JP2000026576A - Polymeric bisphenolsulfonic acid epoxy resin having improved heat resistance and flame retardance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymeric bisphenolsulfonic acid epoxy resin by polymerizing, in a specific method, a crystalline bisphenolsulfonic acid epoxy resin obtained by a specific method. SOLUTION: The objective polymer resin having 0.1 to 10 of degree of polymerization is obtained by thermally reacting a bisphenol sulfone expressed by formula I [X is -R' or -OR' (R' is an alkyl, aryl or the like); Y is a single atom including O] with a compound of formula II (Z is an alkyl, a phenol including a halogen or the like) in the presence of a catalyst to obtain a crystalline bisphenolsulfonic acid epoxy resin of formula III, and thermally reacting the obtained resin with the compound of formula I in the presence of a catalyst. The preferable reaction temperature of the compounds of formula I and formula II is 80 to 200 deg.C. The reaction of the resin of formula III with the compound of formula I is preferably carried out in the temperature range of the melting point to the boiling point of the resin of formula III (20 to 200 deg.C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates generally to epoxy resins and, more particularly, to polymeric bisphenolsulfonic acid epoxy resins having improved heat resistance and flame retardancy.

[0002]

BACKGROUND OF THE INVENTION There are many types of epoxy resins, including BPF epoxy resins, phenol novolak type epoxy resins, rubber and urethane modified epoxy resins. These epoxy resins are used for different purposes, such as paints, adhesives, etc., in the fields of the electrical and electronic industry, industry and construction.

[0003] Epoxy resins of the bisphenol A type according to the relevant art are prepared by the reaction of bisphenol A with epichlorohydrin in the presence of a basic or acidic catalyst. Here, an organic solvent is used if necessary, and the product is obtained by a ring-opening reaction and epoxidation at a temperature of about 40 to 100 ° C.

[0004] In the related art, bisphenol A type epoxy resins (BPA) are prepared by the reaction of formula (6).

[0005]

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By optimizing the molar ratio of X / Y in the above chemical formula (6), a liquid epoxy having an epoxy equivalent of 185 to 187 g / equivalent is converted into an amorphous solid resin having an epoxy equivalent of more than 6,000 g / equivalent. Can be prepared.

[0007]

However, the bisphenol A type epoxy resin prepared by the prior art has low heat resistance, and is not suitable for printed circuit boards (PCBs).
s) cannot be used for various applications requiring a high glass transition temperature Tg.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a polymer bisphenolsulfonic acid having improved heat resistance and chemical resistance by using a sulfur-containing material in the preparation of an epoxy resin. The purpose is to provide an epoxy resin.

Another object of the present invention is to provide a flame-retardant polymer bisphenolsulfonic acid epoxy resin prepared by introducing a halogen into the bisphenolsulfonic acid epoxy resin having high heat resistance. .

Still another object of the present invention is to provide a polymer bisphenolsulfonic acid epoxy resin having improved odor resistance and fluidity by modifying a bisphenolsulfonic acid epoxy resin having flame retardancy. It is to be.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION To achieve the above-mentioned object, a polymer bisphenolsulfonic acid epoxy resin of the present invention is prepared by the following procedure.

First, a crystalline bisphenolsulfonic acid epoxy resin used as an intermediate material is represented by the following formula.
It is prepared according to

[0013]

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Here, X is -R ', -OR' (where R 'is alkyl, aryl or a derivative thereof or a single atom), Y is a single atom containing O, Z
Is an alkyl, aryl or halogen (Br, Cl, I
Or a phenol group containing F).

In order to carry out the reaction of chemical formula 7, bisphenolsulfonic acid epoxy is converted into ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone), alcohol (methanol, ethanol, isopropyl alcohol, butyl alcohol, glycol), water, or water and cellulose. Or a mixture of water and a ketone. This material is then reacted at a temperature of 80-200C in the presence of a basic or acidic catalyst. Especially when the desired product has to be obtained by recrystallization, aromatic solvents (benzene, toluene, xylene, dichlorobenzene) or water-soluble solvents and water can be used.

The crystalline bisphenolsulfonic acid epoxy resin prepared by the reaction of Chemical formula 7 has a melting point of 150 to 200 ° C. and a molecular weight of 200 to 1000 when the epoxy equivalent (EEW) is 180 to 220 g / equivalent. These are white granules.

The crystalline bisphenolsulfonic acid epoxy resin prepared by the reaction of Chemical Formula 7 and bisphenolsulfone, which is a reactant of Chemical Formula 7, are polymerized according to the following Chemical Formula 8 to form the inert amorphous amorphous resin of the present invention. Produces bisphenolsulfonic acid epoxy resin (BPS).

[0018]

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The reaction of the above formula (8) is activated in the presence of an acidic or basic catalyst. Preferably, the catalyst is used in an amount of 0.5 to 10 mol per liter of water or alcohol.

The reaction of formula 8 is based on the melting point of the crystalline bisphenolsulfonic acid epoxy resin and its boiling point (about 20 to 20).
0 ° C.), with an average of 1 to 5 epoxy groups and a degree of polymerization (n) of 0.1 to 10. When the epoxy equivalent is 580 to 750, the polymer bisphenolsulfonic acid epoxy resin obtained by the reaction of Chemical formula 8 has a Tg
It is a yellow powder having a molecular weight of 1000 to 1600 at 65 to 75 ° C.

The present invention also provides a polymer bisphenolsulfonic acid epoxy resin obtained by polymerization of a crystalline bisphenolsulfonic acid epoxy resin having flame retardancy. Polymeric bisphenolsulfonic acid epoxy resins with flame retardancy were prepared in a similar manner to the preparation of bisphenolsulfonic acid epoxy resins described above, except that a halogenated derivative was used to provide flame retardancy. Is done. The following reaction of Scheme 9 is provided to provide a crystalline bisphenolsulfonic acid epoxy resin using a halogenated phenolsulfonic acid to impart flame retardancy.

[0022]

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In the above reaction, R is a halogenated derivative such as alkyl or amine for imparting flame retardancy.

According to the present invention, there is provided a polymerized bisphenolsulfonic acid epoxy resin obtained by the reaction with a bisphenolsulfonic acid represented by Chemical formula 9 and having a flame retardancy obtained by polymerization of a flame retardant crystalline epoxy resin. Is subjected to the reaction of Chemical Formula 10.

[0025]

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The reaction of the chemical formula 10 has a molecular weight of 500-5000.
Resulting in a flame-retardant polymeric bisphenol sulfonic acid epoxy resin having a degree of polymerization (n) of at least 0.1-10.

Further, the present invention modifies the flame-retardant polymer bisphenolsulfonic acid epoxy resin obtained by the reaction of Chemical formula 10 so as to improve the odor resistance and flowability of the epoxy resin. Chemical formula 11 represents a modification reaction of the polymer bisphenolsulfonic acid epoxy resin.

[0028]

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Here, the modifying material is A or B;
Is tribromophenol, tetrabromophenol,
A halogen-containing derivative such as pentabromophenol, and B is a base material containing an acid or a hydroxy group, a phosphorus-containing acid or a hydroxy-containing phosphorus and containing no halogen.

Although the reaction of formula (11) is activated without a solvent, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), aromatic solvents (benzene, toluene, ortho-, para-xylene, dichlorobenzene)
Alternatively, a solvent such as a cellulose-type solvent can be used. The reaction is carried out at atmospheric pressure or lower (1/10 to 8/10 atm), 50 to 200 ° C., and in the presence of an acidic or basic catalyst.

[0031]

[Table 1]

[0032]

[Table 2]

<TBBS Flame Retardancy Test> UL-94 Standard Test: V-0

[0034]

As described above, the present invention has a polymerization degree of 0.1
Polymeric bisphenol sulfonic acid epoxy resins of 10 to 10 are provided using crystalline bisphenol sulfonic acid epoxy resins. The polymer bisphenolsulfonic acid epoxy resin of the present invention has a high Tg and exhibits high heat resistance. The present invention also provides a flame-retardant polymeric bisphenolsulfonic acid epoxy resin and a modified polymeric bisphenolsulfonic acid epoxy resin for enhancing odor resistance and fluidity.

Although the present invention has been described with reference to specific preferred embodiments thereof, changes in form and detail therein are within the scope of the invention as defined in the appended claims. It will be understood by those skilled in the art that they would be made without departing from the spirit and scope.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Wang Son Korea 158-050 Seoul Yangchon-Gumok-dong Shinshikagi-Apartment 1427-907 2-Dong 322-119 Sunwon-Apartment 101-109

Claims (4)

[Claims] 1. A polymer bisphenol sulfonic acid epoxy resin having a degree of polymerization of 0.1 to 10 prepared by polymerizing a crystalline bisphenol sulfonic acid epoxy resin, wherein the crystalline bisphenol sulfonic acid epoxy resin is:
Obtained by the reaction given by formula 1, X is -R ', -OR' (where R 'is alkyl, aryl or a derivative thereof or a single atom);
Y is a single atom containing O, Z is a phenol group containing alkyl, aryl or halogen (Br, Cl, I or F), and the crystalline bisphenolsulfonic acid epoxy resin is
A polymer bisphenolsulfonic acid epoxy resin which is polymerized by a reaction given by Chemical formula 2. Embedded image 2. A crystalline bisphenolsulfonic acid epoxy resin obtained by the reaction given by the chemical formula (3), X is -R ', -OR' (where R 'is alkyl, aryl or a derivative thereof or a single atom);
Y is a single atom containing O; Z is a phenol group containing alkyl, aryl or halogen (Br, Cl, I or F); R is an alkyl or aryl used to impart flame retardancy; A crystalline bisphenolsulfonic acid epoxy resin, which is a halogenated derivative. 3. A polymerized bisphenolsulfonic acid epoxy resin having a degree of polymerization of 0.1 to 10 prepared by polymerizing the crystalline bisphenolsulfonic acid epoxy resin according to claim 2, wherein the polymerization is A polymer bisphenolsulfonic acid epoxy resin characterized by being carried out by the reaction given by Embedded image 4. A modified polymer bisphenol sulfonic acid epoxy resin prepared by modifying the polymer bisphenol sulfonic acid epoxy resin according to claim 3, wherein the modification is performed by a reaction given by Chemical formula 5. , A used as a modifying material is a halogen-containing derivative containing tribromophenol, tetrabromophenol, pentabromophenol, and B is a halogen-free base containing an acid or hydroxy group, a phosphorus-containing acid or a hydroxy-containing phosphorus. The material is a modified polymer bisphenolsulfonic acid epoxy resin.