JPH05117350A - New phenolic compound, its epoxidized substance and their production - Google Patents

Abstract

PURPOSE:To obtain the subject new compound useful as a raw material for high-performance polymers having excellent heat resistance, moisture resistance and mechanical characteristics, providing a new epoxy compound having excellent heat resistance and toughness by reacting the compound with epichlorohydrin. CONSTITUTION:A new phenolic compound of formula I (R1 to R3 are H or 1-6C hydrocarbon; (n) is 0-15; (m) is 0-2) such as compound of formula II. The compound is obtained by reacting a phenol (e.g. phenol or o-cresol) of formula III with a condensation agent (e.g. 4,4'-dimethylolbiphenyl or 4,4'- dimethoxymethylbiphenyl) of formula TV (RE4 is R1) in a ratio of 1mol compound of formula III and 0.01-0.9mol condensation agent of formula IV. The reaction is carried out usually in the presence of an acid catalyst such as hydrochloric acid at -50 to 250 deg.C for 1-20 hours.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phenolic compound useful as a raw material for various high-performance polymers and a method for producing the same, and a novel epoxy compound using the same as a raw material and a method for producing the same. Is.

[0002]

2. Description of the Related Art Polyhydric phenolic compounds represented by bisphenol A are widely used as starting materials for various high performance polymers such as polyester, polycarbonate, polyurethane and epoxy resin. However, with the diversification of applications, improvement in heat resistance, moisture resistance, toughness, etc. is strongly required for these polymer materials.

Therefore, a novel bisphenol compound has been proposed for the purpose of improving these physical properties (JP-A-58-58).
No. 18,331) does not have sufficiently satisfactory physical properties even when a polymer compound obtained by using such a bisphenol as a raw material is used.

[0004]

Therefore, the object of the present invention is to be useful as a raw material for a high-performance polymer having excellent heat resistance and moisture resistance and excellent mechanical properties such as impact resistance. Another novel phenolic compound and a method for producing the same.

[0005]

Means for Solving the Problems That is, the present invention provides the following general formula (1):

[Chemical 6] Is a novel phenolic compound.

The present invention also provides the following general formula (2)

[Chemical 7] And the following general formula (3)

[Chemical 8] The method for producing a novel phenolic compound is characterized by reacting a condensing agent represented by

The present invention also provides the following general formula (4)

[Chemical 9] Is a new epoxy compound represented by.

Furthermore, the present invention provides the following general formula (1)

[Chemical 10] The method for producing a novel epoxy compound is characterized by reacting a novel phenolic compound represented by the formula with epichlorohydrin.

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. Specific examples of the hydrocarbon group represented by R ₃ include phenol, o-cresol, m-cresol, 2,6-xylenol, o-
Ethylphenol, 2,6-diethylphenol, o-
Examples include phenylphenol.

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 can be mentioned.

When the above phenols and the condensing agent are reacted, the molar ratio of both should be 1 mol or less of the condensing agent to 1 mol of the phenol, and preferably 0.0.
It is in the range of 1 to 0.9 mol.

The reaction for reacting the phenols with the condensing agent to produce a phenolic compound 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, solid acids and the like.

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

By reacting the phenolic compound of the present invention with epichlorohydrin, an epoxy compound having a relatively low viscosity and excellent heat resistance, moisture resistance and toughness can be obtained. This reaction can be performed in the same manner as a usual epoxidation reaction.

For example, after dissolving the phenolic compound represented by the above general formula (1) in an excess of epichlorohydrin, it is heated at 50 to 150 ° C. in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. , Preferably 6
A method of reacting in the range of 0 to 120 ° C. for 1 to 10 hours can be mentioned. At this time, the amount of epichlorohydrin used is
0.8 to 1 mol of the hydroxyl group in the phenolic compound
The amount is 2 mol, preferably 0.9 to 1.2 mol.
After completion of the reaction, excess epichlorohydrin was distilled off, the residue was dissolved in a solvent such as toluene and methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent was distilled off to obtain the desired epoxy. The compound can be obtained.

[0016]

The present invention will be described in more detail with reference to the following examples. Example 1 112.8 g phenol in a 500 ml four neck flask
(1.2 mol), 4,4'-di (2-hydroxy-2-
After 27 g (0.1 mol) of propyl) biphenyl and 300 ml of benzene were added and dissolved, the mixture was cooled to about 5 ° C., 100 ml of concentrated hydrochloric acid was added, and the mixture was reacted for 15 hours while stirring. After the reaction
The oil phase obtained by separating the oil and water was neutralized with an aqueous sodium carbonate solution. Then, 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 with benzene to obtain white crystals. The NMR measurement results of the obtained resin are shown in Table 1. Furthermore, from mass spectrometry and elemental analysis, this product has the following formula

[Chemical 11] Was confirmed to be a bisphenol compound.

[Table 1]

Example 2 55 g of the resin obtained in Example 1 was added to epichlorohydrin 330
g, and 0.2 g of benzyltriethylammonium chloride was added, and the mixture was decompressed (about 150 mmH
g) and 22.3 g of 48% aqueous sodium hydroxide solution were added dropwise over 3 hours. During this period, water produced was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the dropping was completed, the reaction was continued for another 30 minutes. After that, the salt produced by filtration is removed, and after further washing with water, epichlorohydrin is distilled off,
66.7 g of 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, molding using phenol novolac resin as a curing agent (160 ° C, 3 minutes)
Then, a cured test piece was obtained. The test pieces were post-cured at 180 ° C. for 12 hours and then subjected to various physical property tests. The results are shown in Table 2.

Comparative Example 2 Using o-cresol novolac type epoxy resin, various physical property tests were conducted in the same manner as in Example 2. The results are shown in Table 2.

[Table 2]

[0019]

By using the novel phenolic compound obtained by the present invention as a starting material, a high-performance epoxy resin can be obtained, and further development of polymer materials such as polyester and polycarbonate can be expected.

[Brief description of drawings]

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

Claims (4)

[Claims] 1. The following general formula (1): A novel phenolic compound represented by. 2. The following general formula (2): And a phenol represented by the following general formula (3): A method for producing a novel phenolic compound, which comprises reacting a condensing agent represented by: 3. The following general formula (4): A new epoxy compound represented by. 4. The following general formula (1): A method for producing a novel epoxy compound, which comprises reacting a novel phenolic compound represented by the formula with epichlorohydrin.