JPH02502026A - Tetrahalophthalate esters as flame retardants for certain resins - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] FIELD OF THE INVENTION As a flame retardant for resins consisting of... The present invention provides at least one tetrahalophthalate ester and Regarding flame retardant compositions containing various types of resins: (A) Acrylonitrile-butadiene-styrene (ABS) terpolymer resin: (B) Polystyrene resin: (C) Polycarbonate resin: (D) Polybutylene terephthalate resin: (E) Styrene-maleic anhydride (SMA) copolymer resin: and CF) Polyolefin and substituted polyolefin resins.

In addition, the compositions of the present invention include 1 present in an effective amount to provide additional flame retardant properties to the resin. It may contain more than one brominated and/or chlorinated compound.

Explanation of related technology... ] is characterized by excellent properties such as chemical resistance, abuse resistance, and stain resistance.

It is known as a thermoplastic resin. Typical properties of ABS resin were developed in 1975 by M. Charles A, published by cGrav-Former 11 Publishers.

Harper's "Plastic and Elastomer Handbook" ook or Plastics and Elastomers) J 1-6 4.1-66 and 1-68. These pages apply mutatis mutandis to strings.

ABS resins are generally derived from acrylonitrile, styrene and butadiene. It is a terpolymer. In most cases, acrylonitrile and styrene are true graft polymers that are grafted onto a rubber phase or a rubber phase; It is further dispersed in a rigid styrene-acrylonitrile (SAN) matrix. stomach. Other ABS resins are elastic and hard copolymers, such as butadiene-acrylic A mechanical polyblend of ronitrile rubber and SAN. (G, C, Eavk ins.

“Condensed Chemical Dictionary,” 10th edition , p. 3° 1981 and U.S. Pat. No. 4.107.232, 4.206.29 No. 0, No. 4.487.886, No. 4.567, No. 218 and No. 4.579.906 (Please refer to each specification; all of these apply mutatis mutandis to strings). The above 1awkins are ABS trees. defines fats as follows: ``Their names refer to the three monomers that produce them.'' Any toughness obtained from two characters namely acrylonitrile-butadiene-styrene A group of rigid thermoplastic resins. Most current ABS resins are made of steel due to compatibility. Elastic polybutadiene grafted with ethylene and acrylonitrile monomers or A true graft polymer consisting of a rubber phase is hard styrene-acrylonitrile (SAN ) are dispersed in a matrix. Historically the first ABS resin elastic and hard copolymers such as butadiene-acrylonitrile rubber and SAN. Mechanical polyblends are also commercially available.

Changing the ratio of these three monomers and using other comonomers and additives By changing the composition of the polymer, ABS resins with a wide range of properties can be created. can get. ” The general chemical structure of ABS is as follows: (where x, y and 2 are independently about 10-1500).

(See U.S. Pat. No. 4,567,218; its teachings apply mutatis mutandis to strings.) Analogs of each of the above monomeric components may be substituted in whole or in part, and they are It should be understood that it falls within the definition of S resin. For example, α-methylstyrene is used instead of ethylene, and methacrylate is used instead of acrylonitrile. Lonitrile may be substituted. Information on various ABS resin compositions and their manufacturing methods A description of this can be found in U.S. Pat. 98.313, 2.713.566, 2.820.773, 2.908. No. 661, 4, No. 107.232, No. 4.173.561, No. 4.200.702 No. 4.206.290, 4, 289.687, 4.355.126, 4 ．． 379.440, 4.456.721, 4, 487.886, and 4. 581.403, and their teachings apply mutatis mutandis to the pillars.

ABS resin is used in automobiles, business machinery, telephones, etc. that require high impact resistance. It is useful in many industrial applications such as , as well as the production of molded articles.

Polystyrene resins are used in packaging materials, refrigerator doors, air conditioning cases, mechanical storage, and electrical equipment. equipment, toys, clocks, TV and radio cabinets, insulation, ice cubes, containers, It has a wide range of uses in furniture structures, home appliances, tableware, etc.

The preparation and description of polystyrene and expandable polystyrene are well known in the art. Ru. They are G. Hawley, “Con-densed Chemical Encyclopedia, 10th edition, pages 838 and 976 (1981) ;　Kirk-Othsar　”　Encyclopedia of Chem ical Technology,” 2nd edition, Volume 9, pp. 847-884 (19 66) and Volume 19, pp. 85-134 (1969): A, E, Pla tt, “Encyclopedia or PolymerScience a nd Technology+” Volume 13, pp. 156-189 (1970); and U.S. Pat. No. 4.281. (No. 167, No. 4.298.702, 4, 419. No. 458, No. 4.497.911, No. 4.548.956, No. 4.596.682 No. 4.618.468, and the teachings of these Applies mutatis mutandis to strings.

For many applications in which styrenic polymers are used, the materials are flammable. To achieve this, it is necessary to add flame retardants. Requires flame retardant styrenic material Applications include radio and television cabinets, toys, electrical equipment, furniture. structures (e.g., U.S. Pat. Nos. 4.341.890 and 4.548.9). (See each specification of No. 56, the contents of these teachings apply mutatis mutandis to SA).

Polycarbonate resins have electrical dimensional stability, high impact strength, toughness and flexibility. It is known as a thermoplastic resin that is characterized by excellent properties such as properties. one Generally they are dihydric phenols and carbonate esters, phosgene or vista. Produced by reaction with loloformate ester. U.S. Patent 2.999.83 No. 5, No. 3.169.121, No. 3, 879.348, No. 4.477, No. 632, 4.477, 637, 4.481.338, 4, 490.504, 4.5 32.282, 4.501.875, 4.594.375 and 4.615 ．． The specifications of No. 832 explain in detail the production of polycarbonate resins, These disclosures apply mutatis mutandis to strings.

Due to their many excellent properties, polycarbonate resins have become a hot topic in engineering It is useful in industrial applications as a plastic resin and in the production of molded articles.

It is known as a thermoplastic resin that is characterized by excellent properties such as properties. one Generally they are terephthalic acid or diesters of terephthalic acid such as dimethyl By polycondensation of terephthalate (DMT) and 1,4-butanediol Manufactured. U.S. Patent Nos. 2.645.319, 3.047.539, 3,95 No. 3.394 and No. 4.024.102 discuss the manufacture of PBT.

Styrene-maleic anhydride (SMA) copolymer resins are used for the manufacture of molded and foamed products. It has a wide range of uses in construction. Generally they suit styrene and maleic anhydride It is produced by copolymerization in appropriate ratios under appropriate conditions.

A method and description of SMA copolymers is provided in U.S. Patent No. 2.769. go4 issue, 2.97 1.939, 3.336.267 and 3.966, 843. The contents of these teachings apply mutatis mutandis to the string.

SMA polymers burn quickly and are commonly used in radio and television cabinets. , for applications requiring flame-retardant polymers such as tables, chairs, and appliance storage. (See U.S. Pat. No. 4.151.218, which applies mutatis mutandis to strings) .

Brominated and/or chlorinated compounds themselves or organic phosphates, boron compounds, etc. As a flame retardant for ABS resin compositions in combination with any other materials The use of U.S. Pat. 4, No. 096.206, No. 4.107.122, No. 4.107.232, 4.1 73.561, 4, 200.702, 4.289.687, 4.579. No. 906, No. 4.355.126, No. 4, No. 378.440, No. 4.567, 218 No. 4.581.403, No. 4.581.409 and No. 4.600.747. Illustrated by the specification. The above patent shall apply mutatis mutandis to strings.

Tetrahalophthalate esters are used as flame retardants. For example, rice National Patent No. 4.018.704 describes the use of these materials as textile finishing agents. The purpose is stated. U.S. Patent Nos. 4.298.517 and 4.397.977 The specification discloses these compounds as flame retardants for halogenated resins. death However, these compounds have not been shown as flame retardants or processing aids for ABS resins. No teachings have been found yet.

Outline of Part 1 The present invention includes a flame-retardant plastic composition comprising the following components as a mixture: It is something that

(1) Resin selected from the following: (A) Acrylonitrile-butadiene - Styrene (ABS) terpolymer resin; (B) Polystyrene resin: (C) Polycarbonate resin; (D) Polybutylene terephthalate resin; (E) Styrene-maleic anhydride (SMA) copolymer resin: and (F) Polyolefin and substituted polyolefin resin.

(n) An effective flame retardant amount of tetra represented by the following general formula introduced into the resin of (1) Halophthalate ester flame retardant processing aid: [In the formula, (a) The ring may have all possible isomeric configurations: (b) R is hydrogen, alkyl or substituted alkyl of 1 to 30 carbons, 2 to 20 carbons; hydroxyalkyl of 3 to 10 carbons, polyhydroxyalkyl of 3 to 10 carbons (wherein %R" is alkyl or substituted alkyl of 1 to 18 carbons, and b is 1 to 50) selected from the group consisting of: (c) R' is hydrogen, alkyl or substituted alkyl of 1 to 30 carbons, 2 to 22 alkenyl or substituted alkenyl of 5 carbons, R here? is alkyl of 1 to 18 carbons: polyhydroxy of 3 to 12 carbons Sialkil 211dan 2wa 1 (A) In the above ABS resin, the acrylic and styrene monomers that make up the resin Some or all of the polymers are methacrylonitrile, α-methylstyrene, or is preferably a meta or styrene-butadiene copolymer.

In a preferred embodiment of the present invention, the homopolymer of (B) and (a) above is In the form of Listyrene foam. The foam preferably comprises repeatable homopolymer units. It is preferably produced by polymerization in the presence of a liquid or a liquid blowing agent. The blowing agent has a boiling point below the softening point of polystyrene and is capable of dissolving polystyrene. do not have. Preferred blowing agents hapropane, butane, pentane, hexane, heptane, silane Kurohegyusan, methyl chloride, dichlorodifluoroethane, 1,1.2) Refluor selected from the group consisting of one or more of 1, 1.2) dichloroethane, and 1, 1.2) dichloroethane. .

(C) Polycarbonate resin has a repeating structural unit of the following formula: where a is greater than 1 and 2 is a divalent aromatic group of a dihydric phenol: (D) The polybutylene terephthalate resin used in the present invention has the following formula: Having a return structural unit: in the formula, a>l.

(E) The SMA resin used in this invention usually has the following shell structural formula: In the formula, m is 1-100 and n is 0-100.

The weight ratio of (styrene):(maleic anhydride) is 1 to 19:1.

(F) Useful polyolefins and substituted polyolefin resins include polyolefins and substituted polyolefin resins. Ethylene (low density, linear low density and high density); polypropylene: ethylene-propylene Pyrene copolymer: ethylene vinyl acetate copolymer; polyvinyl acetate; polyvinyl acetate polyvinyl alcohol derived from poly-4-methylpentene-1: Isobutylene: polyacrylate ester: and polymethacrylate ester Which can be mentioned. Also useful are physical blends of any of the above with: is: polystyrene; styrene-butadiene copolymer: chlorinated polyethylene; Chlorinated polypropylene; polyvinyl chloride; acrylonitrile-butadiene-styrene Ren: polyethylene terephthalate; polybutylene terephthalate: polyphenylene Lennogyushito: and/or polyphenylene oxide/impact-resistant polystyrene Indian thing. Particularly useful are polyethylene; polypropylene: polyacrylate and polymethacrylate: alone or in the physical blend. .

In the above tetrahalophthalate ester (II), R is a carbon atom of 1 to 10 carbon atoms. alkyl or substituted alkyl, A is Br%X is oxygen, p is O~20 (most preferably is O), and q is preferably 1 to 6 (most preferably 1). more preferable R is RI is CB,, CtHs, c, n,, H, -CsBt, -C-Eta, -C- Hlt, the present invention also provides flame retardant effective amounts of one or more of the above tetrahalophthalenes of (I[). Enhanced processing characterized by the introduction of esters into one or more of the above resins. Also included are methods for producing flame-retardant plastic compositions having such properties.

The present invention also includes the above-mentioned tetrahalophthalate compound alone or in combination with other compounds in the resin. of certain resins by introducing them in combination with brominated and/or chlorinated flame retardants. Also included are methods for improving physical properties such as flame retardancy, processability, and impact strength.

The resins are sold on the basis of their impact properties. Unfortunately, that Such materials must be flame retardant with conventional flame retardants to meet regulatory requirements. If not, there is a considerable loss of impact strength.

Representative tetrahalophthalate compounds useful in the practice of the present invention are listed below. (wherein A is Br or CI): Preferred compounds A are as follows: Brominated and/or chlorinated compounds used in combination with tetrahalophthalates is any of the known compounds. Specific examples of preferred halogenated flame retardants include These include: In carrying out the present invention, (It) tetraphthalate itself or (m) other Adding brominated and/or chlorinated flame retardants to (1) the resin in any conventional manner For example, they may be added by blending or extrusion to obtain a homogeneous composition. as necessary Optionally, flame retardant synergists such as antimony oxide (SbyOs) may also be added. Canada In addition, other additives such as heat stabilizers, UV stabilizers, reinforcing agents, organic polymerization Optionally, agents such as mold release agents, blowing agents, coloring agents, etc. may also be included. used in the present invention Tetrahalophthalates alone or other brominated and/or chlorinated compounds A further advantage of the combination with materials is their improved compatibility with resins. .

color 1 hair rich star 2 and j (A) The ABS resin used in the present invention is generally made of acrylonitrile, It is derived from styrene and butadiene and has the following general structure: acrylonitrile butadiene styrene (where x, y and 2 are independently about 10 ~1500). Analogs of each of the above components constituting ABS resin It is understood that full or partial substitutions may be made.

Tetrahalophthalate or tetrahalophthalate and one or more brominated and/or is the ratio of the mixture of chlorinated compounds and ABS resin that imparts flame retardancy to the latter, depending on the application. It ranges from 1:100 to about 1:2 depending on the ratio. In addition, tetrahalophthalate and other brominated and/or chlorinated compounds ranges from 100:0 to 1:99. It is surrounded by

(B) Styrenic resins used in the present invention include the following. Immediately Polystyrene homopolymer in both crystalline and non-crystalline form: expandable polystyrene Ren beads, medium impact polystyrene, high impact polystyrene (HIPS) ), and rubber-modified polystyrene, including ultra-high impact polystyrene.

In the styrene homopolymer, n is greater than 1 for both crystalline and non-crystalline properties, and about 200 It has the following repeating units from 0 to 3000. Non-crystalline forms are generally styrene using a peroxide catalyst as described in U.S. Pat. No. 4,281,067. crystalline stereoregular isotactic The configuration uses Ziegler-Natta catalyst [1. Pa5quon, En cyclopedia of Polymer 5science and Tec hnology, Vol. 13, pp. 14.19-20 and 31 (1970)] .

Expandable polystyrene beads are made by introducing a volatile blowing agent during the polymerization of styrene. It is manufactured by.

Blowing agents used to foam polystyrene are well known. they are liquid Or it is gaseous, does not dissolve the styrene polymer, and has a boiling point below the softening point of the polymer. (see column 6 of US Pat. No. 4,618,468). A suitable blowing agent Fats such as propane, butane, pentane, hexane, heptane, cyclohexane group hydrocarbons or methyl chloride, dichlorodifluoromethane, 1.1.2) Ref. fluoroethane, 1,1.2) dichloroethanato halogen hydrocarbons.

Mixtures of the above may also be used. Typically, the blowing agent is about 2 to 20 wt. used in an amount of %.

Suitable rubber-modified polystyrenes include medium-, high-, and ultra-high-impact polystyrenes. Contains various types. In these compositions, the rubber is dispersed as discrete particles in the polystyrene. (see US Pat. No. 4,341,890). many rubber deformities Synthetic styrenes are made by combining styrene with polybutadiene or styrene-butadiene copolymerization. It is produced by polymerization in the presence of rubber such as rubber (SBR).

During polymerization, some grafting of styrene to the rubber occurs. rubber vs polystyrene The weight ratio of the ingredients ranges from about 2:98 to about 25:75. Generally, lieutenant High-impact polystyrene contains about 4% to about 4% rubber2, and high-impact polystyrene contains about 4% to about 4% rubber. Containing more than about 10% and up to about 25% rubber Encyclopedia of Polymer and Tecbnlog ! ”+ vol. 13, pp. 396 and 400-4o4 (1970).

(C) The polycarbonate resin used in the present invention is disclosed in U.S. Patent No. 3.334. ．． Typical dihydric phenols are used, such as those disclosed in US Pat. this The patents apply mutatis mutandis to the present invention. They are: 2.2 bis-(4 -hydroxyphenyl)-propane; hydroquinone: resocicinol: 2.2bis-(4-hydroxyphenyl)-pentane: 2.4'dihydroxydi Phenylmethane; bis-(2-hydroxyphenyl)-methane: bis-(4-hydroxyphenyl)-methane; Droxyphenyl)-methane; bis-(4-hydroxy-5-nitrophenyl) -Methane: 1.1 bis(4-hydroxyphenyl)-ethane; 3.3 bis(4-hydroxy phenyl)-pentane: 2.2' dihydroxydiphenyl sulfone; 4.4' di Hydroxy diphenyl ether: and 4,4' dihydroxy-2,5-jetoxy 1050 to tetrabromophthalic anhydride of cidiphenyl 1392y (3.0 mol) 9 (3,0 mol) of Methoxy Carbovax 350 with 2z09 of vinegar was added in the presence of sodium chloride.

The mixture was heated at 90° C. for 8 hours in a nitrogen atmosphere. Filter the reaction solution at high temperature and add vinegar. Sodium acid was removed. The analytical data were consistent with the following assigned structural formula. .

Example-12 The compound of Example 1 was added with 34&0y (6.0 mol) of propylene oxide and 2g of toluene. Added ene. The mixture was heated at 606-100°C. Solvent and residual oxyp Removal of lopyrene gave the product in almost quantitative yield. Analysis data is attributed below. It matched the structural formula.

92.89 (0.2 mol) of tetrabromophthalic anhydride to 809 (0.2 mol) Add Carbowax 400 all at once and heat the mixture to 120~130°C. The mixture was heated for 25 hours. Clear, yellow, viscous liquid with virtually quantitative yield of desired product isolated as. Calculated molecular weight: 864; Actual value: 865° Br% calculated value: 3 7.1: The measured M3B, 5° analytical data is consistent with the assigned structural formula below. Ta.

Example 4 2409 (0.24 mol) of the compound of Example 3 was added to 45.39 (0.24 mol) of the compound of Example 3. Add water trimellitic acid and heat at 155° C. for about 7 hours under nitrogen. infrared spec Completion of the reaction was indicated by the virtual disappearance of anhydride absorption at 5.65 torr.

The product was isolated in virtually quantitative yield. Calculated analysis value: 81% 30.3%; molecule Amount 1056; Neutralization equivalent 352: Actual value; 81% 29.4: Molecular weight 1014; Neutralization The equivalent weight 351° spectral data was consistent with the structural formula below.

156.3y (0.18 mol) of the compound of Example 3 to 70.99 (0.18 mol) of 2.3-dibromopropyl trimellitate. While stirring the mixture Heating at 130''-140°C for 6 hours yields the product as a brown opaque oil.

Isolation affords the product in virtually quantitative yield and analysis is consistent with the following structural formula: (and isomers) Example 6 The following preparation was carried out in the same manner as in Example 1 using the following reactants: 96.49 (0.2 mol) 1609 (0.2%) of tetrabromophthalic acid in Carbowax 400 and 1. Oy p -) 300 g toluene containing luenesulfonic acid Add the ingredients all at once. The mixture was added until 3.69 (0.2 mol) of water was collected. Heat reflux. Toluene is removed under reduced pressure to produce a clear viscous liquid in virtually quantitative yield. sell.

86,49 (0.1 mol) of the compound of Example 3 was added to 21.89 (0.1 mol) of the compound of Example 3. Add water pyromellitic acid all at once and heat the mixture to 120~130℃ for 25 hours. to obtain the desired product. Add 1.8y (0.1 mol) of water to open the remaining anhydride groups. After circular analysis, the analytical data is consistent with the assigned structural formula: 86.4y (0.1 mol) of the compound of example 3 was added with 10.99 (0.05 mol of O) Add 7 J of pyromellitic dianhydride at once] and heat the mixture to 120°-130°C for 25 minutes. The desired product is obtained by heating for a certain period of time. The analyzed data is consistent with the following imputation structure: (and isomers) Example 15 86,49 (0.1 mol) of the compound of Example 3 to 21.89 (0.1 mol) of anhydrous Add the phthalic acid in one portion and heat the mixture to 120'-130°C for 25 hours until the desired Obtain the product. The analyzed data conforms to the following imputation structure: To 139.2y (0.3 mol) of tetrabromophthalic anhydride, 1219y (0.1 moles) of polyoxyethylated trimethylolpropane with a molecular weight of 1229 at once. and heat the mixture to 120a-130<0>C for 25 hours to obtain the desired product. minutes The analytical data are consistent with the following assigned structure: 139.2y (0.3 mol) of anhydrous tetra Bromophthalic acid contains 156.89 (0.1 mol) of polyoxy with a molecular weight of 1568. Propylated trimethylolpropane is added and the mixture is heated at 1206-130°C for 2 hours. The desired product was obtained by heating for 5 hours. The analytical data is consistent with the following assigned structural formula: 2 84.09 (1.0 mol) of tetrachlorophthalic anhydride to 350.0y (1.0 mol) 7.Mole) of Methoxy Carbovax 350. Og sodium acetate Add in the presence of the Heat the mixture at 90°C for 8 hours under nitrogen atmosphere. Ru. The reaction solution was filtered at high temperature to remove sodium acetate, and the desired product was almost determined. Obtained in quantitative yield. The analyzed data is consistent with the following imputation structure: 634-09 (1,0 mol) in the composition of Example 18 in 2001 toluene. y (20 mol) of propylene oxide are added. The reaction solution was heated at 60' to 100℃. Heating for 3-5 hours and then concentration yields the product in near quantitative yield.

The analytical data are consistent with the following assigned structure: 284.09 (1,0 mol) of anhydrous tet 200.0y (1.0 mol) of Carbovax 200 to lachlorophthalic acid is added in the presence of 7.09 parts of sodium acetate. The mixture was heated under nitrogen atmosphere for 90 minutes. Heat at ℃ for 8 hours. The reaction solution was filtered at high temperature to remove sodium acetate and The product is produced in near quantitative yield. The analytical data is consistent with the following assigned structure = 484.0 g (1.0%) (200M (1.0%) of the product of Example D 21 116.0910 mol of propylene oxide is added. Heat the reaction solution to 60°~ Warming at 100° C. for 3-5 hours and then concentration gives the product in near quantitative yield.

The analytical data are consistent with the following assigned structure: 284.09 (1,0 mol) of anhydrous tet Laclorophthalic acid was added to 400.09 (1,0 mol) of Carbowax 400. The mixture was heated to 90°C under nitrogen atmosphere. Heat for 8 hours. Filter the reaction solution at high temperature to remove sodium acetate and remove the desired product. product in near quantitative yield. The analyzed data corresponds to the following imputation structure: 46 ．． 49 (1.0 mol) of tetrabromophthalic anhydride was dissolved in 100 touge of toluene. 4.19 (0.1 mol) of polyoxyethylated dimethylamine [(C Es)J(CEtCHtO)sEco at once. The mixture is 100'-11 Heating at 0°C for 4-5 hours and then concentrating gives the desired product in virtually quantitative yield. Obtained. The analyzed data conform to the following imputation structure.

809 (0.2 mol) to 92.8 g (0.2 mol) of tetrabromophthalic anhydride )of (Jeffamine D-400) and heat the mixture to approximately 120°C. Ta. The final product is obtained in almost quantitative yield.

The analytical data are consistent with the following assigned structure: poly(ethylene gelcol 300), 60011Q with toluene to remove the small amount of water present in the glycol. The mixture was refluxed for 1.5 hours (T=117°C). The mixture is cooled to about 100°C and anhydrous Tetrabromophthalic acid 614.5y (1.35 mol) and sodium acetate 1. 629 was added and the mixture was reheated to reflux and held for 25 hours. The mixture is 5 After cooling to 0°C, propylene oxide (156,49,269 mol, 100% (excess) was added and the mixture was heated to 100°C and held for 25 hours. The solution is about 50℃ Once cooled to , it was filtered through a bed of diatomaceous earth and decolorized charcoal. Distill the filtrate The solvent was removed to give the product 904,19 as a viscous liquid. Br% calculation value 47.4, Br% actual value 46.5° The analytical data agrees with the following attribution structure.

This compound uses poly(ethylene glycol 200) instead of poly(ethylene 300). ) was prepared in the same manner as in Example 25 except that The product is a viscous liquid. Br % Calculated value: 51.0° Br% Actual value: 49.3° The analytical data corresponds to the following attribution structure. Ta.

This compound is a poly(ethylene glycol) substitute for poly(ethylene glycol 300). It was prepared in the same manner as Example 25 except that Cole 600) was used. The product is a viscous liquid It is the body. Br% calculated value 39.5° Br% actual value 39.3° The analytical data is based on the following Matches the genus structure.

Prepared in the same manner as Example 25, except that poly(ethylene glycol 400) was used for the did. The product is a viscous liquid.

Br% calculated value 44.2° Br% actual value 44.0° Analytical data Methanol (54, I 9.1.5 mol), tetrabromophthalic anhydride (695.6 g, 1.6 mol) ), and potassium acetate z739 were refluxed for 4 hours with 500 MQ of toluene. Ta.

After cooling the reaction solution to room temperature, propylene oxide (87.12V, 1.5 mol) was added. and the mixture was reacted at 80° C. for 25 hours. The product is viscous after distilling off the toluene. Obtained as a viscous liquid. Br% calculated value 57.5° Br% actual value 57.2° Analysis data is consistent with the following attribution structure.

This compound uses methoxycarbowax 350 and propylene instead of methanol. Prepared in the same manner as Example 29, except that ethylene oxide was used instead of ethylene oxide. It was.

Br% calculated value 37.8° By% measured value 37.2° The analytical data is consistent with the following attribution structure. I will.

This compound was prepared in Example 2 except that 2-methoxyethanol was used instead of methanol. Prepared in the same manner as 9.

The product is a viscous liquid. Br% calculated value 53.6°B"% actual value 5ZO, analysis data The data is consistent with the following attribution structure.

Examples except that Fuchs 350 and epoxy butane were used instead of propylene oxide. Prepared in the same manner as 29.

The product is a viscous liquid. Br% calculated value 36.5° Br% actual value a7.2° min The analytical data corresponds to the following assignment structure.

This compound was made by using 2-ethyl alcohol-1 instead of methanol. Prepared similarly to Example 29. The product is a viscous liquid. Br% calculated value 50. O.

Br% actual value 5z7° The analytical data agrees with the following assigned structure. Prepared in the same manner as Example 29, except that stearyl alcohol was used instead of alcohol. . The product is a viscous liquid. Br% calculated value 41. O, Br% actual value 43.0°min The analytical data are consistent with the following assignment structure.

This compound uses 2,3-dibromo-propanol-1 instead of methanol. It was otherwise prepared in the same manner as in Example 29. The product is a viscous liquid. Br% calculation Value: 64.8° Br% Actual value: 61.9° Analysis data is consistent with the following attribution structure.

This compound uses shrimp chlorohydrin instead of propylene oxide. Prepared similarly to Example 29. Br% calculated value 35.7° Br% actual value 35.4 ゜The analyzed data corresponds to the following attribution structure.

Methoxycarbowax 350 (300,09) in dry toluene (184112) ,0.89 mol) of sodium methoxide (48,0.89 mol) in methanol. , 0.90 mol) was added. The methanol was then distilled off at atmospheric pressure. anhydrous Trabromophthalic acid was then added with additional 501 & toluene (44Z 2f, 0.89 mol). The reaction solution was refluxed for 2 hours, and after cooling to room temperature, shrimp chlorohydrin was added. (10a94y, 1.16 mol) was added. The mixture was refluxed for 20 hours.

After distilling off the solvent and excess shrimp chlorohydrin, a viscous black product was obtained. Br% measurement Value: 37.2° Br% Actual value: 4o, 4° Analysis data are consistent with the following attribution structure.

Meto beef cicarbowax 350 and toluene for 1 hour to distill off a small amount of water. It refluxed for a while. Tetrabromophthalic anhydride (methoxycarbowax 350 and 1= 1 molar ratio) and sodium acetate were added and the mixture was refluxed for 17 hours. to room temperature After cooling, remove excess diazomethane (N-methane with sodium hydroxide) in ethyl ether. (prepared from the decomposition of methyl-N-nitroso-p-)luenesulfonamide); The mixture was left overnight. Excess diazomethane is decomposed by adding acetic acid. , the solvent was distilled off.

The product is a viscous liquid. Br% calculated value 39.2° Br% actual value 37.4° Analysis The data conform to the following imputation structure.

Di(2-ethylhexyl)tetrabromophthalate in spatz etc. [5patz] et al, (1 & E CProduct Re5archand Dev elopement, Vol. 8, ■. , 4, 395 (1969) It was prepared by the procedure described above.

Poly(ethylene glyfur 600) 885.49 (1,40 mol), anhydrous tetra 1298.4 g (280 moles) of bromophthalic acid, 1.359 potassium acetate, and Toluene (1000 g) was placed in a 1 gallon glass-lined reactor and heated to 120°C. Added M. After 4 hours at this temperature, 246.68 tons of ethylene oxide (5,6 0 mol) was pumped into the reactor for 374 hours while maintaining the temperature at 120°C. Ta. After heating for an additional hour, the mixture was cooled to room temperature and excess ethylene oxide was then removed. Discarded and product collected. After removing toluene by evaporation, 99% of the product of 22509 was obtained. Isolated in yield as a viscous liquid. Br% calculated value 39.2° Br% actual value 38.8 ゜The analyzed data is consistent with the following attribution structure.

453.8 y (0.27 mol) of the product of Example 3, 83.4 g (0.8 mol) of acetic anhydride 2 mol), 1.0 g of potassium acetate, and toluene 40011Q were refluxed for 8 hours.

After cooling to room temperature, the reaction solution was transferred to a separatory funnel and first diluted with 1001!016% potassium bicarbonate. solution and then with 10Ii2 of water. After distilling off the solvent, 335.09 ( The product (54% yield) was obtained as a viscous liquid. Br% calculated value 36.8゜By% actual The measured value 329° analysis data is consistent with the following attribution structure.

■-E Rainbow 2 Tetrabromophthalic anhydride 231.9y (0.50 mol), 2-ethylhexano 130.2g (1.0mol) of alcohol and 0.24v of potassium acetate at 120℃ Heat and hold for 4 hours.

The mixture was cooled to 60° C. and 35.99 (0.26 mol) potassium carbonate was added. . The mixture was reheated to 80°C and it was kept at this temperature for 2 hours. Mixture at 60℃ 14.29 (0.14 mol) of triethylamine was added.

The mixture was reheated to 70°C and 113.69 (0.8 mol) of methyl iodide was added to 20 Added within minutes. Heat the mixture to 70-75℃ and keep it at this temperature for 2 hours. It was. The mixture was cooled to room temperature and filtered to remove by-product potassium iodide. Ta. The filtrate was distilled to remove toluene, leaving 290 g of crude product as a pale yellow liquid. I collected them. After extracting the product three times with a 5% potassium carbonate solution at 1001C, 2 Extracted with 1001i2 times of water and once with 30% sodium chloride solution. organic The phase was dried over anhydrous magnesium sulfate overnight. Solvent Magnesium Sulfate was removed from the filtrate by distillation, yielding 204 g of product as a pale yellow liquid in 67% yield. I got it. Br% calculated value 5z6° Br% actual value 5Z2° The analysis data has the following attribution structure matches.

Example 43 Tetrabromophthalic anhydride 231.9y (0.50 mol), 2-[2-methoxy [ethoxy]ethanol 360.59 (3.0 mol), stannous dicate 329 , and refluxing xylene 200MQ for 18 hours at a temperature of 160°C), during which time theoretical water Collected. Remove xylene and excess 2-[2-methoxyethoxy-ethanol under reduced pressure. Distilled to give 332 g of crude product as a wet white solid. 256g of this The material was redissolved in toluene (1000lQ>7.5 % potassium bicarbonate solution and then once with 20011Q water. organic The phase was dried over anhydrous magnesium sulfate overnight. After separating magnesium sulfate, toluene 45 g of a yellow liquid product was obtained. The overall yield is 17%. Br% Calculated value: 46.6° Br% Actual value: 45.7° The analytical data is consistent with the following attribution structure. .

This compound is similar to Example 4 except that 2-[2-ethoxyethoxy]-ethanol is used. It was prepared in the same manner as 3.

This compound uses tocosyl alcohol instead of poly(ethylene glycol 600). (behenyl alcohol) using propylene oxide instead of ethylene oxide. It was prepared in the same manner as in Example 1, except that The product is a viscous liquid. By% calculation Value: 37.7° Br% Actual value: 3a5° Analysis data is consistent with the following assignment structure.

This compound is a tricontyl alcohol substitute for poly(ethyleneglyfur 600). Example 1 except that propylene oxide was used instead of ethylene oxide. Prepared similarly.

This compound contains 2-[methoxyethoxybutycin instead of methoxyethoxytwo Prepared in the same manner as Example 4 except that Bowax 550 was used.

Italy 48-58... In a pensive example, the combination with ABS tree is the embodiment of the present invention. The flame retardancy of the compound is demonstrated for ABS resin. These compositions are flame retardants, oxidants Mix the antimony and ABS on a roller until the compounds are well blended. It was prepared by

These compounds were pelletized at 230-245°C and then the test samples were heated at 230°C. injection molded. tJL-94 vertical combustion test was conducted, and a control example consisting of ABS itself compared with.

ABS = acrylonitrile-styrene-butadiene terpolymer DTBPE=1,2-bis(2,4,6-)ribromophenoxy)-ethane(7 0% bromine) DOTBP=dioctyltetrabromophthalate (45% bromine) AO-antimony oxide J knee L profit worker Example number 5 (Th' yo 11 and ABS”’ 100 100 100 100DTBPE -22115,5 DOTBP --1725,7 AO-444 tlL-94@(1125' Failure V-QV-IV-Q(a) Cyclol ae Ts Borg (Arner Inc., USA) product (b) Control example (100% ABS) (C) Comparative example (without tetrahalophthalate ester) The above results are clearly Figure 2 shows the flame retardancy of the ABS composition of the present invention in comparison to the examples. These compositions contain less Both have flame retardant properties equivalent to the normal flame retardant (DTBPE) used in ABS. .

Umata 25 balls The impact strength of various materials was determined according to ASTM D256.

1 table 11 work υ− ABS+al 100 100 100 100DTBPE -22115,5 DOTBP --1725,7 AO444 (a) Cyclolac@T, Borg-Warner, USA product ( b) Control example (100% ABS) (C) Comparative example (without tetrahalophthalate ester) As can be seen from the above data , the common flame retardant DTBPE is a part of DTBPH which is the ABS-containing flame retardant of the present invention. The impact strength is significantly reduced compared to the examples in which the composition is replaced by a chemical composition.

91 degrees The heat distortion temperature (HDT) of various materials was determined according to ASTM D648.

mAL ABS”’100 100 100 DTBPE 22 11 DOTBP 17 A0 4 4 Heat distortion temperature (HDT) ・264psi (@F) 182 167 166 (a) Cyclolac” Ts Borg-Warner, U, S, A product (b) Control example (100% ABS) (C) Comparative example (without tetrahalophthalate ester) The above data is for ordinary flame retardant When a part of the converting agent DTBPH is replaced by the ester disclosed in the present invention, In this case, the change in HDT is shown to be negligible.

59-64... Compositions with polystyrene resin In the following examples, compositions of the present invention The flame retardancy of the composition is indicated. These compositions contain flame retardants, antimony oxide, and High impact polystyrene is mixed on a roller until the compound is well blended. It was prepared by These compounds were pelletized at 200-260°C, The test material was then injection molded at 230°C. Conducted UL-94 vertical flame retardant test, A control consisting of high impact polystyrene itself was compared.

H1? S = impact-resistant polystyrene DBDPO = decabromodiphenyl oxide (83% bromine) DOTBP=dioctyltetrabromophthalate (45% bromine) AO≠antimony oxide One Bottom - One Reason - Example number 59”’ 60 (e’ 61 62 63 64 composition percentage HIPS”’ 100 84 81.5 72.9 83 go, gDBDPO 1299- DOTBP --5,522,14,316,4AO-4443,72,8 UL-94 @ 0.125' Failure v-o v-o v-o v-o v-.

Creation, 062' Failure V-2V-OV-OV-0, V-2(a) Polys ar.525, Polysar, USA product (b) Control example (100% poly tyrene) (c) Comparative example (without tetrahalophthalate ester) The above results are based on the present invention A common flame retardant (D BDPO) to pinpoint superior flame retardancy.

Examples 58-64 are all run at equal bromine levels.

As seen from the UL-94 results for the 0.062' sample, the present invention disclosed Partial or total replacement of a common flame retardant (DBDPO) by an ester Improving the flame retardancy of listyrene. Examples □ and □ clearly show that the composition of the invention can be used. In some cases, total bromine levels can be reduced and still provide the same or better flame retardancy. This indicates that the

Example 65-70 The impact strength of various materials was determined according to ASTM D2463 by HIPSI” 100 8. 4 81.5 76.4 73.9 80.8DBDPO-1293-- DOTBP --5,516,622,116,4AO-44442,8 (a) Polysar 525 from Polysar, (b) Control example (10 0% polystyrene) (c) Comparative example (without tetrahalophthalate ester) above As seen from the data, the common flame retardant DBDPo has a high impact strength of polystyrene. (see Example 66). Compositions containing the materials of the invention may be It clearly improves the impact strength to the point that it is better than the comparative example.

What-27]-2 soil The processing characteristics of the compound were determined by measuring the extrusion speed during pelletization.

Table II [(B) HIPS”’ 84 81.5 79 76.4DBDP0 12 9 6 3 DOTBP -5,51116,6 AO4444 (a) Polysar 525, product of Polysar USA (c) Comparative example (without tetrahalophthalate ester) The above data clearly shows that the styrene-containing Demonstrates improved processing properties of flame retardant additives.

f175~79...Pairing with polycarbonate resin In the example below, the book The flame retardancy of the compositions of the invention is demonstrated with respect to polycarbonate resins. The composition of these The product combines flame retardant, antimony oxide, and polycarbonate resin on a roller. The ingredients were prepared by mixing until well blended. these compounds The test specimens were pelletized at 160-305°C and then injection molded at 271”C. . A UL-94 vertical combustion test was conducted, and a control example made of polycarbonate resin itself and a compared. The following tests were conducted on various materials according to the appropriate ASTM test methods.

1.Limiting Oxygen Index (L OI’) ASTM D-28632, Melt Flow ASTII D-12383, tensile strength ASTM D-638 PC=polycarbonate polymer B PC = Brominated polycarbonate oligomer (58% bromine) DOTBT=dioctyltetrabromophthalate (45% bromine) DOTBP --4,012,016,0LOI 28 39 37 37 3 7 Melt flow (9/IO minutes) 26.8 19.1 37.5 >100 >100 (a) rLexanJ 141, General Electric, U, S, A Product (b) Comparative example (100% polycarbonate) (C) Comparative example (tetra (without halophthalate ester) (d) PSI = number of bonds per inch I PSI=,01459/c+y' The above results clearly show that the polycarbonate containing the composition of the present invention compared to the control example. This shows a significant improvement in the flame retardancy of the resin. These polycarbonate resin-containing compositions is at least as flame retardant as BPC, a common flame retardant used in polycarbonate. have sex.

Examples 76-79 were all run at comparable bromine levels. Esters disclosed in the present invention ASTM D-12 38, as demonstrated by improved melt flow properties as measured by Enhanced flow properties were obtained.

Polycarbonate resins containing the compositions of the present invention are improved compared to controls. It exhibits tensile properties comparable to those of the common flame retardant RPC. Furthermore, the present invention The polycarbonate resin containing the composition maintains its elongation rate.

The above data demonstrate improved processing of polycarbonate resins containing the compositions of the present invention. It clearly shows the workability.

Examples 80 to 86... Compositions with PBT resins In the following examples, compounds of the invention shows flame retardancy.

These compositions contain flame retardants, antimony oxide and polybutadiene terephthalate. (PBT) on a roller until the compounds are well blended. It was prepared from These compounds were injection molded at 150-216°C. UL-94 A vertical combustion test was conducted and compared to a control consisting of PBT itself. Melt of various materials Flow was determined according to ASTM D-1238.

PBT=polybutylene terephthalate BPC = Brominated polycarbonate oligomer (58% bromine) DOTBP=dioctyltetrabromophthalate (45% bromine) AO = antimony oxide Table 1 (D) Example number 80°’ 81”’ 82 83PBT”’ 100.0 g5.0 g2.8 80.7RPC15,07,5- DOTBP 9.7 19.3 Antimony oxide -5,05,05,0L7L-94 rating @0.125’ V-2V-OV-OV-0 @0.063’ V-2V-O V-OV-0 melt flow (y/10 minutes’) 27.6 36,2 55.1 72.6 (a) Ce1 anex″2000, manufactured by Boecbst-Celanese, υ, S, A. Product (b) Comparative example (100% polybutylene terephthalate) (c) Comparative example (terephthalate) (without trahalophthalate ester) The above results show that the composition of the present invention clearly shows flame retardancy. These compositions are commonly used in PBT (Example 81). It has flame retardancy at least equivalent to that of the conventional flame retardant RPC.

Examples 81-83 are all run at comparable bromine levels. Ordinary by the composition of the present invention As a result of partial or total replacement of flame retardant (BPC), Enhanced flow as indicated by improved melt flow properties measured by Dynamic characteristics can be obtained.

The following tests were performed on various materials using appropriate ASTM test methods.

1. Impact strength □ASTM D-2562, tensile strength □ASTII D-63 83, Heat distortion temperature (HDT) -□ ASTM D-6484, Melt flow --ASTM D-1238PBT"' 100 85.0 g3.8BPC 15,011,3 DOTBP 4.9 Antimony oxide s, os,.

LOI 25 32 32 UL-94 rating @0.125 V-2V-OV-0 @ (1,063V-2V-OV-0 Tensile strength (Psi)'' 7320 8040 7750 Elongation% 10.9 10.3 11.8HDT(’F)/(”C) 127153 149/65 135157 Melt flow (y/10 min) 27.6 36.2 61.9 (a ) “Celanew” 2000, Hoehst-Celanese tJ , s, A, product (b) Control example (100% polybutylene terephthalate) (C ) Comparative example (without tetrahalophthalate ester) (d) PSI = per square inch As can be seen from the above data, the number of bonds, IPSl=, 0145g/cm The polybutylene terephthalate resin composition containing the flame retardant of the present invention is In the control example (Example 84) and in the conventional BPCW retardant used in PBT (Example 85) significantly improved impact strength while maintaining both tensile strength and elongation properties compared to Ru.

In addition, the flame retardant of the present invention has lower heat distortion temperature (HDT) and flow properties compared to the control example. Improving your sexuality to your heart's content.

The above data shows that the improved polybutylene terephthalate-containing composition according to the present invention Clearly shows processability.

87-91... In the example below, the compounds of the present invention are combined with SMA resin. Shows flame retardancy.

The composition is prepared by rolling the flame retardant, antimony oxide and SMA on a roller until the compound is fully absorbed. Prepared by mixing until blended. The compound was incubated at 95-245°C. and injection molded into test samples at 190-204°C.

A tJL-94 vertical combustion test was conducted and compared to a control consisting of SMA itself. Various The melt flow of the material was determined according to ASTM D-1238.

SMA-styrene-maleic anhydride type combination DBDPO = decabromodiphenyl Oxide (83% bromine) DOTBP=dioctyltetrabromophthalate (45% bromine) AO = antimony oxide Table 1 (E) DBDPO-13J 12.4 11.0 6.9DOTBP --2,65, 112,8 antimony oxide 3.5 3.5: 1.5 3.5 UL-94 rating @0.125' Failure V-Q V-Q V-OV-0・0,063' Failure V- Q V-Q V-OV-0 (a) "Dy1ark" 250, Arco Che micals% U S A product (b) Control example (100% styrene-anhydrous male inic acid copolymer) (C) Comparative example (without tetrahalophthalate ester) The results clearly demonstrate the flame retardancy of the composition of the invention relative to the control example. These compounds are , a common commercially available DBDPO flame retardant used in SMA (Example 87) and at least It has the same flame retardancy.

Examples 88-91 are all run at equal bromine levels. Ordinary by the composition of the present invention As a result of partial replacement of flame retardant (DBDPO), as measured by ASTM D-1238. Enhanced flow properties are obtained, as shown by improved melt flow properties. It will be done.

Examples 92-95 The following tests were conducted on various materials using the appropriate A37M test method.

1. Impact strength - ASTM D-2562, tensile strength - ASTM D-638 3. Heat distortion temperature (HDT) - ASTM D-6484, / file) --ASTM D -1238SMA"' 100.0 82.7 81.5 80.4DBDPO-13,812,411,0DOTBP --2,65,1 Antimony oxide -3,53,53,5LOI 1B, 7 27.6 28.6 23. IUL-94 score @0.0125' Failure V-QV-QV-Q@0,063' Failure V-Q V-QV-Q tensile strength (yield XPSI)") 3950 3880 3830 3700 elongation rate % 8.7 7.4 7.7 g, IHDT ('F) 197 197 191 192 Melt flow (9/10 minutes) 1.1B 1.84 2.08 3.32 (a) “Dy1a rk″250, Arco Chemicals%U, S, A, product (b) Control example (100% styrene-maleic anhydride copolymer) (C) Comparative example (tetra (without halophthalate ester) (d) PSI = pounds per inch, I PSI =, 0145117cm” As seen from the above data, the flame retardant of the present invention The SMA resin composition containing the control example (Example 92) and the commercially available DBDPO flame retardant compared to PBT (Example 93), maintaining both tensile strength and elongation properties. while significantly improving impact strength.

In addition, the heat distortion temperature (HDT) of the compositions of the invention was higher than that of both the control and DBDPO. is equivalent to

The above data clearly demonstrate that the styrene-maleic anhydride copolymers containing the compositions of the present invention Demonstrates improved processability of coalescence.

Tekei Sales Neho Seisho (Method) March 6E, 1990 Yoshi, Commissioner of the Patent Office 1) Takeshi Moon Case indication: PCT/US88103839 Name of the invention: Tetrahalophthalate esters as flame retardants person who makes corrections Relationship to the incident: Patent applicant Name: Penwalt Corporation Date of notification of amendment order: February 27, 1990 Target of amendment One copy each of translations of the specification and claims Contents of the amendment as shown in the attached sheet Translation of the description and claims (no change in content) International investigation report

Claims (23)

[Claims] 1. A flame-retardant plastic composition with improved flowability comprising a mixture of: (I) A resin selected from the following: (A) Acrylonitrile-butadiene -Styrene resin; (B) polystyrene resin; (C) polycarbonate resin; (D) Polybutylene terephthalate resin; (E) Styrene-maleic anhydride copolymer Coalescence resin; and (F) polyolefin or substituted polyolefin; and (II) A flame retardant effective amount of a tetrahalophthalate ester flame retardant processing aid. 2. Imparts flame retardancy and improved flow properties to resins selected from: Use of tetrahalophthalate esters as flame retardant processing aids: (A) Acrylonitrile-butadiene-styrene resin; (B) polystyrene resin; (C) polycarbonate resin; (D) Polybutylene terephthalate resin; (E) Styrene-maleic anhydride copolymer Coalescence resin; and (F) polyolefin or substituted polyolefin. 3. Imparts flame retardancy and improved flow properties to resins selected from: A method comprising: (A) an acrylonitrile-butadiene-styrene resin; (B) polystyrene resin; (C) polycarbonate resin; (D) Polybutylene terephthalate resin; (E) Sterene-maleic anhydride copolymer Combined resin; and (F) polyolefin or substituted polyolefin; the resin and flame retardant an effective amount of at least one tetrahalophthalate ester flame retardant additive. A method characterized by: 4. (I) A resin selected from the following: (A) Acrylonitrile-butadiene Ene-styrene resin; (B) polystyrene resin; (C) polycarbonate resin; (D) Polybutylene terephthalate resin; (E) Styrene-maleic anhydride copolymer Coalescing resin; and (F) polyolefin or substituted polyolefin; and (II) Flame retardant effective amount of at least one tetrahalophthalate ester flame retardant auxiliary agent, A method for producing a flame retardant resin having improved fluidity, the method comprising mixing the following. 5. Any one of claims 1 to 4, wherein the tetrahalophthalate ester has the following general formula: Items written in either: ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, (a) the rings may have all possible isomeric configurations; (b) R is hydrogen, alkyl or substituted alkyl of 1 to 30 carbons, 2 to 20 carbons; hydroxyalkyl of 3 to 10 carbons, polyhydroxyalkyl of 3 to 10 carbons, and Beauty ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein R is alkyl or substituted alkyl of 1 to 18 carbons, and b is 1 to 50) selected from the group consisting of; (c) R1 is hydrogen, alkyl or substituted alkyl of 1 to 30 carbons, 2 to 22 alkenyl or substituted alkenyl of 5 carbons, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ where R7 is alkyl of 1 to 18 carbons; polyhydroxy of 3 to 12 carbons; Sialkyl; ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼; ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼; ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (total monomers); ▲ Numerical formulas, chemical formulas, tables, etc. There are ▼ (total monomers); ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼; ▲ Mathematical formulas, chemical formulas, etc. There are scientific formulas, tables, etc. ▼; and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼; (However, R valence of 1 is equal to q) selected from the group consisting of; (d) R2 is independently selected from the group consisting of H and CH2-; (e) R2, R4, R5 and R6 are independently H and alkyl of 1 to 18 carbons; (f) p is an integer from 0 to 50; (g) q is an integer from 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 1 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-ethylhexyltetrabromophthalate. . 9. Any of claims 1 to 8, wherein the weight ratio of (I):(II) is 100:1 to 2:1. Those mentioned in the above. 10. R is 1 to 10 carbon alkyl or substituted alkyl, and A is Br. Claim 5, wherein X is oxygen, p is 0-20, and q is 1-6. 11. R is selected from the following: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, - CH2, -C2H5, -C2H7, -C4H8; -C■H12, -C4H9, - CH6H13, -C8H17, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -C10H 21R1 is CH2, C2H5, C4H8, H, -C2H7, -C6H13, -C 8H17, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -C10H21, or ▲ Mathematical formulas , a chemical formula, a table, etc., and q=1. 12. Contains additional brominated or chlorinated flame retardants or mixtures thereof other than the ester. Any of the preceding claims. 13. Claim 8: The additional flame retardant is selected from the group consisting essentially of: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼(x+y =5-8) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ Mathematical formulas , chemical formulas, tables, etc.▼Here, R′′ and R′′′ are alkylene or substituted a It's Lukiren ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼▲Mathematical formulas, There are chemical formulas, tables, etc.▼ ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼▲Mathematical formulas, There are chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼, and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 14. (A) Acrylonitrile-butadiene whose resin is represented by the following general formula Any one of claims 1 to 13 which is tyrene: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ Acrylonitrile ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ Butadiene ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Styrene (in the formula, x, y and 2 independently range from 10 to 1500). 15. Part or all of the acrylic and styrene monomers that make up the resin are methacrylates. lonitrile or α-methylstyrene, or methacrylonitrile and α-methylstyrene Claim 14 comprising Rustyrene. 16. The resin contains vinyl aromatic monomer, vinyl nitrile monomer, and butadiene monomer 16. Claim 15 comprising monomer units of 17. The resin is (B) polystyrene, and (a) styrene having the following repeating units. Homopolymer of: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (where n is greater than 1 and ranges from about 3000); (b) A homopolymer of styrene similar to (a) modified with rubber, in which rubber is dispersed as discrete particles in the homopolymer matrix, and The weight ratio of rubber to homopolymer is in the range of about 2:98 to about 25:75; Or (c) the weight ratio of butadiene to styrene is within the range of about 2:98 to about 25:75; a copolymer of butadiene and styrene, or (d) a blend of (a) and (b); Polybutadiene and/or styrene-butadiene copolymer is preferred. The product according to any one of claims 1 to 13. 18. A claim in which the polystyrene resin is (B)(a) and is in the form of a foam. 17. 19. The resin is (C) polycarbonate having a repeating structural unit of the following general formula. The product according to any one of claims 1 to 13: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (where a is greater than 1 and Z is a divalent aromatic group of a dihydric phenol). 20. The resin is (D) polybutylene terephthalate, and the repeating structure of the following general formula is The product according to any one of claims 1 to 13, which has a structural unit: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, a>1). 21. The resin is a styrene-maleic anhydride copolymer (E) having the following general formula: The product according to any one of claims 1 to 13: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein m is a number from 1 to about 100, and n is a number from zero to about 100) . 22. Claim 2 wherein the weight ratio (styrene):(maleic anhydride) is 1 to 19:1. 1. 23. The resin (F) is polyolefin and substituted polyolefin, and polyethylene (Low density, linear low density and high density): Polypropylene: Both ethylene propylene Polymer: ethylene vinyl acetate copolymer; polyvinyl acetate; derived from polyvinyl acetate polyvinyl alcohol; poly-4-methylpentene-1; polyisobutylene polyacrylate esters; and polymethacrylate esters; or is any of the above and polystyrene; styrene-butadiene copolymer; chlorinated poly Ethylene; Chlorinated polypropylene; Polyvinyl chloride: Acrylonitrile butadiene - Styrene; Polyethylene terephthalate: Polybutylene terephthalate: Physical blend with liphenylene oxide and/or polyphenylene oxide/ 14. A high impact polystyrene blend according to any one of claims 1 to 13. Of things.