JPS6328469B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing flame retardants.
Specifically, the present invention relates to halogen-containing bisphenol A.
The present invention relates to a method for producing a flame retardant comprising a block copolymerization reaction between an epoxy resin and an oligomer or polymer containing at least one functional group capable of reacting with an epoxy group. The demand for flame retardants for plastics continues to increase every year as the demand for improved safety during use, particularly flame retardance, increases in a wide variety of plastic application fields. In addition, the types of flame retardants used have been brominated phthalic anhydride, brominated diphenyl, brominated diphenyl ether, brominated bisphenol A, ethylene oxide adduct of brominated bisphenol A, and brominated bisphenol. Aromatic halogen compounds such as glycidyl ether compounds of A are used, but when such low-molecular organic compound additive flame retardants are kneaded into molded products, the flame retardant itself may bleed or easily sublimate. Recently, oligomerized or polymerized additive flame retardants have been increasingly used to overcome these drawbacks. Furthermore, reactive flame-retardant plastics using halogen-containing monomers are also beginning to become available. In response to this, the present inventors have also developed an additive-type flame retardant that does not have bleed or sublimation properties of the flame retardant itself. A block copolymer consisting of one oligomer or polymer has been proposed (Japanese Patent Application Laid-open No. 74557/1983 and Japanese Patent Application No. 59187/1983). However, since the reaction temperature is relatively high when producing such block copolymers, there is a possibility that the epoxy resin itself may gel, especially when the molar fraction of the halogen-containing bisphenol A type epoxy resin is high. There was the disadvantage that the reaction temperature and reaction time had to be strictly controlled. In this regard, the present inventors have conducted extensive research in order to establish a more rational manufacturing method, and as a result, have completed the present invention. That is, the present invention relates to (A) general formula (In the formula, R is H or/and CH ₃ group; X is a halogen atom; l is 0 to 15; m and n are integers of 1 to 4.) Halogen-containing bisphenol A
After homogeneously mixing the type epoxy resin and (B) an oligomer or polymer containing at least one functional group capable of reacting with an epoxy group, or pre-reacting the resin to a reaction rate that does not cause gelation, place the epoxy resin in another container that is easy to take out. The invention also relates to a method for producing a flame retardant, which comprises transferring the flame retardant to another location, and then holding the flame retardant under heating to cause a reaction. The halogen-containing bisphenol A type epoxy resin (A) used in the present invention is represented by the following general formula. (In the formula, R is H or/and _CH3 group; X is a halogen atom; l is 0 to 15; m and n are integers of 1 to 4.) This halogen-containing bisphenol A type epoxy resin Preferably, the amount is 20% by weight or more, X is bromine or chlorine, and m and n are 2 to 4.
Further, halogen-containing bisphenol A type epoxy resin is synthesized by condensation of halogenated bisphenol A and epichlorohydrin, for example, and by reaction of diglycidyl ether of halogenated bisphenol A with halogenated bisphenol A. It is also easily synthesized, and its halogen content can be adjusted to any desired ratio by partially cocondensing bisphenol A and glycols. On the other hand, the (B) oligomer or polymer containing at least one functional group capable of reacting with an epoxy group used in the present invention is as described below. Examples of functional groups that can react with such epoxy groups include carboxyl groups, alcoholic and phenolic hydroxyl groups, acid anhydride groups, amino groups, imino groups, acid amide groups, acid imido groups, thiol groups, isocyanate groups, etc. It may be present at the end of the oligomer or polymer backbone or in a branched manner in the middle of the backbone. Oligomers or polymers include polyesters, polycarbonates, polyamides, polyacetals, polyphenylene oxides, polysulfones, polyimides, polyamideimides, polyurethanes, polyalkylene ether glycols, and cocondensates thereof, as well as radically polymerizable monomers containing functional groups. It is mainly composed of vinyl polymers, phenolic resins, etc., and halogenated ones are more preferable in order to increase the halogen content of the flame retardant obtained by block copolymerization reaction, but non-halogenated ones are more preferable. It doesn't matter if it's a monster. Particularly preferred oligomers or polymers include the following halogen-containing monomers as constituents. (1) General formula (In the formula, R ₁ and R ₂ are alkylene groups, X is a halogen atom, m and n are integers of 1 to 4, and Z is -C
( _CH3 ) _2- or _-SO2- , p and q represent integers of 1 to 10. ) These halogen-containing aromatic diols can be prepared, for example, by adding a suitable alkylene oxide such as ethylene oxide or propylene oxide to a halogenated bisphenol A or S, or by reacting an alkylene halohydrin such as ethylene chlorohydrin. It can be obtained by
Depending on the reaction conditions and molar ratio of raw materials used, usually
R ₁ , R ₂ , p, q, etc. are determined. R ₁ and R ₂ are ethylene group or propylene group, p and q are 1 to 1
Particularly preferred are those in which 4.X is bromine or chlorine. Specifically, 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromphenyl]
Propane or sulfone, 2,2-bis[4-
(2-hydroxyethoxy)-3,5-dichlorophenyl]propane or its sulfone 2,2-
Bis[4-(2-hydroxypropoxy)-3,
5-Dibromphenyl]propane or its sulfone, 2,2-bis[4-(2-hydroxypropoxy)-3,5-dichlorophenyl]propane or its sulfone, 2,2-bis[4-
(3-hydroxypropoxy)-3,5-dibromphenyl]propane or its sulfone, 2,
2-bis[4-(3-hydroxypropoxy)-
3,5-dichlorophenyl]propane or sulfone, 2,2-bis[4-(2-hydroxyethoxy)-3-bromphenyl]propane or its sulfone, 2,2-bis[4-(2-hydroxyethoxy)-2 , 3,5,6-tetrabromphenyl]propane or its sulfone. (2) General formula (In the formula, X is a halogen atom, m and n are 1 to 4
Z represents -C( _CH3 ) _2- or _-SO2- . ) These phenol compounds can be obtained, for example, by nuclear halogenation of bisphenol A or S using a halogen molecule, and m and n are determined depending on the reaction conditions used and the molar ratio of raw materials. Particularly preferred are those in which X is bromine or chlorine. Specifically, 2,2-bis(4-hydroxy-3,5-dibromphenyl)propane or its sulfone, 2,2-bis(4-hydroxy-
3,5-dichlorophenyl)propane or its sulfone, 2,2-bis(4-hydroxy-3
-bromphenyl)propane or its sulfone, 2,2-bis(4-hydroxy-3-chlorophenyl)propane or its sulfone, 2,
2-bis(4-hydroxy-2,3,5,6-
Tetrabromophenyl)propane or its sulfone, 2,2-bis(4-hydroxy-2,
Examples include 3,5,6-tetrachlorophenyl)propane or its sulfone. (3) General formula

【formula】

【formula】

[Formula] or

[Formula] (In the formula, X is a halogen atom; R ₃ is a hydroxyl group, an alkoxy group, and a halogen; m is 1 to 4
indicates an integer. ) These dicarboxylic acids or their derivatives or dicarboxylic acid anhydrides can be obtained by nuclear halogenation of their non-halogenated forms using halogen molecules in an appropriate reaction medium, but depending on the reaction conditions and molar ratio of raw materials used. m is determined.
Particularly preferred are those in which X is bromine or chlorine and m is 4. Specifically, tetrabromoterephthalic acid, tetrachloroterephthalic acid, 2,5-dibromoterephthalic acid, 2,5-dichloroterephthalic acid,
Tetrabromoterephthalic acid alkyl ester or acid chloride, tetrachloroterephthalic acid alkyl ester or acid chloride, 2,5-dibromoterephthalic acid alkyl ester or acid chloride, 2,5-dichloroterephthalic acid alkyl ester or acid chloride, tetrabrom Isophthalic acid or acid chloride, tetrachloroisophthalic acid or acid chloride, tribromiisophthalic acid or acid chloride, trichloroisophthalic acid or acid chloride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, dibromonaphthalene dicarboxylic acid, dichloronaphthalene dicarboxylic acid ,
tetrabromnaphthalene dicarboxylic anhydride,
Examples include tetrachlornaphthalene dicarboxylic anhydride. (4) General formula (In the formula, X is a halogen atom, R ₄ is H or/and CH ₃ group, m is an integer of 1 to 4, Z is -C
(CH ₃ ) ₂ − or −SO ₂ −. ) These diglycidyl compounds are synthesized, for example, by condensation of halogenated bisphenol A or S with epihalohydrin, and X is particularly preferably bromine or chlorine. Specifically, 2,2-bis(4-glycidyloxy-3,5-dibromphenyl)propane or its sulfone, 2,2-bis(4-glycidyloxy-3,5-dichlorophenyl)propane or its sulfone, 2, 2-bis(4-methylglycidyloxy-3,5-dibromphenyl)propane or its sulfone, 2,2-bis(4-methylglycidyloxy-3,5-dichlorophenyl)propane or its sulfone,
2,2-bis(4-glycidyloxy-3-bromphenyl)propane or its sulfone,
2,2-bis(4-glycidyloxy-2,
Examples include 3,5,6-tetrabromphenyl)propane and its sulfone. (5) General formula (In the formula, X is a halogen atom, s and t are 2 to 10
m is an integer from 1 to 4, Z is -C(CH ₃ ) ₂
- or -SO ₂ -. ) These diamine compounds are synthesized, for example, by condensation of halogenated bisphenol A or S with an α-chloro or ω-aminopolymethylene compound, and X is particularly preferably bromine or chlorine. Specifically, 2,2-bis[4-(2-aminoethoxy)-3,5-dibromphenyl]propane or its sulfone, 2,2-bis[4-
(2-aminoethoxy)-3,5-dichlorophenyl]propane or its sulfone, 2,2-bis[4-(3-aminopropoxy)-3,5-dibromphenyl]propane or its sulfone,
2,2-bis[4-(3-aminopropoxy)-
3,5-dichlorophenyl]propane or its sulfone, 2,2-bis[4-(4-aminoptoxy)-3,5-dibromophenyl]propane or its sulfone, 2,2-bis[4-(4
-aminoptoxy)-3,5-dichlorophenyl]propane or its sulfone, 2,2-bis[4-(5-aminopentoxy)-3,5-dibromophenyl]propane or its sulfone, and the like. (6) General formula

【formula】

【formula】

【formula】

[Formula] or (In the formula, X is a halogen atom, R ₅ is H or CH ₃
The group m represents an integer of 1 to 4. ) These halogen-containing vinyl monomers can be used, for example, in the condensation reaction of acrylic acid halide, methacrylic acid halide, aryl halide, or methaaryl halide with halogenated phenols, or the dehydration or dehydrochlorination reaction of halogen-substituted hydroxyethane or halogen-substituted chloroethane. , an exchange reaction between vinyl acetate and halogenated benzoic acid, a condensation reaction between fumaric acid halide and halogenated phenol, etc., and X is particularly preferably bromine or chlorine. Specifically, acrylic acid tribromphenyl ester, acrylic acid trichlorophenyl ester, acrylic acid pentabromphenyl ester, acrylic acid pentabromphenyl ester, methacrylic acid tribromphenyl ester, methacrylic acid trichlorophenyl ester , methacrylic acid pentabromphenyl ester, methacrylic acid pentachlorophenyl ester, tribromphenyl aryl ether,
Trichlorphenyl aryl ether, pentabromphenyl aryl ether, pentabromphenyl aryl ether, tribromphenyl metaaryl ether, trichlorphenyl metaaryl ether, pentabromphenyl metaaryl ether, pen Tachlorphenyl metaaryl ether, monobromustyrene, monochlorostyrene, tribromustyrene, trichlorostyrene, pentabromustyrene, pentachlorstyrene, tribromobenzoic acid vinyl ester, trichlorobenzoic acid vinyl ester, pentabromobenzoic acid vinyl ester, pentachlorbenzoic acid acid vinyl ester, fumaric acid ditribromo phenyl ester, fumaric acid ditrichlorophenyl ester,
Examples include dipentabromo phenyl fumarate and dipentachlorophenyl fumarate. In addition to the above components (1) to (6), a small amount of the following halogen-containing compounds may be used in combination. general formula

【formula】

【formula】

【formula】

【formula】

or _{( In the} formula _,
It represents C( _CH3 ) _2- or _-SO2- . ) X is particularly preferably bromine or chlorine, specifically tribromophenol, trichlorophenol, pentabromophenol, pentachlorophenol, tribromobenzoic acid or its ester, trichlorobenzoic acid or its ester, pentabromobenzoic acid or its ester, pentachlorobenzoic acid or its ester, tribromphenylamine, trichlorophenylamine, pentabromphenylamine, pentachlorphenylamine, tribromphenyl glycidyl ether, trichlorophenyl glycidyl ether, pentabromphenyl Glycidyl ether, pentachlorophenyl glycidyl ether, tribromphenyl methyl glycidyl ether, trichloro phenyl methyl glycidyl ether, pentabromphenyl methyl glycidyl ether, pentachloro phenyl methyl glycidyl ether, 2,2-bis(4-aryl) oxy-3,5-dibromphenyl)propane or its sulfone, 2,2-bis(4-aryloxy-3,5-dichlorophenyl)propane or its sulfone, 2,2-bis[4-(3-aryloxy-2 -hydroxypropoxy)-3,5-dibromphenyl]propane or its sulfone, 2,2-bis[4-(3-aryloxy-2-hydroxypropoxy)-3,
5-dichlorophenyl]propane or its sulfone, 2,2-bis[4-(3-methacryloyl-
2-hydroxypropoxy)-3,5-dibromphenyl]propane or its sulfone, 2,2-
Examples include bis[4-(3-methacryloyl-2-hydroxypropoxy)-3,5-dichlorophenyl]propane or its sulfone. There are no restrictions on the method of synthesizing (B) an oligomer or polymer containing at least one functional group capable of reacting with an epoxy group using these various halogen-containing monomer components, and any synthesis method can be applied. The flame retardant of the present invention reacts (A) the halogen-containing bisphenol A-type epoxy resin with (B) an oligomer or polymer containing at least one functional group capable of reacting with an epoxy group in the presence or absence of a catalyst. However, in the past, when producing such a block copolymer, the reaction temperature was relatively high, so especially when the molar fraction of halogen-containing bisphenol A type epoxy resin used was high, epoxy There is a high possibility that the resin itself will gel.
It was necessary to strictly control the reaction temperature and reaction time. In the present invention, (1) first, the above-mentioned (A) and (B) components are mixed uniformly or pre-reacted to a reaction rate with no risk of gelation, (2) transferred to another container or place that can be easily taken out,
(3) Next, by holding it under heating and further reacting, a flame retardant can be obtained easily and with good reproducibility. The production method of the present invention is superior to the conventional production method using a reaction vessel in the following points. (1) Equipment costs can be reduced because there is no need for a special heat medium heated high viscosity reaction vessel, which is expensive as in the past. (2) Reactions between high viscosity polymers are possible if the temperature conditions are appropriately selected. (3) Even if the reaction product partially gels, it can be taken out, there is no need for troublesome post-treatments such as pot washing, and the mole fraction of epoxy compounds, which have a particularly high possibility of gelation, is high. It can be handled with confidence regardless of the preparation ratio. (4) Any reaction time can be set by selecting the amount of catalyst and reaction temperature. (5) The post-reaction temperature is lower than the normal kettle reaction temperature;
Because of the gentle conditions, there is little thermal coloring of the product.
Moreover, the possibility of gelation can be reduced. Next, each reaction step involved in the production method of the present invention will be explained. The step (1) of uniformly mixing both components or pre-reacting to a reaction rate with no risk of gelation is a preparatory step for the post-reaction step (3), and a reaction catalyst is also added as necessary. Although this step is not limited in any way in terms of equipment, a conventional reaction vessel can be used if the melt viscosity does not increase too much even when the two components are melt-mixed and the possibility of gelation reaction occurring is low. However, preferably kneading machines such as single or multi-screw extruders, co-kneaders or heated rolls are used in this step. The step (2) of transferring the reaction product to another container or location that is easy to take out is a treatment step that makes it easy to take out the reaction product, and even if some of the reaction product gels during this step, there will be no problem. No problems arise. This process is also not limited in any way in terms of equipment; usually stainless steel cooling pans or wide-mouthed, shallow-bottomed cans are used, but steel belts or bucket conveyors that pass through the heating zone can also be used. . The step (3) of holding under heating and further reacting is a finishing step that increases the reaction rate of the simple mixture of both components or the remaining reaction components to finally complete the block copolymer, and the reaction time is It can be set arbitrarily by combining the amount of catalyst and reaction temperature. This step is also not limited in terms of equipment, but it is usually preferable to maintain it at a predetermined temperature in a heating oven or dryer. After the finally obtained flame retardant is cooled to room temperature, it is taken out from the container or reaction place, coarsely pulverized, and then finely pulverized by a crusher to form the final product. The reaction conditions for each reaction step are not limited in any way, but the catalysts used are known catalysts used for reactions with epoxy groups and functional groups that can react with them (3).
An appropriate amount is used depending on the set reaction time of the final finishing step. In addition, the heating, that is, the reaction temperature, is usually 250°C or less to prevent gelation of the epoxy resin itself.
Particularly preferably 200°C or less, more preferably 150°C or less
It is carried out at 180℃. As oligomers or polymers containing at least one functional group that can react with an epoxy group, those that provide a flame retardant with good compatibility with thermoplastic resins are recommended in order to suppress deterioration of the physical properties of the flame retardant composition and bleed of the flame retardant. It is preferable. Furthermore, there are no limitations on the molar ratio or weight ratio of both components when producing a block copolymer, but the epoxy equivalent, acid value, hydroxyl value,
It can be arbitrarily limited by taking into consideration the amine value, mercaptan equivalent, isocyanate equivalent, etc. Furthermore, (3)
As a reaction check method in the final finishing process, follow-up measurement of epoxy equivalent, acid value, hydroxyl value, amine value, mercaptan equivalent, isocyanate equivalent, melting point, melting point, melt viscosity or melt index, solution dilution viscosity, etc. by sampling is applied. be done. Thus, a flame retardant composition is obtained in which the obtained flame retardant is blended with a thermoplastic resin together with a flame retardant aid and, if necessary, glass fiber and other fillers.
The flame retardant is usually added in such an amount that the halogen content in the composition is 2 to 20% by weight, preferably 3 to 15% by weight. Further, the flame retardant aid is usually 0.5 to 10% by weight, preferably 1 to 10% by weight in the composition.
The use of such a flame retardant aid, which is used in an amount of 7% by weight, is preferred from the viewpoint of maintaining the physical properties of the flame retardant composition since the amount of flame retardant used can be reduced. Such a flame retardant composition is usually produced by kneading a thermoplastic resin, a flame retardant, a flame retardant aid, and if necessary glass fibers, other fillers, etc. in an extruder. The kneading conditions at that time vary depending on the type of plastic, but it is usually carried out at a temperature in the range of 150 to 300°C, and a suitable mixing time is 0.2 to 30 minutes. If the temperature is too high or the mixing time is too long, the flame retardant (block copolymer) is likely to decompose, so care must be taken. Thermoplastic resins used in flame-retardant compositions include polyesters such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate, polyamides, polycarbonates, polyurethanes, polyphenylene ethers, polyethylene, polypropylene, ethylene/vinyl acetate copolymers, and polyethylene terephthalates. enylene sulfide,
Examples include ABS, polyacetal, polysulfone, etc. Examples of flame retardant aids include antimony trioxide, antimony pentoxide, sodium pyroantimonate, sodium borate, and calcium borate. Furthermore, other additives include calcium carbonate, mica, talc, calcium silicate, coloring agents,
Examples include stabilizers. EXAMPLES Hereinafter, examples will be given to explain the present invention in more detail, but the present invention is not limited thereby. Note that parts and % in the examples indicate parts by weight and % by weight, respectively. Reference Example (A) Synthesis of brominated bisphenol A type epoxy resin: 1110 parts of tetrabromobisphenol A diglycidyl ether [epoxy equivalent (molecular weight per epoxy group): 370], 544 parts of tetrabromobisphenol A and tetra Pour 1.6 parts of a 10% aqueous solution of methylene ammonium chloride into a flask (Tetrabromobisphenol A diglycidyl ether/Tetrabromobisphenol A = 3/2
molar ratio) was heated to 150°C, gradually raised to 190°C after 4 hours, and further held at 190°C for 2 hours. After the reaction was completed, the cooled and solidified product was crushed to obtain yellow granules. The product had a softening point of 130°C, an epoxy equivalent of 1654, and a bromine content of 51.3%, and was confirmed to have the following structure from the IR spectrum and nuclear magnetic resonance spectrum. Example 1 (Production of block copolymer with bromine-containing copolyester) 244 parts of dimethyl terephthalate, 34.2 parts of 1,4-butanediol, 2,2-bis[4-(2-hydroxyethoxy)-3,5 -dibromphenyl]
804.9 parts of propane is charged into a reactor equipped with a stirrer equipped with a rectification column, a distillation condenser, and a distillate receiver, and after the contents are melted, 7.3 parts of a 1% solution of tetrabutoxytitanium in 1,4-butanediol is used as a catalyst.
A transesterification reaction and a polycondensation reaction were carried out at 200°C to obtain a copolymerized polyester having a hydroxyl value of 20, an acid value of 1, and a number average molecular weight (calculated value) of 5343 (yield: about 1000 parts). Next, 52.8 parts of phthalic anhydride was added to this, and the reaction was further carried out at 200°C for 1 hour, resulting in a hydroxyl value of 0 and an acid value of 0.
A copolymerized polyester with 19 terminal carboxyl groups was obtained. In contrast, next, 680 parts of the brominated bisphenol A type epoxy resin synthesized in the reference example and 10% of tetramethylammonium chloride as a catalyst were added.
After gradually adding 1.5 parts of the aqueous solution and confirming uniform melt mixing (185-190°C), the product was taken out into a stainless steel cooling pan (MI
= Melt Index = 12.0, 125℃/2.16Kg
load). Next, this cooling pan was placed in a dryer maintained at 150°C, and after being maintained at the same temperature for an additional 36 hours, the cooling pan was taken out and cooled to room temperature. The product (flame retardant) was an epoxy group-containing block copolymer with MI=0.3 (230° C./10 kg load) and bromine content of 43.0%. Example 2 (Production of block copolymer with copolymerized polyester) Dimethyl terephthalate (7 mol), isophthalic acid (3 mol) and 1,4-butanediol (15
415.5 parts of a polyester with a hydroxyl value of 26, an acid value of 1, and a number average molecular weight (calculated value) of 4155 obtained from mol. The mixture was reacted at 190° C. for 1 hour to obtain a polyester having a hydroxyl value of 0 and an acid value of 27. Next, 361.6 parts of the brominated bisphenol A type epoxy resin synthesized in the reference example and 0.8 parts of a 10% aqueous solution of tetramethylammonium chloride as a catalyst were gradually added to this, and after confirming that they were uniformly melted and mixed, The product at 190°C was once taken out into a stainless steel cooling pan. That is MI=3.5
(190℃/2.16Kg load). Place this cooling pan in a heating oven maintained at 160℃,
After holding at the same temperature for 24 hours, the cooling pan was taken out and cooled to room temperature. The product was an epoxy group-containing block copolymer (flame retardant) with MI=0.05 (230° C./10 kg load) and bromine content of 30.7%. Example 3 (Production of block copolymer with bromine-containing polyester) In the same reactor as in Example 1, tetrabromo phthalic anhydride (0.45 mol), maleic anhydride (0.1 mol), and ethylene glycol (1.3 mol) were added. Preparation,
After heating to melt the contents, zinc acetate as a catalyst was added at 0.2% based on the acid component, and the temperature was raised to 200°C. After reaching 200°C, the remaining tetrabromophthalic anhydride (0.45 mol) was added in two portions, and the reaction was further carried out at 200°C for 2 hours, followed by a step of reducing the pressure to 100 mmHg, and maintained at the same temperature for 2 hours. The product was taken out into a cooling pan and cooled to room temperature to solidify (the product had an acid value of 40, a hydroxyl value of 10,
MI=30 [125℃/2.16Kg load]). The solidified product thus obtained and the brominated bisphenol A type epoxy resin synthesized in Reference Example were each pulverized into powder by a pulverizer. Next, 224 parts of brominated polyester and 280 parts of brominated bisphenol A-type epoxy resin were uniformly premixed in a polyethylene bag or can with a lid, and then melt-kneaded in a twin-screw extruder (average residence time: 5 minutes). ), and the product was taken out into a stainless steel cooling pan. This cooling pan was placed in a heating oven maintained at 160°C, and after being kept at the same temperature for 30 hours, the cooling pan was taken out and cooled to room temperature. Product has MI=18 (230℃/10Kg load), bromine content
It was a block copolymer (flame retardant) with 54.3% epoxy groups. Example 4 (Production of block copolymer with brominated polycarbonate) 350 parts of powdered brominated bisphenol A type epoxy resin synthesized in the reference example and Iupilon FR-30 (brominated bisphenol A) manufactured by Mitsubishi Gas Chemical Co., Ltd. After uniformly premixing 170 parts of polycarbonate (type polycarbonate) in a polyethylene bag or can with a lid, it was melt-kneaded in a twin-screw extruder (average residence time 5 minutes), and then the product was taken out into a stainless steel cooling pan. . This cooling pan (MI=3.5, 150℃/2.16Kg load) was placed in a heating oven maintained at 160℃.
After further holding at the same temperature for 48 hours, the cooling pan was taken out and cooled to room temperature. The product was a block copolymer (flame retardant) having MI=5.0 (190° C./2.16 kg load), bromine content of 52.5%, and epoxy groups. Example 5 (Production of block copolymer with bromine-containing acrylic copolymer) Tribromphenyl acrylate (0.45 mol),
Bromine content 47.1% by suspension polymerization using styrene (0.05 mol) and acrylic acid (0.05 mol),
An acrylic copolymer with an acid value of 11.8 was obtained. After uniformly premixing 230 parts of this brominated acrylic copolymer and 119 parts of the powdered brominated bisphenol A epoxy resin synthesized in the reference example, the mixture was melt-kneaded in a twin-screw extruder (average residence time 3 minutes). ), the product was taken out into a stainless steel cooling pan (MI of product = 20, 125°C/2.16Kg load). This cooling pan was placed in a heating oven maintained at 160° C., and after being further maintained at the same temperature for 40 hours, the cooling pan was taken out and cooled to room temperature. The product was an epoxy group-containing block copolymer (flame retardant) with MI=0.01 (230°C/10 kg load) and bromine content of 48.5%. Comparative Example 1 In Example 2, when the reaction was carried out by holding the molten mixture at 190°C without taking it out into the cooling pan, the melt viscosity of the reaction system increased rapidly after about 3 hours, and the contents gelled. It turned out that it was not usable. Application example 6 (Flame retardant composition) Polybutylene terephthalate with an intrinsic viscosity of 0.9,
30 pieces of chopped strand type glass fiber treated with 53 parts each of polyethylene terephthalate of the same viscosity, 14 parts of the flame retardant obtained in Example 1, 3 parts of antimony trioxide, and an aminosilane coupling agent.
The mixture was uniformly premixed, melt-kneaded at 250°C in a full-flight vented 65 mm extruder, and then cooled to obtain each pellet. Moldings (1/16 inch thick) from these pellets (flame-retardant compositions) are available in the U.S.
Shows V-O flame retardancy according to UL standards.

Claims (1)

[Claims] 1 (A) General formula (In the formula, R is H or/and CH ₃ group; X is a halogen atom; l is 0 to 15; m and n are integers of 0 to 4.) Halogen-containing bisphenol A
The type epoxy resin and (B) an oligomer or polymer containing at least one functional group capable of reacting with an epoxy group are mixed uniformly or pre-reacted to a reaction rate that does not cause gelation, and then maintained under heating. A method for producing a flame retardant characterized by a reaction.