JP3165678B2 - Method for producing epoxy compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a novel epoxy compound.

[0002]

2. Description of the Related Art Polyhydric phenolic compounds represented by bisphenol A are widely and generally used as starting materials for various high-performance polymers such as polyesters, polycarbonates, polyurethanes and epoxy resins. However, with the diversification of uses, improvement of heat resistance, moisture resistance, toughness and the like of these polymer materials is strongly demanded.

Therefore, a novel bisphenol compound has been proposed for the purpose of improving these physical properties (Japanese Patent Application Laid-Open No. 58-1983).
No. 18331) does not necessarily have sufficiently satisfactory physical properties even with a polymer compound obtained from such a bisphenol as a raw material.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing an epoxy compound which is excellent in heat resistance, moisture resistance and mechanical properties such as impact resistance.

[0005]

Means for Solving the Problems] That is, in the present invention,
The following general formula (1)

Embedded image (Wherein, R ₁ , R ₂ , and R ₃ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, n represents an integer of 0 to 15, and m represents an integer of 0 to 2) ) Is used as a raw material.

The phenolic compound is represented by the following general formula (2)

Embedded image (Where R ₃ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents an integer of 0 to 2) and a phenol represented by the following general formula (3)

[0007]

Embedded image (Wherein R ₁ , R ₂ , and R ₄ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms) with a phenol and a condensing agent in the presence of an acid catalyst. Reaction at a molar ratio (condensing agent / phenols) of 0.01 to 0.9
Is obtained by

The present invention, moles of a phenolic compound represented by the above following general formula (1) and epichlorohydrin, reaction temperature 60 to 120 ° C. in the presence of an alkali metal hydroxide and phenolic compound and epichlorohydrin Ratio (epichlorohydrin / phenolic compound) 0.9-1.
The reaction is carried out under the conditions of 2 and the following general formula (4)

Embedded image (Wherein, R ₁ , R ₂ , and R ₃ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, n represents an integer of 0 to 15, and m represents an integer of 0 to 2) And G represents a glycidyl group).

In the phenols represented by the general formula (2), R ₃ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents an integer of 0 to 2. Represented by general formula (2)
Specific examples of the phenols include phenol, o- cresol, m- cresol, 2,6-xylenol, o- ethylphenol, 2,6-diethyl phenol,
o-phenylphenol and the like.

In the condensing agent represented by the general formula (3), R ₁ , R ₂ and R ₄ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the condensing agent represented by the general formula (3) include, for example, 4,4′-dimethylolbiphenyl,
4,4'-dimethoxymethylbiphenyl, 4,4'-diethoxymethylbiphenyl, 4,4'-diisopropoxymethylbiphenyl, 4,4'-dihydroxyethylbiphenyl, 4,4'-
Di (1-methoxy-1-ethyl) biphenyl, 4,4'-di (1-
Isopropoxy-1-ethyl) biphenyl, 4,4'-di (2-
Hydroxy-2-propyl) biphenyl, 4,4'-di (2-methoxy-2-propyl) biphenyl, 4,4'-di (2-isopropoxy-2-propyl) biphenyl and the like.

When the phenol and the condensing agent are reacted with each other, the molar ratio of the condensing agent and the phenols must be not more than 1 mol per 1 mol of the phenols, preferably 0.0
It is in the range of 1 to 0.9 mole.

The reaction for producing a phenolic compound by reacting a phenol with a condensing agent is carried out in the presence of an acid catalyst. The acid catalyst can be appropriately selected from well-known inorganic acids and organic acids, for example, mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid, and p-toluenesulfonic acid; Boron trifluoride, zinc chloride,
Examples thereof include Lewis acids such as aluminum chloride and iron chloride, and solid acids.

This reaction is usually carried out at -50 to 250 ° C for 1 to 1
Performed for 20 hours. In the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, and aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as a solvent.

Furthermore, the phenolic compounds by reaction with epichlorohydrin, heat resistance at a relatively low viscosity, may be moisture-resistant, epoxy compounds having excellent toughness. This reaction can be carried out in the same manner as a usual epoxidation reaction, but is preferably carried out by the following method.

After dissolving the phenolic compound represented by the general formula (1) in an excess of epichlorohydrin, the solution is preferably heated to 50 to 150 ° C. in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Is 60-12
A method of reacting at 0 ° C. for 1 to 10 hours is exemplified. The amount of epichlorohydrin used at this time is in the range of 0.8 to 2 mol, preferably 0.9 to 1.2 mol, per 1 mol of the hydroxyl group in the phenolic compound. After completion of the reaction, excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene and methyl isobutyl ketone.
The desired epoxy compound can be obtained by filtering, washing with water to remove inorganic salts, and then distilling off the solvent.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples.

Example 1 In a 500 ml four-necked flask, 112.8 g of phenol was added.
(1.2 mol), 4,4'-di (2-hydroxy-2-propyl)
27 g (0.1 mol) of biphenyl, 300 ml of benzene
And dissolved, then cooled to about 5 ° C, and concentrated hydrochloric acid 100m
1 was added and reacted under stirring for 15 hours. After the reaction, the oil phase obtained by oil-water separation was neutralized with an aqueous sodium carbonate solution. Thereafter, benzene was distilled off from the oil phase, and most of the excess phenol was removed by steam distillation, and the obtained solid was recrystallized from benzene to obtain white crystals. Table 1 shows the results of NMR measurement of the obtained resin.

Further, the product was found to have the following formula by mass spectrometry and elemental analysis.

Embedded image And a bisphenol compound represented by the following formula:

[0019]

[Table 1]

Example 2 55 g of the resin obtained in Example 1 was used for epichlorohydrin 330.
g of benzyltriethylammonium chloride, and 0.2 g of benzyltriethylammonium chloride was added thereto.
g) and 22.3 g of a 48% aqueous sodium hydroxide solution were added dropwise over 3 hours. During this time, generated water was removed from the system by azeotropic distillation with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was continued for another 30 minutes. Thereafter, salts produced by filtration were removed, and after further washing with water, epichlorohydrin was distilled off.
66.7 g of an epoxy resin was obtained. Epoxy equivalent is 291
And the softening point was 62 ° C. GP of the obtained resin
The C chart is shown in FIG. Using this resin, a phenol novolak resin (manufactured by Arakawa Chemical Industries, Ltd .; Tamanol 75)
8) was molded (at 160 ° C. for 3 minutes) as a curing agent to obtain a cured test piece. The test pieces were subjected to post-curing at 180 ° C. for 12 hours and then subjected to various physical property tests. Table 2 shows the results.

Comparative Example 2 An o-cresol novolak type epoxy resin was used and subjected to various physical property tests in the same manner as in Example 2. Table 2 shows the results.

[0022]

[Table 2]

[0023]

By using the phenolic compound used in the present invention as a starting material, a high-performance epoxy resin can be obtained.

[Brief description of the drawings]

FIG. 1 GPC of the epoxy compound obtained in Example 2
It is a chart.

Claims (1)

(57) [Claims] [Claim 1] The following general formula (1) (Wherein, R ₁ , R ₂ , and R ₃ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, n represents an integer of 0 to 15, and m represents an integer of 0 to 2) ) In the presence of an alkali metal hydroxide at a reaction temperature of 60 to 120 ° C. and a molar ratio of the phenolic compound to epichlorohydrin (epichlorohydrin / phenolic compound) of 0.9 to 1 2. A method for producing an epoxy compound, characterized by reacting under the conditions of 2.