TETRAHALOPHTHALATE ESTERS AS FLAME RETARDANTS FOR CERTAIN RESINS

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 thermo¬ plastics 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 comono- mers 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 appli- cations 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 manufac¬ ture of packaging material, refrigerator doors, air con- ditioner 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-Oth er "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 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, the teachings of which are incorporated herein by reference. 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 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 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, 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 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 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 -eCHCH 2 θ)yR* where R 8 is an alkyl or substituted alkyl of 1 to 18 carbons, and b is 1 to 50; (c) R 1 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 R 7 is an alkyl of 1 to 18 carbons; a polyhydroxyalkyl of 3 to 12 carbons; *. ' ** R* R 4 R 3 R* I I — CHCHNR 3 R*-. — (CHCH NR 3 . and — (CHCH) 3 N; with the proviso that the vtlence of R 1 is equal to q; (d) R 2 is independently selected from the class consisting of H and CH 3 - ; (e) R 3 , R 4 , R 5 , and R 6 are independently selected from the class consisting of H and an alkyl of 1 to 18 carbons; (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 acryl¬ ic 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 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. In a preferred embodiment of the invention, the homo¬ polymer 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, dichloro- difluoroethane, 1,1,2 trifluoroethane, and 1,1,2 tri- chloroethane. (C) The polycarbonate resin has repeated struc¬ tural 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 re¬ peated 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; ethylene- propylene copolymers ; ethylenevinylacetate copolymers; polyvinylacetate; polyvinyl alcohol derived from poly- vinylacetate; 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; polyvinyl- chloride; acrylonitrile-butadiene-styrene; polyethylene- terephthalate; polybutyleneterephthalate; polyphenylene oxide; and/or polyphenylene oxide/high impact polysty¬ rene blends. Of particular use are: polyethylene; poly- propylene; 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 prefer¬ ably 0), and q is 1 to 6 (most preferably 1). More pre¬ ferably R is SUBSTITUTESHEET -CH 2 -C 4 H 9 ; -CeH 3 , -C 4 H 9 -CH6H X3 , - C 2 H 5 , C 4 H 9 , H, -C 3 H 7 , -CQK- LS , -CgHι 7 , -CH 2 —CHC 4 H 9 , -C 10 H 2 i, I C 2 H 5 , or SUBSTITUTESHEET 14 HO- Br , and q - 1 The invention also comprehends a method for pre¬ paring 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. SUBSTITUTESHEET - 15 Representative tetrahalophthalate compounds useful in practicing this invention are as follows (where A is Br or Cl): C0O(CH 2 SUBSTITUTESHEET 15a - H 0) 7 CH 2 CH 3 SUBSTITUTE SHEET 18 18a The preferred compounds are: 0H CH 2 0) 7av CH 3 sυssfi θ e s \ & - 18b - SUBSTITUTE SHEET CH 3 CH 3 I I The R in the above formulas is -CH 2 -CH-0H or -CH-CH 2 -0H. 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 ευ BS -πτu TE SHE ετ 21 Br Br * a y β n* or βubatitn βd alkylanα 22 ϊ 2 -CHCH 2 0 OCH 2 CH. ■CH. 23 In practicing this invention, (II) the tetrahalophthal¬ ate by itself or additionally with (III) .other brominated and/or chlorinated flame retardants is added to (I) the- resin in any convenient manner, such as blending or ex- truding in order to get a uniform composition. Flame retardant synergists such as antimony oxide (Sb 2 0 3 ) 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 op¬ tionally included. A further advantage of the tetra¬ halophthalates 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: 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 24 of the components above that comprise the ABS resins may be substituted in whole or in part. The ratio of tetrahalophthalate or a mixture of tetrahalophthalate and one or more brominated and/or chlorinated compounds to ABS resins that will impart flame retardancy to the latter may vary from 1:100 to about 1:2 depending on the application. In addition, the ratio of tetrahalophthalate to other brominated and/or chlorinated compounds may vary from 100:0 to about 1:99. (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 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 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. Pasquόn in Encyclopedia of Polymer Science and Technology, Vol. 13, pp. 14, 19-20, and 31 (1970)]. 25 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 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% 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 26 high impact polystyrene greater than about 10% to about 25%. [See H. Keskkula in "Encyclopedia of Polymer Sci¬ ence 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 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-hydro ypheny1)-methane; bis-(4-hydroxyphenyl)-methane; bis-(4-hydroxy-5-nitropheny1)-methane; 1,1 bis(4-hydroxypheny1)-ethane; 3,3 bis-(4-hydroxyphenyl)-pentane; 2,2' dihydroxydiphenyl sulfone; 4,4' dihydroxydiphenyl ether; and 4,4' dihydroxy-2,5-diethoxydiphenyl ether. 27 Example 1 To 1,3929(3.0 aoles) of tβtrabromophthalic anhydride were -added 1,050 9(3.0 aoles) of Hβthoxy Carbowax 350 in tha presence of 22.0 g of sodium acetate. The mixture was heated at 90*C for 8 hours in a nitrogen ataosphere. The reaction mixture vas filtered hot to remove the sodium acetate. The analytical data were consistent with the assigned structure. 7av CH 3 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 a-t 60*-100*C. 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: 89/03854 28 Example 3 To 92.19(0.2 mole) of tetrabromophthalie anhydride is added all at once SO 9(0.2 mole) of Carbowax 400 and the mixture heated to 120*-!>130*C for 2.5 hours. The desired product is isolated in essentially quantitative yield as a clear yellow viscous liquid. Calcd. Mol. Wt., 864 found 865. Calcd. % Br, 37,1; found, 38.5. The analytical data are consistent with the assigned structure: Br Br Example 4 To 240 9(0-.24 mole) of the compound of Example 3 is added 45.3 g(0.24 mole) of trimellitic anhydride and heated at 155*C under nitrogen for abut 7 hours. The infrared spectrum indicated the completion of the reaction by the substantial disappearance of the anhydride absorption band at 5.65. The product was isolated in essentially quantitative yield. Analy. Calcd.; 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: cooϊ 29 Example 5 To 136.39(0.18 mole) of the compound of Example 3 is added 70.9 g(0.18 molβ)2,3-dibromopropyl tri βllitatβ. The mixture is heated at 130*-140*C 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: Br , (and isomers) 30 Examples 6 to 11 The following preparation were carried cut as in Example 1 using the reactant set forth below. Tetnbromophtlulic Example No. Anhydride Hydroxy Compound Product Structure 1.0 mote 1.0 mote 3 Examples 6 to 11 - continued The following preparation were carried out as in Example 1 using the reactant set forth below. Tetrabromophthalic Example No. Anhydride Hydroxy Compound Product Structure 10 1.0 mole 11 2.0 mole HCXCH ∑ CHzOfcH (Cartowax 400) 1.0 mole 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-tβluen* l ulfonic acid. The mixture is heated to reflux until 3.6 9(0.2 mole) water was collected. The toluene is removed under reduced pressure-to give a clear viscous liquid in essentially quantitative yield. COO(CH 2 CH 2 0) 5βy H 9/03854 32 Example 13 To §6.4 9(0.1 mole) of the compound of Example 3 is added all a once 21.• 9(0* mole) pyromellitic dianhydride and the mixture heate to 120*-130 # C 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 once 10.9 g(00.05 mole) of pyromellitic dianhydride and the mixture heated to 120*-130*C for 2.5 hours to give the desired product. Th analytical data are consistent with the assigned structure: (aad Example IS To If.4 9(0*1 mole) of the compound of Example 3 is added all once 21.t 9(0.1 aele) of phthalie anhydride and the mixture heate 120*-i30*C for 2.5 hours to give the desired product. The analyt data are consistent with the assigned structure: 33 Example 16 To 139.2 9(0.3 mole) of tetrabromophthalie anhydride is added all at once 122.99(0.1 mole) polyoxyethylated trimethylol propane of molecular weight 1229 and the mixture heated to 120*-130*C 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 al at once 156.8 g (0.1 mole) polyoxypropylatβd trimethylol propane of molecular weight 1568 and the mixture heated to 120*-130*C for 2.5 hours to give the desired product. The analytical data are consisten with the assigned structure: 34 Example 18 To 214,0 9 ( 1.0 mole ) of t β trachlorophthalic anhydride is added 350.0 gd.O mole) of Mβthoxy Carbowax 350 in presence of 7.0 g of sodium acetate. The mixture is heated at 90*C 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 gd.O mole) of the composition of Example 18 is added 116. (2.0 moles) of propylene oxide in 200 ml of toluene. The reaction mixture is heated from 60*-100 # C for 3-5 hours, and then concentrated to give the product in nearly quantitative yield. The analytical data are consistent with the assigned structure: 35 Example 20 To 284.09(1.0 mole) of tetrachlorophthallc anhydride is added 200.0 gd.O mole) of Carbowax 200 in the presence of 7.0 g of so d ium acetate. The mixture is heated at 90*C 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 434.0 g(1.0 mola) of the product of Example 21 is added 116.0 9(2.0 mole) of propylene oxide in 200 ml of toluene. The reaction mixture is warmed at 60*-100 C 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 214.09(1.0 mole) of tetrachlorophthallc anhydride is added 400.0 gd.O mole) of Carbowax 400 in the presence of 7.0 g of sodiu acetate. The mixture is heated at 90*C for • hours in a nitrogen atmosphere. The reaction mixture is filtered hot to remove sodium acetate to generate the expected product in nearly quantitative yie The analytica th the assigned structure: 36 Example 23 To 46.4 9 ( 0.1 sole) of tetrabromophthalie anhydride is added all at once 44.1 9(0.1 mole) of polyoxyethylated dimathylamine [CH 3 ) 2 N(CH 2 CH 2 0) g Hj dissolved in 100 ml of toluene. The mixture was heated at 100*-110 # C 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 92.3 g(0.2 mole) of tetrabromophthalie anhydride is added 80 g(0.2 mole) of (Jeffamine D-400) and the mixture heated to about 120*C. The final product is obtained in almost quantitative yield. The analytical dat are consistent with the assigned structure: 37 Example 2S Poly(ethylene glycol 300), 204.5 g (0.67 mole) was refluxed (T = 117 β C) wich 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 50 β C, propylene oxida, (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 50'C 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. Example ** This compound was prepared by the procedure described 1 in Example 25 except that poly(echylene glycol 200) was used in place of poly(ethylene 300). Product is viscous Liquid. 38 Calcd . % Br , 51.0 . Found % Br, 49.3. Analytical data w is consistent with the assigned structure . Example 27 This compound was praparad by tha procadura described in Example 25 except that polyethylene glycol 600) was us in place of poly(ethylene glycol 300). Product is a viscous liquid. Calcd. % Br, 39.5. Found % Br, 39.2. Analytical data is consistent with. -the assigned stricture. E mp e 21 This compound was prepared by the procedure described iα Example 25 except that poly(ethylene glycol 400) was u∑»d ia place o£ poly(ethylene glycol 300). Product is a viscous liquid. Calcd. Br, 44.2. Found % Br, 44..0. Analytical data is consistent with the as igned structure. 39 Example 29 ' Methanol (54. 1 g, 1.5 mole), tetrabromophthalie 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 houra. 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 Exaaple 29 except that aethox carbowax 350 vas used in place of aethanol and ethylcne oxide in place o-f propyleαe oxide. Calcd. I Br, 37.8. Found m * Br, 37.2. Analytical data is consistent with assigned structure. 40 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 epoxy utane iα place of propylene cxide. Product is a viscous liquid. Calcd. *4 Br, 36.5. Found.*; Br, 37.2. Analytical data is consistent with the assigned structure. Examp e 33. This compound was prepared by the procedure outlined Example 22L except that 2- thylhexanol-l was used in place 41 ■ethanol. 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. % 3r, 41.0. Found Br, 43.0. Analytical data is consistent with the assigned structure. Example 35 This compound was prtpared by the procedure described in Example 29 except that 2 ,3-dibroao-propanol- was used place of aethanol. Product is a viscous liquid. Calcd. % 42 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 1a 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 methox carbowax 350 (300.0 g, 0.89 aole) ia drj toluene (184 ml) was added sodium methoxide 48.0 g, 0.90 mole) ia methanol. The aethanol was then distilled off atmospherically. Tetrabroaophthalic anhydrid was then added (442.2 g, 0.89 aole) along with an additional. 50 al of toluene. The reaction mixture was refluxed for 2 hours and after cooling to room temperature, epichlorchycri (106.94 g, 1.16 moles) was added. The mixture was refluxed 43 for 20 hours. After the solvent and excess epichlorohydrin were distilled, a viscous dark product was obtained. Calcd. X Br, 37.2. Found % Br, 40.4. Analytical data is consistent with assigned structure. Example 38 Me hoxycarbowax 350 and toluene were refluxed for 1 hour in order to distill out a small amount of water. Tetrabromophthalie 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 diarome hane (prepared from the decomposition of N-βethyl-N-nicroso-p-to uene sulfonamide by sodium hydroxide) in ethyl ether was added and the mixture allowed Co stand overnight. The excess diazoae hane 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. 44 Example 35 " Di(2-ethylhexyl) tetrabro ophthalate 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) 835.4 g (1.40 moles), tetrabromophthalie 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, ethylcne oxide, 246.68 g (5.60 moles) was pumped into the reactor in 3/4 hour while maintaining the temperature at 120*C. After one hour Longer of beating, the mixture was cooled to room temperature, the excess ethylβne 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. 45 Calcd. % Br, 39.2. Found % Br, 38.8. Analytical da t a 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 eonsistaac w th the assigned structure. Example 42 Tetrabromophthalie anhydride, 231.9 g (0.50 mole), 2- thylhexano , 130.2 g (1.0 aole). and potassium acetate, 46 0.24 g were heated to and kept at 120 # C for 4 hours. The mixture was cooled to 60 β C and potassium carbonate, 35.9 g (0.26 mole), was added. Reheated mixture to 80*C and kept it at this temperature for 2 hours. Cooled mixture to 6 °C and added triethylamine, 14.2 g (0.14 mole). Reheated mixture to 70*C and added methyl iodide, 113.6 g (0.8 mole) in 20 ainutas. Kaat-ad aixtura to 70-75 a C and kapt it at this temperature for 2 hours. Cooled mixture to room temperature and filtered it in order to remove by-prod_uct 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 nil of a 6.5% potassium carbonate solution followed by 2 tines 100 ml of water and once with a 30% sodium chloride solution. Dried the organic phase over anhydrous majnesiua 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. % Ir, S2.6. Found % Br, 52.2. Analy ical data is consis sac with the assigned structure. 47 Example <3 Tetrabromophthalie anhydride, 231.9 g (0.5 mole), 2-[2- me hoxyethox J-ethanol, 360.5 g (3.0 aoles), stannous oxalate, 2.32 g , and xylene, 200 ml, were refluxed (temp. l60 β C) for 18 hours during which time, theory water was collected. The xylene and excess 2-[2-aβthoxyethoxy]-ethanoL were diatillad undsr rαducsd aasurα to g e 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 imes 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 struc ure. 48 Example .44 This compound was prepared by the procedure outlined in Example 43 except visή»g 2-(2—βthoxy hoxy]-ethanol, Exaπio1e 5 This compound was prepared by the procedure outlined in Example 1 except that docosyl alcohol (behen l 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. Examp e 4t This compound was prepared by the procedure outlined 17 Example 1 except that tricontyl alcohol was used in place 0. 49 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. 50 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 = l,2-bis(2,4,6-tribromophenoxy)-ethane (70% Bromine) DOTBP = Dioctyl tetrabromophthalate (45% Bromine) AO = Antimony Oxide 51 Table I (A) Example No 48 (b) •49 (c) 50 51 ABS (a) 100 DTBPE DOTBP AO UL-94 @ 0.125" Failed @ 0.062" Failed (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). 52 Examples 52-55 Impact strength of the various materials were deter¬ mined according to ASTM D256. NOTCHED IZOD IMPACT (ft-lb/in notch) 3.34 1.26 1.98 1.66 (a) CycolacST, 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. 53 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 DTBPE DOTBP AO 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 inven¬ tion. 54 Examples 59-64 Compositions With Polystyrene Resins In the following examples, the flame retardancy of the compositions of this invention are demonstrated. The compositions were prepared by mixing together the flame retardants, antimony oxide, and high impact poly¬ styrene 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 55 Table 1(B) Example No 59 (b) 60 (c) 61 62 63 64 Percentage Composition HIPS ( ) 100 DBDPO DOTBP AO UL-94 @ 0.125" Failed @ 0.062 Failed (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" speci¬ mens. Examples and clearly demonstrate that the total bromine levels can be reduced when the compo- sitions of this invention are used and still yield comparable or better flame retardancy. 56 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. 57 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 DBDPO 12 DOTBP AO 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. 58 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 com¬ pounds were blended thoroughly. The compounds were pel¬ letized 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) 59 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/cm 2 60 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 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- tion results in greatly enhanced flow characteristics as shown 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 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. 61 Examples 80-86 Compositions With PBT Resins In the following examples, the flame retardancy of the compounds of this invention are demonstrated. The compositions were prepared by mixing together the flame retardants, antimony oxide, and polybutylene terephthalate (PBT) on a roller until the compounds were blended thor¬ oughly. 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 con- trol 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 62 TABLE I (D) (a) "Celanex" 2000, a product of Hoechst-Celanese Corp., U.S.A. (b) control (100% polybutylene terephthalate) (c) comparison (no tetrahalophthalate ester) 63 The above clearly demonstrates the flame retardancy of the compositions of this invention relative to the control. These compositions have at least equivalent flame retardancy to the BPC conventional flame retardant used in PBT (Example 81). Examples 81-83 are all run at equal bromine levels. Partial or total replacement of the conventional flame retardant (BPC) with the compositions of this invention results in enhanced flow characteristics as shown by the improved melt flow properties measured according to ASTM D-1238. Examples 84-86 The following tests were performed on the various materials according to the appropriate ASTM method. 1. Impact Strength - ASTM D-256 2. Tensile Strength - ASTM D-638 3. Heat Deflection Temperature (HDT) - ASTM D-648 4. Melt Flow - ASTM D-1238 64 Example No PBT (a) BPC DOTBP Antimony Oxide LOI 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) W % 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) Ti "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/cm 2 65 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 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 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. 66 SMA = Styrene-Maleic Anhydride Polymer DBDPO = Decabromodiphenyl Oxide (83% Bromine) DOTBP = Dioctyl Tetrabromophthalate (45% Bromine) AO = Antimony Oxide 67 TABLE I (E) Example No 87 (b) 88 (c) 89 90 91 SMA (a) 100.0 DBDPO DOTBP Antimony Oxide UL-94 Rating @ 0.125" Failed V-0 @ 0.063" Failed 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 68 (DBDPO) with the compositions of this invention results in enhanced flow characteristics as shown by the improved melt flow properties measured according to ASTM D-1238. Examples 92-95 The 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 Example No SMA (a) DBDPO DOTBP Antimony Oxide LOI 18.7 27.6 28.6 23.1 UL-94 Rating (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/cm 2 70 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 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 pro¬ cessability of the styrene-maleic anhydride copolymer resin containing compositions of this invention.

Claims: 71 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; 72 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 73 (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; (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 •tCHCH&is*-* 74 where R 8 is an alkyl or substituted alkyl of 1 to 18 carbons, and b is 1 to 50; (c) R 1 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 —C—R 7 where R 7 is an alkyl of 1 to 18 carbons; a polyhydroxyalkyl of 3 to 12 carbons; tι l .,-O '" -, R 3 R 4 R 3 R* R 3 R 4 -C 1 HC *HNR S ,R **; — (C IHC I H)ιNR s <: mά — (C IHC I JOjN; with the proviso that the valence of R 1 a equal to q; (d) R 2 is independently selected from the class consisting of H and CH 3 -; (e) R 3 , R 4 , R 5 , and R 6 are independently selected from the class consisting of H and an alkyl of 1 to 18 carbons; (f) p is an integer of 0 to 50; 75 (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. 6. Claim 5 wherein p is zero, q is one and X is oxygen. 7. Claim 6 wherein R and R 1 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 76 I J -CH 9 CH-0H, -CH 3 , -C Hc . -CH, -C H • -r u r u ^"6 0 13. -<-8Λi7 -CH2CHC 4 H9, -C 10 H 2l C 2 H 5 ; R i is CH 3 , C 2 H 5 , C 4 H g , H, • C 3 H 7 , -C β H 13 , -C 8 H 17 , -CH^-CHC 4 H 9 , -C 10 H 2I> c 2Hs, or 3r 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 ■ 77- 0 OH 0 re tuted alkylene Br TU7Ξ SHEET -78- H0CH 2 CH 2 0 CH 2 CH 2θ SUBSTITUTE SHEET 79 14. Any one of claims 1 to 13 wherein the resin is (A) Acrylonitrile-Butadiene-Styrene of the .formula acry onitrile butadiene styrene 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 meth¬ acrylonitrile 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 80 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 dis¬ persed as discrete particles Into a matrix of said 10 homopolymer and the weight ratio of rubber to homo¬ polymer 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 15 25:75; or (d) blends of (a) and (b); polybutadiene and/or a styrene-butadiene copolymer being preferred. 18. Clai -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) 20 Polycarbonate which has repeated structural units of the formula: 25 81 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. 82 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; poly- isobutylene; polyacrylate esters; and polymeth¬ acrylate esters; or 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.

Inventors: BOHEN JOSEPH MICHAEL, LOVENGUTH RONALD FRANCIS, BOHEN, JOSEPH, MICHAEL, LOVENGUTH, RONALD, FRANCIS
Applicants: PENNWALT CORP, PENNWALT CORPORATION
Application year: 1988
Main classification: C08K5
IPC codes: C08K5, C08L23, C08L25, C08L35, C08L55, C08L67, C08L69