JPS60120715A - Production of epoxyacrylate resin - Google Patents

Abstract

PURPOSE:To produce a light-colored epoxyacrylate resin of a short gel time, by effecting an addition reaction between an epoxy compound and (meth)acrylic acid in the presence of triphenylstibine in an inert gas atmosphere. CONSTITUTION:An epoxyacrylate resin of a Gardner color scale <=1 and an acid value of 1-30 is obtained by effecting an addition reaction between an epoxy compound [e.g., bis(4-hydroxyphenyl)methane] and (meth)acrylic acid at 100- 140 deg.C in the presence of 0.1-5pts.wt., per pt.wt. total compounds, triphenylstibine and, optionally, a reducing agent (e.g., phosphorous acid), addition reaction catalyst (e.g., trimethylbenzylammonium chloride), polymerization inhibitor (e.g., hydroquinone), and liquid polymerizable unsaturated monomer (e.g., styrene) in an inert gas atmosphere.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to the treatment of a liquid polymerizable unsaturated monomer and an epoxy compound and (meth)acrylic acid in an inert gas atmosphere in the presence or absence of a polymerization inhibitor. The present invention relates to a method for producing an epoxy acrylate (l/-) resin which is light in color and has a short gel time by reacting in the presence of Nils pin.

Acrylic acid and/or methacrylic acid [
In the following description, 1(meth)acrylic acid] is commonly referred to as epoxy acrylate resin, which is commonly referred to as epoxy acrylate resin, which has excellent corrosion resistance and mechanical properties.
) Used in corrosion-resistant equipment, automobile parts, etc. However, Evashikin Acry 1 Note resin has a poor resin color compared to general unsaturated H (Lientel resin, and general unsaturated H @ d41J
m lll'1 color of ester resin is 1 to 4 in Gardner
On the other hand, the resin color of epoxy acrylic 1 note resin is Gardner 5 to 9. Therefore, it has excellent corrosion resistance and excellent mechanical properties, and cannot be used for aesthetic purposes such as G1 force 1 or gel coat.

Currently, the method for producing epoxy acrylate resin, which is obtained by adding (meth)acrylic acid to an epoxy compound, involves the use of an epoxy compound, (meth)acrylic acid, an addition catalyst such as a quaternary ammonium salt, and Mix a polymerization inhibitor and liquid polymerizable unsaturated monomer as necessary and heat to 100°C.
It is synthesized by heating and stirring at ~140°C for a certain period of time. In addition, since (meth)acrylic acid capable of homopolymerization is used as a raw material, in order to prevent the polymerization reaction during epoxy acrylate resin synthesis, generally (1) a large amount of inhibitor is added, (2) Countermeasures have been taken such as introducing metallic copper or steel ions, (3) flowing air into the reaction system in hopes of inhibiting oxygen, and (4) lowering the reaction temperature. However, in either method, the synthesis of epoxy acrylate resin is actually carried out in the presence of oxygen in hopes of inhibiting oxygen. It has disadvantages in that it has a poor color and requires a large amount of catalyst for the polymerization reaction because a large amount of inhibitor is added.

As a result of various studies in view of this actual situation, the present inventors found that
We have found a method for stably synthesizing epoxy acrylic 1/-1 resin without any coloring during synthesis and without adding any inhibitors.

However, the present invention provides an epoxy compound (M
In the step of adding (meth)acrylic acid fBl to epoxy compound (5) and (meth)acrylic acid (I3) in the presence of triphenylstibine in an inert gas atmosphere,
) is a method for producing epoxy acrylate resin.

According to the present invention, there is no gelation during the reaction, oxidation coloring of the reactants is prevented, the Gardner color number is 1 or less, and the acid value is 1 to 50.
epoxy acrylate resin can be produced.

In the present invention, the reaction is usually carried out in an inert gas atmosphere for 1
It is carried out by heating to 00 to 140°C and stirring. The amount of triphenylstibine used in the addition reaction step between the epoxy compound and (meth)acrylic acid is usually 0.01 to 5 parts, preferably 0.01 to 5 parts, based on the total of the epoxy compound and (meth)acrylic acid. .1 to 1 part.

In the addition reaction process of an epoxy compound and (meth)acrylic acid according to the present invention, a reducing agent and an addition reaction catalyst are used as necessary to prevent oxidation caused by trace amounts of oxygen I remaining in the reaction system. , a polymerization inhibitor, and a liquid polymerizable unsaturated monomer may be added to carry out the addition reaction. If necessary, a liquid polymerizable unsaturated monomer may be added to the obtained epoxy acrylate resin.

The epoxy compounds used in the method of the present invention include compounds having at least one epoxy group in one molecule, including his(4-hydrocyphenyl)methane, 2 .2-bis(4-hydroxyphenyl)solopane, a compound having a polyvalent hepta-tetrahydric hydroxyl group represented by phenol novolak, and shrimp.
Epoxy resins having at least 1.8 epoxy molecules in one molecule, which are obtained by reacting with epihalohydrin (e.g., colhydrin or methyl epichlorohydrin), are particularly preferably used.

Inert gases include nitrogen, carbon dioxide, argon,
Helium, etc. are used. The reducing agent to prevent oxidation due to trace amounts of oxygen remaining in the reaction system is not particularly limited, and reducing phosphoric acid such as phosphorous acid or monohypophosphorous acid is generally used. Ru. Catalysts used to add (meth)acrylic acid to epoxy compounds are not particularly limited, and include quaternary ammonium salts such as trimethylbenzylammonium chloride, tertiary amines such as dimethylbenzylamine, 2-methyl 4
- Imidazoles such as Ode imiguzole, phosphines such as triphenylphosphine, etc. can be used.

In addition, in the present invention, polymerization inhibitors that may be added include known polymerization inhibitors such as hydroquinones such as methylhydroquinone and hydroquinone, penzoquinones such as barabenzoquinone and baratroquinone, and metal compounds such as copper naphthenate. Examples include inhibitors. Furthermore, as the liquid polymerizable unsaturated monomer added as necessary, any monomer can be used as long as it is copolymerizable with the epoxy acrylate resin, such as (meth)acrylic acid ester, styrene, etc. and substituted derivatives thereof, divinylbenzene, vinyl acetate, diarylphthalate, and the like.

The method of the present invention will be specifically explained below using Examples and Comparative Examples.

Example 1 2 equipped with a stirrer, reflux condenser, gas introduction tube and thermometer
A bisphenol-based epoxy resin with an epoxy equivalent of 187 (manufactured by Chipa Geigy, trade name "Araldite≠26DJ") 959j and methacrylic acid 441f were placed in a four-bottle flask.

Add 2.82 tons of dimethylbenzylamine and 2.8 tons of triphenylstibine, and add 200 meters of nitrogen into the reaction system.
The mixture was reacted at 120° C. for 2 hours and 35 minutes while flowing at a flow rate of 18.6 IIvKOH/r to obtain an epoxy acrylate resin (A-1) with an acid value of 18.6 IIvKOH/r.

Example 2 2 equipped with a stirrer, reflux condenser, gas introduction tube and thermometer
In a four-L-shaped flask, add a 7-volume epoxy resin with an epoxy equivalent of 178 (manufactured by Dow Chemical Company, trade name: i'DE).
N-438J) 6052, acrylic acid 245F,
Trimethylbenzylammonium chloride 2,4?
, triphenylstibine 1. yy, 0.5f phosphorous acid
', hydroquinone 0.32 and ethylene glycol dimethacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., trade name INK ester-IGj) 597 V were added, and nitrogen was introduced into the reaction system at 2
The reaction was carried out at 120° C. for 5 hours and 40 minutes while flowing at 00 m//mg to obtain an epoxy acrylate resin (Human-2) having an acid value of 5 and smqKOH/r.

Example 6 2 equipped with a stirrer, reflux condenser, gas introduction tube and thermometer
A bisphenol-based epoxy resin with an epoxy equivalent of 187 (manufactured by Shell Chemical Co., Ltd., trade name [Epikoat Gaku A28J)] 41.64% to 9.0% was placed in a 0OL reaction vessel. Epoxy t4
60 bisphenol-based epoxy resin (manufactured by Ciba Geigy).

Product name [Araldite≠6071J) 46°45 to 9
．． Add 27.48Kg of methacrylic acid, 261v of triphenylphosphine, 567 triphenylstibine, and 70f of hydroquinone, and add 10T of nitrogen into the reaction system.
The mixture was reacted at 150° C. for 1 hour and 25 minutes while flowing at a flow rate of 16° 4 K OH/9. The obtained epoxy acrylate resin was 8
After cooling to 0°C, it was dissolved in 54.3.2 Kf of styrene monomer to obtain an epoxy acrylate resin (A-3) with an acid value of 11.0 ηKOH/f.

Comparative Example 1 A 2T fourth flask equipped with a thermometer, a reflux condenser, a gas introduction tube, and a thermometer was charged with epoxy f: 187.
Bisphenol-based epoxy resin (Ciba/Igine 1 grade, trade name [Aralgate≠260J) 959g,
Methacrylic acid 441V, dimethylbenzylamine 2
．． Add 8g and triphenylstibine 2.82,
The reaction was carried out at 20°C, but gelation occurred in the flask after 45 minutes.

Comparative Example 2 2 equipped with a stirrer, reflux condenser, gas introduction tube and temperature needle
1 L-sized four-bottle flask, bisphenol-based epoxy resin (manufactured by Ciba Geigy, trade name: "Araldite-#-215 []J) q5qy, 1:187 per epoxy,
Methacrylic acid 441r.

2.87 g of dimethylbenzylamine was added, and the reaction was carried out at 120° C. while flowing nitrogen at 200 mA/m into the reaction system. After 1 hour and 5 minutes, 1 gel was formed.

Comparative Example 6 2 equipped with a stirrer, reflux condenser, gas introduction tube and thermometer
00L reaction vessel, 41N bisphenol epoxy 41N with epoxy equivalent weight 187 (manufactured by Ciel Chemical Co., trade name "Apicoat≠828j") 41.34 to 9.
Epoxy Jit460 bisphenol epoxy resin (manufactured by Ciba Geigy).

Product Name I Araldite ≠ ('+071J) 46°45
9. Methacrylic acid 27,48Kf, triphenylbosphine 231y, hydroquinone 70? It was placed,
Reacted at 130℃ for 1 hour and 65 minutes, acid value 17.3K
OH/f epoxy acrylic 1 note tree) 1 result was obtained. The folded epoxy acrylate resin was cooled to 80°C and then dissolved into 9/8 styrene monomer at 54.32 to give an acid value of 11.6 ■K OH/t epoxy acrylate 1/-.
A resin (C-6) was obtained.

Table 1 shows the performance of each of the epoxy acrylic resins obtained in Comparative Example 6 and Comparative Example 6. From the results in Table 1, it can be seen that by applying the operating method of the present invention, an epoxy acrylate resin with excellent color tone and a short gel time can be obtained.

Table-1 Example 1 Example 2 Example 6 Comparative example 625°C *1

Claims (1)

[Claims] In the step of adding acrylic acid (Bl) to the epoxy compound (3) in the presence or absence of a liquid polymerizable unsaturated monomer and a polymerization inhibitor, triphenylstibine is A method for producing an epoxy acrylate resin, which comprises reacting an epoxy compound (5) with (meth)acrylic acid (Bl) in the presence of an inert gas atmosphere.