the Vinyl chloride polymer are in the range from 1 to 150 parts, preferably 2 to 100 parts and very advantageously 5 to 80 parts Divide, particularly useful proportions of compound (b) per one hundred parts of the vinyl chloride polymer range from 1 to 50 parts, preferably 1 to 20 parts and especially preferably 2 to 15 parts. Appropriate weight ratios Compounds (a) and (b) are from 20: 3. to 0.1: 1, but preferably from 10: 1 to 0.5 and very particularly preferably from 1 to 1: 1.

The chlorine-containing polymer can be either a homopolymer or a copolymer and contains at least 5% chlorine, preferably more than 20% chlorine and very particularly preferably more than hO% chlorine. The following are examples of such polymers, without restricting the invention to them: polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated polybutene, polychloroprene, polyvinylidene chloride, chlorinated poly ~ 4,4-dimethylpentene and chlorinated polyethylene which also contains some chlorosulfonyl groups, e.g. Hypalon.

The following may be mentioned as examples of the copolymers, without restricting the invention to them: Vinyl acetate, vinyl chloride-vinylidene chloride, vinyl chloride Ethylene, vinyl chloride-propylene, vinyl chloride-acrylic acid ester and vinyl chloride-acrylonitrile copolymers, chlorinated ethylene-propylene copolymers and chlorinated Ethylene-butene copolymers. Polymer blends

709818 / 11U - 26 -

mix of other polymers can also be used; to These include, for example, without restricting the invention thereto, the PVC rubber blends, with rubber in particular based on acrylonitrile.

PVC and chlorinated polyolefins such as chlorinated polyethylene are preferred as polymers. \ To the Vinyl chloride polymers are all counted by conventional or other processes, e.g. bulk polymerisation, suspension polymerisation or emulsion polymerization, polymers produced.

As examples of the mixtures of compounds (a) and (b), which are found in the chlorinated aliphatic polymers or allow polymer blends to be used, the following may be mentioned without restricting the invention thereto:

With an ester of a phosphorus acid as compound a): 4,4'-bishydroxymethylbisphenyl and tris (2,3-dichloropropyl) phosphate; 4,4'-bishydroxymethylbiphenyl and tris- (2-bromoethyl) phosphate; 4,4 '-Bis chlorine thy lbiphenyl and Reofos 95; 4.4 ^l -Bishydroxymethylbiphenyl and Reofos 95; 4.4 ^I -Bishydroxymethylbiphenyl and tritolyl phosphate; 4,4'-Bi shydroxyme thy lbiphenyl and triphenyl phosphate; 4,4'-Bishydroxymethylbiphenyl and tris ( 2,3-dibromopropyl) phosphate; 4,4'-bis (hydroxymethyl) lbiphenyl and phenyldi (2-bromoethyl) phosphate; 4,4'-bis (hydroxymethyl) biphenyl and tris (2-chloroethyl) phosphate; 4.4 ^t -Bismethoxymethylbiphenyl and Reofos 95; 4,4'-Bismethoxymethylbiphenyl and tritolyl phosphate; 4,4'-bis-

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methoxyethylbiphenyl and triphenyl phosphate: 4,4'-bismethoxymethylbiphenyl and cresyldiphenyl phosphate; 4,4'-bis (acetoxymethyl) biphenyl and Reofos 95; 4,4 ^T -bis (acetoxymethyl) biphenyl and cresyl diphenyl phosphate; 4,4'-bis (acetoxymethyl) biphenyl and isodecyl diphenyl phosphate; 4,4'-bis-acetoxymethyl-biphenyl and tris [2 - (bromoisopropyl) phenyl] phosphate; 4,4'-bis (acetoxymethyl) -biphenyl and tris (2,3-dibromopropyl) phosphate, 4,4 · ^f ~ bis (acetoxymethyl) biphenyl and phenyl di (2-bromathy1) phosphate; 1,5 ~ bishydroxymethylnaphthalene and tris (2,3-dichloropropyl) phosphate; 1,5-bishydroxymethylnaphthalene and tris (2-bromethyl) phosphate, 1,5-bishydroxymethylnaphthalene and Reofos 95; 1,5- bishydroxymethylnaphthalene and tritolyl phosphate; 1,5-bishydroxymethylnaphthalene and triphenyl phosphate; 1,5-bishydroxymethylnaphthalene and tris (2,3-dibromopropyl) phosphate; 1,4-bishydroxymethylnaphthalene and phenyldi (2-bromoethyl) phosphate, 1,5-bishydroxymethylnaphthalene and tris (2-chloroethyl) phosphate; 1,5-bishydroxymethylnaphthalene and cresyl diphenyl phosphate; 1,4-bismethoxymethylnaphthalene and tris (2,3-dichloropropyl) phosphate; 1,5-bismethoxymethylnaphthalene and tris (2-bromethyl) phosphate; 1,5-bismethoxymethylnaphthalene and Reofos 95; 1,5-bismethoxymethylnaphthalene and tritolyl phosphate; 1,5-bismethoxymethylnaphthalene and triphenyl phosphate; !, ^ - bismethoxymethylnaphthalene and tris (2,3-dibromopropyl) phosphate; 1,5-bismethoxymethylnaphthalene and phenyldi (2-bromoethyl) phosphate; 1,5-bismethoxymethylnaphthalene and tris (2-chloroethyl) phosphate and 1,5-bismethoxymethylnaphthalene and cresyldiphenyl phosphate, both mixtures of phosphoric acid esters as well as

• 7 0 9 8 1 8/1 1 H

- 28 -

Mixtures of the compounds of the formula I can if desired can be used.

b) As examples of mixtures of compounds (a), the aromatic carboxylic acid ester, sulfonic acid ester or Represent carbonic acid esters, and compounds (b) which can be used with vinyl chloride polymers are as follows mentioned, without restricting the invention to:

4.4 ^! -Bischloromethylbisphenyl and di-2-phenoxyethyl phthalate; 4,4'-bischloromethylbiphenyl and dioctyl phthalate; 4,4'-bischloromethylbiphenyl and butylbenzyl phthalate; 4,4'-bishydroxymethylbiphenyl and di-2-phenoxyethyl phthalate; 4,4'-bishydroxymethylbiphenyl and dioctyl phthalate; 4,4'-bishydroxymethylbiphenyl and butylbenzyl phthalate; 4.4 ^! -Bishydroxymethyl-biphenyl and phthalic acid-Linevol-7,9-ester; 4,4'-bishydroxymethylbiphenyl and dibenzyl adipate; 4,4 ^t -Bishydroxymethylbiphenyl and benzoic acid diethylene glycol diester; 4,4'-bishydroxymethylbiphenyl and phenyl diglycol carboxylate; 4,4 ^f -Bishydroxymethylbiphenyl and a polyester based on phthalic anhydride, the end groups with. reacted alcohol "■ ■ or a monovalent acid are 4,4'-Bismethoxymethylbiphenyl and of di-2-phenoxyäthylester; 4,4'-Bismethoxymethylbiphenyl and dioctyl phthalate; 4.4 -Bismethoxymethylbiphenyl and phthalic ^{Linevol-7,9!;} and 4,4'-bismethoxymethylbiphenyl and butylbenzyl phthalate.

Particularly preferred compounds of type (b) correspond to the formulas. ■ ■

7098 18 / 11U

- 29 -

^CH 2 ^X

other

CH ₂ X

where X is Cl, OH, OR or acyloxy.

These compounds are preferably mixed with aromatic Phosphates or haloalkyl phosphates or aryl haloalkyl phosphates, or mixtures thereof, are used. Mixtures of compounds of the above constitution with aromatic phosphates are particularly preferred,

Compounds of type (b) can optionally be mixed with other non-deactivated aromatic compounds with vacancies on the aromatic ring, vie compounds of the formula R CHp X where R and X are those mentioned above Have meanings, use. This further improves the flame retardancy in some cases. As examples such compounds may be mentioned as follows, without restricting the invention thereto: 4,4-acetoxydipheny! methane, 4,4 -Methoxydipheny! Methane, 4,4 -Acetoxy (2,2-dipheny! Propane), 4,4-methoxy (2,2-diphenylpropane), 1,5-acetoxynaphthalene, 1,5-methoxynaphthalene, l-acetoxy-4-phenylbenzene, l-acetoxy-2-phenylbenzene, 1-hydroxymethylnaphthalene, l ~ hydroxymethyl-4-phenylbenzene, Diphenyl ether, biphenyl, terphenyl, polybenzyl, Novolaks and their ethers, e.g. glycidyl ether, polyphenyl ether, 4-hydroxymethylbiphenyl, 4-hydroxymethyldiphenyl ether,

709818/1 1 H.

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4-methoxymethyldiphenyl ether, 4-acetoxyinethyldiphenyl ether, l-hydroxymethyl-2-phenylbenzene, 1-hydroxymethylnaphthalene, Monomethylmonohydroxymethylnaphthalenes and monohydroxymethylphenanthrene.

If necessary, mixtures of phosphorus-containing Esters and / or aromatic carboxylic acid esters, sulfonic acid esters and carbonic acid esters, and also mixtures of the compounds of the formula I, used v / ground.

The compositions according to the invention can also contain other ingredients, for example heat protectants, light stabilizers, antioxidants, fillers, pigments, lubricants, propellants, fungicidal agents, Friedel-Crafts catalysts or precursors, diluents, other processing aids and other flame-retardant additives and smoke-reducing agents include the phenolic compounds exhibiting steric hindrance, ^{e.g. 2.2 f} -thiobis (4-methyl-6-tert.butylphenol), 4,4'-thiobis (3-methyl-6-tert.butylphenol), 2,2'- methylenebis (4-methyl-6-tert-butylphenol), 2,2'-bis (4,4 -phenylol ^t) propane, 2,2 ^f methylenebis (4-ethyl-6-tert-butylphenol), 4,4 '-Methylene bis (2-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis [4-methyl-6- (a- methylcyclohexyl) phenol], 2,6-di (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 1,1,3-tris (2-methyl-l-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tri (3,5-di-tert-butyl-4-hydroxybenzyl) -benzene, ester of ß-4-hydroxy-3,5-di-tert-butylphenylpropion-

709818/1 1 U

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acid with monohydric or polyhydric alcohols, such as methanol, ethanol, octadecanol, hexanediol, nonanediol, thiodiethylene glycol, trimethylolethane or pentaerythritol, 2,4-bisoctylmercapto-6- (4-hydroxy-3,5-ditert.butylanilino) -s-triazine, 2,4-bis (4-hydroxy-3,5-di-tert-butylphenoxy) o-octyl mercapto-s-triazine, 1,1-bis (4-hydroxy-2-methyl-5-tert-butylphenyl) j5-dodecyl mercaptot) utane, 2,6-di-t-butyl-p-cre8ol ₅ 2,2-methylenebis (4-methyl-6-t- "butylphenol), 4-hydroxy-3 > 5-di-tert-butylbenzylphosphonic acid ester, such as Dimethyl ™ , Diethyl or dioctadecyl ester, (3-methyl-4-hydroxy-5-tert, butylbenzyl) malonic acid dioctadecyl ester, s- (3,5-dimethyl-4-hydroxyphenyl) thioglycolic acid octadecylic acid ester and bis (3,5-ditert. buty1-4-hydroxybenzyl) malonic acid esters, such as the didodecyl ester, the dioctadecyl ester and the 2-dodecyl mercaptoethyl ester.

Among the light stabilizers and UV absorbers the following should be mentioned:

Steric hindrance cyclic amines der

Formula I.

Ji,

■ Ρ

3 k '

where q is 1 or 2, X is an organic moiety containing the nitrogen-containing Ring to form a 5-, 6- or 7-membered ring

complements, represents, -R-. and R ₂ methyl or together -

709818/1 1 H.

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26487Q1

represent, R _{3 represents} methyl, R ^ alkyl with 1-5 carbon atoms or, together with R ,, the radicals - (CH ₂ ) ^ -, - (CH ₂ ) ₅ -, -CH ₂ -C (CH ₃ ) ₂ -NH-C (CH ₃ J ₂ -CH ₂ - or -CH ₂ -C (CH ₃ ) ₂ -N (0 ') - C (CH ₃ ) ₂ -CH ₂ -, and if q is 1, Y denotes hydrogen, -O *, hydroxyl, alkyl, substituted alkyl, alkenyl, alkynyl, aralkyl, substituted aralkyl or acyl or, if q is 2, Y denotes alkylene, alkenylene, alkynylene, cycloalkylene or aralkylene, and salts of these amines.

Examples of sterically hindered amines of the formula I include 4-benzoyloxy-2,2,6,6-tetrainethylpiperidine; 4-capryloyloxy-2,2,6,6-tetramethylpiperidine; 4-stearoyloxy-2,2,6,6-tetramethylpiperidine; Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate; Bis (2,2,6,6-tetramethyl-4-piperidyl) dodecane dicarboxylate and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

2- (2 ¹ -hydroxyphenyl) benzotriazoles, such as e.g. B. the 5 ¹ -methyl-, 3 ', 5'-di-tert-butyl-, 5'-tert-butyl-, 5' - (1,1,3,3-tetramethylbutyl) -, 5-chloro-3 ' , 5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-, 3'-sec-butyl-5 ¹ -tert-butyl-, 3'-a-methylbenzyl-5 ' -methyl-, 3 ^f -a-methylbenzyl-5'-methyl ~ 5-chloro-, 4'-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3 ', 5'-di-tert-amyl-, .3'-methyl-5'-carbomethoxyethyl- and 5-chloro-3 ', 5 ^! -Ditert.amylderivat, ■

2,4-bis (2'-hydroxyphenyl) -6-alkyl-s-triazines, such as the 6-ethyl, 6-heptadecyl or 6-undecyl derivative _#

2-hydroxy-benzophenones, such as the 4-hydroxy,

70 98 18/1 IU

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26487Q1

4-methoxy-, 4-octoxy-, 4-decyloxy, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy- or 2'-hydroxy-4,4 ^! -dimethoxy derivative.

1,3-bis ~ (2'-hydroxybenzoyl) -benzenes, such as, for example, 1,3-bis- (2'-hydroxy-4 '-hexyloxybenzoyl) -benzene, 1,3-bis- (2' hydroxy-4 ^t octyloxybenzoyl) benzene and 1,3-bis (2'-hydroxy-4'-dodecyloxybenzoyl) benzene.

Esters of optionally substituted benzoic acid ^ -, such as phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, Bis (4-tert, butylbenzoyl) resorcinol, benzoylresorcinol and the 2,4-di-tert-butylphenyl or octadecyl or 2-methyl-4,6-di-tert-butylphenyl esters 3,5-di-tert-butyl-4-hydroxy ~ benzoic acid.

Acrylic acid esters, such as cc-cyano-ß, ß-diphenylacrylic acid acrylic ester and isooctyl ester, a-Carbometho ^ zinitsaure "· methyl ester, methyl α-cyano-β-methyl-p-methoxycinnamate or butyl ester and N- (β-carbomethoxyvinyl) -2-methylindoline.

Oxalic acid diamide, y / ie ^{e.g. 4.4 t} -dioctyloxyoxanilide, 2.2 ^! -Dio.ctyloxy-5,5 '-ditert. butyloxanilide, 2,2'-didodecyloxy-5,5 -ditert.butyloxanilid, 2-ethoxy ~ 2'-ethyloxanilide, N, N 'bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert.butyl-2 '-äthyloxanilid and its mixture with 2-ethoxy-2'-ethyl ~ 5.4 ^l ditert.butyloxanilid as well as mixtures of ortho- and paramethoxy-disubstituted and o- and p-ethoxy-disubstituted oxanilides.

Nickel compounds, such as nickel complexes of 2,2'-thiobis [4- (l, l, 3,3-tetramethylbutyl) phenol], like the 1: 1 or 1: 2 complex, optionally with additional ones. Ligands, such as n-butyl

709818/1 1 U

. - 34 -

aniine, triethanolamine or N-cyclohexyldiethanolainine, nickel complexes of bis [2-hydroxy-4- (l, l, 3j3j-tetramethylbutyl) phenyl] sulfone, such as the 2: 1 complex, optionally with other ligands such as 2-ethylcaproic acid, nickel -dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-ditert.butylbenzylphosphonic acid monoalkyl esters, such as methyl, ethyl or butyl ester, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenylundecyl ketone oxime, and nickel-3oxime -ditert.butyl 4-hydroxybenzoate.

Examples of the stabilizers optionally present in the compositions according to the invention may be mentioned: tribasic lead sulfate, basic lead carbonate, basic lead phosphite, lead stearate, basic lead stearate, cadmium laurate, Cadmium stearate, cadmium-2-ethylhexanoate, cadmium benzoate, Barium laurate, barium stearate, barium phenolate, barium alkylphenolates, Calcium laurate, calcium stearate, zinc stearate, zinc laurate, zinc 2-ethylhexanoate and other branched metal salts Fatty acids, dibutyl tin dilaurate, dibutyl tin thiodiglycolate, Dibutyl tin thiocarboxylic acid ester, dibutyl tin maleate, other stabilizers based on. Alkyl tin compounds, Alkyl-ß-aminocrotonate and a-bis-crotonate, thioalkylß-aminocrotonate and a-bis-crotonate, a-phenylindole, epoxidized soybean oil (e.g. under the maize name Reoplas 39 commercially available product), other epoxyaliphatic or epoxyaromatic Esters, and glycidyl ethers.

These stabilizers can be used individually or as a mixture. It was found that at lower

709818/1 IU

- 35 -

Stabilizers kept the flame retardancy of the invention Mass shows further improvement; such lower levels are therefore desirable, but not essential, where possible necessary.

Organotin stabilizers, e.g. dibutyl tin maleate, and stabilizing Epoxy compounds, e.g. epoxidized soybean oil (e.g. the product commercially available under the brand name Reoplas 39) preferred.

The heat protection agents can also be used in the presence of others Stabilizers and lubricants are used; as examples of these are to be mentioned: pentaerythritol, triphenyl phosphite, Decyldiphenylphosphb.it. Didecylphenylphosphite, trinonylphenylphosphite, stearic acid, hydroxy-stearic acid, "Low molecular weight" polyethylene wax, paraffin wax, oxidized paraffin wax, fatty alcohols, esters from straight-chain fatty alcohols and straight-chain fatty acids (the acids or alcohols being natural or synthetic Can be of origin), monoesters of glycols and straight-chain fatty acids, and methylene-bis-stearamide.

Useful pigments include both organic ones as inorganic pigments and their mixtures. As examples of the optionally used organic pigments, there may be mentioned called phthalocyanine compounds, such as metal phthalocyanine compounds, e.g. copper phthalocyanine compounds, metal-free Phthalocyanine compounds or chlorinated metal phthalocyanine compounds or metal-free phthalocyanine compounds, e.g.

709818 / 11U

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26487Q1

chloromethylated phthalocyanine. Other useful organic pigments include azo (monoazo or diazo) pigments, Azo metal salts, anthraquinone and metal complexes. Examples of inorganic compounds that may be used Pigments include titanium dioxide, carbon black, or iron oxide.

By adding Friedel-Crafts catalysts to the compositions according to the invention, it is possible in some cases achieve a significant improvement in flame retardancy. This effect is shown in particular by the aromatic chloromethylated compounds Additives.

Suitable Friedel-Crafts catalysts, which can be both Brönsted and Lewis acids, include aluminum chloride, Zinc chloride, iron (III) chloride, magnesium chloride, tin (II) chloride, tin (IV) chloride, butyl tin trichloride, Phosphoric acid and p-toluenesulfonic acid. Continue to let latent catalysts can also be used, e.g. those caused by the action of heat or by the action of the thermal decomposition of a vinyl chloride polymer released hydrochloric acid, to a Friedel-Crafts catalyst being transformed. Such latent catalysts include zinc carbonate, tin (II) octoate, tin (II) oxalate and Trialky! Phosphate.

Suitable fillers include asbestos, glass fibers, kaolin and talc.

Useful secondary plasticizers or extenders are those commercially available under the brand name Cereclor chlorinated paraffin, which is available under the brand name Dow Resin 276-V2

709818 / 11U

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commercially available styrene resin and that under the brand name Iranolin PDL18 commercially available hydrocarbon derivative.

The compositions according to the invention can also contain other conventional flame-retardant additives, e.g. antimony oxide, contain.

As examples of the ranch depressants that may be used ferrozene, alumina hydrate and lead tetraphenyl may be mentioned.

If desired, mixtures of the esters of the phosphorus-containing Acids can be used with one or more known phosphorus-free plasticizers, e.g. in the form of a Mixture of phosphate esters with phthalic acid esters or a mixture of phosphate esters with adipic acid ester !!.

However, the proportion of the ester of the phosphorus-containing acid in such mixtures is preferably at least 50% and particularly preferably 75%. When using certain haloalky! Phosphates, alone or in a mixture with ary! Phosphates, however, satisfactory results can still be achieved with proportions of up to 90% of the phosphorus-free plasticizer.

If desired, mixtures of the aromatic compounds with other PVC plasticizers, e.g. Use mixtures of phthalic acid esters with phosphate esters or mixtures of adipic acid esters with phosphate esters.

As examples of the phosphorus-free plasticizers which may be used in the compositions according to the invention The following may be mentioned without restricting the invention thereto: The di (butoxyethyl), di-2-ethylhexyl,

709818 / 11U

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"linevo 1-7,9-, diisooctyl-, dicapryl-, dinonyl-, Isodecyl, Linevol 9,11, diisodecyl and polybutylene esters of adipic acid, the di-2-ethylbutyl and di-2-ethylhexyl esters of azelaic acid, bis (dimethylbenzyl) ether, o-nitrodiphenyl, Polyethylene glycol monophenyl ether, toluene ethyl sulfonamide, Di (a-phenylethyl) ether, azelaic acid dicapryl ester, the di-nbutyl, Di-alphol-7,9, diisooctyl, dicapryl and dinonyl esters of sebacic acid, triethylene glycol dicaprylate, the isooctyl / isodecyl ester the AGS acids, isooctyl epoxystearate, the nonyl, isooctyl, isodecyl and n-heptyl esters of the AGS acids, Succinic acid diisodecyl ester, carbonic acid butoxyethyl diglycol ester, Citric acid tributyl ester, the triethyl, tributyl and tri (2-ethylhexyl) ester of acetylcitric acid, 2,2 (2-ethylhexamide) diethyldi (2-ethylhexanoate), polyethylene glycol di-2-ethylhexanoate and the 2-butoxyethyl and tetrahydrofuryl esters der oleic acid, di-n-butyl, diisobutyl, di-2-ethylbutyl, Isobutylnonyl, di-n-heptyl, di-2-ethylhexyl, Diisooctyl, dicapryl, di-n-octyl, isooctyl / isodecyl, linevol-7,9, Linevol-9.11- (Linevol-7.9 and Linevol-9.11 are mixtures predominantly straight-chain alcohols with 7 and 9 or 9 and 11 carbon atoms) ', di ~ 2-phenylethyl, ditridecyl, butylbenzyl and dimethyl glycol esters of phthalic acid, triisooctyl trimellitic acid, Butylphthalyl-butylglykollat, Triraellithsäuretrioctylester, the dibenzyl, diphenyl and di-2-phenoxyethyl esters of phthalic acid, triphenyl trimellitic acid, pyro-

- 39. 709818/1 1 H.

mellitic acid traphenyl ester, ethyl benzoyl benzoate, dipropylene glycol dibenzoate, Benzyl benzoate, the Dipherioxyäthyl- and bis (phenylpolyäthylenglykol) esters of diglycolic acid, lauric acid phenoxyethyl ester, Oleic acid phenoxyethyl ester, the diphenyl, dibenzyl, benzyloctyl, octylphenyl and butylbenzyl esters of adipic acid, dibutoxyethyl and di- (2-ethylhexyl) esters of sebacic acid, stearic acid 2-butoxyethyl ester, Acetophenone, epoxy type plasticizers such as epoxidized fatty acid glycerides, polymeric epoxy plasticizers and epoxidized Ethylhexyl acetate, aliphatic nitrites, sebacic acid disks » zyl ester, di (2-phenoxyethyl) adipate, butylbenzyl sebacate, Phthalic acid / succinic acid-n-octyl-n-decyl ester, the phenyl diglycol, cresyl diglycol and bis (dimethylbenzyl) - esters of carbonic acid, the diethylene glycol and dipropylene glycol benzoic acid diesters, citric acid tribenzyl esters, the alkylsulfenic acid esters of phenols, e.g. the under under the brand name "Mesamoll" and o-cresyl p-toluenesulfonate.

If compound a) is an aromatic carboxylic acid, sulfonic acid or carbonic acid ester, phosphate esters, e.g. tri (2-ethylhexyl) phosphate, tri (2-chloroethyl) phosphate, Trinonyl phosphate or tri (butoxyethyl) phosphate, use as plasticizer.

Different polyesters can also be used, e.g. polyesters derived from adipic acid and a glycol,

- 40 709818/11-U

Where 'the end groups have been reacted with an alcohol or a monobasic acid; polyester derived from AGS acids (a commercially available mixture of adipic acid, glutaric acid and succinic acid) and a glycol, the end groups having been reacted with an alcohol or a monobasic acid; polyesters derived from phthalic anhydride and one or more glycols, the end groups optionally having been reacted with an alcohol or a monohydric acid; polyesters derived from a phthalic acid / adipic acid mixture and a glycol, the end groups optionally having been reacted with an alcohol or a monohydric acid; and polyester derived from a mixture of phthalic acid and AGS acids and a glycol, the end groups optionally having been reacted with an alcohol or a monobasic acid. It is also possible to use lactone-modified, for example ε-caprolactone-modified, polyesters of the types mentioned above. ·

As mixtures of the preferred esters of phosphorus acids with other plasticizers, stabilizers, Fillers, etc. come. E.g. the following are considered:

1. Phosphate ester. + Esters of aliphatic dicarboxylic acids (ADSE) + chlorinated hydrocarbons or hydrocarbon extenders

2. Phosphate ester + phthalic acid ester

3. Phosphate ester + phthalic acid ester + chlorinated hydrocarbons or hydrocarbon extenders

709818/1 114

- 41 -

4. Phosphate ester + phthalic acid ester + ADSE

5. Phosphate esters + phthalic acid esters + ADSE + chlorinated hydrocarbons or hydrocarbon extenders

6. Phosphate esters + chlorinated hydrocarbons or hydrocarbon extenders

7. Phosphate ester + ADSE

8. Phosphate ester + polyester

9. Phosphate ester + polyester + ADSE

10. Phosphate ester + polyester + phthalic acid ester

11. Phosphate ester + polyester + phthalic acid ester + ADSE

12. Aryl phosphate ester - »- haloalkyl phosphate ester + Phthalic acid ester

13. Kalogen alkyl phosphate ester + alkyl phosphate ester + Phthalic acid ester

14. Aryl phosphate ester + haloalkyl phosphate ester + Phthalic acid ester + ADSE

15. Phosphonate ester + phthalic acid ester.

-. Further examples of the compositions according to the invention are Mixtures of haloalkyl phosphate esters and phosphorus-free Plasticizers, among which mixtures the following may be mentioned: Tris (2-chloroethyl) phosphate + aryl alkanesulforic acid, Tris (2-chloroethyl) phosphate + phthalic acid butylteneyl ester, Tris (-2-chloroethyl) phosphate + dioctyl phthalate, tris (2-chloroethyl) phosphate + Triinellitic acid ester, tris (2-chloroethyl) phosphate + Dioctyl adipate and tris (2-chloroethyl) phosphate + one derived from phthalic anhydride and a glykoi Polyester, the end groups with an alcohol or

709818/1114 - 42 -

sr

a monobasic acid have been reacted.

As mixing ratios of the haloalkyl phosphate ester with the phosphorus-free plasticizer comes one area from 1: 1 to 100: 1, preferably 1: 1 to 10: 1 and particularly preferably 1: 1 to 5: 1; a mixing ratio of 1: 1 is particularly preferred.

Furthermore, any of the above-mentioned combinations, any individual esters of phosphorus-containing acids or mixtures of such esters or, if appropriate, combinations thereof with optionally phosphorus-free. Plasticizers, each together with silicon dioxide, barium metaborate, SbpO ^ and their stretching, Al (OH), or "aluminate trihydrate", Carbon, calcium carbonate, clay-like fillers and stearic acid coated calcium carbonate, individually or in any Combinations.

Furthermore, any of the above combinations can be used together with PVC stabilizers, e.g. calcium / barium stabilizers, Cadmium / barium / zinc stabilizers, tribasic lead sulfate, pasty white lead, carboxylic acid thio-tin compounds and tin carboxylic acid compounds, with proportions of the PVC stabilizer from 0.01 to 7 parts per hundred parts of the polymer come into consideration.

If ester combinations or plasticizer combinations are used, the mixing ratios can vary widely Move boundaries; Usually the purpose of the Polymer and e.g. the question of whether it is a. black or transparent polymer, the mixing ratio

709818/1 1 U

- 43 -

affect ratio. Such amendments are general Knowledge of a professional.

The aromatic compounds used according to the invention of the formula R (CIO: I are either known or can be omitted further prepare according to well known procedures. To the Example can be the aromatic starting compound by reaction be chloromethylated with formaldehyde and hydrogen chloride gas. This implementation is in "Organic Reactions", Vol. I, 63 (1942). Other .invention Compounds can be produced by further nucleophilic exchange reactions of the chlorine atom.

Examples of such reactions are:

R.CH ₂ Cl + EOH + CH ₃ OH -> R.CH ₂ OCH ₃ R.CK ₀ Cl + CH ^ COOK -> R.CH ₀ OCOCH ^

+ KOH - ^ R.CH ₂ OH

R.CH ₂ OCOCH ₃

R.CH ₂ Cl

R.CH ₂ Cl + KCN - } R.CH ₂ CN R.CH ₂ Cl + (CH ₃ J ₂ NH -> R.

R.CH ₂ Cl + (C ₂ H ₅ ) ₂ NC-S-Na -> R.CH ₂ SCN (C ₂ H ^) ₂

S S

R.CH ₂ Cl + HCOONa -> R.CH ₂ OOCH

R.CHpCl compounds can also be produced by side chain chlorination of methyl groups, ie by reacting R.CH ₃ compounds with chlorine gas.

Groups different from -CH ₂ Cl can be introduced directly into the aromatic nucleus by single-stage reactions. A lecture on such implementations is in

709818 / 11U

- 44 -

"Formation of CC Bonds", Vol. I, by Jean Mathieu and Jean Weill-Raynal, can be found. The following are examples of CH ₂ X groups that can be introduced directly into the aromatic nucleus:

-CH ₂ Cl, -CH ₂ OH, -CH ₂ OCH ₃ , -CH ₂ OCOCH ₃ , -CH ₂ SC ₂ H ₅ , -CH ₂ SC ₆ H ₅ , -CH ₂ N (CH ₃ ) 2 and -CH ₂ N (C ₂ H ₅ ^.

Other and less direct ways of preparing the compounds of the formula R (CHpX) use. For example, one can add an aldehyde group either directly, - by reaction with carbon oxide, or by hydrolysis introduce a dialkoxymethylated or dihalomethylated aromatic into an aromatic compound. The aldehyde group can then be reduced to the hydroxymethyl group.

R.CHCl ₉ )

^) + H ₉ O - } R.CHO R.CH (0C ₂ H ₅ ) ₂ ) ^ ·

R. CHO -> R. CH ₂ OH

The hydroxymethylated aromatic compound can also be used as an intermediate for the preparation of other R (CH ₀ X) compounds, for example according to the following scheme. R.CH ₂ OH + C ₆ H ₅ CH ₂ Cl -> R.CH ₂ OCH ₂ C ₆ H ₅ R.CH ₂ OH + (CH ₃ CO) ₂ O -> R.CH ₂ OCOCH ₃
R.CH ₂ OH + CH ₃ C ₆ H ₄ SO ₂ Cl -> R.CH ₂ OSO ₂ C ₆ H ₄ CH ₃

Further details of some production processes for the compounds according to the invention are described below. The exemplary embodiments of these methods relate to some specific derivatives, but also to the preparation of Derivatives of other aromatic R groups are suitable.

709818 / 11U - 45 -

Procedure A. 4,4'-bis (chlorineethyl) biphenyl

0.1 mol of diphenyl, 0.075 mol of paraforaldehyde, 0.07 mol of zinc chloride and 50 ml of cyclohexane are treated with dry hydrogen chloride gas at 55-60 ° C. for 20 hours while stirring. The reaction mixture is poured into water and the organic constituents are extracted with cyclohexane. By evaporating the cyclohexane solution to dryness, 0 _} 06 mol of the product = 60 percent of theory. Th. Obtained from melting point 137 ° -8 C. Derivatives of this compound can be prepared by conventional methods. Method B. 4,4'-bis ( methoxy meth yl) biphenyl

0.1 mol of 4.4 ^t -3is (chloromethyl) biphenyl (prepared by process A mentioned above), 0.4 mol of potassium hydroxide and 150 ml of methanol are stirred under reflux for 4 hours. The reaction mixture is neutralized with concentrated hydrochloric acid and filtered. The filtrate is evaporated to dryness at 80 ° C. under a water jet vacuum and the residue is subjected to fractional distillation. Collecting of 154 ⁰ C to 156 ° C at 0.2 Torr fraction passing over. Yield = 0.075 mol = 75 percent of theory Melting point = 47-49 ° C.

Method C. 4,4'-bis (acetoxymethyl) biphenyl

The mixture is stirred 0.1 mole of 4,4-bis ^f (chiοmethyl) biphenyl (prepared according to above of Method A), 0.25 moles of potassium acetate and 100 ml of glacial acetic acid for 17 hours reflux, filtered and the Reaktionsgeraisch the filtrate evaporated at 80 ⁰ C under a water jet vacuum to dryness. By

709818/1 1 U - 46 -

crystallization of the residue from methanol is 0.068 mol of product = 68 percent of theory. obtain; Melting point =

86 ° -87 ° C.

Method D. 4,4 * -bis (hydroxymethyl) biphenyl

0.1 mol of 4.4 ^t -bis (acetoxymethyl) biphenyl (prepared by process C mentioned above), 0.4 mol of sodium hydroxide (as a 23 percent aqueous solution) and 50 ml of ethanol are stirred under reflux for 3 hours. The reaction mixture is filtered and the precipitate is washed with water and dried; Yield 0.08 mol of product = 80 percent of theory; Melting point = 195 ° -97 ° C.

Ve process E. Polyester from 4,4' -bis (hydroxymethyl) biphenyl und.phthalic anhydride

It is heated 0.2 mole of 4,4'-bis (hydroxymethyl) biphenyl (upward-called method D prepared), 0.1 moles phthalic anhydride, 10 ml of xylene and 1.0 g of dibutyl tin oxide to 200 ⁰ C and removed the resulting water azeotropically. After 3 hours there is no more water; the reaction mixture is cooled and a white solid product with a melting point of 124 ° -14O ° C. is obtained.

Procedure F. Hydrolysis of 4 _s 4'-bis (Chloi-Methyl) biphenyl prepared polymer

0.1 mol of 4,4'-bis (chlorinethyl) biphenyl is stirred (prepared by method A above), 0.5 mol of potassium hydroxide and 250 ml of water under reflux for 30 hours, cooled the reaction mixture and then shaken out repeatedly with hot chloroform. . The chloroform extracts are combined

709818/1 114

- 47 -

and evaporated to dryness, and receives a white solid product with a melting point == 14O ° - 155 ⁰ C. Procedure G. Bishydr oxymethylbisphenol-A respectively. 2,2-bis (3 -hydroxymethyl-4- hydroxyphenyl) propane

3.75 moles of formaldehyde (as a 37% strength by weight aqueous solution) are added to a mixture of 1.5 moles of bisphenol A, 3s3 moles of sodium hydroxide and 1.200 g of water, and the resulting solution is stirred for 43 hours at room temperature. After neutralizing the reaction mixture with dilute hydrochloric acid, the product precipitates as a plastic solid and is dissolved in ether. The ether layer is dried and the solvent is distilled off at 60 ° C. and 20 torr. (Ie, 98% of theory 1.48 mol.) Gives a brown solid with melting range of 45 ~ 65 ⁰ C.
Method H. Bisace toxymethylbisphenol A diacetate

16.0 mol of acetic anhydride and 0.98 mol of anhydrous sodium acetate are added to 1.0: mol of bishydroxymethylbisphenol A and the mixture is heated to 100 ^° C. for 5 hours while stirring. Half of the acetic anhydride is then ^{heated to 50 °} C. at 20 torr distilled off. The distillation residue is cooled to room temperature, diluted with water and the product is extracted with toluene. After the toluene has been distilled off under reduced pressure, the product is obtained as a yellow, viscous oil (0.12 mol, ie 93 pounds of theory). Method I. 1.5 ~ bis ( bromomethyl) naphthalene

A mixture of 0.32 mol of 1,5-dimethylnaphthalene is added. 600 ml carbon tetrachloride and 0.3 g dibenzoyl peroxide in

709818/1 1 U - 48 -

one equipped with a stirrer, thermometer and water separator Pistons. The contents of the flask are heated to 77 ° C. and add 0.70 mol of N-bromosuccinimide and 1.5 g of dibenzoyl peroxide are added alternately over the course of 55 minutes. The reaction mixture becomes viscous and after the addition of 900 ml of carbon tetrachloride, the reaction is continued for 3 hours under reflux. The product is filtered off and Washed hot with 400 ml of carbon tetrachloride. The filtrate is concentrated on a rotary evaporator to half the initial volume and filters off a further portion of the product. A beige solid is obtained (0.09 mol, i.e. 28% of theory).

F Ver Ahr e_n_ J. Bi s- (3- (2 ' -hydroxyphenoxy) -2-hydroxy propyl) ether of 1,4-butanediol

This compound is obtained by adding 1 mole of bis-2,3-epoxypropyl ether to 2 moles of o-hydroxymethylphenol of 1,4-butanediol.

In part, the mixture of compounds (a) and (b) itself acts as a plasticizer for the chlorine-containing polymer to serve; if this is not the case, conventional plasticizers can be added.

For example, the flexibility of the polymer can be ^{improved by adding 4.4 t} -bis (methoxymethyl) biphenyl. If the last-mentioned plasticizer is used in various mixing ratios with Reofos 95, with a constant total plasticizer content of 70 percent, the following results are obtained:

709818/1114

- 49 -

26A8701

4,4'-bis (methoxyraethyl)
biphenyi
Parts More aromatic
Ester
(Reofos 95)
Parts Readings 5
10
20 ·
35 65
60
50
35 IKHG 69.0
68.0
65.5
63.0

If desired, the flame resistance can be improved without using the compositions according to the invention Deterioration and possibly even with improvement in the pliability of the PVC compounds. By adding conventional Plasticizers for the purpose of improving the pliability of PVC, the anti-fouling properties are reduced. Surprisingly it has now been found that certain compositions according to the invention have good flame retardancy can achieve good suppleness at the same time. On the other hand, in some cases, improved flame retardancy becomes without simultaneous increase in suppleness may be desirable. and that can also be done with the compositions according to the invention achieve.

Certain compositions according to the invention also show reduced smoke development. This must be described as surprising, since improved flame retardancy usually occurs leads to increased smoke development.

The compositions according to the invention can be used for a wide variety of objects. For example

70 98 18/11 U
- 50 -

rigid PVC masses according to the invention can be used in roof coverings, Window frames, hard foam extruded profiles, e.g. rub strips and door frames, cover plates and systems for the chemical industry. As examples of Applications of self-supporting PVC masses are floor coverings, foils, panels, insulation cables and casings, elastomers Foams, tapes for electrical insulation and for association purposes, vehicle components such as dashboards, Crash pads and floor mats, toys and novelties, various molded parts, e.g. made by blow molding Bottles, records, sporting goods, tools. and tubing for general and medical purposes called. Examples of applications for PVC-coated fabrics or PVC-coated papers include floor coverings, like '■ PVC-coated felt or PVC-coated Jute or carpets coated with PVC on the back, tarpaulins, conveyor belts, ventilation hoses, airborne Halls, weather curtains, room dividers, wall coverings, Leather cloth, e.g. for upholstery and seat cover in motor vehicles and in the home, clothing, e.g. baby pants, footwear and outerwear, tents, roof coverings, sheet metal coating (both by lamination and plastisol coated), hoses, surface coatings and dip-coated objects, e.g. B. Container.

The following examples, where parts are to be understood as parts by weight, illustrate the invention.

709818/1 1 U - 51 -

Examples 1 - 121

PVC masses are used with the various in the Tables listed compositions prepared, the amounts given relate to weight. the Masses contain 100 parts PVC and heat protection agent.

The masses are placed on a laboratory two-roll mill for 15 minutes mixed at 165 C and then pressed on a heated press to 150 mm 150 mm 2.5 mm plates. the Plates are then aged for 5 days at a constant temperature of 23 ° C.

At the end of this treatment, the IKHG (International Rubber Hardness Degrees = Internationaler Rubber hardness according to BS9O3) and the oxygen / index = oxygen value (01 according to ASTM 2863) of the plates.

In order to enable a comparison with compositions without compound (b), comparative examples are also given. The corresponding comparisons can be found in the tables. The smoke development (Tables 3 and 17) is measured by means of a Aminco NBS chamber using the "flaming" test method, measured. D represents the maximum specific optical density, as measured value with correction due to soot build-up on the light source and the windows of the photocell, represent.

A comparison of Examples A and D of Table 1 shows that by changing the composition of the mass from 70 percent Reofos 95 (Reofos 95 is a triaryl phosphate made from isopropylphenol and phenol) to 50

709818/1114

- 52 -

Percent Reofos 95 plus 20 percent di-2-ethylhexyl phthalate the oxygen index is lowered by 4 units. Surprisingly but it was found that when changing a similar order of magnitude in cases of the erfindungsgeraässen Measures, in Examples 1-13 »the oxygen index increases.

■ 709818/1114

- 53 -

O U O r-l O t-1 - / vO O in OO • t CO vO O Il • / —V
in O vO CN in in ■ υ (U σ \ VO CN in VO P-.O <f P. vO r- CT » CT » CO ce bO M. O _O in O VO r-l Sr- rj m CS Vw / CO CN m co VO sw: co β r-l «V et co «: O «V r-l CO r-l «V CN in co W) O CN CN OO I. CN nCJ ^ -s co Cl C. CO CO CO CN CO Ö "■ * UH ßrH in CT » VO TJ CN CO T CN CO ^ CTi CO CO I.
r-J r-l i-l PQ 9 r-l O <5 CD • r-l CJ / -N. CJ / - VO CQ + J U Φ Cr-I CN ν— / CN O CM (U I. co ^v ' I- CO U-4 ¹ I. W. U ti ^ / -v
O O" y ν
O P ^ 1 ο ¹ CN O O" • ¹ co υ O O" vO CJ m r-l φ r-l in in CO O I. P-M S- / Vw / P. in V / O CT » CJ pi CJ Nw / ν— / VO in • i-l CQ O . v_ / v_y 4- » O I.
(U O CO O in r-l Xi in in O I. T in m JS P. CQ he" in CT » Y M-I O T CT » CT » m m U I.
I. o ³ O CJ CT » CT » O 3
r-l CO CO CO Φ O CO CQ U
ill Φ O CO O pi CO O O CQ CQ r-l <w O «W i-l CO I. M-I M-I O O • rl O O O O O O M-I M-I Φ φ φ O φ r-l φ Φ O O pi φ pi pi pi φ φ pi pi pi * O O O O O CO P. • Η O r-l CN r-l r ^ O ε Φ CN CN CO r-l CJ ι
r-ί Φ CJ O (U • —I Il ο Il «^ CJ -U P. Il ο CQ co he" • O (U p.m • I • E he » PiO P. CO «H Evo CO CO ß Φ £ CJ CJ cö , CN CN C. CN CN I. wCO I. X id Ed Ti O O Ed O = CJ Q) I. I. O O PQ O O I. I. O Oil pi P. ¥ < PQ Q T P. • in vO CO

709818/11 U - 54 -

At-
No. R. X CH.
OH η TABLE 1 Her
positional
procedure Or
Kp. ■ Connection
ung (I)
Parts pho-containing
Ester
(Parts) Kataly
sator
(Parts) MEASURED VALUES IKffi 10 -0-C CE-
O 2 ·
2 D. M.p. =
1 ₅ 2 ° - ₅ V. 10
20th Reofcs 95 '(60)
Reofos 95 (50) Yo 01 79
95 11 Cl 2 \ j » Smp .. = 20 · Reofos 95 (50) - 58.5
41.5 64 * —I i c?: _
CH- Ca ₅ Cl 5 A. M.p. =
175 ° -75 ° C 20th Reofos 95 (50) SnCl-
0) ² 55.5 »9818/111 15th · / ^ 5
ι 20th Reofos 95 (50) SnCl-
(0.2?) !
72
to
CD C- 55.2 VJI

2 parts of a heat stabilizer were added to the masses based on barium / cadmium added.

Table 2 gives the results obtained by adding conventional plasticizers to the compositions according to the invention Effect on. The significant increase in the oxygen index when using the compositions according to the invention comes from the Comparison of Examples 14 and 15 with Comparative Examples EuF.

709818/11

1Ψ-

TABLE 2

O CO CO

OO

Ui - *

at
game
No. R. - X η Manuf
lungsver
travel M.p.
or
Kp. Connect
manure (I)
(Parts) phosphorus-containing
ger ester
(Parts) Kataly
sator
(Parts) MEASURED VALUES IKHG 14th OH 2 D. M.p. =
95-197 ⁰ C. 13th Reofos 95 (40)
DOP (10) - % OI Ver
equal
at-
game E - - - - - - Reofos 95 (40)
DOP (10) - 37.1 15th OH 2 D. M.p. =
95-197 ⁰ C. 13th Reofos 95 (30)
DOP (20) - 32.3 Ver
equal
at-
game F - - - - - Reofos 95 (30)
DOP (20) - 33.0 30.3

LSi

cn

co -j CD

R. X η TABEL 2 (continued) Connection
ung (I) phosphorus-containing
Ester Kataly
sator MEASURED VALUES IKHG . i
I. OH
OCH,
5 2
2 Srap. or Parts (Parts) (Parts) % OI 35 ■ 58) 4 I.
I. at
game OH ² Her
positional Kp. 10) ·
• ]
¹⁰ ] Rcofos 95 (50) ;> 3 _} 0 No. OH 2 ancestors M.p. =
! 92-197 ⁰ C
Mp =
47-49 ⁰ C 20th TXP (50)
¹ 16 D.
■
B. M.p. =
! .95-197 ⁰ C τ ?? (50) - 17th D. M.p. =
1.9 3-197 ^c ι- 18th D.

The mass was given 2 parts of a heat stabilizer based on barium / cadmium added.

TXP = trixylyl phosphate, ^

TPP - triphenyl phosphate

DOP = phthalic acid (di-2-a ^L fchylhexyl) ester

cn

CO

CD

The Raucb.dich.temesswerte masses according to the invention are given in Table 3. From these it emerges that certain compositions according to the invention (Examples 19 and 20) show less smoke development and a higher oxygen index than comparative example G. That must be surprising because improvement of the flame retardancy by conventional flame retardants is normally of accompanied by increased smoke development.

It can be seen that the oxygen index is significantly higher in the presence of the aromatic compound (b) and that furthermore in certain cases the suppleness is also improved. The PVC compounds are therefore both pliable as good flame retardant.

-.59 709818/1 1 U

TABLE 3: Density of smoke evolved from PVC compounds

CD
CO
GO

Example no.

Manufacturing
procedure

Smp. Or Kp.

Compound (I) parts

containing phosphorus

Ester

(Parts)

smoke

Max

YESS VALUES

% OI

Comparative example G

19th

20th

Heofos 95

(70)

444

M.p. = 195-197 ^

20th

Eeofos 95

(50)

521

M.p. = 195-19.7

Iteofoc 95

558

52.0

40.2

2 parts of a heat stabilizer based on barium / cadmium were added to the mass.

CD

OQ O

26Α8701

Table 4 en-thäli; Type b compounds that
together with Reofos 95 (one according to GB patent specification
No. 1 146 173 manufactured! Triaryl phosphate). It can be seen from Table 4 that Examples 21 52 show better values for the oxygen index than comparative example H. Furthermore, certain examples also show improved pliability, measured by the IKHG method, in addition to the improved oxygen index. These examples include 21, 23, 25, 26, 35, 36, 42 and 51. The property of good suppleness with a high oxygen index has not been achieved in the prior art. Examples 21, 23,
25, 29, 42 and 44 show such good suppleness
high oxygen index.

- 61 -

Table 4

Example! Ir.

■ procedure Kp

Her-

place

lung

Or

Connection (I) parts

containing phosphorus
Ester
(Parts)

stabilizer
(Parts)

MEASURED VALUES

% OI IKHG

22nd

23 24

25 26

27

ti

IT

If

Il HGO

0 I! CHoCO

N (CH ₃ ) ₂ O HO- / CH ₃ CO

C ₂ H ₅ O

Polymer

H ₂ OCCH ₂ CH ₂ -C-IOH

C C

A C / D

78 ° - SO ⁰ C

L15 ^e ~ ll6 ^c C.

35 ^Ö -86 ° C.

20th

65-130 ° C.

19o ° -95 ^e C.

ioofos 95
(50)

Dibutyl tin maleate (2)

45.7

Barium / cadmium] 39 laurate (2.0)

Irgast from 17 MOK (0.5)

Barium / cadmium laurate. (2.0)

Dibutyl tin maleate (2)

Barium / cadmium laurate (2.0)

, 4 ^ ■ 5.2 33.3

51.9 54.5

69.5

83.0 67.0 73.0

69, θ! 64.5

Dibutyl tin maleate (2)

+2.1

91.0

CO .P-CO

Table 4 (continued)

Example no.

28

29

HIGH

- ] OH

Poly-

merisat

Polymer

Manufacturing process

Smp. Or Kd.

Connection (I)

phosphorus-containing ester
(Parts ).

20 '

Reofos 95 (50)

Stabilizer (parts)

Dibuty1-tin paint (2)

Dibuty1 tin maleate (2)

MEASURED VALUES

% OI IKHG

45.5

71.0

86.0

81

Table 4 (continued)

Example] No.

33

OH

! OH

CHCH ₂ O-

-OH

Il OCCH,

Ηξγ-

place

lungs

imp. or

Connection (I) parts

tough
liquid

ZO

solid

Miasse

ZO

: uh
liquid

232-234 ^c

'C

20th

containing phosphorus
Ester
(Parts)

(70)

P. 95
)

Stabilizer (parts)

MEASURED VALUES

% OI IKHG

Dibutyl tin maleate (2)

Reofos 95 I dibutyl tin 41.6 (50) smaleate (2)

Roofοs 95
(50)

fReofos 95
(50)

Dibutyl tin maleate (2)

Dibuty1-tin maleate (2)

Reofos 95
(50)

Dibutyl tin maleate (2)

35.5

34.9

71

90

72

36.7

CT) OO

Table 4 (continued)

Example Sr.

Manufacturing process

Top. or

Kp.

Connection (I) parts

containing phosphorus
Ester
(Parts)

stabilizer
(Parts)

MEASURED VALUES

% OI IKHG

₃ C 00-iÖ) - @ - OOCCH ₃

CC

OCCHL 3

HO - ^ 5

S _

CH ₃ CO - ^) -

_f 3

OCCH ₃

OCH

I! CH ₃ CO

OH

I! OCQi,

■ Β

135-6 ⁰ C /
0.7 Torr)

65-70 ⁰ C

45-65 ° C

20th

20th

20th

20th

zälie
liquid

20th

Reofos 95
(50)

Dibutyl tin maleate (2)

35.5

76

37.0

65

37.0

34.8

66

96.0

34.0

75.5

Table 4 (continued)

Example no.

39

40

41

42

44

C (WO) -CH ₉ O CH

CK

[οίο].

X η

! I

OCCKo

I!

OCCIL

OH

OH OCH,

CO _n H

OH

Manufacturing process

Or

tough
liquid

43-6O ⁰ C

Connection (I) parts

20th

20th

127-loO ^e C

phosphorous
ster
(Parts)

Reofos 95
(50)

MEASURED VALUES

stabilizer
(Parts)

% OI

IKHG

Irgast from 17 MOK
(0.5)

Dibutyl tin maleate (2)

39.2

35.0

74.0

79.0

Barium / Cadmium Laurate (2)

45.9

64.0

Dibutyl tin paint (2)

38.7

59.6

90.0

88.0

Table 4 (continued)

example
No.

45

46

47

OH

OCCH,

OH

CH ₂ -

T *

CH,

H0- <£

Eo

OH

CH.

OH

production method

(Implementation temp.
= 65 ⁰ C)

Smp. Or Kp.

1O5-11O ^U C

tough

liquid

Solid, decomposes from 220 C

Connection (I) parts

20th

containing phosphorus
Ester
(Parts)

Reofos 95
(50)

Stabilizer (parts)

Dibutyl tin maleate (2)

MEASURED VALUES

% OI IKHG

40.5

38.3

71

co

CXD CD

Table 4 (continued)

at
game
No. R. X η Her-
place
lung
verabren Or
Kp. Ver
bind
ung (I)
Parts phosphorus-
more substantial
Ester
(Parts) stabilizer
(Parts) MEASURED VALUES IKHG 49
50
51 . OH
OH
-OCH ₂ CH ₂ OH
Il
C ₇ H ₅ OCO 2
2
2
2 •
D.
•
A.
A. /
t 20th
20th
20th
20th Reofos 95
(50)
It
It
It Dibuty 1- tin
male inat (2)
It
Dibutyl tin
maleinat (^ T % 01 88
65 34.9
37.7
35.4
37.6

. Table 5 lists various types of phosphorus-containing esters that were tested together with 4,4'-bishydroxymethylbiphenyl. Examples 52-66 show significant improvement in Oxygen Index over Comparative Examples I-Q. . ^:

- 69 -7 Π q β 1 Π / ι ι 1 /

Tabel

example

No.

four-thirds of the Lungsverfatran

M.p.
Kp.

or

Connection (I) parts

phosphorus-containing ester
(Parts)

Stabilizer (parts)

% Oxygen Index

Zl ι

53

I 54

J 55

M.p.
195-197 ° C.

M.p.
195-197 ° C

M.p.
195-197 ⁰ C.

20th

20th

20th

Diphenyl octyl phosphonate (50)

Dibutyl tin maleate (2)

P = O

with X = H or Br (bromine content 28.5%) (50)

"(70)

Diphenyl deoyl phosphate (50)

"(70)

ti π

it

34.5

28 51.7

47.0 41.2

28.0

Table 5 (continued)

Example no.

Manufacturing ■ process

Or
Kp.

Connection (I) parts

phosphorus-containing ester (parts)

Stabilizer (parts)

MEASURED VALUES

% Oxygen Index

56

OH

OH

OH

OH

OH

OH

p
195-197 ⁰ C.

M.p.
195-196 ⁰ C.

p
195-196 ⁰ C.

20th

20th

20th

20th

20th

20th

Reofos 95 (10) Tris- (2-chloroethyl; -pho sphat

Reofos 95 (25) tris (2-chloroethyl ) -pho sphat (25)

Reofos 95 (25) tris (2,3-dibromopropyl) phosphate (25)

Tris- (2-chloroethy1) pho sphat (50)

Tris (2-chloroethyl) phosphate

Reoplast

Reoplast 39 (4)

Reoplast 39 (4)

Reoplast 39 (4) dibutyl tin maleate (0.5)

Dibutyl tin maleate (2)

Epoxidized soybean oil commercially available under the brand name Reoplast 39 (4)

69.4

71.6

76.9

72.4

69.1

82.3

Table 5 (continued)

example

No. 62

63 L M N-64 O

OH

OH

OH

Her-

place

lungs

Or

Kp.

Connection
ung (I)
Parts

M.p.
195-196 ° C

M.p.
195-196 ° C

M.p.
195-196 ° C

20th

20th

20th

containing phosphorus
Ester
(Parts)

Trioctyl phosphate
(50)

Reofos 95 (70)

Tris- (2-chloroether) pho sphat

Trio octyl phosphate

Tris (2,3-dibromopropyl phosphate (50)

Tris (2,3-dibromopropyl) phosphate (70)

stabilizer
(Parts)

Dibutyl tin maleate (2.0)

Irgast from 17 MOK (0.5)

Dibutyl tin maleate (2)

Dibutyl tin maleate (2)

Dibutyl tin maleate (2)

Dibutyl tin maleate (2)

Dibutyl tin maleate (2)

MEASURED VALUES

% Oxygen Index

32.9

34.5 32.0 38.0

25.0 84.0 56.2

CD OO O

Table 5 (continued )

ο to co

Example no.

65

P 66

) CH,

OH

Production method

Or
Kp.

Connection
ung (I)
Parts

M.p.
47-49 C

M.p.
195-196 ° C

phosphorus-containing ester (parts)

Γο> 0! ρ

—0

CH ₃ -C-CH ₃

O / O P -0 (50)

CH ₂ Cl

Stabilizer (parts)

Dibutyl tin maleate (2)

Dibutyl tin maleate (2)

Dibutyl tin maleate (2)

Dibutyl tin maleate (2)

MEASURED VALUES

% Oxygen Index

49.6

41.6 61.5

40.0

The effect of various stabilizers / catalysts on the oxygen index of the compositions according to the invention is shown in Table 6. Preferred stabilizers / catalysts are (a) organotin compounds, as in the examples 68, 69, 70, 71, 72, 73, 78, 79 and 81 given, (b) epoxy compounds as given in Examples 74, 75 and 76 and (c) Silicon compounds as indicated in Example 73.

- 74 -

709818/1 114

Table 6

at
game
No. R. * U X η H he
st el-
1
processors Or
Kp. Ver
bind
ung (I)
Parts phosphorus-
more substantial
Ester
(Parts) stabilizer
(Parts) MEASURED VALUES
% Oxygen
index 67 ft OH 2 D. M.p.
195-197 ⁰ c. 20, Reofos 95 (50) tribasic lead sulfate
(6) 43.7 68 u · Il OH 2 D. M.p.
195-197 * 0. 20th ti Dibutyl tin oxide (2) 60.5 69 ft Il "OH 2 D-. IT 20th It Dibuty1-ζ inn-maleinat
(2.5) 66.7 70 It OH 2 D. tf 20th Il Irgast from 15 MOK (1.0) 60.1 71 OH 2 D. 20th Il Irgastab 17 (MOK) (0.5) 55.0 ' 72 OH 2 D. ·. . ■ dd 20th It Irgastab T36 (2) 65.2 73 OH 2 D ·. If 20th It Si (OCH ₂ CH ₂ OCH ₃ ) ₄ (2) 63.6 74 OH 2 D. ! I 20th Il under the brand name
Reoplast 39 in stores
available epoxy
dated soybean oil (4) 63.3 75 OH 2 · D. Il 20th It under the brand name
Lankroflex L in stores
available stabilizer
epoxy-based (4) 61.5

■ <P co

(DO «DO

Table 6 (cont. R. etching) η Her-
place
lung
ver & hcen. Or
Kp. Ver
bind
ung (I)
Parts phosphorus-
more substantial
Ester
(Parts) stabilizer
(Parts) MEASURED VALUES
% Oxygen
index X 2 D. M.p.
195-197 ⁰ C. 20th Reofos 95 (50) OCH ₀ CH ₀ OR
JL
ROCH ₂ -gj- CH ₂ OR 59.6 at
game
No. OH CH ₂ OR 76 R «-CH ₂ CH ^ CH ₀ ti 2 B. Smp. _
47-49 ° C 20th It Barium / cadmium laurate
(2) 37.7 dd OCH ₃ 2 dd If Il ti Dibutyl tin maleate
(D 49.6 77 Il 2 It If dd It Irgast from 17 MOK (0.3) 48.2 78 ti Il 2 C. M.p.
86-87 C ti It Barium / cadmium laurate
(2.0) 36.5 79 Il U
Il
DCCH ₃ 2 C. It It Il Irgast from 17 MOK (0.5) 45.2 80 It Reofos 95 (70) I.
Blank samples with each
one of the aforementioned
Stabilizers (1-4
Parts) 31-32 81 R.

CD CX)

26A8701

Table 7 contains examples of various mixing ratios of the compounds (a) and (b) and various Health concentra ons of additives. It can be seen that even with the addition of only 5 parts of compound (b) (Examples 87 and 89) a significant increase in the oxygen index can be achieved.

If 30 parts of compound (b) are used, as in Example 83, a PVC with a very high oxygen index is obtained very good smoothness preserved; the combination of these properties can be based on the previous status of Technology not achieve.

- 77 709818 / 11H

Table 7

co

«Ο -j. CO

at
game R. X η Her-
place
lung Or Ver
bind
ung (Jp) phosphorus-
more substantial
Ester stabilizer MEASURED VALUES IKHG No. OCH ₃ 2 procedure Kp. Parts (Parts) (Parts) % OI 56.0 82 H It Il B. M.p.
47-49 ⁰ C 25th Reofos 95 (50) Dibutyl-tin
maleinat (1) 48.2 51.5 83 ti dd ti dd dd 30th Reofos 95 (70) Il 48.4 77 84 dd It It It It 20th Reofos 95 (30) ti ' 43.6 68 85 ti dd dd ti ti 30th Reofos 95 (30) dd 45.2 86.5 86 ! I OH ti dd dd 11.5 Reofos 95
(28.5) ti 39.3 77.0 • 87 dd dd dd D. M.p.
195-197 ⁰ C. 5 Reofos 95 (70) Dibutyl tin
maleinat (2) 46.5 87.0 88 ti dd dd dd dd 20th Reofos 95. (70) dd 61.7 94.0 89 - - - dd dd 5 Reofos 95. (5O) dd 49.2 99.0 S. - - - - - - Reofos 95 (30) it 36.0 91.0 T - - - - - - Reofos 95 (50) It 33.2 71.0 U - - - Reofos 95 (70) ti 32.0

Table 8 shows examples of the invention
Masses made with a conventional PVC plasticizer, ie
Dioctyl phthalate. From this table it can be seen that even with the presence of conventional PVC plasticizers, the oxygen index values can be increased significantly.

- 79- 7 0 9 818/1 1 14

Table 8

example

production method

Sm ^- D. or
Kp '.

Connection
ung (I)
Parts

phosphorus-containing ester
(Parts)

PVC plasticizer
(Parts)

Stabilizer (parts)

MEASURED VALUES

% Oxygen Index

90

-J
O
co
GO V
91 co ^ l
- * co W. 92 X 93

94

95

OH

OH

OH

OCH,

M.p.
195-197 ° C

M.p.
195-197 ° C

M.p.
195-197 C

M.p.
47-49 ⁰ C

15th

15th

15th

10

Reofos 95 (40)

Reofos 95 (30)

Reofos 95 (25)

Reofos 95 (40)

Reofos 95 (30)

Reofos 95 (40)

Diobyl phthalate
(10)

Dioatyl phthalate
(20)

Phthalic acid diolyl ester
(25)

Dioctyl phthalate
(10)

"(20)

"(10)

Dibutyl tin maleate (2)

I!

!!
Il

48.5

32.1 39.0

30.6 35.0

29.6 37.1

34.1 35.9

In the examples given in Table 9, a compound b is combined with a further aromatic compound with empty positions on the aromatic ring, mixed.

- 81 -

708818 / .11U

H
Eh
CD

CQ CQ

OO

ι -ö η

in Ö ίΐΟ · Η

ω · η ö ω

> ». Q 3 Eh

O H OH

ω ο

to

•H

CQ

co -p

sd H ω

VO

■ I CO

CD

bOI ^

U ω d uxi (DP PO Cd ffi CQr-J ><H

cn

O = J O

O = U O

ι ω

-H-H

a ca g;

νθ νΤν

709818/1 1 1 k _ 82

co co

M O

• Η U <ΰ H O H • Η -P ■ Η , Q CO Φ CD PI -P

CO CQ-

H ω -P ω Η

CÖ-P · Η

ω -ρ ω

3U

U ^ Φ Φ faOhH rrt Φ Ή

! "Η -ρ φ

co

O LO Ii ι ν_ ^ ·

O Φ ir, ω ο ο m

ο ω «η Pd CTx

O H

Ö bO-H

η ö ό

O rH

t-4

Q>

a a

COW

P ο

VD

τ-4 O ο

ι- « . ι m cn

U ω C ω-μ ρ

ffi CQH

CQ

W) I

φ cd

j. a

co

O ^ CTv

- 83 ■

709818 / 11U

26487Q1

In the examples given in Table 10, mixtures of monomeric and telomeric compounds are used together with Phosphate esters used as additives.

The part used in Examples 100, 101 and 102 is produced as follows:

4,4-bis (methoxymethyl) biphenyl (0.5 mol), diphenyl ether (0.5 mol) and tin (IV) chloride as catalyst (0.2 ml) are warmed to 150 ^° C. with stirring and the treatment is started at 150 ° C., with the methanol formed being distilled off, until 16 g (0.5 mol) of methanol are collected. The reaction mixture is allowed to cool, it is placed on a rotary evaporator and traces of methanol and tin (IV) chloride are driven off under vacuum at 80.degree. A very viscous brown product remains.

Yield = 190 g.

- 84 709818/1 1 U

Table 10

at
game
No. R. X η Her-
place
lung
ver
travel Or
Kp. Ver
bind
ung (I)
Parts phosphorus-
more substantial
Ester
(Parts) Additive- ·
middle
(Parts). stabilizer
(Parts) MEASURED VALUES IKHG 100
101
102 OH
OCH ₃ 2
2 D.
B. 195- -
197 ⁰ C.
47-49 ^e C. 10
10 ·
■ /
1 Reofos 95
(50)
Reofos 95
(50)
Reofos 95
(50). * (10)
* (10)
* (10) Dibutyl tin
maleinat (2)
Dibutyl tin
maleinat (2)
Dibutyl tin
maleinat (2) % OI 78.0
85.0
68.5 45.7
60.7
45.3

• x CH ₃ OI

-CH ₉ -OCH,

CJ9 OO O

26A8701

Table 11 shows examples of the use of the compositions according to the invention in a vinyl chloride / vinylidene chloride copolymer. From Table 11 it can be seen that when the compositions according to the invention are used in the abovementioned copolymer, the oxygen index is increased by more than 20 units
can be increased.

- "86 7098 18/1 1 H.

Table 11. Vinyl chloride / vinylidene chloride copolymer (Breon CS.100 / 30)

at
game
No. R. X η Her-
place
lung
ver
travel Or
Kp. Ver
bind
ung (I)
Parts phosphorus-
hal tiger
Ester
(Parts) Stabilizer (parts) ' MEASURED VALUES IKHG Y
103 OH 2 D. M.p.
195-197 ⁰ C. 20th Reofos 9.5
(50)
Il Dibutyl tin maleate (2)
It Il Il % 01 91
92 34.0
54.9

26A8701

Table 12 serves to further explain the
Invention by specifying compositions according to the invention which contain PVC plasticizers or extenders. It can be seen from the table that all of the examples according to the invention have a higher oxygen index than the comparative examples.

- 88 -

709818 / 11U

Tabel

Example no.

104

105

A ^! 106

B ^! 107

108

D '

109

E '

OH

DCH,

OH

OH

OH

OH

Her-

place

lung

ver

travel

Smp. Or Kp.

M.p.
195-197 ° C

M.p.
47-49 ⁰ C

195-197 ^U C

195-197 ⁰ C.

195-197 ^U C

195-197

Connection (I) parts

phosphorus-containing ester (parts)

20 20

20th

20th

20th

20th

Reofos 95 (25)

dd

I?

PVC plasticizer or
Extender
(Parts)

Cerechlor
S52 (25)

Bisoxlex
PCB (25)

Reoplex 903
(25)

Citroflex
A4 (25)

Mesamol (25)

stabilizer
(Parts) '

MEASURED VALUES

96.01

IKHG

Dibutyl tin maleate (2)

Reoplas 39
(4)

Dibutyl tin maleate (2)

44.5 35.7

33.5 31.7

28.6 31.6

29.2 36.5

29.2 36.6 27.1

64.8

■ ■ 26A8701

Table 13 gives examples of the use of the inventive compositions in chlorinated polyethylene, from the table it can be seen that a significant increase of the Oxygen Index is achievable.

These compositions are the examples PVC similarly prepared on a laboratory two-roll mill, but in the absence of Yfärmeschutzmittels is carried out, and the 36% strength and 46% ig-chlorinated polyethylene at 18O ⁰ C and 100 ⁰ C rolled.

~ 90- 709818/1 ίΗ

Table 13. Chlorinated polyethylene

at
game
No. R. - X n Her-
place
lung
procedure Snrp. or
Kp. ' Ver
bind
ung (I)
Parts phosphorus-
more substantial
Ester Chlorine content
of
chlorinated
Polyethylene
% Stabilizers • Oxygen
index F ¹ - -, - - - Reofos
95
(50) 36 - 22, ^ 110 - OH 2 D. M.p.
195-
197 ⁰ C. 20th Reofos
95
(50) 36 - 39.9 G ¹ - - - - Reofos
95
. (5O) hz - 26 j I 111 OH- 2 M.p.
195-
197 ^e Ci 20th Reofos
95
(50) concentration camp 59; 7

Table 14 serves to further explain the invention by means of examples of compositions according to the invention, the Contains PVC plasticizers. The table shows that all examples according to the invention have a higher oxygen Have index than the respective comparative examples.

- 92 709818 / 11U

Table 14

at
game
No, R. X η Her-
place
lung
proceed Smp »
or
KP, Ver
bind
ung (I)
Parts phösphor-
more substantial
Ester
(Parts) stabilizer
(Parts). . phosphorus-free
¥ eichinacher
(Parts) ί Measuring
•values
0.1- 112 -CH ₂ OH 2 D. 127-
i6o 20th Tris (2-chlorine-
■ ethyl) phosphate
(lÖ) ep oxidized s
Soybean oil
(4) Phthalic acid.
dioctyl ester
(40) 31.2 J ¹ - - - - » f » 25.4 113 -CH ₂ OH 2 D. 127-
16 0 20th Tris (2-chlorine-
ethyl) pho sphat
(.15) Phthalic acid
dioctyl ester
(35) 4j, l κ ¹ - - - - ti ff 27.4 114 (ojo)
I. -CH ₂ OH 2 D. 127-
l60 20th TrIs (2-chloro
Oethyl) pho sphat
(20) tf Phthalic acid
dio.ctylester
(50) 50.7 L ¹ - - - - U
, Jf 28.3

co --α

Table 15 contains further examples according to the invention.

- 94 -709818/1 114

Tabel

- »VO I.

Example no.

115

116

117

118

119

SH

OH

OCH ₂ CH-CH ₂

learning

positional

/Experienced

M.p.
or
Kp.

Connection (I) parts

phosphorus-containing ester
(Parts)

Reofοs 95 (50)

Reofos 95 (50)

Reofos 95 (50)

Reofos 9: (50)

Reofos 95 (50)

Stabilizer (parts)

Dibutylz innmaleinate (21)

MEASUREMENT CITY

O.I.

35.3

61.8

IKHG

39.7

33

84.5

Tabel 15 (port setting)

Example no.

Her-

positional

of fäiren

M.p.
or

Kp.

Ψβν-

Dind-Jng (I)
Parts

Phosphorus-containing ester (parts)

Stabilizer (parts) '

MEASURED VALUES

O.I.

IKHG

120

121

OC- <g>

OH OCH

20th

Rcofos 95 (50)

Dibutyl tin maleate (21)

20th

Reofos 95

36.4

36.4

M ¹ HeοTos 95

(50) (70!

TI 1 »

34.0

32.

26A8701

Examples 122-130

PVC compounds are made with various plasticizers and aromatic carboxylic acid ester compounds specified in the table, in the quantities listed in the table (parts by weight) manufactured. The masses contain 100 parts of PVC and 2 parts of a cadmium / barium heat protection agent.

The masses are mixed for 15 minutes on a laboratory two-roller frame at 165 ^° C. and then pressed on a heated press to give 150 mm × 150 mm × 2.5 mm plates. The plates are then aged for 5 days at a constant temperature of 23 ° C.

The IKHG will complete this treatment (International Rubber Hardness Degrees = international rubber hardness degree according to BS903) and the Oxygen Index = oxygen value (OI according to ASTM 2863) of the plates.

In order to enable a comparison with compositions without compound (b), comparative examples A to G are also given. Table 16 shows the corresponding comparisons.

-'97 709818 / 1.1 U

TABLE 16

O CO CO

VO

oo

Example no.

ο η

• H (D

ω -η η ρ, B

fclO W

Φ (D ρ

122

123

3 D ₁

P-, cd ω

124;

125

Cl

Cl

Cl

Cl

Manufacturing process

travel

Or

Kp.

M.p. =
137 ° _8 ° C

Connection (I) parts

O O

M.p. =
137 -8 ⁰ C

20th

10

O O

20th

20th

aromatic ester
(Parts)

Dioctyl phthalate
(DOP) (70)

(70)
(50)

(50)

(60)

Catalyst (parts)

SnCl, (D '

(70)
(70)

Phthalic acid butyl

benzyl ester

(BBP) (50)

(BBP) (50)

SnCl, (D '

SnCl,

MEASURED VALUES

% OI

22.3

22 _? 7 24.2

27.8 25.4

SnCl,

(D ^£

SnCl,

(D ^c

24.7 25.3

33.4

27.7

IKHG

66

66 80

71 68.5

66

66

77

66

CX) CD

TABLE 16

130

rIn

CH

-0-C

-o-c

I! ο

CH,

CH,

CH ₃ O

Cl

Her-

place

lung

ver

travel

Smp. Or

Kp.

Sm. =
47 ^ΰ -9 ° (

Connection (I) parts

20th

20th

20 aromatic ester
(Parts)

(50)

(50)

Phthalic acid di-2-phenoxyethyl ester (50)

Phthalic acid di-2-phenoxyethyl ester (50)

(50)

Phthalic acid di-2-phenoxyethyl ester (70)

(70)

catalyst
(Parts)

SnCl,
(I) ''

SnCl

SnCl,

(D '

SnCl,

(D '

DOP is a phthalic acid ester based on 2-ethylhexanol.

MEASURED VALUES

01

25.6

27.4

27.5

33.5

26.7

25.8 28.0

IKHG

60

60

76

84

78

90 91

Comparing Example B with Examples 122 and 123 in Table 16, it can be seen that with the inventive A significant increase in the oxygen index can be achieved by the masses. In Example 129, neither the as a plasticizer, aromatic esters nor compound I of the composition used any conventional flame retardant Components, and yet an oxygen index of 33.5 units can be achieved, which is the order of magnitude of the usual corresponds to the values achievable with conventional flame-retardant plasticizers.

In example 124, too, the Oxygen Index of 33.4 percent achieved with the specified mass is higher than from Chlorine content of the total mass could be foreseen, although compound I contains chlorine.

It can be seen that the oxygen index is significantly higher in the presence of the aromatic compound (b) and that in certain cases the suppleness is also improved. So, the PVC masses exhibit both suppleness as well as good flame resistance.

- 100 -

709818 / 11H

Claims (1)

PATENT APPLICATION: 1. . Mass based on a chlorine-containing aliphatic Polymer, characterized in that it (a) an ester of a phosphorus acid, an aromatic carboxylic acid ester, Sulphonic acid esters or carbonic acid esters or a mixture thereof, and Cb) a compound of the formula I R (CH ₂ X) _n in which P. denotes an aromatic hydrocarbon radical or heterocyclic radical, η an integer of at least 2 and the X are the same or different and each represent a leaving group. 2. Composition according to claim 1, characterized in that an ester of a phosphorus acid is present as the ester. 3 * mass according to claim 1, characterized in that an aromatic carboxylic acid ester, sulfonic acid ester or carbonic acid ester is present as the ester. 4. Composition according to claim 1, characterized in that the chlorine-containing aliphatic polymer is a thermoplastic is present. 5. Composition according to claim 1, characterized in that the chlorine-containing polymer is a homopolymer or copolymer with a chlorine content of at least 5% . 6. Composition according to claim 5, characterized in that the chlorine-containing polymer contains more than 20? G of chlorine. 7. Composition according to claim 6, characterized in that the chlorine-containing polymer contains at least 40% chlorine. 8. Composition according to claim 1, characterized in that 709818/1114 - 101 - the chlorine-containing polymer is present in a blend with another polymer. 9. Composition according to claim 1, characterized in that the chlorine-containing polymer is a vinyl chloride homopolymer or copolymer or a chlorinated polyolefin is present. 10. Composition according to claim 2, characterized in that the ester of a phosphoric acid is an ester of phosphoric acid, a phosphonic acid, a phosphinic acid, the phosphorous acid or whose dewatering products are present « 11. Composition according to claim 2, characterized in that the ester is a fully esterified compound. 12. Composition according to claim 2, characterized in that an ester of pentavalent phosphorus is present as the ester. 13. Composition according to claim 12, characterized in that as an ester a triaryl phosphate, an alkyl diaryl phosphate Tris-haloalkyl phosphate, a mixture of these aryl / haloalkyl phosphates or a mixed arylhaloalkylphosphate is present. 14. Composition according to claim 3, characterized in that the carboxylic acid ester is a phthalic acid ester, benzoic acid ester or mellitic acid ester is present. 15. Composition according to claim 3, characterized in that the aromatic ester is an ester with non-deactivated Benzene nucleus is present. 16. Composition according to claim 3, characterized in that the aromatic ester is butylbenzyl phthalate or 709818/11 U - 102 - Phthalic acid bis-phenoxyethyl ester is present. YJ. . Composition according to Claim 3, characterized in that the aromatic ester present is an ester conventionally used as a plasticizer for vinyl chloride polymers. 18. Composition according to claim 1, characterized in that the group R represents a monocyclic, dicyclic or polycyclic, fused or non-fused group. 19. Composition according to claim 1, characterized in that R contains more than one independent aromatic radical, these radicals being linked by carbon-containing or heteroatom-containing groups or groups containing both carbon atoms and heteroatoms. 20. Composition according to claim 19, characterized in that the linking group consists of recurring aryl groups or heterocyclic groups, the linkage of is derived from a -CHpX group. 21. Composition according to claim 20, characterized in that further, non-linking, -CI ^ X groups are present. 22. Composition according to claim 19, characterized in that the linkages comprise no more than 3 carbon atoms. 23 · Composition according to claim 1, characterized in that R by one or more halogen atoms or alkyl groups with 1 to 12 carbon atoms, alkenyl or alkynyl groups with 2 to 12 carbon atoms, cycloalkyl groups with 5 to 12 Carbon atoms, hydroxyl groups, alkoxy groups with 1 to carbon atoms (which optionally contain an epoxy group) , Cyclοalkoxy groups with 5 to 12 carbon atoms, 709818 / 11U - 103 - Acyloxy groups having 1 to 12 carbon atoms, carboxyl groups or carboxyalkoxy groups having 2 to 12 carbon atoms, or their. Mixtures, is substituted,
24. Composition according to claim 1, characterized in that R is an otherwise unsubstituted or alkyl-substituted dicyclic, tricyclic or tetracyclic radical
represents. 25 * .Mass according to claim 1, characterized in that X is OH, SH, NH ₂ , CO ₂ H, PO ₃ H ₂ , OB (OH) ₂ or a derivative thereof, or halogen. 26. Composition according to claim 1, characterized in that X OR ¹ , SR ¹ , NHR ¹ , NR ¹ R ² , OB (OR ¹ ) (OR ² ) ₂ , -YCZ yV ο -Y-P or -Y-S-Z .22 Il YR M 1 2 in relation to Y, Y and Y independently of each other -0-, -NH-, -NR ¹ - or -S- are or are absent, ZH, R ¹ , OR ¹ , SR ¹ , ITH ₂ , NHR ¹ 1 2
or NR R or a direct back connection of C to R or CH ₂ R is ¥ 0, S, NH or NR ¹ , L is or S is or is absent, M is or is absent and R is straight-chain or branched alkyl with 1 to 12 carbon atoms, alkenyl or alkynyl with 2 to 12 carbon atoms, Cycloalkyl or cycloalkenyl with 5 to 12 carbon atoms, or aralkyl, aralkenyl or alkaryl with 709818 / 11U - 104 - 7 "means to 12 carbon atoms and R means the same definition as R corresponds to and can be the same as R or different from R represents. 27 · Composition according to claim 1, characterized in that the leaving group is a salt of an acidic or basic group. 28. Composition according to claim 1, characterized in that X represents OH, OR ¹ , OCOH or OCOR ¹ , where R ¹ corresponds to the definition given in claim 26. 29. Composition according to claim 1, characterized in that the compound R (CHpX) is one of the formulas XGlI XOH or corresponds, in which X represents OH, OR ¹ or OCOR ¹ , where R ¹ corresponds to the definition in claim 26. - 105 - 709818/1 1 U 26487Q1 30. Composition according to claim 28 or 29, characterized in that R " ¹ " represents methyl, phenyl or benzyl, 31. Composition according to claim 2 or 3, characterized in that 0.1 to 150 parts of the ester of a phosphorus acid or 1 to 150 parts of the aromatic ester per 100
Parts of the chlorine-containing polymer are used. 32. Composition according to claim 31, characterized in that 2 to 100 parts of the ester of a phosphorus acid are used or the aromatic ester is used per 100 parts of the chlorine-containing polymer. 33. Composition according to claim 32, characterized in that one clones 5 to 80 parts of the ester of a phosphorus-containing acid
or the aromatic ester is used per 100 parts of the chlorine-containing polymer. 34. Composition according to claim 1, characterized in that 1 to 50 parts of a compound of formula I per 100 parts of the chlorine-containing polymer begins. 35. Composition according to claim 34, characterized in that 1 to 35 parts of a compound of the formula I are used per 100 parts of the chlorine-containing polymer and that the composition
contains an ester of a phosphorus acid. 36. Composition according to claim 35, characterized in that 2 to 25 parts of a compound of the formula I are used per 100 parts of the chlorine-containing polymer and that the composition
contains an ester of a phosphorus acid. 37 »· Composition according to claim 34, characterized in that 1 to 20 parts of a compound of formula I per 100 parts - 106 - 709818/1 1 U of the chlorine-containing polymer begins and that the mass contains an aromatic ester. 38. Composition according to claim 37, characterized in that 2 to 15 parts of a compound of the formula I are used per 100 parts of the chlorine-containing polymer begins and that the mass contains an aromatic ester. 39. Composition according to claim 1, characterized in that it also contains a non-deactivated aromatic compound with vacant positions on the aromatic ring. 40. Composition according to claim 39, characterized in that the non-deactivated aromatic compound of the formula RCHpX, in which R and X have the same meaning as in the compound R (CHpX) corresponds to. 41. Composition according to claim 1, characterized in that they also heat protection agents, light protection agents, antioxidants, Fillers, pigments, lubricants, blowing agents, fungicidal agents, Friedel-Crafts catalysts or their precursors, Extenders, processing aids, other flame retardant Contains additives or smoke control agents, or mixtures thereof. 42. Composition according to claim 41, characterized in that an organotin compound or any other stabilizer is used Epoxy compound is present. 43- "Composition according to claim 1, characterized in that X represents chlorine and that the composition also contains a Friedel-Crafts catalyst.
44. Composition according to claim 41 or 43, characterized in that - 107 709818/1 1 U that the Friedel-Crafts catalyst aluminum chloride, zinc chloride, Iron (3) chloride, magnesium chloride, tin (2) chloride, Tin (4) chloride, butyl tin trichloride, phosphoric acid or is p-toluenesulfonic acid. 45. Composition according to claim 1, characterized in that it also contains a phosphorus-free plasticizer and an ester a phosphorus acid or an aromatic ester and a plasticizer different from the latter ester contains. 46. Composition according to claim 45, characterized in that the proportion of the phosphorus-free plasticizer corresponds at most to the proportion of the ester of a phosphorus-containing acid. 47- mass according to claim 46, characterized in that the proportion of the phosphorus-free plasticizer is a maximum of one third of the proportion of the ester of a phosphorus acid is equivalent to. 48. Composition according to Claim 45, characterized in that it contains a haloalkyl phosphate and that the proportion of phosphorus-free plasticizer is at most 90% of the Phosphate / plasticizer mixture. 49. Composition according to claim 1, characterized in that the compounds (a) and (b) are in a weight ratio from 20: 1 to 0.1: 1 is used. 50. "Composition according to claim 36, characterized in that the compounds (a) and (b) in the weight ratio from 10: 1 to 0.5: 1 is used. 51. Composition according to claim 50, characterized in that - 108 709818 / 1.1 U the compounds (a) and (b) in the weight ratio of 5: 1 Ms 1: 1 begins. 52. Composition according to claim 1, characterized in that it is a vinyl chloride polymer and (a) an aromatic carboxylic acid ester, sulfonic acid ester or carbonic acid ester or, preferably, an aromatic one Phosphate ester and (b) a compound of the formula X), in which R is an aromatic hydrocarbon radical or aromatic heterocyclic R.est, η is an integer from 2 to 12 and X represents an optionally negatively charged leaving group. 53 · Composition according to claim 52, characterized in that the vinyl chloride polymer is a homopolymer or a copolymer is present with other monomers, 54. Composition according to claim 52 or 53, characterized in that the vinyl chloride polymer is PVC. 55. Composition according to claim 52, characterized in that a conventionally used as a plasticizer is used as the aromatic ester ester used for vinyl chloride polymers is present. 56. Composition according to claim 55, characterized in that the aromatic phosphate ester is derived from a phenol or Phenol mixture derives. 57 · Composition according to claim 51, "characterized in that a triaryl phosphate is present as the aromatic phosphate ester. 58. Composition according to claim 52, characterized in that the aromatic carboxylic acid ester, sulfonic acid ester or carbon - 109 - 7Q9818 / 11U acid ester is derived from a phenol. 59. Composition according to claim 52, characterized in that the aromatic carboxylic acid ester is a phthalic acid ester,
Benzoic acid ester or mellitic acid ester is present. 60. Composition according to claim 52, characterized in that the R group is monocyclic, dicyclic or polycyclic,
is fused or non-fused. 61. Composition according to claim 6O, characterized in that the non-fused dicyclic and polycyclic aromatic Residues are linked directly or via heteroatoms or carbon-containing groups. 62. Composition according to claim 52, characterized in that R is represented by one or more halogen atoms or alkyl groups with 1 to 4 carbon atoms, cycloalkyl groups with 5 to 12
Carbon atoms, hydroxyl groups, alkoxy groups with 1 to carbon atoms, cycloalkoxy groups with 5 to 12 carbon atoms, carboxyl groups, carboalkoxy groups with 2 to 4 carbon atoms or mixtures thereof. 63. Composition according to claim 52, characterized in that R is an unsubstituted or alkyl-substituted dicyclic, represents tricyclic or tetracyclic radical. 64. Composition according to claim 52, characterized in that X represents OH, SH, NHp or a derivative thereof, or halogen. ' 65. Composition according to claim 52, characterized in that X OR ¹ , SR ¹ , NIIR ¹ , NR ¹ R ² , OSO ₂ R ¹ , - 110 - 70 9 S 1 g / 1 1 U -V-C-Z or ^ V-P YR ¹ in which V is -0-, -NH-, -NR ¹ - or -S-, is YO or S, ZH, R ¹ , OR ¹ , SR ¹ , NH ₂ , NHR ¹ or NR ^{1 is} R ² , R ¹ alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, aralkyl or alkaryl with 7 to 12 carbon atoms or aryl with 6 to 12 carbon atoms, optionally with one or more halogen, hydroxyl, epoxy, Nitrile, ether and / or ester substituents, 2 1 means and R corresponds to the same definition as R and may be the same as R. or different from R. 66. Composition according to claim 52, characterized in that X represents a halogen atom, OH, OR ¹ , OCOH or OCOR ¹ , where R ¹ corresponds to the definition given in claim 65. 67 «Composition according to claim 52, characterized in that the compound R (CH ₂ X) _{n of} the formula XCIl ₀ 1 »1 1 corresponds, in which X is Cl, OH, OR or -COR, where R corresponds to the definition given in claim 65, represents. 68. Composition according to claim 52, characterized in that it also contains heat protectants, light stabilizers, antioxidants, Fillers, pigments, Friedel-Crafts catalysts - 111 - 709818/1 IU gates or their preliminary products, extenders, lubricants and / or other flame-retardant additives.
69 · Process for improving the flame retardancy of a chlorine-containing aliphatic polymer, characterized in that one a) an ester of a phosphorus acid, an aromatic carboxylic acid ester, sulfonic acid ester or carbonic acid ester or a mixture of these, and b) a compound of the formula IR (CH ₂ X) _n (I) in which R denotes an aromatic hydrocarbon radical or heterocyclic radical, η is an integer of at least 2 and the Xs are identical or different and each represent a leaving group,
incorporated into the polymer. 70. Mass to improve the flame retardancy of a
chlorine-containing aliphatic polymer, characterized in that it a) an ester of a phosphorus acid, an aromatic carboxylic acid ester, sulfonic acid ester or carbonic acid ester or a mixture of these, and b) a compound of the formula IR (CH ₂ X) _n (I) in which R denotes an aromatic hydrocarbon radical or heterocyclic radical, η is an integer of at least 2 and the Xs are identical or different and each represent a leaving group,
contains. 709818/1 1 U - 112 -