DE2818960A1 - NON-AROMATIC CARBON, HYDROGEN AND OXYGEN POLYMER COMPOUNDS - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann - Dr. K. Koenigsbeitjer
Dipl.-Phys. R. Holzbauer - Dipl.-Ing. F. Klinoiseieen - Dr. F. Zumstein jun.

BODO Munich 2 - erftuhaussttmSe 4 - phone roll no. 225341 - Telegrams Zumpat - Telex 52S979

Case 3-11123 / MA 1702 / =

i CIBA-GEIGX AG, CH-4002 Basel / Switzerland

Non-aromatic carbon, "hydrogen" and "oxygen" containing Polymer masses

The present invention relates to new flame retardant,
non-aromatic carbon, hydrogen and oxygen-containing polymer compositions. It has surprisingly been found that the flame retardancy of such polymers can be increased by using novel flame retardant preparations.

809844/1066

The subject of the present invention is accordingly a kettle made of a non-aromatic carbon, hydrogen- and oxygen-containing polymers as well

a) an ester of a phosphorus acid and

b) a compound of formula I.

R (CH ₂ X) _n (I)

wherein R is an aromatic hydrocarbon or heterocyclic Represents a remainder, η stands for an integer of at least 2 and the X are the same or different and one Represent leaving group, exists.

In the compounds of the formula I, the aromatic or heterocyclic rings can each contain O to 6 -CH JC groups, preferably 1 to 3 and particularly preferably 1, provided that there are at least 2 -CHpX groups per molecule.

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

The aromatic nucleus preferably has a free ortho position next to the -CH ^ K group, and this is preferably in such a position that no intramolecular ring closure can take place.

The leaving group X in formula I is halogen, -OH,

609844/1081

-SH, -NH ₂ , -CO ₂ H, -PO ₃ H ₂ , OB (OH) ₂ or their derivatives, for example -OR ¹ , -SR ¹ , -NHR ¹ , -NR ¹ R ² , -OB (OR ¹ XOR ² )

7S- ² '- ^Y "I \' · - ^Y -§- ^z >

M. »^ 22 M.

V - ■ X, Y ^ R ■

1 2
wherein Y, Y and Y are independently -0-, -NH-, -N- or -S- or are absent, but preferred

wise for -0- or -S-, Z for H, R ¹ , OR ¹ , -SR ¹ , NH ₂ , NHR ¹ , NR ¹ R ² or a direct bond, the C again with R or

linked to a CH ₂ bonded to R, but preferably for

1 d.

H or R, W stands for 0, S, NH or NR, but preferably stands for 0 or S, L stands for 0 or S or is absent, but preferably stands for 0, M stands for 0 or is absent, but preferably stands for 0 , and where R is straight-chain or branched alkyl with 1 Ms 12, preferably 1 to 4, but particularly preferably 1, carbon atoms, 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 6 to 15, preferably 6 to 12, carbon atoms and particularly preferably phenyl or naphthyl.

Optionally, R is represented by one or more halogen,

- 3 8098U / 108B

Hydroxyl, epoxy, nitrile, amine, amide, ether, carboxyl

or substituted ester groups or combinations thereof,

2, however, it is preferably unsubstituted. R has one of the meanings given for R. The leaving group can also be a salt of an acidic or basic X group.

However, among the non-limiting examples Compounds of the formula I with X = OH or a derivative preferred by this group.

A monocyclic or optionally condensed di- or polycyclic aromatic radical can be present as R. It can represent a mixture of condensed and non-condensed groups. If there is more than one separate aromatic radical, these can be linked directly or via groups containing carbon or heteroatoms or combinations of groups containing carbon and heteroatoms Lead groups in which there are -CHpX groups as connecting function (s), in which XR and / or R contains, ~, of which at least one is an R or -CH ₉ R group. \ The group R can therefore be an oligomer which contains the above-mentioned aromatic hydrocarbon and heterocyclic radicals and is formed by addition or condensation reactions.

809844/1011

The connection functions are preferably short-chain Groups with preferably at most 3 carbon atoms. The connection functions particularly preferably do not have any adjacent carbon atoms- The group R can be otherwise unsubstituted or 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 4, carbon atoms, Cycloalkyl groups with 5 to 12 carbon atoms, hydroxyl groups, optionally containing an epoxy group Alkoxy groups with 1 to 12, preferably 1 to 4, carbon atoms, 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 having 2 to 12, preferably 2 to 4, carbon atoms or mixed therewith be substituted. However, R is preferably an otherwise unsubstituted or alkyl, preferably methyl, substituted one di-, tri- or tetracyclic radical. R is particularly preferably an otherwise unsubstituted di-, tri- or tetracyclic radical aromatic residue.

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

Non-limiting examples of the radical R in formula I include those which are derived from the following systems: when R is monocyclic '.

1 benzene

2 toluene '

- 5 -8098U / 10ÖS

3 xylenes ^

4 ethylbenzene

5 Mesltylen

6 durol

7 isodurol

β f-cumene or cumene

9 anisole

10 phenyl acetate

11 chlorobenzene

12 bromobenzene

13 pyridine

14 triazine

15 pyrimidine

16 pyrazine

17 pt-butylphenol

Preferably, R is derived from residues 1-10 and 17. yenn R is non-condensed bicyclic

1 biphenyl

2 diphenylmethane

3 1,1-diphenylethane \

4 1,2-diphenylethane · · -

5. 2,2-diphenylpropane

6 diphenylcarbinol

7 benzophenone

8 phenyl benzoate

9 Diphenylessigelure (and dtren Eeter)

10 diphenylither

- 6 -I098U / 10M

11 diphenylacetonitrile

12 diphenyl sulfide

13 diphenyl disulfide

14 diphenyl sulfoxide

15 diphenyl sulfone

16 diphenylamine

17 Ν, Ν-diphenylmethylamine

18 diphenylmethylphosphine

19 Diphenylmethylphosphine Oxide

20 diphenyl octyl phosphate

21 dipyridyl

22 3,3'-dimethyl mphenyl

23 2,2'-dimethylbiphenyl

24 4,4'-dimethylbiphenyl

25 2,2'-diphenyl-dicarboxylic acid

26 stilbene

27 benzoin

28 benzil

29 benzilic acid

30 dibenzyl sulfate '

31 dibenzyl oxalate

32 diphenyl succinate

33 diphenyl carbonate

34 Octyl distyryl phosphinate

35 ferrocene

36 diphenyl succinate

37 ethylenedioxydiphenyl

8098AA / 108B

Al,

Among them are those of No. 1, 2, 10 and

derivative radicals preferred. when R condensed is bicvclic

1 naphthalene

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

Of these, naphthalene and methylnaphthalene are preferred. when R is tricyclic non-condensed

1 terphenyl

2 triphenylmethane

3 dibenzylbenzene

40, O-Dipheny! Hydroquinone

5 0,0-diphenylresorcinol

6 triphenylamine

809SU / 1086

7 triphenylphosphine

8 triphenylphosphine oxide

9 triphenyl phosphate

10 tricresyl phosphate

11 trixylyl phosphate

12 Isopropylphenyl / phenylphosphate (for example such » which are commercially available under the trademarks Reofos 50, 65 and 95 and according to the British Patent Code No. 1 146 173)

13 triphenylantimony

14 tribenzyl phosphate

15 diphenyl styryl phosphonate

16 triphenyl orthoformate

Of these, the radicals derived from No. 1, 2, 3, 5 »6, 8, 9» 10, 11 and 12 are preferred. when R condensed is triangular

1 anthracene

2 phenanthrene

3 phenylnaphthalene

4 acenaphthene

5 acenaphthylene

6 dihydroanthracene

7 anthrene

8 xanthan gum

9 xanthone

10 fluorene

11 fluorenone

809644/1011

12 acridine

13 phenanthridine

14 phenazine

15 benzcinnoline

16 carbazole

17 Dibenzfuran

18 dibenzthiophene

19 phenothiazine

20 phenoxazine

21 α-methylstyrene dimer

22 styrene dimer

23 biphenylene

24 1-methylanthracene

These include those from No. 1, 2, 3, 4, 5, 10,

16, 17, 21, 22 and 24 derived residues are preferred. when R is non-condensed tetracyclic

1 quaterphenyl

2 tetraphenylmethane

3 triphenylbenzene

4 2,4,6-triphenyltriazine

5 N, N ¹ , N ⁿ triphenylmelamine

6 N, N ¹ , N "-triphenyl isocyanuric acid

7 tetraphenyltin

8 tetraphenyl lead

9 tetraphenylethane

10 tetrabenzyl orthosilicate

11 2,4,6-triphenoxytriazine

- 10 -

8098U / 108B

12 tetraphenyl silicate

Of these, the radicals derived from Nos. 2, 4, 5, 6 and 11 are preferred .. when R is condensed tetracyclic

1 dinaphthyl

2 fhenylanthracene

3 phenylphenanthrene

4 N-fhenylacridone

5 N-phenylcarbazole

6 N-phenylphenothiazine

7 N-phenylphenoxazine

8 9-phenylacridine

9 2,3-diphenylquinoxaline

10 triphenylene

11 aceanthrene

12 pyrene

13 naphthacene

14 fluoranthene

15 chryses

16 dinaphthyl methane

Of these, the radicals derived from dinaphthyl and N-phenylcarbazole are preferred. when R is higher than tetracyclic polycyclic

1 9,10-diphenylanthracene

2 sexiphenyl

3 carrots

4 9,9-diphenylxanthene

- 11 -

8098U / 108B

5 9,9-diphenylacridane

6 hexacene

7 hexaphs

8 pyranthrene

9 Hexaphenylmelamine when R is an oligomer

1 polyphenyl

2 polybenzyl

3 polyxylylene

4 polystyrenes

5 polynaphthylenes

6 polybenzyl ether

7 polyester from a Ms-hydroxymethylaromatic compound

8 polyphenyl ethers

9 Polyesters from Dihydric Phenols Non-limiting examples of Group X in Formula I.

are ;

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

, -0CH ₂

O 0 II I. , -OCH » -OCCH ₃ "

-OC-

, -OCOC ₂ H ₅ ,

I!

- 12 -

809844/1088

Il

-OOKHCK

-OCNI

4 * s

-OCXHCl *

.S

-OCK (CK.

-OCKH

-OSO,

CH.

■ O

~ ^{S CCH}

3 ^f

• SCOCh 'ι -SC-OC ₂ H,

-SCN

-NHCH

₃ ,

-K (CHj) ₂ ,

Il ■

KHC CHj, -KHC

NH

II

-NHC - OCH,,

, -NHC NH ₂ , -NHC NK-C ΝΗ _£ ,

NH

NH NH

- 13 -

8098U / 108B

, -COII, -COCH ₃₁ -P (OH) _{2 1} -

. Examples of salts include alkali, ammonium or amine salts of acidic compounds, as well as inorganic ones or organic or quaternary salts of basic compounds, e.g.

Non-limiting examples of specific compounds of the formula I when R is monocyclic are 1,4-bis (carboxymethyl) benzene 1,4-bis (methoxycarbonylmethyl) benzene 1,4-bis-hydroxymethylbenzene 1,4-bis methoxymethylbenz oil 1,4-bis-benzoxymethylbenzene 1,4-bis-chloromethylbenzene 1,4-bis-acetoxymethylbenzene 2,4,6-tris-chloromethylmesitylene 3,6-bis-methoxymethyldurol 2,4,6-tris-acetoxymethylphenol acetate 2, 6-bis-hydroxymethylpyridine 2,6-bis-hydroxymethyl-4-t-butylphenol 1,3,5-tris-hydroxymethylbenzene

- 14 809844/1085

2818980

1,4-bis-hydroxymethyl-2,3,5,6-tetrachlorobenzene when R non-condensed bicyclic is 4,4'-bis (chloromethyl) biphenyl 4,4 -bis- ^f (bromomethyl) biphenyl 4, 4 · -Bis- (carboxymethyl) -biphenyl 4,4'-bis- (methoxycarbonylmethyl) -biphenyl 4,4 ^f -Bis- (hydroxymethyl) -biphenyl 4,4 * -bis- (methoxymethyl) -biphenyl 4,4 ^f -Bis- (phenoxymethyl) -biphenyl 4,4 * -Bis- (benzyloxymethyl) -biphenyl 4,4 * -Bis- (acetoxymethyl) -biphenyl 4,4 ^l -Bis- (formyloxymethyl) -biphenyl α, α * -Bitolyl -diphosphonic acid disodium salt 4-hydroxymethyl-4 * -methoxymethylbiphenyl 4-hydroxymethyl-4 * -acetoxymethylbiphenyl 4.4 ^l -Bis- (dimethylaminomethyl) -biphenyl 4,4 * -Bis- (methylcarbamoyloxymethyl) -biphenyl

4,4 * -bis- (trimethylaminomethyl) -biphenyl-dichloride

2,4-bis- (acetoxymethyl) -6-phenyl-phenol acetate 4,4 * -Bis- (hydroxymethyl) -diphenylmethane 4 ₁ 4 ^I -bis- (methoxymethyl) -diphenylmethane 4,4 * -Bis- (benzyloxymethyl) - diphenylmethane 4,4 * -bis- (formyloxymethyl) -diphenylmethane 4,4 * -bis- (carbamoyloxymethyl) -diphenylmethane

3 »3 * -Bis- (acetoxymethyl) -4,4 · -bis-acetoxy-diphenylmethane

4,4 -Bis- (hydroxymethyl) -benzophenone 4 _> 4 ^l -Bis- (methoxymethyl) -diphenylether

- 15 -809ΘΑΑ / 108Β

4,4'-bis (acetoxymethyl) diphenyl ether 4,4'-bis (hydroxymethyl) diphenyl sulfone 3,3 ^f -Bis- (acetoxymethyl) -4,4 '-Ms-acet oxy-diphenyl sulfone N, N -Bis- (4-hydroxymethylphenyl) -methylamine bis- (4-hydroxymethylphenyl) -octyl phosphate 4,4'-bis- (methoxymethyl) -3,3'-dimethyl-diphenyl 2,2-bis- (3'-acetoxymethyl- 4'-acetoxyphenyl) propane bis (3- (2'-hydroxymethylphenoxy) -2-hydroxypropyl) ether of 1,4-butanediol.

when R is condensed "is bicyclic 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- (hydroxymethyl) -naphthalene 1,5-bis- (methoxymethyl) -naphthalene 1,5-bis- (formyloxymethyl) -naphthalene ■ 1,5-bis- (acetoxymethyl) -naphthalene 1-methyl-bis- (chloromethyl) -naphthalene 2-methyl-bis- (chloromethyl) -naphthalene 1-methyl-bis- (hydroxymethyl) -naphthalene 2-methyl-bis (hydroxymethyl) naphthalene 1-methyl-bis (methoxymethyl) naphthalene

- 16 -

809844/1011

2-methyl-bis- (methoxymethyl) -naphthalene 558-bis- (chloromethyl) -tetralin 5 j8-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) -is ο quinoline 4,8-bis- (acetoxymethyl) -isoquinoline 5 , 8-bis- (chloromethyl) -quinoxaline 5 j 6-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) -benzfuran 4,7-bis- (methoxymethyl) -benzfuran 4,7-bis- (chloromethyl) -benzfurane 4,7-bis- (hydroxymethyl) -benztriazole 4,7-bis- (formyloxymethyl) -benztriazole if R is non-condensed tricvclic 1,4-di- (4 · -chloromethylphenyl) -benzene 1,4-di- (4'-hydroxymethylphenyl) -benzene 1,4-di- (4-formyloxymethylphenyl) -benzene tri- (4-methoxymethylphenyl) -methane tri- (4-hydroxymethylphenyl ) -methane,

- 17 8098U / 108B

Tr i- (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'-chlorine thylbenzyl) -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) -resorcinol Tri- (4-hydroxymethylphenyl) -amine Tri- ( 4-methoxymethylphenyl) -amine tri- (4-formyloxymethylphenyl) -phosphine tri- (4-benz oyloxymethylphenyl) -phosphine tri- (4-carbamoyloxymethylphenyl) -phosphine tri- (4-dimethylaminomethylphenyl) -phosphine oxide tri- (4-bromomethylphenyl) -phosphine oxide tri- (4-benzoyloxymethylphenyl) -phosphine oxide tri- (4-chloromethylphenyl) -phosphate tri- (4-methoxymethylphenyl) -phosphate

Di (4-hydroxymethylphenyl) mono- (p-methoxymethylphenyl) phosphate Tri- (4-methoxymethyl-meta-kresyl) -phosphate, monophenyl-di- (4-methoxymethylphenyl) -phosphate Monophenyl-mono- (4-hydroxymethylphenyl) -mono- (p-methoxymethylphenyl) )-phosphate

Di (methoxymethylphenyl) mono- (2-isopropylphenyl) phosphate Di (hydroxymethylphenyl) mono- (4-isopropylphenyl) phosphate

- 18 -

8098U / 1085

Tris- (2,4-di-butoxymethyl-6-phenyl-phenyl) -borate when R condensed is tricyclic 1,4-dihydroxymethylanthracene 5-hydroxymethyl-1,4-di (methoxymethyl) -anthracene

1, A-di (hydroxymethyl) -5,8-di (methoxymethyl) anthracene

2,7-di (acetoxymethyl) anthracene 1,4,7-tris (acetoxymethyl) acenaphthylene 1 »^» 7-tris (dimethylaminomethyl) acenaphthylene 1,4,5,8-tetra (hydroxymethyl) fluorene 1,4,5,8-tetra (acetoxymethyl) xanthene 114 ·, 5-tri- (brominethyl) -xanthene 1,4,5,8-tetra (dimethylaminomethyl) carbaz ol 1 »4-, 518-tetra- (carbamoyloxymethyl) -acridine 3- »4» 6,9-tetra- (benzoyloxymethyl) -phenaz in 2,7,10-tris (chloromethyl) phenanthridine 1 »^» 6 »9-Tetra- (methoxymethyl) -phenoxazine 1,4,6,9-tetra (hydroxymethyl) phenothiazine

1,3,3-trimethyl-1-phenyl-4,7-di (methoxymethyl) indane

if R is non-condensed tetracyclic, it is tetra- (3,5-dihydroxymethylphenyl) -methane tetra- (4-methoxymethylphenyl) -methane tetra- (4-formyloxymethylphenyl) -methane tetra- (4-dimethylaminomethylphenyl) -methane 1,3,5 -Tri- (3,5-dichloromethylphenyl) -benzene 1,3,5-tri- (4-methoxymethylphenyl) -benzene 1,3,5-tri- (4-carbamoyloxymethylphenyl) -benzene 1,3,5-tri - (4-benzoyloxymethylphenyl) benzene

- 19 8098U / 1086

N, N ', N "-Tri- (3,5-dihydroxymethylphenyl) -melamine N, N', N" -Tri- (3,5-diformyloxymethylphenyl) -melamine N, N ', N "-Tri- (4 -methoxymethylphenyl) -melamine 2,4,6-tri- (3,5-dichloromethylphenyl) -triazine 2,4,6-tri _r (3,5-dicarbamoyloxymethylphenyl) -triazine 2,4,6-tri- (4- acetoxymethylphenyl) -triazine N, N ¹ , N "-Tri- (3,5-dihydroxymethyphenyl) -isocyanurate tetra- (3,5-diformyloxymethylphenyl) -tin tetra- (4-hydroxymethylphenyl) -tin tetra- (4-chloromethylphenyl) -tin tetra- (4-acetoxymethylphenyl) -lead tetra- (4-bromomethylphenyl) -lead i tetra- (4-methoxymethylphenyl) -lead tetrakis- (2-butoxymethylphenyl) -silicate when R condensed is tetracyclic 2-phenyl-5 , 8-dibromomethylanthracene 2-phenyl-5,8-dihydroxymethylanthracene 2-phenyl-5,8-diformyloxymethylanthracene 3-phenyl-3 _f 6-dimethoxymethylphenanthrene 3-phenyl-3,6-diacetoxymethylphenanthrene 3-phenyl-3,6-dihydroxymethylphenanthrene N -Phenyl-2, o-dichloromethylcarbazole N-phenyl-2, ö-dicarbamoyloxymethylcarbazole N-phenyl-2,7-dimethoxymethylphenothiazine N-phenyl-2,4,6-tribromo methylphenothiazine N-phenyl-2,4,6-triacetoxymethylphenoxazine 2,5-diphenyl-5,8-diformyloxymethylquinoxaline

-ZO-

809844/1086

ORIGINAL INSPECTED ^C0PY

2,3-Diphenyl-5 , 8-dihydroxymethylquinoxaline if R is higher than tetracyclic polycyclic 2,6-dimethoxymethyl-9,10-diphenylanthracene 2,8-dichloromethyl rubrene
2,6-dihydroxymethyl-9,9-d £ phenylxanthene 2,6-diacetoxymethyl-9,9-diphenylxanthene-2, e-dicarbamoyloxymethyl-g, 9-diphenylxanthene 1,4,6,9,12,15-hexamethoxymethylhexacene polyether 4,4'-BJs-chloromethyldiphenyl and ethylene glycol Chloromethylated polystyrene polyester from 4,4-bis- (hydroxymethyl) -diphenyl and phthalic anhydride

Polyester from 4,4 ^f -Bis- (hydroxymethyl) -diphenyl and succinic anhydride

Polyurethane made from 1,5-bis (hydroxymethyl) naphthalene and Toluene diisocyanate

Polyether made from 1,5-bis (chloromethyl) naphthalene and ethylene glycol

Polybenzyl ether from the hydrolysis of 4,4'-bis (chloromethyl) diphenyl.

The compound of the formula I can also be an oligomer of the formula

(A) _a (-CH ₂ -) _b [-CH ₂ (OCH ₂ ) _m OCH ₂ -] _c (-CH ₂ X) _d II, where A is at least one aromatic hydrocarbon or heterocyclic radical and X is OH or a derivative thereof means, a stands for 2 to 20, but is equal to b + c + 1, b for 0 to 19, c for 0 to 19, d for 0 to 2a and m for 0 to 10,

- 21 -

8098U / 1086

ORIGINAL INSPECTED

preferably 0-5 and particularly preferably 0, where there are at least two (-CHpX) groups per molecule and the group (-CH ₂ OCH ₂ -) counts as (-CH ₂ X).

It should be noted that the values of a, b, c, d and m are average values for the average molecule of the formula II represent.

Aromatic radicals A are, for example, benzene, naphthalene, furan, anthracene, biphenyl and diphenyl ether. The aromatic radical A is optionally substituted once or twice. It is preferably unsubstituted, but in the case of substitution it preferably has only one substituent. Suitable substituents include halogen, alkyl groups with 1 to 4 carbon atoms, haloalkyl groups with 2 to 4 carbon atoms and the group OR ³ , where R ^{5 stands} for hydrogen, alkyl with 1 to 4 carbon atoms or acyl with 1 to 4 carbon atoms.

The compounds represented by Formula II are mixtures of oligomers of different molecular weights. The radicals A are _{linked by (-CH 2} -) - or [-CH ₂ (OCH ₂ ) _m OCH ₂ -] groups, these two bridging groups not being bonded to one another but only to one radical A. The groups (-CH ₂ X) are bonded to a radical A.

Preferably more than 50 M0I-J6 of the residues A are derived and particularly preferably over 75 MoI-Ji! from naphthalene.

Those oligomers which have a number average molecular weight of 300 to 3,500 are preferred, particularly preferred

- 22 8098U / 1086

those which have a number average molecular weight of 350-1,500 and very particularly preferably 400 to 1,000. It is preferable that the naphthalene residues _{are linked by (-CH 2} OCH ₂ -) and these bridges in 1,4-; 1.5-; 1,6-; 1.7-; 2.5-; 2,6- or 2,7-position should be bound to the naphthalene radical. The bridges should particularly preferably be attached to the naphthalene radical in the 1,4 or 1,5 position.

Non-limiting examples of individual oligomers of constitution II are those which are linked by the group -CHpOCHo and have two or more -OLjX groups per molecule. Preferred constitutions optionally present as a component of the oligomer mixture are listed below. The -CH ₂ OCH ₂ - group is counted as a -CHpX group, the latter having the same meaning as given above.

(XCH ₂ )

DO

CH ₂ OCH ₂

(XCH

CH ₂ OCH ₂

CH ₂ OCH ₂

where m = O or 1 and X = OH, -0OCCH ₃ , -OBenzyl or -OPhenyl.

- 23 -

8098U / 1Q86

Specific examples of oligomers as components in Mixtures of oligomers are listed in Table A.

R ¹

-CH ₂ (OCH ₂ ) _m OCH ₂ J

R ⁵

- 24 -

8098U / 108B

Table A.

l4

No. a "b C. m 0 'd - R ¹ r5 R. 1 0 0 1 0 CVJ .— ■ - • - -CHgOH *
2 1 1 1 - o CVJ -CH ₅ . - - -CHgOCH ₅ • 3 2 1 2 0 2 -CHgBr ■ - CH ₅ " -CHgOH 4th "3 2 2 0
0 CVl -CH-. - -CHgBr -CHgOH 'UN VO 4 '
5 1
1 4th
5 3 2
• *
2 - ■ _ OH ₃ -CH OCH
1
-CH OCCH- 7th 6th 2 5 0 2 Λ1ΤΤ - - " -CHgOH 8th 8th 2 6th 0 2 - OH ₃ CHj -CHgOCCH, 9 .. 8th 1 8th 6th CVJ -CHgOCHg <g) 10 5 1 VJl 0 CVl - · - -CHgOH 11 1 0 2 2 - - -CHgOH

The phosphoric acids include derivatives of phosphoric acid, a phosphonic acid, a phosphinic acid and phosphorous acid and its dehydration products. Salts of partial esters are useful, however the full esters will preferred.

Non-limiting examples of esters of phosphoric acid are ;

1 triphenyl phosphate

2 cresyl diphenyl phosphate

- 25 -

8098U / 108B

3 phenyl xylyl phosphate

4 tritolyl phosphate

5 trixylyl phosphate

6 phenyl / isopropylphenyl phosphates (for example those which are commercially available under the trademark "Reofos 95, 65 and 50 and according to the British patent specification No. 1 146 173.)

7 phenyl / sec-butylphenyl phosphate

8 phenyl / p-t-butylphenyl phosphate

9 di (2-cumylphenyl) phenyl phosphate

10 di (4-benzylphenyl) phenyl phosphate

11 tri- (4-t-butylphenyl) phosphate

12 tri- (4-nonylphenyl) phosphate

13 Tri- (4-t-amylphenyl) phosphate

14 tri- (4-chlorophenyl) phosphate

15 tri- [4- (bromoisopropyl) phenyl! Phosphate

16 tri- [4- (chloroisopropyl) phenyl] phosphate

17 Diphenyl (2-bromophyl) 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-bromoethyl) phosphate ^ 24 Phenyl di (2-chloroethyl) phosphate

25 phenyl di (2,3-dichloropropyl) phosphate

26 Phenyl di (2,3-dibromopropyl) phosphate

- 26 -

.8098 * 4/1086

27 phenyl di-n-octyl phosphate

28 Eienyl di-n-decyl phosphate

29 tri- (2-chloroethyl) phosphate

30 tri- (2-bromoethyl) phosphate

31 tri- (2,3-dibromopropyl) phosphate

32 tri- (2,3-dichloropropyl) phosphate

33 trioctyl phosphate

34 tridecyl phosphate

35 triallyl phosphate

JCH ₀ ClO CCH ₀ CH ₀ Cl I ² I / ²

CXCH ₂ CH ₂ O POCB ₂ CCH ₂ OP. ClCH ₂ CB ₂ OL ₂ Cl

37 Trl- (meta-ethylphenyl) phosphate

38 Calcium dianmonium phosphate salt of diphenyl hydrogen phosphate Non-limiting examples of esters of phosphonic acids :

39 Diphenyl phenyl phosphonate

40 di (4-bromophenyl) phenylphosphonate

41 - Di- (4-t-butylphenyl) phenylphosphonate

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

- 27 8098AA / 108B

48 di- (4-chlorophenyl) -n-butylphosphonate

49 Di- (4-bromophenyl) -n-hexylphosphonate

50 di- (2-isopropylphenyl) -n-octylphosphonate

51 phenyl n-octyl-n-hexyl phosphonate

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

53 diethyl phenyl phosphonate

54 Diethyl diethanolaminomethylphosphonate Non-limiting examples of esters of phosphorous acids

55 n-octyl distyryl phosphinate

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

57 phenyl distyryl phosphinate

58 n-Octyl-distyrylphosphinate Non-limiting examples of esters of the phosphorous satire :

59 triphenyl phosphite

60 trioctyl phosphite

61 tri-4-nonylphenyl phosphite

62 tri-2,3-dibromopropyl phosphite

63 diphenyl hydrogen phosphite

64 dioctyl hydrogen phosphite

Preferred compounds include the esters of pentavalent phosphorus and very particularly the triaryl phosphates and trihaloalkyl phosphates, e.g., compounds 1 to 10 and 29 to 32, as well as their mixtures or mixed aryl phosphates, Haloalkyl phosphates and aryl haloalkyl phosphates.

It goes without saying that if an ester is one

- 28 -

Phosphorus acid also has the formula R (CH ₂ X) _n , this is to be regarded as component (b) and should be used together with another ester of a phosphorus acid to which the formula R (CH 2 X) does not fit. However, if another R (CHoX) component is present, the ester of a phosphorus acid of the formula R (CH ₂ X) _{n can be} viewed as the ester component (b).

The compositions according to the invention can contain the compounds (a) and (b) included in any proportions. Fractions of ester (a) of a phosphorus-containing one are particularly useful Acid from 0.1 to 150 parts, preferably 1 to 150 parts, particularly preferably 2 to 100 parts and very particularly preferably 5 to 80 parts, each per hundred parts of polymer. "Of compound (b), proportions of 1 to 50 parts are preferred 1 to 35 parts, particularly preferably 2 to 25 parts and very particularly preferably 2 to 15 parts, each per hundred parts polymer, especially useful. The compounds (a) and (b) can be used in a weight ratio from 20: 1 to 0.1: 1, but preferably from 10: 1 to 0.5: 1 and very particularly preferably from 5: 1 to 1: 1 can be used.

Non-limiting examples of polymers which can be used in accordance with the invention are regenerated cellulose and cellulose derivatives, for example cellulose diacetate, copolymers of polymethylene ethers, for example a formaldehyde / ethylene oxide copolymer, as well as polyacrylates and polymethacrylates such as polymethyl acrylate and polymethyl methacrylate, polyesters and polyethers.

- 29 B098U / 1Ö & B

Particularly preferred components (b) are those of the formulas

X CH

and

where X is Cl, OH, OR or acyloxy. These connections are preferably used in a mixture with aromatic phosphates, haloalkyl phosphates, aryl haloalkyl phosphates or their mixtures. Mixtures of the compounds of the above constitution are particularly preferred with aromatic phosphates.

If appropriate, component (b) can be mixed with other non-deactivated aromatic compounds having free positions on the aromatic ring, such as compounds of the formula RCH ₂ X, in which R and X are as defined above. In some cases this can provide a further increase in flame retardancy. Non-limiting examples of such compounds are:

- 30 809844/1088

4,4'-diacetoxy-diphenylmethane, 4,4'-dimethoxy-diplaenylniethan, 4,4 * -diacetoxy- (2,2-diphenylpropane), 4,4 * -dimethoxy- (2,2-diphenylpropane), 1,5-diacetoxynaphthalene, 1,5-dimethoxynaphthalene, l-acetoxy-4-phenylbenz ol, l-acetoxy-2-phenylbenz ol, 1-hydroxymethylnaphthalene, l-hydroxymethyl-4-phenylbenzene, Diphenyl ether, biphenyl, terphenyl, polybenzyl, novolak and novolak ethers e.g. glycidyl ether, polyphenyl ether, 4-hydroxymethylbiphenyl, 4-hydroxymethyl diphenyl ether, 4-methoxymethyl diphenyl ether, 4 — acetoxymethyl diphenyl ether, 1-hydroxymethyl - 2-phenylt> enzene, Monomethyl monohydroxymethylnaphthalenes and monohydroxymethylphenanthrene.

In some cases, these compounds are formed during the preparation of compound (b), especially when this is an oligomer.

If desired, mixtures of phosphorus-containing esters as well as mixtures of compounds of the formula I can be used insert.

The compositions according to the invention can also contain other ingredients, for example thermal stabilizers, light stabilizers, antioxidants, fillers, pigments, lubricants, blowing agents, fungicides, Friedel-Crafts catalysts or their precursors, extenders, other processing aids and other flame-retardant additives and smoke-reducing agents. Suitable antioxidants include, for example, the sterically hindered phenol compounds: 2,2 »-thio-bis- (4-methyl-6-tert-butylphenol), 4,4 ^l -thio-bis- (3-methyl-6-tert .butylphenol), 2,2 «-methylene

-31 8098U / 1Q8B

Ms- (4-methyl-6-tert-butylphenol), 2.2 ^! -Bis- (4,4'-phenylene) propane, 2,2 »-Methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4'-, methylene-bis (2-methyl- 6-tert.butylphenol), 4,4'-butylidenebis (3-methyl-6-tert.butylphenol), 2.2 ^f -methylene-bis- [4-methyl-6- (α-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-4-hydroxy-5-tert-butylphenyl) -butane, 1,3,5-trimethyl-2,4,6-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -benzene , ß-4-Hydroxy-3,5-di-tert-butylphenylpropionic acid ester with monohydric or polyhydric alcohols such as methanol, ethanol, octadecanol, hexanediol, nonanediol, thiodiethylene glycol, trimethylolethane or pentaerythritol, 2,4-bis-octylmercapto-6- (4th -hydroxy-3,5-di-tert-butylanilino) -s-triazine, 2,4-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6-octylmerlcaptos-triazine, 1,1- Bis- (4-hydroxy-2-methyl-5-tert-butylphenyl) -3-dodecyl mercaptobutane, 2,6-di-t-butyl-p-cresol, 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid esters such as the dimethyl, diflthyl or dioctadecyl ester, (3-methyl-4-hydroxy-5-tert-butyl benzyl) malonic acid dioctadecyl ester, S- (3,5-dimethyl-4-hydroxyphenyl) thioglycolic acid octadecyl ester and bis (3,5-di-tert Butyl-4-hydroxybenzyl) malonic acid such as the didodecyl, dioctadecyl ^ and 2-dodecyl mercaptoethyl esters.

Suitable as light stabilizers and UV absorbers inter alia sterically hindered cyclic amines of the formula III

- 32 8098U / 108S

X N

and their salts, in which q is 1 or 2, X is an organic grouping which complements the nitrogen-containing ring to form a 5-, 6- or 7-membered ring, R ₁ and R _{2 are} methyl or together - (CH ₂ ) c -, R ^ 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 ) ₂ -CH ₂ - or -CH ₂ ~ C (CH ₃ ) ₂ -N (0 ') - C (CH ₃ ) ₂ -CH ₂ - and, if q is 1, Y is hydrogen, -O *, hydroxyl, "alkyl, substituted alkyl, alkenyl, alkynyl, aralkyl, substituted aralkyl or aryl or, if q is 2, alkylene, alkenylene, alkynylene, cycloalkylene or aralkylene.

Sterically hindered cyclic amines of the formula III are for example 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-capryloyloxy-2,2,6,6-tetramethylpiperidine, 4-stearyl oxy-2,2,6,6-tetramethylpiperidine, Sebacic acid bis (2,2,6,6-tetramethyl-4-piperidyl) ester, Dodecanedioic acid bis (2,2,6,6-tetramethyl-4-piperidyl) ester and sebacic acid bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester.

2- (2! -Hydroxyphenyl) -benzotriazoles such as, for example

- 33 8098U / 10S5

5'-methyl-, 3 ', 5'-di-tert-butyl-, 5'-tert-butyl-, 5' - (1,1,3,3-tetramethylbutyl) -, 5-chloro-3 ' , 5 ^f -di-tert-butyl-, 5-chloro-3'-tert-butyl-5-methyl-, 3'-sec-butyl-5'-tert-butyl-, 3'-a-methylbenzyl- 5'-methyl-, 3'-a-diethylbenzyl-5 'methyl-5-chloro-, 4'-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3', 5'-di-tert. amyl, 3'-methyl-5'-carbomethoxy-thyl and 5-chloro-3 ', 5'-di-tert-amyl derivative.

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

2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4 ^T -Trihydroxy- or 2'- Hydroxy-4,4'-dimethoxy derivative.

1,3-bis- (2 ^l -hydroxybenzoyl) -benzenes such as, for example, 1,3-bis- (2-hydroxy-4'-hexyloxybenzoyl) -benzene, 1,3-bis- (2'-hydroxy-4 ' octyloxybenzoyl) benzene and 1,3-bis (2'-hydroxy-4'-dodecyloxybenzoyl) benzene.

Esters of optionally substituted benzoic acids such as for example phenyl salicylate, octylphenyl salicylate, Dibenzoylresorcinol, bis- (4-tert-butylbenzoyl) -resorcinol, benzoylresorcinol and the 2,4-di-tert-butylphenyl, Octadecyl or 2-methyl-4,6-di-tert-butylphenyl ester of 3 »5-di-tert-butyl-4-hydroxybenzoic acid.

Acrylic esters such as cc-cyano-ß, ß-diphenylacrylic acid ethyl or isooctyl ester, methyl α-carbomethoxycinnamate, a-cyano-ß-methyl-p-methoxycinnamic acid methyl or -butyl ester and N- (ß-carbomethoxyvinyl) -2-methyl-

- 34 809844 / 108B

indoline. ¥ f

Qxalsäurediamide such as 4,4 ^f -Di-octyloxyoxanilid, 2,2 * -Di-octyloxy-5,5 ■ · -di-tert. -butyl-oxanilide, 2.2 ^f -Di-dodecyloxy-5.5 ^f -di-tert-butyl-oxanilide, 2-ethoxy-2 »-ethyl-oxanilide, N, N-bis- (3-di- methylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2 ^l -ethyl oxanilide and its mixture with 2-ethoxy-2 ^f -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 nickel complexes of 2.2 ^l thio-bis [4- (l _> l, 3,3-tetramethylbutyl) phenol] such as the 1: 1 or 1: 2 complex, optionally with other ligands such as n —Butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel complexes of bis- [2-hydroxy-4— (1,1,3,3-tetramethylbutyl) phenyl] sulfone such as the 2: 1 complex, optionally bit other ligands such as 2-ethylcaproic acid, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert.butyldenzylphosphonic acid monoalkyl esters such as methyl, ethyl or butyl esters, nickel complexes of ketoximes such as 2-hydroxy. 4-methylphenyl-undecyl ketone oxime and nickel-tS-di-tert-butyl-4-hydroxy-benzoate.

ff

Suitable pigments include organic and inorganic pigments or mixtures thereof. Becomes an organic pigment used, for example, an optionally metal-containing phthalocyanine such as copper phthalocyanine metal-free phthalocyanine or a chlorinated metal-containing or metal-free phthalocyanine, e.g. a chloromethylated one

- 35 809844/1086

Phthalocyanine, in question. To other organic pigments include the azo pigments (monoazo or diazo), azo metal salts, Anthraquinone and metal complexes. If an inorganic pigment is used, titanium dioxide, carbon black, for example, are used or iron oxide in question.

By adding Friedel-Crafts catalysts to the mass, a significant Achieve an increase in flame retardancy. This effect is shown in particular by the aromatic chloromethylated additives.

As Friedel-Crafts catalysts, which are used by both Brßnstedals can also be Lewis acids, among others, aluminum chloride, zinc chloride, ferric chloride, magnesium chloride, Tin-II-chloride, tin-IV-chloride, butyltin trichloride, Phosphoric acid and p-toluenesulfonic acid. Furthermore ISsst also use a latent catalyst, e.g. one that is produced by the action of heat or by the one during thermal decomposition Hydrogen chloride released by vinyl chloride polymer is converted into a Friedel-Crafts catalyst Such latent catalysts include zinc carbonate, tin (II) octoate, Tin-II-oxalate and trialkyl phosphates.

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

Other conventional flame retardant additives such as antimony oxide can also be present.

The aromatic compounds of the formula R (CH ^) _n used according to the invention are either known or can easily be prepared by established methods. Examples-

- 36 8098U / 1086

wise you can get the basic aromatic compound by reaction with formaldehyde and hydrogen chloride gas chlorinethylate. This reaction is described in "Organic Reactions", Volume I, 63 (1942). Replacement of Chlorine atoms through other nucleophiles can result in further compounds according to the invention.

Examples of these reactions are: R-CH ₂ Cl + KOH + CH ₃ OH - »R-CH ₂ OCH ₃ R-CH ₂ Cl + CH ₃ COOK -> R-CH ₂ OCOCH ₃

R-CH ₉ OCOCH,)

^ 5 + KOH -> R. CH ₉ OH R-CH ₂ Cl) *

R-CH ₂ Cl + KCN - »R-CH ₂ CN

R-CH ₂ Cl + (CH ₃ ) ₂ NH > R.CH ₂ N (CH ₃ ) ₂

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

S S

R-CH ₂ Cl + HCOONa -> R-CH ₂ OOCH

R.CH ₂ C1 compounds can also be prepared by side chain chlorination of methyl groups, ie by reacting R.CH ₃ compounds with chlorine gas.

Groups other than -CH ₂ Cl can be introduced directly into an aromatic nucleus by one-step reactions. An overview of such reactions can be found in "Formation of CC Bonds", Volume I by Jean Mathieu and Jean ¥ eill-Raynal, CH ^ groups which can be introduced directly into an aromatic nucleus are, for example: -CH ₂ Cl , -CH ₂ OH, -CH ₂ OCH ₃ , -CH ₂ OCOCH ₃ , -CH ₂ SC ₂ H ₅ , -CH ₂ SO ₆ H ₅ , -CH ₂ N (CH ₃ ) ₂ and -CH ₂ N (C ₂ H ₅ ) ₂ -

- 37 -809844 / 10S ₁ B.

Other, less direct routes to the -TypePUS connections are available. For example can either be achieved directly by reaction with carbon dioxide or by hydrolysis of a dialkoxymethylated or dihalomethylated aromatic compound introduce an aldehyde group into an aromatic compound. Then can you then reduce the aldehyde group to a hydroxymethyl group.

R.CHCIp)

) + H ₉ O * R.CHO

R.CH (OCpH ₅ ) ₂ ) ^

R.CHO »R.CH ₂ OH

The hydroxymethylated aromatic compound can also be used as an intermediate in the preparation of other R (CH ₂ X ^ ₁ compounds, for example 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
RXH ₂ OH + CH ₃ C ₆ H ₄ SO ₂ Cl -ν R-CH ₂ OSO ₂ C ₆ H ₄ CH ₃

The oligomers according to the invention can be prepared by conventional methods; for example: a) by reacting naphthalene with formaldehyde in the presence of an acidic catalyst to form oligomers of constitutions with predominantly methylene bridges (-CH ₂ -) and acetal bridges (- (CH ₂ O) _n -CH ₂ -) and some dimethylene ether bridges (-CH ₂ -O-CH ₂ -), or b) by chloromethylation of naphthalene to produce mixtures of mono-, di- and higher chloromethylnaphthalenes, which then form oligomers with predominantly dimethylene ether bridges

- 38 8098U / 10SS

(-CH ₂ -O-CH ₂ -) and methylene bridges (-CH ₂ ) are hydrolyzed and oligomerized, or c) by reacting a chloromethylated aromatic compound, e.g. benzyl chloride, with formaldehyde or one of its precursors such as trioxymethylene and an acidic catalyst, whatever a chloromethylated diarylmethane, for example bis-chloromethyl-diphenylmethane results. The latter is hydrolyzed and oligomerized with aqueous sodium carbonate or converted into the hydroxymethyl derivatives via the acetoxymethyl compounds and then oligomerized with an acidic catalyst.

Production methods for compounds according to the invention are given below in more detail. The production of certain special derivatives serves as an example of these methods, but these can be used to produce derivatives of other aromatic R groups. Method A. 4,4 ^f -Bis- (chloromethyl) -biphenvl

0.1 mol of diphenyl and 0.075 mol of parafformaldehyde are treated with stirring; 0.07 mol of zinc chloride and 50 ml of cyclohexane for 20 hours at 55 ° -6O ° C with dry hydrogen chloride gas. The reaction mixture is poured into water, the organic material is extracted with cyclohexane and evaporated to dryness, which gives 0.06 mol of product = 60 percent of theory, melting point = 137.degree.-8.degree. Subsequently, derivatives of this compound are prepared using standard methods. Method B. 4,4 * -Bis- (methoxwethvl) -diphenyl

0.1 mol of 4.4 ^t -bis- (chloromethyl) -biphenyl (prepared according to method A above), 0.1 mol

- 39 809844/1086

Potassium hydroxide and 150 ml of methanol at reflux for 4 hours. The reaction mixture is neutralized with concentrated hydrochloric acid, filtered, ^{evaporated to dryness at 80 °} C. in a water jet vacuum and the residue is fractionally distilled. The fraction boiling between 154 ° C. and 156 ° C. at 0.2 torr is recovered. Product yield = 0.075 moles = 75 percent of theory.

Melting point = 47 ° -49 ° C.
Method C. 4.4 ^t -Bis- (acetoxymethyl) -biphenvl

While stirring, 0.1 mol of 4,4'-bis (chlorinethyl) biphenyl (prepared according to method A above), 0.25 mol of potassium acetate and 100 ml of glacial acetic acid are refluxed for 17 hours. The reaction mixture is filtered and the filtrate is evaporated to dryness at 80 ° C. in a water jet vacuum. When the residue is recrystallized from methanol, 0.068 mol of product = 68 percent of theory.
Melting point = 86 ° -87 ° C.
Method D. 4,4'-bis (hvdroxvmethvl) -diphenyl

While stirring, 0.1 mol of 4.4 ^l -bis (acetoxymethyl) - "biphenyl (prepared according to method A above), 0.4 mol of sodium hydroxide as a 23 percent aqueous solution and 50 ml of ethanol are refluxed for 3 hours . The The reaction mixture is filtered and the precipitate is washed with water and dried, which gives 0.08 mol of product = 80 percent of theory, melting point = 195 ° -97 ° C.

The following examples illustrate the invention.

- 40 809844/1085

■■■■ & ■

Examples 1 and 2 and comparative examples k and B (Table 1) .

Polymethyl methacrylate (100 parts) is mixed in the melt with the other components listed in Table 1 in a Brabender Plasti-Corder. The polymer is first allowed to gel and then the remaining components are added in small amounts over 10 minutes and the entire formulation is then mixed for 5 minutes. The compound mass is then removed, converted into etoe form and, using the following cycle, pressed into plates 152.4 × 76 × 2 × 2.54 mm. Heat the press, then place the mold in the press and apply low pressure for 5-10 minutes while the sample warms up to the press temperature. Then a pressure of 40 kg / cm is applied for 2-3 minutes. The heating is then switched off and the press is cooled to approximately 100 ^° C. with water before the pressure is released and the mold is removed. Then the mold is allowed to cool to 40-50 ⁰ C, before taking out the sample.

Example 3 and Comparative Example C (cellulose diacetate) (Table 1) .

Mixing is carried out in the melt as in Example 1, again using a temperature of 230.degree. It is also pressed as in Example 1, but using a temperature of 230 ^° C.
Example 4 and Comparative Example D (viscose) (Table 1)

It is mixed in the melt and pressed as described in Example 1 using a temperature of

- 41 . 809844/1085

Example 5 and Comparative Example E (Kemetal) (Table 2) The mixture is mixed in the melt and pressed as described in Example 1, but a temperature of 200 ^° C. is used in both stages.

- 42 809844/1085

Tabel

at
game
No. R. X η Manuf
lungs
method Enamel
Point Parts
Connect
dung I Phosphorus- '.
more substantial
Ester
(Parts) polymer 0.1.
% 1 OH 2 D. 195-
197 ^C C 10 Triphenyl
phosphate
(25) Polymethyl
methacrylate 30.1 A. - - - - - TI It 17.6 2 "(ei)" ® · OH 2 D. 195-
197 ° C 5 Tris- (2,3-
dibromopropyl
phosphate'
Uo) Il 25.3 B. - - - - - ti It 22.9 3 OH 2 D. 195-
197 ° C 10 Triphenyl
phosphate
(25) Cellulosic
diacetate 26.2 C. - - - - - - Il It 24.3 4th -OCH ₃ 2 B. Enamel
Point
47_49 ° C 5 Triphenyl-.
phosphate viscose 21.1 D. - - - - - - Il ti 19.4

Table 2. Kemetal (Formaldehvd / Aethvlenoxvd)

O CO OO

at
game
No. R. X η Manufacturing
method Enamel
Point Parts
Connect
dung I Phosphorus-
more substantial
Ester
(Parts) Other additions ¹ OI
% 5
E. -OH 2 D. 195-
197 "C 10 Triphenyl
phosphate
(25)
It sodium
(2)
Il 26.6
19, A

From the tables above it can be seen that the oxygen index (O.I.) is higher when the masses are a compound of formula I, as if such a compound is absent. This indicates an improvement in flame retardancy there.

- 45 -8098U / 1085

Claims (34)

Claims; 1. Masses, characterized in that they consist of a non-aromatic containing carbon, hydrogen and oxygen Polymers as well (a) an ester of a phosphorus acid and (b) a compound of formula I. R (CH ₂ X) _n (I) where R is an aromatic hydrocarbon or heterocyclic radical, η is an integer of at least 2 and the X are identical or different and are each halogen, -OH, -SH, -NH ₂ , -CO ₂ H, -PO ₃ H ₂ , OB (OH) ₂ or their derivatives. 2. Compositions according to claim 1, characterized in that the polymer is regenerated cellulose, a cellulose derivative, a polymethylene ether copolymer, a polyacrylate, polymethacrylate polyester or polyether is present. 3 · masses according to claim 2, characterized in that as polymer cellulose diacetate, a formaldehyde / ethylene oxide copolymer, Polymethyl acrylate or polymethyl methacrylate is present. 4. Compounds according to claim 1, characterized in that component (a) is an ester of phosphoric acid, a phosphonic acid, of a phosphinic acid or of phosphorous acid or of a dehydration product of such acids. 5. Compounds according to claim 4, characterized in that the ester present is a full ester of a phosphorus acid. 6. Compositions according to one of the preceding claims, characterized in that the ester of component (a) is a 809844/1 ⁴ 08 ~ p ORIGINAL INSPECTED 2818980 Triaryl phosphate, trihaloalkylphosphate, a mixed one Aryl / haloalkyl phosphate, an alkyl diaryl phosphate or Dialkylaryl phosphate is present. 7. Compounds according to claim 1, characterized in that R in the formula is a monocyclic or optionally condensed
represents di- or polycyclic group. 8. Compounds according to claim 1, characterized in that R is more than one separated by carbon and / or ■ contains heteroatom-containing groups linked aromatic radical. 9 · Compounds according to claim 8, characterized in that the linking group present is one that is to be repeated Aryl or heterocyclic groups leads, where a -CH ^ X group is the connecting function. 10. masses according to claim 1, characterized in that
R single or multiple by halogen atoms, alkyl groups with 1 to 4 carbon atoms, cycloalkyl groups with 5 to 12
Carbon atoms, hydroxyl groups, optionally one
Epoxy group-containing alkoxy groups with 1 to 12 carbon atoms, cycloalkoxy groups with 5 to 12 carbon atoms, aralkyloxy groups with 7 to 12 carbon atoms,
Acyloxy groups with 1 to 12 carbon atoms, carboxyl groups or carboalkoxy groups with 2 to 12 carbon atoms
or is substituted therewith mixed. 11. masses according to claim 1, characterized in that R is an otherwise unsubstituted or alkyl-substituted di-, is tri- or tetracyclic radical. - 47 -809844/1085 12. Compounds according to claim 1, characterized in that X OR ¹ , SR ¹ , NHR ¹ , NR ¹ R ² , OB (OR ¹ ) (OR ² ), -YCZ, Il W Y ¹ R ¹ ° / Il - ^Y -K or -YSZ 1 2
denotes in which Y, Y and Y independently of one another are -O-, -NH-, -NR ¹ - or.-S- are or are absent, Z is H ₉ R ¹ , OR ¹ , -SR ¹ , NH ₂ , NHR ¹ , NR ¹ R ² or a direct bond, the C again linked to R or a CHp bonded to R, W is 0, S, NH or NR ¹ , L is 0 or S or is absent, M is 0 or is absent, 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, aralkyl, aralkenyl or alkaryl with 7 to 12 carbon atoms or aryl with 6 to 2 1 Represents carbon atoms, and R is one of those given for R. Has meanings. 13. Compounds according to claim 1, characterized in that X in formula I is OH or a derivative thereof. 14. Compounds according to claim 1, characterized in that component (b) is a compound of the formula - 48 - 809844 / 108B XCH is or is oligomers thereof, wherein X is for Cl, OH, OR or acyloxy, where R is the claim 12 has given meaning. 15. Hassen according to claim 1, characterized in that component (b) is an oligomer of the general Formula II (A) _a (-CH ₂ -) _b [-CH ₂ (OCH ₂ ) _m OCH ₂ -] _c (-CH ₂ X) _d (H) where A is at least one aromatic hydrocarbon or heterocyclic radical, X has the meaning given in claim 13, a is 2 to 20, but is equal to b + c + 1, b is 0 Ms 19, c is 0 to 19, d stands for 0 to 2a and m, for 0 to 10, where there are at least two (-CH ₂ X) groups per molecule, the group (-CH ₂ OCH ₂ -) counts as (-CH ₂ X) and the groups (-CH ₂ -), [-CH ₂ (OCH ₂ ) _m OCH ₂ -] and (-CH ₂ X) are all only bonded to radicals A. 16. Compounds according to claim 15, characterized in that m is zero. 17. Masses according to claim 15, characterized in that that A is a benzene, naphthalene, furan, anthracene, biphenyl or diphenyl ether residue. - 49 - 8098U / 108B . j 18. Hassen according to claim 15, characterized in that A optionally by one or two of the substituents halogen, Alkyl groups with 1 to 4 carbon atoms, haloalkyl groups with 2 to 4 carbon atoms or OR groups, where R is hydrogen or alkyl or acyl having 1 to 4 carbon atoms, is substituted. 19. Compounds according to claim 15, characterized in that over 50 Hol- # of the radicals A are derived from naphthalene. 20. Hassen according to claim 15, characterized in that more than 75 mol% of the radicals A are derived from naphthalene. 21. Hassen according to claim 15, characterized in that the oligomer has a number average molecular weight of 300 to 3,500 owns. 22. Hassen according to claim 21, characterized in that the oligomer has a number average molecular weight of 350 to 1,500. 23 * Hassen according to claim 22, characterized in that the oligomer has a number average molecular weight of 400 to 1,000. 24. Hassen according to claim 15, characterized in that A is derived from naphthalene and the radicals by (-CH ₂ OCH ₂ -) - groups in 1,4-, 1,5-, 1,6-, 1,7-, 2,5-, 2,6- or 2,7-position on the naphthalene radical are linked. 25. Hassen according to claim 24, characterized in that the bridges are bonded to the naphthalene radical in the 1,4- or 1,5-position are. 26. Hassen according to claim 1, characterized in that - 50 - 809844/1088 they also thermal SfcfrPi saftoren, light stabilizers, UV absorbers, Antioxidants, fillers, pigments, lubricants, blowing agents, fungicides, mold release agents, optical Contains brighteners, other flame-retardant additives or other processing aids. 27. Compounds according to claim 1, characterized in that 0.1 to 150 parts of component (a) are present per 100 parts of polymer. 28. Compounds according to claim 27, characterized in that for 100 parts of polymer 2 to 100 parts of component (a) are present. 29. Compounds according to claim 28, characterized in that for 100 parts of polymer 5 to 80 parts of component (a) "are available. 30. Compounds according to claim 1, characterized in that there are 1 to 50 parts of compound (b) per 100 parts of polymer. 31. Compositions according to claim 30, characterized in that there are 2 to 25 parts of compound (b) per 100 parts of polymer. 32. Compounds according to claim 31, characterized in that there are 2 to 15 parts of compound (b) per 100 parts of polymer. 33. Compounds according to claim 1, characterized in that the weight ratio of compound (a) to compound (b) 20: 1 to 0.1: 1 is. 34. Compounds according to claim 33, characterized in that the ratio is 10: 1 to 0.5: 1 . 35 · masses according to claim 34, characterized in that the ratio is 5: 1 to 1: 1. - 51 - 809844/1086