JPS59500918A - Method for increasing the molecular weight of epoxy resins using phosphonium trifluoroacetate catalysts - 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] Increasing the molecular weight of epoxy resins using phosphonium trifluoroacetate catalysts how to make it big To date, the molecular weight of epoxy resins is a dump in U.S. Patent No. 5,477.990. and in Canadian Patent No. 893,191 and U.S. Patent No. 3.948,855. has been enhanced in the presence of the phosphonium catalyst disclosed by Berry. death However, the amount of catalyst used was sufficient to keep the epoxide value close enough to the theoretical epoxide value percentage. Although it provides a resin with a high acid value ratio, it does not provide improved properties.

U.S. Patent Nos. 4,325,918 and 4,370.465 disclose that the obtained Epoxy resin with increased molecular weight has a lower epoxide value than the theoretical epoxide value percentage improved by using sufficient amount of phosphonium catalyst to have a ratio of Discloses the production of increased molecular weight epoxy resins with improved physical properties.

The method of the present invention produces an epoxy 4.67 ov46 lower than the theoretical epoxide value percentage. Molecular weight increased epoxy resin produced by the method described in No. 5 The molecular weight increased epoxy resin has a desirable lower color than that produced by Provides xy resin. Epoxy obtained by analysis from theoretical epoxide value percentage The difference obtained by reducing the Sid value ratio is 0.5 to 4, often 1 to 2. Ru. The increased molecular weight epoxy resin made by the method of this invention can be used for electrical lamination. Suitable for use in manufacturing products.

2 The present invention is directed to (A) a divalent compound having an average of more than 1 glycidyl ether group per molecule; Epoxy resins that are phenol or thiophenol and glycidyl ether -) divalent (C) the presence of a phosphonium compound; In a method of increasing the molecular weight of epoxy resin by reacting with Using phosphonium trifluoroacetate as the catalyst, component (G) and a method characterized by the following.

Dihydric phenol that can be used in the present invention (the formula has 1 to 8 glycidyl groups) each X is independently hydrogen, chlorine, bromine or 1 to 10 carbon atoms. is a hydrocarbon group having carbon atoms, each Z is independently O or S, and X is 0 or &j1 and n is EKW of 156 to 40 based on calculations where X is hydrogen. 0, preferably 177 to 190) This includes compounds represented by

Diglycidylenes of 4Hc Hisphenol A and Tetrabromobisphenol A -tel is particularly suitable.

The phenol or thiophenol compound having the general formula (wherein A, X, Z and Y are as described above), such as compounds represented by Contains roquinone, renorsinol and bisphenol.

Particularly suitable divalent phenolic compounds are bisphenol A and tetrabromobis Al with phenol A.

The small sulfonium trifluoroacetate salt catalyst used in this invention is substantially pure. (or it may be a tetrahydrocarbylphosphonium compound) Purification other than filtration of solid precipitated by-products of reactions with trifluoroacetic acid or its salts It can also be made on the spot.

Suitable phosphonium compounds that can be used in the present invention include, for example, the general formula (wherein each R is independently a hydrocarbon having 1 to 20, preferably 1 to 6 carbon atoms) or substituted hydrocarbyl) Contains compounds with sulfonium cation groups. at least one of H, preferably 2 and most preferably 5 phosphorus atoms are aryl or alkaryl groups. an aromatic group, i.e. an aryl group or an aromatic group, such that the aromatic group It is a rukyl group.

"Hydrocarbyl" means alkyl, aryl, alkaryl, aralkyl or cyclic Alternatively, it may be an acyclic alkyl group. Substituted hydrocarbyl refers to its hydrocarbyl The building group is an example of C4Br.

Containing one or more substituents such as No.2 and mixtures thereof means.

The R group contains substituents that do not deactivate the catalyst under the conditions under which the catalyst is used. Also good.

The phosphonium group has at least one aromatic group directly bonded to the phosphorus atom and and at least one alkyl group.

Suitable anions include, for example, GIJ, Br, and chloride, carbon, etc. Rubonate, dicarboxylate, phosphate, nitrate, sulfate, nitrite, sulfite Including acid salts, borates, chromates and mixtures thereof.

The two phenols and the diglycidyl ether of the dihydric phenol are The theoretical epoxide proportion of the product obtained has a desirable value.

Of course, the amount of catalyst will vary depending on the type of catalyst used, but for most catalysts, is 0.1 to 1.5 parts by weight of catalyst per 100 parts by weight of glycidyl ether of dihydric phenol. Parts by weight, preferably 0.2 to 0.8 parts by weight, can be used.

Although the reaction conditions used to produce epoxy resins with increased molecular weight vary, , 1000 DEG to 200 DEG C., preferably 120 DEG to 160 DEG C. can be used. common Lower temperatures require longer reaction times, while higher temperatures require shorter reaction times. Ru.

The reaction used was not particularly critical and 1 mmH9~1[]Onsig(0, 1-7.9. ．． 1 kPa, ). However, 5~20r+s It is usually preferred to use a pressure of 13 φ to 2 9 Pa).

Any of the known curing agents may be used in the present invention to cure the epoxy resin. Can be used. Such curing agents include, for example, amines, amides, guanidines, phenols, etc. Substances containing basic hydroxyl groups: carboxylic acid, carboxylic anhydride, imidanol, biguanite and a mixture thereof.

Particularly suitable curing agents are, for example, dicyandiamide and butramethylguanidine. guanidines such as phenols, polyhydric phenols, and mixtures thereof.

The amount of curing agent used depends on the type of curing agent used and on the resulting cured resin. depending on the nature of the Lee and Neville.

HANDBOOK OF EPOXY RESINS, McCra, w Hi Ill., 1967.

Percentage of theoretical epoxide (·Sat, calculated by the formula: EqER−Epoxy Epoxide equivalent weight from resin 6 EqDHP = phenolic hydroxy equivalent from dihydric phenol WtF, R-Used weight of epoxy resin W1; DHP = Weight of divalent phenol used.

The actual percentage of epoxide (epoxide analysis percentage) is the percentage of tetrabromide in glacial acetic acid. Liberate the hydrogen bromide generated by addition of ethyl ammonium and oversalt in glacial acetic acid. By titrating with basic acid and using crystal violet as an indicator, Determined experimentally. Epoxy groups can be combined with perchloric acid and tetraethylammonium bromide. Reacts stoichiometrically with hydrogen bromide generated from the reaction. Epoxy groups react When stored, free hydrogen bromide discolors crystal violet.

The phosphonium salt used as an epoxy molecular weight increasing catalyst in Example (Coating 1) The refluoroacetate salt was prepared by the synthesis described below.

71 Josaku 9-500918 (a) ■ Trademark of The Dowsha Chemical Company The procedure (A) described above is an example It was used to produce the catalysts used in 1-5.

The above procedure (c) uses the catalysts used in Examples 6-8, Karasu and 1o-12. used for manufacturing.

The above procedure (CI) was used to produce the catalysts used in comparative experiments A-C. was used.

The above procedure was used to prepare the catalyst used in Example 9.

General procedure for resin production Reaction vessel with pressure regulator, stirrer, temperature control and nitrogen purge instructions Identification of the desired amount of diglycidyl ether and the desired amount of low molecular weight dihydric phenol dihydric phenol or thiophenol was added. There is nothing special about the mixture. 5°C/min (0,083°C/sec) with a constant flow of N2 over the reactor. heated at a rate of When the temperature of the mixture reached 60'C, the A predetermined amount of the specific phosphonium salt was added. The mixture (in Table I A or B) was heated at the desired reaction conditions to give the desired product.

The reaction conditions (A) were temperatures of 160°C, 140°C, and 150°C for 1 hour (3600°C). ) and finally heat the reaction mixture for 2 hours (7200 seconds) at a temperature of 160°C. consists of doing. The reactor) is directly heated to 150℃ while generating heat. , and then heating at 160°C for 6 hours (10800 seconds).

Liquid with average epoxide equivalent weight of 1799, epoxide proportion of 23.90 Average epoxide equivalent weight of diglycidyl ether to bisphenol of 188.6 diglycidyl ether of liquid bisphenol A with an epoxide proportion of 22.8 -7 le.

Epoxy resin C A liquid having an average epoxide equivalent weight of 22Z5 and an epoxide 9 proportion of 18.9. It was a diglycyl compound of 2,2'-diallylbisphenol A.

Equivalent weight of phenolic hydroxyl group of dihydric phenol or thiophenol A272 and a bisphenol having a phenolic hydroxyl equivalent weight of 114 and an odor of 58.85%. Alcohol A was a dihydric phenol.

Dihydric phenol or thiophenol C 2,2'-diallylbisphenol having a phenolic hydroxyl equivalent weight of 155 A, 4,4' having a thiophenolic equivalent weight of 118 dihydric phenols - Phenoxybenzenethiol, phenolic decahydrate of divalent thiophenol 125 4,4'sulfonyldiphenol, dihydric phenol with acid group equivalent weight 14 Special edition 1984-500918 (5)

Claims (1)

[Claims] 1. (A) Dihydric phenol having an average of more than 1 glycidyl ether group per molecule and (B) a glycidyl ether of glycidyl phenol or thiophenol. phenol or thiophenol compound (q catalytic amount of phosphonium catalyst). A method of increasing the molecular weight of epoxy resins consisting of reacting in the presence of The use of phosphonium trifluoroacetate as the catalyst component (Gl) and a method of patenting it. 2. The catalyst is trifluoroacetic acid or its salt and halogenated as an anion. substance, carboxylate, dicarboxylate, carboxylate, carboxylic acid leadide, phosphide Contains nitrates, nitrates, sulfates, nitrites, sulfites, borates, or chromates. 2. The method of claim 1, wherein the phosphonium compound is formed in situ from a phosphonium compound. The catalyst is trifluoroacetic acid and ethyltriphenylphosphonium acetate. - A method according to claim 2, which is prepared in situ from an acetic acid complex salt.