CA1337310C - Tetrahalophthalate esters as flame retardants for certain resins - Google Patents

Abstract

Flame retardant plastic resin compositions with improved flow characteristics containing a tetrahalo-phthalate ester; the use of the tetrahalophthalate ester as a flame retardant processing aid in a resin;
a method for imparting 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 (A) Acrylonitrile-Butadiene-Styrene, (B) Polystyrene, (C) Polycarbonate, (D) Polybutylene Terephthalate, and (E) Styrene-Maleic Anhydride Copolymer.

Description

TETRAHALOPHTHALATE ESTERS AS FLAME RETARDANTS FOR
CERTAIN RESINS

Back~round 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:
(A) Acrylonitrile-Butadiene-Styrene (ABS) Terpolymer Resins;
(B) Polystyrene Resins;
(C) Polycarbonate Resins;

(D) Polybutylene Terephth~l~te Resins; and (E) Styrene-Maleic Arhydride (SMA) Copolymer Resins.
Additionally, the inventive composition may contain one or more bromin~tecl 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 such as chemical resistance, abuse resistance, stain resistance, etc. A discussion of typical ~,opellies 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. ABS resins are terpolymers which are, in general, derived from acrylonitrile, styrene, and butadiene.
Most are true graft polymers in which acrylonitrile and styrene are grafted onto a polybutadiene 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-nitrile rubber and SAN. (See G.C. Hawkins, 3 ~337310 "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. 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 con~i~tin~ 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, e.g., butadiene-acrylonitrile rubber and SAN, historically the first ABS resins, are also marketed.
Varying the composition of the polymer by chs~nging 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 H- H H H H H H H
C--C --C--C=C--C C--C
H CN H H H ~

wherein x, y, and z may independently vary from about 10 to about 1,500. (See U.S. Patent 4,567,218). It should be understood that analogs of each of the monomeric components above may be substituted in whole or in part, and is within the definition of ABS resin. For example, a-methylstyrene may be substituted for styrene and methacrylonitrile for acrylonitrile. Descriptions of the compositions of various ABS resins and how they are prepared may be found in U.S. Patent Nos.
2,505,349; 2,550,139; 2,698,313; 2,713,566; 2,820,773, 2,908,661; 4,107,232;
4,173,561; 4,200,702; 4,206,290; 4,289,687; 4,355,126; 4,379,440; 4,456,721;
4,487,886; and 4,581,403.
The ABS resins are useful in many commercial applications such as automotive, business machines, telephone, etc., where high impact strength is required as well as in the production of molded articles.
Poly~lylt;ne resins find extensive use in the m~nllf~cture of packaging material, refrigerator doors, air conditioner cases, m~t~hine housings, electrical equipment, toys, clock, TV, and radio cabinets, thermal insulation, ice buckets, containers, furniture construction, appliances, dinnerware, etc. The plepaldlion and description of polystyrene and expandable poly~lylelle are well known in the art. They are discussed in G. Hawley, "Condensed Chemical Encyclopedia", 10th Edition, pp 838 and 976 `''~

_ 5 l 3373 1 0 (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.
For many applications where styrenic polymers are used, there is a need to add flame retardants since these 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.
Polycarbonate resins are ~nown 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 chloro-formate 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 polycar-bonate resins.

6 133:731û

Because of their many excellent properties, polycar-bonate 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 re-sistance to brittleness, low friction and wear, chemical resistance, etc. In general, they are prepared by the 10 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.

Styrene-Maleic Anhydride (SMA) copolymer resins find extensive use in the manufacture of molded articles and foamed products. In general, they are prepared by copoly-merizing styrene and maleic anhydride in the proper ratio 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 SMA polymers burn rapidly and are generally not used in applications which require fire retardant polymers such as radio and television cabinets, tables, chairs, appliance housings and the like. (See ~.S. Patent 4,151,218), The use of brominated and/or chlorinated compounds by themselves or in combination with other materials such 5 as organic phosphates, boron compounds, etc. as flame retardants for ABS 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; 4,107,122; 4,107,232; 4,173,561;
4,200,702; 4,289,687; 4,579,906; 4,355,126; 4,378,440;
lO 4,567,218; 4,581,403; 4,581,409; and 4,600,747.
Tetrahalophthalate esters have been used as flame-proofing 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 15 these compounds as flame retardants for halogenated resins.
However, no teachings have been found which show these compounds as flame retardants or processing aids for ABS res ns.

Summary of the Invention This invention encompasses flame retardant plastic compositions which comprise the following ingredients in mixture.

(I) a resin which is selected from among:
(A) Acrylonitrile-Butadiene-Styrene (ABS) Terpolymer Resins;
(B) Polystyrene Resins;
(C) Polycarbonate Resins;
(D) Polybutylene Terephthalate Resins;
and (E) Styrene-Maleic Anhydride (SMA) Copolymer Resins.
10 (II) a flame retarding effective amount incorporated in the resin of (I) of a tetrahalophthalate ester flame retardant processing aid of the formula:

~ C-X-(CHCH2O)p -wherein:
(a) the ring can have all possible isomeric arrangements;
(b) R is selected from the group consisting of hydrogen, an alkyl or substituted alkyl of 1 to 30 carbons, hydroxyalkyl of 2 to 20 carbons, polyhydroxyalkyl of 3 to 10 carbons, and `_ 9 1 3373 1 0 ~CHCHp~RIs where R8 is an alkyl or substituted alkyl of 1 to 18 carbons, and b is 1 to 50;
(c) Rl is selected from the group consisting of hydrogen, an alkyl or substituted alkyl of 1 to 30 carbons, alkenyl or substituted alkenyl of 2 to 22 carbons; O

where R7 is an alkyl of 1 to 18 carbons;
a polyhydroxyalkyl of 3 to 12 carbons;

t ) o 2~(COOH)1 ~O 3 --C~COOCH2--CH--CH2.

ROOC
ROOC

--CH2--CH--NH--C~ (all isomers), o --C (Ah ROC ~ (all isom~rs), IR3 l 4 IR3 l 4 IR3 IR4 --CHCHNR5R6,--(CHCH)2NR5. and--(CHCH)3N;
with the proviso that the valence of R' is equal to q, (d) R2 is independently selected from the class consisting of H and CH3 -;

~J

1 3373 ~ O

(e) R3, R4, R5, and R6 are independently selected from the class consisting of H and an alkyl of 1 to 18 carbons;
(f) p is an integer of O to 50;
S (g) q is an integer of 1 to 6;
(h) X is selected from O to NH; and (i) A is selected from Cl or Br.
Preferably, the weight ratio of (I) to (II) is within the range of about 100:1 to about 2:1.
10 (III) Brominated and/or chlorinated flame retardants other than (I) which optionally may be present.

Detailed Description of the Invention The above composition can also contain other brominated and/or chlorinated flame retardants. Preferred 15 other brominated flame retardants are selected from the group ccnsisting of lOa rS ~ ~ Dr5 Hr~ ~ H2CH2 ~ - Hr~

~0~
Brx Bry O o (x + y , 5-8~ B ~ C ~ Br Br ~ /NCH2CH2N < ~ Br O O O
Br4 ~JcocH2cH2ocH2cx2oE
~ ICIOCH2~CHC~3 -- O OH
J~1}5 Br Br Br5 <~

Br ~ r Br Br ~ COR~OH
Br ' ~
I COR OH
where R~ and R~'are alkylene or substituted alkylene ,Br ~, C,-CEE2Br Br Br . : .

lOb Br CH3 r _ Br_ Br Br n Br Br CH3 Br 8r Br HOCH2CH20 ~ CH ~ H2CH20H Br ~ OCB2CB20 ~ Br 8r Br 8r Br Br CH Br -)' ' 3 ~ ~ OH

8r Br B ~ , ~ 2~CHCH28r ~ Br5 C82'CHCH20 ~ ~ CCH2C8-CI{2 ~ 8rX

~2 ~ ~ C ~ ~2cH20CCH=c~2 ~ ~nd 8r ~ OH
Br - lOC 1337310 Preferred Resins (A) In the above ABS resin, a portion or all of acryl-ic and styrenic monomers comprising the resin include 20 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 of ~rom about 10 to about 1500.
(B) The polystyrene resin is selected from one of the following:
(a) a homopolymer of styrene having the following 5 repea~able unit H H
C C
~ H
wherein n is within the range of greater than 1 to about 3,000i (b) a homopolymer of styrene as in (a) modified with rubber in which the rubber is dispersed as discrete 15 particles into a matrix of said homopolymer and the weight ratio of rubber to homopolymer is within the range of from about 2:98 to about 25:75; or (c) a copolymer of butadiene and styrene in which the weight ratio of butadiene to styrene is within the range 20 of about 2:98 to about 25:75; or (d) blends of (a) and (b); polybutadiene and/or a styrene-butadiene copolymer being preferred.
In a preferred embodiment of the invention, the homo-polymer of (B)(a) above is in the form of a polystyrene 25 foam. The foam is preferably 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 12 l 3373 1 0 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, dichloro-5 difluoroethane, 1,1,2 trifluoroethane, and 1,1,2 tri-chloroethane.
(C) The polycarbonate resin has repeated struc-tural units of the formula:
o ~ Z OC--wherein a is greater than 1 and z is a divalent aromatic radical of a dihydric phenol;
lS (D) The polybutylene terephthalate resins that may be used in the present invention have the following re-peated structural units of the formula:
O O
- OCH2CH2CH2CH2OC ~ C -wherein a > 1.
(E) The SMA resins that may be used in the present invention usually have the following general structural 25 formula: H H H H H H

--C ~ C -C C -C
O=C C=O ¦ H ¦ H
n wherein m is 1 to 100 and n is 0 to 100. The weight ratio of (styrene):(maleic anhydride) may be 1-19:1.

It is preferred that in the above tetrahalophthalate ester (II), R is an alkyl or substituted alkyl of 1 to 10 5 carbons, A is Br, X is oxygen, p is 0 to 20 (most prefer-ably 0), and q is 1 to 6 (most preferably 1). More pre-ferably R is -CH6Hl3 -2C3HOH~-cHHcHc;H2Hs~c;cHH7~ -C~Hg; -C~Hl3, -C~Hg C2Hs; Rl is CH3, C2Hs, C4Hg, H, -C3H~, -C~Hl3, -C8Hl~, -CH~ CHC~Hg, -CloH2l, C2Hs, or -14 l 3373 1 0 ~C Br CH3 1l _~ ~r, and q = 1.

Br Br The invention also comprehends a method for preparing a flame retardant plastic composition having enhanced processability properties which comprises incorporating a flame re~dillg effective amount of one or more of the above tetrahalophth~ te 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 tetrahalophth~l~te 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.

~.
., Representative tetrahalophth~l~te compounds useful in practicing this invention are as follows (where A is Br or Cl):
A A
A~CooH A~COOH

A COO(CH2CHp)9H A~COO(CH2CHp)~CH3 A A

A~COOH A~T~COOCH2--CH--OH

A ~ C--NH(CH2CHp)9H A ~ COO(CH2CHp)7CH3 A O A

A~COOCHI--CH--OH A~COOR A

A COO(CH2CHlha~CH3 A COO(CH2CHp)~ CI A
A O
A fH3 A
A ~ ~ X cOOcH2--CH--OH A ~ COOCH2(CHz)6CH3 A COO(CH2CHp)2H A COOCH2(CH2)6CH3 A A
A Coo~cH2cH2o)~cH3 A~COOC2H5 A~A

A ~COO(CH2CHp)7CH3 A f A
A COOCH2 ~CH--OH

A COOH

A ~ COO(CH2CHpho~cH3 A J ~ A
A Coo(cH2cH2o)7cH3 A ~ ~COOCH2~CH2)10cH3 ~ ~ COOCH2CH--OH

A ~ COO(CH2CHphCH3 A ~ COO(CH2CHp)7CH2CH3 . ~, A

A CHl 16 1 3 3 7 3 1 0 A~COOCH2CH--OH A~coocH2cH--OH

COO(CH2CHp)~C~I) A~CoO(cH2cH~o~5ocH3 A ~ [COOCH2CH--OH ~ ~COOCH2CH--OH

A COO(CH2CHp)4--C A

A CH~ o ~
A~ COOCH2--CH--OH R--OC ~ A

A COO(CH2CHp),~, C f A

A~COO(CHzCHpbH A~coo2cH2cHp)~2H

COOH
COOH

A X ~ COO(CHzCHp~H A ~ COO(CH2CHp)~H

COO(CHzCHphCH~ COO(CH2CHp)~CH3 A~COOH A~A
COOH

A~COOH - --I HH--OH

C80(CH2CHpk~H COO(CH2CHPh--CH

~, COOH --CH2--CH2~
N--~CH2~2 17CH3 A ~ COO(CH2--CH2--0~50 --CH2--CH2~

A ~ CoocH2-cHp~-cH2-cH-N(cHl~ A ~ COO(CH2CHp ~-CH2-lCH~-CHO

A o COOH (CHOH~ ~ COOIH~

A~coo(cH2cHpb --C ~f COO(CH--CHp)3(CH2CHp)l~H
_ 2 COO~CH2CHP)9cH2cH2N~cH)k A~A
COOH
A fH3 CH3 1 ~
A ~ COOCH2-CH-OH HOCH-CHpC ~ A

A ~ COO(CH2CHp)l 1~ C~A

COOH

A~$A A~COO[CH2CH20b--CCH3 COO(CH2CHp)15H

A~NH(cH - cHpb-33cH2 - cH - NHlc~A

COOH --CH2--CH2~
~ ~ N(cH2h-l7cH3 A ~f Ct~O(CH2--CHpb 50 --CH2--CH2 _ 2 COOH ~ ~ COOH

,~ CONH(CH2--CHPb ~o --CH2 COO(CH2CHP)~--CH2--CH2N~CH3)2 Coo(cH2cHpj7cH~ A

A~-4~ A~COO~CH2CH20)o 25CHzCH2N(CH2)l7CH3 A ~ Co~CH ~ HphCH3 A ~ COOCH~CH~Ob-lCI-~CHz)l~~CH~

A ~ CH3 A~COOH COOH ~COOCH2--CH--OH

COO~CH2CH20)9--~C~COOCH2~H--CIH2 ~CONH(CH2CH20)7CHl 9r ~ COOCH~CH-OH 9r ~ COOCH~CH-OH

C ~ CH2CHp~7~CH3 B~CO-NH(CH2CH20)7~H~

8r C~O(CH2CHp)7,"CH3 CH~CH20~7~CH3 ~ Br Br ~ C ~ CH~CH--OH O~C ~ Br Br ~ COOCH~H-OH ~O~C ~ ~r 8r Co~ cH20)l~--C 11~ llr COO(CH2CHp), C Br F3r O ~r ~ ~ OOOC~H~ C~H~C ~ ~

llr COO(CH~CH20h~ C 11-e L~

~ ;s , ~

The R in the above formula is --CH2--CH--OH or--CH--CH2--OH

The brominated and/or chlorinated compounds that may be used in combination with the tetrahalophth~l~tes are any of those that are well known in the art. Preferred halogenated flame retardant examples are 8r Br Br Br Br HO~C~OH Br~O~O~Br Br Br Br Br " Br HOCH CHzO~ C~ OCH~CH~OH br~ OCH~CHzO~ br Br Br ~C~ Br ~}Br5 BrBr Br CH2=CHCHp~CH~OCH2CH=CH2 ~Br~

(~ = 4~o6) Br Br Br CHl=CcOcH2cH20~cH~ocH2cHtoccH=cH2 Br~OH

Br Br Br O O
Il 11 Brs~ _~ Br~,~X NCH2CH2N ~ Br~
Il 11 O O
O O
Il 11 ~0~ ~ NCH2CH2N

Br,~ Br~, O O
(~ + y = 5-8) Bt4 ~ COCH2CHCH3 Br5 Br Br 1~')~Br''~COR"OH ~Ç~ CH2Br Br~BrICoOR'''OH Br where R" nd R"' ~re rlkyl~n~ or ~ Ikyl~

In practicing this invention, (II) the tetrahalophth~l~te by itself or additionally with (III) other bromin~ted and/or chlorinated flame retardants is added to (I) 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 (Sb203) may also be added if desired. In addition, other additives such as thermal stabiliærs, ultraviolet stabilizers, reinforcing agents, organic polymers, mold release agents, blowing agents, colorants, and the like may also be optionally included. A further advantage of the tetrahalophth~lates 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 (A) 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 H ~ H H
_f_f _C-C=C-f c f c~y'~ butadienc styrenc wherein x, y and z may independently vary from about 10 to about 1,~00. It is understood that analogs of each . ~

1''`'''``~' 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 5 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 10 about 1:99.
(B) 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 15 include medium impact polystyrene, high impact polysty-rene (HIPS), and super high impact polystyrene.
The homopolymers of styrene, both crystalline and non-crystalline, have the following repeatable unit wherein n is greater than 1 to about 2000-3000. The 20 non-crystalline forms are generally prepared by poly-merizing styrene with peroxide catalyst such as those described in U.S. Patent 4,281,067 while the crystal-line stereoregular isotactic form uses Ziegler-Natta catalysts [See I. Pasquon in Encyclopedia of Polymer 25 Science and Technology, Vol. 13, pp. 14, 19-20, and 31 (1970)].

l 3373 1 0 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 5 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, 10 pentane, hexane, heptane, cyclohexane or halogen hydro-carbons 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 20%
15 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).
20 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 25 about 2:98 to about 25:75. In general the moderate impact polystyrene will contain about 2 to about 4% rubber, the ""- 1 3373 1 0 high impact polystyrene greater than about 10% to about 25%. [See H. Keskkula in "Encyclopedia of Polymer Sci-ence and Technolo~y" Vol. 13, pp. 396 and 400-404 (1970)].
(C) The polycarbonate resins that may be employed in the 5 present invention use typical dihydric phenols such as are disclosed in U.S. Patent 3,334,154, which is incor-porated 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;
bis-(4-hydroxy-5-nitrophenyl)-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.

-Example 1 To 1,392 g (3.0 moles) of tetrabromophthalic anhydride were added 1,050 g (3.0 moles) of Methoxy Carbowax 350TM in the presence of 22.0 g of sodium acetate.
The ~ Lule was heated at 90C for 8 hours in a nitrogen atmosphere. The reactioniX~UlC was filtered hot to remove the sodium acetate. The analytical data were consistent with the assigned structure.

Elr~COO(CHzCHzO)7a~CH3 Example 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 llli~ule was heated at 60-100C. 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~COO(CHzCH20)7~,~CH3 ~r f COO--CHz--fH--OH
~r CH3 28 l 3373 1 0 Example 3 To 92.8 g (0.2 moles) of tetrabromophthalic anhydride is added all at once 80 g (0.2 mole) of Carbowax 400TM and the mixture heated to 120 - 130C for 2.5 hours.
The desired product is isolated in essentially ~lualllilaLive yield as a clear yellow viscous liquid. Calcd. Mol. Wt., 864; found 865. Calcd. % Br, 37.1; found, 38.5. The analytical data are consistent with the assigned structure.

Br~COOH

Br l~r COO(CH2CH2CH20)gH.

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 155C under nitrogen for about 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.; % Br, 30.3%; Mol. Wt. 1056;
neutralization equivalent, 352; Found: % Br, 29.4; Mol. Wt., 1014; neutralization equivalent, 351. The spectral data was consistent with the structure:

Br~COOH COOH

8rJ~ COO~CH2CH2CH20 )~ COOH
Br O

Example 5 To 156.3 g (0.18 mole) of the compound of Example 3 is added 70.9 g (0.18 mole) 2,3-dibromopropyl trimellitate. The ~ e is heated at 130-140C for 6 hours with stirring to give the product as a brown opaque oil. Isolation afforded the product in essentially 4u~~ live yield and the analysis is consistent with the structure being:

Br~COOH COOH

BrJ~COO(CH2CH2CHp)g--C~ Br Br (~d isomen) Exarnples 6 to 11 The following p~ ions were carried out as in Exarnple 1 using the reactant set forth below.

Tct-~b.~ lpi~
E~mplc No.A-~lyd.;dc Hydro~y ~ ' Product Structurc 6 1.0 mole HOCH2CHpCH2CH2OH Br 1 0 mole Pr~,~COOH

8r f COO(CH2CH20)2H
Elr 7 1.0 mole HO(CH2CH2O)~H Br (Carbow~ 200)TM 13r~COOH

Br ~~ COO(CH2CH2O)~H
av.
Elr 8 1.0 mole HO(CH2CH2O)13H Br (Carbowa~ 6'00)TM
10 mole Br~T~COOH

Br ~ COO~CH2CH20)13H
Br av.

9 1.0 mole HO(CH2CH2O)23H ~r (Carbowa~ l000)TM E3r~g~COOH

Br ~ COO~CH2CH2O33H
av.
Br t, -31 l 3373 1 0 Examples 6 to 11 - continued The following ~ ald~ions were carried out as in Example 1 using the reactant set forth below.

T.L~
E~mple No. Anhydride Hydro~y CC , ~u ' Product Structure 1.0 mole HO(CH2CH20)~H. Br (rOI~ ~l E-2000)X
t O mole Br~COOH

Br ~ COO(CH2CH20)4sH
Br av.
I l 2.0 mole HO(CH2CH20hH Br Br (C~rl:lowu~ 400)*
1.0 mole Br~COOH HOOC ~ ~ Br Br ~ COO(CH2CH20hC I Br Br O Br Example 12 To 96.4 g (0.2 mole) of tetrabromoterephthalic acid is added all at once 160 g (0.2 mole) of Carbowax 400* and 300 g toluene co~ g 1.0 g P-toluene sulfonic acid. The ~ c; is heated to reflux until 3.6 g (0.2 mole) water was collected. The toluene is removed under reduced P1eS~Ue to give a clear viscous liquid in essentially quantitative yield.
COOH
r~ r COO(CH2CH20ha~

* Trade-mark ,.~

32 1 3373 ~ 0 Example 13 To 86.4 g (0.1 mole) of the compound of Example 3 is added all at once 21.8 g (0.1 mole) pyromellitic dianhydride and the lni~ e heated to 120-130C for 2.5 hours to give the desired product. Water, 1.8 g (0.1 mole), is added to open the rcm~ining anhydride group and the analytical data are consistent with the assigned structure:

Br~COOH HOOC

Br~COO(CH2CHp)g~C~COOH.
Br O ~
COOH
Example 14 To 86.4 g (0.1 mole) of the compound of Example 3 is added all at once 10.9 g (00.05 mole) of pyromellitic dianhydride and the mixture heated to 120-130C for 2.5 hours to give the desired product. The analytical data are con~i~tenl with the assigned structure: 1l 8r~COOH ~COOH
Br COO(CH2Ch20)9 HOOC
Br av. 2 a (u~d omers) Example 15 To 86.4 g (0.1 mole) of the compound of Example 3 is added all at once 21.8 g (0.01 mole) of phthalic anhydride and the ~ e heated to 120-130~C for 2.5 hours to give the desired product. The analytical data are consistent with the assigned structure:
8r COOH HOOC

Br~ COO(CH2CHPh--C~) Br Br Example 16 To 139.2 g (0.3 mole) of tetrabromophthalic anhydride is added all at once 122.9 g (0.1 mole) polyoxyethylated trimethylol propane of molecular weight 1229 and the mixture heated to 120-130C for 2.5 hours to give the desired product. The analytical data are con~i~tent with the ~igne(l structure:

Br B-~COOH --CH2~

8r ~ COO(CH2CHp~--CH2 Example 17 To 139.2 g (0.3 mole) of tetrabromophthalic anhydride is added all at once 156.8 g (0.1 mole) polyoxypropylated trimethylol propane of molecular weight 1568 and the ~lliXlUle heated to 120-130C for 2.5 hours to give the desired product. The anal,vtical data are consistent with the assigned structure:

Br Br~COOH --CH2~
1~)1 7H3 --CH2~C--C2Hs Br --1' COO(CH2CH20)90~ CH2 Br _ 3 , .

Example 18 To 284.0 g (1.0 mole) of tetrachlorophthalic anhydride is added 350.0 g (1.0 mole) of Methoxy Carbowax 350* in presence of 7.0 g of sodium acetate. The ~ Lule is heated at 90C for 8 hours in a nitrogen atmosphere. The reaction lllixlule is filtered hot to remove sodium acetate to give the expected product in nearly qu~llilalive yield.
The analytical data are consistent with the assigned structure:

Cl~ ~ ~COO(CH2CHp)7a~CH3 Example 19 To 634.0 g (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 60-100C for 3-5 hours, and then concentrated to give the product in nearly quantitative yield. The analytical data are consistent with the assigned structure:

Cl_ ~ l ,COO(CH2CHp)~aVCH3 Cl ~ COOCH2f H--OH
a CH3 $ Trade-mark ,...
,~

-Example 20 To 284.0 g (1.0 mole) of tetrachlorophthalic anhydride is added 200.0 g (1.0 mole) of Carbowax 200* in the presence of 7.0 g of sodium acetate. The mixture is heated at 90nC for 8 hours in a nitrogen atmosphere. The reaction mixture is filtered hot to remove sodium acetate to generate the expected product in nearly quanlil~live yield. The analytical data are conci~tent with the assigned structure:

Cl~ ~ ~COO(CH2CHlO)~arH

Cl--~COOH

Example 21 To 484.0 g (1.0 mole) of the product of Example 21 is added 116.0 g (2.0 moles) of propylene oxide in 200 ml of toluene. The reaction mixture is warmed at 60-100C for 3-5 hours, and then concentrated to give the product in nearly quantitative yield. The analytical data are con~i~tent with the assigned structure:

Cl~cootcH2cH2o)4arH

Cl f COOCH~--fH--OH
Cl CH3 Example 22 To 284.0 g(1.0 mole) of tetrachlorophthalic anhydride is added 400.0 g(1.0 mole) of Carbowax 400* in the presence of 7.0 g of sodium acetate. The mixture is heated at 90C for 8 hours in a nitrogen atmosphere. The reaction mixture is filtered hot to remove sodium acetate to generate the expected product in nearly quantitative * Trade-mark yield. The analytical data are consistent with the assigned structure:
cl cl Cl~ COO(CH2CH20)g"~H

Cl COOH
Example 23 To 46.4 g (0.1 mole) of tetrabromophthalic anhydride is added all at once 44.1 g (0.1 mole) of polyoxyethylated dimethylamine (CH3)2N(CH2CH2O)gH) dissolved in 100 ml of toluene. The mixture was heated at 100-110C for 4-5 hours and then concentrated to give the desired product in essentially quantitative yield. The analytical data are consistent with the assigned structure:

O 8r (CH3hN(--CH2CH20--)9arlCI~xBr Example 24 To 92.8 g (0.2 mole) of tetrabromophthalic anhydride is added 80 g (0.2 mole) H2N--CH--CH2UocH2--CH--]5.60rNH2 (Jeffamine D-400) and the mixture heated to about 120C. The final product is obtained in almost quantitative yield. The analytical data are consistent with the assigned structure:

Br 8r~COOH ICH3 CH3 8r Elr CONHCH--CH2(ocH2--CH--)5.6~NH2 ~"

-Example 25 Poly(ethylene glycol 300), 204.5 g (0.67 mole) was refluxed (T = 117C) with 600 ml of toluene for 1.5 hours in order to remove a small amount of water present in the glycol. The ~ e was cooled to about 100C and tetrabromophthalic anhydride, 614.5 g (1.35 moles) and sodium acetate, 1.62 g were added and the mixture was reheated to reflux and held for 25 hours. After the mixture was cooled to 50C, propylene oxide, (156.4 g, 2.69 moles, 100% excess) was added and the mixture heated to and held at 100C for 2.5 hours. When the solution cooled to about 50C it was filtered through a bed of diatomaceous earth and decolorizing charcoal. The filtrate was distilled to remove the solvent to give 904.1 g of product as a viscous liquid.
Calcd. % Br, 47.4. Found % Br, 46.5. Analytical data is consistent with the assigned structure.

Br~OOCH2CI CH3 CH3C112COl~

Br Br C0 (CH~CH20)~7--ICI Br Br Example 26 This compound was prepared by the procedure described in Example 25 except that poly(ethylene glycol 200) was used in place of poly(ethylene 300). Product is viscous liquid.

., Calcd. % Br, SlØ Found % Br, 49.3. Analytical data was consistent with the assigned structure.

Br O H H O Br Br ~ COCH2CCH3 CH3CH2COC ~ 8r Br ~ CO (CH2CH20)4_s--C Br Br O O Br Example 27 This compound was prepared by the procedure described in Example 25 except that poly(ethylene glycol 600) was used in place of poly(ethylene glycol 300). Product is a viscous liquid. Calcd. % Br, 39.5. Found % Br, 39.3. Analytical data is consistent with the assigned structure.

Br 1l H H O Br Br~COCH2CCHj CH3CI H2COC`~T'Br Br~CO--(CH2CH20)~2 ~ICI~Br Example 28 This compound was prepared by the procedure described in Example 25 except that poly(ethylene glycol 400) was used in place of poly(ethylene glycol 300). Product is a viscous liquid. Calcd. % Br, 44.2. Found % Br, 44Ø Analytical data is consistent with the assigned structure.

Br~COCH2CCH3 CH3ÇH~COC~8r Br Br ICI O ~CH2CH20)8_~ 0 Br Br ~_ t337310 Example 29 Methanol (54. 1 g, 1.5 mole), tetrabromophthalic anhydride (695.6 g, 1.6 moles), and potassium acetate, 2.73 g were refluxed for 4 hours with 500 ml of toluene.
After cooling the reaction mixture to room temperature, propylene oxide (87.12 g, 1.5 moles) were added and the lllixlule reacted at 80C for 2.5 hours. Product was obtained as a viscous liquid after distilling out the toluene. Calcd. % Br, 57.7. Found % Br, 57.2. Analytical data is consistent with assigned structure.

Br r~~ OCH~CHCH~
Br O OH

Example 30 This compound was prepared by the procedure similar to that described in Example 29 except that methoxycarbowax 350 was used in place of methanol and ethylene oxide in place of propylene oxide. Calcd. % Br, 37.8. Found % Br, 37.2.
Analytical data is consistent with assigned structure.

Br 8 Br~ ~ ~COtCH2CH20)7CH3 EIr ~--COCH2CH20H
Br O

-Example 3 1 This compound was prepared by the procedure in Example 29 except that 2-methoxyethanol is used in place of methanol. Product is viscous liquid. Calcd. % Br, 53.6. Found % Br, 52Ø Analytical data is consistent with assigned structure.

8r O H
Elr~COCH~CCH3 8r Br IC~OCH2CHpCH3 Example 32 This compound was prepared by the procedure outlined in Example 29 except that methoxycarbowax 350 was used in place of methanol and epoxybutane in place of propylene oxide. Product is a viscous liquid. Calcd. % Br, 36.5. Found % Br, 37.2.
Analytical data is consistent with assigned structure.

Br O H
ll l 8r~ OH

Br~f CO(CH2CH20hCH3 Hr O

Example 33 This compound was prepared by the procedure outlined in Example 29 except that 2-ethylhexanol-1 was used in place of methanol. Product is a viscous liquid.

~, Calcd. % Br, 50Ø Found % 52.7. Analytical data is consistent with the assigned structure.

Br 1O H
8r ~,COCH2CCH3 Br~f COCH2fHC4Hg Bt O C2H~

Example 34 This compound was prepared by the procedure described in Example 29 except that stearyl alcohol was used in place of methanol. Product is a viscous liquid. Calcd.
% Br, 41Ø Found % Br, 43Ø Analytical data is consistent with the assigned structure.

Br O H
Br ~ COCH2CCH3 Br~~~ CO(CH2)17CH3 Br o Example 35 This compound was prepared by the procedure described in Example 29 except that 2,3-dibromo-propanol-1 was used in place of methanol. Product is a viscous liquid. Calcd. % Br, 64.8. Found % Br, 61.9 Analytical data is consistent with the assigned structure.

Br 1l `1 Bt_T~,COCH2CCH3 Brf ~COCH2CHCH28r Br 0 8r Example 36 This compound was prepa~ed by the procedure outlined in Example 29 except that epichlorohydrin was used in place of propylene oxide. Calcd. % Br, 35.7. Found % Br, 35.4. Analytical data is consistent with the assigned structure.

Br 01 H
Br~COCH2CCHzCI

Br~ Iclo(cH2cH2o)7cH3 Example 37 To a solution of methoxycarbowax 350 (300.0 g, 0.89 mole) in dry toluene (184 ml) was added sodium methoxide (48.0 g, 0.90 mole) in methanol. The methanol was then distilled off atmospherically. Tetrabromophthalic anhydride was then added (442.2 g, 0.89 mole) along with an additional 50 ml of toluene. The reaction mixture was refluxed for 2 hours and after cooling to room temperature, epichlorohydrin (106.94 g, 1.16 moles) was added. The mixture was refluxed for 20 hours. After the solvent and `_ 133731Q

excess epichlorohydrin were distilled, a viscous dark product was obtained. Calcd. %

Br, 37.2. Found % Br, 40.4. Analytical data is con~i~t~nt with assigned structure.

8r 0 Br~COCH2CH\ ~CH2 Br~ CO~CH2CH20)~CH3 Br O

Example 38 Methoxycarbowax 350 and toluene were refluxed for 1 hour in order to distill out a small amount of water. Tetrabromophthalic anhydride (1:1 mole ratio with methoxycarbowax 350) and sodium acetate were added and the mixture refluxed for 17 hours. After cooling to room l~ dlule, an excess of diazomethane (prepared from the decomposition of M-methyl-N-nitroso-p-toluene sulfonamide by sodium hydroxide) in ethyl ether was added and the llli~ e allowed to stand overnight. The excess diazomethane was decomposed by adding acetic acid and the solvent removed by distillation. Product is viscous liquid. Calcd. % Br, 39.2. Found % Br, 37.4.
Analytical data is consistent with the assigned structure.

Br O

Br~ COtCH2CH20)~CH3 Br O

"r -44 13373iO

Example 39 Di(2-ethylhexyl) tetrabromophth~l~te was prepared by the procedure described by Spatz et. al (I & EC Product Research and Development, Vol. 8. No. 4, 395 (1969).

Br~OCH2CHG,Hg E3r Br o C2H5 Example 40 Poly(ethylene glycol 600) 885.4 g (1.40 moles), tetrabromophthalic anhydride, 1298.4 g (2.80 moles), potassium acetate, 1.35 g, and toluene (1000 g) were charged into a one-gallon glass-lined reactor and heated to 120~C. After 4 hours at this temperature, ethylene oxide, 246.68 g (5.60 moles) was pumped into the reactor in 3/4 hour while m~ g the temperature at 120C. After one hour longer of heating, the mixture was cooled to room temperature, the excess ethylene oxide was then vented, and the product collected. After stripping off the toluene, 2250 g of the product was isolated in 99% yield as a viscous liquid. Calcd. % Br, 39.2. Found % Br, 38.8.

133731 ~

Analytical data is consistent with the assigned structure.

o 1o Br~,~COCH2CH20H HOCH2CH20 C~}, Br~
COtCH2CH20)12-lJ C
O O

Example 41 To the product of Example 3, 453.8 g (0.27 mole), acetic anhydride, 83.4 g (0.82 mole), pol~SSiulll acetate, 1.0 g, and toluene, 400 ml, were refluxed for 8 hours.
After cooling to room temperature, the reaction mixture was transferred to a separatory funnel and extracted first with 100 ml of a 16% potassium bicarbonate solution and then with 100 ml of water. After ~ tilling off the solvent, 335.0 g (64% yield) of product was obtained as a viscous liquid. Calcd. % Br, 36.8. Found % Br, 32.9.
Analytical data is consistent with the assigned structure.

O H O O H O

8r~ CH3 CH3 ~ Br~
CO(CH2CH20)12-l- C
O O

Example 42 Tetrabromophthalic anhydride, 231.9 g (0.50 mole), 2-ethylhexanol, 130.2 g (1.0 mole), and potassium acetate, 0.24 g were heated to and kept at 120C for 4 hours.

46 133731 ~

The mixture was cooled to 60C and potassium carbonate, 35.9 g (0.26 mole), was added. Relle~tecl mixture to 80C and kept it at this t~ ?elalule for 2 hours. Cooled i~lule to 60C and added triethylamine, 14.2 g (0.14 mole). Reh~tecl lllixlule to 70C and added methyl iodide, 113.6 g (0.8 mole) in 20 mim-tes Heated mixture to 70-75C and kept it at this temperature for 2 1/2 hours. Cooled llli~lule 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. Extracted this product with 3 times 100 ml of a 6.5% potassium carbonate solution followed by 2 times 100 ml of water and once with 30% sodium chloride solution. Dried the organic phase over anhydrous m~gnesium sulfate overnight. Filtered off magnesium sulfate and after removing the solvent from filtrate by rli~till~tion, 204 g of product was obtained in 67% yield as a pale yellow liquid.
Calcd. % Br, 52.6. Found % Br, 52.2. Analytical data is consistent with the assigned structure.

~ COCH3 BrJ,~ H
COCH2C--C~,Hg O C~H5 47 ~ 3373 1 0 Example 43 Tetrabromophthalic anhydride, 231.9 g (0.5 mole), 2-[2-methoxyethoxy]-ethanol, 360.5 g (3.0 moles), stannous oxalate, 2.32 g, and xylene, 200 ml, were refluxed (temp.
160C) for 18 hours during which time, theory water was collected. The xylene and excess 2-[2-methoxyethoxy]-ethanol were distilled under reduced ples~u~e to give 332 g of crude product as a wet white solid. Redissolved 256 g of this material in toluene (1000 ml) and extracted it with 3 times 200 ml of a 7.5% potassium bicarbonate solution followed by one extraction with 200 ml of water. Dried the organic phase with anhydrous m~gnesium sulfate overnight. After removing the m~gnesium sulfate by filtration, toluene was removed by (li~till~tion to give 45 g of a yellow liquid product. Overall yield is 17%. Calcd. % Br, 46.6. Found % Br, 45.7. Analytical data is con~ tent with the assigned structure.

8r~COCH2CHpCH2CH20CH3 COCH2CH20CH2CHpCH3 Exarnple 44 This compound was prepared by the procedure outlined in Example 43 except using 2-[2-methoxyethoxy]-ethanol.

Bt~COCH2CllpCH2CH20C2H5 COCH2CHpCH2CH20C2H5 Example 45 This compound was prepared by the procedure outlined in Example 1 except that docosyl alcohol (behenyl alcohol) 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. Analytical data is consistent with the assigned structure.

O H
~ COCH2¢0H
E3r4~ CH3 CO(CH2321CH3 Example 46 This compound was prepared by the procedure outlined in Example 1 except that tricontyl alcohol was used in place of poly(ethylene glycol 600) and propylene oxide in place of ethylene oxide. Product is a viscous liquid.

O H
ll l ~ COCH2COH
l~r~,--~ CH3 CO(CH2)29CH3 Example 47 This compound was prepared by the procedure outlined in Example 4 except that methoxycarbowax 550 was used in place of 2-[2-methoxyethoxy]-ethanol.

8r4 ~ CO(CHzCH20)iICH3 CO(CH2CHp)lICH3 -Examples 48-58 --- Compositions With ABS Resins In the following examples, the flame retardancy of the compounds of this invention are demonstrated with respect to ABS resins. The compositions were prepared 5 by mixing together the flame retardants, antimony oxide, and ABS on a roller until the compounds were blended thoroughly. The compounds were pelletized at 230-245C
and then injection molded into test specimens at 230C.
The UL-94 vertical burn test was run and compared to a 10 control consisting of ABS itself.

ABS = Acrylonitrile-styrene-butadiene terpolymer DTBPE = 1,2-bis(2,4,6-tribromophenoxy)-ethane (70% Bromine) DOTBP = Dioctyl tetrabromophthalate (45% Bromine) AO = Antimony Oxide Table I (A) Example No 48(b) 49(c) 50 5l ABS(a) 100 100 100100 DTBPE - 22 11 5.5 5 DOTBP - - 1725.7 UL-94 @ 0.125"Failed V-0 V-0 V-0 @ 0.062" Failed V-l V-l V-l 10 (a) Cyclolac~ T, a product of Borg-Warner Co., U.S.A.
(b) control (100% ABS) (c) comparison (no tetrahalophthalate ester) The above clearly demonstrates the flame retardancy of the ABS compositions of this invention relative to 15 the control. These compositions have at least equivalent flame retardancy to the conventional flame retardant used in ABS (DTBPE).

-Examples 52-55 Impact strength of the various materials were deter-mined according to ASTM D256.

Table II(A) 5 Example No _(b) 53(C) 54 55_ ABS(a) 100 100 100 100 DTBPE - 22 11 5.5 DOTBP - - 17 25.7 (ft-lb/in notch) 3.34 1.26 1.98 1.66 (a) Cycolac~T, a product of Borg-Warner Co., U.S.A.
(b) control (100% ABS) 15 (c) 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 20 compositions of this invention.

Examples 56-58 Heat Reflection Temperature (HDT) of the various materials were determined according to ASTM D648.

Table III(A) 5 Example No. 56(b)57(c) 58 ABS(a) 100 100 100 AO ~ 4 4 10 HEAT DEFLECTION TEMP. (HDT) @ 264 psi (F) 182 167 166 (a) Cycolac~ T, a product of Borg-Warner Co., U.S.A.
(b) control (100% ABS) 15 (c) 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 inven-tion.

Examples 59-64 --- Compositions With Polystyrene Resin~
In the following examples, the flame retardancy of the compositions of this invention are demonstrated.
The compositions were prepared by mixing together the 5 flame retardants, antimony oxide, and high impact poly-styrene on a roller until the compounds were blended thoroughly. The compounds were pelletized at 200-260C
and then injection molded into test specimens at 230C.
The UL-94 vertical burn test was run and compared to a 10 control consisting of the impact polystyrene itself.

HIPS = High Impact Polystyrene DBDPO = Decabromodiphenyl Oxide (83% Bromine) DOTBP = Dioctyl Tetrabromophthalate (45% Bromine) AO = Antimony Oxide -Table I(B) Example No 59(b) 60(C) 61 62 63 64 Percenta~e Composition HIPS(a) 100 84 81.5 73.9 83 80.8 DOTBP - - 5.5 22.1 4.316.4 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 (a) Polysar~ 525, a product of Polysar, Inc., U.S.A.
(b) control (100% polystyrene) (c) comparison (no tetrahalophthalate ester) The above results clearly demonstrate the superior 15 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 20 flame retardant (DBDPO) with the esters disclosed in this invention improves the flame retardancy of the polystyrene as can be seen by the UL-94 results for the 0.062" speci-mens. Examples 63 and 64 clearly demonstrate that the total bromine levels can be reduced when the compo-25 sitions of this invention are used and still yieldcomparable or better flame retardancy.

, ~
.....

Examples 65-70 Impact strength of the various materials were determined according to ASTM D2463.

Table II(B) 5 Example No 65(b)66(C) 67 68 69 70 HIPS(a) 100 84 81.5 76.4 73.9 80.8 DOTBP - - 5.5 16.6 22.1 16.4 AO - 4 4 4 4 2.8 10 Gardner Impact (in-lb/mil) 0.096 0.067 0.0700.084 0.115 0.095 (a) Polysar~ 525 from Polysar, Inc.
(b) control (100% polystyrene) 15 (c) 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 20 the impact strength to a point where it is better than the comparison example.

57 l 3373 1 0 Example 71-74 The extrusion rates were measured during pelletiza-tion 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 DOTBP - 5.5 ll 16.6 Extruder Flow Rate (lbs/hr) 3.4 3.7 4.2 7.9 (a) Polysar~ 525, a product of Polysar, Inc., U.S.A.
15 (c) comparison (no tetrahalophthalate ester) The data above clearly demonstrates the improved processability of the styrene-containing flame retardant of this invention.

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 5 prepared by mixing together the flame retardants, antimony oxide, and polycarbonate resin on a roller until the com-pounds were blended thoroughly. The compounds were pel-letized at 160-305C and then injection molded into test specimens at 271C. The UL-94 vertical burn test was run 10 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
method.
1. Limited Oxygen Index (LOI) - ASTM D-2863 2. Melt Flow - ASTM D-1238 3. Tensile Strength - ASTM D-638 PC = Polycarbonate polymer BPC = Brominated Polycarbonate Oligomer (58% Bromine) DOTBP = Dioctyl Tetrabromophthalate (45% Bromine) TABLE I (C) Example No 75(b) 76(c) 77 78 79 PC(a) 100.0 87.5 86.6 84.9 84.0 BPC - 12.5 9.4 3.1 5 DOTBP - - 4.0 12.0 16.0 Melt Flow 26.8 19.1 37.5 >100 >100 (g/10 min) Tensile Strength 10 at Yield (PSI)(d)9210 10220 10010 10100 10300 % Elongation at Yield 17.9 18.8 17.4 14.3 15.9 (a) "Lexan" 141, a product of General Electric, U.S.A.
15 (b) control (100% polycarbonate) (c) comparison (no tetrahalophthalate ester) (d) PSI = pounds per square inch. 1 PSI = .0145 g/cm2 The above clearly demonstrates the significant im-provement in flame retardancy of the polycarbonate resin containing compositions of this invention relative to the control. These polycarbonate resin containing compositions 5 have at least comparable flame retardancy to the conven-tional 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 inven-10 tion results in greatly enhanced flow characteristics asshown by the improved melt flow properties measured ac-cording to ASTM D-1238.
The polycarbonate resin containing compositions of this invention show improved tensile properties when 15 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 20 processability of the polycarbonate resin containing compositions of this invention.

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 5 retardants, antimony oxide, and polybutylene terephthalate (PBT) on a roller until the compounds were blended thor-oughly. The compounds were pelletized at 150-216C and then injection molded into test specimens at 235C. The UL-94 vertical burn test was run and compared to a con-10 trol consisting of PBT itself. Melt flow of the variousmaterials were determined according to ASTM D-1238.

PBT = Polybutylene Terephthalate BPC = Brominated Polycarbonate Oligomer (58% Bromine) DOTBP = Dioctyl Tetrabromophthalate (45% Bromine) AO = Antimony Oxide TABLE I (D) Example No 8o(b) 81(C) 82 83 PBT(a~ 100.0 85.0 82.8 80.7 BPC - 15.0 7.5 5 DOTBP - - 9.7 19.3 Antimony Oxide - 5.0 5.0 5.0 UL-94 Rating @ 0.125" V-2 V-0 V-0 V-0 @ 0.063" V-2 V-0 V-0 V-0 10 Melt Flow 27.6 36.2 55.1 72.6 (g/10 min) (a) "Celanex" 2000, a product of Hoechst-Celanese Corp., U.S.A.
(b) control (100% polybutylene terephthalate) 15 (c) 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 equivalent flame retardancy to the BPC conventional flame retardant 5 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 10 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 64 l 33731 0 TABLE II (D) Example No 84(b~ 85(c) 86 PBT(a) 100 85.0 83.8 BPC - 15.0 11.3 5 DOTBP - - 4.9 Antimony Oxide - 5.0 5.0 UL-94 Rating @ 0.125 V-2 V-0 V-0 @ 0.063 V-2 V-0 V-0 Notched Izod 0.45 0.33 0.60 (lbs/inch) Tensile ~ength 7320 8040 7750 (PSI) % Elongation 10.9 10.3 11.8 HDT (F)/(C) 127/53 149/65 135/57 Melt Flow 27.6 36.2 61.9 (g/10 min) 20 (a) "Celanex" 2000, a product of Hoechst-Celanese Corp., U.S.A.
(b) control (100% polybutylene terephthalate) (c) comparison (no tetrahalophthalate ester) (d) PSI = pounds per inch. 1 PSI = .0145 g/cm2 -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 5 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 10 (HDT) and flow properties relative to the control.
The data above clearly demonstrates the improved processability of the polybutylene terephthalate con-taining 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 20 were pelletized at 95-245C and then injection molded into test specimens at 190-204C. 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.

SMA = Styrene-Maleic Anhydride Polymer DBDPO = Decabromodiphenyl Oxide (83% Bromine) DOTBP = Dioctyl Tetrabromophthalate (45% Bromine) AO = Antimony Oxide -TABLE I (E) Example No 87(b) gg(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 5 DOTBP - - 2.6 S.1 12.8 Antimony Oxide - 3.5 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 10 Melt Flow 1.16 1.84 2.08 3.32 6.76 (g/10 min) (a) "Dylark" 250, a product of Arco Chemicals, U.S.A.
(b) control (100% styrene-maleic anhydride copolymer) (c) 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 (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 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 ~ 69 l 3373 1 0 TABLE II (E) Example No 92(b) 93(c) 94 95 SMA(a) 100.0 82.7 81.5 80.4 DBDPO - 13.8 12.4 11.0 5 DOTBP - - 2.6 5.1 Antimony Oxide - 3.5 3.5 3.5 LOI 18.7 27.6 28.6 23.1 UL-94 Rating @ 0.0125" Failed V-0 V-0 V-0 @ 0.063" Failed V-0 V-0 V-0 Notched Izod 2.34 1.02 1.56 1.96 (lbs/inch) Tensile Strength (Yield) 3950 3880 3830 3700 (PSI)( ) 15 % Elongation 8.7 7.4 7.7 8.1 HDT (F) 197 197 191 192 Melt Flow 1.16 1.84 2.08 3.32 (~/10 min) ~,t (a) "Dylark" 250, a product of Arco Chemicals, U.S.A.
20 (b) control (100% styrene-maleic anhydride copolymer) (c) comparison (no tetrahalophthalate ester) (d) PSI = pounds per inch. 1 PSI = .0145g/cm2 As can be seen from the data above, SMA resin composi-tions containing the flame retardants of this invention greatly improve the impact strength relative to the control (Example 92) and the DBDPO commercial flame rètardant with 5 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 pro-cessability of the styrene-maleic anhydride copolymer resin containing compositions of this invention.

Claims (8)

1. A flame retardant composition comprising:-(I) a resin which is selected from among:-(A) acrylonitrile-butadiene-styrene resin;
(B) polystyrene resin;
(C) polycarbonate resin;
(D) polybutylene terephthalate resin; and (E) styrene-maleic-anhydride copolymer resin; and (II) a flame retarding effective amount of a tetrahalophthalate ester flame retardant having the formula:- wherein:-(a) R is selected from the group consisting of:-(i) hydrogen;

(ii) an alkyl or substituted alkyl of 1 to 30 carbons where the resin is selected from styrene and polybutylene terephthalate, or of 1 to 9 carbons where the 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 where the resin is acrylonitrile-butadiene-styrene, and where R8 is an alkyl or substituted alkyl of 1 to 18 carbons, or of 1 to 8 carbons where the resin is acrylonitrile-butadiene-styrene and b is 1 to 50;

(v) (b) R1 is selected from the group consisting of:-(i) hydrogen where the resin is selected from styrene, polycarbonate, acrylonitrile-butadiene-styrene and styrene-maleic-anhydride;
(ii) an alkyl or substituted alkyl or 1 to 30 carbons where the resin is selected from styrene and polybutylene terephthalate, or of 1 to 9 carbons where the resin is selected from polycarbonate, acrylonitrile-butadiene-styrene and styrene-maleic-anhydride; and (iii) alkenyl or substituted alkenyl of 2 to 22 carbons, where R7 is selected from the group consisting of an alkyl of 1 to 18 carbons, and where the resin is selected from polycarbonate, styrene, acrylonitrile-butadiene-styrene and styrene-maleic-anhydride resins, a polyhydroxyalkyl of 3 to 12 carbons;

, (all isomers), (all isomers), , , and ;

with the proviso that where the resin is selected from polycarbonate and polybutylene terephthalate resins the valence of R1 is equal to q;
(c) R2 is independently selected from the class consisting of H and CH3;
(d) R3, R4, R5 and R6 are independently selected from the class consisting of H and an alkyl of 1 to 18 carbons;
(e) p is an integer of 0 to 50;
(f) q is an integer of 1 to 2;
(g) X is selected from 0 and NH;
(h) A is selected from Cl or Br; provided further that, where the resin is selected from polycarbonate, polybutylene terephthalate and styrene-maleic-anhydride, when p is zero and X is oxygen that R and R1 are other than a neopentyl group; and (III) and where the resin is polystyrene, 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 wherein n is within the range of greater than 1 to about

3,000.

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, 2 or 3 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 2.

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

6. A composition according to claim 5, wherein said other brominated flame retardants are selected from the group consisting essentially of where R'' and R''' are alkylene or substituted alkylene

7. A composition according to any one of claims 2, 3, or 6 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.

8. A composition according to claim 7 wherein said blowing agent is selected from the group consisting of at least one of propane, butane, pentane, hexane, heptane, cyclohexane, methyl chloride, dichlorodifluorethane, 1,1,2 trifluoroethane, and 1,1,2 trichloroethane.