JP2000063310A - New bisphenol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new bisphenol compound having a trisphenylmethane-type skeleton and useful e.g. as a raw material for photoresist for the production of semiconductor, etc. SOLUTION: The objective compound is expressed by formula I (R1 is H or methyl; R2 is a 1-4C alkyl; (m) is 0-2), e.g. 4-[1,1-bis(3-cyclohexyl-4- hydroxyphenyl)methyl]biphenyl. The objective compound can be produced by the dehydrative condensation reaction of a carbonyl compound of formula II, i.e., 4-formylbiphenyl, etc., with a cyclohexylphenol compound of formula III in a reaction solvent such as methanol in the presence of an acid catalyst such as hydrochloric acid and a cocatalyst such as a 1-18C mercaptan at 10-80 deg.C under nitrogen gas stream for about 3-36 hr under stirring.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel bisphenol compound and, more particularly, to a novel bisphenol compound having a trisphenylmethane-type skeleton and each having a cyclohexyl group as a substituent. A novel 4-cyclohexylphenol structure linked via a biphenylalkylidene group
[1,1-bis (3-cyclohexyl-4-hydroxyphenyl] alkyl] biphenyls [0002] Such bisphenol compounds include, for example, materials for photoresists for semiconductors, LCDs, etc., and sealing of integrated circuits. Materials for epoxy resin or hardener used for anti-blocking materials, electrical insulating materials, etc., polycarbonate resin raw materials,
It is useful as an acrylate resin raw material, a developer used for thermal recording, an anti-fading agent, and the like. In addition, it is also useful as an additive such as a bactericide, a fungicide and a fungicide. [0003] Conventionally, bisphenol compounds have been used as raw materials for epoxy resins and curing agents therefor for various electrical and electronic device parts, polycarbonate resin raw materials, and the like.
It is widely and widely used as an acrylate resin material, a developer for thermal recording, and as an additive such as an antioxidant, a bactericide, and a fungicide. In recent years, in recent years, in the field of electrical and electronic equipment parts, with the demand for smaller and higher performance equipment, organic materials used for them have also been improved in conventional mechanical and thermal properties. Without stopping,
Improvements in various performances such as long-term stability against moisture, electrical insulation, and low dielectric properties are increasingly required. Conventionally, among bisphenol compounds, trisphenylmethane type bisphenol compounds are disclosed, for example, in JP-A-6-199717, 4,4'-.
[(4-hydroxyphenyl) methylene] bis [2-methylphenol] is disclosed in
4 '-[(4-hydroxyphenyl) methylene] bis [2
-Cyclohexyl-5-methylphenol] and 4,4'-
[(2-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol] is disclosed. When the bisphenol compound of the trisphenylmethane type has a large number of phenyl groups in the molecule, that is, when the density of the phenyl nucleus is high, the use of such a bisphenol compound as a raw material enables low water absorption. It is expected to provide a resin having excellent electrical properties such as insulation properties and low dielectric properties, in addition to water resistance and heat resistance such as heat resistance and low moisture absorption. Accordingly, for example, Japanese Patent Application Laid-Open No. Sho 62-12278.
No. 2 and Japanese Patent Application Laid-Open No. 62-289536 also propose a bisphenol compound having a molecule in which a biphenyl group is introduced instead of a phenyl group. However, this is a trisphenylmethane type bisphenol compound in which two cyclohexylphenol structures each having cyclohexyl as a substituent are bonded via a biphenylalkylidene group, 4- [1,1-bis (3- Cyclohexyl-4-hydroxyphenyl] alkyl] biphenyls have not been known in the prior art [0008] The present invention relates to a novel bisphenol compound as described above, 4- [1, It is an object of the present invention to provide 1-bis (3-cyclohexyl-4-hydroxyphenyl] alkyl] biphenyls, according to the present invention. [0010] Wherein R ₁ represents a hydrogen atom or a methyl group; R ₂ represents an alkyl group having 1 to 4 carbon atoms;
It is an integer of 2. The present invention provides a novel 4- [1,1-bis (3-cyclohexyl-4-hydroxyphenyl] alkyl] biphenyl represented by the following formula: DETAILED DESCRIPTION OF THE INVENTION Novel bisphenol compound according to the present invention That is, 4- [1,1-bis (3-cyclohexyl-4-hydroxyphenyl] alkyl] biphenyls are represented by the general formula (I), wherein the alkyl group (R ₂ ) is Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group or a butyl group, etc. Particularly, in the present invention, the alkyl group is preferably a methyl group, and a hydroxyl group Therefore, the bisphenol compound according to the present invention is preferably, for example, (1) 4
-[1,1-bis (3-cyclohexyl-4-hydroxyphenyl] methyl] biphenyl, (2) 4- [1,1-bis (3-cyclohexyl-4-hydroxy-6-methylphenyl] methyl] biphenyl ( 3) 4- [1,1-bis (3-cyclohexyl-4-hydroxyphenyl] ethyl] biphenyl, (4) 4-
[1,1-bis (3-cyclohexyl-4-hydroxy-
6-methylphenyl] ethyl] biphenyl and the like, but are not limited thereto. The novel bisphenol compound according to the present invention can be obtained by reacting the bisphenol compound of the general formula (II) in the presence of an acid catalyst and a cocatalyst. A carbonyl compound represented by the formula:
-Formyl biphenyl or 4-acetyl biphenyl;
General formula (III) (Wherein R ₂ represents an alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 2), and can be obtained by a dehydration condensation reaction with a cyclohexylphenol represented by the following formula: . When 4-formylbiphenyl is used as the carbonyl compound, 4- [1,1-bis (3-
Cyclohexyl-4-hydroxyphenyl] methyl] biphenyl can be obtained, and when 4-acetylbiphenyl is used as the carbonyl compound,
[1,1-bis (3-cyclohexyl-4-hydroxyphenyl] ethyl] biphenyl can be obtained In the cyclohexylphenol represented by the general formula (III), as described above, the alkyl group Examples include, for example, a methyl group, an ethyl group, a linear or branched propyl group or a butyl group and the like, and particularly, a methyl group is preferable, and a methyl group is located at a meta position with respect to a hydroxyl group. Therefore, such cyclohexylphenols include 2-cyclohexylphenol and 2-cyclohexylphenol.
Cyclohexyl-5-methylphenol, 2-cyclohexyl-5-ethylphenol, 2-cyclohexyl-
5-isopropylphenol, 2-cyclohexyl-5
-T-butylphenol and the like. In the production of the bisphenol compound according to the present invention, the cyclohexylphenol is used in an amount of at least 2 parts by mol, usually in the range of 2 to 30 parts by mol, preferably 1 part by mol of the above carbonyl compound.
It is used in the range of 2 to 20 parts by mole, particularly preferably in the range of 3 to 6 parts by mole. In the reaction between the cyclohexylphenols and the carbonyl compound, a reaction solvent may or may not be used. When a reaction solvent is used, for example, an aliphatic alcohol solvent, an aliphatic ketone solvent, an aromatic hydrocarbon solvent, or a mixed solvent thereof is used. The alcohol solvent may be selected from methanol, ethanol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, isobutyl alcohol in consideration of the reaction raw materials to be used, the solubility of the obtained product, reaction conditions, and the economics of the reaction. Alcohol, n-butyl alcohol and the like can be mentioned. As the aliphatic ketone solvent,
For example, isopropyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diisopropyl ketone and the like can be mentioned. Also, as the aromatic hydrocarbon solvent,
For example, toluene, xylene, cumene and the like can be mentioned. Such a solvent is usually used in an amount of 10 to 1000 parts by weight, preferably 30 to 300 parts by weight, based on 100 parts by weight of the carbonyl compound used, but is not limited thereto. Absent. In the present invention, the acid catalyst is preferably an acid soluble in a reaction solvent. Therefore, for example, hydrogen chloride gas, hydrochloric acid, sulfuric acid, sulfuric anhydride, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, Preferred specific examples include trifluoromethanesulfonic acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, and trifluoroacetic acid. Particularly, hydrochloric acid is preferably used. For example, in the case of 35% hydrochloric acid, such an acid catalyst is used in an amount of 1 to 500 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the carbonyl compound. In the production of the bisphenol compound according to the present invention, it is preferable to use a co-catalyst together with the above-mentioned acid catalyst. Examples of the co-catalyst include, for example, those having 1 to 18 carbon atoms.
And inorganic or organic sulfur compounds such as mercaptans, hydrogen sulfide, thiophenols, thioacids, and dialkyl sulfides. Such a co-catalyst is
Usually, based on 1 mol part of the carbonyl compound,
It is used in the range of 0.005 to 0.2 mol part, preferably 0.01 to 0.1 mol part. The reaction between the cyclohexylphenol and the carbonyl compound is usually carried out at a temperature in the range of 10 to 80 ° C., preferably 20 to 60 ° C., while stirring under a nitrogen stream for about 2 to 36 hours. Usually, it may be performed for about 10 to 24 hours. According to the method of the present invention, after completion of the reaction, an appropriate crystallization solvent is added to the obtained reaction mixture, and then an alkali such as sodium hydroxide is added to adjust the pH of the reaction mixture to 5 or less.
Neutralization until about 7 is obtained, and if crystals precipitate, they are filtered and dried to obtain the bisphenol compound according to the present invention. If necessary, a higher purity product can be obtained by recrystallization from an appropriate crystallization solvent. After completion of the reaction, an appropriate organic solvent is added to the obtained reaction mixture, and then an alkali such as sodium hydroxide is added to neutralize the reaction mixture until the pH becomes about 5 to 7. After removing and washing the obtained oil layer with water, an appropriate crystallization solvent is added, and the precipitated crude crystals are filtered and recrystallized from an appropriate crystallization solvent to obtain a purified product of the target bisphenol compound. Can be. In the present invention, the crystallization solvent includes
Usually, aromatic hydrocarbons such as toluene, xylene and cumene, and aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane are preferably used. As described above, the bisphenol compound according to the present invention has a trisphenylmethane type skeleton,
Two cyclohexylphenol structures each having a cyclohexyl group as a substituent are linked via a biphenylalkylidene group. Therefore, the bisphenol compound according to the present invention, when used as a raw material, gives a resin having excellent water resistance such as low water absorption and low moisture absorption, and excellent electrical properties such as insulation and low dielectric properties. Thus, for example, materials for photoresists for semiconductors, LCDs, etc., materials for epoxy resins or hardeners used for sealing materials for integrated circuits, electric insulating materials, etc., developers for thermal recording and color fading prevention It is also useful as an additive such as a bactericide, a fungicide and a fungicide. In particular, the bisphenol compound according to the present invention has a high density of aromatic nuclei in the molecule. Therefore, by using this as a resin material such as a polycarbonate resin or a polyacrylate resin, or a photoresist material, the heat resistance of the bisphenol compound is increased. And moisture resistance and the like can be improved. Further, the bisphenol compound according to the present invention can be used as a starting material to carry out various reactions, for example, a substitution reaction or a hydrogenation reaction on a phenolic aromatic ring, a reaction on a phenolic hydroxyl group, etc., to give various derivatives. It can be. First, as a specific example of obtaining a derivative by a substitution reaction on a phenolic aromatic ring, for example, an olefin such as isobutene, an alcohol, a carbonyl compound, an alkyl halide or the like is added to the bisphenol compound of the present invention by an acid or base catalyst. Various alkyl-substituted derivatives can be obtained by an alkylation reaction in the presence of For example, an acyl-substituted bisphenol compound can be obtained by reacting an acid halide such as acetyl chloride or an acid anhydride in the presence of a Lewis acid. According to the Kolbe-Schmidt reaction in which carbon dioxide is reacted under pressure and heat, a carboxyl-substituted bisphenol compound can be obtained. By reacting a nitrating agent such as nitric acid-acetic acid, a nitro-substituted bisphenol compound can be obtained. By performing a methylolation reaction with formaldehyde, a bisphenol compound having a methylol group can be obtained. An acetyl-substituted bisphenol compound can be obtained by acetylation with acetic anhydride in an alkaline aqueous solution, and an aldehyde-substituted bisphenol compound can be obtained by formylation with chloroform in an alkaline aqueous solution. By halogenating with a halogenating reagent, a halogen-substituted bisphenol compound can be obtained, and by reacting a diazonium salt,
An azo-substituted bisphenol compound can be obtained. By reacting formaldehyde with a secondary amine, an aminomethyl-substituted bisphenol compound can be obtained. According to the reaction with nitrous acid, a nitroso-substituted bisphenol compound can be obtained. By reacting with other phenols in the presence of an acid or alkali catalyst,
A novolak resin can be obtained. Next, specific examples of obtaining a derivative by reacting with a phenolic hydroxyl group include, for example, alkyl halide, allyl halide,
By reacting epichlorohydrin or the like, the corresponding bisphenol ether compounds can be obtained. In particular, in order to convert the phenolic hydroxyl group to t-butoxycarbonylmethyl ether, the bisphenol compound according to the present invention is dissolved in an appropriate solvent, and t-butyl chloroacetate and potassium carbonate are added to the resulting solution. Can be obtained by heating under stirring.
Glycidyl ether obtained by dissolving the bisphenol compound according to the present invention in an appropriate solvent and reacting with epichlorohydrin can be used as an epoxy resin. If such glycidyl ether is further reacted with acrylic acid or methacrylic acid, an epoxy (meth) acrylate can be obtained. By reacting an acid anhydride, an acid chloride, or the like with the phenolic hydroxyl group, a bisphenol ester can be obtained. In particular, if a phenolic hydroxyl group is reacted with, for example, 1,2-naphthoquinonediazide-4-sulfonyl chloride,
A naphthoquinonediazidesulfonic acid ester of a bisphenol compound can be obtained. In addition to the above, various polycyclic aromatic ring hydrogenated compounds can be obtained by subjecting the bisphenol compound according to the present invention to complete hydrogenation or partial ring hydrogenation of the aromatic ring by, for example, gas phase reaction under pressure. Obtainable. EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 (Production of 4- [1,1-bis (3-cyclohexyl-4-hydroxyphenyl) methyl] biphenyl) 1584 g of o-cyclohexylphenol, 158 g of concentrated hydrochloric acid, 158 g of methanol and 55 g of dodecylmercaptan 546 g of 4-formylbiphenyl was added over 3 hours while maintaining the temperature at 40 ° C. while stirring, and the mixture was reacted at 40 ° C. for 6 hours. After adding toluene, an aqueous sodium hydroxide solution was added to neutralize the acid catalyst, and the precipitated crystals were filtered to obtain 953 g of the desired bisphenol compound as orange crystals having a purity of 98.6%. The ratio was 61.6 with respect to 4-formylbiphenyl.
%Met. Melting point: (Differential scanning calorimetry (DSC method)
Measurement was not possible. ) Mass spectrum (molecular ion peak): 516 Proton nuclear magnetic resonance spectrum (solvent DMSO-D _6,
Standard TMS): [Table 1] Example 2 (4- [1,1-bis (2-methyl-4-hydroxy-5
-Cyclohexylphenyl] methyl] biphenyl 2-cyclohexyl-5-methylphenol 136
g of methanol (170 g) solution, 170 g of concentrated hydrochloric acid, 170 g of methanol and 4 g of dodecylmercaptan were charged into a four-necked flask, and 434 g of 4-formylbiphenyl was added over 2 hours while maintaining the temperature at 40 ° C. with stirring. Thereafter, the reaction was carried out at a temperature of 40 ° C. for 6 hours. After the completion of the reaction, toluene was added to the reaction mixture, and then an aqueous sodium hydroxide solution was added to neutralize the acid catalyst. The temperature was raised to 70 ° C., and the aqueous layer was separated. After the obtained oil layer was washed with water, n-heptane was added thereto for crystallization, and the precipitated crystals were filtered to obtain 1253 g of crude crystals of the target bisphenol compound. This is recrystallized from toluene,
987 g of white crystals having a purity of 99.7% were obtained. The yield is 4-
It was 76.1% based on formylbiphenyl. Melting point: 203 ° C. (DSC method) Mass spectrum (molecular ion peak): 544 Proton nuclear magnetic resonance spectrum (solvent DMSO-D ₆ ,
Standard TMS): [Table 2]

Claims (1)

[Claim 1] A compound represented by the general formula (I): (Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 2).