JPH04170423A - Production of phenol polymer - Google Patents

Abstract

PURPOSE:To obtain a useful phenol polymer at a low cost by reacting a phenol compd. with dicyclopentadiene in the presence of a specific alkanesulfonic acid catalyst. CONSTITUTION:A phenol polymer is prepd. by reacting a phenol compd. with dicyclopentadiene in the presence of an alkanesulfonic acid catalyst of the formula, such as methanesulfonic acid (CH3SO3H), ethanesulfonic acid (C2H5SO3 H), propanesulfonic acid (C3H7SO3H), or butanesulfonic acid (C4H9SO3H), among which methanesulfonic acid is pref. industrially. The reaction is pref. conducted by adding dicyclopentadiene dropwise to the phenol compd. contg. the catalyst at a specified temp. and can be traced by high-performance liq. chromatography.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing polymers derived from phenolic compounds. Such phenol polymers can be used as thermosetting resins using crosslinking agents such as hexamethylenetetramine, and can also be used as raw materials and curing agents for epoxy resins. Particularly in recent years, it has been expected to be used as a semiconductor encapsulant.

[Conventional technology]

Conventionally, methods for producing such phenol polymers have been disclosed in (A) Japanese Patent Publication No. 41-14099, CB) Japanese Patent Application Publication No. 47-35000, and (C) Japanese Patent Application Publication No. 61-168.
No. 624, (D) Japanese Unexamined Patent Publication No. 63-99224,
(E) Unexamined Japanese Patent Publication No. 62-4720, (F) Unexamined Japanese Patent Publication No. 62-4720
-257924 Publication, (G) U.S. Patent No. 3,336,3
No. 98, (I1) U.S. Patent No. 3,536,734 and (T) Journal of the Japan Petroleum Institute, Volume 27, No. 3 (I
984), pages 207-213.

[Problems to be Solved by the Invention] Classifying the above-mentioned known production methods, (B), (G) and (I) are methods in which the reaction is carried out without a catalyst at a temperature of 200"C or higher in an autoclave; , (A), (C
) , (D) , (E) , (F) , (H) and (
I) is a method using a Lewis acid catalyst as a free sol fluorine catalyst. However, the catalysts used are exclusively boron trifluoride and its complexes.

In the above production method, the former method without catalyst is
Since it is necessary to carry out the reaction under pressure and high temperature in an autoclave, the cost increases in terms of equipment and energy.

In addition, since the reaction is carried out at high temperatures, side reactions such as the cleavage reaction of the raw material synchropentadiene and homopolymerization without phenol occur, resulting in problems such as a decrease in side reactions to produce the desired alternating copolymer. Ru. (Saturn et al., Journal of the Japan Petroleum Institute,
Volume 27, k3 (I984) pages 207-209)
In addition, the latter method using a free sol fluorine catalyst is
It is mainly disclosed as a method for producing alternating copolymers. In this reaction, the most preferred catalyst is a trifluoride/boron catalyst, and this catalyst is used in all known techniques. However, the drawback of this boron trifluoride catalyst is that it cannot be used with ordinary materials because extremely corrosive substances are produced in the presence of moisture or decomposition due to heating.

Furthermore, JP-A-62-257924 (F) describes that a sulfonic acid salt of diphenyl oxide can be used as an acid catalyst. Although such aromatic sulfonic acids are solid, they are compatible with the polymer produced by the reaction and are difficult to separate and remove.

A common drawback in all cases in which aromatic sulfonic acids, boron trifluoride, or other Lewis acids are used as catalysts is that the catalyst and its decomposition products remain in the polymer.

This poses a serious problem in the field of electronic materials such as semiconductor encapsulants.

On the other hand, among the known techniques, (D) JP-A-63-99224
In order to solve the above problems, the publication proposes a method in which after the reaction, a solvent is added to dissolve the polymer and the polymer is washed with a large amount of water. However, in this method, unreacted phenol must be removed together with the catalyst components by washing with water, and it is necessary to recover the solvent and to make the washing water containing a large amount of phenolic compounds pollution-free.

In this way, the known methods that use Lewis acids such as boron trifluoride and aromatic sulfonic acids as catalysts have many problems in the quality and production of the resulting polymers, so they are not suitable for industrial use. At present, it is extremely difficult to adopt this method as a manufacturing method.

(Means for solving I1!1!) The present inventors have overcome the various problems described above and have developed an alternating copolymer of a phenol compound and synchropentadiene that can be used in the fields of epoxy resins and semiconductor encapsulants. We have conducted extensive research into methods for producing the polymer as the main component, and as a result, we have completed the present invention.

That is, the present invention involves reacting a phenol compound and synchlopentadiene in the presence of an alkanesulfonic acid catalyst represented by the general formula (I) (where n is an integer of 1 to 4). This is a method for producing a phenol polymer, which is characterized by:

The alkanesulfonic acid of formula (I) used as a catalyst in the method of the present invention is specifically methanesulfonic acid (
CH3SO311), ethanesulfonic acid (CJsSO
J), propanesulfonic acid (C,)HtSO3H) and butanesulfonic acid (C,)19SOJ), but methanesulfonic acid is industrially preferred.

The amount of catalyst used in the method of the present invention is 0.0000000000000000000000000000000000000000,000.
It may be 5% by weight or more, and the upper limit is not limited, but considering economic efficiency, it is 0.5 to 100% by weight, preferably 1% by weight.
．． It ranges from 0 to 50% by weight.

These alkanesulfonic acids used in the present invention are usually
Since it is a liquid and its boiling point is close to that of the raw material phenol compound, it is easy to remove. That is, when the unreacted raw materials are recovered by distillation after the reaction is completed, the alkanesulfonic acid can also be recovered at the same time.

Moreover, there is an advantage that the recovered alkanesulfonic acid can be reused together with the recovered phenol compound.

If ionic impurities are more strictly a problem, a method is used in which unreacted raw materials are removed by vacuum distillation, followed by adding a solvent and washing with water for separation.

Examples of the phenolic compound used in the method of the present invention include -hydric or dihydric phenol, bisphenol, and trisphenol. Specifically, phenol, 0-
Cresol, m-cresol, p-cresol, 0-ethylphenol, p-ethylphenol, 0-isopropylphenol, p-n-propylphenol, p-
5ec-butylphenol, P-cyclohexylphenol, p-chlorophenol, 0-bromophenol, p-bromophenol, resorcinol, catechol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane, 4,4”-thiodidi Examples include, but are not limited to, phenol, dihydroxydiphenylmethane, and trishydroxyphenylmethane.

In the reaction in the method of the present invention, the ratio of the phenol compound to synchropentadiene is 1 to 20.
The amount is twice the molar amount, preferably 1.3 to 10 times the molar amount.

The reaction is usually carried out by heating and polymerizing in the absence of a solvent, but there is no disadvantage in carrying out the reaction using an inert solvent. The reaction temperature is in the range of 20 to 200°C, preferably 40 to 160°C. Reaction time is 2-15
It takes about an hour.

A general embodiment of the reaction in the method of the present invention may be a method in which all raw materials containing the catalyst are charged at once and the temperature is raised to a predetermined temperature as it is, but preferably, the phenol containing the catalyst is heated at a predetermined temperature. A good method is to react the compound while dropping synchropentadiene. The progress of the reaction can be monitored by high performance liquid chromatography.

After the reaction is completed, the unreacted raw materials and catalyst may be recovered by vacuum distillation and then discharged as they are to obtain a polymer, or the polymer solution in which toluene, methyl isobutyl ketone, etc. are added and dissolved is washed with water, and then the solvent is removed. The polymer may be obtained by

[Example〕 Next, the present invention will be explained in more detail with reference to Examples.

Example 1 470 g (5 moles) of phenol and 30 g of methanesulfonic acid as a catalyst were charged into a glass reactor equipped with a temperature needle and a stirring device, and the temperature was raised while stirring and maintained at 90°C. Then, 132.2 g (1 mol) of synchropentadiene was added dropwise to this over 5 hours. After dropping, lower the internal temperature to 150°C
The reaction was completed by aging at this temperature for 5 hours. Next, this viscous reaction solution was heated under vacuum to an internal temperature of 16.
After raising the temperature to 0°C and distilling and recovering unreacted phenol, it was immediately discharged and allowed to cool. The obtained dark red polymer mass is a copolymer of phenol and synchropentadiene represented by the general formula [I[) (II) [where m is an integer of 1 or more], and was measured by GPC. As a result, its composition (Are
a%) were as follows.

m-049゜1% m-126.5% m = 2 13.8% m≧3 10.6% The yield was 285 g, and the softening point of this polymer was JIS-
As a result of measurement using the ring and ball method using -2548, 104'C
The hydroxyl equivalent was 178.1 g/eq.

In addition, no change was observed in the reactor even after the reaction.

Example 2 In a glass reactor equipped with a thermometer and a stirring device, 282 g (3 mol) of phenol and ethanesulfone #8 as a catalyst were added.
2g of synchropentadiene was charged, and the temperature was raised while stirring and maintained at 90"C. Next, 132.2g of synchropentadiene was added to this.
(I mol) was added dropwise over 4 hours. After 0 drops, the internal temperature was lowered to 1
The reaction was completed by raising the temperature to 50°C and aging for 5 hours at this temperature.Next, this viscous reaction solution was heated to an internal temperature of 160°C under vacuum to remove unreacted Phenol etc. were recovered by distillation. To this distillation residue, 500 g of toluene was mixed to obtain a homogeneous solution, and 500 g of water was added under stirring.

After maintaining the reflux state for 1 hour, the mixture was allowed to stand still and the mixture was separated into two layers. The lower aqueous layer was removed, and toluene was distilled off from the upper toluene layer under vacuum. When the mixture was immediately discharged and allowed to cool, a brownish-brown polymer mass was obtained.

The yield was 272 g, and the softening point was 120"C. As a result of analysis by GPC in the same manner as in Example 1, the composition (^
rea%) were as follows.

m=　0　　　　40.5% m-124,7% m=2 15.8% m cod 3 9.5% m≧4 9.5% The hydroxyl equivalent was 211 g/eq.

In addition, even after six reactions in which the pn of the separated aqueous layer was 6.2, no change was visually observed in the reactor.

Example 3 In the reaction of Example 1, 540 g (5 mol) of p-cresol was used instead of phenol, and the reaction and post-treatment were carried out in the same manner as in Example 1 to obtain the following formula (II) (II) [in the formula , m has the same meaning as in formula (I)] was obtained. The softening point of this polymer was 93°C, and the area x of the polymer measured by GPC was as follows.

m -047,2% m-126,9% m -214,6% m≧3 11.3% The hydroxyl equivalent of this polymer was 185 g/eq.

Even after the reaction, no visible change was observed in the reactor.

Comparative Example 1 A glass reactor equipped with a temperature needle and a stirring device was charged with 470 g (5 moles) of phenol and 5 g of phenol/boron trifluoride complex 1-1-, with a boron trifluoride content of 26%. ,
The temperature was raised to 90°C while stirring. Then, 132 g of synchropentadiene was added dropwise over 4 hours at an internal temperature of 90 to 100"C. After the addition, aging was carried out for 5 hours to complete the reaction. Next, this viscous reaction solution was mixed into Example 1. When unreacted phenol was recovered in the same manner, white smoke was observed to be generated from the contents at the end of distillation.The remaining amount was dissolved in toluene in the same manner as in Example 2, washed with water, and subjected to electrostatic distribution.Lower layer The PL of the aqueous layer was 3.2, and after the acidic 0 reaction, slight corrosion was observed in a part of the reactor.

〔Effect of the invention〕

The present invention provides a method for easily producing useful phenol polymers! offer

Conventionally known reaction methods have problems with the quality of the polymer and the material quality associated with corrosion of the equipment, making it impossible to produce it industrially at all.The method of the present invention completely solves these problems. However, since useful phenol polymers can be supplied at low cost, it will greatly contribute to industrial development.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) A phenol compound and synchropentadiene are represented by the general formula (I) C_nH_2_n_+_1SO_3H (I) (however,
A method for producing a phenol polymer, characterized in that the reaction is carried out in the presence of an alkanesulfonic acid catalyst represented by the formula (n represents an integer of 1 to 4).