JPH02170812A - Polyarylphenol - Google Patents

Abstract

NEW MATERIAL:A compound of the formula (R is methyl or halogen; p is 0-3; n is 1-10). USE:Curing agents, a comonomer for maleimide resin, and an epoxy resin intermediate useful for IC sealing, matrix resins for fiber-reinforced composite materials, heat-resistant adhesives, coatings, resists, etc. PREPARATION:An allyl ether of a polyphenol prepared by reaction between the corresponding polyphenol and allyl halide is heated to effect Claisen rearrangement.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel polyallylphenol.

In detail, we will introduce new polyallylphenol compounds that can be used as epoxy resin intermediates, curing agents, and comonomers for maleimide resins, which are useful in engineering C sealants, matrix resins for fiber-reinforced composite materials, heat-resistant adhesives, paints, resist agents, etc. It is related to.

[Conventional technology]

Conventionally, alkenylphenol (organyl reaction) obtained from phenol and allyl chloride has been used.
c Reaction) If p 27 1949
), diallylbisphenol obtained from bisphenol (U.S. Pat. No. 2,910,455), and the like are known as known substances. In addition, compositions comprising these alkenylphenols and maleimide compounds (Japanese Patent Publication No. 55
-39242), compositions comprising alkenylphenols, maleimide compounds, and hydrazides are also known.

[Line problem to be solved by the invention]

However, when a conventionally known alkenylphenol is used, a high temperature and a long time are required to complete the crosslinking reaction, and the heat resistance of the resulting crosslinked product is also insufficient.

The present invention aims to provide a novel polyallylphenol useful as an epoxy resin intermediate, a curing agent, and a comonomer for maleimide, which has excellent heat resistance and moldability.

[Means to solve the problem]

That is, the present invention provides polyallylphenol represented by the following general formula.

HOCH2CI(-C& (wherein, R represents a methyl group or an I-logon atom, p
represents O or an integer of 1 to 4, and n represents an integer of 1 to 10. ) The polyallylphenol of the present invention can be produced by heating the allyl ether of a polyphenol obtained by reacting the corresponding polyphenol with allyl halide to cause Claisen rearrangement.

The polyphenols used in the production of the polyallylphenol of the present invention include polyphenols obtained by heating phenols and terephthalaldehyde under a t-acidic catalyst (Japanese Patent Application Laid-Open No.
7-141419) is used. Generally, phenols are treated with terephthalaldehyde and used in excess (4 to Zoox moles), and when the excess is present, the molecular weight of the resulting polyphenol becomes small. If the amount is less than 4 times the mole, the resulting polyphenol will have too high a molecular weight,
During allyl etherification, it becomes insoluble in organic solvents, which is not preferable. The reaction temperature is in the range of 80°C to 180°C, and the condensation reaction is completed in 2 to 8 hours. Although a reaction solvent is not required, organic solvents such as benzene toluene may be used.

In the production of polyphenols, the phenols used include phenol and 1-, 2- and 3-substituted phenols having methyl groups and/or halogen atoms as substituents, in which no substituent exists at both ortho or ortho-para positions at the same time. can be mentioned. Examples of such phenols include phenol, 0
-cresol, m-cresol, k-cresol, 2.
3-dimethylphenol, 3=4-dimethylphenol, 2-bromophenol, 3-bromophenol, 4-
Bromophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2.3-dibromophenol, 2.3-dichlorophenol, 2-bromo-
Examples include 3-methylphenol, 2-chloro-3methylphenol, and 2.3.5-trimethylphenol.

Furthermore, among the above-mentioned phenols, when one having a substituent at the ortho position is used, untransferred allyl ether remains after Claisen rearrangement, but the amount thereof is very small.

The reaction between polyphenol and allyl halide is carried out under basic conditions. The allyl etherified reaction product, Kyosho, and the corresponding phenolate are reacted with the same mole of allyl halide (allyl chloride, allyl bromide, or allyl iodide) at room temperature to 100°C for 1 to 5 hours. , the reaction proceeds quantitatively.

The polyallyl phenol of the present invention can be obtained by heating the obtained allyl ether of the polyphenol to cause Claisen rearrangement. The rearrangement reaction is usually carried out using N,N-dimethylaniline, N,N-diethylaniline, tetralin,
The process begins with heating to a high temperature of around 200° C. in the presence or absence of a high boiling point solvent such as paraffin oil or calpitol.

When the polyalphenol thus obtained is used as a curing agent for epoxy resins and maleimide resins, cured products with excellent heat resistance can be obtained.

In the case of an epoxy resin, the typical curing method is to mix the epoxy resin and polyalkenylphenol with 0.5 to 2.0 equivalents of hydroxyl group, preferably 0.8 equivalent to 1 equivalent of epoxy group.
~1.2 equivalents, and the curing catalyst (tertiary amine, quaternary ammonium salt, phosphorus compound, etc.)
After adding 0.01 to 5 parts by weight to 0 parts by weight, 15
Polymerization is carried out by heating at 0°C to 250°C for 10 minutes to 5 hours. The obtained cured product has excellent moisture resistance and adhesion in addition to heat resistance, so it is useful for printed wiring boards, C sealants, conductive pastes, resistor paints, solder resists, etc. .

In addition, in the case of maleimide resin, the maleimide resin and polyallylphenol are mixed with 0 alkenyl groups per equivalent of imide group.
．． Mix at a blending ratio of 5 to 1.5 equivalents and heat at 180°C to 2.
A cured product can be obtained by heating at 50°C for 1 to 24 hours. During curing, use a third
It is also possible to add 0.1 to 1.0 parts by weight of a reaction accelerator such as a grade amine, a quaternary ammonium salt, a BF3 salt, imidazole, or a peroxide. This blended system is particularly excellent in heat resistance and low thermal expansion, so it is useful as a matrix resin for CFRP, multilayer printed wiring boards, engineering C sealing agent, and precision molding material. It can also be expected to shorten the molding cycle.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 (Synthesis of polyphenol) Phenol 1800f and terephthalaldehyde 161? After adding 49f of hydrochloric acid and raising the internal temperature to ioo°C, the reaction was continued for an additional 2 hours. After the reaction is complete, methyl isobutyl keto y (M I
B K ) 500 rIltf was diluted and washed three times with 300 al of distilled water to remove the catalyst.

The obtained reaction solution was transferred to a rotary evaporator and MI
BK and excess phenol were removed under reduced pressure to obtain a reddish-brown glassy polyphenol (precursor).

[Softening point 127-132°C] (Synthesis of allylphenol) Charge n-propyl alcohol lt1 sodium hydroxide 122f into an IT four-loaf flask equipped with a stirrer, thermometer, condenser, and dropping funnel, and make it homogeneous. After the mixture was stirred until 300 tons of polyphenol was added, the reaction was continued for an additional hour. After 280 d of allyl chloride was added dropwise over 10 minutes, the reaction solution was heated to 100° C. and stirred for 3 hours to complete allyl etherification. After removing the salt produced as a by-product from each house, n-propyl alcohol was recovered under reduced pressure. 400% of the obtained allyl ether compound
Dissolved in calpitol of d, inside! 190'~200℃
After heating for 6 hours to effect Claisen rearrangement, carboxylate was completely distilled off under vacuum to obtain reddish-brown glassy polyallylphenol (softening point: 68-73°C).

IR and NMR of this product are shown in FIGS. 1 and 2.

Example 2-7 Corresponding polyallylphenols were obtained from the starting materials shown in Table 1 by the same operation as in Example 1.

The properties are also shown in Table 1.

[Brief explanation of the drawing]

Figure 1 shows the infrared absorption spectrum of polyallylphenol obtained in Example 1 (J I 5COA-3@1n
Frared Spectrophotometer,
Figure 2 shows the nuclear magnetic resonance absorption spectrum (JEOL JNM-PMX60SI).
FIG. 2 is a diagram showing an NMR spectrometer, weight aa form solvent, TMS standard). Patent applicant: Mitsubishi Yuka Co., Ltd. Agent: Masahisa Hase Patent attorney: Patent attorney Takaya Yamamoto

Claims (1)

[Scope of Claims] Polyallylphenol represented by the following general formula ▲Numerical formula,
There are chemical formulas, tables, etc.▼ (In the formula, R represents a methyl group or a halogen atom, p represents an integer from 0 to 3, and n represents an integer from 1 to 10.)