JPS62240311A - Production of powdery resol type phenolic resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin of stabilized properties, with little content of free monomer, having narrow molecular weight distribution, by adding both water-soluble additive and water to a specific solution-like resol type phenolic resin to separate a resin solid content out followed by separation and drying of the resultant solid resin. CONSTITUTION:A solution-like resol type phenolic resin with a water dilution capability <=100wt% is incorporated with (A) 10-200wt% of a water-soluble additive comprising (i) di- or triglycol, (ii) its monosubstituted ether and (iii) aligomer therefrom and (B) >=100wt% of water each on a resin solid content basis to separate a resin solid content out. The resulting resin is separated by e.g. filtering followed by drying e.g. under a vacuum, thus obtaining the objective powdery resin of stabilized properties with little free monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a method for efficiently and stably producing a resol-type solid phenol resin with very little free phenol and a narrow molecular weight in powder form. be.

``Prior art'' Unlike novolak resins, resol-type solid phenolic resins do not decompose curing agents such as hexamethylenetetramine and paraformaldehyde during heat curing and generate harmful gases, so they are suitable for @-type use. It is used in a wide range of applications, including binders, binders for friction materials, binders for fiber sheets and mats, and molding materials using molding powder and glass fibers. Various methods for producing such resol-type solid phenol resins have been known and are being practiced industrially. The most common method involves allowing the reaction to proceed to a predetermined degree of condensation in a reaction vessel, followed by dehydration and condensation under reduced pressure, and then transferring the product onto a pulsed steel belt or cooling pan. However, in this method, after the main reaction, the reaction rate is significantly reduced in the dehydration condensation step under reduced pressure, it is difficult to determine the desired end point, and it also causes thickening and poor fluidity. However, it takes a long time to pan out, and as a result, there is a fundamental drawback that the properties of the resin differ between the front and rear parts of the pan out. Furthermore, in order to prevent gelation due to self-heating on the cooling pan, it is necessary to limit the thickness of the resin taken out onto the IJ pan to 20 m or less, which reduces productivity and reduces industrial scale. It cannot be said that this is necessarily an appropriate production method. In addition, the resulting lumpy resin generally has a low melting point, so it is difficult to crush it.

Furthermore, in the conventional method, it is difficult to reduce the amount of free phenol to 5% or less.

``Problems to be Solved by the Invention'' As mentioned above, the conventional method does not allow stable in-lot properties, FC resol-type solid phenol kerosene (fat does not melt), and furthermore, in the pulverization process, it becomes powdery. In this case, it is generally difficult to powderize the resin due to its low melting point.Furthermore, it is extremely difficult to reduce the amount of free additives in the product by conventional methods to 5% or less. , the product has a broad molecular weight distribution.

Therefore, the present invention greatly improves the problems of the above-mentioned conventional method, and it is possible to produce a resol type solid phenol resin with stable loft properties without a pulverization process by turning it into a powder.
The present invention provides a method for constructing J-frameworks. Moreover, the obtained grade (11iJ) has a small amount of free phenol and a narrow molecular weight distribution, has good dripping performance on substrates and aggregates, and has a fast curing speed. Since stabilization of properties is very important in terms of quality control, the present invention is also useful from the perspective of quality control.

"Means for solving the problem: Structure of the invention" The present invention is
Bath-type phenol resin J]IN (hereinafter simply referred to as liquid phenol resin) with water dilution capacity of 100 M% or less
water-soluble di- or tri-glycols, monosubstituted ethers, and one or more types of low polymerization polymers (hereinafter referred to as
(referred to as a water-soluble additive) to the resin solid content from 10 to
By adding 20031 [volume%] and further adding water at 10011L mass% or more, the resin solid content is precipitated, and the precipitated resin is treated with P, and after washing with water and drying, powdered resol type phenol 4111m is obtained. This is a sign of clarity. This process has the same result as the following 11th order.
-Can be obtained.

(11 Add water-soluble additives to liquid phenolic resin to water to precipitate solid fat content.

(2) A water-soluble additive aqueous solution is added to the liquid phenol resin to precipitate the resin solid content.

(3) Adding liquid phenol resin to an aqueous solution of water-soluble additives to precipitate resin solids.

In the present invention, similar resins can be obtained by any of these methods, but the resins obtained in this way are powder-like and have a small amount of free phenols and have a narrow molecular weight distribution. It is something.

The liquid resol type phenolic resin used in the present invention includes phenol or its equivalent substance such as phenol, cresol, resorcinol, bisphenol or bisphenol oligomer, and aldehyde such as formaldehyde, paraformaldehyde, hexamethylenetetramine or butyraldehyde. Ammonia, amines, alkali metal oxides and hydroxides, alkaline earth metal oxides and hydroxides, and salts thereof, alone or in a mixture of 2 to 3 m, with the feed substance or its equivalent substance. It is used as a catalyst and produced by reacting with a known and commonly used method, and has a water dilutability of 100% by weight or less.

In the present invention, a mixed solution of a novolak solution # prepared by dissolving a known and commonly used novolac in a solvent and the above-mentioned resol type phenol resin can also be used. Additionally, high molar ratio novolac precondensates can also be used.

The water-soluble additives used in the present invention are water-soluble di- or tri-glycols, their mono-polymerized ethers, and their low molecular weight polymers, such as ethylene glycol, 1,2- 7'lopanediol, 1.3-
Propanediol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, low-molecular polyethylene glycol, etc. can be used alone or in combination of two or three of them.

"Effect" The mechanism of precipitation of m fat by the method of the present invention is roughly as follows.
It is estimated as follows. In other words, when the resin precipitates due to water dilution of the resin solution or more, the water-soluble additive surrounds the precipitated resin and acts like a hardening colloid. This book is considered to be a book that prevents binding between Jaj fats. Moreover, in this case, it is considered that low molecular weight substances such as free monomers in the 4JR fat are eluted into the aqueous phase, so that a resin with a small amount of free monomers can be obtained.

Example 1 Phenol 50019 and 37% formaly 100017 were placed in a four-loaf flask equipped with a condenser and a stirrer, and while stirring, 25 g of 50% sodium hydroxide was added.
After reacting at 0°C to a water dilution capacity of 100% by weight, cooling,
The resin solution (1) was obtained by neutralizing to pH 7 with gA acid.

After blending 40 parts of 1,3-propanediol with 100 parts of this resin liquid, 200 parts of water was added to obtain an imitation dillinate solution.

This platelet was passed through a well-known method and then dried under vacuum at 40° C. to obtain 11ff powder.

Comparative Example 1 Add 2 parts of water to 11,100 parts of the resin liquid obtained in Example 1.
When 0.00 parts were added, the mixture separated into an aqueous layer and a resin liquid layer, making it impossible to obtain microplatelets.

Ratio Softness Example 2 After adding 40 parts of methanol to 100 parts of the resin liquid obtained in Example 1, adding t-200 parts of water, the mixture was separated into a water layer and a resin liquid layer to obtain fine particles. I couldn't.

Example 2 In a four-bottle flask equipped with a condenser and a stirrer, a mixture of meth and vala-cresol was added to 5011137% formalin 80.
01 Add gold and add 21 [' of 25% ammonium water while stirring.
The reaction was carried out at 70°C for 3 hours to form a suspension of resin g, (II
) was obtained.

After blending 20 parts of ethylene glycol monoethyl ether with 100 parts of this resin liquid, a fine particle suspension was obtained by adding 200 parts of water. This was treated in the same manner as in the examples to obtain a powdered resin.

Comparative Example 3 When 200 parts of water was added to 100 parts of the resin liquid (II) obtained in Example 2, it was separated into a water layer and a resin liquid layer, making it impossible to obtain fine particles.

Example 3 Into a four-bottle flask equipped with a condenser and a stirrer f, put phenol 50 [1,37% formalin 1100 #], add 1511 pieces of triethylamine while stirring, and heat at 80°C.
(The resin liquid layer reacts until the water dilution ability reaches 100%.)
I got it.

A mixture of 50 parts of ethylene glycol and 100" parts of this resin liquid was added to 300 parts of an aqueous layer to obtain a fine particle suspension.

This was treated in the same manner as in Example 1 to obtain a powdered resin.

Comparative Example 4 When 100 parts of the resin (gtlI) obtained in Example 3 was added to 300 parts of a water layer, the mixture was separated into a water layer and a resin liquid layer, and no fine particles could be present.

Example 4 Alcohol-soluble resol type phenolic resin Pryophen J-325 (manufactured by Dainippon Ink and Chemicals, water dilution ability 1)
A microparticle suspension was obtained by adding 150 parts of water to 70 parts of glycerin per 100 parts (below 00xi-%, resin solid content 60%).

This was treated in the same manner as in Example 1 to obtain a powdered resin.

Comparative Example 5 100 parts of Pryophen J-325 and 1 part of water
When 50 parts were added, the mixture was separated into an aqueous layer and a resin liquid layer, and fine particles could not be obtained.

Comparative Example 6 An attempt was made to obtain a powdered resin by filtering and separating emulsion-type phenol mih fluorophene TD-4302 (manufactured by Inu Nippon Ink Chemical Industry Co., Ltd.), but it agglomerated and could not be made into a powder. Ta.

Table 1 shows the properties of the resins obtained in Examples.

``Brief explanation of the drawings 1 Figures 1 and 2 are charts showing the molecular weight distribution in the resin liquid obtained in Example 1 and the resin liquid (precipitated powder resin), respectively. .

Table 1 "Effects of the Invention" As described above, according to the method of the present invention, a fast-curing resol-type phenolic resin with a low content of free monomers,
It can be efficiently manufactured in powder form without any pulverization process. Further, resin types that could not be solidified by conventional methods can also be manufactured by using the method of the present invention.

Agent Patent Attorney Katsutoshi Takahashi 1 Figure ≠ 5 one, yo
I Yuu-4shu 3-Tomi 2 Keiko Tsushima Osamu 3' hand
Continuing amendment (method) 1. Indication of the case Patent Application No. 82335 of 1985 2. Name of the invention Process for producing powdered resol type phenolic resin 3. Person making the amendment Relationship to the case Patent applicant Address: 174 Tokyo 3-35-58 Sakashita, Itabashi-ku, Miyako (28B)
) Dainippon Ink & Chemicals Co., Ltd. Representative Shigekuni Yomura 4, Agent Address: 6-6, Dainippon Ink & Chemicals Co., Ltd. 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Subject to amendment (1) Statement of the description Detailed Description of the Invention Column (2) Brief Description of Drawings in the Specification Column 7, Contents of Amendment (1) r “Brief Description of Drawings” in Lines 1 to 4 of Page 13 of the Specification Figure 1 is a chart showing the fabric. ” will be deleted.

(2) After page 14, line 7 of the specification, add an item and column for a brief explanation of the drawings (attached circular).

that's all Attachment %Gan No. 61-82335

[Brief explanation of drawings]

Figures 1 and 2 are charts showing the molecular weight distribution of the resin liquid (1) obtained in Example 1 and the resin liquid (precipitated powder resin), respectively.

Claims (1)

[Scope of Claims] 1) Water-soluble di- or tri-glycols and their monosubstituted ethers and low polymer polymers (
(hereinafter referred to as water-soluble additives), the resin solids are precipitated by adding 10 to 200% by weight of the resin solids and 100% or more of water, and the precipitated resin is separated and dried. A method for producing a powdered resol type phenolic resin with stable properties and low free monomer content. 2) Claim 1, in which a phenol resin with a water-soluble additive is added to water to precipitate the resin solid content.
Manufacturing method described in section. 3) The manufacturing method according to claim 1, wherein the phenol resin is added to the water-soluble additive aqueous solution to precipitate the resin solid content.