JP4939521B2 - Method for producing 4,4'-biphenyldiylmethylene-phenol resin - Google Patents

Description

  The present invention relates to a method for producing 4,4'-biphenyldiylmethylene-phenol resin.

  Among phenol novolac epoxy resins, epoxy resins having a 4,4′-biphenyldiylmethylene-phenol skeleton are excellent in low water absorption and toughness, and are used as materials for semiconductor encapsulants and printed wiring board laminates. 4,4′-biphenyldiylmethylene-phenol resin is useful as an epoxidation raw material or epoxy curing agent for such an epoxy resin.

  For the production of the above 4,4′-biphenyldiylmethylene-phenol resin, a polycondensation reaction between a conventionally known phenol and an aralkyl compound that introduces an alkylene group bonded to the phenyl ring is used as a method for producing a phenol polymer. can do. The form of the condensation reaction is usually a dehydration reaction, a dealcoholization reaction or a dehydrochlorination reaction, depending on the terminal group of the aralkyl compound (condensation agent). Specifically, a dehydration reaction when a hydroxymethyl-terminated aralkyl compound is used (see Patent Document 1, etc.), a dealcoholization reaction when an alkoxyalkyl-terminated aralkyl compound is used (see Patent Documents 2 to 4, etc.), or a halogeno This is a dehydrochlorination reaction in the case of using an alkyl-terminated aralkyl compound (see Patent Documents 5 to 9, etc.). These reactions are usually carried out using an excess amount of phenol relative to the aralkyl compound, for example, at a reaction temperature of 50 ° C. to 200 ° C. After the reaction, the excess phenol is distilled off.

  Catalysts include aluminum chloride, stannous chloride, sulfuric acid, hydrochloric acid, phosphoric acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, oxalic acid, maleic acid, granular clay, stannic chloride, zinc chloride, stannic chloride Acidic compounds such as iron, iron chloride, boron trifluoride, acidic clay, synthetic zeolite, mercuric sulfate, and silver sulfate are known.

  Among the above, as a catalyst used for the dehydrochlorination reaction, Friedel-Crafts type catalysts such as granular clay, stannic chloride, zinc chloride, ferric chloride, etc. Of these, the use of stannic chloride is recommended (see Patent Document 5). Although there is no example of para-xylene chloride in this document, an organic solvent may be added to the reaction mixture if necessary, and chlorinated aromatic compounds having an inert aromatic ring such as chlorobenzene are mentioned. ing.

  Since a large amount of hydrochloric acid as a reaction catalyst is generated in the dehydrochlorination reaction, the dehydrochlorination reaction using aromatic bishalogenomethyl as a condensing agent can also be performed without a catalyst (see Patent Document 6). This document describes that, if necessary, an organic solvent having a boiling point of 110 ° C. or higher and inert to the reaction of toluene or monochlorobenzene may be used. Examples are given using dichloro-p-xylene as the aromatic bishalogenomethyl, but without the use of organic solvents.

  It is described that in the reaction using 4,4′-bischloromethylbiphenyl as the aromatic bishalogenomethyl, the hydrochloric acid as the catalyst may be added in advance as well as hydrogen chloride generated during the reaction (Patent Document 7). , 8). Here, although the reaction can be carried out without a solvent, it is preferable to use a lower alcohol such as methanol, aeranol or isopropyl alcohol, and an example using methanol is shown.

  In addition, in the reaction of 4,4′-bischloromethylbiphenyl and phenol in the presence of a basic substance for neutralizing by-produced hydrogen chloride (see Patent Document 9), an acidic substance is used when it is not under acidic conditions. An example is proposed in which p-toluenesulfonic acid is added. Here, it is described that alcohols such as methanol, ethanol and propanol, ketones such as methyl isobutyl ketone, toluene, xylene, ethylene glycol, diethylene glycol and acetic acid can be used if a solvent is used for the reaction.

JP-A-4-110317 Japanese Patent No. 322834 Japanese Patent No. 2952094 Japanese Patent Publication No. 47-13782 Japanese Patent Publication No. 47-15111 Japanese Patent No. 2866747 JP 2001-64340 A JP 2001-40053 A JP 2008-56944 A

  The present invention provides a method for producing 4,4′-biphenyldiylmethylene-phenol resin more efficiently in a shorter time than in the past by increasing the polymerization rate of 4,4′-bischloromethylbiphenyl and phenols. The purpose is to do.

The present invention as described below is provided to solve the above problems. That is, in the method for producing 4,4′-biphenyldiylmethylene-phenol resin according to the present invention, 4,4′-bischloromethylbiphenyl and a phenol are saturated at least one selected from methylcyclohexane and decalin. The reaction is carried out in the presence of a p-toluenesulfonic acid catalyst in an alicyclic hydrocarbon solvent to obtain 4,4′-biphenyldiylmethylene-phenol resin .

  In this invention, the manufacturing method of the above 4,4'-biphenyl diyl methylene-phenol resin can also be provided as a manufacturing method of the epoxy resin which includes the manufacturing process of the raw material resin of epoxidation.

  According to the production method of the present invention, 4,4'-biphenyldiylmethylene-phenol resin can be produced efficiently with a high polymerization rate, excellent productivity, and efficiency. Therefore, the 4,4'-biphenyldiylmethylene-phenol resin useful as an epoxidized raw material for epoxy resin or an epoxy curing agent can be provided at a lower cost than in the past.

Hereinafter, the present invention will be described in detail.
The phenols used in the present invention are not particularly limited as long as various compounds are commercially available and can undergo a polycondensation reaction with 4,4′-bischloromethylbiphenyl, preferably phenol, o-cresol, Mention may be made of m-cresol, p-cresol, 2,6-xylenol or mixtures thereof. Of these, phenol is most preferably used from the viewpoint of the characteristics and economical efficiency of the resin to be produced.

  The production method of 4,4′-bischloromethylbiphenyl used in the present invention is known. For example, a method of reacting biphenyl, paraformaldehyde, hydrogen chloride using a catalyst such as zinc chloride (special feature). 46-29908), a method of reacting biphenyl, paraformaldehyde and hydrochloric acid in a solvent such as a lower aliphatic carboxylic acid (Japanese Patent Publication No. 40-3774), biphenyl, paraformaldehyde and thionyl chloride using a catalyst such as zinc chloride. It can be produced by a reaction method (Japanese Patent Laid-Open No. 3-1888029). The method for producing 4,4'-bischloromethylbiphenyl described in these patent publications is described herein by reference. The 4,4'-bischloromethylbiphenyl used in the present invention may be produced using the method described above or any other production method. It is also available as a commercial product.

  The reaction between 4,4'-bischloromethylbiphenyl and phenols is usually preferably carried out using an excess of phenols relative to the theoretical equivalent. This is because the softening point of the resulting phenol resin can be controlled by adjusting the excess amount of phenols. That is, when the amount of phenol in the raw material is increased, the softening point is lowered, and when the amount of phenol is reduced, the softening point is improved. A preferable range for the charge ratio of 4,4'-bischloromethylbiphenyl and phenols is phenol / 4,4'-bischloromethylbiphenyl = 1.1 / 1 to 15/1 (molar ratio). When the proportion of phenol is smaller or larger than this, it is difficult to obtain 4,4'-biphenyldiylmethylene-phenol resin having an industrially useful softening point.

  In the present invention, in particular, p-toluenesulfonic acid is used as the catalyst. Paratoluenesulfonic acid is preferably used in an amount of 0.01 to 10 mass%, preferably 0.1 to 5 mass%, based on the total amount of raw materials. If the amount of the catalyst is less than this range, the reaction rate becomes slow. If the amount of the catalyst is more than this range, it is not preferable because it is not only expensive in cost but also changes in characteristics such as the softening point.

In the present invention, as a reaction solvent, methyl cyclohexane, decalin (decahydronaphthalene) is. These may be used alone or in combination of two or more .
The said solvent can be used in 0.1-100 mass% with respect to raw material whole quantity, Preferably it is 1-50 mass%, More preferably, it is 5-30 mass%. If the amount of the solvent is less than this range, the polymerization rate is slow, and if the amount of the solvent is more than this range, the amount of resin that can be produced in the same reaction vessel is reduced, resulting in a decrease in productivity. Become.

In the present invention, as described above, the reaction between 4,4′-bischloromethylbiphenyl and phenols is performed using methylcyclohexane or decalin as a reaction solvent, particularly under a paratoluenesulfonic acid catalyst. Saturated fat, which is a hydrogenated product of an aromatic compound, compared to other acid compounds such as hydrochloric acid, or when an aromatic compound is used even if the solvent is an alcohol or the same number of ring members, or when there is no solvent. By using a cyclic hydrocarbon, a particularly high polymerization rate can be obtained. There is no known technique that teaches such a raw material, a specific catalyst, and such a specific effect in the specific catalyst, and is a knowledge provided for the first time by the present invention.

  The reaction solvent is preferably recovered together with phenol by distillation and reused in a mixture with phenol.

  In the production method of the present invention, the reaction temperature is not particularly limited. Usually, it is in the range of −50 ° C. to 250 ° C., preferably 20 ° C. to 200 ° C., more preferably 30 ° C. to 150 ° C. When the reaction temperature is lower than this range, the polymerization rate becomes slow, and when the reaction temperature is higher than this range, side reaction products are likely to be generated.

In the present invention, the industrially useful softening point of the 4,4′-biphenyldiylmethylene-phenol resin obtained as described above is usually 50 to 100 ° C., preferably 60 to 90 ° C.
The resulting 4,4′-biphenyldiylmethylene-phenol resin can be glycidyletherified to obtain an epoxy resin having a 4,4′-biphenyldiylmethylene-phenol skeleton. Glycidyl etherification can be carried out using a known method for glycidyl etherification of a phenol polymer, for example, Patent Documents 7 and 9. These patent publications are hereby incorporated by reference.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
(analysis)
Analysis of reaction mixture: Using a high performance liquid chromatograph (High Performance Liquid Chromatograph 20A series, manufactured by Shimadzu Corporation), analysis was carried out based on the solvent mixture ratio of acetonitrile and water. The content of 4,4′-bischloromethylbiphenyl remaining in the reaction mixture was calculated in area%.
Softening point: Measured in a glycerin bath at a heating rate of 5 ° C./min using a ring and ball softening point measuring apparatus (MEDTEC 25D5-ASP-MG type).

( Reference example )
83.5 g (0.89 mol) of phenol (manufactured by Wako Pure Chemical Industries, Ltd.) in a 1 liter reaction vessel (separate flask) equipped with a stirrer, thermometer, reflux device, inert gas introduction tube, and oil bath. , About 3.4 times the theoretical amount), 4,4′-bischloromethylbiphenyl (manufactured by Wako Pure Chemical Industries, Ltd.) 66.0 g (0.26 mol), paratoluenesulfonic acid 0.5 g (raw material) 0.33% with respect to the total amount) and 33.5 g of cyclohexane (22.4% with respect to the total amount of raw materials) were added, and the temperature was raised to 70 ° C. to initiate the reaction.
Immediately after the start of the reaction, a small amount of sample was sampled every predetermined time and measured by high performance liquid chromatography to examine the consumption rate of 4,4′-bischloromethylbiphenyl.
After 4 hours of reaction, the temperature was heated to 140 ° C., and excess phenol was removed by distillation under reduced pressure to obtain the desired product (4,4′-biphenyldiylmethylene-phenol resin) having a softening point of 74.5 ° C. . The time course of the remaining amount of 4,4′-bischloromethylbiphenyl is shown in FIG.

( Example 1 )
In the reference example , the same reaction was repeated except that decalin was used instead of cyclohexane to obtain the desired product (4,4′-biphenyldiylmethylene-phenol resin) having a softening point of 74.0 ° C. The results are shown in FIG.

( Example 2 )
In the reference example , the same reaction was repeated except that methylcyclohexane was used in place of cyclohexane to obtain the desired product (4,4′-biphenyldiylmethylene-phenol resin) having a softening point of 75.0 ° C. The results are shown in FIG.

(Comparative Example 1)
In the reference example , the same reaction was repeated except that hydrochloric acid was used instead of p-toluenesulfonic acid to obtain the desired product (4,4′-biphenyldiylmethylene-phenol resin) having a softening point of 72.0 ° C. The results are shown in FIG.

(Comparative Example 2)
In the reference example , except that hexane was used in place of cyclohexane, the same reaction as in the reference example was repeated to obtain the desired product (4,4′-biphenyldiylmethylene-phenol resin) having a softening point of 73.0 ° C. The results are shown in FIG.

(Comparative Example 3)
In the reference example , except that toluene was used instead of cyclohexane, the same reaction as in the reference example was repeated to obtain the desired product (4,4′-biphenyldiylmethylene-phenol resin) having a softening point of 71.5 ° C. The results are shown in FIG.

(Comparative Example 4)
In the reference example , the same reaction as in the reference example was repeated except that methanol was used in place of cyclohexane and hydrochloric acid was used in place of paratoluenesulfonic acid, and the desired product (4,4′- Biphenyldiylmethylene-phenol resin) was obtained. The results are shown in FIG.

(Comparative Example 5)
In the reference example , except that cyclohexane was not used, the same reaction as in the reference example was repeated to obtain the desired product (4,4′-biphenyldiylmethylene-phenol resin) having a softening point of 73.4 ° C. The results are shown in FIG.

It is a graph which shows the 4,4'-bischloromethylbiphenyl residual amount with respect to reaction time in a reference example, an Example, and a comparative example.

Claims (1)

4,4′-bischloromethylbiphenyl and a phenol are reacted in a solvent of a saturated alicyclic hydrocarbon which is at least one selected from methylcyclohexane and decalin in the presence of a paratoluenesulfonic acid catalyst, A process for producing 4,4′-biphenyldiylmethylene-phenol resin, which yields 4,4′-biphenyldiylmethylene-phenol resin.