EP0339074A4

EP0339074A4 - Tetrahalophthalate esters as flame retardants for certain resins

Info

Publication number: EP0339074A4
Application number: EP19880909875
Authority: EP
Inventors: Joseph Michael Bohen; Ronald Francis Lovenguth
Original assignee: Pennwalt Corp
Current assignee: Arkema Inc
Priority date: 1987-10-30
Filing date: 1988-10-28
Publication date: 1991-07-03
Also published as: FI893189A7; BR8807274A; CA1337310C; DK323589D0; ES2018098A6; DK323589A; HUT54720A; EP0339074A1; FI893189L; JPH02502026A; AU2126392A; FI893189A0; WO1989003854A1; HU886711D0

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 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, and (F) Polyolefin or Substituted Polyolefin.

Description

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: (A) Acrylonitrile-Butadiene-Styrene (ABS) Terpolymer Resins;

(B) Polystyrene Resins;

(C) Polycarbonate Resins; (D) Polybutylene Terephthalate Resins;

(E) Styrene-Maleic Anhydride (SMA) Copolymer Resins; and

(F) 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 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. These pages are hereby incorporated by reference. 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, "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, e.g., 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

wherein x, y, and z may independently vary from about 10 to about 1,500. (See U.S. Patent 4,567,218, the teachings o which are incorporated herein by reference.) 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, α-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 teachings of which are incorporated herein by reference.

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.

Polystyrene resins find extensive use in the manufacture 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, appli¬ances, 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 (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 teachings of which are incorporated herein by reference.

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, 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 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 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 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 by themselves or in combination with other materials such 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; 4,567,218; 4,581,403; 4,581,409; and 4,600,747. 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 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 resins.

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;

(E) Styrene-Maleic Anhydride (SMA) Copolymer Resins; and

(F) Polyolefin and Substituted Polyolefin Resins (II) a flame retarding effective amount incorporated in the resin of (I) of a tetrahalophthalate ester flame retardant processing aid of the formula:

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

where R⁸ is an alkyl or substituted alkyl of 1 to 18 carbons, and b is 1 to 50; (c) R¹ 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, where R⁷ is an alkyl of 1 to 18 carbons; a polyhydroxyalkyl of 3 to 12 carbons;

with the proviso that the vaience of R¹ is equal to q;

(d) R² is independently selected from the class consisting of H and CH₃ - ; (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 0 to 50; (g) q is an integer of 1 to 6;

(h) X is selected from 0 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. (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 other brominated flame retardants are selected from the group consisting of

Preferred Resins

(A) In the above ABS resin, a portion or all of acrylic and styrenic monomers comprising the resin include methacrylonitrile or α-methylstyrene, or methacrylonitrile and α-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 from about 10 to about 1500.

(B) The polystyrene resin is selected from one of the following:

(a) a homopolymer of styrene having the following repeatable unit

wherein n is within the range of greater than 1 to about 3,000;

(b) a homopolymer of styrene as in (a) modified with rubber in which the rubber is dispersed as discrete 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 of about 2:98 to about 25:75; or

(d) blends of (a) and (b); polybutadiene and/or a styrenebutadiene copolymer being preferred.

In a preferred embodiment of the invention, the homopolymer of (B)(a) above is in the form of a polystyrene 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 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.

(C) The polycarbonate resin has repeated structural units of the formula:

wherein a is greater than 1 and z is a divalent aromatic radical of a dihydric phenol; (D) The polybutylene terephthalate resins that may be used in the present invention have the following repeated structural units of the formula:

wherein a > 1.

(E) The SMA resins that may be used in the present invention usually have the following general structural formula:

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

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

It is preferred that in the above tetrahalophthalate ester (II), R is an alkyl or substituted alkyl of 1 to 10 carbons, A is Br, X is oxygen, p is 0 to 20 (most preferably 0), and q is 1 to 6 (most preferably 1). More preferably R is

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

The preferred compounds are:

The R in the above formulas is

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 halogenated flame retardant examples are

In practicing this invention, (II) the tetrahalophthalate by itself or additionally with (III) other brominated and/or chlorinated flame retardants is added to (I) theresin in any convenient manner, such as blending or extruding in order to get a uniform composition. Flame retardant synergists such as antimony oxide (Sb₂O₃) may also be added if desired. In addition, other additives such as thermal stabilizers, 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 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

(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:

y acrylonitrile butadiene styrene wherein x, y, and z may independently vary from about 10 to about 1,500. It is understood that analogs of each 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.

(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 include medium impact polystyrene, high impact polystyrene (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 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)]. 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 20% 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 high impact polystyrene greater than about 10% to about 25%. [See H. Keskkula in "Encyclopedia of Polymer Science and Technology" Vol. 13, pp. 396 and 400-404 (1970)]. (C) 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; 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 1,3929(3.0 aoles) of tetrabromophthalic anhydride were added 1,050 9(3.0 moles) of Methoxy Carbowax 350 in tha presence of 22.0 g of sodium acetate. The mixture was heated at 90ºC for 8 hours in a nitrogen atmosphere. The reaction mixture vas filtered hot to remove the sodium acetate. The analytical data were consistent with the assigned structure.

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 mixture was heated at 60º-100ºC. 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:

Example 3

To 92.19(0.2 mole) of tetrabromophthalie anhydride is added all at once 80 g(0.2 mole) of Carbowax 400 and the mixture heated to

120º-130ºC for 2.5 hours. The desired product is isolated in essentially quantitative 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:

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 155ºC 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.; IBr, 30.31; Mol. wt. 1056; neutralixatioa equivalent, 352; round: IBr, 29.4; Mol. wt., 1014; neutralisation equivalent, 351. The spectral data was consistent with the structure:

OOH

C0O (CH₂CH₂CH₂0) _j-C H ( J/"" ^cooϊ 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 mixture is heated at 130º-140ºC for 6 hours with stirring to give the product as a brown opaque oil. Isolation afforded the product in essentially quantitative yield and the analysis is consistent with the structure being:

Examples 6 to 11

The following preparation were carried cut as in Example 1 using the reactant set forth below.

Examples 6 to 11 - continued

The following preparation were carried out as in Example 1 using the reactant set forth below.

Example 12

To 96.4 9(0.2 mole) of tetrabromoterephthalic acid is added all once 160 9(0.2 mole) of Carbowax 400 and 300 9 toluene containing 1.0 g P-toluene sulfonic acid. The mixture is heated to reflux until 3.6 g(0.2 mole) water was collected. The toluene is removed under reduced pressure to give a clear viscous liquid in essentially quantitative yield.

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 mixture heated to 120º-130ºC for 2.5 hours to give the desired product. Water, 1.8 g(0.1 mole), is added to open the remaining anhydride group and the analytical data are consistent with the assigned structure:

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 120º-130ºC for 2.5 hours to give the desired product. The analytical data are consistent with the assigned structure:

Example 15

To 86.4 g(0.1 mole) of the compound of Example 3 is added all at once 21.8 g(0.1 mole) of phthalie anhydride and the mixture heated to 120º-130ºC for 2.5 hours to give the desired product. The analytic data are consistent with the assigned structure:

Example 16

To 139.2 g(0.3 mole) of tetrabromophthalie anhydride is added all at once 122.9 g(0.1 mole) polyoxyethylated trimethylol propane of molecular weight 1229 and the mixture heated to 120º-130ºC for 2.5 hours to give the desired product. The analytical data are consistent with the assigned structure:

Example 17

To 133.2 g(0.3 mole) of tetrabromophthalie anhydride is added all at once 156.8 g (0.1 mole) polyoxypropylated trimethylol propane of molecular weight 1568 and the mixture heated to 120º-130ºC for 2.5 hours to give the desired product. The analytical data are consistent with the assigned structure:

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 mixture is heated at 90ºC for 8 hours in a nitrogen atmosphere. The reaction mixture is filtered hot to remove sodium acetate to give the expected product in nearly quantitative yield. The analytical data are consistent with the assigned structure:

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 60º-100ºC for 3-5 hours, and then concentrated to give the product in nearly quantitative yield. The analytical data are consistent with the assigned structure:

Example 20

To 284.09(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 90ºC 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 yield

The analytical data are consistent with the assigned structure:

Example 21

To 484.0 g(1.0 mole) of the product of Example 21 is added

116.0 g(2.0 mole) of propylene oxide in 200 ml of toluene. The reaction mixture is warmed at 60º-100ºC for 3-5 hours, and then concentrated to give the product in nearly quantitative yield. The analytical data are consistent with the assigned structure:

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 90ºC 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 yield

The analytical data are consistent with the assigned structure:

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 dimathylamine [CH₃)₂N(CH₂CH₂O)₉H] dissolved in 100 ml of toluene. The mixture was heated at 100º-110ºC 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:

Example 24

To 92.8 g(0.2 mole) of tetrabromophthalie anhydride is added 80 g(0.2 mole) of

(Jeffamine D-400) and the mixture heated to about 120ºC. The final product is obtained in almost quantitative yield. The analytical data are consistent with the assigned structure:

Example 25

Poly(ethylene glycol 300), 204.5 g (0.67 mole) was refluxed (T = 117ºC) with 600 ml of toluene for 1.5 hours in order to remove a small amount of water present in the glycol. The mixture was cooled to about 100°C and tetrabromophthalie anhydride, 614.5 g (1.35 moles) and sodium acetate, 1.62 g were addei and the mixture was reheated to reflux and held for 25 hours. After the mixture was cooled to 50ºC, propylene oxide, (156.4 g, 2.69 moles, 100% excess) was added and the mixture heated to and held at 100°C for 2.5 hours. When the solution cooled to about 50ºC it was filtered through a bed or diatomaceus 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 % 3r, 46.5. Analytical data is consistent with the assigned structure.

r

Example 26

This compound was prepared by the procedure described in Example 25 except that poly(echylene glycol 200) was used in place of poly(ethylene 300). Product is viscous Liquid. Calcd . % Br , 51.0 . Found % Br, 49.3. Analytical data was consistent with the assigned structure .

Example 27

This compound was prepared by the procedure described in Example 25 except that polyethylene 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.

Example 21 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, 44.0. Analytical data is consistent with the assigned structure.

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 mixture reacted at 80°C 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.

Example 30

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

Example 31

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, 52.0. Analytical data is consistent with the assigned structure.

Example 32

This compound was prepared by the procedure outlined in Example 29 except that aethoxycarbowax 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 the assigned structure.

Example 33 This compound was prepared by the procedure outlined Example 29 except that 2-ethylhexanol-1 was used in place methanol. Product is a viscous liquid. Calcd. % Br, 50.0. Found % 52.7. Analytical data is consistent with the assigned structure.

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, 41.0. Found % Br, 43.0. Analytical data is consistent with the assigned structure.

Example 35

This compound was prepared by the procedure described in Example 29 except that 2,3-dibroao-propanol-1 was used place of methanol. Product is a viscous liquid. Calcd. % Br, 64.8. Found % Br, 61.9. Analytical data is consistent with the assigned structure.

Example 36

This compound was prepared by the procedure outlined in Example 29 except that epichlorohydrin was used in place of propylene oxide . Calcd . % Br , 35 .7. Found % 35 .4. Analytical data is consistent with the assigned structure .

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 aethanol was then distilled off atmospherically. Tetrabromophthalic anhydride was then added (442.2 g, 0.89 mole) along with an additional. 50 al of toluene. The reaction mixture was refluxed for 2 hours and after cooling to room temperature, epichlorchycrin (106.94 g, 1.16 moles) was added. The mixture was refluxed for 20 hours. After the solvent and excess epichlorohydrin were distilled, a viscous dark product was obtained. Calcd. % Br, 37.2. Found % Br, 40.4. Analytical data is consistent with assigned structure.

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 temperature, an excess of diazomethane (prepared from the decomposition of N-methyl-N-nitroso-p-toluene sulfonamide by sodium hydroxide) in ethyl ether was added and the mixture 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.

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

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 maintaining the temperature at 120ºC. After one hour Longer of beating, 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. Analytical data is consistent with the assigned structure.

Example 41

To the product of Example 3, 453.8 g (0.27 mole), acetic anhydride, 83.4 g (0.82 mole), potassium 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 al of water. After distilling 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.

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 120ºC for 4 hours. The mixture was cooled to 60ºC and potassium carbonate, 35.9 g (0.26 mole), was added. Reheated mixture to 80ºC and kept it at this temperature for 2 hours. Cooled mixture to 60°C and added triethylamine, 14.2 g (0.14 mole). Reheated mixture to 70ºC and added methyl iodide, 113.6 g (0.8 mole) in 20 minutes. Heated mixture to 70-75ºC and kept it at 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. 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 a 30% sodium chloride solution. Dried the organic phase over anhydrous magnesium sulfate overnight. Filtered off magnesium sulfate and after removing the solvent from filtrate by distillation, 204 g of produce 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. 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. 160ºC) for 18 hours during which time, theory water was collected. The xylene and excess 2-[2-methoxyethoxy]-ethanol were distilled under reduced pressure to give 332 3 of crude product as a wet white solid. Redissolved 256 g of this material in toluene (1000 al) 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 magnesium sulfate overnight. After removing the magnesium sulfate by filtratin, toluene was removed by distillation to give 45 g of a yellow liquid product. Overall yield is 17%. Calcd. % Br, 46.6. Found % Br, 45.7. Analytical data is consistent with the assigned structure.

Example 44

This compound was prepared by the procedure outlined in Example 43 except using 2-(2-ethoxyethoxy]-ethanol,

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.

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.

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.

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 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°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

(70% Bromine) DOTBP = Dioctyl tetrabromophthalate (45% Bromine) AO = Antimony Oxide

Table I (A)

Example No 48^(b) 49^(c) 50 51

ABS^(a) 100 100 100 100

DTBPE - 22 11 5.5 DOTBP - - 17 25.7 AO - 4 4 4

UL-94 @ 0.125" Failed V-0 V-0 V-0 @ 0.062" Failed V-1 V-1 V-1

(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 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 determined according to ASTM D256.

Table 11(A)

Example No 52^(b) 53^(c) 54 55

ABS^(a) 100 100 100 100

DTBPE - 22 11 5.5

DOTBP - - 17 25.7

AO - 4 4 4

NOTCHED IZOD IMPACT

(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) (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 compositions of this invention. Examples 56-58

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

Table III(A) Example No, 56 ^(b) 57^(c) 58

ABS (a) 100 100 100 DTBPE - 22 11 DOTBP - - 17 AO - 4 4

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) (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 invention. 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°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

Table 1(B)

Example No 59^(b) 60^(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

(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 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 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. Examples 65-70

Impact strength of the various materials were determined according to ASTM D2463.

Table 11(B)

Example No 65^(b) 66^(c) 67 68 69 70

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

(a) Polysar® 525 from Polysar, Inc.

(b) control (100% polystyrene) (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 the impact strength to a point where it is better than the comparison example. 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

DBDPO 12 9 6 3 DOTBP - 5 . 5 11 16 . 6 AO 4 4 4 4

Extruder Flow Rate (lbs/hr) 3.4 3.7 4.2 7.9

(a) Polysar® 525, a product of Polysar, Inc., U.S.A. (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 prepared by mixing together the flame retardants, antimony oxide, and polycarbonate resin on a roller until the compounds were blended thoroughly. The compounds were pelletized at 160-305°C and then injection molded into test specimens at 271°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 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 - DOTBP - - 4.0 12.0 16.0

LOI 28 39 37 37 37

Melt Flow 26.8 19.1 37.5 >100 >100 (g/10 min)

Tensile Strength 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. (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 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 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 retardants, antimony oxide, and polybutylene terephthalate (PBT) on a roller until the compounds were blended thoroughly. The compounds were pelletized at 150-216°C and then injection molded into test specimens at 235°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

TABLE I (D)

Example No 80^(b) 81^(c) 82 83

_PBT(a) 100.0 85.0 82.8 80.7

BPC - 15.0 7.5 - 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

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) (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 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

TABLE II (D)

Example No 84^(b) 85^(c) 86 P_BT(a) 100 85.0 83.8

BPC - 15.0 11.3 DOTBP - - 4.9

Antimony Oxide - 5.0 5.0 LOI 25 32 32

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 Strength 7320 8040 7750 (PSI)^(d)

% 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)

(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 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°C and then injection molded into test specimens at 190-204°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. 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) 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 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 (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

TABLE II (E)

Example No 92^{(b )} 93^(c) 94 21 SMA^(a) 100.0 82.7 81.5 80.4 DBDPO - 13.8 12.4 11.0 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)^(d) % 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

(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)

(d) PSI = pounds per inch. 1 PSI = .0145g/cm² 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

1. A flame retardant plastic composition with improved flow characteristics comprising the mixture of:

(I) a resin which is selected from among: (A) Acrylonitrile-Butadiene-Styrene resin;

(B) Polystyrene resin;

(C) Polycarbonate resin;

(D) Polybutylene Terephthalate resin;

(E) Styrene-Maleic Anhydride Copolymer resin; and

(F) Polyolefin or Substituted Polyolefin; and

(II) a flame retarding effective amount of a tetrahalophthalate ester flame retardant processing aid.

2. The use of a tetrahalophthalate ester as a flame retardant processing aid to impart flame retardancy and improved flow characteristics to a resin which is selected from among: (A) Acrylonitrile-Butadiene-Styrene resin;

(B) Polystyrene resin;

(C) Polycarbonate resin;

(D) Polybutylene Terephthalate resin;

(E) Styrene-Maleic Anhydride Copolymer resin; and (F) Polyolefin or Substituted Polyolefin.

3. A method for imparting flame retardant and improved flow characteristics to a resin selected from among: (A) Acrylonitrile-Butadiene-Styrene resin;

(B) Polystyrene resin; (C) Polycarbonate resin;

(D) Polybutylene Terephthalate resin;

(E) Styrene-Maleic Anhydride Copolymer resin; and

(F) Polyolefin or Substituted Polyolefin; comprising mixing with said resin a flame retardant effective amount of at least one tetrahalophthalate ester flame retardant aid.

4. A method for manufacturing a flame retardant resin with improved flow characteristics comprising mixing (I) a resin which is selected from among:

(A) Acrylonitrile-Butadiene-Styrene resin;

(B) Polystyrene resin; (C) Polycarbonate resin;

(D) Polybutylene Terephthalate resin;

(E) Styrene-Maleic Anhydride Copolymer resin; and

(F) Polyolefin or Substituted Polyolefin; with (II) a flame retarding effective amount of at least one tetrahalophthalate ester flame retardant aid,

Any one of claims 1 to 4 wherein said tetrahalophthalate ester has the formula

wherein:

(a) the ring can have all possible isomeric arrangements;

with the proviso that the valence of R¹ a equal to q; (d) R² is independently selected from the class consisting of H and CH₃ -;

(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 0 to 50; (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.

6. Claim 5 wherein p is zero, q is one and X is oxygen.

7. Claim 6 wherein R and R¹ are alkyl groups and A is Br.

8. Claim 7 wherein the ester is di-2-ethylhexyl tetrabromophthalate.

9. Any one of claims 1 to 8 wherein the weight ratio of (I) to (II) is within the range of 100:1 to 2:1.

10. Claim 5 wherein 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.

11. Claim 5 wherein R is selected from among

12. Any preceeding claim wherein (II) includes additional brominated or chlorinated flame retardants or mixtures thereof other than said ester.

13. Claim 8 wherein said additional flame retardants are selected from the group consisting essentially of

14. Any one of claims 1 to 13 wherein the resin is (A) Acrylonitrile-Butadiene-Styrene of the formula

wherein x, y and z may independently vary from 10 to 1,500.

15. Claim 14 wherein a portion or all of acrylic and styrenic monomers comprising the resin include methacrylonitrile or α-methylstyrene, or methacrylonitrile and α-methylstyrene.

16. Claim 15 where the resin comprises monomeric units of a vinyl aromatic monomer, a vinyl nitrile monomer, and a butadiene monomer

17. Any one of claims 1 to 13 wherein the resin is (B) Polystyrene and is one of:

(a) a homopolymer of styrene having the following repeatable unit wherein n is within the range of greater than 1 to about 3,000; (b) a homopolymer of styrene as in (a) modified with rubber in which the rubber is dispersed as discrete 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 of about 2:98 to about 25:75; or (d) blends of (a) and (b); polybutadiene and/or a styrene-butadiene copolymer being preferred.

18. Claim 17 wherein the Polystyrene resin is (B)(a) and is in the form of a foam.

19. Any one of claims 1 to 13 wherein the resin is (C) Polycarbonate which has repeated structural units of the formula:

wherein a is greater than 1 and z is a divalent aromatic radical of a dihydric phenol.

20. Any one of claims 1 to 13 wherein the resin is (D)

Polybutylene Terephthalate and has repeated structural units of the formula:

wherein a > 1.

21. Any one of claims 1 to 13 wherein the resin is (E) a Styrene-Maleic Anhydride Copolymer which has the formula

wherein m is a number from 1 to about 100 and n is a number from zero to about 100.

22. Claim 21 wherein the weight ratio (styrene) : (maleic anhydride) is 1-19:1.

23. Any of claims 1 to 13 where the resin is (F) a

Polyolefin and Substituted Polyolefin comprising polyethylene (low density, linear low density, and high density); polypropylene; ethylenepropylene copolymers; ethylenevinylacetate copolymers; polyvinylacetate; polyvinyl alcohol derived from polyvinylacetate; poly-4-methyl pentene-1; polyisobutylene; polyacrylate esters; and polymethacrylate esters; or physical blends of any of the above with: polystyrene; styrene-butadiene copolymers; chlorinated polyethylene; chlorinated polypropylene; polyvinylchloride; acrylonitrilebutadiene-styrene; polyethyleneterephthalate; polybutyleneterephthalate; polyphenylene oxide; and/or polyphenylene oxide/high impact polystyrene blends.