JP2993727B2 - Method for producing phenolic polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a polymer derived from a phenol compound. Such a polymer can be used as a thermosetting resin by using a crosslinking agent such as hexamethylenetetramine, and can also be used as a raw material or a curing agent for an epoxy resin. In particular, in recent years, applications as semiconductor encapsulants are expected.

[Conventional technology]

Conventionally, such a method for producing a phenol polymer has been disclosed in (A) JP-B-41-14099 and (B)
JP-A-35000, (C) JP-A-61-168624,
(D) JP-A-63-99224, (E) JP-A-62-4720
Gazette, (F) U.S. Pat. No. 3,336,398, (G) U.S. Pat. No. 3,536,734, and (H) Journal of Petroleum Institute, No. 27
Vol. 3, No. 3, (1984) pp. 207-213.

[Problems to be solved by the invention]

The above-mentioned known production methods are classified into (B), (F) and (H) in an autoclave without a catalyst at 200 ° C.
On the other hand, the method of reacting at the above temperature is as follows:
(C), (D), (E), (G) and (H) disclose methods using Lewis acid catalysts as Friedel Crafts catalysts. However, the catalysts used are exclusively boron trifluoride and its complexes.

The former method, which is carried out without a catalyst, requires a reaction at a high temperature under pressure in an autoclave, which increases equipment and energy costs. In addition, since the reaction is performed at a high temperature, a side reaction such as a cleavage reaction of the raw material dicyclopentadiene or a homopolymerization containing no phenol occurs, and thus there is a problem that a production ratio of a preferable alternating copolymer is reduced. .

(Tsuchiya et al., Journal of the Petroleum Institute, Vol. 27, No. 3 (1984) 207-20
The latter method using a Friedel Crafts catalyst is disclosed mainly as a method for producing an alternating copolymer. The most preferred catalyst in this reaction is a boron trifluoride-based catalyst, and this catalyst is used in any of the known techniques. However, the disadvantage of this boron trifluoride catalyst is that
An extremely corrosive substance is generated due to the presence of water or decomposition by heating, and cannot be used with ordinary materials. Further, a common drawback when using boron trifluoride or other Lewis acid catalysts is that the catalyst and its decomposition products remain in the polymer. This is a serious defect in the field of electronic materials such as semiconductor encapsulants. Among the known techniques, Japanese Patent Application Laid-Open No. 63-99224 (D) proposes a method of dissolving the polymer by adding a solvent after the reaction, and washing with a large amount of water, in order to solve the above problem. I have. However, in this method, the unreacted phenol must be washed and removed together with the catalyst component, and it is necessary to recover the solvent and to make the washing water containing a large amount of a phenol compound pollution-free.

As described above, the known method using a Lewis acid catalyst typified by boron trifluoride has many problems in the quality and production of the obtained polymer, so that it is very difficult to use it as an industrial production method. It is difficult at present.

[Means for solving the problem]

Means for Solving the Problems The present inventors have overcome the above-mentioned various problems, and have earnestly studied a method for producing a polymer mainly composed of an alternating copolymer of a phenol compound and dicyclopentadiene, which can be used in the field of an epoxy resin or a semiconductor encapsulant. investigated. As a result, the present invention has been completed.

That is, the present invention relates to a method for producing a phenol polymer, comprising reacting a phenol compound with dicyclopentadiene using a sulfonic acid type strongly acidic ion exchange resin as a catalyst.

The sulfonic acid type strongly acidic ion exchange resin used in the method of the present invention is an ion exchange resin in which polystyrene is crosslinked with divinylbenzene and the exchange group is sulfonic acid. Further, the proton of the sulfonic acid may be partially exchanged with a metal ion.

The ion exchange resin used in the method of the present invention may be in various forms such as powder, sphere, net, and membrane. Further, this ion exchange resin can be used in either a gel type or a macroporous type.

When the reaction is carried out using the ion exchange resin as a catalyst as described above, a method for separating the catalyst from the reaction system is easy. For example, a method of filtering is most typical. When a film-form, granular-form, or net-form ion-exchange resin is used as a catalyst, they can be used as a part of a reaction apparatus.
This means that the catalyst can be used repeatedly.

On the other hand, the polymer produced by the method of the present invention does not have any problem caused by the catalyst component unlike the polymer obtained by a known method. That is, a high quality polymer can be obtained without mixing of ionic impurities into the polymer. In addition, the method of the present invention can be said to be an industrially suitable method because there are no problems regarding the material of the reaction apparatus or problems such as wastewater treatment.

In the method of the present invention, the catalyst can be used in either a batch system or a continuous system, and the amount of the catalyst used may be 5 wt% or more based on all raw materials. 5 to 200% by weight, preferably 10 to 100% by batch method
The wt% range is often used.

Phenol compounds used in the method of the present invention include monohydric or dihydric phenols, bisphenols and trisphenols. Specifically, phenol, o
-Cresol, m-cresol, p-cresol, o-
Ethylphenol, p-ethylphenol, o-isopropylphenol, pn-propylphenol, p-
sec-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, p
-Bromophenol, resorcin, catechol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-thiodiphenol, dihydroxydiphenylmethane, trishydroxyphenylmethane, and the like, but are not limited thereto. Not something.

In the method of the present invention, the use ratio of the phenol compound to dicyclopentadiene is 1 to 20 times,
Preferably, it is in the range of 1.3 to 10-fold mol.

In general, the reaction is generally carried out by heat polymerization in the absence of a solvent, but there is no inconvenience even if the reaction is carried out using a solvent inert to the reaction. The reaction temperature is 20-150 ° C., preferably 40
In the range of ~ 130 ° C. The reaction time is between 10 and 80 hours.

A general embodiment of the present invention may be a method in which all the raw materials including the catalyst are charged at once and the temperature is raised to a predetermined temperature as it is, but preferably, the dicyclohexane is contained in the phenol compound containing the catalyst at the predetermined temperature. A method in which the reaction is performed while pentadiene is added dropwise is preferable. The progress of the reaction can be monitored by high performance liquid chromatography.

After completion of the reaction, the target phenol polymer can be obtained by a method such as separating the catalyst by filtration or the like and recovering unreacted raw materials by vacuum distillation.

〔Example〕

 Next, the present invention will be described in more detail by way of examples.

Example 1 A glass reactor equipped with a thermometer and a stirrer was charged with 56.4 g (0.6 mol) of phenol and 40 g of a sulfonic acid type ion-exchange resin (Levatit K-2611 manufactured by Bayer) as a catalyst. Then, the internal temperature was raised to 90 ° C. with stirring, and 26.44 g (0.2 mol) of dicyclopentadiene was added dropwise over 4.5 hours. After completion of the dropwise addition, the internal temperature was maintained at 115 ° C., and aging was performed for 35 hours to complete the reaction. This was immediately hot filtered at the same temperature to recover the ion exchange resin as a catalyst. The reaction solution was directly subjected to vacuum distillation to recover unreacted phenol. The residue was discharged while hot and allowed to cool, yielding a brown polymer. The yield was 52 g, and the softening point of this polymer was JIS-
As a result of measurement by a ring and ball method using K-2548, it was 98 ° C.
This polymer has the following general formula (I) (Wherein, n represents an integer of 1 or more), which is a copolymer of dicyclopentadiene and phenol represented by the following formula:
%) Was as follows when represented by the number of repeating units n of the formula (I).

Phenol 0.3% n = 0 69.1% n = 1 19.7% n ≧ 2 10.9% The hydroxyl equivalent of this polymer was 171.5 g / eq. After the reaction, no apparent change was observed in the reactor.

Example 2 The reaction was performed again using the ion exchange resin recovered in Example 1 as it was. The procedure was performed in the same manner as in Example 1 except that the aging reaction time was 42 hours.

The yield was 56.9 g, and the softening point of this polymer was 95 ° C. As in Example 1, the composition (Area%) of this polymer measured by GPC was as follows.

Phenol 0.5% n = 0 67.0% n = 1 20.9% n ≧ 2 11.6% The hydroxyl equivalent of this polymer was 174.2 g / eq. After the reaction, no apparent change was observed in the reactor.

Example 3 In the reaction of Example 1, 64.8 g (0.6 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) [Wherein n has the same meaning as in formula (I)]. The softening point of this polymer is 8
The composition (Area%) of the polymer measured by GPC at 6 ° C. was as follows.

p-cresol 0.6% n = 0 66.0% n = 1 20.5% n ≧ 2 12.9% The hydroxyl equivalent of this polymer was 177 g / eq. After the reaction, no apparent change was observed in the reactor.

Comparative Example 1 In a glass reactor equipped with a stirrer and a thermometer, 470 g (5 mol) of phenol and 11.5 g of a phenol / boron trifluoride complex having a boron trifluoride content of 26% were added, and the temperature was raised to 90 ° C. with stirring. Warmed. Next, 132 g of dicyclopentadiene was heated at the internal temperature.
The solution was added dropwise at 90 to 100 ° C over 4 hours. After dropping, the mixture was aged for 5 hours to complete the reaction. Next, unreacted phenol was recovered from this viscous reaction liquid in the same manner as in Example 1. At the end of distillation, generation of white smoke was observed from the contents. After dissolving the residue in toluene and washing with heated water,
Separated. The pH of the aqueous layer was 3.2 and acidic. After the reaction, slight corrosion was observed in a part of the reactor.

〔The invention's effect〕

The phenolic polymer produced by the method of the present invention is a high-quality polymer that does not contain any ionic impurities associated with the remaining catalyst component, which has been a problem in the past.

Further, the method of the present invention is a method suitable for industrially producing a useful phenol polymer in that the catalyst can be used repeatedly without the problem of corrosion of the apparatus.

Claims (1)

(57) [Claims] 1. A method for producing a phenol polymer, comprising reacting a phenol compound with dicyclopentadiene using a polystyrene-based sulfonic acid type strongly acidic ion exchange resin crosslinked with divinylbenzene as a catalyst.