JPS62477A - Novel epoxy resin and production thereof - Google Patents

Abstract

NEW MATERIAL:A novel epoxy resin expressed by formula I. USE:An epoxy resin composition with superior heat resistance, impact resistance, heat-shock resistance, water resistance and mechanical properties such as strength. PREPARATION:One mol diamine expressed by formula II is subjected to addition reaction with 4-40mol epihalohydrin (epichlorohydrin, etc.), and 4-8mol alkali are added thereto and stirred at 20-80 deg.C to carry out dehydrohalogenation reaction. After the reaction has finished, salts, catalysts, etc., in the reaction mixture are filtered and the solvent is distilled away at 50-170 deg.C under reduced pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel epoxy resin and a method for producing the same.

<Prior Art> Epoxy resins have excellent mechanical properties, heat resistance, adhesive properties, and electrical insulation properties, and are therefore widely used in fields such as structural materials, adhesives, sealants, and paints. Currently, commonly used epoxy resins include bisphenol A type epoxy resins, phenol novolak type epoxy resins, and tetraglycidyl compounds of diaminodiphenylmethane. (“High functionality and application development of epoxy resins J
CMC Corporation) <Problems to be Solved by the Invention> However, in recent years, requirements for the performance of resin materials have become increasingly sophisticated and diversified. Epoxy resins are no exception, and in all of the above-mentioned applications, there is a strong demand for further improvements in mechanical properties such as heat resistance, #J impact resistance, thermal shock resistance, water resistance, and strength. , bisphenol AQ epoxy resin,
Since only two glycidyl groups can be contained in one molecule, the crosslinking density during curing is relatively low, and the heat resistance and strength of the cured product are not satisfactory. In addition, phenol novolac type epoxy resins and diaminodiphenylmethane tetraglycidyl compounds contain three or more glycidyl groups in one molecule, so they have a high crosslinking density during curing, and the cured products have excellent heat resistance, but are flexible. However, the impact resistance was not satisfactory.

Means and Works for Solving the Problems The inventors of the present invention have developed a method that has the general advantages of epoxy resins, but also has excellent properties such as heat resistance, impact resistance, thermal shock resistance, water resistance, and strength. With the aim of providing an epoxy resin that provides an epoxy resin composition with excellent mechanical properties, as a result of intensive research, a new epoxy resin and a method for producing the same were discovered, and the present invention was completed.

That is, the present invention is a novel epoxy resin represented by the following formula (1), which is further dehalogenated with an alkali after adding shrimp halohydrin to a diamine represented by the following formula [...] (hereinafter referred to as "diamine"). This is a method for producing a novel epoxy resin represented by the following formula (1), which is characterized by carrying out a hydrogenation reaction.

The present invention will be explained in detail below.

The epoxy resin of the present invention can be produced by any method, but preferably, it can be produced by a two-step method in which a diamine is used as a raw material and an addition reaction is performed with epihalohydrin, followed by a dehydrohalogenation reaction using an alkali. .

The addition reaction is usually carried out using epihalohydrin as a reactant and solvent, using 4 to 40 mol, preferably 8 to 20 mol, per 1 mol of diamine, at a temperature of 30°C to epihalohydrin reduction, preferably 40 to 90°C. This can be done by stirring at a temperature. The reaction time varies depending on the reaction temperature, but is usually 1 to 50 hours.

Examples of epihalohydrin include shrimp chlorhydrin/
, shrimp bromohydrin, shrimp iodohydrin, β-methylepichlorohydrin, β-methyl shrimp bromohydrin, β-methyl shrimp iodohydrin, and the like can be used.

In the dehydrohalogenation reaction, after the addition reaction, 4 to 8 mol of alkali is usually added to 1 mol of the raw material diamine, and the mixture is stirred at a temperature of 20 to 80°C, preferably 30 to 60°C. This can be done by The reaction time varies depending on the reaction temperature, but is usually 0.5 to 10 hours.

In the dehydrohalogenation reaction, ketones such as methyl ethyl ketone and methyl isobutyl ketone may be used as the solvent, and as the alkali, lithium hydroxide,
Sodium hydroxide, potassium hydroxide, etc. are used in solid form or as an aqueous solution.

Further, in both the addition reaction and the dehydrohalogenation reaction, a quaternary ammonium salt, a quaternary phosphonium salt, a quaternary arsonium salt, a crown ether, or the like can be used as a catalyst to promote the reaction. These catalysts can be used in any amount of 0.001 to LO mole per mole of diamine, preferably in an amount of 0.01 to 0.1 mole.

After the dehydrohalogenation reaction is completed, the salt, catalyst, etc. in the reaction mixture are filtered off, and the solvent is distilled off under reduced pressure at a temperature of 50 to 170°C, thereby obtaining the desired epoxy resin.

The epoxy resin of the present invention thus obtained can be used as an epoxy resin alone or in combination with other epoxy resins. There are no particular restrictions on the epoxy resins used in combination, and one or more of various epoxy resins may be used in combination depending on the application.

Further, as a curing agent for curing the present epoxy resin, various curing agents similar to those used in known epoxy resins can be used.

Furthermore, in addition to other epoxy resins and curing agents, this epoxy resin also contains plasticizers, organic solvents, reactive diluents, extenders, fillers, reinforcing agents, pigments, and flame retardants. Various additives such as , thickeners and flexibility imparting agents can be blended.

In addition, the epoxy resin cured product obtained from the epoxy resin of the present invention has excellent mechanical properties such as heat resistance, impact resistance, thermal shock resistance, water resistance, and strength, so epoxy resins have been used conventionally. Although it is useful in all fields, it is particularly useful as adhesives, sealants for ICs, etc., and matrix sanitizing agents for FRP, etc.

<Examples> Examples are shown below to specifically explain the present invention, but they do not limit the present invention.

Example 1 2,2'-bis(4-aminophenoxyphenyl)propane 513f (125 mol) and epichlorohydrin 21 (25.5 mol) were added to a 313-day glass flask equipped with stirring, reflux condenser, and thermometer. The mixture was charged and stirred at 55°C for 30 hours to carry out an addition reaction.

Next, the pressure inside the reaction system was reduced (15 to 25 ffHg), and unreacted epichlorohydrin 141 was recovered at 70°C.

This distillation residue was dissolved in methyl ethyl ketone 161,
Sodium hydroxide (purity 9696) 2191 (5,2
5 mol), tetramethylammonium bromide 8.11
After adding (0,0525 mol), the mixture was stirred at 50° C. for 3 hours to complete the dehydrohalogenation reaction.

The formed salt, excess alkali, and catalyst were filtered off, and the solvent was distilled off from the filtrate under reduced pressure at 70°C and 2 ffHg, and the temperature was further raised to 160°C to completely distill off the solvent. Epoxy resin 772f represented by the formula was obtained.

The obtained epoxy resin is a reddish-brown transparent and very viscous liquid with an epoxy equivalent of 163 and a chlorine content of O.17.
It was wt%. In the mass spectrometry analysis, a reference peak (All-1) = 634 was observed.

The elemental analysis results of this product are shown in Table 1, and the I H-NMR and 13C-NMR spectrograms are shown in FIGS. 1 and 2, respectively. The calculated values in Table 1 correspond to the chemical structure shown by the following formula. -aminophenoxyphenyl)propane 205F (0.5 mol), and 620 ml (8.0 mol) of l'epichlorohydrin.
The mixture was stirred at 70°C for 12 hours to carry out an addition reaction.

Next, the reaction solution was cooled to 50°C, and 100f (2.4 mol) of sodium hydroxide (purity 96%) and 3.71 (0,024 mol) of tetramethylammonium bromide were added. The dehydrohalogenation reaction was completed by stirring for an hour.

The formed salt, excess alkali, and catalyst were filtered off, and the solvent was distilled off from the filtrate under reduced pressure at 70°C and 2HHg.The temperature was then raised to 160°C to completely distill off the solvent, and the epoxy resin was removed. 301F was obtained.

The obtained epoxy resin is a reddish-brown transparent and very viscous liquid with an epoxy equivalent of 164 and a chlorine content of 0.13.
It was Wj96.

Reference Example 1 The epoxy resin obtained in Example I was mixed with an epoxy curing agent (4
, 4'-diaminodiphenylsulfone),
It was cured at 180°C for 2 hours.

A test piece was cut out from the obtained cured plate and rated according to JIS standard 7.
A tensile test was conducted according to 113.

The results are shown in Table 2. In addition, in Table 2, the TI (glass transition temperature) was measured by taking sample 1511F from the cured plate and using a DuPont 990 DSC.
The test piece was immersed in hot water at 100°C for 20 hours, and the water absorption rate was determined from the difference in weight between before and after.

In addition, Table 2 also shows the results of similar tests using Ebiko) 828 (manufactured by Yuka 7koru Co., Ltd.) and ELM434 (manufactured by Sumitomo Chemical Industries, Ltd.) instead of the epoxy resin of the present invention. I put it on there just for the sake of it.

Table 2 Epoxy resin cured products using the epoxy resin of the present invention are as follows:
While having a breaking elongation comparable to that of the cured product of Epikote 828, it exhibits superior performance than Epicoat 828 in terms of strength, elastic modulus, Ty, and water absorption. Also, E
Even when compared to LM434, it has significantly better strength, elongation at break, and water absorption, especially elongation at break.

<Effects of the Invention> According to the present invention, it has the general advantages of epoxy resins,
Moreover, a new epoxy resin and a method for producing the same have been provided which provide a cured epoxy resin with excellent mechanical properties such as heat resistance, impact resistance, thermal shock resistance, water resistance, and strength.

[Brief explanation of drawings]

FIG. 1 and FIG. 2 respectively show the novel epoxy tree BH-NMR (60MH,) 13c of the present invention.
This is a spectrogram of mNIVIR (67,8Mh). Patent application Daitoshi Co., Ltd. Figure 1 Figure 2

Claims (2)

[Claims] (1) A new epoxy resin represented by the following formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・〔I〕 (2) There are mathematical formulas, chemical formulas, tables, etc. for the diamine represented by the following formula [II] ▼... [II] After adding epihalohydrin, perform a dehydrohalogenation reaction with an alkali. A method for producing a novel epoxy resin represented by the following formula [I], which is characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・〔I〕