JP2866747B2 - Method for producing phenolic polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polymer material derived from a phenolic compound. Such a phenol polymer is used as a thermosetting resin using a cross-linking agent such as hexamethylenetetramine, and can also be used as a raw material and a curing agent for an epoxy resin.

[0002]

2. Description of the Related Art Conventionally, as a phenol polymer, a novolak resin produced by reacting a phenol compound with formaldehyde is typical. In order to improve the properties of the novolak resin such as hard and brittleness and poor oxidation stability, phenolic polymers using aralkyl compounds (JP-B-47-15111, JP-B-47-13782) Gazette, Japanese Patent Publication 52-1
No. 4280) has been developed.

[0003] These phenolic polymers are represented by the following formula (I)
I) R— (CH ₂ OR ′) _a (II) (wherein R represents an aromatic group such as a phenylene group, R ′ represents a lower alkyl group, a represents 2 or 3) and the following formula (III) An aralkyl compound represented by R- (CH ₂ X) _a (III) (wherein R and a have the same meaning as in the above formula (II), and X represents a halogen atom), for example, a compound of the formula (II) As compounds, α, α '
-Dimethoxy-p-xylene, and the compound of the formula (III) includes α, α′-dichloro-p-xylene, one of which is a phenol compound or a mixture of a phenol compound and an aromatic compound. And manufactured from.

However, in the production of such phenolic polymers, a catalyst is required in each case. These catalysts are acidic compounds. For example, the following compounds are exemplified in the above-mentioned known technology. In other words, clay minerals, sulfate, p-toluenesulfonic acid, stannic chloride is diethyl sulfate and Friedel-Crafts catalyst, zinc chloride, ferric chloride and the like,
Copper and silver compounds have also been shown to be effective. Of these, stannic chloride has been selected as the most suitable catalyst.

On the other hand, in recent years, developments in the field of electronic materials are expected as applications of phenolic polymers. For example, an epoxy resin and a curing agent as a semiconductor sealing material,
In these applications in addition to the structural performance of the resin, incorporation of ionic impurities such as electrical performance to the right and left Rukin genus component and an acidic substance is extremely problematic. Therefore, the presence of the catalyst component in the phenolic polymer and the novolak resin is pointed out as a serious defect, and improvement is required.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for industrially inexpensively producing a useful phenol polymer containing no ionic impurities as described above.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems. As a result, the present invention has been achieved. That is, the present invention provides a compound represented by the general formula (I) R- (CH ₂ X) ₂ (I) wherein R represents a phenylene group, an alkyl-substituted phenylene group, a biphenylene group, a divalent diphenyl ether residue or a naphthylene group; X represents a halogen atom), and a method for producing a high-purity phenol polymer characterized by reacting an aromatic bishalogenomethyl compound represented by the formula (1) with a phenol compound without a catalyst.

[0008] The aromatic bishalogenomethyl compound as a raw material used in the production method of the present invention is represented by the general formula (I). R in the general formula (I) is a phenylene group, an alkyl-substituted phenylene group, a biphenylene group, a divalent diphenylether residue or a naphthylene group;
Specifically, the following groups (Formula 1)

[0009]

Embedded image And X represents a halogen atom.

Such starting compounds include, for example, 1,2-di (chloromethyl) benzene, 1,2-di (bromomethyl) benzene, 1,3-di (chloromethyl) benzene,
1,3-di (fluoromethyl) benzene, 1,4-di (chloromethyl) benzene, 1,4-di (bromomethyl) benzene, 1,4-di (fluoromethyl) benzene, 1,4-di (chloro Methyl) -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 (bromomethyl) biphenyl,
4,4′-bis (chloromethyl) diphenyl ether,
2,7-di (chloromethyl) naphthalene and the like. Among them, chlorine compounds are industrially preferable.

As the phenol compound, phenol,
p-cresol, o-cresol, m-cresol, p
-Ethylphenol, o-ethylphenol, p-isopropylphenol, pn-propylphenol, p
-Sec-butylphenol, o-sec-butylphenol, p-tert-butylphenol, o-ter
t-butylphenol, p-tert-amylphenol, p-tert-octylphenol, nonylphenol, dodecylphenol, p-cyclohexylphenol, o-phenylphenol, p-phenylphenol, p-cumylphenol, p-α-methylbenzylphenol , P-chlorophenol, p-bromophenol, α-naphthol, β-naphthol, resorcin, catechol, hydroquinone, pyrogallol, phloroglucinol, p-aminophenol, m-aminophenol, 2,2-bis (4-hydroxy Phenyl) propane, 4,4′-thiodiphenol, and the like, but are not limited thereto.

In the method of the present invention, these phenol compounds are added to the bishalogenomethyl compound in an amount of 1.3 to 1%.
The reaction is carried out using a 5-fold molar range. When the molar ratio is less than 1.3 times, the softening point of the product becomes high and it is difficult to use the compound. Preferably,
It is 1.3 to 10 times mol.

The reaction temperature ranges from 50 to 200 ° C.,
In order to shorten the reaction time as much as possible, it is preferable to carry out the reaction at 100 ° C. or higher. The reaction time depends on the temperature,
A range of 2 to 10 hours is sufficient.

The reaction may be carried out while all the raw materials are charged at once and the temperature is raised, or may be carried out by adding an aromatic bishalogenomethyl compound while keeping the phenol compound at a predetermined temperature in advance. If necessary, an organic solvent may be used for the reaction. As the organic solvent, a solvent inert to the reaction, such as toluene or monochlorobenzene, having a boiling point of 110 ° C. or higher is used. The amount of the solvent used is arbitrary, but usually 0.1 to
It may be used in a range of 10 weight times.

In the reaction of the present invention, a halogen hydrogen gas is generated as the reaction proceeds, and this gas is removed from the system by passing an inert gas such as nitrogen gas through the system, or is removed under reduced pressure. The method is frequently used. After the reaction, the unreacted phenol compound, the solvent, and the like are removed by a method such as distillation under reduced pressure to obtain the high-purity phenol polymer of the present invention.

The phenolic polymers obtained by the process of the present invention is to carry out the reaction without a catalyst, that attributable to the catalyst component
It does not contain any ionic impurities of the metals, and the like. In addition, hydrogen halide by-produced in the reaction can be completely removed by performing the reaction of the present invention at a relatively high temperature, and further by performing the reaction under vacuum when recovering unreacted raw materials. Therefore, the acid component in the obtained polymer can be almost ignored. This is also proved by the fact that no halogen atom is detected by elemental analysis as described in the examples below.

Such a phenol polymer containing no metal component or acid component cannot be achieved by a method using an aralkyl alcohol derivative represented by the general formula (II) as a raw material. That is, α, α'-dimethoxy-p-xylene and p-
Taking xylylene glycol as an example, it is because the presence of the above-mentioned catalyst is indispensable to react these monomers with a phenol compound to obtain a phenol polymer.

On the other hand, general formula (I) or general formula (II)
A catalyst has also been required for the poly-α-halogenomethyl compound represented by I). However, as a result of the study by the present inventors, it has been surprisingly found that the aromatic bishalogenomethyl compound represented by the general formula (I) reacts with the phenol compound without a catalyst to obtain a polymer. . Initially, this was thought to be due to the presence of impurities,
The present inventors have found that the reaction can proceed in the absence of a catalyst component because the object is achieved even when a pure compound purified by distillation is used. This is a discovery that cannot be expected at all from the above-mentioned known technology.

[0019]

The present invention will be described in more detail with reference to the following examples. Example 1 A glass reactor equipped with a thermometer and a stirrer was charged with 156 g (1.7 mol) of phenol, and the temperature was raised while stirring to keep the internal temperature in the range of 100 to 110 ° C. Next, while maintaining the same temperature range, 175 g (1 mol) of α, α′-dichloro-p-xylene was added in portions over 2 hours. On the way, the generated hydrogen chloride gas was suctioned by an aspirator and collected in a washing bottle. After the addition was completed, the internal temperature was raised to 150 ° C. over 3 hours. After this, the temperature range 150
The reaction was completed by aging at １６０160 ° C. for 6 hours. Next, unreacted phenol was recovered from the reaction solution under vacuum. During this process, the internal temperature is up to 170 ° C and the vacuum pressure is 2
mmHg. The viscous reaction solution from which the unreacted phenol was recovered was immediately discharged to a porcelain dish, and allowed to cool to obtain a pale yellow, transparent, hard and brittle polymer (yield 198).
g). This is represented by the following formula (IV):

[0020]

Embedded image A phenolic polymer represented by the following formula:
w) is 2700 and the softening point is 85.5 ° C. (JIS-K-2
207) and the hydroxyl equivalent was 176 g / eq. 30 g of this polymer was mixed with 300 ml of pure water at a temperature of 95 ± 5.
Extraction was performed at 20 ° C. for 20 hours. After cooling, a supernatant was obtained. The eluant chloride ion of the supernatant was determined by ion chromatography to be 0.74 ppm. In addition,
Elemental analysis was also performed on the polymer, but no chlorine component was detected.

Example 2 In Example 1, 17.5 g (0.1%) of α, α'-dichloro-m-xylene was added to 94 g (1 mol) of phenol.
Mol) was used in the same manner as in Example 1 to obtain a pale yellow transparent formula (V) shown below.

[0022]

Embedded image 25.5 g of a phenol polymer represented by the formula was obtained. High performance liquid chromatography (GPC) of this polymer
As a result of the analysis, the composition (Area%) was as follows. n = 0 76.8%, n = 1 17.9% n = 2 4.3%, n ≧ 3 1.0% The softening point was 34 ° C. and the hydroxyl equivalent was 154 g / eq.

Example 3 Phenol and α, α'-dichloro-P-xylene were purified by distillation to obtain high-purity products having a purity of 99.9% or more. 23.5 g of the phenol thus obtained
(0.25 mol) and 17.5 g (0.1 mol) of α, α′-dichloro-p-xylene were charged into a glass reactor,
The internal temperature was raised to 150 ° C. over 3 hours while passing nitrogen gas. When the internal temperature reached about 70 ° C., generation of hydrogen chloride gas started, and the reaction was carried out while collecting this gas with a gas washing bottle. The reaction was completed by aging for 8 hours at an internal temperature of 150 to 160 ° C. Post-treatment after the reaction was carried out in the same manner as in Example 1 to obtain 24 g of a pale yellow transparent polymer.
This is a phenolic polymer represented by the formula (IV), and analyzed by high performance liquid chromatography.
The composition (Area%) was as follows. n = 0 55.2%, n = 1 27.4% n = 2 13.6%, n ≧ 3 3.8% The softening point was 52 ° C., and the hydroxyl equivalent was 163 g / eq. As a result of elemental analysis of this polymer, no chlorine component was detected.

Example 4 In Example 1, α-naphthol 432.6 was added to 175 g (1 mol) of α, α′-dichloro-p-xylene.
g (3 mol), except that the following formula (VI) was used.

[0025]

Embedded image 375 g of a polymer represented by the following formula was obtained. As a result of analysis by high performance liquid chromatography, the composition of the polymer (Are
a%) was as follows. n = 0 42.5%, n = 126.0% n = 2 15.2%, n ≧ 3 16.2% The softening point of this polymer was 98 ° C.

[0026]

The method of the present invention is a novel method in which condensation is carried out without using any catalyst, and the phenolic polymer obtained by this method is a high-purity, good polymer containing no acid component or metal component. It is. Such a resin meets the demands in the field of electronic materials and the like, and greatly contributes to industrial development.

Continuation of the front page (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 61/00-61/12 C07C 37/00-37/88 C07C 39/00-39/44 WPI / L (QUESTEL)

Claims (1)

(57) [Claims] 1. A compound of the general formula (I) R- (CH ₂ X) ₂ (I) wherein R is a phenylene group, an alkyl-substituted phenylene group, a biphenylene group, a divalent diphenyl ether residue,
Or a naphthylene group, and X represents a halogen atom)
A method for producing a high-purity phenol polymer, comprising reacting an aromatic bishalogenomethyl compound represented by the formula with a phenol compound without a catalyst.