AU626532B2 - Tetrahalophthalate esters as flame retardants for certain resins - Google Patents

Description

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:I

626532 $A 9 OPI DATE 23/05/89 AOJP DATE 29/06/89 APPLN. ID 27854 89

PCT

PCT NUMBER PCT/US88/03839 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 89/ 03854 CO8K 5/12 Al (43) International Publication Date: 5 May 1989 (05.05.89) (21) International Application Number: PCT/US88/03839 (71) Applicant (for all designated States except US): RPENNWALT C-ORP&R--AfT-N [US/US]; Pennwalt Building, Three Park- (22) International Filing Date: 28 October 1988 (28.10.88) way, Philadelphia, PA 19102 (US).

(31) Priority Application Numbers: 115,688 (72) Inventors; and 115,211 (75) Inventors/Applicants (for US only) BOHEN, Joseph, Michael 173,344 [US/US]; 540 Norwyck Drive, King of Prussia, PA 19406 173,343 LOVENGUTH, Ronald, Francis [US/US]: 854 Spring 173,691 Valley Road, Doylestown, PA 18901 (US).

(32) Priority Dates: 30 October 1987 (30.10.87) (74) Agent: GREENFIELD, Mark, Pennwalt Corporation, October 1987 (30.10.87) Pennwalt Building, Three Parkway, Philadelphia, PA 19102 March 1988 (25.03.88) (US).

March 1988 (25,03.88) March 1988 (25,03.88) (81) Designated States: AT (European patent), AU, BB, BE (European patent), BG, BJ (OAPI patent), BR. CF (OAPI patent), (33) Priority Country: US CG (OAPI patent), CH (European patent). CM (OAPI patent), DE (European patent), DK, Fl. FR (European pa- Parent Applications or Grants tent), GA (OAPI patent), GB (European patent), HU, IT (63) Related by Continuation (European patent), JP, KP, KR, LK, LU (European patent), US 115,688 (CIP) MC, MG, ML (OAPI patent), MR (OAPI patent), MW, NL Filed on 30 October 1987 (30,10.87) (European patent), NO, RO, SD, SE (European patent), SN US 115,211 (CIP) (OAPI patent), SL, TD (OAPI patent), TG OOAPl patent), Filed on 30 October 1987 (30.10.87) US.

US 173,344 (CIP) Filed on 25 March 1988 (25,03.88) Published US 173,343 (CIP) With international search report.

Filed on 25 March 1988 (25.03.88) US 173,691 (CIP) Filed on 25 March 1988 (25.03.88) (54) Title: TETRAHALOPHTHALATE ESTERS AS FLAME RETARDANTS FOR CERTAIN RESINS (57) Abstract Flame retardant plastic resin compositions with improved flow characteristics containing a tetrahalophthalate ester; the use of the tetrahalophthalate ester as a flame retardant processing aid in a resin; a method for impart',g flame retardant and improved flow characteristics to a resin; and a method for manufacturing a flame retardant resin with improved flow characteristics; wherein the resin is selected from among Acrylonitrile.Butadiene-Styrene, Polystyrene, (C) Polycarbonate, Polybutylene Terephthalate, and Styrene-Maleic Anhydride Copolymer, and Polyolefin or Substituted Polyolefin.

it

I

IC WO89/03854 PCT/US88/03839 1 TETRAHALOPHTHALATE ESTERS AS FLAME RETARDANTS FOR CERTAIN RESINS Background of the Invention Field of the Invention--- This invention relates to flame retardant compositions containing at least one tetrahalophthalate ester and a certain resin, which is selected from: Acrylonitrile-Butadiene-Styrene (ABS) Terpolymer Resins; Polystyrene Resins; Polycarbonate Resins; PCT/US88/03839 WO 89/03854 PCT/US88/383 2 Polybutylene Terephthalate Resins; Styrene-Maleic Anhydride Copolymer Resins; and Polyolefin and Substituted Polyolefin Resins.

Additionally, the inventive composition may contain one or more brominated and/or chlorinated compounds present in an amount effective to provide additional flame retardancy to the resin.

Statement of Related Art--- ABS resins are known in the art as a class of thermoplastics which are characterized by excellent properties j such as chemical resistance, abuse resistance, stain resistance, etc. A discussion of typical properties of ABS resins are described on pages 1-64, 1-66, and 1-68 of Charles A. Harper's "Handbook of Plastics and Elastomers" which is published by McGraw-Hill Book Company in 1975.

i These pages are hereby incorporated by reference. ABS resins are terpolymers which are, in general, derived i from acrylonitrile, styrene, and butadiene. Most are true graft polymers in which acrylonitrile and styrene are grafted onto a polybu'tadiene or rubber phase which may further be dispersed in a rigid styrene-acrylonitrile (SAN) matrix. Other ABS resins are mechanical polyblends of elastomeric and rigid copolymer, e.g. butadiene-acrylo- 'A WO 89/03854 PCT/US88/03839 4 3 nitrile rubber and SAN. (See G.C. Hawkins, "Condensed Chemical Dictionary", 10th Edition, p. 3, 1981 as well as U.S. Patent Nos. 4,107,232; 4,206,290; 4,487,886; 4,567,218; and 4,579,906 all of which are incorporated herein by reference. Hawkins, supra, defines ABS resin as: "Any group of tough, rigid thermoplastics deriving their name from the three letters of the monomers which produce them; Acrylonitrile-Butadiene-Styrene. Most contemporary ABS resins are true graft polymers consisting of an elastomeric polybutadiene or rubber phase, grafted with styrene and acrylonitrile monomers for compatibility, dispersed in a rigid styrene-acrylonitrile (SAN) matrix.

Mechanical polyblends of elastomeric and rigid copolymers, butadiene-acrylonitrile rubber and SAN, historically the first ABS resins, are also marketed.

Varying the composition of the polymer by changing the ratios of the three monomers and use of other comonomers and additives results in ABS resins with a wide range of properties." The general chemical structure of ABS is

C

CN R wherein x, y, and z may independently vary from about

PCT/U

WO 89/03854 4 to about 1,500. (See U.S. Patent 4,567,218, the which are incorporated herein by reference.) It understood that analogs of each of the monomeric above may.be substituted in whole or in part, and the definition of ABS resin. For example, u-meth may be substituted for styrene and methacrylonitr acrylonitrile. Descriptions of the compositions ABS resins and how they are prepared may be found Patent Nos. 2,505,349; 2,550,139; 2,698,313; 2,71 2,820,773; 2,908,661; 4,107,232; 4,173,561; 4,20C 4,206,290; 4,289,687; 4,355,126; 4,379,440; 4,45E 4,487,886; and 4,581,403, the teachings of which incorporated herein by reference.

The ABS resins are useful in many commercial cations such as automotive, business machines, te etc., where high impa4ct strength is required as a S88/03839 i te.;chings of should be components is within ylstyrene :ile for of various in U.S.

L3,566; ',702; 1,721; are applilephone, e e1 as manufacin the production of molded articles.

Polystyrene resins find extensive use in thE ture of packaging material, refrigerator doors, air conditioner cases; machine housings, electrical equipment, toys, clock, TV, and radio cabinets, thermal insulation, ice buckets, containers, furniture construction, appliances, dinnerware, etc. The preparation and description of polystyrene and expandable polystyrene are well known in the art. They are discussed in G. Hawley, "Condensed Chemical Encyclopedia", 10th Edition, pp 838 and 976 -i WO 89/03854 PCT/US88/03839 I (1981); Kirk-Othmer "Encyclopedia of Chemical Technology", 2nd Edition, Vol. 9, pp 847-884 (1966) and Vol. 19, pp 85-134 (1969); A.E. Platt in "Encyclopedia of Polymer Science and Technology", Vol. 13, pp 156-189 (1970); and U.S. Patent Nos. 4,281,067; 4,298,702; 4,419,458; 4,497,911; 4,548,956; 4,596,682; and 4,618,468, the i teachings of which are incorporated herein by refaLence.

i For many applications where styrenic polymers are used, there is a need to add flame retardants since these i 10 materials are flammable. Some of the applications which require flame retarded styrenics are radio and TV cabinets, toys, electrical equipment, furniture construction, etc.

(See, for example, U.S. Patent Nos. 4,341,890 and 4,548,956, the teachings of which are incorporated herein by reference.) Polycarbonate resins are known in the art as a class of thermoplastics that are characterized by excellent properties such as electrical, dimensional stability, high impact strength, toughness, and flexibility. In general, they are prepared by the reaction of a dihydric phenol with a carbonate ester, phosgene, or a bis chloroformate ester. U.S. Patent Nos. 2,999,835; 3,169,121; 3,879,348; 4,477,632; 4,477,637; 4,481,338; 4,490,504; 4,532,282; 4,501,875; 4,594,375; and 4,615,832 describe in detail the preparation of various classes of polycarbonate resins, the teachings of which are incorporated 1 I a w- iii- WO 89/03854 PCT/US88/03839 6 herein by reference.

Because of their many excellent properties, polycarbonate resins are useful in many commercial applications as engineering thermoplastics and in the manufacture of molded articles.

Polybutylene terephthalate (PBT) resins are known in the art as a class of thermoplastics that are characterized by excellent properties such as thermal stability, good resistance to brittleness, low friction and wear, chemical resistance, etc. In general, they are prepared by the polycondensation of terephthalic acid or a diester of terephthalic acid, such as dimethyl terephthalate (DMT), with 1,4 butanediol. U.S. patents 2,645,319; 3,047,539; 3,953,394; and 4,024,102 describe in detail the preparation of PBT, the teachings of which are incorporated herein by reference.

Styrene-Maleic Anhydride (SMA) copolymer resins find extensive use in the manufacture of molded articles and foamed products. In general, they are prepared by copolymerizing styrene and maleic anhydride in the proper ratio r' and under the appropriate conditions. The preparation and description of SMA copolymers are described in U.S. Patent Nos. 2,769,804; 2,971,939; 3,336,267; and 3,966,843, the teachings of which are incorporated herein by reference.

SMA polymers burn rapidly and are generally not used in applications which require fire retardant polymers such Q 89/03854PCT/U S88/ 03839 7 as radio and television cabinets, tables, chairs, appliance housings and the like. (See U.S. Patent 4,151,218 which is incorporated by reference).

The use of brominated and/or chlorinated compounds V 5 by themselves or in combination with other materials such as organic phosphates, boron compounds, etc. as flame retardants for AB resin compositions are well known in the art and are exemplified by U.S. Patent Nos, 4,051,101; 4,051,105; 4,096,206; 4,107,12,2; 4,107,232; 4,173,561; 4,200,702; 4,289,687; 4,579,906; 4,355,126; 4,378,440; 4,567,218; 4,581,403; 4,581,409; a.nd 4,600,74?. The aforesaid patents are incorporated herein by reference.

Tetrahalophthalate esters have been used as flameproofing materials. For example, U.S. Patent No. 4,098,704 describes the use of these materials as textile finishing agents. U.S. Patent Nos. 4,298,517 and 4,397,977 disclose these c-impounds as flame retardants for halogenated resins, compounds as flame retardants or processing aids Lor resins.

Summary of the Inventioz This invention encompasses flame rctardant plastic compositin which comprise the following ingredients in mixture.

WO 89/03854 PCT/US88/03839 8 a resin which is selected from among: Acrylonitrile-Butadiene-Styrene (ABS) Terpolymer Resins; Polystyrene Resins; Polycarbonate Resins; Polybutylene Terephthalate Resins; Styrene-Maleic Anhydride (SMA) Copolymer Resins; and Polyolefin and Substituted Polyolefin Resins.

(II) a flame retarding effective amount incorporatea in the resin of of a tetrahalophthalate ester flame retardant processing aid of the formula: wherein: the ring can have all possible isomeric arrangements; R is selected from the group consisting of hydrogen, an alkyl or substituted alkyl of 1 to 30 carbons, hydroxyalkyl of 2 to carbons, polyhydroxyalkyl of 3 to 10 carbons, and 4, liT. a, -a WOI 89/03854 PCT/US88/03839 9 R2 tCHCH 2 0o.+R 8 where R 8 is an alkyl or substituted alkyl of 1 to 18 carbons, and b is 1 to RI is selected from the group consisting of hydrogen, an alkyl or substituted alkyl of 1 to 30 carbons, aikenyl or substituted alkenyl of 2 to 22 carbons, 0

-C-R

where R 7 is an alkyl of 1 to 18 carbons; a polyhydroxyalkyl of 3 to 12 carbons; S(COOH) 1. 3 0 C N oeCOsH*-CH-CH 1 0 A A ROOC OOC 0

CH

3 (AM -C orl aoe) (rla irommg (l-CHl-CH NH-C(sors) R(All iSO Me 0 R3R4 R3 RI R3R4 (1 II( II -CHCNRSR' -(CHCH) 2

NR

5 and -(CHCH)3N with the proviso that the valence of RI is equal to q;

R

2 is independently selected from the class consisting of H and CH 3 1].

'V

*1 .~1

I

Ii I1 11 Ii WO 89/03854 PCT/US88/0383,9

R

3

R

4

R

5 and R 6 are independently selected from the class consisting of H and an alkyl of 1 to 18 carbons; p is an integer of 0 to q is an integer of 1 to 6; X is selected from 0 to NH; and A is selected from Cl or Br.

Preferably, the .,.ight ratio of to (II) is within the range of about 100:1 to about 2:1.

(III) Brominated and/or chlorinated flame retardants other than which optionally may be present.

Detailed Description of the Invention The above composition can also contain other brominated and/or chlorinated flame retardants. Preferred other brominated flame retardants are selected from the group consisting of Preferred Resins In the above ABS resin, a portion or all of acrylic and styrenic monomers comprising the resin include methacrylonitrile or a-methylstyrene, or methacrylonitrile and a-methylstyrene. The preferred ABS resin is comprised of monomeric units of a vinyl aromatic monomer, a vinyl nitrile monomer, and a butadiene monomer and the number of units of each monomer is independently within the range WO 89/03354 PCT/US88/03839

I

of from about 10 to about 1500.

The polystyrene resin is selected from one of the following: a homopolymer of styrene having the following K, 5 repeatable unit i- H H

H

,I wherein n is within the range of greater than 1 to about 3,000; S(b) a homopolymer of styrene as in mod.fied with rubber in which the rubber is dispersed as discrete particles into a matrix of said homopolymer and the weight ratio of rubber to h:omopolymer is within the range of from about 2:98 to about 25:75; or a copolymer of butadiene and styrene in which the weight ratio of butadiene to styrene is within the range 4 20 of about 2:98 to about 25:75; or 4 blends of and polybutadiene and/or a styrene- J butadiene copolymer being preferred.

i In a preferred e'iDoliment of the invention, the homo- Spolymer of above is in the form of a polystyrene foam. The foam is preferably prepared by polymerizing the repeatable homopolymer unit. in th'e presence of a liquid or gaseous blowing agent and said agent has a boiling point th I is below the softening point of the

I

WO 89/03854 PCT/US88/03839 12 polystyrene and does not dissolve said polystyrene.

The preferred blowing agents are selected from the group consisting of one or more of propane, butane, pentane, hexane, heptane, cyclohexane, methyl chloride, dichlorodifluoroethane, 1,1,2 trifluoroethane, and 1,1,2 trichloroethane.

The polycarbonate resin has repeated structural units of the formula: 0 a wherein a is greater than 1 and z is a divalent aromatic radical of a dihydric phenol; The polybutylene terephthalate resins that may be used in the present invention have the following re- Speated structural units of the formula: 0 0 OCH2CH2CH20C- wherein a 1.

The SMA resins that may be used in the present invention usually have the following general structural formula: 1 F HH H H H C-C- C-C C- O=C C=0 H H L v 1 WO89/03854 PCT/US88/03839 i 13 j wherein m is 1 to 100 and n is 0 to 100. The weight ratio of (styrene):(maleic anhydride) may be 1-19:1.

i Polyolefins and substituted polyolefin resins tnat are useful include: polyethylene (low density, linear low density, and high density); polypropylene; ethylenepropylene copolymers; ethylenevinylacetate copolymers; i polyvinylacetate; polyvinyl alcohol derived from polyi vinylacetate; poly-4-methyl pentene-1; polyisobutylene; i polyacrylace esters; and polymethacrylate esters. Also useful are physical blends of any of the above with: Spolystyrene; styrene-butadiene copolymers; chlorinated polyethylene; chlorinated polypropylene; polyvinylchloride; acrylonitrile-butadiene-styrene; polyethyleneterephthalate; polybutyleneterephthalate; polyphenyl oxide; and/or polyphenylene oxide/high impact polysty rene blends. Of particular use are: polyethylene; po propylene; polyacrylate; and polymethacrylate; either alone or in the foregoing physical blends.

It is preferred that in the above tetrahalophthalate ester R is an alkyl or substituted alkyl of 1 to J carbons, A is Br, X is oxygen, p is 0 to 20 (most preferably and q is 1 to 6 (most preferably More preferably R is SUBS1'TUTE SHEET WO 89/03854 WO 8903854PCT/US88/03839 -13 a-

OH

3 -Ch 2 CH-OH, -CH 3 -CH6H, 3

-C

8

H

17

-CH

2

C

-C37,-C 6

H

1 3

-C

8

H

17

-C

2

-CH

HC

4

H

9

,-C

1 0

H

2 1 2

H

5 Rl is CH 3

-C

4

H

9

-C

6

H

1 3 C 4

H

9

C

2 Hs C 4

H

9

H,

-CH

2

-CHC

4

H

9

-C

1 0

H

2 1

U

2 11 5 or SUBSTITUTE

SIHEET

4 PCT/US88/038 3 9 WO 89/03854 t 14 o 0 -C Br CHa 0 SHCH Br and q i.

HO- CCH 2 0C OC Br Br The invention also comprehends a method for preparing a flame retardant plastic composition having enhanced processability properties which comprises incorporating a flame retarding effective amount of one or more of the above tetrahalophthalate esters of (II) in one or more of the above resins.

This invention also comprehends the method of improving the flame retardancy, processability, and physical properties such as impact strength of the specified resins by incorporating in the resins the tetrahalophthalate compounds as described above alone or in combination with other bromine and/or chlorinated flame retardants.

The above resins are sold on the basis of their impact properties. Unfortunately, when such materials have to be flame retarded with conventional retardants to meet code requirements, there is a significant loss of impact strength.

B SUBSTITUTE

SHEET

WO 89/03854 PCT/US88/03839 WO 89/03854 PCT/US88/0383,9

I

15 Representative tetrahalophthalate compounds useful in practicing this invention are as follows (where A is Br or Cl)

A

A' COO (CH 2

CH

2 O) 9

H

COOI{

COO(CH

2

CH-

2 0) -CH 3

CH

3 COOCh 2

-CH-OH

COO(CH

2

CH

2 O) 7

CH

3

COOH

C-NI{(CH

2

CH

2 O) 9

H

II 1 A 0 A CH 3

COOCH

2

-CH-OH

COO(CH

2

CH

2

O)

7 a CH 3

A

A0 COOR ROC

COO(CH

2

CH

2 o) 1 4

-C

I I 0

CH

3

COOCH

2

-CH-OH

COO(CH

2

CH

2

O)

2

H

COOCH

2

(CH

2 6

CH

3

COOCH

2

(CH

2 6

CH

3 SUBSTITUTE

SHEET

4 4 WO 89/03854 WO 8903854PCT/US88/03839 15a

COOC

2

H

5

'COO(CH

2

CH

2 O) 7

CH

3

COOH

COO(CH

2

CH

2

O)

7 avCM 3

COO(CH

2

CH

2 0) -CH 3 A A AO A

COOCH

2

CH-OH

"H

3

COOH

AA

AOA

COO(CH

2

CH

2 O) 7

CH

3

COOCH

2

(CH

2 10

CH

3

COO(CH

2

CH

2 O) 7

CH

3

CH

3

COOCH

2

I--O

COO(CH

2

CH

2 O)7-CH 2

CH

3 SUBSTIT'UTE

SIHAEET

WO 8/3516PCT/US88/038?39 89035 16 A CH3 ACOOk7H2CW-OH A COO-k-FirH-OH A OC2NOzH)IC3 A *COO(CH7CH-O)50CH3

AA

A CH3 ACF A %COOCH 2 CrH-QH ACOH 2

-H

o 0 A coCHZCH 2 OM4-C *A A A A CH 3 0 A A COOCH2-CH-OH R-OC A 0 cCH 1 cH 2 5 0 -c*A A A A A A A A COOH AOH A A COOCZHOgH COOC2~OsH A A A A A COO'(HC)H A A0CzHO~

AA

COOCHCNOIH 0C2HOlH A AAA A COON A AH

COOOH

AIAA* COOKC2H2,7 I n2 COOK CH2H20CH3 AOC2-N 2,jCN-

AA

WO 89/03854

'COON

CHI

'COO(CHrCH2O)-C-JZ-%CHN(C3)2 PCT/US88/03839 17

A

A COON A* COCC)h 0oCH 2(CH.IA-CHO A OH 0

N

-C

I

Jz 0

COON

CH3

COO(CHZCH

2 0)gCH 2

CH

2

N(CH

3 )7 A CH 3 CH) 0 A A COOCH-C-OHu HO.cH-CH/cC A A *CCO)CH 2 CH2)-, C' A A 0 A COON A A A A COON AA A* COO(CH 2( Co0(CHCHO)lSH A A A A CON OOC A CH3

H

A*CjN'%H- CHZ)-3CH-CH-NHC A A 0 A F A A COON I A kk C0NN(CH-CNO-j0 -z/ LA0 Nr' zH __ki 7 WO 89/03854 PCT/US88/03839 18 COO (CH 2

CH

2 O) 7

CH

3

A

A CO CCOHC 6 H S A COO(CH 2

CH

2 2

SCH

2

CH

2

N(CH

2 17

CH

3

A

COOC

2

H

COO(CH

2 -C1 2 0) 7

CH

3

A

A COOH A COO(CH 2

CH

2

O)

9

-C-(CH

2 1 6

-CH

3 A 0

A

A COOH Q

OH

A-OO(HC2)- C COOO."H 2

CH-CH

2 A 0 A A ,CON1(CH 2

CH

2 O) 7

CH

3 vvES'-T UT,, c -ET 4

I

PCT/US88/03839

I

rWQ 89/03854 PCT/US88/03839 18a The preferred compounds are: Br CH 3 Br UUUOkH 2 uk-uH Br

COO(CH

2

CH

2

O)

7 a vCH3 Br Br Br

COOC

2

HS

B t COO(CH 2

CH

2

O)

7 a CH 3

CH

3 CO-NH(C112

CH

2 0) 7 a CH 3 )7a CH 3

COOCH

2

CHOH

0 Br RO-C Br 0

II.-

1 4 -cv Br Br Br Br CH 3 0 ~1 11I C(wOCH 2 C-OH

RO-C,

0 COO(CH2

CH

2 0) 1 0

-C

sues. TIT-v.C.11.

WO 8903854PCT/US88/03839 WO 89/03854 18b 0 Br :00C 2

H

0

II

:00o(CH 2

CH

2 o) 14

C

Br C 2 Hs Br C0OCH 2 ChG 4

H

9 Br COOCHZCHC 4

H

9 Br C 2

H

8H117 SUBSTITUTE

SHEET

4 >j1~ W0k89/03854 PCT/US88/03839 -19-

CH

3

GH

3 The R in the above formulas is -CH 2 -CH-OR or -UH-C-H 2

-OH.

The brominated and/or chlorinated compounds that may be used in combination with the tetrahalophthalates are any of those that are well known in the art. Preferred halogcniated flame retardant examples are SajBSTlTUT'raw

[I

WO 89/03854 PTU8/33 PCT/US88/0383,9 Ir X3 a Dr CH HOCH CHO 0 c Dr ar or n B Dr Br ar.<j:..OCH 2

CH

2 0 Q C Br ar Br Br Sr (xu 4 to 6) Er

~H

2 f CH 2 O Q Sr Br Dr Dr CN

CR

2

-CRCR

2 O c

CCN

2 C-CH 2 Sr iOCH c 0 3'.

1 2 CR 2 0CCHOCR 2 or or C 3 or WO %89/03854 WO~89O3854PCT/US88/03839 Or Dr 5 00 Br 47 D2Kr 4 0 y a- D (x y U5-8) 0 11

O

2 CH 2 CE3 2 01 0 on g' or

B

U

Dr Or or 0 9 colof 0 where RO aM Rol ae A1kYIGM* or subtituted alkyle"t Dr 4 WO 89/03854 PCTJUS88/03839 22 Sr CH 3 Dr Hor~/ 13K~0 3r Sr Dlr ar Dr 0. Q- Br n r Br Br Br OCH 2 CH 2 0r Br Br HiOCH,, H 0O c: Br Sr SM r CH 2CHCH2O 0 C OCH 2

CMCH

2 Br B r B.-caa Br C 3

B

OR

t Br Br c.m 2 CHC 2 O 0 Br

H

,CCOCH c,~ Dr

CH

3 C

OCH

2

CM=CM

2 CM 3 CS r Ir Dr~Ir a 5 O F_ r S WOJ89/03854 PCT/US88/03839 23 In practicing this invention, (II) the tetrahalophthalate by itself or additionally with (III) other brominated and/or chlorinated flame retardants is added to the ;resin in any convenient manner, such as blending or extruding in order to get a uniform composition. Flame retardant synergists such as antimony oxide (Sb 2

O

3 may also be added if desired. In addition, other additives such as thermal stabilizers, ultraviolec stabilizers, reinforcing agents, organic polymers, mold release agents, blowing agents, colorants, and the like may also be optionally included. A further advantage of the tetrahalophthalates alone or in combination with other brominated and/or chlorinated compounds as used in this invention is their improved compatibility with the resins.

Detailed Resin Descriptions The ABS resins that may be used in this invention are, in general, derived from acrylonitrile, styrene, and butadiene and have the following general structure: H CNH acrylonitrile butadiene styrene wherein x, y, and z may independently vary from about to about 1,500. It is understood that analogs of each .2 WO 89/03854 PCT/US88/03839 24 of the components above that comprise the ABS resins may be substituted in whole or in part.

The ratio of tetrahalophthalate or a mixture of tetrahalophthalate and one or more brominated and/or chlorinated compounds to ABS resins that will impart flame retardancy to the latter may vary from 1:100 to about 1:2 depending on the application. In addition, the ratio of tetrahalophthalate to other brominated and/or chlorinated compounds may vary from 100:0 to about 1:99.

The styrenic resins that may be used in the present invention are the following: polystyrene homopolymer, both crystalline and non-crystalline forms; expandable polystyrene beads, and rubber-modified polystyrene which include medium impact polystyrene, high impact polystyrene (HIPS), and super high impact polystyrene.

The homopolymers of styrene, both crystalline and t non-crystalline, have the following repeatable unit wherein n is greater than 1 to about 2000-3000. The non-crystalline forms are generally prepared by polymerizing styrene with peroxide catalyst such as those described in U.S. Patent 4,281,067 while the crystalline stereoregular isotactic form uses Ziegler-Natta catalysts [See I. Pasquon in Encyclopedia of Polymer Science and Technology, Vol. 13, pp. 14, 19-20, and 31 (1970)].

PCT/US88/0 3 8 3 9 W0,89/03854 Expandable polystyrene beads are those that are prepared by incorporating a volatile expanding or blowing agent during the polymerization of styrene. The blowing or expanding agents that may be used to cause polystyrene to foam are well known in the art. They may be liquid or gaseous, do not dissolve the styrene polymer, and have boiling points below the softening point of the polymer (See Column 6 in U.S. Patent 4,618,468). Suitable blowing agents are aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclohexane or halogen hydrocarbons such as methyl chloride, dichlorodifluoromethane, 1,1,2 trifluoroethane, 1,1,2 trichloroethane and the like.

Mixtures of the above may also be used. Typically, expanding agents are used in amounts of about 2 to by weight.

Rubber-modified polystyrenes that are suitable include medium, high, and super high impact polystyrenes. In these compositions, the rubber is dispersed in the polystyrene matrix as discrete particles (See U.S. Patent 4,341,890).

Many rubber-modified styrenes are prepared by polymerizing styrene in the presence of a rubber such as polybutadiene or a styrene-butadiene copolymer (SBR). Some grafting of the styrene to the rubber takes place during polymerization.

The weight ratio of the rubber to polystyrene may vary from about 2:98 to about 25:75. In general the moderate impact polystyrene' will contain about, 2 to about 4% rubber, the WO 89/03854 PCT/US88/03839 26 high impact polystyrene greater than about 10% to about [See H. Keskkula in "Encyclopedia of Polymer Science and Technology" Vol. 13, pp. 396 and 400-404 (1970)1.

The polycarbonate resins that may be employed in the present invention use typical dihydric phenols such as are disclosed in U.S. Patent 3,334,154, which is incorporated herein by reference. They are as follows: 2,2 bis-(4-hydroxyphenyl)-propane; hydroquinone; resorcinol; 2,2 bis-(4-hydroxyphenyl)-pentane; 2,4' dihydroxydiphenyl methane; bis-(2-hydroxyphenyl)-methane; bis-(4-hydroxyphenyl)-methane; 1,1 bis(4-hydroxyphenyl)-ethane; 3,3 bis-(4-hydroxyphenyl)-pentane; 2,2' dihydroxydiphenyl sulfone; 4,4' dihydroxydiphenyl ether; and 4,4' dihydroxy-2,5-diethoxydiphenyl ether.

k.

WO,89/03854 I PCT/US88/03839 27 Example 1 To 1,392 9(3.0 moles) of tetrabromophthalic anhydride were added 1,050 g(3.0 moles) of Methoxy Carbowax 350 in the presence of 22.0 g of sodium acetate. The mixture was heated at 900C for 8 hours in a nitrogen atmosphere. The reaction mixture was filtered hot to remove the sodium acetate. The analytical data were consistent with the assigned structure.

Br COO(C 2 2 0) 7 CavC3 Br CoCoH Br Examole 2 To the compound of Example 1 were added 348.0 g (6.0 moles) of propylene oxide and 2.0 liters of toluene. The mixture was heated at 60*-1001C. The solvent and residual propylene oxide were removed to give the product in almost quantitative yield. The analytical data were consistent with the assigned structure: Br CO (C 2CE20) Cz3 Br C13 l

I

It 11 4 '1 Ii Ij

I

PCT/US88/0 38 3 9 WO 89/03854 28 Example 3 To 92.4 g(0.2 mole) of totrabronophthalic anhydride is added all at once 10 9(0.2 mole) of Carbovax 400 and the mixture heated to 120*-130*C for 2.5 hours. The desired product is isolated in essentially quantitative yield as a clear yellow viscous liquid.

Calcd. Mol. Nt., 864; found 865. Calcd. 3r, 37,1; found, 38.5. The analytical data are consistent with the assigned structures Br Br COOH Br C oo(cEaca 2 Ca 2 0) 9 a Br Example 4 To 240 g(0.24 mole) of the compound of Example 3 is added 45.3 g(0.24 mole) of trimellitic anhydride and heated at 155*C under nitrogen for abut 7 hours. The infrared spectrum indicated the completion of the reaction by the substantial disappearance of the anhydride absorption band at 5.65. The product was isolated in essentially quantitative yield. Analy. Calcd.; tBr, 30.3%; Mol. Wt.

1056; neutralization equivalent, 3521 Found tBr, 29.41 Mol. Wt., 1014; neutralization equivalent, 351. The spectral data was consistent with the structure:

(CZ

2

CR

2

CB

2 0) 9- 0

COOI

4 i 1 1111-111-1--1--~woM89/03854 PCT/US88/03839 Example To 15.3 g(O.18 sale) of the compound of Izaaple 3 is added 70.9 q(o.l3 Issle) 2,3-dibrsooprpyl triellitate. The mixture is heated at 1300-1409C for 6 hour with stirring to give the product as a brown opaque oil. Isolation afforded the product in ehsentially quantitative yield and the analysis is consistent with the structure being: Dr Dr COOS Dr 0c (H 2 2 O) 9 C COCCH

C

S-CH

21 1 2 Dr 3r (and isomers) WO 8903854PCT/US88/038 3 9 IZzammleU 6 to 11 The following preparation were carried cut as in Zzaaple 1 using the reactant not forth below.

Tetrabrixophthahic EL4mple No. Anhy,-de Hydroxy Comnpound Product Stricture 6 1.0 mole HOCH 2 zCH-,OCH2CH 2 0H Br oleBr COOH ar CCUD(CH 2

CH

2

O)

2

H

V Br 1 1.0 =1-i HC(CH2C12)4-I Br (C.Arowax 200) OrCOOH Br COO(CH2CH 2 O)4E 4 aV.

Br 11 8 .mole HO(CHZCHZO)ujH Br Bf COOH Dr COO(CH 2

CH

2 0)i 3

H

AV,

Br 9 1.0 MOW FIO(CHZCMz2hH Dr COOH Dr~OOC2(H2CH)3lL aar 9 :WO 89/O38S4 PCT/US88/03839 EXAMPIGS 6 to 11 continued, The following preparation were carried out a~i in Example 1 usinq the reactant set forth ilow.

Tetrabromophthalic Examnple No, Anhydride Hydroxy Compound Product Structure 1.0 mole HO(CH2CH 2 O)45H Br (Polyglycol E-2000) BrCO moleBrCO Br COO(CH 2

CH

2 0) 45

H

Br v mole HO(CH 2

CH

2

O)

9 H Br Br (CArbowax 400)t mol Br COOK HOOC Br Br COO(CHzCH 2 Br 0 I Br 0 Br aV.

Exampyle 12 To 96.4 9(0.2 sale) of tatrabromtterophthalic acid is added all once 160 q(0.2 sale) of Carbowax 400 and 300 q toluene containing; q 1-toluavi, suJlfonic acid. The mixture is heated to retlux untiL 3.6 q(0.2 mle) waer was collected. The toluene is removed under reduced pressure.to give a clear viscous liquid in essentially quantitative yield. co 3: Dr Rr'2 ,RE PT/US88/0383 WO 89/03854 32 Examye 13 To 85.4 g(O.1 Mole) of the compound of zxample 3 is added all at once 21.8 g(0.1 mole) pyromellitic dianhydride andthe mxture heated to 1200-1309C for 2.5 hours to give the desired product. Water, 1.8 g(0.1 mole), is added to open the reaminng anhydride group and tha analytical data are consistent with the assigned structure: Br Br COOH HOOC Br COCHZCHZ2CO Br 0

COOH

Mx=ma1e 14 To 86.4 g(0.1 moole) of the compound of Example 3 in added all a+ once 10.9 q(00. 05 mole) of pyromellitic dianhydrido~ and the mixture i heated to 1200-1300C for 2.5 houzs to give the deuisie product. The analytical data are consistent with the assigned structure: D~r

-C

or CD-CO(CHCHZq

S--C

Examele 1 To 44.4 90O.1 sole) of the compound of Example 3 i added all at once 21.3 q(.l sole) of phthalic anhydride and the mixture heated t 1200-1300C for 2.5 hours to give the desired product. The analytic data are consistent with the assigned structures ar COOK HCH B r C O C H 2 C H 2 0 9 C 0 Dr Dr, O 5 PCT/US88/038 3 9 33 To 139.2 9(0.3 sole) of tetrabromophthalic anhydride in added all at once 122.9 g(.1 mole) polyozyethylated trimethylol propane of molecular weight 1229 and the mixture heated to 120*-130*C for hours to give the desired product. The analytical data are consitent with the assigned structure: Or Br COON -CH2 (1 -CH 2 Br CCO<CH2C2O) CH2 Br Example 17 To 139.2 g(Q.3 mole) of tetrabromophthalic anhydride in added all at once 156.8 q (0.1 mole) polyowypropylated trizethylol propane of molecular weight 1568 and the mixture heated to 1201-1300C for hours to give the desired product. The analytical data are consistent with the assigned structure: Br 0011 -CH2 CHJ -CH Or 00(^CH 2

CH

2 0 CH2 ii Or 11L WO 89/03854 PCT/US88/03839 34 Example 1 To 284.0 9(1.0 mole) of tetrachlorophthalic anhydride is added 350.0 9(1.0 mole) of Methoy Carbazx 350 in presence of 7.0 g of sodium acetate. Tha nistur iz heated at 909C for 8 hours in a nitrogen atmosphero. The reaction mixture is filtered hot to ramove sodium acetate to give the expected product in nearly quantitative yield. The analytical data arQ consistent with the assigned structure: C1 al CCC(CH2'CXizO)m'C~i C1 COOH Example 19 To 634.0 9(1.0 mole) of the composition of Example 18 is added 116.g(2.0 moles) of propylene oxide in 200 ml of toluene. The reaction mixture is heated from 60*-1000C for 3-5 hours, and then concentrated to give the product in nearly quantitative yield. The analytical data are consistent with the assigned structure: a C1 CO(CCHCH)7*,C 1

COOCHCH-OH

0 CH) PCT/IUS8/0383 9 WQ89/03854 Example To 284.0 g9l.0 sole) of ta z:a hlorophthalic anhydride is added 200.0 Q(1.0 mole) of CarboEax 200 .46 the presence of 7.0 g of sodium acetate. Tb mixtx. is heated at. 90C for 8 hours in a nitrogen atmosphere. The reaction mixture in filtered hot to rmove sodiu acetate to generate the expect.! product in nearly quantitative yield The analytical data are consiptent with the aanigid atructure: A C1 C) CooWCH2CH 2 0)44lA C1 COOH Example 21 C To 434.0 g(1.0 mola) of tne product of Zeample 21 in added 116.0 g(2.0 molt) of propylene oxide in 200 ml of toluene. The reaction mixture is warmed at 600-1004C for 3-5 hours And then *:oncentrated to give the product in nearly quantitative yield. The analy$tical data art consistent vitIh the assigned stru.ture: a C1 COOCH-CH-OH rxa-?1e 22 a CHa To 2S4.0 9(1.0 rlel of tetraehlorophthalic anhydride is added ti(1.0 mole) Of Carbowaz 400 in the presence of 7.0 g of sodium acetate. Tu he Stixt is heate4 at 904C for i hours in a nitrogen atmophere. The reaction mixture is filtered hot to remove sodium acetate to generate the expected product in nearly q44titative yiJd T, j analytical data are consistent with the aSgiglied structure: C C 3 COO.N I;iCH z0)% Coo"KH

E,

PCT/US89/03839 WO 89/03854

GG

K ExamBle 23 To 46.4 9(0.1 male) of tetrabromophthalic anhydride is added all at once 44.1 9(0.1 sale) of polyoxyethylated dimethylamine (CH N(CZ C3 0) H1 dissolved in 100 m! of toluene. The mixture was heated at 1000-1100C for 4-5 hours and then concentrated to give the desired product in essentially quantitative yield. The analytical data are consistent vith the assigned structuza: 0 Br HOC rr zCrzO- Example 24 0 Ek To 92.3 9(0.2 mole) of tetrabromophthalic anhydride is added g(0.2 molm) of H CH 2 2-CH 2 oCE 2 2 (J effam ne 0-400) and the mixturs heated to about 1209C. The final product 4,s obtained in almost quatitative yield. The analytical datCare consistent 'ith the ea-aiqu(d structure:

OOH

,1 WO, 89/03854 PCT/US88/03839 37 Laio1e Poly(ethylene glycol 300), 204.5 S (0.67 mole) was refluxed (T 117*C) with 600 ml of toluene for 1.5 hours in order to remove a small amount of water present in the glycol. The mLxture was cooled to about 100 0 C and tetrabromophthalic anhydride, 614.5 S (1.35 molas) and sodiuz acetate, 1.62 3 were addei and the mixture w.as reheated to reflu=x and held for 25 hours. After the mixture was cooled to 50*C, propylene oxide, (156.4 Z, 2.69 mole!, 100' excess) was added and the mixture heated to and held a: 100*C for 2.5 hours. When the solution cooled to about it was filtered through a bed or diatomace-as ear: and decolorizing charcoal. The filtrate was distilled to r!::ve the solvent to give 904.1 S of product as a viscous l.cqua.d.

Calcd. Br, 47.4. Found 3r, 46.3. Analytical data iconistent with the assigned structure.

Br 0 H 0 Br Br COOCH2CCH3 CH3CH 2 COC Br OH OH Br

CC'(CH

2 CH0). C Br Br 0 0 Br Lx amoe q26 This compound was prepared by the proctdgre describei in Example 25 except that ply(ethylent glycol 200) was used Lni place of poly(ethylent 300). Product is viscous liquid.

wO 89/03854 PCT/US88/03839 Calcd. Br, 51.0. Found Br, 49.3. Analytical dac2 .,s consistent with the assigned structure.

Lxamrle 27 This compound wan pr-p~rad by zh2 proczdira descrbed in Lx-xaple 25 except that poly(ethylaze t1ycol 600) was use ii place of poly(ethylene gS1cOl 300). PraCdUc is a v4.!C3L-5 liquid. Calcd. Br, 39.5. Foumd I, Br, 39.3. AnalyticaL data is consistent with th. assigned strc.u.e.

o H I I COCH2CCH3

I

Un ~1 This coupound was prepared by the przcuurt desc:ribed in LvAnpipe 2s zcept that poly(ethylene ;LycaL 4CO) was us* in place of ,Irzfhylone glycol 300). Prmduc: is a viscmS liqut.d. Calcd. Br, 44.2. found Br, 44.0. Azalyzica1 data is consisttc with the assignied str.-cturt.

Br 0 H H 0 o k IOHCH CH3CHCOC

D

C0-(CZ42ICg 2 O -C o It 4S WQ 89/03854 PCT/US88/03839 39' Examole 29' Methanol (54. 1 S, 1.5 mole), tetrabromophthalic anhydride (645.6 S, 1.6 moles), and potassium acetate, 2.73 S were refluxed for 4 hours with 500 ml of toluene.

After cooling th'e reaction mL'xturia to room temperature, propylene oxide (87.12 S, 1.5 moles) were added and the mixture reacted at 80 0 C for 2.5 hours. Product was obtaiaed as a viscous liquid after distilling out the toluene.

Calcd. I Br, 57.7. Found Br, 57.2. Analytical dazz -s consistent with assigCed struccure.

Br 0 Br COCH3 Br COCH 2

CCH

Dr 0 OK EJamolt 3o This compound was prepared by the procedure similar to that described in Liample 29 except that methoxycarbowax 350 was used in place of methanol, and ethylene oxide ii place d~ propylene a.ide. Calcd. Br. 37.8. Found Br, 37.2.

malytical daca is consistent with assigned structure.

of 0 Dr C0tCHCHZOhCH3 Br COCHICH 2

OH

r 0 2I PCT/US88/0: WO 89/03854 Lxamzle 31 This compound was prepared by the procedure in Ex' 29 except that 2-mechoxyehanol is used in place of methanol. Product is viscous liquid. Calcd. Br, 53 Found Br, 52.0. Analytical data is consistent with.

assigned scructure.

Br 0 H Br COCH 2 CCH3 Br COCH 2 CHZOCH3 IOr 0 E.a~moe 32 This compound was prepared by the procedure ou:L: tpLe29 except that methoxycarbtuwr 350 was used i: of methanol and epoxybutane jo placi of propylene cxi Prodjct is viscous l--quid. Calcd. Br, 36.5. Fou.

Br, 37.2. Analytical data is consistent with the ass 0 H Or COCHCC 2

HS

Or Cc(CICHzO)CH) Or 0 3839 ample .6.

the nc: :in L C '0 E£xamole 3-1.

This compound was prepared by the procedure outlined Exampl e fI except that 2-ethylhexanol-I was used in place -fl- WO.89/03854 PCT/US88/03839 41 methanol. Product is A viscous liquid. Calcd. Br, 50.0.

Found 52.7. Analytical data is consistent with the assigned structure.

Bf 0 H r COCHZCCH3 Q OH Dr 0 CH Examiole 34 Th:.s compound was prepared by the procedure described in Lample 29 except zhat stearyl alcohol was used in place of methanol. Product is a viscous liquid. Calcd. 3:, 41.0. Found Br, 43.0. Analytical data is consisen: h the asrigned structure.

o H I& COCHCCH3

OH

*CO(CH2)17CH3I or 0 LO Exaavle This compound was prepared by the procedure described in LExampLe 2 9 except that 2,3-dibromo-propanol-l was used place of methanol. Product is a viscous Liquid. Calcd. 4 WO 89/03854 PCT/US88/03839 Br, 64.8. Found %1 Br, 61.9. Analytical data is consistenc with the assigned structure.

Br 0 H I I Br

COCH

2

CCH

3 0 OH Br COCH2CHCH 2 Br 11 1 Br 0 Dr Lxamole 36 This compound was prepared b:r the procedure outlined in Lxampte 29 except that epichlorohydrin uas used in place of propylene oxide. Calcd. Br, 35.7. Found 7. 35.4.

knaly:ical data is consistent with the assined structure.

Br 0 H N I Dr COCH7CCH 2 C0 o OH Br j(CH-.CHZO)CH3 Br 0 ExamoLe 37 To a solution of methoycarbowax 350 (300.0 S, 0.89 ole) in dry toaene (184 ml) was added sodium mechoxidt (468.0 0.90 zolt) in methanol. The methanol was then distilled off azospherically. Tetrabraeophthalic anhydrie was cre added (442.2 z, 0.89 mole) along with an addjitj:naL =I of toluene. The reaction &initurt was refluxed !or 2 hours and after cooling to room temperature, epichlore.vJcrn (10'6.94 s, 1.16 mots) Was added. The nixture was rluxed 4 f PCT/US88/038 3 9 WO,89/03854 43

K

for 20 hours. After the solvent and excess epichlorohydrin were distilled, a viscous dark product was obtained. Calcd.

7. Br, 37.2. Found Br, 40.4. Analytical data is consistent with assigned structure.

ar 0 Br COCH2CH- CH: or CO(CH 2 CH7')7CH3 D1 D 0 Lcamole Methoycabowax 350 and toluene were refluzed for I hour in order to distill out a oanll amount of water.

Tetrabromaphthalic anhydride (1:1 mole ratio with methoxycarbowa.-. 350) and sodium acetate were added and the 3 mixture refluxed for 17 hours. After cooling to rcom ezperaturt, an exccess of diazomethant (prepared from the decomposition of NI-aethyl-H-uitroso-p-coluene sulfonamrde by sodiua hydroxide) in ethyl ether was added and the mixture allowed to stand overnight. The excess diazometbane was decosposed by adding acetic acid and the solvent removed by distillation. Product is viscous liquid. Calcd. Br, 39.2. Found Br, 37.4. Anlytical data is consistent wL-: the assigned structure.

Dr 0 Dr-r~tCCC~j 1

CQ~

Wr 0-(-CH 2 CHzO),CH3

ID

Dr 0 At WO 89/03854 PTU8/33 PCT/US88/03839 V 44 LN Aa1 e 3 9 Di(2-ethylhexyl) tetrabromophthalate vas prepared by the procedure described by Spatz et. a&I (I EC Product Research and Development, Vol. 8, No. 4. 395 (1969).

Br 0 Br COCH2CHCAHq Br COCH 2 CHCA.H9 Br 0 C 2 F, L'mamIle 4 0 Poly(ethylene Zlycol 600) 835.4 z (1..40 moles) I te crab romophthal ic anhydride, 1298.4 (2.80 moles), Z 5 potassium acetate, 1.35 S, and toluene (1000 Z) were charged into a one-gall.on glass-Lined reactor and heated to 1201C.

Alter 4 hours at this temperature, ethylene oxide, 246,68 U (5.60 moles) was pumped into the reactor in 3/4 hour while H maintainimg the temperaturR at 120*C. Alter one hour lon~tr of heating, the mi.ture was cooled to room temperature, the ebcess ethylene oxide was then vented, and the product collected. After stripping off the toluene, 2250 S of the product was isolated in 99% yield as a viscous liquid.

i i WO,89/03854 PCT/US88/03839 Calcd. Br 39.2. Found Br, 38.8. Analytical data is consiscent with the assigned structure.

o 0 LI II COCH2CH20H HOCH 2 C0(CH2CH20)12-1j

C

II; It o 0 Lxamuoe 41 To the product of LF.izple 3, 453.8 j (0.27 mole), acetic anhydride, 83.4 S (0.82 molt), potassium acetate, S, and toluene, 400 ml, were reflu.xd for 8 hours. After cooling to room temperature, the reaction mixture was transferred to a separato-y funnel and eitracted first wich 100 ml of a 16% potassium bicarbonate solution and then .iz 100 ml of water. Aftr distilling off the solvent, 235.0 z (64*4 yield) of product was obtained as a viscous liuid.

Calcd. Br, 36.8. Found Ir, 32.9. Analytical data is consiistent wih the assigned structure.

0 H 0 OH 0 CoCH 2 COCCH3 C )COCCHZOC I I -f~CH3 ~CO(C~iC2O)i 2..t3 C14--Br I I 0 0 Lx'alet 42 Tatrabrooptlialic anhydride, 231.9 z (0.50 mole) Z-ethylhcxanol, 130.2 g (1.0 sole), aud potassium acetate,

'I;

WO 89/03854 PCT/US88/03839 46 0.24 were heated to and kept at 1206C for 4 hours. The mixture was cooled to 600C and potassium carbonate, 35.9 g (0.26 mole), was added. Reheated mixture to 80*C and kept it at this temperature for 2 hours. Cooled mixture to and added triethylamine, 14.2 S (0.14 mole). Reheated mixture to 70"C and added methyl iodide, 113.6 g (0.8 mole) in 20 minutes. Hanted mni:.ura to 70-75'C ad kept it a; this temperature for 2\ hours. Cooled mixture to room temperature and filtered it in order to remove by-product potassium iodide. The filtrate was distilled to remove toluene and 290 g of crude product was collected as a pale yellow liquid. Eitcracted this product with 3 times 100 ml of a 6.5% potassium carbonate solution followed by 2 :ires 100 ml of water and once with a 30% sodium chloride solution. Dried the organic phase over anhydrous magnesium sul ate overnighc. Filtered off magnesium suiate and after removing the solvent from filtrate by distillation, 204 g of product was obtained in 67% yield as a pale yellow liqud.

Caled. 52.6. Found Br, 52.2. Analytical data is consiceant with the assigned structure.

tOC8 oro 4COC2 C4 9 9 o c 2 as 4 C.s PCT/US88/03 8 3 9 WVO 89/03854 47 ExMale 43 Tetrabromophthalic anhydride, 231.9 S (0.5 mole), 21[2methoxyethox -ethanol, 360.5 Z (3.0 aoles), stannoUs oxalate, 2.32 S, and xylene, 200 al, were refluxed (temp.

1601C) for 18 hours durinZ which tize, theory water was collected. The xylene and excess 2-12-nethoxthxy oxy]-ethanol were dictilid uzdar riduced *?rpaura to -iva 332 j oi crude product as a wet white solid. Redissolved 256 2 of this material in toluene (1000 ml) and tractcd it with 3 timzs 200 al of a 7.57 potassium bicarbonate solution followed by one extraction with 200 ml of water. Dried the oranic phase with anhydrous magnesium sulfata overni~ht. After removing the magnesium sull'ate by filtratin, toluene was removed by distillatiin% to give 45 1 of a yellow liquid product. Overall yield is Calcd. Br, 46.6. Found Br, 45.7. Analytical data is consistent with the assigned structure.

0 cOCHICH 2 OCHCH2OCH3 Br4_C CCH,,,20C,,C,,0CH,

I

PCT/US88/03839 WO 89/03854 48 V LxAM~le .44 This compound was prepared by the procedure outlined in L'cample 43 e.cept s'nje5 2-(Z-athoxyatoxyj-erhanol.

0 C0CH2CH 2 0CH 2 CH2C2Hs Br4 4C C~CCCH 2 CXHC ZGC-2C C2H 0 i 1 c ssotIe 45 i:4 This compound was prepared by the procedure outlined in L'tample I except that docosyl alcohol (behenyl alcozhoL) was used in place of poly(ethylene glycol 600) and propylene oxide in place of ethylene oxide. Product is a viscous liquid. Calcd. Br, 37.7. Found Br, 36.5. mlyticat dAtA is consistent with the assigned szructurt, 0 H iCCOCH2COH I 8rCH3 co(CH 2 2 1 CH3 0 L-tainDI 441 This copound was prepared by the procedure ouclined vn LampLe I .cePt thatr IricnyL alcohol was used in pLact o WO 89/0i385-4 PCT/US88/03839 49 poly(e.thylene jglyc~1. 600) ard4 propyleme oxide in place of ethyltme oxide. Product is a Visctouz liquid.

0OH

COCH'COH

Ecx, Lxammle 47 Thi~i COMPoUnO. 'Wa3 prepared by the proced~ure outlined irm Lcample 4 except that methoxycarbowa.x 550 oias usAd f. place of 2-[2-methoyyetioxyJ-e hanol.

0 CO(CH2CH 2 O)i jCH3 S WO 89/03854 PCT/US88/038 3 9 Examples 48-58 Compositions With ABS Resins I In the followi- r examples, the flame retardancy of the compounds of this invention are demonstrated with Srespect to ABS resins. The compositions were prepared by mixing together the flame retardants, antimony oxide, and ABS on a roller until the compounds were blended thoroughly. The compounds were pelletized at 230-245°C and then injection molded into test specimens at 230 0

C.

The UL-94 vertical burn test was run and compared to a control consisting of ABS itself.

ABS Acrylonitrile-styrene-butadiene terpolymer DTBPE 1,2-bis(2,4,6-tribromophenoxy)-ethane Bromine) DOTBP Dioctyl tetrabromophthalate (45% Bromine) AO Antimony Oxide WQ 89/03854 PCT/US88/03839 :1 Table I (A) Example No 48 (b 4 9 50 521 ABS 100 100 100 100 DTBPE 22 11 DOTBP 17 25.7 AO 44 4 UL-94 0.125" Failed V-0 V-0 V-0 0.062"1 Failed V-1 V-i V-i Cyclolac@ T, a product of Borg-Warner Co., U.S.A.

Ii(b) control (100% ABS) comparison (no tetrahalophthalatp, ester) The above clearly demonstrates the flame retardancy of the ABS compositions of this invention relative to the control. These compositions have at ledst equivalent flame retardancy to the conventional flame retardant used vt in ABS (DTBPE).

-4a WO 89/03854 PCT/US88/03839 Examples 52-55 Impact strength of the various materials were determined according to ASTM D256.

Example No ABS(a)

DTBPE

DOTBP

AO

52 (b) 100 Table II(A) 5 3 54 100 100 22 11 17 4 4 100 25.7 4 NOTCHED IZOD IMPACT (ft-lb/in notch) 3.34 1.26 1.98 1.66 14 fl 3 i L~r

.:I

C

Cycolac@T, a product of Borg-Warner Co., U.S.A.

control (100% ABS) 15 comparison (no tetrahalophthalate ester) As can be seen from the data above, the conventional flame retardant, DTBPE, greatly reduces the impact strength of ABS compared to those examples where a portion of the DTBPE is replaced by the ABS-containing flame retardant compositions of this invention.

,I

:1

I

WO 89/03854 PCT/US88/03839 53 Examples 56-58 Heat Reflection Temperature (HDT) of the various materials were determinea according to ASTM D648.

Table III(A) 56 57 (c) Example No.

ABS(a)

DTBPE

DOTBP

100 100 22 58 100 11 17 4 HEAT DEFLECTION TEMP. (HDT) 264 psi (oF) 182 167 166 Cycolac® T, a product of Borg-Warner Co., U.S.A.

control (100% ABS) comparison (no tetrahalophthalate ester) The data above shows that there is negligible charge in HDT when a portion of the conventional flame retardant, DTBPE, is replaced by the esters disclosed in this invention.

WO 89/03854 PCT/US88/03839 54 Examples 59-64 Compositions With Polystyrene Resins In the following examples, the flame retardancy of the compositions of this invention are demonstrated.

The compositions were prepared by mixing together the flame retardants, antimony oxide, and high impact polystyrene on a roller until the compounds were blended thoroughly. The compounds were pelletized at 200-260°C and then injection molded into test specimens at 230 0

C.

The UL-94 vertical burn test was run and compared to a control consisting of the impact polystyrene itself.

HIPS High Impact Polystyrene DBDPO Decabromodiphenyl Oxide (83% Bromine) DOTBP Dioctyl Tetrabromophthalate (45% Bromine) AO Antimony Oxide V2_hf 1* I~WO 89/03854 PCT/US88/03839 Table I(B) Example No 59 6 0 c 61 62 63 64 Percentage Composition HIPS(a) 100 84 81.5 73.9 83 80.8 DBDPO 12 9 9 DOTBP 5.5 22.1 4.3 16.4 AO 4 4 4 3.7 2.8 UL-94 0.125" Failed V-0 V-0 V-0 V-0 V-0 0.062 Failed V-2 V-0 V-0 V-0 V-2 Polysar@ 525, a product of Polysar, Inc., U.S.A.

control (100% polystyrene) comparison (no tetrahalophthalate ester) The above results clearly demonstrate the superior flame retardancy of the styrene-containing flame retardant composition of this invention over the conventional flame retardant used in polystyrene (DBDPO).

Examples 58 through 64 are all run at equal bromine levels. Partial or total replacement of the conventional flame retardant (DBDPO) with the esters disclosed in this -f-f invention improves the flame retardancy of the polystyrene as can be seen by the UL-94 results for the 0.062" specimens. Examples and clearly demonstrate that the total bromine levels can be reduced when the compositions of this invention are used and still yield comparable or better flame retardancy.

c- 1 W 089/03854 PCT/US8S/03839 56 Examples 65-70 Impact strength of the va ious materials were determined according to ASTM 2463.

Table II(B) Example No 6 5 b 6 6 c 67 68 69 HIPS(a) 100 84 81.5 76.4 73.9 80,8 DBDPO 12 9 3 DOTBP 5.5 16.6 22.1 16.4 AO 4 4 4 4 2.8 Gardner Impact (in-lb/mil) 0.096 0.067 0.070 0.084 0.115 0.095 Polysar® 525 from Polysar, Inc.

control (100% polystyrene) comparison (no tetrahalophthalate ester) As can be seen from the data above, the conventional flame retardant, DBDPO, greatly reduces the impact strength of the polystyrene (see Example 66). The compositions containing the material of the invention clearly improve the impact strength to a point where it is better than the comparison example.

WO 89/03854 PCT/US88/03839 57 Example 71-74 The extrusion rates were measured during pelletization to determine the processing characteristics of the compounds.

Table III(B) Example No 71 c 72 73 74 HIPS(a) 84 81.5 79 76.4 I DBDPO 12 9 6 3 DOTBP 5.5 11 16.6 AO 4 4 4 4 Extruder Flow Rate (Ibs/hr) 3.4 3.7 4.2 7.9 Polysar® 525, a product of Polysar, Inc., U.S.A.

comparison (no tetrahalophthalate ester) The data above clearly demonstrates the improved Sprocessability of the styrene-containing flame retardant i of this invention.

I t WO 89/03854 58 PCT/US88/03839 Examples 75-79---Compositions With Polycarbonate Resins In the following examples, the flame retardancy of the compositions of this invention are demonstrated with respect to polycarbonate resins. The compositions were prepared by mixing togecher the flame retardants, antimony oxide, and polycarbonate resin on a roller until the compounds were blended thoroughly. The compounds were pelletized at 160-305 0 C and then injection molded into test specimens at 271 0 C. The UL-94 vertical burn test was run and compared to a control consisting of the polycarbonate resin itself. The following tests were performed on the various materials according to the appropriate ASTM ,e thod.

i i r i

I,

;i j ii

I

i j 1i j n ~iiL Limited Oxygen Index (LOI) Melt Flow Tensile Strength ASTM D-2863 -STM D-1238 ASTM D-638 PC BPC DOTBP Polycarbonate polymer Brominated Polycarbonate Oligomer (58% Bromine) Dioctyl Tetrabromophthalate (45% Bromine) 'r -7 91WOi 89/03854 Example No PC (a)

BPC

DOTBP

PCT/US88/03839 78 79 TABLE I (C) 75 7 6 (c) 100.0 87.5 12.5 28 39 26.8 19.1 9210 10220 17 9 18. 8 77 86.6 9.4 4.0 84.9 3.1 12.0 84.0 16.0 Melt Fiow muin) 37 37 37.5 >100 >100 10010 10100 10300 17.4 14.3 15.9 Tensile Strength at Yield (PSI)(d) Elongation at Yield "Lexan" 141, a product of General Elecztric, U.S.A.

control (100% polycarbonate) comparison (no tetrahalophthalate ester) PSI= pounds per square inch. 1 PSI .0145 g/CM 2

L

WO 89/03854 PCT/US88/03839 The above clearly demonstrates the significant improvement in flame retardancy of the polycarbonate resin containing compositions of this invention relative to the control. These polycarbonate resin containing compositions have at least comparable flame retardancy to the conventional flame retardant, BPC, used in polycarbonate.

Examples 76-79 are all run at equal bromine levels.

Partial or total replacement of the conventional flame retardant, BPC, with the esters disclosed in this invention results in greatly enhanced flow characteristics as shown by the improved melt flow properties measured according to ASTM D-1238.

The polycarbonate resin containing compositions of this invention show improved tensile properties when compared to the control, and comparable to that of the conventional flame retardant, BPC. Furthermore, the polycarbonate resin containing compositions of this invention maintain percent elongation.

The data above clearly demonstrates the improved processability of the polycarbonate resin containing compositions of this invertion.

I

w, WO 89/03854 PCT/US88/03839 61 Examples 80-86 Compositions With PBT Resins In the following examples, the flame retardancy of the compounds of this invention are demonstrated. The compositions were prepared by mixing together the flame retardants, antimony oxide, and polybutylene terephthalate (PBT) on a roller until the compounds were blended thoroughly. The compounds were pelletized at 150-216 0 C and then injection molded into test specimens at 235 0 C. The UL-94 vertical burn test was run and compared to a control consisting of PBT itself. Melt flow of the various materials were determined according to ASTM D-1238.

PBT Polybutylene Terephthalate BPC Brominated Polycarbonate Oligomer (58% Bromine) DOTBP Dioctyl Tetrabromophthalate (45% Bromine) AO Antimony Oxide WO 9/0854PC T/US88/03839 WO 89/03854 TABLE I (D) Example No 80 81 82 83 PBT 100.0 85.0 82.8 80.7 BPC -15.0 7.5 DOTBP 9.7 19.3 Antimony Oxide -5.0 5.0 UL-94 Rating 0.125" V-2 V-0 V-0 V-0 0.0631" v-2 V-0 V-0 V-0 Melt Flow 27.6 36.2 55.1 72.6 min) "Celanex" 2000, a product of Hoechst-Celanese Corp., U.S .A.

control (100% polybutylene terephthalate) comparison (no tetrahalophthalate ester) WO 89/03854 PCT/US88/03839 63 The above clearly demonstrates the flame retardancy of the compositions of this invention relative to the control. These compositions have at least equivalent flame retardancy to the BPC conventional flame retardant used in PBT (Example 81).

Examples 81-83 are all run at equal bromine levels.

Partial or total replacement of the conventional flame retardant (BPC) with the compositions of this invention results in enhanced flow characteristics as shown by the improved melt flow properties measured according to ASTM D-1238.

Examples 84-86 The following tests were performed on the various materials according to the appropriate ASTM method.

1. Impact Strength ASTM D-256 2. Tensile Strength ASTM D-638 3. Heat Deflection Temperature (HDT) ASTM D-648 4. Melt Flow ASTM D-1238 WO 89/03854 Example No PBT (a)

BPC

DOTBP

Antimony Oxide

LOT

UL-94 Rating 0.125 0.063 PCT/tJS88/03839 64 TABLE II (D) 84 85 86 100 85.0 83.8 15.0 11.3 4.9 -5.0 25 32 32 V-2 V-0 V-0 V-2 V-0 V-0 0.45 0.33 0.60 7320 8040 7750 Notched Izod (lbs/inch) Tensile 5 eng th

(PSI)

Elongation 10.9 10.3 11.8 HDT 0 0

C)

Melt Flow min) 127/53 27 .6 149/65 135/57 36.2 61.9 tiCelanexi 2000, a product of Hoechst-Celanese Corp., U.S .A.

control (100% polybutylene terephthalate) comparison (no tetrahalophthalate ester) PSI =pounds per inch. 1 PSI =.0145 g/CM 2 WWO 89/03854 PCT/US88/03839 As can be seen from the data above, polybutylene terephthalate resin compositions containing the flame retardants of this invention greatly improve the impact strength relative to the control (Example 84) and the BPC conventional flame retardant, (Example 85) used in PBT while maintaining both tensile strength and percent elongation properties.

In addition, the flame retardants of this invention significantly improve the heat distortion temperature (HDT) and flow properties relative to the control.

The data above clearly demonstrates the improved processability of the polybutylene terephthalate containing compositions according to this invention.

Examples 87-91 Compositions With SMA resins In the following examples, the flame retardancy of the compounds of this invention are demonstrated. The compositions were prepared by mixing together the flame retardants, antimony oxide, and SMA on a roller until the compounds were blended thoroughly. The compounds were pelletized at 95-245 0 C and then injection molded into test specimens at 190-204 0 C. The UL-94 vertical burn test was run and compared to a control consisting of SMA itself. Melt flow of the various materials were determined according to ASTM D-1238.

PCT/US88/03839 WO 89/03854 66 SNA =Styrene-Maleic Anhydride Polymer DBDPO Decabromodiphenyl Oxide (83% Bromine) DOTBP Dioctyl Tetrabromophthalate (45% Bromine) AO Antimony Oxide WO 89/03854 PCT/US88/03839 67 TABLE I (E) Example No 87 88 c 89 90 91

SMA

a 100.0 82.7 81.5 80.4 76.8 DBDPO 13.8 12.4 11.0 6.9 DOTBP 2.6 5.1 12.8 Antimony Oxide 3.5 3.5 3.5 UL-94 Rating 0.125" Failed V-0 V-0 V-0 V-0 0.063" Failed V'-0 V-0 V-0 V-0 Melt Flow 1.16 1.84 2.08 3.32 6.76 min) "Dylark" 250, a product of Arco Chemicals, U.S.A.

control (100% styrene-maleic anhydride copolymer) comparison (no tetrahalophthalate ester) The above clearly demonstrates the flame retardancy of the compositions of this invention relative to the control.

These compositions have at least equal flame retardancy to the DBDPO commercial conventional flame retardant used in SMA (Example 87).

Examples 88-91 are all run at equal bromine levels.

Partial replacement of the conventional flame retardant WO 89/03854 PCT/US88/03839 68 (DBDPO) with the compositions of this invention results in enhanced flow characteristics as shown by the improved melt flow properties measured according to ASTM D-1238.

Examples 92-95 The followinig tests were performed on the various materials according to the appropriate ASTM method.

1. Impact Strength ASTM D-256 2. Tensile Strength ASTM D-638 3. Heat Deflection Temperature (HDT) ASTM D-648 4, Melt Flow ASTM D-1238 WO 89/03854 PTU8/33 PCT/US88/03839 Example No SMIA(a)

DBDPO

DOTBP

Antimony Oxide TABLE II (E) 92 93 (c) 100.0 82.7 13.8 3.5 94 81.5 12.4 2.6 3.5 28.6 80.4 11.0 5.1 23 .1 18.7 27. 6 UL-94 Rating 0.01251 0.063"f Failed t'ailed NochdIzod 2.34 (lbs/inch) Tensile Strength (Yield) 3950 (PSI) (d) Elongation 8.7 KOT (OF) 197 V-0 v-0 1 .02 3880 7.4 197 v-0 1.56 3830 7.7 191 V-0 v-0 1.96 3700 3.1 192 Melt Flow 1.16 1.84 2.08 3.32 min) "Dylark" 250, a product of Arco Chemicals, U.S.A.

control (100% styrene-maleic anhydride copolymer) comparison (no tetrahalophthalate ester) PSI =pounds per inch. 1 PSI =.0145g/crn 2 WO 89/03854 PCT/US88/03839' As can be seen from the data above, SMA resin compositions containing the flame retardants of this invention greatly improve the impact strength relative to the control (Example 92) and the DBDPO commercial flame retardant with PBT (Example 93), while maintaining both tensile strength and percent elongation properties.

In addition, the heat distortion temperature (HDT) of the compositions of this invention are comparable to both the control and to DBDPO.

The data above clearly demonstrates the improved processability of the styrene-maleic anhydride copolymer resin containing compositions of this invention.

Claims (10)

1. A flame retardLa.n composition comprising:- a resin which is selected from among:- acrylonitrile-butadiene-styrene resin; polystyrene resiul polycarbonate resin; polybutylene terephthalate resin; and styrene-maleic-anhydride copolymer resin; and (II) a flame retarding effective amount of a tetrahalophthalate ester flame retardant having the formula:- ROOC 2 p S(A) X- 4 q 4* S S..

4. wherein:- (a) R is selected from the group consisting of:- hydrogen; (ii) an alkyl or substituted alkyl of 1 to carbons where the resin is selected from styrene and polybutadiene teephhalate, or of 1 to 9 carbons where tSi resin is selected from polycarbonate, acrylonitrile-butadiene-styrene, and styrene-maleic-anhydride; (iii) hydroxyalkyl of 2 to 20 carbon and polyhydroxyalkyl of 3 to 10 carbons where the resin is selected from styrene, polycarbonate and styrene-maleic-anhydride; (iv) hydroxyalkyl of 2 to 30 carbons and polyhydroxyalkyl of 3 to 10 carbons -72- where the resin is acrylonitrile-butadiene-styrene, and CHCH 2 O 4 b R 8 where R8is an alkyl or substituted alkyl of 1 to 18 carbonsi or of 1 to 8 carbons where the resin is acrylonitrile-butadiene-styrene and b is 1 to R1is selected from the group consisting of:- (i hydrogen where the zesin is selected from styrenL. polycarbonate, acrylonitrile-butadiene-styrene anid styrene-maleic-anhydride; an alkyl or substituted alkyl of 1 to carbons where the resin is selected from styrene and polybutylene tsrephthalate, or of 1 to 9 carbons where the resin is ~.:selected from polycarbonate, ~.acrylonitrile-butadiene-styrene and styrene-maleic-anhydride; and 25 (iii) alkenyl or substituted alkenyl of 2 to 22 carbon~s, *0 where R7is selected from the group consisting of an alkyl of 1 to 18 carbons, and where the resin is selected from polycarbonate, styrene,I acrylonitrile-butadiene-styrene and styrene-maleic-aiihydride resins, a poly'hydroxyalkyi of 3 to 12 carbons; L -73- 4 I J ~COO") to 3 L 0 or2 -C (J COOCH 2 -CH -CH 2 &0 A A C OUH HOOC CH 3 -CH -CHi-NH-_C 0 (all isomers) 0 1 11 -C (A) V 4i (all isomers) R~ -(CHCH) 2 NR and -(CHCH) 3 N; with the proviso that where the resin is selectd f rom 25 polycarbonate and polybutylene terephthalate resins the valence of R 1is equal to q; 2 R is independently selected f rom the class N ~~~consisting of H and CH 3 R r neednl R 3 R 4 R, and R ar nendtl selected from the class consisting of H and an alkyl of 1 to 18 carbons; p is an 1nteger of 0 to q is an integer of 1 to 6; X is selectotA from 0 to NH; A is selected fi,m C1 or Br; provided further that, where the resin is selected from polycarbonate, polybutylene terephthalate and when p is zero and X is oxygen that R and R1 are other than a neopentyl group; and IJL -74 (iii) and where the resin is styrene, a liquid or gaseous blowing agent. 2. A flame retardant composition in accordance with claim 1 wherein the resin is a homopolymer of styrene having the following repeatable unit H H C--C n wherein n is within the range of greater than 1 to about 3,000. S" 3. A composition according to claim 2 wherein the weight ratio of resin to flame retardant is within the range of 100:1 to 2:1. 4. A composition according to any one of claims 1 to 3 20 wherein in said tetrahalophthalate ester of (ii) R is an alkyl or substituted alkyl of 1 to 10 carbons, A is Br, X is oxygen, p is 0 to 20, and q is 1 to 6.

5. A composition according to claim 4 wherein R is CH -CIH 2 CH-OH, -CH3, -C 2 Hs, -C 3 H7 C 4 H 9 -C 6 H13, -C4H9 -CH 6 H 1 3 -C 8 H 1 7 -CH 2 CHC 4 H 9 -C ,oH2 1 C 2 Hs; RI is CH 3 C 2 H 5 C 4 Hg, H, -C 3 H 7 -C 6 H 1 3 -C 8 H 1 7 -CH 2 -CHC 4 H 9 -CIOH2 1 C2Hs, or -C Br CH3 0 and q- 1. St Br c/ i I

6. A composition according to any one of claims 1, 2, 3, 4, or 5 wherein (ii) includes ther brominated or chlorinated flame retardants or mixtures thereof.

7. A composition according to claim 6 wherein said brominated flame ret ardants are selected from the group consisting essentially of so* *n' .4 .L V 4 76 OBr5 r Br y 5-9) 0 0 Br CHIQj Br~ 00 0 0 2I 2 I I I 0 0 C C C. C C C C.. C .C C C C CC C. C. C C C. C C C C C 0 Brcf CC CHCCH,CH.,OH B r Br Br Br 0 I CaR" OH where R" and R'are alkylene or substit.uted alikylene r 2 N Br Brs BrF rB nBB Br C Br Br L B HOCH 2 CH 2 0 Q OC H H Br 2U 2 Br<-OCH CH 0 -Cc\B Br H3 BrBrr Br B Br ,H3 Br CHV 0 KUjcQ OCH 2 CHCH Br O Br Br Q Br Br Q Br~ Br 3 1to 3r B C 3 2zC C 2 l~y C O 2 '-tuCHC 2 Br B3 9 *99 Br O Br -78-

8. A composition according to any one of claims 2 to 7 wherein the homopolymer is prepared by polymerizing the repeatable homopolymer unit in the presence of a liquid or gaseous blowing agent and said agent has a boiling point that is below the softening point of the polystyrene and does not dissolve said polystyrene.

9. A composition according to claim 8 wherein said blowing agent is selected from the group consisting of one or more of propane, butane, pentane, hexane, heptane, cyclohexane, methyl chloride, dichlorodifluorethane, 1,1,2 trifluoroethane, and 1,1,2 trichloroethane. A composition according to any one of claims 2 to 9 wherein the polystyrene is prepared by polymerizing the repeatable homopolymer unit in the presence of a liquid or gaseous blowing agent and said agent has a boiling point that is below the softening point of the polystyrene and .i does not dissolve said polystyrene.

11. A composition according to claim 10 wherein said blowing agent is selected from the group consisting of one S 20 or more of propane, butane, pentane, hexane, heptane, S* cyclohexane, methyl chloride, dichlorodifluoroethane, 1,1,2 trifluoroethane, and 1,1,2 trichloroethane.

12. A composition according to claim 1 substantially as hereinbefore described with reference to any one of the 25 examples. DATED: 14 May, 1992. PHILLIPS ORMONDE FITZPATRICK ATTORNEYS FOR:- ATOCHEM NORTH AMERICA, INC. I/' 8827i pL1,4f i I I: I:I INTERNATIONAL SEARCH REPORT Inotrn~:;on;il Application N2 pcY~r/tT~RR/(flR7 I. CLASSIFICATION OF iUBJECT MATTER (it several classification symbols apply, indicate all) 6 P n: C I.s p io 1 0: t C I anid IP C IPC(4) C08K 5/12 US. CL: 524/288 521/97, 146 II, FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols US 521/97, 146 524/288 Documentation Searched other than Minimum Documentation :o the Extent that such Documents are Included in the Fields Searched I II., DOCUMENTS CONSIDERED TO BE RELEVANT 9 Clteqory Citat,'on of Document, i with indication, where appropriate, of the relevant passages 12 Relevant to Claim No 3 Y US, A, 4,397,977 (SANDLER ET AL) 09 AUGUST 11-23

1983. SEE COL. 1, LINES 19 TO 23 AND COL. LINES 31 TO Y US, A, 4,098,704 (SANDLER ET AL) 04 JULY 1-23 1978. SEE COL. 1, LINE 1 TO COL. 2, LINE 57. Y V.M. BHATNAGER "FIRE RETARDANTS: PROCEED- 1-23 INGS 0V 1974 INTL. SYMPOSIUM ON FLAMMABLITY AND FIRE RETARDANTS" MAY 1-2, 1974 BY 'ECHNOMIC PUB. CO. (WESTPORT, CONNECTICUT) SEE PAGES 170 TO 171, ESPECIALLY FIGURES S AND 6. Y JS, A, 4,032,481 (PILLAR 28 JUNE 1977. SEE 1-18, 21-23 2OL. 1, LINES 54 TO Y JS, A, 3,766,249 (HOWELL ET AL) 16 OCTOBER 1-18, 21-23 L973. SEE COL. 2, LINES 43-56. Y JS, A, 3,966,676 (RICHTER ET AL) 29 JUNE 1-13, 19 1976. SEELCOL. 3, LINE 32 TO COL. 4, LINE AND 23 4. SSpecial categories of cited documents: 10 later document published alter the international filinq att A document dening te general state ot the art vhich is not or priority date and not in conflict with the application ut considered to, b o particular relevance acited to understand the principle or theory underlying Ile cnsdered o e l arcular relevance invention earlier document but published on or alter the international document of particular relevance: the claimed invert n filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance: the claimed invent on citation or other special reason (as specifed) cannot be considered to Involve an inventive step when :-e document referring to an oral disclosure, use, exhibition or document is combined with one or more other such dc:u- other means ments, such combination being obvious to a person s5 id document published prior to the international iling date but in the art, later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Comoletion of the International Search Date of Mailing of this International Search Report 08 DECEMBER 1988 0 2FEB 1989 Intirnatlonal Searching Authority ISA/US Signatut of Authorized Ofcer VERONTCA P. mrwn International Application No. PCT/US88/03839 Ill. DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category Citation of Document, with indication, where appropriate, of the relevant passages Retevant to Claim No JP, A, 53-120755 (SUMITOMO CHEMICAL KK) 21 OCTOBER 1978. SEE ABSTRACT. US, A, 4,024,102 (STACKMAN ET AL) 17 MAY 1977. SEE COL. 3, LINE 49 TO COL. 4, LINE 7. US, A, 4,295,886 (GRESHEM) 20 OCTOBER 1981. US, A, 3,775,165 (YOUNG ET AL) 27 NOVEMBER 1973. US, A, 3,947,421 (SEDYL) 30 MARCH 1976. SEE .CflTh 2, LINES 33 TO 61. 'US, A, 4,107,231 (WURMB ET AL) 15 AUGUST 1978. SEE COL. 1, LINES 1 TO 1-13, 19. 23 1-13, 23 1-1.3, 23 1-13, 23. 1-13, 23 -1,20. Form PCTIISA210 (extra srie) (Rlev. 11.87)