JPH0768339B2 - Method for producing halogen-containing polyhydroxypolyether resin - Google Patents

Description

The present invention relates to a halogenated polyhydroxypolyether resin known as a flame-retardant coating-soluble or flame-retardant molding resin, which cannot be produced conventionally. Another object of the present invention is to provide a method for producing a linear halogenated polyhydroxypolyether having a high polymer purity. "Problems to be Solved by Prior Art and Invention" Conventionally, diglycidyl polyhydroxypolyether resins obtained by reacting p, p 'bisphenol A with diglycidyl ether and p, p' bisphenol with epichlorohydrin are old. It is a substrate with excellent hardness, flexibility, chemical resistance, and electrical properties, which has strong adhesiveness and abrasion resistance, and is industrially used for electric wire coating films, films, coatings, etc. It is applied to a wide range of fields such as electronics, paints, and adhesion. However, in recent years, it has become indispensable to improve the purity characteristics, heat resistance and flame retardancy of the material. Therefore, since the conventional diglycidyl polyhydroxypolyether resin has become unsatisfactory, a substantially linear polymer high-purity halogenated polyhydroxypolyether resin having excellent heat resistance and flame retardance is required. It was Further, from the viewpoint of fire prevention, the demand for fire safety of textile products has increased, and a high-performance flame retarding agent has been demanded in the fields of synthetic fibers and thermoplastic resin molding. However, various studies have been made in this field as well, such as adding a halogenated flame retardant (eg, tetrabromophthalic anhydride, tetrabromobisphenol A, hexabromobenzene) or using a low molecular halogenated bisphenol A type epoxy resin. The flame retardancy is imparted by adding a high molecular weight epoxy resin thereof (Japanese Patent Publication No. 52-22653, No. 53-11017, JP-A No. 60-71713, UPS 4605708). However, the halogenated diglycidyl ether used in these has a low molecular weight, and even with a high molecular weight epoxy resin, the molecular weight does not reach a satisfactory level. A high temperature heat treatment is carried out in an extruder with a shaft vent to increase the molecular weight, and the product is transferred to a tray or the like and heat treated as it is in the presence of impurities. Therefore, the reaction of branching in the molecule progresses and the melting characteristics are deteriorated or discolored, causing various problems. The required performance as a thermoplastic resin-soluble flame retardant is to maintain a permanent flame retardant effect,
Although it does not discolor significantly when exposed to high-temperature molding conditions, and there is no dripping when the product burns, etc.In halogenated polyhydroxypolyether resins, unreacted low molecular weight substances and synthetic catalysts remain. It has been a cause of the above performance being significantly deteriorated. The present invention provides a method for producing a high-purity, high-molecular weight halogenated polyhydroxypolyether resin which is substantially linear and has very few impurities such as unreacted low-molecular weight substances and catalysts. The polyhydroxypolyether resin sufficiently satisfies the above characteristics. In the known prior art, for example, a method of reacting in a hydrophilic solvent and then vigorously stirring in a large amount of water to extract a solid substance has been proposed. It is disadvantageous to the end, and cannot be done at all. The inventors have found the present invention as a result of earnest research.

"Means for Solving Problems" The present invention relates to a method for producing a halogen-containing polyhydroxypolyether resin, which is a substantially equimolar reaction between halogenated bisphenols and halogenated bisphenols diglycidyl ether or halogens. Non-reactive high boiling point reaction solvent that dissolves raw materials and products in the presence of a catalyst in a substantially equimolar reaction of a mixture of a bisphenol dihalogenated bisphenol and a halogenated bisphenol diglycidyl ether and a bisphenol diglycidyl ether 100 ℃ ~ 2
After reacting at 20 ℃ until the reduced viscosity becomes 0.20 or more,
A halogen characterized by diluting with a reaction solvent to adjust the nonvolatile concentration to 20 to 60% by weight, and gradually adding a low boiling point solvent in which the reaction product is hardly soluble to the reaction mixture to separate and precipitate the reaction product. A method for producing a high-purity halogen-containing polyhydroxypolyether resin having a content of 20 to 62% by weight.
The product obtained by this production method has a phenolic acid value of 1 m.
It is a high-purity halogenated polyhydroxypolyether resin which has gKOH / g or less and an epoxy value of 2 mgKOH / g or less, and which has not been obtained by the prior art and contains substantially no epoxy group.

Examples of halogenated bisphenols used in the present invention have the general formula (In the formula, Xi and Xi ′ may be the same or different and are a halogen atom, that is, a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, and R ₂ is, for example, —S—, —SO ₂ —, an alkylene group. Is a methyl group, an ethylene group, a trimethylene group, or a tetramethylene group, and i and i ′ are integers of 1 to 4). Typically, 2,2 bis (4-hydroxy-2,3,5,6 tetrabromophenyl) propane, 2,2 bis (4-hydroxy-2,3,5,6 tetrachlorophenyl) propane, 2 , 2 bis (4-hydroxy-2,
3,5 tribromophenyl) propane, 2,2 bis (4-hydroxy-2,3,5 trichlorophenyl) propane, 2,2 bis (4-hydroxy-3,5 dibromophenyl) propane,
2,2 bis (4-hydroxy-3-bromophenyl) propane, 2,2 bis (4-hydroxy-3chlorophenyl)
Propane, 2,2 bis (4-hydroxy-2,3,5,6 tetrabromophenyl) methane, 2,2 bis (4-hydroxy-2,2
3,5, tribromophenyl) methane, 2,2bis (4-hydroxy-2,3dibromophenyl) methane, 2,2bis (4-
Hydroxy-3 bromophenyl) methane, 2,2 bis (4
-Hydroxy-2,3,5,6 tetrabromophenyl) sulfone, 2,2 bis (4-hydroxy-2,3,5,6 tetrabromophenyl) sulfide and the like can be mentioned. Examples of diglycidyl ethers of halogenated bisphenols include diglycidyl ethers prepared by a known method from halogenated bisphenols represented by the general formula [I] and epichlorohydrin, and the diglycidyl ethers and halogenated bisphenols. It is a diglycidyl ether polymerized by a known method with phenols. Typically, it is brominated bisphenol A diglycidyl ether (YDB-400, manufactured by Tohto Kasei Co., Ltd.) and other bifunctional epoxy resins such as bisphenol A diglycidyl ether, diphenyl sulfone diglycidyl ether, tetrabromo. You may use diphenyl sulfone diglycidyl ether etc. together in 0-66 weight part range. The halogenated bisphenols used for the purpose of the present invention have a purity (area percentage) by liquid chromatography of preferably 99.5% or more, and in diglycidyl ether, α-glycol content and Hydrolyzed chlorine 3m eq / 100g, 500p
Good results are obtained by containing a high-purity epoxy group of pm or less.

The reaction solvent used in the present invention is a non-reactive, high-boiling point aliphatic cyclic ketone, high-boiling point aromatic hydrocarbon, or ethylene glycol lower alkyl ether ester, which is used alone or as a mixture of the above-mentioned solvents to produce a reaction product. It is used in a concentration range of 25 to 80 parts by weight. It is necessary to select the mixed solvent composition within a range in which it can be dissolved in the reaction product. Examples of the high boiling aliphatic cyclic ketones include cyclohexanone and methylcyclohexanone. As the high boiling aromatic hydrocarbon, tri or tetramethylbenzene,
Alkyl (C = 2-4) toluene, alkyl-substituted aromatic solvent such as branched alkylbenzene (C = 3-36), diethylbenzene, ethylene glycol lower alkyl ether ester as ethylene glycol diethyl ether, ethylene glycol monoethyl ether Acelate, ethylene glycol monobutyl ether, etc. are mentioned. It is preferable that the boiling point is in the range of 100 ° C to 220 ° C. The catalyst used in the present invention is an organic compound or a salt thereof, and a known catalyst which is usually used in the reaction between a phenolic OH and an epoxy group can be used. For example, there are tertiary amines, quaternary ammonium salts, and morphine compounds such as triphenylphosphine and salts thereof, and typically, tetramethylammonium chloride, triphenylphosphine, triphenylphosphonium bromide,
Examples include butoxyl-2-hydroxybropyrtriphenylphosphonium bromide. In order to obtain the substantially linear and high molecular weight halogenated polyhydroxy polyether resin of the present invention, diglycidyl ether is added in an amount of 0.95 to 1 mol of halogenated bisphenol in the above solvent.
In the range of 1.05 mol, more preferably 0.985 to 1.015
The reaction is carried out in a substantially equimolar range, and the reaction is carried out at a temperature in the range of 110 ° C to 220 ° C near the boiling point of the reaction solvent, and the reaction is continued until the reduced viscosity becomes 0.20 or more. Reduced viscosity is 0.
It is necessary to manage within the range of 20 to 0.4, preferably
It is in the range of 0.25 to 0.35. In the reduced viscosity of 0.20 or less, the reaction is not fully completed, the physical properties of the low molecular weight is a lot of the reduction of the physical properties of course, it is difficult to precipitate crystals in the crystallization operation of the subsequent steps, and This is a disadvantage because it lowers the yield. On the other hand, when the ratio is 0.4 or more, the reaction solution becomes thick and stirring becomes impossible, and gelation occurs. Substantially 5 hours or more of reaction time is required. The reaction is terminated when the reduced viscosity reaches 0.20 or more, but 1 to 5% of unreacted low-molecular compound remains in the reaction product at this point. ing. The most characteristic point of the present invention is as follows. The reaction solution after completion of the reaction is a viscous transparent liquid, and the reaction solution is diluted with the reaction solvent while stirring to lower the temperature to adjust the concentration of nonvolatile components in the range of 20 to 60% by weight. Next, the reaction is carried out while cooling the aromatic hydrocarbons, ketones, alcohols, and aliphatic hydrocarbons, which are low-boiling solvents that are difficult to dissolve in the reaction, in the range of 2 to 6 times the reaction solvent. When added to the liquid, only the polymer reaction product is selectively deposited and separated. When the addition of the entire amount is completed, the unreacted low molecular weight compound and most of the catalyst used in the reaction are selectively dissolved in the reaction solvent, and this precipitate and the reaction solvent can be overseparated. The precipitate is washed with the same solvent or alcohols added after completion of the reaction, and dried under vacuum in a drying chamber at a temperature of 60 to 100 ° C. The white product thus obtained contains halogen in the range of 20 to 62% by weight, and has a very small amount of low molecular weight compounds and impurity ions. In addition, it is a halogenated polyhydroxypolyether resin that has a phenolic acid value of 1 mgKOH / g or less and an epoxy value of 2 mgKOH / g or less and that is substantially free of epoxy groups and has excellent thermal stability. The separated reaction solution can easily be separated into low-boiling point solvents by using a distillation apparatus according to the type of solvent and can be recycled and reused. Further, a low-molecular compound and a catalyst contained in the reaction solvent and the solution can be used, and the amounts may be corrected. Therefore, in the method of the present invention, it is epoch-making that it is a high-purity product with no waste water that poses a problem in terms of pollution, and cannot be overwhelmed by conventional manufacturing methods. As a solvent for precipitating the product, aromatic hydrocarbons, ketones, alcohols, and aliphatic hydrocarbons, which are low boiling point solvents having a boiling point difference from the reaction solvent, are typically benzene, toluene, methyl ethyl ketone, and methyl. Examples thereof include isobutyl ketone, methanol, ethanol, normal hexane and the like.

"Function" The production method according to the present invention is characterized in that a highly pure halogenated polyhydroxypolyether resin having a substantially linear and high molecular weight is obtained. That is, it has a reduced viscosity of 0.20 or more, contains 20 to 62% by weight of halogen, and has substantially no epoxy group as shown by a phenolic acid value of 1 mgKOH / g or less and an epoxy value of 2 mgKOH / g or less. . Select diglycidyl ether with low purity and low impurities by liquid chromatography of halogenated diphenylols used as a raw material, and in the reaction of halogenated bisphenols with the diglycidyl ether, branched side reaction and discoloration easily occur at 220 ° C. It is possible to avoid the above high temperature reaction and keep it at a low temperature in the presence of a solvent to prevent side reactions and discoloration. However, a low molecular weight unreacted product still remains in the reaction product. In these reaction mixtures, there is a difference in solubility between the polymer reaction product, the low-molecular unreacted product, and the catalyst, and the polymer reaction product can be easily separated from the solvent by selecting the solvent composition and solvent concentration. Can be Further, the polymer product is an application of the property that solvent solubility is very different depending on the size of the molecular weight. Further, by gradually adding the low boiling point solvent to the reaction liquid after the reaction, the dissolving ability thereof can be gradually decreased, so that the polymer reaction product can be taken out as a uniform fine powder precipitate. The low boiling point solvent is capable of selectively extracting low molecular weight unreacted substances, catalysts and the like, and is stably dissolved in the solvent. By these actions, the high molecular reaction product and the low molecular unreacted substances and impurities such as catalysts can be easily separated. The quantitative methods of the reduced viscosity, epoxy value and phenolic acid value of the product obtained in the present invention are shown below.

Reduced viscosity This is a value measured by dissolving 0.2 g of a sample in tetrahydrofuran to prepare a 100 ml solution and using a Canon-Fenske viscometer in a thermostat at 25 ° C.

Epoxy Value Add 5 ml of hydrochloric acid / pyridine = 16/484 (volume ratio) solution and 100 g of benzyl alcohol to 3 g of the sample and stir at 20 times occasionally.
After refluxing for 1 minute, the unreacted pyridinium chloride is back titrated with 0.1N alcoholic KOH.

Phenolic acid value Add 25 g of a mixed solvent of toluene / benzyl alcohol = 2/1 (weight ratio) to 3 g of the sample and dissolve by heating at 100 ° C, then add 0.1N.
Determined by titration with alcoholic KOH.

Hereinafter, the present invention will be described in detail with reference to examples, but the invention is not limited thereto.

"Examples and Comparative Examples" Example 1 150.3 g of an epoxy equivalent of 401.3 g / eq of tetrabromobisphenol A-epichlorohydrin type epoxy resin (YDB-400, Toto Kasei Co., Ltd., Br = 48.9% by weight), an epoxy equivalent 186.8 g / eq and bisphenol A-epichlorohydrin type epoxy resin (YD-128, manufactured by Toto Kasei Co., Ltd.) 19.5 g,
Tetrabromobisphenol A (abbreviated as TBA below) 13
0.2 g, mixed solvent of cyclohexanone and solvent naphtha as solvent (mixing weight ratio 1/1, hereinafter abbreviated as mixed solvent) 53 g
Was charged in a separable flask of 1 and stirred and heated while purging with nitrogen. When the internal temperature reached 110 ° C, 250 ppm of catalyst butoxyl 2-hydroxypropyltriphenylphosphonium bromide was added.

Furthermore, the temperature is gradually raised and the reaction is carried out at 160 ° C ± 5 ° C. After 3 hours, 47 g of the mixed solvent and 250 ppm of the catalyst phosphonium salt were added because the viscosity gradually increased. After 2 hours, 62 g of a mixed solvent was added. Further, the mixture was reacted for 7 hours under stirring. The reduced viscosity of the product at this time was 0.27 cst. Then, the temperature was lowered to around 100 ° C. while adjusting the nonvolatile content to 40% by weight with a mixed solvent, 338 g of methanol was added, and the mixture was crystallized while stirring. Pass this crystal over with methanol at 40 ℃ ~
After stirring and washing at 50 ° C. for 30 minutes, it was overdried. 291.3 g of white, finely divided product was obtained. Table 1 shows the measurement results of the properties.

Example 2 As in Example 1, 178.1 g of YDB-400, 121.9 g of TBA, and 53 g of solvent cyclohexanone (hereinafter abbreviated as anone) were charged and the temperature was raised while purging with nitrogen. 150 ppm of tetramethylammonium chloride was added as a catalyst and stirred. While 150 ℃
React at ± 5 ° C. Anon 47 because it gradually thickens
g and 150 ppm of catalyst were added. The mixture was further diluted with anone with stirring and reacted for a total of 10 hours. The reduced viscosity of the product at this time was 0.28 cst. After that, use anon to remove the non-volatile
The weight ratio was adjusted to 338 g of n-hexane, and crystallization was performed while stirring. Pass this crystal over with ethanol at 40 ℃
After stirring and washing at -50 ° C for 30 minutes, it was overdried. Table -1 shows the measurement results of the properties of 293 g of the product obtained.

Example 3 YDB-400 150.3 g, YD with the same charging amount as in Example 1
-128 19.5 g, TBA 130.2 g, mixed solvent 53 g were charged, and the catalyst butyltriphenylphosphonium bromide was 250 ppm.
Add and react as in Example 1 (product reduced viscosity 0.26cs
After t) and dilution, the nonvolatile content was adjusted, 338 g of methyl ethyl ketone was gradually added, and the mixture was crystallized with stirring.
The crystals were washed with methanol and overdried to obtain 292.5 g of a product. Table 1 shows the measurement results of the properties.

Example 4 Similar to Example 2, 178.1 g of YDB-400, 121.9 g of TBA, and 53 g of a mixed solvent after completely separating methanol from the mixed solvent separated and recovered after crystallization of the product in Example 1
Charged and reacted in the same manner as in Example 2 using 2-ethyl, 4-methylimidazole as a catalyst (reduced viscosity of product:
Then, 338 g of toluene was gradually added as a crystallization solvent, which was diluted with the above-mentioned collected mixed solvent to cause crystallization, which was then filtered and washed with toluene at 50 ° C. or lower for 30 minutes.
After overdrying, 293.4 g of product was obtained. The properties are shown in Table 1.

Comparative Example 1 Immediately after completion of the charging reaction in the same manner as in Example 1, desolvation was immediately performed using a rotary evaporator at 120 ° C. and 3 torr for 30 minutes, and then a lump resin was melted in a vacuum oven at 230 ° C. I took it out. 298.8 g of a tan product (reduced viscosity 0.24 cst) was obtained. The properties are shown in Table 1.

Comparative Example 2 After the charging reaction was completed in exactly the same manner as in Example 2, the same treatment as in Comparative Example 1 was carried out. 298.5 g of a tan product was obtained (reduced viscosity 0.26 cst). The properties of are shown in Table-1.

"Effects of the Invention" The present invention provides a high-purity halogenated polyhydroxypolyether resin of high molecular weight, which cannot be obtained by conventional techniques, and can be obtained in a high yield, and is a pollution problem. It can be produced industrially advantageously without generation of Further, the product obtained according to the present invention is substantially linear and has a high polymer purity, and also has excellent heat resistance and flame retardancy brought about by the molecular structure, excellent hardness, flexibility and chemical resistance. In addition, it has excellent thermal stability and electrical characteristics. Therefore, it is industrially useful as a heat-resistant and flame-retardant substrate for electric and electronic paints, adhesives, self-fusing electric wire coatings, films and the like. Further, it is expected to have excellent properties as a flame retardant for synthetic fibers and thermoplastic resin moldings, and has a wide range of functions such that transparent moldings having a high refractive index can be obtained. It can be expected to be applied as an engineering plastic with flame retardancy.

Claims (3)

[Claims] 1. A substantially equimolar reaction between a halogenated bisphenol and a halogenated bisphenol diglycidyl ether, or a substantially equal reaction between a halogenated bisphenol and a mixture of a halogenated bisphenol diglycidyl ether and a bisphenol diglycidyl ether. In a molar reaction, the reduced viscosity is 100 ° C to 220 ° C using a non-reactive high-boiling point reaction solvent that dissolves raw materials and products in the presence of a catalyst.
After reacting until it becomes 20 or more, it is diluted with the reaction solvent to adjust the non-volatile content to 20 to 60% by weight, and the reaction product is prepared by gradually adding the low boiling point solvent in which the reaction product is hardly soluble to the reaction mixture. The halogen content of 20
A method for producing a high-purity halogen-containing polyhydroxypolyether resin having a content of ˜62% by weight. 2. The method for producing a high-purity halogen-containing polyhydroxypolyether resin according to claim 1, wherein the reaction solvent having a high boiling point is cyclohexanone or a mixture of cyclohexanone and an alkyl-substituted aromatic solvent. 3. The low boiling point solvent is methanol, methyl ethyl ketone, normal hexane, and toluene, and the solvent for separating and depositing the reaction product is in the range of 2 to 6 times the reaction solvent. A method for producing the high-purity halogen-containing polyhydroxypolyether resin described.