NO763705L - - Google Patents

Description

Fire retardant paste Chlorine-containing, aliphatic

polymer composition.

The invention relates to new flame retardant compounds

nings of chlorine-containing, aliphatic polymers. It particularly concerns polymers and copolymers based on vinyl chloride.

Plasticized PVC is usually made more fire retardant

by adding compounds containing phosphorus, halogen,

antimony, boron or aluminium. For example, phosphate esters or antimony oxide are used.

Surprisingly, it has been found that the fire resistance of PVC

and plasticized PVC in particular can be significantly increased by using new flame retardant compositions.

In particular, they can fire-retardant properties of certain

esters of phosphoric acids are significantly improved by the use of certain additional additives. As a result, it can. either greater fire resistance is achieved without increasing the phosphorus content or the same fire resistance can be achieved with a lower phosphorus content. It has also been found that the fire resistance of plasticized PVC can be significantly increased by using fire retardant compositions that do not contain any of the usual fire retardant elements. In other cases where fire retardants are present, are. the fire retardancy achieved by

use, present composition greater than what could be predicted from the total fire-retardant element content in the composition.

Accordingly, the present invention provides'

a composition comprising a chlorine-containing aliphatic polymer and.

a) an ester of phosphoric acid, an aromatic carboxylate, sulfonate. or carbonate esters or mixtures thereof and b) a compound of formula I

wherein R means an aromatic hydrocarbon or heterocyclic

containing residue, n is an integer of at least 2 and each X is the same or different and means a residue group.

Preferably, the chlorine-containing aliphatic poly-'

more. a thermoplastic polymer.

In the compounds of formula I, each aromatic or heterocyclic ring may contain from 0 to 6 -CH 2 X groups, preferably 1 to 3 and especially 1, provided that there are at least 2 — CH 2 X groups per molecule.

Thus, n can mean from 2" to 12, preferably from

2 to 6 and especially from 2 to

The aromatic core preferably has a free ortho position closest to the -CH2X group and the CH2X group is preferably positioned so that intramolecular cyclization is not enabled.

The residue group X in formula I means halogen, -OH, -SH,

-NHp, -COpH, -PO,H2,■OB(OH)2 and their derivatives, for example -OR , -SR , -NHR , -NR<1>R<2>, -OB(OR<1>)(OR <2>). Non-limiting examples of such derivatives and other X groups can be shown by the general formula

where

12 • '

Y, Y and Y are independent of each other, -0-, -MH-, -N-, -S- or is absent but preferably means -0- or^R<1>-S-, Z means H, R <1>, OR1, -SR1, NH2, NHR<1>, NR<1>R<2>or a direct bond, connecting C back to R or to a CH2-linked it

'W

to R, but preferably means H or R<1>;

W is 0, S, NH or NR<1>, but preferably 0 or S;

L means 0, S or is absent, but preferably means 0;

M means 0 or is absent, but preferably means 0;

and wherein R1 means a straight or branched alkyl chain of 1 to 12 carbon atoms, preferably 1 to 4, preferably 1, alkenyl or alkynyl of 2 to 12 carbon atoms, preferably 2 to 4, cycloalkyl or cycloalkenyl of 5 to 12, preferably 6 carbon atoms, aralkyl, 'aralkenyl or alkaryl with 7 to 12 carbon atoms, preferably benzyl or naphthyl methyl or aryl with 6 to 15, preferably 6 to 12 carbon atoms,

especially phenyl or -naphthyl. R<1> can optionally be substituted

.with one or more halogen, hydroxy, epoxy, nitriles, amine,

amide, ether, carboxyl or ester groups or combinations thereof, but are preferably unsubsti. 'tu' tease, R 2 has the same meaning as R<1> and can be similar. or different. The residual group can also be a salt of an acidic or basic X group.

However, among the non-limiting examples, preferred are compounds of formula I wherein X is OH or

a derivative of this group.

The aromatic residue R can be mono-, di- or polycyclic and these can be condensed or non-condensed.

It can be a mixture of condensed and non-condensed groups. Where more than one separate aromatic residue is present, they may be linked directly or through groups containing carbon or heteroatoms or groups containing combinations of carbon and heteroatoms. These connecting groups can also

be chosen to form repeating aryl or heterocyclic groups in which the connecting function or functions are -CH?X-■ 1 2

groups, wherein X contains R and/or R , at least one of which is R or .-CHgR group. The group R can therefore be oligomers, containing the above-mentioned aromatic hydrocarbons and heterocyclic residues, formed by addition or condensation reactions

tions. When such bridging functions are present, however, it is preferred that other non-bonding -C^X functions are also present in the system.

The pore linking functions are preferably short-chain groups, preferably with no more than -3 carbon atoms. More specifically, the connecting functions do not have neighboring C atoms. The group R may otherwise be unsubstituted or may be substituted with

one or more halogen atoms or alkyl groups with 1 to 12 carbon atoms, preferably 1 to 4, alkenyl or alkynyl groups with 2 to 12 carbon atoms, preferably 2 to 4, cycloalkyl groups with 5 to 12 carbon atoms, hydroxyl groups, alkoxy groups with 1 to 12, preferably 1 to 4 carbon atoms which may contain an epoxide group, cyclo alkoxy 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 mixtures thereof. However, R is preferably an unsubstituted or alkyl, preferably methyl, substituted di-, tri- or tetracyclic radical. In particular, R is an otherwise unsubstituted di-, tri-

or tetracyclic' aromatic residue.

The group X preferably means a group OH,. OR<1>, OCOH or OCOR<1>, in which R^ has the above meaning, but preferably methyl, phenyl or benzyl.

In formula I, non-limiting examples of the radical R include those derived therefrom. the following systems:

Where R is monocyclic:

1 benzene

2 toluene

3 xylene

4 ethylbenzene

5 myethylen

6 the duration

7 isodur

8 ij;-cumen or cumen

9 anisole

10 phenyl acetate.

11 chlorobenzene

12 bromobenzene

13 pyridine

14 triazine

15 pyrimidine

16 pyrazine

17 p-t-butyl phenol

Preferably, R is derived from residues 1-10 and 17.

Where R is non-fused bicyclic:

1 biphenyl

2 diphenylmethane

3 1:1-diphenylethane

H 1:2-diphenylethane

5 2:2-diphenylpropane

6 diphenylcarbinol 7 benzophenone 8 phenylbenzoate...

9 diphenylacetoacetic acid (and its esters)

10 diphenyl ether

11 diphenylacetonitrile

12 diphenyl sulfides

13 diphenyl disulfides

14 diphenyl sulfoxides

15 diphenylsulfones

16 diphenylamines

17 N,N-diphenylmethylamines

18 diphenylmethylphosphines

19 diphenyl methylphosphine oxides

20 diphenyloctyl phosphates

21 dipyridyl

22 3,3<1->dime.tylbiphenyl

23 2J2<1->dimethylbiphenyl

24 4,41-Dimethylbiphenyl

25 2,2^-diphenyldicarboxylic acid

26 stilbenes

27 benzoin

28 benzyl

29 benzylic acid.e

30 dibenzyl sulfates

31 . dibenzyl oxalates

32 dibenzyl succinates

33 diphenyl carbonates

34 octyl di-styryl phosphinates

35 ferrocenes

36 diphenyl succinates

37 ethylenedioxydiphenyl

Of these, residues ■ derived from Nos. 1, 2, 10 and 15 are preferred.

Where R is condensed bicyclic:

1 naphthalenes

2 methylnaphthalenes

3 Methoxynaphthalenes

4 tetralin

5 quinoline

6 isoquimoline

7 quinoxaline V."

8 quinazoline

9 Phthalazine

10 phthalimide

11 indole

12 benzofuran

13 benzimidazole

14 benzothiazole

15 benzotriazole

Of these, naphthalene and methylnaphthalene are preferred.

Where R is non-fused tricyclic:

In terphenyl

2 triphenylmethane

3 dibenzylbenzene

4 0,O-diphenylhydroquinone

5 0,0-diferiylresorcinql «i

6 triphenylamino

7 triphenylphosphine

8 triphenylphosphine oxide

9 triphenyl phosphate

10 tricresyl phosphate

II trixylyl phosphate

12 isopropyl phenyl/phenyl phosphate (e.g. these sold under the trade name Reofos 50, 65 and 95, and manufactured as described in U.K. patent application no. 1,146,173).

13 triphenylantimony

14 tribenzyl phosphate

15 diphenylstyrylphosphonate

16 triphenyl orthoformate .

Of these, remainders derived from the numbers are preferred

1, 2, 3, 5, 6, 8, 9, 10, 11 and 12.

Where R is condensed tricyclic:

1 anthracene

2 phenanthrene

.3 phenylnaphthalene

4 ace night

5 the acenaphthylene

6 dihydroanthracene

7 entrances

8 the xanthine

9 xanthone

10 fluorene 11 fluorenone

12 acridine

13 phenanthridine

14 phenazine

15 benzoquinoline

16 carbazole

17 dibenzofuran

18 dibenzothiophene

19 phenothiazine

20 phenoxazine

21 α-methylstyrene dimer

22 styrene dimers

23 the biphenyl

24 1-meth.ylanthracene

Of these, residues derived from the numbers 1, 2, 3, 4, 5, 10, 16, 17, 21, 22 and 24 are preferred.

Where R- is non-fused tetracyclic:

1 quaterphenyl

2 tetraphenylmethane

3 triphenylbenzene

4 2,4,6-triphenyltriazine

5 N, N^N^-trif enylmelamine

6 N,N1N1'1"-triphenyl isocyanuric acid

7 ■tetraphenyltin

8 tetraphenyl lead

9 tetraphenylethane

10 tetrabenzyi orthosilicate

11 2,4,6-triphenoxy-triazine

12 tetraphenyl silicate

Of these, residues derived from the numbers 2, 4, 5, 6 and 11 are preferred.

Where R is fused tetracyclic:

1 dinaphthyl

2 phenylanthracene

3 phenylphenanthrene

4 'N-f eny lacridone

5 N-phenylcarbazole

6 N-phenylphenothiazine

7 N-phenyl lf enoxazine 8 9-phenylacridine 9 2:3-diphenylquinoxaline 10 triphenylene

11 aceantren.

12 pyrene

13 the naphthacene

14 the fluoranthene

15 the intersection

16 dinaphthylmethane

Of these, residues derived from dinaphthyl are preferred

and N-phenylcarbazole. Where R is polycyclic higher than tetracyclic:

1 .9,10-dif eny lantracene

2, .-hexiphenyl

3 rubric

4 9j9~diphenylxanthene

5 9j9-Diphenylacridone

6 hexacene

7 hexaphene

8 pyranthrene

9 hexaphenylmelamine Where R is an oligomer:

1 polyphenyl 6 polybenzyl ether

2 poly(methylene phenylene) 7 polybenzyl ester

3 polyxylylene 8 polyphenyl ether

4 polystyrene 9 polyphenyl ester

5 the polynaphthylene

In formula I, non-limiting examples for group X are:

-Cl, -Br, -OH, -OCH5, -OC^, -OC^Hg, OCH2CH = CH2, OCH=CH2

Non-limiting examples of special compounds

els of formula I are

where R is monocyclic:

1,4-bis(carboxymethyl)benzene

1,4-bis(methoxycarbonylmethyl)benzene

1,4-bis hydroxymethylbenzene 1,4-bis methoxymethylbenzene 1,4-bis benzoxymethylbenzene

1,4-bis chloromethylbenzene

1,4-bis acetyloxymethylbenzene 2,4,6-tris chloromethylmesitylene

3,6-bis methoxymethyldurene

2,4,6-tris acetoxymethyl acetate

2,6-bis hydroxymethylpyridine

2,6-bis hydroxymethyl-4-t-butylphenol

lj3>5_tris hydroxymethylbenzene

1,4-bis hydroxymethyl-2,3j5a 6 tetrachlorobenzene

where R is non-fused bicyclic: 4,^-bis(chloromethyl)biphenyl .-"',.. 4,^-bis(bromomethyl)biphenyl 4,4^-bis(carboxymethyl)biphenyl 4,4^-bis( methoxycarbonylmethyl)biphenyl

4,4^-bis(hydroxymethyl)biphenyl

4, n-bis(methoxymethyl)biphenyl

4, 4^-bis(phenyloxymethyl)biphenyl 4, i^-bis(benzyloxymethyl)biphenyl

4,4<1->bis(acetyloxymethyl)biphenyl

Examples of salts include alkali metal, ammonium or amine salts of acid compounds and inorganic or organic or quaternary salts of basic compounds, e.g.

4,4^-bis(formyloxymethyl)biphenyl

et jCt^-bitoly 1 diphosphonic acid disodium salt 4-hydroxyrnety 1-4^-methoxymethyl biphenyl 4-hydroxymethyl-4 ■'"-acetoxymethyl biphenyl 4 , 4 "'"-bis (dimethyl lam i nome ty 1) bif eny 1 4 ,4^-bis(methylcarbamoyloxymethyl)bipheoyl 4, 4 "'"-bis (tri ime ty laminom et y 1 )biphenyl dichloride 2,4-bis(acetoxymethyl)-6-phenyl phenol acetate 4 y 4"'"-bis (Hydroxymethyl )diphenylmethane 4,k "'"-bis (methoxymethyl 1)diphenylmethane 4,41-bis(benzyloxymethyl)diphenylmethane k,4^-bis(formyloxymethyl)diphenylmethane 4,4<1-> bis(carbamoyloxymethyl)diphenylmethane 3,3'-bis-(acetoxymethyl)-k,4'-bis-acetoxy-diphenylmethane 4,4"''-bis(hydroxymethyl)benzophenone

4,4 "'"-bis (hy dr oxymethyl )di f enyl ether

4,4<1->bis(methoxymethyl)diphenyl ether

4, 4"'"-bis(acetyloxymethyl) diphenyl ether 4,4<1->bis(hydroxymethyl)diphenylsulfone 3,3'-bis-(acetoxymethyl)-4,4'-bis-acetoxy-di-phenylsulfone N,N-bis(4-hydroxymethyl phenyl)methylamine bis(4-hydroxymethyl phenyl)octyl phosphate 4, 41-bis (methoxymethyl)-3 j 3-^-dimethyl ld i f eny 1 2.2- bis-(3'- Acetoxymethyl-4'-acetoxy-phenyl)-propane bis-(3-(2<1->hydroxymethylphenoxy)-2-hydroxypropyl)ether of 1,4-butanediol

where R is fused bicyclic: 1,4-bis(chloromethyl)naphthalene

1,4-bis(hydroxymethyl)naphthalene

1, 4-bis (methoxymethyl l>iaf talen

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(hydroxymethyl)naphthalene

1,5-bis(methoxymethyl)naphthalene

1,5-bis(formyloxymethyl)naphthalene

1,5-bis(acetoxymethyl)naphthalene

1- methyl1-bis-(chloromethyl)naphthalene 2- methyl1-bis-(chloromethyl)naphthalene 1- methyl1-bis-(hydroxymethyl)naphthalene 2- methyl1-bis-(hydroxymethyl)naphthalene 1- methyl1-bis(methoxymethyl)naphthalene 2 - methyl-bis(methoxymethyl)naphthalene 5,8-bis(chloromethyl)tetralin 5 j 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 5j8-bis(chloromethyl)quinoxaline 5,8-bis(hydroxymethyl)quinoxaline 5,8-bis(formyloxymethyl)quinoxaline 5,8-bis(chloromethyl)phthalazine 3,6-his(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 4,7-bis(formyloxymethyl)benzotriazole where R is non-fused tricyclic: 1,4-di(4<1->chloromethylphenyl)benzene 1,4-di(4<1->hydroxymethylphenyl)benzene 1 , 4-di (4"'"-formyloxymethylphenyl)benzene tri(4-methoxymethylphenyl)methane tri(4-hydroxymethylphenyl)methane tri (; 4-chloromethylphenyl)methane I, 4-di ( 4''"-methoxymethyl lb enzyl )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,O^di(4-chloromethylphenyl)hydroquinone 0,O^di(4-methoxymethylphenyl)hydroquinone 0,0<1>di(4-benzoyloxymethylphenyl)hydroquinone

0,O^diC4-dimethylaminomethylphenyl)resorcinol

tri(4-hydroxymethylphenyl)amine

tri('4-methoxymethylphenyl)amine

tri(4-formyloxymethylphenyl)phosphine

tri(4-benzoyloxymethylphenyl)phosphine

tri(4-carbamoyloxymethylphenyl)phosphine

tri(4-dimethyl aminomethyl phenyl) phosphine oxide

tri(4-bromomethylphenyl)phosphine oxide

tri(4-benzoyloxymethyl phenyl) phosphine oxide

tri(4-chloromethyl phenyl) phosphate

tri(4-methoxymethyl phenyl) phosphate

di(4-hydroxymethyl phenyl)mono(p-methoxymethyl phenyl)phosphate tri(4-methoxymethyl-meta-cresyl)phosphate

mono-phenyl di(4-methoxymethyl phenyl) phosphate

mono-phenyl, mono(4-hydroxymethyl phenyl),. mono(p-methoxymethyl phenyl)phosphate di(methoxymethyl phenyl), mono(2-isopropyl phenyl)phosphate di(hydroxymethyl phenyl), mono(4-isopropyl phenyl)phosphate tris(2,4-di-butoxymethyl-6-phenyl- phenyl) borate

where R is condensed tricyclic:

1,4-di-hydroxymethyl anthracene 5-hydroxymethyl-1,4-di(methoxymethyl)anthracene

1,4-di-(hydroxymethyl)-5 j 8-di(methoxymethyl)anthracene 2,7-di(acetoxymethyl)anthracene

1,4,7-tris(acetoxymethyl)acenaphthylene

1j4,7-tris(dimethylaminomethyl)acenaphthylene

1 »^ i 5 i8-tetra(hydroxymethyl)fluorene

1>4,5,8-tetra(acetoxymethyl)xanthene

1>^ »5-tri(bromomethyl)xanthene

1»^»5>8-tetra(dimethyl aminomethyl)carbazole

1 i^ >5»8-tetra(carbamoyloxymethyl)acridine 1,4,6,9-tetra(benzoyloxymethyl)phenazine

2,7,10-tris(chloromethyl)phenanthridine 1>4j6,9-tetra(methoxymethyl)phenoxazine

1*4,6,9-tetra(hydroxymethyl)phenothiazine

1> 3.” 3-tri-methyl 1-1-phenyl-4,7-di(methoxymethyl)indane where R is non-fused tetracyclic: tetra(3,5-di-hydroxymethyl phenyl)methane

tetra(4-methoxymethyl phenyl)methane

tetra(4-formyloxymethyl phenyl)methane tetra(4-dimethyl aminomethyl phenyl)methane 1j 3,5-tri(3,5-dichloromethyl phenyl)benzene X, 3 j 5_tri ( 4-nietoxymethyl phenyl)benzene 1j3>5-tri( 4-carbamoyloxymethyl phenyl)benzene lj3j5_tri(4-benzoyloxymethyl phenyl)benzene NjN^jN^-triC 3j 5-dihydroxymethyl 1 phenyl )melamine NJN1,N"'"'''-tri(3J 5_f ormyloxymethyl phenyl )melamine N,N ,N'L1-tri( 4-methoxymethyl phenyl)melamine . 2j4,6-tri(3,5-di-chloromethyl phenyl)triazine 2,4,6-tri(3,5-di-carbamoyloxymethyl phenyl)triazine 2,4j6-tri(4-acetoxymethyl phenyl)triazine NjN^jN^ -triO j 5-dihydroxymethyl phenyl) isocyanurate tetra(3}5_diformyloxymethyl phenyl)tin tetra(4-hydroxymethyl phenyl)tin

tetra(4-chloromethyl phenyl)tin

tetra(4-acetoxymethyl phenyl) lead

tetra(4-bromomethyl phenyl) lead

tetra(4-methoxymethyl phenyl)lead tet.rachis-(2-butoxymethyl-phenyl)silicate where R is condensed tetracyclic: 2-phenyl-5>8-dibromomethyl anthracene 2-phenyl1-5»8-dihydroxymethyl anthracene ' 2- phenyl-5,8-di-formyloxymethyl anthracene 3- pheny1-3j6-dimethoxymethyl phenanthrene 3-phenyl-3s6-di-acetoxymethyl phenanthrene 3-phenyl-3,6-di-hydroxymethyl phenanthrene N-phenyl-2, 6-di-chloromethyl carbazole N-phenyl-2,6-di-carbamoyloxymethyl carbazole N-phenyl-2,7-dimethoxymethyl phenothiazine N-phenyl-2,4,6-tri-bromomethyl phenothiazine N-phenyl-2, 4 j 6-tri-acetoxymethyl phenoxazine 2,3~diphenyl-5j 8-di-formyloxymethyl quinoxaline 2j3-diphenyl-5,8-di-hydroxymethyl quinoxaline where R is polycyclic higher than tetracyclic: 2,6-di-methoxymethyl~9 ,10-diphenyl anthracene 2,8-di-chloromethyl rubrene

2,6-di-hydroxymethyl-9s9-diphenyl xanthene 2,6-di-acetoxymethyl-9j9-diphenyl xanthene 2,6-di-carbamoyloxymethyl-9,9-diphenyl xanthene

w

1j ^ j 6.9 >12,15-hexa-methoxymethyl hexacene

poly(44'-dibenzyl) phthalate

polyethylenedioxy (44'-dibenzyl1)

chloromethylated polystyrene

polyester from 4,4 bis(hydroxymethyl)biphenyl and phthalic anhydride polyester from 4,4'bis(hydroxymethyl)biphenyl and succinic anhydride polyurethane from 1,5 bis(hydroxymethyl)naphthalene and toluene diisocyanate

polyether from 1,5 bis(hydroxymethyl)naphthalene and ethylene glycol polybenzyl ether from hydrolysis, of 4,4' bis(chloromethyl)biphenyl

Phosphoric acid includes derivatives of phosphoric acid, phosphonic acid, phosphinic acid, phosphoric acid and their dehydration products. Salts of partial esters can be used, but the complete esters are preferred. Esters of phosphoric acids are particularly preferred.

Not. limiting examples for phosphor esters based

on phosphoric acid is:

1 triphenyl phosphate

2 cresyl diphenyl phosphate

3 phenylxylyl phosphate

4 tri-tolyl phosphate

5 tri-xylyl phosphate

6 phenyl/isopropylphenyl phosphate (e.g. those sold under the trademark "Reofos 95>65 and 50" and manufactured as described

in British Patent No. 1,146,173).

7 phenyl/secbutylphenyl phosphate

8 phenyl/p-t-butylphenyl phosphate

9 di(2-cumylphenyl)phenyl phosphate

10 di(4-benzylphenyl)phenylphosphate

11 tri(4-t-butylphenyl)phosphate

12 tri-(4-nonylphenyl) phosphate

13 tri-(4-t-amylphenyl)phosphate

14 tri-(4-chlorophenyl)phosphate

15 tri-<y>~"4-(bromoisopropyl)phenyl7f osph at

16 tri-/_ 4-(chloro isopropyl) f eny_l7f osf at

17 diphenyl-(2-bromomethyl)phosphate

18 diphenyl-(2-chloroethyl)phosphate

19 diphenyl-(2,3-dibromopropyl) phosphate

20 diphenyl-(2,3-dichloropropyl) phosphate

21 diphenyl-n-octyl phosphate

22 diphenyl-n-decyl phosphate

23 phenyl di (2-bromomethyl) phosphate

24 phenyl di (2-chloroethyl)phosphate

25 phenyl di (2,3-dichloropropyl) phosphate

26 phenyl di (2,3-dibromopropyl)phos fat

27 phenyl di-n-octyl phosphate

■ 28 phenyl di-n-decyl phosphate

29 tri (2-chloroethyl) phosphate

30 tri (2-bromomethyl)phosphate

31 tri (2,3~dibromopropyl)phosphate

32 tri (2,3-dichloropropyl) phosphate

33 tri-octyl phosphate

34 tri-decyl phosphate

35 tri-allyl phosphate

37 tri-(meta ethylphenyl)phosphate

38 calcium di-ammonium phosphate salt of diphenyl hydrogen phosphate

Non-limiting examples of esters. based on phosphonic acid:

39 diphenyl,' phenylphosphonate

40 di-(4-brimiphenyl)phenylphosphonate

41 di-(4-t-butylphenyl)phenylphosphonate

42 di-(2-isopropylphenyl) phenylphosphonate

43 di-(4-benzyl phenyl)phenylphosphonate

44 diphenylstyrylphosphonate

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

46 diphenyl n-octylphosphonate

47 diphenyl n-decylphosphonate

48 di-(4-chlorophenyl). n-butyl phosphonate 49 di-(4-bromophenyl) n-hexyl phosphonate

50 di-(2-isopropylphenyl) n-octylphosphonate

51 phenyl-n-octyl n-hexylphosphonate

52 bis-2,3-dibromopropyl 2,3-dibromo-propyl phosphonate

53 di-ethyl phenyl phosphonate

54 di-ethyl, di-ethanolamino methyl phosphonate

Non-limiting examples of esters based on phosphinic acid:

55 n-octyl di-s'tyryl phosphinate

56 n-octyl di-(1,2-dibromo-2-phenyl ethyl)phosphinate

57 phenyl di-styryl phosphinate

58 n-octyl di-styryl phosphinate

Non-limiting examples of esters based on phosphoric acidification:

59 triphenyl phosphite

60 tri-octyl phosphite

6l''tri-^-nonyl phenyl phosphite

62 tri-2:3-dibromopropyl phosphite 63 diphenyl hydrogen phosphite

64 dioctyl hydrogen phosphite'

Preferred compounds are the esters of pentavalent phosphorus and more particularly triaryl phosphates and trihaloalkyl phosphates, for example compounds 1 to 10 and 29 to 32 and mixtures thereof, or mixed aryl phosphates, haloalkyl phosphates

phates and arylhaloalkyl phosphates.

It should be understood that where an ester of .a phosphoric acid

also has the formula R(CH2X)n, it is considered to be a compound with the formula R(CH2X)n and should be used in connection with another ester of a phosphoric acid that does not have the formula R(CH2X)n. Except-

if another RCCI^X^ component is present a ■ phosphoric acid ester of formula RCCHgX^ may be considered the ester component.

Different types of aromatic groups containing carboxylate esters can be used, for example phthalates, benzoates and mellitates.

Carboxylated esters include:

di-n-butyl phthalate

diisobutyl phthalate

di-2-ethyl butyl phthalate

iso butyl nonyl phthalate

di-n-heptyl phthalate

di-2-ethyl hexyl phthalate di-iso-octyl phthalate di-capryl phthalate di-n-octyl phthalate iso-octyl iso-decyl phthalate "Linevol" 7.9 phthalate

"Linevol" 9.11 phthalate

("Linevol" 7,9 and "Linevol" 9,11 are mixtures of predominantly straight-chain alcohols with 7 and 9 and 9 and 11 carbon atoms respectively) di-2-phenylethyl phthalate

di-tri-decyl phthalate

butyl benzyl phthalate

dimethyl glycol phthalate

tri-isooctyl trimellitate

butyl phthalyl butyl glycolate

tri-octyl mellitate

dibenzyl phthalate

diphenyl phthalate

di-2-phenoxyethyl phthalate

tri-phenyl mellitate

tetra-phenylpyromellitate

ethyl benzoyl benzoate

di-propylene glycol dibenzoate

benzyl benzoate

diphenoxyethyl diglycolate

bis(phenylpolyethyleneglycol)diglycolate

phenoxyethyl laurate

phenoxyethyl oleate

diphenyl adipate

di-benzyl adipate

benzyl octyl adipate

octylphenyl adipate

butyl benzyl adipate

di-benzyl sebacate

di-(2-phenoxyethyl)adipate)

butyl benzyl sebacate

n-octyl-n-decyl phthalate/succinate phenyl diglycol carbonate

cresyl diglycol carbonate

bis-(dimethylbenzyl)carbonate

di-ethylene glycol dibenzoate

In addition, different polyesters can be used, for example polyesters derived from phthalic anhydride and one or more glycols, optionally end-capped with an alcohol or mono-basic acid; polyesters derived from a mixed phthalic/adipic acid and a glycol, optionally end-capped with an alcohol or mono-basic acid; polyesters derived from mixed phthalic/AGS acids (a commercial mixture of adipic, glutaric and succinic acids) and a

glycol, optionally end-capped with an alcohol or mono-basic acid. In addition, polyesters of these two types can be used

modified with a lactone, e.g. ^-caprolactone.

Other suitable compounds of type a:

diethylene glycol dibenaoate

tribenzyl citrate

alkyl sulfonate esters of phenols, e.g. products sold under the trademark "Mesamoll".

o-cresyl-p-toluenesulfonate

triphenyl orthoformate

diphenyl carbonate

Preferably, the aromatic ester is one that is commonly used as a plasticizer for vinyl chloride polymers, and more specifically

or it is an ester derived from a phenol.

Also preferred are aromatic esters having a non-deactivated benzene nucleus, e.g. butyl benzoyl phthalate and bisphenoxyethyl phthalate.

The compositions according to the invention can contain compound (a) and compound (b) in any ratio. Particularly suitable proportions of phosphoric acid ester (a) per 100 parts chlorinated aliphatic polymer is 0.1 part to 150 parts, preferably 1 part to 150 parts, more particularly 2 parts to 100 parts and especially 5 parts to 80 parts. Particularly suitable conditions of compound (b) per 100 parts of chlorinated aliphatic polymer is 1 part to 50 parts, preferably 1 part to 35 parts, more particularly 2 parts to 25 parts and preferably 2 parts to 15 parts. Particularly suitable ratios of aromatic esters (a) per 100 parts vinyl liphoride polymer is 1 part to 150 parts, preferably 2 parts to 100 parts and especially 5 parts to 80 parts. Particularly suitable forhides of compound (b) per 100 parts vinyl chloride polymer is 1 part to 50 parts, especially 1 part to 20 parts and preferably 2 parts to 15 parts. The compounds (a) bg (b) can be used in weight ratios from 20:1 to 0.1:1, but preferably from 10:1 to 0.5 and especially from 1 to 1:1.

The chlorine-containing polymer may be a homopolymer

or a co-polymer containing at least 5% chlorine, preferably more than 20% chlorine and especially more than 40% chlorine. Non-limiting examples of such polymers are polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated polybutene, polychloroprene, polyvinylidene chloride, chlorinated poly-4,4-dimethylpentene, chlorinated polyethylene also containing some chlorosulfonyl groups, e.g. . "Hypalon".

Non-limiting examples of copolymers are vinyl chloride/vinyl acetate, vinyl chloride/vinylidene chloride, vinyl chloride/ethylene, vinyl chloride/propylene, vinyl chloride/acrylic ester copolymers, vinyl chloride/acrylonitrile, chlorinated ethylene/propylene copolymers, chlorinated ethylene/butene copolymers. Poly blends with other polymers can be used, of which non-limiting examples are PVC/rubber blends, especially a rubber-based acrylonitrile.

The polymer is preferably PVC or a chlorinated polyolefin such as chlorinated polyethylene. The vinyl chloride polymer includes the polymers produced by one of the known or other methods such as mass, suspension or emulsion polymerisation.

Non-limiting examples of mixtures of compound (a) and (b) which may be used with the chlorinated aliphatic polymers or polyblends are set forth below; Compound (a) is phosphoric acid ester: 4,4,-bis-hydroxymethyl-biphenyl and tris(2,3-dichloropropyl)phosphate 4,4,-bis-hydroxymethyl-biphenyl and tris(2-bromoethyl)phosphate 4,4,- bis-chloromethyl-biphenyl and "Reofos 95"

4,4'-bis-hydroxymethyl-biphenyl and "Reofos 95"

4,4'-bis-hydroxymethyl-biphenyl and tritolyl phosphate

4,4'-bis-hydroxymethyl-biphenyl and triphenyl phosphate

4,4'-bis-hydroxymethyl-biphenyl and tris(2,3-dibromopropyl)phosphate 4,4<*>-bis-hydroxymethyl-biphenyl and phenyl-di-(2-bromomethyl)phosphate 4,4'-bis- (hydroxymethyl)biphenyl and tris(2-chloroethyl)phosphate 4,4'-bis-methoxymethyl-biphenyl and "Reofos 95"

4,4'-Dis-methoxymethyl-biphenylDg tri-tolyl phosphate

4,4'-bis-methoxymethyl-biphenyl and triphenyl phosphate

4,4'-bis-methoxymethyl-biphenyl and cresyl-diphenyl phosphate 4,4t-bis(acetoxymethyl)biphenyl and "Reofos 95"

4,4<»->bis(acetoxymethyl)biphenyl and cresyl-diphenylphosphate 4,4'-bis(acetoxymethyl)biphenyl and iso-decyl-diphenylphosphate 4,4'-bis(acetoxymethyl)biphenyl and tris (2-(bromoisopropyl) phenyl] -

phosphate

4,4'-bis(acetoxymethyl)biphenyl and tris2,3-dibromopropyl)phosphate 4,4'-bis(acetoxymethyl)biphenyl and phenyl-di(2-bromomethyl)phosphate 1,5-bis-hydroxymethyl-naphthalene and tris(2,3-dichloropropyl)phosphate

1,5-bis-hydroxymethyl-naphthalene and tris (2-bromomethyl) phosphate 1,5-bis-hydroxymethyl-naphthalene and "Reofos 95"

1,5-bis-hydroxymethyl-naphthalene and tritolyl phosphate

1,5-bis-hydroxymethyl-naphthalene and triphenyl phosphate

1,5-bis-hydroxymethyl-naphthalene and tris(2,3-dibromopropyl)phosphate 1.4-bis-hydroxymethyl-naphthalene and phenyl-di(2-bromomethyl)phosphate 1.5-bis-hydroxymethyl-naphthalene and tris(2-chloroethyl) phosphate

1,5-bis-hydroxymethyl-naphthalene and cresyl-diphenyl phosphate 1,4-bis-methoxymethyl-naphthalene and tris(2,3-dichloropropyl)phosphate 1,5-bis-methoxymethyl-naphthalene and tris(2-bromomethyl)phosphate 1,5-bis -methoxymethyl-naphthalene and "Reofos 95n

1,5-bis-methoxymethyl-naphthalene and tritolyl phosphate

1,5-bis-methoxymethyl-naphthalene and triphenyl phosphate

1,4-bis-methoxymethyl-naphthalene and tris(2,3-dibropropyl)phosphate 1,5-bis-methoxymethyl-naphthalene and phenyl-di(2-bromomethyl)phosphate 1,5-bis-methoxymethyl-naphthalene and tris(2-chloroethyl) phosphate 1,5-bis-methoxymethyl-naphthalene and cresyl-diphenyl phosphate

Mixtures of phosphate esters can be used, if desired, as mixtures of compounds of formula I.

b) Non-limiting examples of mixtures of compound (a) which are aromatic carboxylate-, sulfonate-

or carbonate esters and (b) which can be used with the vinyl chloride polymer are listed below: 4,4'-bis-chloromethyl-biphenyl and di-2-phenoxyethyl phthalate 4»4<*->bis-chloromethyl-biphenyl and di-octyl phthalate

4»4<*>-bis-chloromethyl-biphenyl and butyl benzyl phthalate 4,4<*>-bis-hydroxymethyl-biphenyl and di-2-phenoxyethyl phthalate 4>4<*->bis-hydroxymethyl-biphenyl and di-octyl phthalate

4»4'-bis-hydroxymethyl-biphenyl and butyl benzyl phthalate 4,4'-bis-hydroxymethyl-biphenyl and "Linevol" 7,9-phthalate

4,4'-bis-hydroxymethyl-biphenyl and di-benzyl adipate

4,4'-bis-hydroxymethyl-biphenyl and diethylene glycol dibenzoate 4,4<1>-bis-hydroxymethyl-biphenyl and phenyl-diglycol carbonate 4»4'-bis-hydroxymethyl-biphenyl and a polyester derived from phthalic anhydride terminated with an alcohol or mono-basic acid

4,4'-bis-methoxymethyl-biphenyl and di-2-phenoxyethyl phthalate 4,4'-bis-methoxymethyl-biphenyl and di-octyl phthalate

4,4'-bis-methoxymethyl-biphenyl and "Linevol"-7,9-phthalate

4»4*-bis-methoxymethyl-biphenyl and butyl-benzyl phthalate Compounds of type (b) which are particularly preferred are those of formula

where X means Cl, OH or OR^ or acyloxy.

These compounds are preferably used in admixture with aromatic phosphates or halo-alkyl phosphates or aryl-haloalkyl phosphates or mixtures thereof. Most preferred are mixtures of compounds of the above structure and aromatic phosphates.

Compounds of type (b) can optionally be mixed with other non-deactivated, aromatic compounds containing vacant positions on an aromatic ring such as compounds of formula RCHgX where R and X have the above meaning. In some cases, further improvement of fire retardancy can be achieved thereby. Non-limiting examples of such compounds are:

4,4^Tacetoxy-diphenyl-methane

4,4^-Methoxy-diphenyl-methane

4»4^-acetoxy(2,2-diphenylpropane)

4,4^-Methoxy(2,2-diphenylpropane)

1,5-acetoxynaphthalene

1,5-Methoxynaphthalene

1-acetoxy-4-phenylbenzene

1-acetoxy-2-phenylbenzene

1-Hydroxymethylnaphthalene

1-hydroxymethyl-4-phenylbenzene

diphenyl ether

biphenyl

terphenyl

polybenzyl

"Novolaks" and "Novolak^ ethers, eg glycidyl ethers

polyphenyl ethers

4-Hydroxymethyl-biphenyl

4-hydroxymethyl-diphenyl ether

4-Methoxymethyl-diphenyl ether

4-acetoxymethyl-diphenyl ether

1-hydroxymethyl-2-phenylbenzene

1-Hydroxymethylnaphthalene

mono-methyl-mono-hydroxymethylnaphthalenes

mono-hydroxymethyl-phenanthrene

Mixtures of phosphoric esters and/or aromatic carboxylate, sulphonate and carbonate esters can be used, if desired, as mixtures of compounds of formula I.

The compositions according to the invention may also contain other substances. For example, they may contain heat stabilizer, light stabilizer, antioxidants, fillers, pigments, lubricants, propellants, fungicides, Friedel Crafts catalysts or precursors, drier, other process aids and other flame retardant additives and smoke suppressants.

Suitable antioxidants include the sterically hindered phenolic compounds, e.g. 2,2'-thio-bis-(4-niethyl-6-tert.butylphenol), 4,4<*>-thio-bis-(3-methyl~6-tert.butylphenol), 2,2,-methylene -bis(4-methyl-6-tert.butylphenol), 2,2,-bis(4,4<f>-phenyloi)propane, 2,2'-methylene-bis-(4-Qtyl-6-tert. butylphenol), 4,4'-methylene-bis-(2-methyl-6-tert.butyl-phenol), 4»4'-butylidene-bis-(3-iaethyl-6-tert.butylphenol), 2, 2T -methylene-bis [4-methyl-6-(α-methyl-cyclohexyl)-phenol], 2,6-di(2-hydroxy-3-tert.butyl-5-methylbenzyl)4-methyl-phenol, 2 ,6-di-tert.butyl-4-methylphenol, 1,1,3-tris-(2-methyl-4-hydroxy-5-tert.butyl-phenyl)-butane, 1,3,5-trimethyl-2 ,4»6-tri(3,5-di-tert.butyl-4-hydroxy-benzyl)-benzene, esters of p-4-hydroxy-3>5-di-tert.butylphenyl-propionic acid with monohydric or polyhydric alcohols such as methanol, ethanol, octadecanol, hexanediol, nonanediol, thiodiethylene glycol, trimethylol-ethane or pentaerythritol, 2,4-bis-octylmercapto-6-(4-hydroxy-3»5-di-tert.butylanilino)-s-triazine, 2 ,4-bis-(4-hydroxy-3,5-di-tert.butylphenoxy}6-octyl-capto-s-triazine, 1,1-bis(4-hydroxy-2-methyl-5-tert.butylphenyl) -3-dodecyl-mercapto-butane, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis(4-niethyl-6-t-butylphenol), 4-nydroxy-3»5- di-tert-butylbenzyl-phosphonic acid esters, such as dimethyl, diethyl or dioctadecyl ester, (3-methyl-4-hydroxy-5-tert-butylbenzyl)-malonic acid dioctadecyl ester, s-(3»5-dimethyl-4-hydroxyphenyl)-thio -glycolic acid octadecyl ester and esters of bis-(3»5-di-tert.butyl-4-hydroxybenzyl-malonic acid such as didodecyl ester, dioctadecyl ester and 2-dodecyl mercaptoethyl ester).

Suitable light stabilizers and UV absorbers include sterically hindered cyclic amines of formula I

and salts thereof where q means 1 or 2, 2 means an organic residue which completes the nitrogen-containing ring to give a 5-membered, 6-membered or 7-membered ring, JU and R2 means methyl or together means -(CHg)^- , R^ means methyl, R^ means alkyl with 1-5 carbon atoms or together with R^ means the radicals -(C<H>2)^-, -(CH2)5-, -GH2-C(CH3)2-Iør -C(CH3)2-<C>H2- or -CHg-CtCH^Jg-HtO-CtCH^Jg-CHg- and, if q is 1, Y means hydrogen, -0, hydroxyl, alkyl, substituted alkyl, alkenyl , alkynyl, aralkyl, substituted aralkyl or acyl or, if q is 2, Y means the alkylene, alkenylene, alkynylene, cycloalkylene or aralkylene.

Examples of sterically hindered, cyclic amines of formula I are 4-benzoyloxy-, 2,2,6,6-tetramethylpiperidine;

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)-dodecanediote and bis-(1,2,2,6 ,6-pentamethyl-4-piperidyl)-sebacate.

2-(2'-hydroxyphenyl)-benzotriazoles such as 5'-methyl-, γ,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 *-tert .butyl-, 3'-a-methylbenzyl-5f-methyl-, 3'-a-methylbenzyl-5'-methyl-5-chloro-, 4<1>-hydroxy-, 4'-methoxy-, 4, -octoxy-, y ,5<*->di-tert.amyl-, 3<f>methyl-5<*>-carbo-methoxyethyl- and 5-chloro-3<T>»5,-di-tert. amyl derivatives.

2,4-bis-(2*-hydroxyphenyl)-6-alkyl-s-triazines,

such as, for example, 6-ethyl, 6-heptadecyl or 6-undecyl derivatives.

2-hydroxy-benzophenones such as, for example, 4-nihydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2'^-trihydroxy- or 2,-hydroxy -4>4,-dimethoxy derivatives.

1,3-bis-(2'-hydroxybenzoyl)-benzene such as 1,3-bis-{2'-hydroxy-4*-hexyloxy-benzoyl)-benzene, 1,3-bis-(2*^-hydroxy-4*-octyloxy-benzoyl)-benzene and 1,3-bis -(2'-hydroxy-4'-dodecyloxy-benzoyl)-benzene• Esters of optionally substituted benzoic acids such as for example phenylsalicylate, octylphenylsalicylate, dibenzoylresorcinol, bis-(4-tert.butylbenzoyl)-resorcinol, benzoylresorcinol and 3»5- di-tert.butyl-4-hydroxybenzoic acid 2,4-di-tert.butylphenyl-ester or octadecyl ester or 2-methyl-4,6-di-tert.butyl-phenyl-ester.

Acrylates such as a-cyano-pT8-diphenyl-acrylic acid ethyl ester or isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-B-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester and N-(B-carbomethoxy- vinyl)-2-methyl-indoline.

Oxalic acid diamides such as 4»4'-dioctyl-. oxy-oxanilide, 2,2,-di-octyloxy-5,5<*>-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2f-ethyl-oxanilide, S,K<*->bis-(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert.butyl-2'-ethyl-oxanilide and its mixture with 2-ethoxy- 2'-ethyl-5>4'-di-tert.butyl-oxanilide and mixtures of ortho- and para-methoxy- as well as o- and p-ethoxy-disubstituted oxanilides.

Nickel compounds such as, for example, nickel complexes of 2,2'-thio-bis-(4-(1,1,3,3-tetramethylbutyl)-phenol), such as the 1:1 or the 1:2 complex, optionally with further ligands such as n- butyl-amine, triethanolamine or H-cyclohexyl-diethanolamine, nickel complexes of bis-f2-hydroxy-4-(1,1,3,3-tetramethylbutyl)-phenyl-sulfone as the 2:r complex, optionally with the addition of ligands such as 2-ethylcaproic acid, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3»5-di-tert. butylbenzyl phosphoric acid raonoalkyl esters such as methyl, ethyl or butyl ester, the nickel complex of ketoximes such as of 2-hydroxy-4-methyl-phenyl-undecylketonoxime and nickel-3»5-di-tert.butyl-4-hydroxy- benzoate.

The compositions can, for example, contain as stabilizers:

tribasic lead sulfate

basic lead carbonate

basic lead phosphite

lead stearate

basic lead stearate

cadmium laurate

cadmium stearate

cadmium 2-ethyl hexeate

cadmium benzoate

barium laurate

barium stearate

barium phenate

barium alkylphenates

calcium laurate

calcium stearate

zinc stearate

zinc chloride

zinc 2-ethyl hexoate or other metal salts of branched

fatty acids

dibutyltin laurate

dibutyltin thiodiglycolate

dibutyltin thiocarboxylate esters

dibutyl tin maleate

stabilizers^based on other alkyltins

alkyl-S-amino-crotonates and ce-bls-crotonates

thio-alkyl-8-amino-crotonates and α-bis-crotonates

a-phenyl-indole

epoxidized soybean oil (for example, the product sold under the trademark "Reoplas 39")

other epoxy aliphatic or aromatic esters

glycidyl ethers

These stabilizers can be used alone or in any combination. Although not essential, when possible, the lowered level of stabilizers has been found to further increase the flame retardancy of the discussed compositions.

Preferred heat stabilizers are organotin stabilizers, e.g. ek3. dibutyltin maleate and epoxy stabilizers, e.g. epoxidized soybean oil (as sold under the trademark "Reoplas 39").

They can also be used with other stabilizing<p>g lubricating components such as:

pentaerythritol

triphenyl phosphite

decyl-diphenyl phosphite

didecylphenyl phosphite

trinonyl-phenyl phosphite

stearic acid

hydroxystearic acid

"Low" molecular weight polyethylene wax

paraffin wax

oxidized paraffin wax

fatty alcohols

esters of straight-chain fatty alcohols and straight-chain fatty acids

(in which the acids or alcohols are natural or synthetic)

monoesters of glycols and straight-chain fatty acids

methylene-bis-st'eararaid

Suitable pigments include organic and inorganic pigments or mixtures thereof. If an organic pigment is used, it can for example be a phthalocyanine which can be a metal phthalocyanine such as copper phthalocyanine, a metal-free phthalocyanine or a chlorinated metal or metal-free phthalocyanine, for example a chloromethylated phthalocyanine. Other organic pigments include azo pigments (monoazo or diazo), azo metal salts, anthraquinone and metal complexes. If an inorganic pigment is used, it can be, for example, titanium dioxide, carbon black or iron oxide.

The additional Friedel Grafts catalysts to the composition can in some cases give a marked increase in fire retardancy. This effect is particularly observed with aromatic chloromethyl additives.

Suitable Friedel Crafts catalysts either Bronsted or Lewis acids include aluminum chloride, zinc chloride, ferric chloride, magnesium chloride, stannous chloride, stannous chloride, butyltin trichloride, phosphoric acid p-toluenesulfonic acid. In addition, a latent catalyst can be used, e.g. one which is transferred to a Friedel Crafts catalyst by heat or by hydrogen chloride liberated by thermal decomposition of the vinyl chloride polymer. Such latent catalysts include zinc carbonate, stannous octoate, stannous oxalate and tri-alkyl phosphates.

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

Suitable secondary plasticizers or thickeners are chlorinated paraffin sold under the trade name<R>Céreclor", styrene resin sold under the trade mark R Dot? Resin 276-V2" and hydrocarbon derivatives sold under the trade name "Iranolin PDL18". Other common flame retardant additives may be present such as antimony oxide.

Examples of smoke suppressants that may be present include ferrocene, aluminum hydrate, and tetraphenyl lead.

Mixtures of the phosphoric acid esters can be used, if desired, together with one or more known phosphorus-free plasticizers, e.g. such as mixtures of phosphate and phthalate esters or mixtures of phosphate and adipate esters.

However, preferably the phosphoric acid ester is present at a concentration of at least 50%, preferably at a concentration of 75%, in any such mixture. However, where certain haloalkyl phosphates are used alone or in admixture with aryl phosphates, satisfactory results can be obtained with up to $90 phosphorus-free plasticizer.

Mixtures of the aromatic compounds can also be used, if desired, together with other PVC plasticizers, e.g. mixtures of phthalate esters and phosphates or mixtures of adipate and phosphate esters.

Non-limiting examples of phosphorus-free plasticizers that can be used in connection with compositions mentioned in the invention are:

di(butoxyethyl)adipate

di-2-ethylhexyl adipate

"Linevol"-7,9-adipate

di-iso-octyl adipate

di-capryladipate

di-nonyl adipate

iso-octyl, iso-decyl adipate

"Linevol^-9,11-adipate

di-iso-decyl adipate

polybutylene adipate

di-2-ethylbutyl azelate

di-2-ethyl hexyl azelate bis(diethylbenzyl)ether

o-nitro-diphenyl

polyethylene glycol monophenyl ether toluene ethyl sulfonamide

di(α-phenylethyl) ether

di-caprylazelate

di-n-butyl sebacate

di-alf0I-7,9-sebacate

di-iso-octyl-sebacate

di-capryl sebacate

di-nonylsebacate

tri-ethylene-glyco1-di-caprylate

iso-octyl-iso-decyl esters of AGS acids iso-octyl-epoxystearate

nonyl esters of AGS acids

iso-octyl esters of AGS acids

iso-decyl esters of AGS acids

n-heptyl esters of AGS acids

di-iso-decyl-succinate

butoxyethyl diglycol carbonate

tributyl citrate

acetyl triethyl citrate

acetyl tributyl citrate

acetyl tri(2-ethylhexyl) citrate

2,2 (2-ethylhexaide) diethyl-di (2-ethylhexoate) pblyethylene-glycol-di-2-ethylhexoate 2-butoxyethyl-oleate

tetrahydrofuryl oleate

Must compound a) is an ester of a phosphoric acid:

di-n-butyl phthalate

diisobutyl phthalate

di-2-ethylbutyl phthalate

iso-butyl-nonyl-phthalate

di-n-heptyl phthalate

di-2-ethyl hexyl phthalate

di-iso-octyl phthalate

di-capryl phthalate

di-n-octyl phthalate

iso-octyl-iso-decyl-phthalate

"Linevol"-7,9-phthalate

"Linevol"-9,11-phthalate

("Linevol<n>-7,9 and "Linevol"-9»H are mixtures of predominantly straight-chain alcohols of 7 and 9, and 9 and 11 carbon atoms respectively) di-2-phenylethyl phthalate

di-tridecyl phthalate butyl benzyl phthalate dimethyl glycol phthalate

tri-iso-octyl tri-mellitate

butyl phthalyl butyl glycolate

tri-octyl-tri-mellitate

dibenzyl phthalate

diphenyl phthalate

di-2-phenoxyethyl phthalate

tri-phenyl-tri-mellitate

tetra-phenyl-pyromellitate

ethyl benzoyl benzoate

di-propylene glycol dibenzoate

benzyl benzoate

diphenoxyethyl diglycolate

bis(phenyl-polyethylene-glycol) diglycolate

phenoxyethyl laurate

phenoxyethyl oleate

di-phenyl adipate

di«benzyl adipate

benzyl octyl adipate

octyl-phenyl-adipate

butyl benzyl adipate

dibutoxyethyl sebacate

di-(2-ethylhexyl) sebacate

2-butoxyethyl stearate

acetophenone

epoxy plasticizers, such as

epoxidized fatty glycerides

polymerized epoxy plasticizers

epoxidized ethyl hexyl oleates

aliphatic nitrites

When compound a) is an ester of a phosphoric ester, the plasticizer can also be:

di-benzyl sebacate

di-(2-phenoxyethyl)adipate

butyl benzyl sebacate

n-octyl-n-decyl phthalate/succinate

phenyl diglycol carbonate

cresyl diglycol carbonate

bis-(dimethyl-benzyl)carbonate

di-ethylene glycbl-dibenzoate

dipropylene glycol dibenzoate

tribenzyl citrate

alkyl sulfonate esters of phenols, e.g. products sold under the trademark "Mesamoll".

o-cresyl-p-toluenesulfonate

When compound a) is an aromatic carboxylate, sulfonate or carbonate ester, phosphates can be used as plasticizers, e.g. tri-(2-ethylhexyl) phosphate, tri-(2-chloro-ethyl) phosphate, tri-nonyl phosphate or tri(butoxyethyl) phosphate.

In addition, different polyesters can be used, for example polyesters derived from adipic acid and a glycol end-capped with an alcohol or mono-basic acid; polyesters derived from AGS acids (a commercial mixture of adipic, glutaric and succinic acids) and a glycol end-terminated with an alcohol or mono-basic acid; polyesters derived from phthalic anhydride and one or more glycols, optionally end-capped with an alcohol or mono-basic acid; polyesters derived from a mixed phthalic/adipic acid and ethylene glycol, optionally end-capped with an alcohol or monobasic acid; polyesters derived from mixed phthalic/AGS acids and a glycol and optionally end-capped with an alcohol or mono-basic acid. In addition, polyesters of these types modified with a lactone can be used, e.g. -caprolactone.

Examples of mixtures of the preferred esters of phosphoric acids with other plasticizers, stabilizers, fillers, etc. include the following: 1 phosphates + aliphatic dicarboxylic acid esters (ADAE) + chlorinated hydrocarbons or hydrocarbon delayers

2 phosphates + phthalates

3 phosphates + phthalates -f chlorinated hydrocarbons or hydrocarbon drier

4 phosphates + phthalates + ADAE

5 phosphates + phthalates + ADAE + chlorinated hydrocarbons or hydrocarbon softeners 6 phosphates + chlorinated hydrocarbons or hydrocarbon softeners

7 phosphates + ADAE

8 phosphates + polyesters

9 phosphates + polyesters + ADAE

10 phosphates + polyesters + phthalates

11 phosphates + polyesters + phthalates + ADAE

12 aryl phosphates + haloalkyl phosphates + phthalates

13 haloalkyl phosphates + alkyl phosphates + phthalates

14 aryl phosphates + haloalkyl phosphates + phthalates + ADAE

15 phosphonates + phthalates

Further examples of compositions falling within the scope of the invention are mixtures of haloalkyl phosphates and non-phosphorous plasticizers and include the following:

tris(2-chloroethyl)phosphate aryl ester of an alkanesulfonic acid

+ "butyl benzyl phthalate

w + di-octyl phthalate

+ esters of tri-mellitan anhydride

tris(2-chloroethyl)phosphate + di-octyl adipate

+ polyester based on phthalic anhydride,

a glycol end-capped with an alcohol or mono-basic acid.

The ratio between haloalkyl phosphate and non-phosphorous plasticizer that can be used is from 1:1 to 100:1, preferably 1:1 to 10:1, especially 1:1 to 5:1 and preferably 1:1.

In addition, one of the above combinations or any single phosphoric acid ester or mixture of phosphoric acid esters or combinations thereof can be used with or without other possibly phosphorus-free plasticizers in silicon oxide, barium metaborate, SbgO^ and diluted forms thereof, A1(0H)^

or<n>aluminium trlhydrate'<R>, carbon, calcium carbonates, leirfy 11 substances and stearic acid coated calcium carbonate alone or in combination.

Some of the above combinations can also be used with PVC stabilizers such as calcium/barium, cadmium/barium/zinc, tribasic lead sulphate, white lead påsta, thiotin bg tin carboxylate used in amounts from 0.01 to 7 parts per 100 parts polymer.

If combinations of esters or plasticizers are used, the conditions can be varied over a wide range and will usually depend on the end use of the polymer and, for example, whether black or clear polymer is desired. Such variations will be easily found by professionals.

The aromatic compounds of formula RtCHgX)^

which are used according to the invention are either known or can be easily prepared from known methods. For example, the main aromatic compound can be chloromethylated by reaction with formaldehyde and hydrogen chlorine gas. This reaction is discussed in "Organic Reactions", vol. I, 63 (1942). Replacement of the chlorine atom with other nucleophiles can give other compounds according to the invention.

Examples of these reactions are:

R.GHgCl compounds can also be prepared by side-chain chlorination of raethyl groups, i.e. by reacting R.CH^ compounds with chlorine gas.

Groups other than -CHgCl can be introduced directly into an aromatic nucleus by a one-step reaction. Reactions of this type are discussed in "Formation of C-C Bonds", vol. I by Jean Mathieu and Jean Weill-Raynal. Examples of CHgX groups that can be directly introduced into aromatic nuclei are:

Other, less direct, routes to R(CHgX)a-type compounds can be used. For example, an aldehyde group can be introduced into an aromatic compound either directly by reaction with carbon monoxide or by hydrolysis of a di-alkylmethylated or di-halomethylated aromatic compound. The aldehyde group can then be reduced to a hydroxymethyl group.

The hydroxymethylated aromatic compound can also be used as an intermediate in the preparation of other R(CH0c X)c0l compounds, for example

More detailed methods for the preparation of compounds used according to the invention are given below. These methods here exemplify the preparation of certain specific derivatives, but can be used to prepare derivatives of other aromatic R groups.

Method A. 4. 4-T-bis(chloromethyl)biphenyl

0.1 mol diphenyl, 0.075 mol paraformaldehyde, 0.07 mol zinc chloride and 50 oil cyclohexane were treated with dry hydrogen chloride gas with stirring at 55-60°C for 20 hours. The reaction mixture was poured into water and the organic material extracted with cyclohexane which was evaporated to dryness to give 0.06 moles of product = 60# of theoretical mp 137-138°C. Derivatives of this compound were then prepared using standard methods.

Method B. 4. 4f-bis(methoxymethyl)biphenyl

0.1 mol of 4,4'bis(chloromethyl)biphenyl (prepared by method A above), 0.4 mol of potassium hydroxide and 150 ml of methanol were refluxed for 4 hours with stirring. The reaction mixture was neutralized with concentrated hydrochloric acid and filtered. The filtrate was evaporated to dryness at 80°C under water pump vacuum and the residue fractionally distilled. The fraction boiling between 154 and 156°C at 0.2 mm Hg pressure was collected. The yield of the product = 0.075 mol f- 75 fJav the theoretical with melting point 47-49°<C>«

Method C. 4. 4' bisacetoxymethyl) biphenyl

0.1 mol of 4»4<r>bis(chloromethyl)biphenyl (prepared by method A above), 0.25 mol of potassium acetate and 100 ml of glacial acetic acid were refluxed for 17 hours with stirring. The reaction mixture was filtered and the filtrate evaporated to dryness at 80°C under water jet vacuum. The residue was recrystallized from methanol to give 0.068 mol of product = 66<4>/l of the theoretical. Melting point 86-87°C.

Method D. 4»4' bis(hydroxymethyl)biphenyl

0.1 mol of 4»4<f>bis(acetoxymethyl)biphenyl (prepared according to method C above), 0.4 mol of sodium hydroxide as a 23 µl aqueous solution and 50 ml of ethanol were refluxed for 3 hours with stirring. The reaction mixture was filtered and the precipitate was washed with water and dried to give 0.08 mol of product = 80%

of the theoretical with melting point 195-197°C.

Method E. Polyester from 4F4' bis(hydroxymethyl)biphenyl and phthalic anhydride

0.2 mol of 4,4'bis(hydroxymethyl)biphenyl (prepared by method D above), 0.1 mol of phthalic anhydride, 10 ml of xylene and 1.0 g of dibutyltin oxide were heated at 200°C and the water formed was removed by azeotropic distillation. After 3 hours,

when no more water was formed, the reaction mixture was cooled to give a white solid, m.p. 24-140°C.

Method F. Polymer from hydrolysis of 4, 4' bis(chloromethyl) biphenyl

.0.1 mol of 4,4'bis(chloromethyl)bl.phenyl (prepared by method A above), 0.5 mol of potassium hydroxide in 250 ml of water were stirred under reflux for 3° hours. The reaction mixture was cooled and extracted repeatedly with hot chloroform. The chloroform extracts were combined and evaporated to dryness to give a white solid, mp 140-155°C.

Method G. Bis- hydroxymethyl- bis- phenol A or 2, 2- bis-(3- hydroxymethyl-4-hydroxy- phenyl)- propane

To a mixture of 1.5 mol of bis-phenol A, 3.3 mol of sodium hydroxide and 1200 g of water was added 3.75 mol of formaldehyde (as a 37% w/W aqueous solution). The resulting solution was stirred at room temperature for 43 hours. After neutralization of the reaction mixture with dilute hydrochloric acid, the product precipitated as a plastic solid which was dissolved in ether. The ether layer was dried and the solvent removed by distillation at 60°C and 20 mm Hg. The product was a brown solid, mp 45-65°C (1.48 mol, 98% of theory).

Method H. Bis-acetoxymethyl-bis-phenol A-dl-acetate

To 1.0 mol of bis-hydroxymethyl-bis-phenol A were added 16.0 mol of acetic anhydride and 0.98 mol of anhydrous sodium acetate. The mixture was heated and stirred at 100°C for 5 hours. Half of the acetic anhydride was then removed by distillation up to 50°C at 20 mm Hg. The distillation residue was cooled to room temperature, diluted with water, and the product extracted with toluene. Removal of toluene by distillation under reduced pressure gave the product as a yellow, viscous oil (0.12 imol,

93 $ of the theoretical).

Method I. 1, 5-bis(bromomethyl)naphthalene

A mixture of 0.32 mol of 1,5-dimethylnaphthalene, 600 ml of carbon tetrachloride and 0.3 g of dibenzoyl peroxide was placed in a reaction flask equipped with a stirrer, thermometer and water separator. The contents of the flask were heated to 77°C and 0.70 mol of H-bromosuccinimide was added together with 1.5 g of dibenzoyl peroxide alternately over 55 minutes. The reaction mixture became thick and 900 ml of carbon tetrachloride was added and then the reaction was continued under reflux for 3 hours. The product was then filtered and washed with 400 ml of hot carbon tetrachloride. The volume of the filtrate was reduced to half on a rotary evaporator and a further amount of product filtered off. The product was a beige solid (0.09 mol, 28 of theory).

Method J. Bis-(3-(2'-hydroxyphenoxy)-2-hydroxypropyl)ether of 1,4-butanediol

This was achieved by adding 1 mole of the bis-2,3-epoxypropyl ether of 1,4-butanediol to 2 moles of o-hydroxymethyl-phenol.

The mixture of compound (a) and (b) can plasticize the chloride-containing aliphatic polymer itself, but if not, ordinary plasticizers can be added.

For example, an improvement in flexibility can be achieved with 4»4<*>bis(methoxymethyl)biphenyl. If it is used at different degrees with "Reofos 95">a constant, total plasticizer level of 70 phr, the following result is obtained:

By using compositions according to the invention, an improvement in fire retardancy can be achieved, if desired, without loss and in some cases with an increase in flexibility of the PVC compositions. When common plasticizers are added to increase the flexibility of PVC, a reduction in fire retardancy occurs. Surprisingly, it has been found that by using certain compositions according to the invention, a high degree of fire retardancy can be achieved together with high flexibility. However, in other cases, an increase in fire resistance may be desired without an increase in flexibility and this can also be achieved by using the compositions according to the invention.

In addition, certain compositions according to the invention show an improvement in smoke development. This is surprising as usually an improvement in flame retardancy leads to an increase

in smoke.

The compositions according to the invention are suitable for use in many articles. Examples of the use of rigid PVC compositions according to the invention are in roof coverings, window frames, foamed, rigid extrusions, e.g. enclosures, slabs and fences, slabs and chemical plant. Examples of the use of unsupported PVC compounds are in floor coverings, films, sheets, cables as insulation and sheets, elastomeric foam, electrical insulation tape and surgical tape, automotive components such as dashboards, bumpers, and mats, toys and novelties, castings such as blow molded bottles, plates , sporting goods, toys and hardware flexible bags and medical tubing. Examples of the use of PVC-coated textiles or paper are in floor coverings such as felt or jute-coated PVC or PVC-coated wallpaper, tarpaulins, conveyor belts, ventilation pipes, air-inflatable buildings, clothing, room dividers, wall coverings, leather clothing, for example as bolsters and seat covers for transport vehicles and in some homes, upholstery items e.g. baby nappies, foot coverings and outer coverings, tents, roof-coated steel, either laminated or plastisol-coated, elastic stockings, surface coatings and dip-coated articles, e.g. mind.

The invention will be explained in more detail with the help of some examples in which "parts" means parts by weight.

Examples 1 - 121

PVC compositions produced using different flame retardant compositions as indicated in the tables, the quantity being given by weight. The compositions contained 100 parts PVC and heat stabilizer.

The compositions were formed on a laboratory two-roll mill for 15 minutes at 165°C and then pressed into sheets 15 cm x 15 cm x 0.25 cm in a hot press. The sheets were then stored for 5 days at a constant temperature of 23°C. IRHD (International Rubber Hardness Degrees BS9O3) and oxygen index (01, ASTM 2863) were then measured on the sheets.

In order that comparisons can be made with compositions that do not contain compound (b), comparative examples are included. The relevant comparisons are shown in the tables. Measurement of smoke emission (Tables 3 and 17) was carried out with an Åminco KBS cabinet using the flame method. D max is the maximum specific optical density obtained during the test corrected for soot deposition on the light and photocell windows.

By comparing Examples A and D in Table 1,

it can be seen that by changing the composition from 70P°r "Reofos 95" ("Reofos 95" is a tri-aryl phosphate made from isopropyl-phenol/phenol) to 50 phr "Reofos 95" plus 20 phr di-2- ethyl hexyl phthalate shows a reduction in the oxygen index of 4". However, it has surprisingly been found that when changes of a similar type were made so that compositions according to the invention are used, examples 1 - 13" an increase in the oxygen index occurs.

Table 2 shows the effect of adding ordinary plasticizer to the composition according to the invention. Comparison of examples 14 and 15 with comparative examples E and F shows the marked increase in oxygen index which occurs when compositions according to the invention are used.

Table 3 indicates smoke density measurements carried out on

compositions according to the invention. Study of table 3 shows that certain compositions according to the invention (examples 19 and 20) have lower smoke generation and higher oxygen index than comparison example G. This is surprising as an improvement in flame retardancy with ordinary flame retardants usually leads to an increase in smoke generation.

It is seen that the oxygen index is much higher when aromatic compound (b) is present and also in certain cases the flexibility is improved. Thus, the PVC compositions are both flexible and have a high flame retardancy.

Table 4 indicates compounds of type b developed in connection with "Reofos 95" (tri-aryl phosphate prepared as indicated in British patent no. 1,146,173)» Table 4 shows that examples 21-52 have superior oxygen index values compared with Comparative Example H. Also certain of the examples as well as showing improvements in oxygen index also show improved flexibility as measured by IRHD. Such examples are 21, 23, 25" 26, 35" 36" 42, 51" Properties of good flexibility together with a high oxygen index are currently not achievable using conventional technology. Examples 21, 23, 25»29»42»44 show properties with good flexibility together with a high oxygen index.

Table 5 indicates the different types of phosphorous esters which have been used in connection with 4»4<*>-bis-hydroxymethyl-biphenyl. Examples 52 - 66 show a considerable improvement in oxygen index compared to the comparative examples I to Q.

Table 6 shows the effect of various stabilizers/catalysts on the oxygen index of compositions according to the invention. Preferred stabilizers/catalysts are (a) organo-tinri compounds as shown in examples 68, 69, 7°»71, 72, 73, 78, 79 , 8l, (b) epoxy compounds as shown in Examples 74, J% 76 and (c) silicone compounds as shown in Example 73»

Table 7 gives** examples of different ratios of compound (a) and (b) and different total levels of additives. It can be seen that even at addition levels as low as 5 parts of compound (b) (Examples 87 and 89) a marked increase 1 oxygen index can be achieved.

As 3^ parts of compound (b) are used which in example 83 gives a PVC compared with a very high oxygen index together with good flexibility, a combination of properties that cannot be achieved with known technology. Table 8 gives examples of compositions according to the invention which have not been mixed with a common PVC plasticiser, di-octyl phthalate. Table 8 shows that even in the presence of ordinary PVC plasticisers, a significant increase in the oxygen index can be achieved.

Table 9 &- r examples where compound b is mixed with another aromatic compound containing free positions on an aromatic ring.

Table 10 gives examples where mixtures of monomeric and telomeric compounds are used as additives with phosphate esters.

The telomere used in the examples 100,

101 and 102 were prepared as follows: _ 4,41-bis-(methoxymethyl)biphenyl (0.5 mol), diphenyl ether (0.5 mol) and stannous chloride catalyst (0.2 ml) were heated with stirring to 150° C. The heating was continued at 150°C and the methanol formed was distilled off until 16 g (0.5 mol) of methanol had been collected. The reaction mixture was cooled, transferred to a rotary evaporator and traces of methanol and stannous chloride were removed under vacuum at 80°G to give a very viscous brown product.

Yield 190 grams.

Table 11 gives examples of the use of compositions according to the invention in a vinyl chloride/vinylidene chloride copolymer. Table 11 shows that an increase in the oxygen index of greater than 20 units can be achieved when compositions according to the invention are used in this copolymer.

Table 12 further shows the invention by specifying compositions according to the invention containing PVC plasticizers or thickeners. Table 12 shows that all the examples according to the invention have a superior oxygen index compared to the same alignment example apples.

Table 13 shows examples of compositions according to the invention used in chlorinated polyethylene. The table shows that a significant increase in oxygen index can be achieved.

These compositions were prepared in a similar manner to the P?C examples on a laboratory two-roll mill, but no heat stabilizer was added and the milling temperature was 100°C and 100°C resp. for 36$ and 46 fo kbred polyethylene.

Table 14 further shows the invention and compositions added to the invention containing PVC plasticizers. Table 14 shows that all the examples according to the invention have a superior oxygen index compared to comparison samples.

Table 15 shows further examples according to the invention..:

Examples 122-130

PVC compositions were prepared by using different plasticizers and aromatic carboxylate esters compounded as indicated in the table and in the amounts indicated (parts are parts by weight). The compositions contained 100 parts PVC and 2 parts of a kadraium/barium heat stabilizer.

The composition was formed on a laboratory two-roll mill for 15 minutes at 165°C and then pressed into 15 x 15 x 0.25 cm sheets in a heated press. The sheets were then stored for 5 days at a constant temperature of 23°C.

After this time, IRHD (International Rubber Hardness: Begrees BS9O3) and oxygen index (0I, ASTM 2863) were measured on the sheets.

In order that the comparison can be made with compositions that do not contain compound (b), comparative examples A to G are included. The comparison appears in table l6.

I. table 16 in comparison of example B with examples 122 and I23 shows that a marked increase in oxygen index can be achieved by using the compositions according to the invention. In Example 129, none of the usual flame retardant elements are present in the aromatic ester plasticizer or

compound I of the composition, but an oxygen index of 33.5 units was obtained, which is as high as is normally obtained with ordinary fire retardant plasticizers.

Also in example 124, although compound I contains chlorine, the oxygen index of 33" 4 fa when using the composition is higher than could be predicted from the chlorine content of the system.

It can be seen that the oxygen index is much higher when aromatic compound (b) is present and also in certain cases the flexibility is improved. Accordingly, the PVC compositions are

both flexible and have a high flame retardancy.

Examples 131 - 15Q

PVC compositions were prepared using various plasticizers and aromatic compounds.

Each composition contains 100 parts by weight of PVC, 20 parts by weight of aromatic compound and 2 parts by weight of dibutyl tin maleate. The respective amount of aromatic ester plasticizer appears in the table.

The compositions were mixed in a laboratory two-roll mill for 15 minutes at 165°C and then pressed into sheets 15 x 15 x 0.25 cm in a heated press. The sheets were stored in

5 days at a constant temperature of 23°C

After this time, IRHD (International Rubber Hardness Degrees BS903) and oxygen index (01, ASTM 2863) were measured on the sheets as well as D-max and Clash & Berg values. The measurement

of smoke development was done with an Aminco-MBS cabinet using the flame method. D-max. is the maximum specific optical density obtained during the test for soot deposition on light and photo-cell windows.

In each sample, control experiments were carried out, i.e. experiments which do not include the use of any aromatic compound.

Claims (68)

1. Composition comprising chlorine-containing, aliphatic polymer and (a) an ester of phosphoric acid, an aromatic carboxylate-, sulfonate or carbonate esters or mixtures thereof and (b) a compound of formula I R(CH 2 X ) n wherein R means an aromatic hydrocarbon or heterocyclic radical, n is an integer of at least 2 and each X which is the same or different means a group. 2. Composition according to claim 1, characterized in that the ester is an ester of phosphoric acid. 3" Composition according to claim 1, characterized in that the ester is an aromatic carboxylate, sulfo nat or carbonate esters. 4. Composition according to claim 1, characterized in that the kThor-containing, aliphatic polymer is a thermoplastic polymer. 5" Composition according to claim 1, characterized in that the chlorine-containing polymer is a homopolymer or copolymer containing at least 5% chlorine. 6. Composition according to claim 5, characterized in that the chlorine-containing polymer contains more than 20% chlorine. :; 7« Composition according to claim 6, characterized in that the chlorine-containing polymer contains more than 40% chlorine. 8. Composition according to claim 1, characterized in that the chlorine-containing polymer is a poly mixture with other polymers. 9" Composition according to claim 1, characterized in that the chlorine-containing polymer is vinyl chloride homo-copolymer or a chlorinated polyolefin. 10. Composition according to claim 2, characterized in that the phosphoric acid is a phosphoric acid, a phosphonic acid, a phosphoric acid, a phosphoric acid or their dehydration products. 11. Composition according to claim 2, characterized in that the ester is a full ester. 12. Composition according to claim 2, characterized in that the ester is an ester of pentavalent phosphorus. 13. Composition according to claim 12, characterized in that the ester is triaryl-phosphate, alkyl-diaryl-phosphate, tf-halo-alkyl-phosphate, mixtures of these aryl/haloalkyl-mixed phosphates or mixed aryl-haloalkyl-phosphates. 14. Composition according to claim 3" characterized in that the carboxylate is a phthalate, benzoate or .mellitat. 15. Composition according to claim 3"1, characterized in that the aromatic ester is one with a non-deactivated benzene core. 16. Composition according to claim 3, characterized in that the aromatic ester is butyl-benzoyl-phthalate or bis-phenoxy-ethyl-phthalate. 17. Composition according to claim 3" characterized in that the aromatic ester is one that is usually used as a plasticizer for vinyl chloride polymers. 18. Composition according to claim 1, characterized in that the group R is mono-di- or polycyclic, condensed or non-condensed. 19" Composition according to claim 1, characterized in that R comprises more than one separate, aromatic residue connected through groups containing carbon or hetero atoms or through groups containing a combination of carbon and hetero atoms. 20. Composition according to claim 19, characterized in that the connecting groups are one which form repeating aryl or heterocyclic groups in which the connecting functions are derived from a -CHgX group. 21. Composition according to claim 20, characterized in that other non-connecting -CHgX functions are also present. 22. Composition according to claim 19, character!-, characterized in that the connecting functions have no more than 3 carbon atoms. 23" Composition according to claim 1, characterized in that R is substituted with one or more halogen atoms, 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 12 carbon atoms which may contain an epoxide group, cyclo-alkoxy groups with 5 to 12 carbon atoms, acyloxy groups with 1 to 12 carbon atoms, carboxyl groups or carbo-alkoxy groups with 2 to 12 carbon atoms or mixtures thereof. 24" Composition according to claim 1, characterized in that R is an otherwise unsubstituted or an alkyl-substituted di-, tri- or tetracyclic residue. 25 • Composition according to claim 1, characterized in that X is OH, SH, M2 , COgH, PO^Hg, OB(OH)2 or a derivative thereof or halogen. 26. Composition according to claim 1,' characterized in that X is OR <1> ,SR<1> , NHR<1> ,NR 3* 2,O BlOR <1> )(0É <2>)2 , where Y,Y<1> and Y <2> means independent, -0-, -NH-, -NR <1-> , -S- or is absent, Z means H,R<1> ,OR<1> , SR <1> , NH2, NHR1, NR3*2 or one direct bond connecting C back to R or CHpR, W means 0, S, NH or BOB <1> , L means 0, S or is absent, M means 0 or is absent, .R1 is a straight or branched alkyl chain with 1 to 12 carbon atoms, alkenyl or alkynyl chain 2 to 12 carbon atoms, cycloalkyl or cycloalkenyl of 5 to 12 carbon atoms, aralkyl, aralkenyl or alkaryl of 7 to 12 carbon atoms, and R 2 has the same meaning as R 1 and may be the same or different. 27" Composition according to claim 1, characterized in that the group is a salt of an acid or base group. 28. Composition according to claim 1, characterized in that I is OH, OR <1>, OCOH or OCOR <1> where R <1> has the meaning stated in claim 26. 29. Composition according to claim 1, characterized in that the compound R(CH,,X)n is one with formula where X means OH, OR1 or OCOR1, R1 has the meaning stated in claim 26. 30. Composition according to claim 28 or 29" characterized in that R1 means methyl, phenyl or benayl. 31. Composition according to claim 2 or 3, characterized in that 0.1 to 150 parts of phosphoric acid ester or 1 to 150 parts of aromatic ester are used per 100 parts chlorine-containing polymer. 32. Composition according to claim 3i> characterized in that 2 to 100 parts of phosphoric acid ester or aromatic ester are used per 100 parts chlorine-containing polymer. 33. Composition according to claim 32> characterized in that 5 tii 80 parts of phosphoric acid or aromatic ester are used per 100 parts chlorine-containing polymer. 34" Composition according to claim 1, characterized in that 1 to 5° parts of the compound of formula I are used per 100 parts chlorine-containing polymer. 35. Composition according to claim 34" characterized in that 1 to 35 parts of compound with formula I per 100 parts of chlorine-containing polymer and a phosphoric acid ester are present. 36. Composition according to claim 35, characterized in that 2 to 25 parts of the compound of formula I are used per 100 parts of chlorine-containing polymer and a phosphoric acid ester are present. . 37" Composition according to claim 34" characterized in that 1 to 20 parts of the compound of formula I per 100 parts of chlorine-containing polymer and an aromatic ester are present. 38. Composition according to claim 37" characterized in that 2 to 15 parts of the compound of formula I are used per 100 parts of chlorine-containing polymer and an aromatic ester are present. 39. Composition according to claim 1, characterized in that it also contains a non-deactivated, aromatic compound containing free positions on an aromatic ring. 40. Composition according to claim 39, characterized in that the non-deactivated, aromatic compound is one of formula ECH^ I where R and X are the same as for the compound R(CH2 X)n . 41.. Composition according to claim 1, characterized in that it also contains heat stabilizer, light stabilizer, antioxidant, filler, pigment, lubricant, propellant, fungicide, Friedel Crafts catalyst or, precursor, retarder, processing aids, other flame retardant additives, or smoke suppressants or mixtures thereof. 42> Composition according to claim 41" characterized in that it contains as stabilizer, an organo-tin compound or any epoxy compound. 43» Composition according to claim 1, characterized in that X is chlorine and a Friedel Crafts catalyst is also present. 44" Composition according to claims 41 to 43" characterized in that the Friedel Crafts catalyst is aluminum chloride, zinc chloride, ferric chloride, magnesium chloride, stannous chloride, stannous chloride, butyltin trichloride or phosphoric acid or p-toluenesulfonic acid. 45" Composition according to claim 1, characterized in that it also contains a phosphorus-free plasticizer and a phosphoric acid ester or an aromatic ester and a plasticizer different from the aromatic ester. 46. Composition according to claim 45" characterized in that the amount of the phosphorus-free plasticizer reaches up to the amount of the phosphoric acid ester. 47" Composition according to claim 46" characterized in that the amount of the phosphorus-free plasticizer is up to one third of the amount of phosphoric acid ester. 48. Composition according to claim 45" characterized in that a halo-alkyl phosphate is present and the amount of the phosphorus-free plasticizer is up to 90 % of the mixture of phosphate and plasticizer. 49" Composition according to claim 1, characterized in that the compounds (a) and (b) are used in a weight ratio of from 20:1 to 0.1:1. 50" Composition according to claim 36, characterized in that compounds (a) and (b) are used in a weight ratio of from 10:1 to 0.5:1. 51" Composition according to claim 50, characterized in that compounds (a) and (b) are used in a weight ratio of from 5:1 to 1:1. 5? Composition according to claim 1, characterized in that it comprises a vinyl chloride polymer and (a) an aromatic carboxylate, sulphonate or carbonate ester or preferably an aromatic phosphate ester, and (b) a compound of formula R(CH2 2)n in which R means an aromatic hydrocarbon or aromatic heterocyclic residue, n means an integer from 2 to 12 and X means a group capable of carrying a negative charge. 53" Composition according to claim 52" characterized in that the vinyl chloride polymer is a homopolymer or a copolymer 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 the aromatic ester is one that is usually used as a plasticizer for vinyl chloride polymers. 56. Composition according to claim 55, characterized in that the aromatic phosphate ester is derived from a phenol or mixtures of phenols. 57" Composition according to claim 5" characterized in that the aromatic phosphate ester is triaryl phosphate. 58" Composition according to claim 521, characterized in that the aromatic carboxylate, sulfonate or carbonate ester is derived from a phenol. 59" Composition according to claim 52, characterized in that the aromatic carboxylate ester is a phthalate, a benzoate or a mellitate. 60. Composition according to claim 52, characterized in that the group R is mono-, di- or polycyclic, condensed or non-condensed. 61. Composition according to claim 60, characterized in that the non-condensed di- and polycyclic aromatic residue is connected directly or through heteroatoms or a carbon-containing group. 62. Composition according to claim 52, characterized in that R is substituted 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 4 carbon atoms, cycloalkoxy groups with 5 to 12 carbon atoms, carboxyl groups, carbo alkoxy 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 di-, tri- or tetracyclic residue. 64" Composition according to claim 52, characterized in that 2 is OH, SH, NHg or a derivative thereof or halogen. 65. Composition according to claim 52" characterized in that X is OR <1> , SR <1> , NHR <1> , NR3*2, OSOpR <1> , or where V is -0-, -NH-, -NR<1-> or -S-, Y is 0 or S, Z is H,R<1> , OR <1,> SR <1> , NHg, NHR1 or NR <X> R <2> , R1 means alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, aralkyl or alkaryl with J to 12 carbon atoms, or aryl with 6 to 12 carbon atoms which may be substituted with one or more halogen, hydroxy, epoxy, nitrile, ether and/or ester groups, R 2 has the same meaning as R 1 and is the same or different. 66. Composition according to claim 52" characterized in that I is a halogen atom, OH, OR <1>, OCOH or OCOR1, where R <1> has the meaning stated in claim 65. 67. Composition according to claim 52" characterized in that the compound R(CHpX)n is one with the formula where X means Cl, OH, OR <1> or as R1 has the meaning specified in claim 65. 68. Composition according to claim 52" characterized in that it also contains heat stabilizer, light stabilizer, antioxidant, filler, pigment, Friedel-Crafts catalyst or precursor, delayer, lubricant and/or flame retardant additive. 69• Method for improving the fire retardancy of a chlorine-containing, aliphatic polymer, characterized in that it is incorporated into the polymer a) an ester of phosphoric acid, an aromatic carboxylate, sulphonate or carbonate ester or mixture thereof and b) a compound of formula I wherein R means an aromatic hydrocarbon or a heterocyclic radical, n is an integer of at least 2 and each X are the same or different and mean a residue group. 70" Composition for improving fire retardancy of a chlorine-containing, aliphatic polymer, characterized in that it contains a) one. ester of a phosphoric acid, an aromatic carboxylate, sulphonate or carbonate ester or mixture thereof and b) a compound of formula I wherein R means an aromatic hydrocarbon or heterocyclic residue, n means an integer of at least 2 and each X is the same or different and means a residue group.