JPH04110323A - Preparation of phenol polymer - Google Patents

Abstract

PURPOSE:To prepare a phenol polymer without generating a hydrogen halide at a reduced cost by reacting a specific aralkyl compd. with a phenol or, if necessary, a mixture thereof with an arom. compd. CONSTITUTION:A phenol or a mixture thereof with an arom. compd. is prepd. Separately, an arom. bishydroxymethyl compd. is thermally reacted in the presence of sulfamic acid, catalyst to give an aralkyl compd. comprising a polymer of the formula [wherein R is (alkyl-substd.) phenylene, biphenylene, a divalent diphenyl ether residue, or naphthylene; and n is 1-100]. The aralkyl compd. is reacted with the phenol or the mixture in an amt. of 1.3-15mol based on one mol of the structural units of the aralkyl compd. in the presence of an acid catalyst at 120-200 deg.C for 2-10hr to give a phenol polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field] The present invention relates to a method for producing polymeric materials derived from phenolic compounds. Such phenolic polymers are
In addition to being used as a thermosetting resin using a crosslinking agent such as hexamethylenetetramine, it can also be used as a raw material and curing agent for epoxy resins.

[Conventional technology]

Conventionally, a typical phenol polymer is a novolak resin produced by reacting a phenol compound with formaldehyde.

In order to improve the performance of this novolak resin, such as its hardness and brittleness and poor oxidation stability, we developed a phenolic resin using an aralkyl compound (Japanese Patent Publication No. 47-1511).
1, Special Publication No. 47-13782) has been developed.

This phenol resin has the following formula (II) (wherein, R represents an aromatic group such as a phenylene group, R" represents a lower alkyl group, and a does not represent 2 or 3) and the following formula (
III) (wherein R and a represent the same meanings as in the above formula (n),
(X represents a halogen atom) Examples of aralkyl compounds represented by formula (II) include α,α'-dimethoxy p-xylene;
The compound of formula (III) is α,α'-dichloro p
-xylene, prepared from one of these and a phenolic compound or a mixture of a phenolic compound and an aromatic compound.

Among these aralkyl compounds, α, α°-dichloro p-
In the method using xylene as a raw material, hydrogen chloride is generated during the condensation reaction, so there are problems such as problems with the material of the equipment and residual chlorine ions in the resulting resin. Also,
In the method using α,α゛-dimethoxy-p-xylene as a raw material, in order to obtain this ditoxide, α,α°-cyclop-xylene is treated with a large amount of methanol and then distilled. There are problems such as methanol recovery and an increase in the number of steps.

[Problems to be Solved by the Invention] An object of the present invention is to provide a method for obtaining a useful phenol polymer using an inexpensive aralkyl compound that does not have the above-mentioned problems.

[Failure to solve the problem]

The present inventors have made extensive studies to solve the above problems. As a result, the present invention has been achieved.

Accordingly, the present invention provides a method for producing a phenol polymer by reacting a compound containing an aromatic nucleus with an aralkyl compound, wherein the compound containing an aromatic nucleus is a phenol compound or one kind of each of a phenol compound and an aromatic compound. Or, a mixture of two or more of them can be used as the above aralkyl compound (General 2N) (wherein R is a phenylene group, an alkyl-substituted phenylene group, a biphenylene group, a divalent diphenyl ether residue or a naphthylene group, and n is 1 (indicates an integer from 100 to 100) In the presence of an acid catalyst, 1. The present invention relates to a method for producing a phenol polymer, characterized in that the reaction is carried out at 3 to 15 times the molar amount.

Phenol compounds used in this method include phenol, p-cresol, 0-cresol, m-cresol,
p-ethylphenol, 0-ethylphenol, p-isopropylphenol, pn-propylphenol
, p-8eC-butylphenol, o-5ec-butylphenol, p-tert-butylphenol, 〇-t
ert-butylphenol, p-tert-amylphenol, p-tert-octylphenol, nonylphenol, dodecylphenol, p-cyclohexylphenol, 0-phenylphenol, p-phenylphenol, p-cumylphenol, p-α-methyl Hensylphenol, p-chlorophenol, p-bromophenol, α-naphthol, β-naphthol, resorcinol, catechol, hydroquinone, pyrogallol, phloroglycitur, p-aminophenol, m-aminophenol, 2,2 Examples include, but are not limited to, -his(4-hydroxyphenyl)propane, 4,4'-diodiphenol, and the like.

Aromatic compounds used in the present invention include m-xylene,
L3,5-)limethylbenzene, 1,2,4.5-tetramethylbenzene, L2,3.4-tetramethylbenzene, m-diisopropylbenzene, 1.3.5-1-
Examples include diisopropylbenzene, diphenyl ether, diphenyl ether, triphenyl, diphenylamine, diphenyl sulfide, diphenylanthracene, and naphthalene.

The aralkyl compound used in the present invention is a polymer represented by (I). Such polymers can be prepared by known methods, for example, a method in which an aromatic bishydroxymethyl compound is subjected to a heating reaction with a sulfamic acid catalyst (M, J., Lord;
Journal of the American Chemical Society, Volume 72.

2216 pages, 1.950 years).

In formula (I), n (the number of nuclei) is in the range of 1 to 100, and although it can be used even if it exceeds this range, it is not preferable because a gel-like substance is produced as a by-product in the obtained phenol polymer.

R in formula (I) is a phenylene group, an alkyl-substituted phenylene group, a biphenylene group, a divalent diphenyl ether residue, or a naphthylene group, and is specifically represented by H3 or the like.

In the method of the present invention, when reacting an aralkyl compound using only a phenol compound, it may be carried out alone or two or more kinds may be used in combination. Further, when a phenol compound and the above-mentioned aromatic compounds are used as a mixture, one or more types of each can be used. In this case, any ratio of the phenol compound to the aromatic compound can be selected, but preferably the phenol compound is 1 part
It is sufficient if it is 0 heavy view% or more.

In the method of the present invention, the reaction may be carried out so that the total amount of the phenol compound or the mixture of the phenol compound and the aromatic compound is in the range of 1.3 to 15 mol per mol of these aralkyl compounds. If it is less than 1.3 mol, the softening point of the product will be high and it will be difficult to use, and if it is more than 15 mol, no significant effect will be observed.

Preferably it is 1.3 to 10 mol. Note that 1 mole of the aralkyl compound means 1 linking unit of formula (1), that is, (-0
CH2-R-CH,-).

The method of the invention uses an acid catalyst. Examples of this acid catalyst include mineral acids such as sulfuric acid and phosphoric acid, methanesulfonic acid, p-
) Organic sulfonic acids such as luenesulfonic acid, super strong acids such as trifluoromethanesulfonic acid and heteropolyacids, free sol fluorine catalysts such as zinc chloride, stannic chloride, and ferric chloride, acid clay, synthetic zeolite, etc. Organic solid acid catalysts such as inorganic solid acids, sulfonic acid type ion exchange resins, and perfluoroalkanesulfonic acid type ion exchange resins can be used. Among these, preferred catalysts are methanesulfonic acid, trifluoromethanesulfonic acid, and tin chloride.

There is no limit to the amount of catalyst used, but an amount of 0.001% to 1% by weight based on the total raw materials is usually sufficient.

The reaction temperature is in the range of about 120-200'C, and in order to shorten the reaction time as much as possible, it is preferable to carry out the reaction at 140°C or higher.

A reaction time of 2 to 10 hours is sufficient. Furthermore, an organic solvent may be used in the reaction if necessary.

As this organic solvent, a solvent inert to the reaction and having a boiling point of 110° C. or higher, such as toluene or monochlorohenzene, is used. Although the amount of this solvent to be used can be selected arbitrarily, it is usually carried out in a range of 0.1 to 10 times the weight of all raw materials.

After the reaction, unreacted phenol compounds, aromatic compounds, etc. are removed by distillation under reduced pressure or the like.

In the reaction of the present invention, water is produced as the reaction progresses, but this water can be removed from the system by bubbling inert gas such as nitrogen gas, or azeotropically by using a solvent. is often used.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 138 (] mol) of p~lxylylene glycol in the reactor
and 0.17 g of sulfamic acid as a catalyst,
While bubbling nitrogen gas, the temperature was raised to 200°C, and the reaction was carried out for 20 minutes. After the reaction, the mixture was immediately discharged and solidified to obtain a white resin. When this product was analyzed by GPC, it was confirmed that it was an oligomer with an average number of nuclei (n) of 8.

Also, from the infrared absorption spectrum, it is 1100 to 1150 cm.
-' absorption peculiar to dimethyl ether was observed.

Yield was 115g.

In this case, 1.10 g (equivalent to 0.91 mol) of the above oligomer, 141 g (1.5 mol) of phenol, and 1 g of methanesulfonic acid as a catalyst were charged into a reactor.
By raising the temperature while aerating nitrogen gas? ! 140-1
The reaction was carried out at 50''C for 5 hours. The produced water was removed from the system along with nitrogen gas exhaust.

After the reaction is complete, a small amount of unreacted phenol remains, so
This was distilled off under vacuum and then discharged to obtain 195 g of a pale yellow transparent phenol resin.

The average molecular weight of this phenol resin was measured by GPC and was found to be 2,050.

This resin had a hydroxyl equivalent (g/eq) of 186 and a softening point (JIS L2548) of 84°C.

Example 2 40.6 g of m-xylylene glycol (0,
294 mol) and 0.04 sulfamic acid as catalyst
g was charged, the temperature was raised while nitrogen gas was passed through, and the reaction was carried out at an internal temperature of 180°C for 30 minutes.

When the reaction product at this time was analyzed by GPC, it was found to be an oligomer with an average number of nuclei (n) of approximately ]O.

To this reaction mixture, 28.2 g (0.3 mol) of phenol and 36 g (0.3 mol) of L3.5-)limethylhenzene were charged, and the reaction was carried out while raising the temperature. Finally, the internal temperature was raised to 150"C over 2 hours, and then heated at the same temperature for 3.
The reaction was completed by aging for a period of time.

After the reaction was completed, unreacted raw materials were collected in the same manner as in Example 1 to obtain 75 g of a pale yellow transparent resin. This resin had an average molecular weight of 1640, a hydroxyl equivalent (g/eq) of 249, and a softening point of 71°C.

Example 3 A reaction was carried out using p-xylylene glycol and sulfamic acid in the same manner as in Example 1, and an oligomer having an average number of nuclei (n) of 25 was synthesized. 60.5 g of this oligomer
(equivalent to 0.5 mol), 540 g of 0-cresol
(5 moles), 1 g of methanesulfonic acid was used, and the reaction and post-treatment were carried out in the same manner as in Example 1 to obtain 140 g of orthocresol resin.
I got it. The average molecular weight of this resin is ij: 420,
Hydroxyl group N (g/eq) is 166, softening point is 4]°C
Met.

[Effects of the Invention] When producing a phenol polymer, the method of the present invention uses a polymer represented by formula (1) instead of an aralkyl compound containing a halogen or an ether group. This polymer is extremely advantageous because it can be produced by an inexpensive process and the entire amount of the product can be used as a raw material for the present invention.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) In the method for producing a phenol polymer by reacting a compound containing an aromatic nucleus with an aralkyl compound, the compound containing an aromatic nucleus may be a phenol compound or a combination of a phenol compound and an aromatic compound. One type or a mixture of two or more of each is used as the aralkyl compound of the general formula (
I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is a phenylene group, an alkyl-substituted phenylene group, a biphenylene group, a divalent diphenyl ether residue, or a naphthylene group, and n is an integer from 1 to 100. ) Using a polymer represented by the formula (I), in the presence of an acid catalyst, the amount of the aromatic nucleus-containing compound is 1.3 to 15 times per unit of linkage of the polymer represented by the general formula (I). A method for producing a phenol polymer, which comprises reacting in moles.