JP3090991B2 - Method for producing phenolic polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polymer derived from a phenol compound. Such a phenol polymer is used as a thermosetting resin by 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. In particular, in recent years, applications as semiconductor encapsulants are expected.

[0002]

2. Description of the Related Art Conventionally, such a method for producing a phenol polymer is disclosed in (A) JP-B-41-14099, and (B)
JP-A-47-35000, (C) JP-A-61-168624, (D) JP-A-63-99224, (E) JP-A-62-47
No. 20, (F) US Pat. No. 3,336,398, (G) US Pat. No. 3,536,734, and (H) Journal of the Japan Petroleum Institute.
Vol. 3, No. 3, (1984), pp. 207-213. Classifying the above-mentioned known production methods, (B),
(F) and the method described in (H), (A), (C),
(D), (E), (G) and (H).

[0003] The former method uses an autoclave without a catalyst.
The reaction is carried out at a temperature of 200 ° C. or higher. In these production methods, it is necessary to carry out the reaction at a high temperature under pressure in an autoclave, so that the cost for equipment and energy is increased. 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 Japan Petroleum Institute, Vol. 27, No. 3 (1984), pp. 207-209).

The latter method is a method using a Lewis acid catalyst as a Friedel-Crafts catalyst, and the method using this Friedel-Crafts catalyst is disclosed mainly as a method for producing an alternating copolymer. . In this reaction, the most preferred catalyst is a boron trifluoride-based catalyst, and the catalyst used in any of the known techniques is exclusively boron trifluoride and its complex. However, a drawback of this boron trifluoride-based catalyst is that it cannot be used with ordinary materials because extremely corrosive substances are generated due to the presence of water or decomposition by heating. A drawback common to the use of 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) discloses that after the reaction to solve the above problem,
A method of adding a solvent and washing with a large amount of water has been proposed.
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 non-polluting. 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, and is extremely difficult to produce industrially. The situation.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to react a phenol compound with dicyclopentadiene,
The purpose of the present invention is to provide a resin mainly composed of an epoxy resin and an alternating copolymer which can be used in the field of a semiconductor encapsulant. Is to provide a way.

[0006]

Means for Solving the Problems The present inventors have made intensive studies in order to solve these objects, and as a result, completed the present invention. That is, the present invention relates to a perfluoro compound represented by the general formula (I) C _n F _{2n + 1} SO ₃ H (I) (wherein n is an integer of 1 to 8). A method for producing a phenol polymer, which comprises reacting in the presence of an alkanesulfonic acid catalyst.

According to the method of the present invention, the quality of the obtained phenolic polymer is excellent, and a high-quality polymer free from ionic impurities due to the remaining catalyst component, which has been a problem in the past, can be obtained. It is possible to industrially produce useful phenolic polymers, for example, there is no problem in terms of production, and there is no problem in the material accompanying the corrosion of the apparatus, and the catalyst can be used repeatedly.

The perfluoroalkanesulfonic acid of the catalyst used in the method of the present invention is represented by the general formula (I). Specifically, trifluoromethanesulfonic acid (CF ₃ SO ₃ H), pentane Fluoroethanesulfonic acid (C ₂ F ₅
SO ₃ H), heptafluoropropanesulfonic acid (C ₃ F ₇ SO
₃ H), nonafluorobutanesulfonate _{(C 4 F 9 SO 3 H} ), undecafluoro-penta acid _{(C 5 F 11 SO 3 H} ), tridecafluoro hexane sulfonic acid _{(C 6 F 13 SO 3 H} ) , pentadecafluorooctyl heptanoic acid _{(C 7 F 15 SO 3 H} ) and heptadecafluorooctanesulfonic acid _{(C 8 F 17 SO 3 H} ) and the like. Industrially, trifluoromethanesulfonic acid is preferred.

[0009] Perfluoroalkanesulfonic acids are generally classified as superacids (Kobayashi, Synthetic Organic Chemistry,
Vol. 33, No. 11 (1975), pp. 861-862), for example, the acid strength (H ₀ ) of trifluoromethanesulfonic acid is 42
7 times, much stronger than sulfuric acid (acid strength is 30 times that of nitric acid). Therefore, the amount of these catalysts used in the method of the present invention may be very small. Specifically, for all raw materials,
The range is 0.001 to 1.0% by weight, preferably 0.01 to 0.25% by weight. With such a small amount of use, in most cases,
Even if the catalyst remains in the polymer, no problem occurs. Moreover, in trifluoromethanesulfonic acid,
Since the boiling point is generally lower than the boiling point of the raw material phenol compound, it can be removed at the same time as the unreacted raw material is recovered. Moreover, there is an advantage that the recovered trifluoromethanesulfonic acid can be reused together with the recovered phenol compound.

When ionic impurities in the obtained phenolic polymer are more strictly problematic, unreacted raw materials and the like are removed by vacuum distillation, a solvent is added and dissolved, and the mixture is washed with water and separated. As a method other than washing with water and a method other than washing with water, a method of neutralizing a trace amount of acidic substance remaining in the phenol polymer is adopted. Compounds used in the neutralizing method are oxides, carbonates, and hydroxides of alkaline earth metals such as barium, magnesium, and calcium, and specifically, calcium oxide, magnesium oxide, barium oxide, and carbonate. Calcium, magnesium carbonate, barium carbonate, magnesium hydroxide or barium hydroxide, etc., when using the resulting phenolic polymer for semiconductor encapsulant applications, barium compounds are preferred, particularly preferably barium carbonate or barium hydroxide It is. The amount of the neutralizing agent used is equal to or less than the equivalent of the catalyst used in the reaction, but usually, most of the catalyst is recovered.
About 5 equivalents are used.

The reaction apparatus applicable to the method of the present invention includes a glass or glass lining apparatus, SUS30
4. An apparatus made of a general-purpose material such as SUS316 can be used. This is a great advantage in that conventionally used boron trifluoride-based catalysts cannot be used because they are so corrosive to any reactor material.

In order to carry out the method of the present invention industrially,
The following SUS materials were subjected to a corrosion test. Test material: SUS304 test piece SUS316 test piece Immersion liquid: Reaction stock solution prepared by reacting 100 g of phenol and 0.128 g of trifluoromethanesulfonic acid catalyst with 28.2 g of dicyclopentadiene Corrosion test conditions: 170 ° C. × 120 hours Test result: 170 ° C. × 120 hours weight loss rate (%) Corrosion rate (mm / year) SUS304: 0.045 0.026 SUS316: 0.048 0.028 As a result, the test condition was changed to a severe condition of 170 ° C. Nevertheless, the annual corrosion rate is 0.026-0.028mm
And the surface condition of the test piece is good, and it is determined that these materials can be used in the method of the present invention.

The phenolic compound used in the method of the present invention includes monohydric or dihydric phenol, bisphenol, trisphenol and the like. Specifically, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-isopropylphenol, pn-propylphenol, p-sec-butylphenol, p-cyclohexyl Phenol, p-chlorophenol, o-bromophenol, p-bromophenol, resorcin, catechol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-thiodiphenol, dihydroxydiphenylmethane and trishydroxy Examples include, but are not limited to, phenylmethane.

In the method of the present invention, the use ratio of the phenol compound is in the range of 1 to 20 moles, preferably 1.3 to 10 moles per mole of dicyclopentadiene. 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. Examples of usable solvents include aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as 1,2-dichloroethane, 1,1,2-trichloroethane and monochlorobenzene. The reaction temperature ranges from 20 to 200 ° C, preferably from 40 to 160 ° C.
The reaction time is between 2 and 50 hours.

An embodiment of the reaction in the method of the present invention is as follows.
In general, 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, preferably while dropping dicyclopentadiene at a predetermined temperature on the phenol compound including the catalyst. The reaction method is good. The progress of the reaction can be monitored by high performance liquid chromatography. After completion of the reaction, the unreacted raw materials and the catalyst are recovered by vacuum distillation and then discharged as they are to obtain a polymer, or a polymer solution in which toluene, methyl isobutyl ketone or the like is added and dissolved is washed with water, and then the solvent is removed. To obtain a polymer.

[0016]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 Phenol was added to a glass reactor equipped with a thermometer and a stirrer.
1,645 g (17.5 mol) and 1 g of trifluoromethanesulfonic acid as a catalyst were charged, and the mixture was heated to 120 ° C. while stirring. Then 463 g of dicyclopentadiene (3.5
Mol) was added dropwise over 5 hours. After the dropwise addition, aging was performed at the same temperature for 5 hours to complete the reaction. Next, the viscous reaction solution was heated to an internal temperature of 160 ° C. under vacuum, and unreacted phenol and the like were distilled and recovered, immediately discharged, and allowed to cool. The obtained dark red polymer mass was a copolymer of phenol and dicyclopentadiene, and was a polymer represented by the general formula (II) (formula 1) as measured by GPC.

[0017]

Embedded image Its composition (Area%) was as follows.

Phenol 0.3% m = 0 47.2% m = 1 27.0% m = 2 14.6% m ≧ 3 10.9% Yield 1003 g The softening point was 103 as a result of measurement by the ring and ball method according to JIS-K-2548.
° C and the hydroxyl equivalent was 174.7 g / eq. In addition, no change was visually observed in the reactor.

Example 2 A glass reactor was charged with 270 g (2.5 mol) of p-cresol and 0.5 g of pentafluoroethanesulfonic acid as a catalyst, and the mixture was heated to 90 ° C. while stirring. Then, 132.2 g (1 mol) of dicyclopentadiene was added dropwise thereto over 4 hours. After the dropwise addition, the mixture was aged for 5 hours in a temperature range of 90 to 100 ° C. to complete the reaction. Next, this viscous reaction solution was heated to an internal temperature of 160 ° C. under vacuum, and unreacted p
-Cresol and the like were recovered by distillation. 500 g of toluene was poured into this distillation residue to make a homogeneous solution, and 500 g of water was added with stirring. After maintaining the reflux state for 1 hour and then standing still 2
The layers were separated. The lower aqueous layer was removed, and toluene was distilled off from the upper toluene layer under vacuum. Immediately after discharging and cooling, a brown polymer mass was obtained. The yield was 280 g and the softening point measured by the ring and ball method according to JIS-K-2548 was 128 ° C. As a result of analysis by GPC in the same manner as in Example 1, it was a polymer represented by the general formula (III) (Formula 2), and the composition (Area%) was as follows.

[0020]

Embedded image q = 0 31.5% q = 1 23.0% q = 2 15.6% q = 3 12.2% q ≧ 4 17.7% The hydroxyl equivalent was 205 g / eq. The pH of the separated aqueous layer was 6.1, and no apparent change was observed in the reactor.

Example 3 Phenol 28. was placed in a 50-liter SUS304 reactor.
2 kg (300 mol) and 25 g of trifluoromethanesulfonic acid as a catalyst were charged, and the internal temperature was kept at 42 ° C. Next, dicyclopentadiene 4.
95 kg (37.5 mol) were charged dropwise over 2.5 hours with stirring. After charging, the mixture was stirred at an internal temperature of 50 ° C. for 2 hours, and then heated and heated to 120 ° C. After aging at the same temperature for 2 hours, the temperature was further increased by heating and kept at 150 ° C. The reaction was completed by aging at the same temperature for 3 hours. Next, unreacted raw materials and catalyst components were recovered and removed from the reaction solution using a Smith type thin film still to obtain 11.1 kg of a phenol polymer represented by the formula (II). The composition (Area%) was measured by GPC and was as follows.

Phenol trace m = 0 67.7% m = 1 21.4% m = 2 7.2% m ≧ 3 3.7% The softening point measured by the ring and ball method according to JIS-K-2548 is 92 ° C. And the hydroxyl equivalent was 170 g / eq. The content of heavy metals in the resin was determined by atomic absorption spectroscopy.
2.6 ppm, Ni: 1 ppm or less, Cr: 1 ppm or less, Mn: 1 ppm or less. The extracted water electrical conductivity of this resin was determined by the following method. That is, 30 g of the resin was extracted with 300 ml of distilled water at 95 ° C. for 20 hours, and the supernatant was measured using a conductivity meter (DS-8M manufactured by Horiba, Ltd.). As a result, the extracted water electric conductivity was 9.2 μm.
s / cm.

Example 4 470 g of phenol containing the catalyst component recovered in Example 3
(5 mol) was charged into a glass reactor, and a reaction was carried out in the same manner as in Example 1 using 132 g (1 mol) of dicyclopentadiene. After the reaction, unreacted phenol and the like were recovered by distillation, and 0.1 g of barium carbonate was suspended in 5 g of water and added to the residual phenol polymer in a molten state. After this, again,
The mixture was aged for 1 hour while removing volatile components under reduced pressure, and discharged. The yield was 284 g, the softening point was 103.5 ° C., the hydroxyl group equivalent was 173 g / eq, and the extraction water electric conductivity of this phenol polymer was 2.1 μs / cm.

Comparative Example 1 In a glass reactor, 470 g (5 mol) of phenol and 11.5 g of a phenol / boron trifluoride complex having a boron trifluoride content of 26% were used.
And heated to 90 ° C. under stirring. Then, 132 g of dicyclopentadiene was added dropwise over 4 hours at an internal temperature of 90 to 100 ° C. After dropping, the mixture was aged for 5 hours to complete the reaction. Next, unreacted phenol and the like were recovered from the viscous reaction solution in the same manner as in Example 1. At the end of the distillation, generation of white smoke from the contents was observed. The residue was dissolved in toluene as in Example 2, washed with water and separated.
The pH of the lower aqueous layer was acidic at 3.2. Slight corrosion was observed in a part of the device.

[0025]

The present invention provides a method for easily producing a useful phenol polymer. The conventionally known reaction methods have problems with the quality of the polymer and the material accompanying the corrosion of the apparatus, and thus cannot be produced industrially at all. It is a great contribution to industrial development that the method of the present invention can completely solve such problems and can supply useful phenol polymers at low cost.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 61/00-61/02

Claims (8)

(57) [Claims] 1. A perfluoroalkane sulfone represented by the general formula (I) C _n F _{2n + 1} SO ₃ H (I) (wherein n is an integer of 1 to 8). A method for producing a phenol polymer, wherein the reaction is carried out in the presence of an acid catalyst. 2. The method according to claim 1, wherein the molar ratio of the phenol compound to dicyclopentadiene is 1 to 20: 1. 3. The method for producing a phenolic polymer according to claim 1, wherein the perfluoroalkanesulfonic acid is trifluoromethanesulfonic acid. 4. The method for producing a phenolic polymer according to claim 1, wherein the perfluoroalkanesulfonic acid catalyst is recovered by distillation together with an unreacted phenol compound. 5. The method according to claim 1, wherein the recovered phenol compound and the perfluoroalkanesulfonic acid catalyst are reused. 6. The method for producing a phenolic polymer according to claim 1, wherein the unreacted phenolic compound and the perfluoroalkanesulfonic acid catalyst are recovered by distillation, and the obtained phenolic polymer is washed with water. 7. The method according to claim 1, wherein after the unreacted phenol compound and the perfluoroalkanesulfonic acid catalyst are recovered by distillation, a trace amount of acid remaining in the obtained phenol polymer is neutralized with an alkaline earth metal compound. The method for producing a phenolic polymer according to claim 1. 8. The method for producing a phenolic polymer according to claim 7, wherein the alkaline earth metal compound is a hydroxide or carbonate of barium.