JPH09263617A - Heat-resistant phenolic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat-resistant phenolic resin having lowered melt viscosity and excellent fluidity and useful for molded article, etc., by the cocondensation reaction of a specific phenolic compound, etc., with an aldehyde. SOLUTION: The objective phenolic resin is produced by the cocondensation reaction of (A) a phenolic compound of formula I (X is single bond, 1,4- cyclohexylene, COO, etc.; A is 1,4-phenylene or 1,4-, 2,6- or 2,7-naphthalene; (n) is 1-3) (e.g. 4,4'-biphenol), (B) a phenolic compound of formula II (R1 is OH, H or a 1-4C alkyl) (e.g. phenol) and (C) a compound of formula III (B1 and B2 are each 1,4-phenylene, 2,6-naphthalene, etc.; Y1 and Y2 are each a <=10C organic residue, O, CO, COO, etc.; R2 is OH or NH<2> ; (m) is 0 or 1; (n) is 0-3) (e.g. bisphenol A) with an aldehyde such as formaldehyde. The amounts of the components B and C to be compounded to 1mol of the component A are 0.05-0.5mol each and the amount of the aldehyde is preferably 0.5-4mol based on 1mol of the total phenols.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a phenol resin having excellent heat resistance and fluidity.

[0002]

2. Description of the Related Art Phenolic resins having various molecular weights are synthesized by reacting phenols with aldehydes in an acidic or alkaline manner. When the phenol resin is molded and cured, the melt viscosity is a major factor in the moldability. Generally, the melt viscosity has a strong correlation with the molecular weight, and the lower the molecular weight, the smaller the melt viscosity and the better the moldability. However, there is a drawback that properties such as strength and toughness deteriorate when the low molecular weight phenolic resin is cured. Conventionally, it has been difficult to achieve both low viscosity and high strength of phenol.

[0003]

The present invention was obtained as a result of extensive studies to solve such problems of the phenol resin, and the object is to have excellent heat resistance and fluidity. To provide a phenolic resin.

[0004]

[Means for Solving the Problems] Phenols represented by the following general formula (1), phenols represented by the general formula (2) and compounds represented by the following general formula (3) are co-condensed with aldehydes. As a result, the inventors have found that the heat resistance and fluidity can be improved, and have conducted intensive studies. As a result, the present invention has been achieved.

[0005]

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[0006]

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[0007]

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In the phenol resin of the present invention, since the phenols used have a rigid structure, the rigid structure parts can be oriented with each other, the melt viscosity is lowered and the fluidity during molding is improved. Further, the packing of the segments is good and the micro Brownian motion is suppressed, so that the heat resistance is improved.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. Examples of the phenols of the general formula (1) used in the present invention include 4,4′-biphenol, 4,4′-dihydroxystilbene, 2,6-dihydroxynaphthalene, dihydroxyquarterphenyl and the like, or a mixture thereof. is there. Examples of phenols of the general formula (2) include phenol, catechol, resorcin, hydroquinone and cresol. Examples of the compound of the general formula (3) include bisphenol A, bisphenol F, diaminodiphenylmethane, 4,4′-dihydroxybenzophenone, 4,4′-oxybisphenol, 1,3-bis (hydroxyphenyl) tetramethyldisiloxane, Aromatic hydrocarbon-modified phenolic resin, other alkyldiene, phenol or aniline, Friedel-Crafts reaction at both ends hydroxyphenyl or aminophenyl functional linear aliphatic compound, α, ω-dibromoalkanes Examples thereof include linear aliphatic compounds having hydroxyphenyl or aminophenyl functional groups obtained at both ends. Examples of aldehydes are formaldehyde, acetaldehyde,
There are simple substances such as paraformaldehyde or a mixture thereof.

The phenols of the general formula (2) mixed with 1 mol of the phenols of the general formula (1) are 0.05 mol or more and 0.5 mol or more.
It is less than or equal to mol. The amount of the compound of the general formula (3) mixed with 1 mol of the phenol of the general formula (1) is 0.05 or more and 0.5 mol or less. Phenols of general formula (1) and general formula (2)
The amount of aldehyde compounded in 1 mol of the mixture of the phenols and the compound of the general formula (3) is 0.5 mol or more and 4 mol or less. As a catalyst for the addition condensation reaction of phenols and aldehydes, acids such as oxalic acid, hydrochloric acid, formic acid, acetic acid, sulfuric acid, diethylsulfuric acid, paratoluenesulfonic acid or sodium hydroxide, potassium hydroxide, ammonia, triethylamine Such as alkalis alone or 2
Can be used in combination with more than one type. Solvents or suspension media used when reacting phenols, aldehydes, benzene, toluene, xylene, methanol,
Ethanol, tetrahydrofuran, dimethyl sulfoxide, water and the like can be used. The above phenols are heated and reacted with the above catalyst to be condensed while dehydrating. A phenol resin can be obtained by performing dehydration / demonomer.
Examples of the phenol resin curing agent of the present invention include bifunctional or higher functional epoxy resins, isocyanates, formaldehyde resins, hexamethylenetetramine, and the like. From the heat resistance of the cured product, it is preferable to use hexamethylenetetramine. The amount of hexamethylenetetramine added is 3 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the phenol resin composition. If the amount is less than 3 parts by weight, the curing will be insufficient and 2
If the amount exceeds 0 part by weight, the decomposition gas of hexamethylenetetramine causes the molded product to swell and crack.

[0011]

The present invention will be described below with reference to examples. However, the present invention is not limited to these examples. Further, “parts” described in Examples and Comparative Examples
And “%” all indicate “parts by weight” and “% by weight”.

[Example 1] 50 parts of 4,4'-biphenol, 10.2 parts of phenol, 24.6 parts of bisphenol A were added to a reactor equipped with a stirrer, a reflux condenser and a thermometer.
% Formaldehyde aqueous solution (25.6 parts) (molar ratio to the above-mentioned three kinds of phenols: 0.65) and oxalic acid dihydrate (1 part) were added, and the mixture was heated under reflux for 30 minutes while stirring on a water bath. One part of oxalic acid dihydrate was further added, and the mixture was heated under reflux for another 1 hour. The reaction system was cooled by adding 400 parts of water.
The resin was allowed to settle and the aqueous phase was separated by decantation. Remaining water content under reduced pressure of 50-100mmHg, 120 ℃
It was heated and distilled off. Cooled to room temperature, number average molecular weight 680
Was obtained.

Example 2 A reactor equipped with a stirrer, a reflux condenser and a thermometer was equipped with 50 parts of 4,4'-dihydroxystilbene, 8.9 parts of phenol, and bisphenol A21.
5 parts, 9.4 parts of paraformaldehyde (molar ratio to the above-mentioned three kinds of phenols 0.65), 1 part of oxalic acid dihydrate and 400 parts of methanol were added, and the mixture was heated under reflux for 30 minutes while stirring on a water bath. One part of oxalic acid dihydrate was additionally charged, the mixture was heated under reflux for an additional 1 hour, and then the reaction system was cooled. Water was added and the resin was precipitated and separated. The residual water was distilled off by heating at 120 ° C. under a reduced pressure of 50 to 100 mmHg. After cooling to room temperature, a phenol resin having a number average molecular weight of 580 was obtained.

[Example 3] 50 parts of 4,4'-biphenol, 10.2 parts of phenol, 24.6 parts of bisphenol A and 12.4 parts of paraformaldehyde were placed in a reactor equipped with a stirrer, a reflux condenser and a thermometer. (Mole ratio of 0.75 to the above 3 kinds of phenols), dimethyl sulfoxide 100
And 1 part of paratoluenesulfonic acid were added, and the mixture was heated at 100 ° C. for 1 hour and then heated to 150 ° C. and further heated for 1 hour. After cooling, water was added to precipitate and separate the resin. The residual water was distilled off by heating at 120 ° C. under a reduced pressure of 50 to 100 mmHg. After cooling to room temperature, a phenol resin having a number average molecular weight of 800 was obtained.

[Example 4] 50 parts of 2,6-dihydroxynaphthalene, 11.8 parts of phenol, and bisphenol A2 were placed in a reactor equipped with a stirrer, a reflux condenser and a thermometer.
8.5 parts, paraformaldehyde 12.4 parts (molar ratio to the above three kinds of phenols 0.65), oxalic acid dihydrate 1 part and dimethylsulfoxide 100 parts were added, and 1 part was added.
The mixture was heated at 00 ° C for 1 hour, then heated to 150 ° C, and further stirred for 1 hour while heating. After the reaction, water was added to precipitate and separate the resin. 50 to 100 mm of remaining water
The mixture was heated at 120 ° C. under reduced pressure of Hg, and evaporated. After cooling to room temperature, a phenol resin having a number average molecular weight of 730 was obtained.

"Comparative Example 1" 100 parts of phenol and 10 parts of water were added to a reactor equipped with a stirrer, a reflux condenser and a thermometer.
Parts, 68.8 parts of 37% aqueous formaldehyde solution (molar ratio to phenol 0.8) and 1 part of oxalic acid dihydrate were added, and the mixture was heated under reflux with stirring for 30 minutes on a water bath. One part of oxalic acid dihydrate was further added, and the mixture was heated under reflux for another 1 hour. The reaction system is cooled by adding 400 parts of water. The resin was allowed to settle and the aqueous phase was separated by decantation. The residual water was distilled off by heating at 120 ° C. under a reduced pressure of 50 to 100 mmHg. When cooled to room temperature, a phenol resin having a number average molecular weight of 700 was obtained.

"Comparative Example 2" 100 parts of phenol and 28.9 parts of paraformaldehyde were added to a reactor equipped with a stirrer, a reflux condenser and a thermometer (molar ratio to phenol: 0.
8), 5 parts of oxalic acid dihydrate and 400 parts of methanol were added, and the mixture was heated under reflux with stirring on a water bath for 30 minutes.
An additional 5 parts of oxalic acid dihydrate was added and the mixture was heated under reflux for an additional 1 hour. The reaction system was cooled and the resin was precipitated and separated by decantation. 50-100 mmHg of remaining water
It was distilled off by heating at 120 ° C. under reduced pressure. When cooled to room temperature, a phenol resin having a number average molecular weight of 500 was obtained.

[Preparation of Phenolic Resin Composition] Example 1
~ 4, the phenolic resin solids obtained at room temperature obtained in Comparative Examples 1 and 2 were crushed, and the phenolic resin compositions were separately prepared in the following proportions. Phenolic resin 45 parts Hexamethylenetetramine 7 parts Calcium hydroxide 3 parts Calcium carbonate 45 parts This composition is used at a temperature of 160 ° C. and a pressure of 200 kg / cm 2 for 10 times.
After molding for 1 minute, post-curing was performed at 180 ° C. for 3 hours to prepare a test piece. The linear expansion coefficient and the deflection temperature under load (load: 1.82 MPa) of this test piece were measured.
Table 1 shows the measurement results. In addition, Examples 1 to 4 and Comparative Example 1
Table 2 shows the results obtained by measuring the melt viscosity (130 ° C.) of the phenol resins of Nos. 2 to 2 by a cone plate viscometer.

[0019]

[Table 1]

[0020]

[Table 2]

As is clear from Table 1, all of the phenolic resins of Examples 1 to 4 have a smaller linear expansion coefficient, higher deflection temperature under load, and excellent heat resistance than the conventional phenolic resins of Comparative Examples 1 and 2. It is clear that Further, the melt viscosity is reduced and the fluidity is improved.

[0022]

The heat-resistant phenol resin of the present invention has excellent heat resistance and fluidity.

Claims (1)

[Claims] 1. A phenol resin obtained by co-condensing a phenol represented by the general formula (1), a phenol represented by the general formula (2) and a compound represented by the general formula (3) with aldehydes. Embedded image Embedded image Embedded image