JP2001294661A - Method for curing polyfunctional phenol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for curing a polyfunctional phenol compound and/or a naphthol compound by which the gelation is extremely rapid and cured products thereof are excellent in heat resistance. SOLUTION: A polyfunctional phenol compound or a naphthol compound having >=2 phenolic hydroxyl groups in one molecule or both are brought into contact with a metal alkoxide and cured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for curing a phenol compound and / or a naphthol compound. The present curing method can be cured at room temperature, and the resulting cured product is a foam, which is suitable for coating or carrying a hard foam, a catalyst, and the like.

[0002]

2. Description of the Related Art A cured product of a phenol compound has heat resistance,
Because of its excellent electrical and mechanical properties, it is used in various fields. Since a polyfunctional phenol compound and a naphthol compound require a considerable amount of time to gel, a curing method with a rapid gelation is demanded.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for increasing the gelation rate of a phenol or naphthol compound.

[0004]

Means for Solving the Problems As a result of various studies to solve the above problems, the present inventor has found that a polyfunctional phenol compound or a naphthol compound is blended with a metal alkoxylated compound to obtain a polyfunctional phenol compound or a naphthol compound. The present inventors have found that a gelled product can be obtained at a very high speed, and have reached the present invention.

That is, the present invention relates to a method for curing a polyfunctional phenol, which comprises contacting a polyfunctional phenol compound and / or a naphthol compound having two or more phenolic hydroxyl groups in a molecule with a metal alkoxylated compound. , 2. The above-mentioned 1., wherein the metal alkoxylated compound is alkoxytitanium. 2. The method for curing a polyfunctional phenol described in item 3. (1) The metal alkoxylated compound is used in a ratio of 0.1 to 0.8 mol per 1 equivalent of the phenolic hydroxyl group in the polyfunctional phenol compound and / or the naphthol compound. Or 2. 3. Curing method of the polyfunctional phenol described in the item 4. The above 1. 2. Or 3. And a cured product obtained by the curing method described in any one of the above.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polyfunctional phenol compound and naphthol compound used in the present invention are not particularly limited as long as they have two or more phenolic hydroxyl groups in one molecule. Specific examples of the polyfunctional phenol compound and naphthol compound that can be used include bisphenol A, tetramethylbisphenol F, bisphenol F, bisphenol S, bisphenol K, biphenol, tetramethylbiphenol, hydroquinone, methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, -Ter. Butyl hydroquinone, resorcinol, methyl resorcinol, catechol, methyl catechol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, etc., bi- or bifunctional compounds, phenols, or condensates of naphthols with aldehydes, phenols or naphthols Condensates of phenols or naphthols with bismethoxymethyl biphenyl, condensates of phenols with isopropenyl acetophenone, reaction products of phenols with dicyclopentadiene, and the like. These can be obtained by a known method.

The phenols exemplified above include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, catechol, resorcinol, methylresorcinol, hydroquinone, phenylphenol, bisphenol A, bisphenol F, bisphenol K, bisphenol S, Biphenol, tetramethylbiphenol and the like can be mentioned.

Similarly, naphthols include 1-naphthol, 2-naphthol, dihydroxynaphthalene,
Examples thereof include dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, and trihydroxynaphthalene.

Further, aldehydes include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, benzaldehyde, chlorbenzaldehyde, bromobenzaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, Examples include melinaldehyde, sebacinaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, and hydroxybenzaldehyde. The above-mentioned phenol compounds and naphthol compounds used in the present invention are used alone or in combination of several kinds. It is also possible to use a mixture of one or more phenol compounds and naphthol compounds. Furthermore, phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, 1-naphthol, 2-naphthol and the like
A phenol compound or naphthol compound having only one phenolic hydroxyl group in the molecule can be used in combination as long as the effects of the present invention are not impaired.

The metal alkoxylated compound used in the present invention is not particularly limited as long as it has a structure in which hydrogen of a hydroxyl group of an alcohol is replaced with a metal. Examples thereof include alkoxysilane, alkoxytitanium, and alkoxyaluminum. Is preferred. Alkoxy titanium preferably used in the present invention may be a commercially available product, tetramethoxy titanium,
Specific examples that can be used include tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxytitanium, and diisopropoxy (ethylacetoacetate) titanium.

In the present invention, the amount of the metal alkoxylated compound to be used is generally 0.1 to 0.8 mol, preferably 0.15 to 0.6 mol, per equivalent of the phenolic hydroxyl group in the phenol compound and the naphthol compound. If the amount of the metal alkoxylate is less than 0.1 mol, the gelation of the phenol compound and the naphthol compound does not sufficiently proceed, which may be undesirable. On the other hand, when the content is 0.8 mol or more, the phenol compound hardly contributes to curing, which is economically disadvantageous.

The curing reaction proceeds at an extremely high rate only by adding a predetermined amount of the metal alkoxy compound to the polyfunctional phenol compound and / or the naphthol compound, and a gel is obtained. The metal alkoxylated compound may be added, for example, to the polyfunctional phenol compound and / or the naphthol compound with stirring. In addition, when the polyfunctional phenol compound, the naphthol compound and / or a mixture of both are liquid at the time of the addition, the reaction can be carried out as it is. After dissolving the naphthol compound,
The metal alkoxylate may be added with stirring. Further, the polyfunctional phenol compound and / or the naphthol compound can be used in a liquid state by heating to a temperature higher than the softening point or the melting point. Specific examples of the solvent that can be used in the above include acetone, methyl ethyl ketone, and methyl isobutyl ketone. The amount of the solvent used may be such that the polyfunctional phenol compound and / or the naphthol compound and the metal alkoxylate can be uniformly mixed, and it is not necessary that the polyfunctional phenol compound and / or the naphthol compound be completely dissolved. After mixing, foaming is immediately performed without using any means such as heating, and a foamable gel is obtained. The mixing and reaction of the polyfunctional phenol compound and / or naphthol compound with the metal alkoxylate can also be performed using a roll, kneader, extruder, or the like. After the addition,
By removing generated alcohol (and solvent) from the obtained gelled product under heating or reduced pressure, a cured product having voids due to foaming can be obtained.

Furthermore, a curing agent such as tetramethylhexamine can be further added to the thus obtained cured product of the present invention to reinforce the network structure. In this case, the obtained cured product is preferably further heated at 70 to 200 ° C. to perform post-curing. In the curing method of the present invention, a filler such as silica and calcium carbonate, a release agent, a coloring agent, and the like are also added to the polyfunctional phenol compound and / or the naphthol compound, if necessary, as long as the curing reaction is not hindered. You can do it.

Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 A semi-solid phenol novolak resin (manufactured by Nippon Kayaku Co., Ltd., phenolic hydroxyl equivalent: 101 g /
eq. , 200 Pa. s / 50 ° C., 5 g of phenolic hydroxyl group (0.0495 equivalent) was added to 5 g of acetone, and the phenol novolak resin was dissolved in acetone. Under stirring at room temperature, 2.8 g of tetraisopropoxy titanium (0.
(0099 mol) was added and the mixture was further stirred and mixed, and a gel was formed within 1 minute. This gel was dried at 120 ° C., and the produced isopropyl alcohol and acetone used as a solvent were removed to obtain a hardened brown solid in a foamed state. This was pulverized and kept at 200 ° C. for 10 minutes, but it was confirmed that the resin was sufficiently cured without flowing of the resin and mutual adhesion of the foamed and cured particles.

Example 2 In an aluminum cup, 5.5 g (0.1 equivalent of phenolic hydroxyl group) of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 15 g of acetone at about 100 ° C., and tetraisopropoxy was added at room temperature. 4. Titanium (manufactured by Junsei Chemical Co., Ltd.)
7 g (0.02 mol) was added, and the mixture was uniformly stirred and mixed, and a gel was formed within 1 minute. This gel is
After drying at ℃ and removing acetone and isopropyl alcohol formed, a hardened brown solid was obtained in a foamed state. This was pulverized and kept at 200 ° C. for 10 minutes, and it was confirmed that the resin was sufficiently cured without flowing of the resin and mutual adhesion of the foamed and cured particles.

Example 3 In an aluminum cup, 4.0 g (0.05 equivalent of phenolic hydroxyl group) of 1.5 dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 15 g of acetone at about 100 ° C., and then room temperature. Then, 2.8 g (0.01 mol) of tetraisopropoxytitanium (manufactured by Junsei Chemical Co., Ltd.) was added, and the mixture was uniformly stirred and mixed, whereby a gelled product was formed within 1 minute. The gel was dried at 120 ° C. to remove acetone and isopropyl alcohol produced, and a hardened black-brown solid was obtained in a foamed state. This is crushed, and at 200 ° C.
It was held for 0 minutes, but it was confirmed that the resin was sufficiently cured without the resin flowing and the foamed cured particles not adhering to each other.

Example 4 5 g of the semi-solid phenol novolak used in Example 1 was
The mixture was heated and melted at 00 ° C., 2.5 g (0.0088 mol) of tetraisopropoxytitanium was added under heating, and the mixture was uniformly stirred and mixed, and a gel was formed within 1 minute. Then, when the isopropyl alcohol generated at 130 ° C. was removed, a brown solid which was cured in a foamed state was obtained.
This was pulverized and kept at 200 ° C. for 10 minutes, but it was confirmed that the resin had not flowed and the foamed hardened particles did not adhere to each other, and that the hardening had progressed sufficiently.

[0019]

The method of curing a polyfunctional phenol or naphthol compound according to the present invention is a curing method having a very high curing rate, and a product from which the produced alcohol is removed is a heat-resistant cured product. The cured product of the present invention can be used as a rigid foam for heat insulating materials, various carriers, and the like.

Claims (4)

[Claims] 1. A method for curing a polyfunctional phenol, comprising contacting a polyfunctional phenol compound and / or a naphthol compound having two or more phenolic hydroxyl groups in one molecule with a metal alkoxylate. 2. The curing method according to claim 1, wherein the metal alkoxylate is an alkoxytitanium. 3. The polyfunctional compound according to claim 1, wherein the metal alkoxylated compound is used in an amount of 0.1 to 0.8 mol per 1 equivalent of the phenolic hydroxyl group in the polyfunctional phenol compound and / or the naphthol compound. Phenol curing method. 4. A cured product obtained by the curing method according to any one of claims 1, 2 and 3.