Preparation of Bromine-Containing Polymers Useful as Flame Retardants

Patent metadata

Field	Value
Publication number	US-2017145151-A1
Application number	US-201515323847-A
Country	US
Kind code	A1
Filing date	Jul 7, 2015
Priority date	Jul 8, 2014
Publication date	May 25, 2017
Grant date	—

Abstract

The invention relates to a process for preparing bromine-containing polymer, comprising a Friedel-Crafts alkylation reaction of tetrabromoxylylene dihalide, or tetrabromoxylylene dihalide in combination with pentabromobenzyl halide, with a reactant having one or more six-membered aromatic rings, wherein the reaction takes place in a solvent in the presence of a Friedel-Crafts catalyst, and isolating from the reaction mixture the bromine-containing polymer. The so-formed polymers and their use as flame retardants form additional aspects of the invention.

First claim

1 . A process for preparing bromine-containing polymer, comprising a Friedel-Crafts alkylation reaction of tetrabromoxylylene dihalide, or tetrabromoxylylene dihalide in combination with pentabromobenzyl halide, with a reactant having one or more six-membered aromatic rings, wherein the reaction takes place in a solvent in the presence of a Friedel-Crafts catalyst, and isolating from the reaction mixture the bromine-containing polymer.

2 . A process according to claim 1 , wherein a combination of tetrabromoxylylene dihalide and pentabromobenzyl halide is used.

3 . A process according to claim 1 , wherein the tetrabromoxylylene dihalide is tetrabromo-para-xylylene dibromide and the pentabromobenzyl halide is pentabromobenzyl bromide.

4 . A process according to claim 1 , wherein the reactant having one or more six-membered aromatic rings is a compound of Formula (II):

where R is a linear or branched aliphatic chain; k is an integer from 0 to 3; m is 0 or 1; Z is selected from the group consisting of null, O, S and a linear or branched alkylene, whereby a bromine-containing polymer having a repeat unit of Formula I is obtained:

wherein R, k, m and Z are as defined above; each of al and a2 is independently an integer from 1 to 3; each of b1 and b2 is independently an integer from 1 to 3, such that a 1 +b 1 ≦3 and a 2 +b 2 ≦3.

5 . A process according to claim 4 , wherein the reactant is a compound of Formula II selected from the group consisting of:
toluene, where in Formula II, R═CH 3 , k=1, m=0; xylene, where in Formula II, R═CH 3 , k=2, m=0; ethylbenzene, where in Formula II, R═C 2 H 5 , k=1, m=0; diphenyl ether, where in Formula II, k=0, Z═—O, m=1; diphenylmethane, where in Formula II, k=0, Z′—CH 2 —, m=1; and 1,2-diphenylethane, wherein in Formula II, k=0, Z═—(CH 2 ) 2 —, m=1.

6 . A process according to claim 5 , wherein toluene is reacted with tetrabromo-para-xylylene dibromide and pentabromobenzyl bromide in halogenated aliphatic hydrocarbon solvent to give a bromine-containing polymer comprising chains of Formula III (where n indicates the number of repeat units):

7 . A process according to claim 5 , wherein 1,2-diphenylethane is reacted with tetrabromo-para-xylylene dibromide and pentabromobenzyl bromide in halogenated aliphatic hydrocarbon solvent to give a bromine-containing polymer comprising chains of Formula V (wherein n indicates the number of repeat units):

8 . A polymer having —CH 2 C 6 Br 4 CH 2 — and A units arranged alternately along the polymer backbone chain:
≈≈CH 2 C 6 Br 4 CH 2 -A-CH 2 C 6 Br 4 CH 2 -A-CH 2 C 6 Br 4 CH 2 -A-CH 2 C 6 Br 4 CH 2 -A≈≈

wherein A comprises one or more six-membered aromatic rings.

9 . A polymer according to claim 8 , further comprising —CH 2 C 6 Br 5 side groups attached to at least a portion of the six-membered aromatic rings of the backbone chain, wherein at least one carbon atom of said six membered aromatic ring(s) is bonded to the aliphatic carbon of said —CH 2 C 6 Br 5 group.

10 . A polymer according to claim 9 , composed of chains represented by Formula P:

wherein n is the number of repeat units; Ar indicates a structure comprising one or more six-membered aromatic ring(s), wherein at least one carbon atom of said six membered aromatic ring(s) is bonded to an aliphatic carbon of the —CH 2 C 6 Br 4 CH 2 — group; where x, which indicates the number of —CH 2 C 6 Br 4 CH 2 — moieties in the unit, is equal to or greater than 1; and y, which indicates the number of —CH 2 C 6 Br 5 pendent groups in the repeat unit, is 1, 2, 3, or 4.

11 . A polymer according to claim 8 , having chains with repeat units represented by Formula (I):

wherein R is a linear or branched aliphatic chain; k is an integer from 0 to 3; a 1 and a 2 are independently an integer from 1 to 3; b 1 and b 2 are independently an integer from 1 to 3; m is 0 or 1; a 1 +b 1 ≦3 and a 2 +b 2 ≦3, Z is selected from the group consisting of null, O, S and a linear or branched alkylene.

12 . A polymer according to claim 11 , composed of repeat units of Formula I, where m=0, R is CH 3 and k is 1.

13 . A polymer according to claim 12 , composed of repeat units of Formula I, where a 1 =b 1 =1, said polymer being represented by Formula III:

where n is the number of repeat units.

14 . A polymer according to claim 11 , composed of repeat units of Formula I, where m=1 and k=0.

15 . A polymer according to claim 14 , composed of repeat units of Formula IV:

wherein Z is selected from the group consisting of O, —CH 2 —, and —CH 2 —CH 2 —, with al and a2 being independently either 1, 2 or 3 and with b1 and b2 being independently 0, 1 or 2, having bromine content of not less than 60% by weight.

16 . A polymer according to claim 15 , composed of repeat units of Formula IV, where z is —CH 2 —CH 2 —.

17 . A polymer according to claim 16 , composed of repeat units of Formula IV where b1=b2=2, said polymer being represented by Formula V:

wherein n is the number of repeat units.

18 . A flame-retarded composition, comprising a flammable material and the bromine-containing polymer according to claim 17 .

19 .- 21 . (canceled)

Assignees

• Bromine Compounds Ltd

Inventors

• Gelmont Mark
• Yuzefovich Michael
• Piotrowski Andrew
• Yoffe David
• Frim Ron
• Hirschsohn Yaniv

Classifications

• C08L51/04

  grafted on to rubbers · CPC title

• C08G61/02 Primary

  Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes · CPC title

• C09K21/14

  Macromolecular materials · CPC title

• C08G2261/148

  Side-chains having aromatic units · CPC title

• C08L25/06

  Polystyrene · CPC title