JPH04202219A - Production of phenol polymer - Google Patents

Abstract

PURPOSE:To produce a phenol polymer at a low cost by reacting an aromatic compound with a polymer obtained by hydrolyzing a specified aralkyl compound. CONSTITUTION:A useful phenol polymer is produced at a low cost industrially by reacting an aromatic compound comprising a phenol compound or a mixture of at least one phenol compound with at least one aromatic compound with an aralkyl derivative comprising a polymer of formula II (wherein R is (alkyl- substituted) phenylene, biphenylene, a bivalent diphenyl ether residue or naphthylene; and n is 1-100) obtained by hydrolyzing an aralkyl compound of formula I (wherein R is as defined above) in the presence of an acid catalyst in such a ratio that 1.3-15mol of the aromatic compound is used per unit of the polymer of formula II. This process is very advantageous because it is not only economical but also quite nonproblematic in the material of an apparatus.

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 side for epoxy resins.

[Conventional technology]

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

This novolac resin has drawbacks such as being hard and brittle and having poor oxidation stability.
No. 15111 and Japanese Patent Publication No. 13782 (1977) have been developed.

This phenol resin has the following formula (I[[)C in the formula, R
represents an aromatic group such as a phenylene group, R'' represents a lower alkyl group, and a represents 2 or 3) and the following formula (IV) (wherein R and a represent the same meaning as the above formula (yl)) , X represents a halogen atom), for example, the compound of formula (III) is α,α°-dimethoxy-p-xylene, and the compound of formula (■) is α,rl-dichloro-p-xylene.
-xylene, prepared from one of these and a phenolic compound or a mixture of a phenolic compound and an aromatic compound.

As this aralkyl compound, 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 with the material of the equipment and the residual chlorine ions in the resulting resin. on the other hand,
In the method using α,α°-dimethoxy-p-xylene as a raw material, in order to obtain this dimethoxylated product, α,α“-dichloro-p-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.

On the other hand, the present inventors have developed the general formula (V) R+CH! as a means to solve the above problems. 0H)t (V) (wherein,
We discovered and previously proposed a method using an aralkyl compound represented by the above formula (I [[)] or a condensate thereof), in which R has the same meaning as I[[].

The aralkyl compounds and condensates thereof used in these methods are, for example, p-xylylene glycol, which is the most typical aralkyl compound of type (V). p-xylylene glycol has the general formula ( IV) α,
It is produced by hydrolyzing α°-dichloro-P-xylene (Japanese Patent Application Laid-Open No. 60-32737). It is also known that the condensate can be obtained by condensing glycols using an acid catalyst such as a sulfamic acid catalyst or a p-toluenesulfonic acid catalyst (M. J. Road; Journal of American Chemical Society, vol. 72, p. 2216, 1950, Chemical Abstracts, vol. 73, 15464k, 197
0 years.

(U.S. Pat. No. 3,769,249).

However, regarding the method for producing glycols as described above, in JP-A-60-32737, relatively expensive alkali metal carbonates and bicarbonates must be used, and the reaction must be carried out at low concentrations. It is not only economically disadvantageous because it needs to be carried out using an aqueous solution of water, but also the yield decreases due to purification, and it also requires effort to make wastewater treatment pollution-free. In addition, one more step is required to produce the condensate, and the condensation reaction requires a change from the alkaline conditions of the hydrolysis reaction to the acidic conditions, so problems with the material of the equipment cannot be ignored.

[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned problems and provide a method for industrially producing a useful phenol polymer at low cost. Specifically, when producing a phenol polymer, the purpose is to carry out a reaction using an improved aralkyl derivative.

[Means to solve the problem]

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

That is, the present invention provides a method for producing a phenol polymer by reacting a compound containing an aromatic nucleus with an aralkyl derivative, in which the compound containing an aromatic nucleus is a phenol compound, or one type or each of a phenol compound and an aromatic compound. A mixture of two or more types is used as the above aralkyl derivative, -format (1) R+CH,CI! >2 (1)
(In the formula, R represents a phenylene group, an alkyl-substituted phenylene group, a biphenylene group, a divalent diphenyl ether residue, or a naphthylene group). In the presence of an acid catalyst, 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 of 1 to 100. The present invention relates to a method for producing a phenol polymer, which is characterized in that a compound containing an aromatic nucleus is reacted in an amount of 1.3 to 15 times the mole per link unit of the polymer represented by the above-mentioned formula (n).

The polymer represented by the general formula (II) used in the present invention is directly produced by subjecting the bistarolomethyl compound represented by the general formula (I) to a hydrolysis reaction in the presence of a base. A feature of the present invention is that the polymer represented by the general formula (ff) thus obtained is directly reacted with a compound containing an aromatic nucleus to obtain a phenol polymer.

Aralkyl derivatives used in the method of the present invention, namely the general formula (
Conventionally, the polymer represented by II) is obtained by hydrolyzing a bistarolomethyl compound of the -format (I), and is obtained by hydrolyzing a bistarolomethyl compound of the -format (V).
) as a by-product when producing glycol, and attention was paid to its suppression (Japanese Patent Application Laid-Open No. 60-327
No. 37) 0 The method of the present invention actively utilizes this polymer, which has conventionally been a by-product, as a raw material. Therefore, in the method of the present invention, in the hydrolysis reaction of the compound of form (I), the type of base, the ratio of dilution water, etc., which were strictly limited in the past, are not matched at all.

That is, as the type of base used in the hydrolysis reaction of the present invention, carbonates, bicarbonates, and hydroxides of alkali metals can be used.

Specifically, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, etc. are used. Industrially preferred is sodium hydroxide, which is inexpensive.

The amount of these bases to be used may be 2 equivalents or more, preferably 2.1 to 3.
It may be within the range of 5 equivalents.

It is sufficient that the amount of dilution water used is 1 to 511 times the amount of the raw material, preferably 2 to 10 times in consideration of economic efficiency.

The reaction temperature is usually carried out at a water reflux state, but in order to speed up the progress of the reaction, the boiling point can be raised and the reaction carried out under pressure without causing any problems. The reaction temperature range is 80-150°C. The pressure is in the range of -10 atm.

The reaction time ranges from 1 to 50 hours, preferably from 2 to 30 hours.

In addition, in this hydrolysis reaction, benzene, toluene,
It may be carried out in two layers using a water-immiscible solvent such as monochlorobenzene, and in order to accelerate the reaction, quaternary ammonium salts, quaternary phosphonium salts, crown ethers, nitrogen-containing quenched polyethers may be used. The reaction may also be carried out by adding a phase transfer catalyst such as polyethylene glycols.

The polymer produced after the reaction is left standing and then separated, or
It can be solidified by cooling and isolated by filtration.

The raw material compound used in this hydrolysis reaction is represented by the general formula (1), and the resulting polymer is represented by the general formula (I[).

R in the general formulas (I) and (I[) of the present invention is a phenylene group, an alkyl-substituted phenylene group, a biphenylene group, a divalent diphenyl ether residue, or a naphthylene group, and specifically, CFI.

It is expressed as

Examples of such raw material compounds include 1,2-di(chloromethyl)benzene, 3-di(chloromethyl)benzene, 1,4-di(chloromethyl)benzene, 1.4
-di(chloromethyl)-2,5-dimethylbenzene,
1,3-di(chloromethyl)-4,6-dimethylbenzene, 1,3-di(chloromethyl)-2,4-dimethylbenzene, 4.4'-bis(chloromethyl)biphenyl, 4.4' -bis(chloromethyl)diphenyl ether, 217-di(chloromethyl)naphthalene.

In addition, in the − format (I[), n (number of nuclear bodies) is 1 to 1
00, and although it can be used above this range, it is not preferable because a gel-like substance is produced as a by-product in the obtained phenol polymer.

Next, a process for producing a phenol polymer by reacting the aralkyl derivative obtained by the above method with a compound containing an aromatic nucleus will be described.

Compounds containing aromatic nuclei include phenolic compounds and aromatic compounds.

Phenol compounds include phenol, p-cresol, 0-cresol, m-cresol, p-ethylphenol, 〇-ethylphenol, p-isopropylphenol, p-n-propylphenol, p-5ee-
Butylphenol, o-5ec-butylphenol, p
-tert-butylphenol, o-tert-butylphenol, p-tert-amylphenol, p
-tert-octylphenol, nonylphenol,
dodecylphenol, p-cyclohexylphenol,
0-phenylphenol, p-phenylphenol, p
-cumylphenol, p-α-methylbenzylphenol, P-chlorophenol, p-bromophenol, α
- Naphthol, β-naphthol, resorcinol, catechol, hydroquinone, pyrogallol, phloroglycitur, P-aminophenol, m-aminophenol,
2,2-bis(4-hydroxyphenyl)propane, 4
, 4'-thiodiphenol, etc., but are not limited to these.

Moreover, as an aromatic compound, m-xylene, 1.3.
5-) dimethylbenzene, L2,4.5-tetramethylbenzene, 1,2,3.4-tetramethylbenzene,
Examples include m-diisopropyruhenzene, 1,3.5-)liisopropylbenzene, diphenyl ether, dibenzyl ether, triphenyl, diphenylamine, diphenyl sulfide, diphenylanthracene, and naphthalene.

In the method of the present invention, when reacting an aralkyl derivative using only a phenol compound, it may be carried out alone or in combination of two or more, or a phenol compound and the above-mentioned aromatic compound may be reacted. When used in combination, one or more 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 should be 10% by weight or more.

In the method of the present invention, the reaction may be carried out in such a manner 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 derivatives. 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 moles. In addition, 1 mol of aralkyl derivative means 1 connected unit of general formula (II), that is,
It is based on (-○CH, -R-CH2-).

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, and P-
Organic sulfonic acids such as toluenesulfonic 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 o, ooi 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 monochlorobenzene, 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 passing an inert gas such as nitrogen gas through it, or azeotropically by using a solvent. methods are often used.

〔Example〕

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

Example 1 84 g of 1,4-bis(chloromethyl)benzene was placed in a reactor equipped with a thermometer, stirrer and reflux condenser.
(0.5 mol), 300 g of 20% caustic soda aqueous solution (1
, 5 mol) and 5 d of toluene were charged and the mixture was heated under reflux to 1
The reaction was completed after stirring for 5 hours. The reaction temperature during this period was 97 to 98°C, and the contents were in a state in which small droplets of oil were dispersed in the alkaline aqueous layer.

After the reaction, the droplets were solidified by slow cooling, filtered, washed with water, and dried under vacuum (yield: 57 g).

The obtained pale yellowish white small particles have general formula (I[) in which R is p-
It is an aralkyl derivative which is a phenylene group, and the average number of nuclei (n) by GPC was about 6.

The softening point measured by the ring and ball softening point measurement method according to JIS K-2548 was 68°C.

Next, 79 g (0.84 mol) of phenol and 0.67 g of methanesulfonic acid as a catalyst were charged into a reactor with respect to 55 g of the aralkyl derivative obtained in this reaction.
Raise the temperature while aerating nitrogen gas until the internal temperature reaches 140-15
The reaction was carried out at 0°C for 4 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 107 g of a pale yellow transparent phenolic resin.

The average molecular weight of this phenol resin was measured by GPC and was found to be 1,650.

The hydroxyl equivalent (g/eq) of this resin was 183, and the softening point (JIS K-2548) was 79°C.

Example 2 1,3-bis(chloromethyl) was added to the same reactor as Example 1.
84 g (0.5 mol) of benzene, 84 g of water and 5 d of toluene were charged and kept under reflux under stirring.

In this, 107 g of 45% caustic soda aqueous solution (1,2
mol) was added dropwise over 13 hours. After this, internal temperature 9
The reaction was completed by aging for 5 hours under reflux at 8 to 100°C. After the reaction is complete and the internal temperature has dropped to 80°C, add 100al of toluene! was added and allowed to stand to separate into two layers.

The lower aqueous layer was removed, and the toluene layer was washed with 200 d of warm water and separated.

In this toluene layer, the general formula R is m-phenylene group, and GP
This contained an aralkyl derivative having an average number of C nuclei of about 4.5, and this was used directly in the next reaction.

A toluene solution containing 270 g (2.5 mol) of 0-cresol and the aralkyl derivative obtained in the above reaction was charged into a reactor, 1 g of methanesulfonic acid was added as a catalyst, and the reaction was carried out while raising the temperature. Ta.

The reaction was carried out while distilling off the solvent toluene and the water produced, and when the temperature reached 150° C., aging was carried out for 3 hours to complete the reaction.

After the reaction was completed, unreacted raw materials were collected in the same manner as in Example 1 to obtain 126 g of a pale yellow transparent resin. This resin had an average molecular weight of 560, a hydroxyl equivalent of 173, and a softening point of 59°C.

Example 3 84 g of 1,4-bis(chloromethyl)benzene was hydrolyzed in the same manner as in Example 2 to obtain a toluene solution of an aralkyl derivative having an average number of nuclei of R-12.

Next, this aralkyl derivative and 47 g of phenol (0
, 5 mol) and diphenyl ether (17 g (0.1 mol)) were charged into the reactor, and methanesulfone fl was added as a catalyst.
The reaction was carried out in the same manner as in Example 2, in which 6 g of lO was added and the reaction was carried out while raising the temperature, to obtain 89 g of a pale yellow transparent resin. The average molecular weight of this resin is 2150 and the softening point is 84.
℃, and the hydroxyl equivalent was 225.

〔Effect of the invention〕

As detailed above, when producing a phenol polymer by the method of the present invention, a bistarolomethyl compound is hydrolyzed by an inexpensive method, and the entire amount thereof is used as a raw material. Therefore, it is an extremely advantageous method that is not only economical but also has no problems with the material of the device.

Patented beauty 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 derivative, 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 of the above aralkyl derivatives can be used as the aralkyl derivative of the general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a phenylene group, an alkyl-substituted phenylene group, a biphenylene group, a divalent diphenyl ether residue, or a naphthylene group) General formula (II) obtained by hydrolysis ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (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) , n is an integer of 1 to 100), in the presence of an acid catalyst, each unit of the polymer represented by general formula (II) contains the above aromatic nucleus. A method for producing a phenol polymer, which comprises reacting a compound at 1.3 to 15 times the mole.