JP5551151B2 - New epoxy compounds - Google Patents

Description

  The present invention relates to a novel epoxy compound, and more particularly to a dioxiranyl alkoxy compound having a 1,4-dioxyphenyl-bicyclohexene skeleton. Such an epoxy compound according to the present invention is useful as a heat-resistant reactive compound because it has four cyclic hydrocarbon groups at the center of the molecule and oxirane groups at both ends of the molecule.

Conventionally, many compounds are known as epoxy compounds. In recent years, in the field of electronic materials and the like, there has been a demand for epoxy compounds having improved heat resistance performance over conventional compounds. In response to such a demand, for example, an epoxy compound having a rigid molecular skeleton such as a p-terphenyl skeleton or a p-quaterphenyl skeleton having a phenyl group bonded in a chain form has a heat resistance and low water absorption. It is expected to be useful from the viewpoint of flame retardancy and low thermal expansion. However, such an epoxy compound, for example, 4,4 ′ ″-di (glycidyloxy) -p-quaterphenyl (Non-Patent Document 1, Tables 5 and 6) has poor solvent solubility and a high melting point. It is difficult to manufacture industrially, and when such an epoxy compound is made into a resin, high temperatures are required and handling is difficult. Similarly, an epoxy compound having a p-terphenyl skeleton has a high melting point and is difficult to handle.
Furthermore, a diglycidyl ether compound of 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) -1-cyclohexene having a cyclohexenyl skeleton in the central skeleton (Patent Document 1) is also known. However, such an epoxy compound is not sufficient to improve the performance of imparting heat resistance and mechanical strength.

JP 2005-206814 A

Proceedings of the 4th International Conference on Calorimetry in High Energy Physics, 1994

  The present invention has been made in order to meet the above-mentioned demand, and provides an epoxy compound that is easy to handle and has improved performance of conventional epoxy compounds, particularly excellent heat resistance, and excellent solubility in solvents. The task is to do.

  The inventors of the present invention have intensively studied to solve the above-mentioned problems. As a result, when two central phenyl rings in the p-quarterphenyl skeleton are bicyclohexene rings, the molecular length is approximately the same as that of the p-quarterphenyl skeleton. While maintaining, surprisingly, it becomes an easy-to-handle epoxy compound having a low melting point and excellent solvent solubility, and can be easily industrially manufactured, and such an epoxy compound has mechanical strength, flexibility, The present invention has been completed by finding out that it is excellent in performance improvement such as heat resistance, low water absorption, low thermal expansion, and imparting flame retardancy.

（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄は各々独立して炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシル基又はフェニル基を表し、ａ、ｂ、ｃ、ｄは各々独立して０又は１〜４の整数を表し、Ｒ₅、Ｒ₆、Ｒ₇は各々独立して水素原子又は炭素原子数１〜４のアルキル基を表す。）で表される。That is, the epoxy compound according to the present invention is
General formula 1

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or a phenyl group, and a, b, c , D each independently represents an integer of 0 or 1 to 4, and R ₅ , R ₆ and R ₇ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. .

（式中、Ｒ₁、Ｒ₄、ａ、ｄ、Ｒ₅、Ｒ₆、Ｒ₇は一般式１のそれと同じである。）で表されるエポキシ化合物は本発明の好ましい態様である。In the general formula (1), when b and c are 0,
General formula 2

An epoxy compound represented by the formula (wherein R ₁ , R ₄ , a, d, R ₅ , R ₆ , R ₇ are the same as those in formula 1) is a preferred embodiment of the present invention.

The novel epoxy compound according to the present invention is represented by the above general formula (1), and is, for example, a corresponding raw material as compared with the conventionally known 4,4 ′ ″-di (glycidyloxy) -p-quarterphenyl. It can be easily produced industrially from bisphenols. In addition, since the epoxy compound of the present invention has a low melting point, it can lower the curing temperature when it is made into a resin and has high solvent solubility and is easy to handle as a resin raw material.
In addition, since it has a 4,4′-di (phenyl) bicyclohexene skeleton in which a benzene ring is linearly bonded to both ends of two cyclohexene rings, an epoxy resin using such an epoxy compound as a raw material has a mechanical strength and a good strength. Excellent flexibility, heat resistance, low water absorption, low thermal expansion, high thermal conductivity and / or flame retardancy.

で示されるエポキシ化合物において、式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄は各々独立して炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシル基又はフェニル基を表す。ａ、ｂ、ｃ又はｄが２以上の場合、Ｒ₁、Ｒ₂、Ｒ₃又はＲ₄はそれぞれ同一でも違っていてもよい。The following general formula 1 of the present invention

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or a phenyl group. . When a, b, c or d is 2 or more, R ₁ , R ₂ , R ₃ or R ₄ may be the same or different.

The alkyl group having 1 to 8 carbon atoms is a linear, branched or cyclic alkyl group, and these alkyl groups are substituted with 1 to 2 aromatic hydrocarbon groups such as a phenyl group. May be. Preferably, it is a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.
Specific examples of the alkyl group having 1 to 8 carbon atoms include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a cyclohexyl group, a cyclopentyl group, and a substituted alkyl group such as benzyl. Groups and the like.

The alkoxyl group having 1 to 8 carbon atoms is a linear, branched or cyclic alkoxyl group, and these alkoxyl groups are substituted with 1 to 2 aromatic hydrocarbon groups such as a phenyl group. You may do it. Preferably, it is a linear or branched alkoxyl group having 1 to 4 carbon atoms or a cycloalkoxyl group having 5 to 8 carbon atoms. Specific examples of the alkoxyl group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, a cyclohexyloxy group, and a cyclopentyloxy group.
Further, when R ₁ , R ₂ , R ₃ , and R ₄ are phenyl groups, the phenyl group has 1 to 3 alkyl groups having 1 to 8 carbon atoms and / or alkoxyl groups having 1 to 8 carbon atoms. It may be replaced. Specific examples include a phenyl group, a 4-methylphenyl group, and a 4-methoxyphenyl group.

In the formula, a, b, c, and d each independently represent 0 or an integer of 1 to 4, and when b or c is 2 or more, R ₂ from the viewpoint of ease of production and economy. Or it is preferable that each R < ₃ > is not couple | bonded with the same carbon atom. In the formula, b and c are preferably the same for the same reason as described above, and both b and c are more preferably 0, 1 or 2. When b and c are both 1 or 2, R ₂ and R ₃ are preferably both alkyl groups, more preferably methyl groups. The substitution position of R ₂ and R ₃ is preferably a position other than the 1,1′-position of the 1,1′-bicyclohexane-3,3′-diene skeleton, and the 3,3′-position, 5,5′-position or 3 , 3 ′, 5, 5 ′.
In the formula, a and d are preferably the same, and more preferably a and d are both 0, 1 or 2. When a and d are 1 or 2, the substitution position on the phenyl nucleus is preferably ortho to the ether group.

In the formula, it is preferable that at least one of R ₁ , R ₂ , R ₃ and R ₄ is a phenyl group, since flame retardancy and heat resistance are expected to be further improved. More preferably, at least one of R ₁ and R ₄ is a phenyl group.
In the formula, R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms is, for example, a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group. It is done. R ₅ , R ₆ and R ₇ are preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.
For example, in the general formula (1), a and d are 0 or 1, b and c are 0, R _{5 to} R ₇ are hydrogen atoms, and R ₁ and R ₄ are alkyl groups having about 1 to 3 carbon atoms. In this case, the epoxy compound is preferable in that it has molecular orientation such as liquid crystal.

（式中、Ｒ₁、Ｒ₄、ａ、ｄ、Ｒ₅、Ｒ₆、Ｒ₇は一般式１のそれと同じである。）で表されるエポキシ化合物であり、より好ましい態様としては、Ｒ₅、Ｒ₆、Ｒ₇が共に水素原子である場合の、
一般式３

（式中、Ｒ₁、Ｒ₄、ａ、ｄ、は一般式１のそれと同じである。）で表されるエポキシ化合物である。Therefore, for the epoxy compound represented by the general formula (1) according to the present invention, as a preferred embodiment,
In the general formula (1), when b and c are 0,
General formula 2

(Wherein R ₁ , R ₄ , a, d, R ₅ , R ₆ and R ₇ are the same as those in general formula 1), and a more preferred embodiment is R ₅ , R ₆ and R ₇ are both hydrogen atoms,
General formula 3

(Wherein R ₁ , R ₄ , a and d are the same as those in general formula 1).

４，４'−ビス（４−グリシジルオキシ−３−メチルフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、

４，４'−ビス（４−グリシジルオキシフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−３−エチルフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−３−イソプロピルフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−３−ｔ−ブチルフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−３−シクロヘキシルフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−３，５−ジメチルフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−２，５−ジメチルフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−３−イソプロピル−５−メチルフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−３−メトキシフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−３−シクロヘキシルオキシフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−３−フェニルフェニル）−３，３'−ジメチル−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−３−メチルフェニル）−３，３'−ジメチル−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシフェニル）−３，３'−ジメチル−１，１'−ビシクロヘキサン−３，３'−ジエン、
４−（４−グリシジルオキシ−３−フェニルフェニル）−４'−（４−グリシジルオキシ−３−メチルフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−グリシジルオキシ−３−フェニルフェニル）−５，５'−ジメチル−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−（２−メチルオキシラニルメトキシ）−３−フェニルフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−（２−メチルオキシラニルメトキシ）−３−メチルフェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン、
４，４'−ビス（４−（２−メチルオキシラニルメトキシ）フェニル）−１，１'−ビシクロヘキサン−３，３'−ジエン等が挙げられる。As such an epoxy compound, for example,
4,4′-bis (4-glycidyloxy-3-phenylphenyl) -1,1′-bicyclohexane-3,3′-diene,

4,4′-bis (4-glycidyloxy-3-methylphenyl) -1,1′-bicyclohexane-3,3′-diene,

4,4′-bis (4-glycidyloxyphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-3-ethylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-3-isopropylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-3-tert-butylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-3-cyclohexylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-3,5-dimethylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-2,5-dimethylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-3-isopropyl-5-methylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-3-methoxyphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-3-cyclohexyloxyphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-3-phenylphenyl) -3,3′-dimethyl-1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-3-methylphenyl) -3,3′-dimethyl-1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxyphenyl) -3,3′-dimethyl-1,1′-bicyclohexane-3,3′-diene,
4- (4-glycidyloxy-3-phenylphenyl) -4 ′-(4-glycidyloxy-3-methylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-glycidyloxy-3-phenylphenyl) -5,5′-dimethyl-1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4- (2-methyloxiranylmethoxy) -3-phenylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4- (2-methyloxiranylmethoxy) -3-methylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4- (2-methyloxiranylmethoxy) phenyl) -1,1′-bicyclohexane-3,3′-diene and the like can be mentioned.

（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、ａ、ｂ、ｃ、ｄは一般式（１）のそれと同じである。）
一般式（５）

（式中、Ｒ₅、Ｒ₆、Ｒ₇は一般式（１）のそれと同じであり、Ｘはハロゲン原子を表す。）
Ｘは好ましくは塩素原子、臭素原子である。The production method of the epoxy compound represented by the general formula (1) according to the present invention is not particularly limited, and a known production method, for example, bis (4-hydroxyphenyl) represented by the general formula (4) Examples thereof include a method in which bicyclohexenes and a halogenated alkyloxirane represented by the general formula (5) are reacted in the presence of a quaternary ammonium salt and / or a base.
General formula (4)

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , a, b, c and d are the same as those in the general formula (1).)
General formula (5)

(In the formula, R ₅ , R ₆ and R ₇ are the same as those in the general formula (1), and X represents a halogen atom.)
X is preferably a chlorine atom or a bromine atom.

  Next, the bis (4-hydroxyphenyl) bicyclohexene of the general formula (4) and the halogenated alkyloxirane of the general formula (5) are reacted in the presence of a quaternary ammonium salt and / or a base. The method for producing the epoxy compound represented by the general formula (1) according to the above will be described in more detail.

In order to obtain the epoxy compound represented by the general formula (1), a bis (hydroxyphenyl) compound represented by the general formula (4) corresponding to the structure of the epoxy compound may be used as a raw material. Therefore, as the bis (4-hydroxyphenyl) bicyclohexene represented by the general formula (4), for example,
4,4′-bis (4-hydroxy-3-phenylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxy-3-methylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxyphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxy-3-ethylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxy-3-isopropylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxy-3-tert-butylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxy-3-cyclohexylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxy-3,5-dimethylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxy-2,5-dimethylphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxy-3-methoxyphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxy-3-cyclohexyloxyphenyl) -1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxy-3-phenylphenyl) -3,3′-dimethyl-1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxy-3-methylphenyl) -3,3′-dimethyl-1,1′-bicyclohexane-3,3′-diene,
4,4′-bis (4-hydroxyphenyl) -3,3′-dimethyl-1,1′-bicyclohexane-3,3′-diene,
4- (4-hydroxy-3-phenylphenyl) -4 ′-(4-hydroxy-3-methylphenyl) -1,1′-bicyclohexane-3,3′-diene,
Examples include 4,4′-bis (4-hydroxy-3-phenylphenyl) -5,5′-dimethyl-1,1′-bicyclohexane-3,3′-diene.

Such bis (4-hydroxyphenyl) bicyclohexenes are not particularly limited in terms of the production method, but according to known methods such as JP-A No. 2000-034248, WO 2004/035513, etc., for example, 4,4′-bicyclohexanone is reacted with phenols to obtain 4,4,4 ′, 4′-tetrahydroxyphenyl-bicyclohexane corresponding to the target product, and 100 parts by weight of the obtained bicyclohexane is added. In the presence of an alkali catalyst such as sodium hydroxide and potassium hydroxide in an amount of about 0.1 to 15 parts by weight with respect to 100 parts by weight of the bicyclohexane in a reaction solvent such as about 100 to 800 parts by weight of tetraethylene glycol. At a temperature of about 180 ° C. to 250 ° C., when pyrolysis is performed under normal or reduced pressure, The end point of decomposition reaction, after completion of the reaction, from the reaction mixture obtained, the desired bis (4-hydroxyphenyl) bicycloalkyl cyclohexenes can be good purity prepared by the process of crystallization or the like.
Alternatively, according to the method described in JP-A-58-140028, 4,4′-bicyclohexanediones and 4-alkoxybenzene magnesium bromide corresponding to the target raw material bis (4-hydroxyphenyl) bicyclohexene And 4,4′-bis (4-alkoxyphenyl) -1,1′-bicyclohexane-3,3′-diene, and the resulting bis (4-alkoxyphenyl) The desired bis (4-hydroxyphenyl) bicyclohexenes can also be obtained by removing the alkyl group of the alkoxyl group from a known method such as boron tribromide and replacing it with a hydrogen atom. Two or more types of 4-alkoxybenzene magnesium bromides may be used in the synthesis of the bis (4-alkoxyphenyl) s.

  Examples of the halogenated alkyloxirane represented by the general formula (5), which is another raw material for obtaining the epoxy compound represented by the general formula (1), include chloromethyloxirane (epichlorohydrin), bromomethyloxirane, 2-chloromethyl-2-methyloxirane (β-methylepichlorohydrin), 2-bromomethyl-2-methyloxirane, 2-chloromethyl-3-methyloxirane, 2-chloromethyl-2-methyl-3-ethyloxirane, 2 -Chloromethyl-2,3-dimethyloxirane and the like. These compounds may be used alone, or two or more of them may be used as necessary.

  In addition, the amount of the halogenated alkyloxirane of the general formula (5) used in the reaction can be used as a solvent itself, and is usually 2 per 1 mol of the raw material bis (4-hydroxyphenyl) bicyclohexene. It is used in a range of -100 mol times, preferably 2-50 mol times.

  Examples of the basic compound include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, etc. And inorganic salts such as alkali metal carbonates, and organic amines such as pyridine and triethylamine. Examples of the quaternary ammonium salt include tetrabutylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, benzyltrimethylammonium chloride and the like. The amount of the basic compound and quaternary ammonium salt used is usually 0.05 to 1 mol, preferably 0.1 to 0.5 mol, per mol of the raw material bis (4-hydroxyphenyl) bicyclohexene. Used in the double range. A reaction method in which a reaction is started in the presence of a quaternary ammonium halide such as tetrabutylammonium bromide, and an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate is additionally added when the raw material bicyclohexene disappears during the reaction. Is preferred.

In addition, the amount of the inorganic base to be added when the raw material bicyclohexene disappears is usually 0.1 to 10 moles, preferably 1 to 5 moles per mole of the raw material bicyclohexenes.
These basic compounds may be used as they are or as an aqueous solution.
In the reaction, a solvent may be used as necessary.

  Examples of the organic solvent include aliphatic hydrocarbons such as n-pentane and n-hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and ethylbenzene, and hydrophilic solvents. Alcohols such as methanol, ethanol, n-propanol and n-butanol, glycols such as ethylene glycol and trimethylene glycol, aliphatic ketones such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone, acetonitrile, propionitrile, etc. Aliphatic nitriles, aliphatic ethers such as dimethyl ether and diethyl ether, alicyclic ethers such as 1,4-dioxane and tetrahydrofuran, N, N-dimethylformamide, N-methyl-2-pyrrolidone and the like Bromide such, and dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.

The usage-amount of a solvent is 0.1-50 weight part normally with respect to 1 weight part of raw material bicyclohexene, Preferably it is 1-20 weight part.
The reaction temperature is usually 20-100 ° C, preferably 30 ° C-70 ° C. The reaction may be carried out under normal pressure conditions or under reduced pressure conditions. The reaction time can be monitored by measurement such as liquid chromatography, and is usually completed in the range of 10 to 30 hours. Furthermore, after completion of the supply of the halogenated alkyloxirane and the basic compound, in order to complete the epoxidation reaction, 20 to 100 ° C., preferably 30 to 70 ° C., for about 1 to 5 hours, if necessary, the reaction system Is kept under stirring.

  After completion of the reaction, the method of isolating the target epoxy compound as crystals from the obtained reaction end mixture is in accordance with conventional methods. For example, after the reaction is completed, the reaction system is cooled, and distilled water and necessary are added to the reaction end mixture. In accordance with the above, the above-mentioned solvent is added and stirred, and then the alkali halide and halogenated alkyloxirane present in the system are removed, further neutralized if necessary, and the precipitated crystals are separated by filtration. Alternatively, the crystals may be dissolved once without being filtered and then crystallized, and the crystals may be filtered out. If necessary, for example, the purity of the crystals is low, crystallization or precipitation may be performed once to several times to further purify the crystals.

  The present invention will be described in more detail with reference to examples.

Example 1
Synthesis of 4,4′-bis (4-glycidyloxy-3-methylphenyl) -1,1′-bicyclohexane-3,3′-diene In a 300 mL four-necked flask equipped with a stirrer, 4,4 ′ -10.0 g of bis (4-hydroxy-3-methylphenyl) -1,1'-bicyclohexane-3,3'-diene (4H-DHQP-DM), 1.7 g of tetrabutylammonium bromide, epichlorohydrin After charging 74.1 g and replacing the system with nitrogen gas, the mixture was stirred at 50 ° C. for 12 hours. To the reaction solution, 3.2 g of sodium hydroxide was added and further stirred for 12 hours. After completion of the reaction, 30 g of toluene and 40 g of distilled water were added, and the mixture was stirred at 30 ° C. for 1 hour, and the precipitated crystals were separated by filtration. The obtained crystals were dried at 50 ° C. under reduced pressure and 4,4′-bis (4-glycidyloxy-3-methylphenyl) -1,1′-bicyclohexane-3,3′-diene in the form of white powder. 7 g was obtained. When differential scanning calorimetry was performed on the obtained compound, it was confirmed that there were endothermic peaks at two locations of 146 ° C and 227 ° C.

Yield: 90% (vs. 4H-DHQP-DM)
Purity: 93% (according to high performance liquid chromatography method)
Melting point: 146 ° C. (by differential scanning calorimetry)
Proton NMR measurement result (400 MHz, CDCl ₃ )
1.36-1.51 (m, 4H), 2.00 (br, 4H), 2.25 (s, 6H), 2.30-2.50 (m, 6H), 2.78 (dd, 2H), 2.90 (t, 2H), 3.37 (m, 2H), 3.97 (dd, 2H), 4.21 (dd, 2H), 6.03 (s, 2H), 6. 75 (d, 2H), 7.14-7.19 (m, 4H)

Reference example 1
Synthesis of 4,4′-bis (4-hydroxy-3-phenylphenyl) -1,1′-bicyclohexane-3,3′-diene In a 2 L four-necked flask equipped with a reflux condenser and a dropping funnel, o-Phenylphenol 603.1 g, methanol 27.8 g, toluene 60.3 g and dodecyl mercaptan 7.8 g were charged, and the inside of the container was replaced with hydrochloric acid gas. Then, the temperature of the flask was kept at 40 to 45 ° C. A mixture of 77.7 g of phenol, 50 g of methanol, and 77.7 g of 1,1′-bicyclohexane-4,4′-dione was dropped into the flask over 1 hour, and the reaction was performed with stirring. After completion of dropping, the reaction was further continued at 40 to 45 ° C. for 6 hours with stirring. After completion of the reaction, the mixture was neutralized by adding a 16% aqueous sodium hydroxide solution. Subsequently, toluene, methyl isobutyl ketone, and methanol were added to and mixed with this solution, and then the aqueous layer was removed. After adding water to the obtained oil layer, stirring at 60 ° C. and washing with water, the operation of removing the water layer was performed several times. The reflux unit provided in the flask was replaced with a distillation pipe, and the oil layer after washing with water was concentrated. To this, 6.0 g of 48% aqueous sodium hydroxide and 50 g of tetraethylene glycol were added, and the temperature was raised to 200 ° C. While maintaining, the pressure was reduced until the internal pressure became 20 mmHg, and the reaction was carried out with stirring for 8 hours and 30 minutes while distilling the produced o-phenylphenol at the same temperature. The resulting residue was cooled, neutralized by adding acetic acid, methyl isobutyl ketone and water, and then the aqueous layer was extracted. Next, after adding water to the obtained oil layer and stirring and washing with water, the operation of removing the aqueous layer was performed twice, the oil layer after washing with water was concentrated, toluene was added, and the mixture was cooled to room temperature and precipitated crystals. The product was filtered off and dried to give 4,4′-bis (3-phenyl-4-hydroxyphenyl) -1,1′-bicyclohexane-3,3′-diene 82 having a purity of 95% (according to high performance liquid chromatography). 0.1 g was obtained.

Example 2
Synthesis of 4,4′-bis (4-glycidyloxy-3-phenylphenyl) -1,1′-bicyclohexane-3,3′-diene In Reference Example 1, a 300 mL four-necked flask equipped with a stirrer was used. 10.0 g of 4,4′-bis (4-hydroxy-3-phenylphenyl) -1,1′-bicyclohexane-3,3′-diene (4H-DHQP-DP) obtained and tetrabutylammonium bromide 0 .8 g and epichlorohydrin 55.5 g were charged, and the system was replaced with nitrogen gas, followed by stirring at 50 ° C. for 15 hours. To the reaction solution, 3.4 g of potassium hydroxide was added and further stirred for 3 hours. After completion of the reaction, 30 g of toluene and 40 g of distilled water were added, and the mixture was stirred at 30 ° C. for 1 hour. The precipitated crystals were separated by filtration, and washed with 20 g of toluene and 20 g of distilled water. The obtained crystals were dried at 50 ° C. under reduced pressure and 4,4′-bis (4-glycidyloxy-3-phenylphenyl) -1,1′-bicyclohexane-3,3′-diene in the form of white powder. 3 g was obtained.

Yield: 84% (vs. 4H-DHQP-DP)
Purity: 98% (high performance liquid chromatography method)
Melting point: 186 ° C (differential scanning calorimetry)
Proton NMR measurement result (400 MHz, CDCl ₃ )
1.38-1.52 (m, 4H), 2.03 (br, 4H), 2.28-2.55 (m, 6H), 2.66 (dd, 2H), 2.79 (t, 2H), 3.25 (m, 2H), 3.97 (dd, 2H), 4.19 (dd, 2H), 6.10 (s, 2H), 6.93 (d, 2H), 7. 25-7.34 (m, 4H), 7.38-7.43 (m, 6H), 7.55 (d, 4H)

Claims (2)

General formula (1)

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or a phenyl group, and a, b, c , D each independently represents an integer of 0 or 1 to 4, and R ₅ , R ₆ and R ₇ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Epoxy compound. In the general formula (1), when b and c are 0, the general formula (2)

The epoxy compound of Claim 1 represented by (In formula, R < ₁ >, R < ₄ >, a, d, R < ₅ >, R < ₆ >, R < ₇ > is the same as that of General formula 1.).