JPH01207318A - Novel epoxy resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title resin giving a cured product having excellent properties such as heat distortion temperature, by carrying out a ring opening addition reaction of a specific bifunctional phenol compound with an epihalohydrin compound and then dehydrohalogenation by the action of an alkali metal hydroxide. CONSTITUTION:A bifunctional phenol compound expressed by formula I (R1, R2 is H or 1-5C alkyl) as a raw material [e.g., 1,3-bis(hydroxyphenoxy)-2- propanol] is subjected to ring opening addition reaction with an epihalollydrin compound expressed by formula II (X is halogen) (preferably epichlorhydrin), preferably in the presence of a catalyst such as tetramethylammonium chloride. Next, dehydrohalogenation is performed by the action of an alkali metal hydroxide (e.g., sodium hydroxide) to afford the aimed compound expressed by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel epoxy resin that can provide a cured product exhibiting excellent cured physical properties, and a method for producing the same.

(Prior art and its problems) Generally, epoxy resins are used as electrical equipment materials, paints, adhesives,
It is widely used in civil engineering and construction materials, composite materials, etc., and properties such as heat resistance, chemical resistance, and flexibility are required depending on these uses.

However, no epoxy resin is known that satisfies all of these required properties, and for this reason, bisphenol-epichlorohydrin-based epoxy resins are usually used.
It is often used in combination with other epoxy resins that are superior in the required properties. Incidentally, conventionally commercially available diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, etc. are liquid at room temperature and have the advantage of being easy to mix with hardening agents, fillers, etc.; The heat deformation temperature of this material is about 150° C. at most, and there is still room for improvement in heat resistance.

In addition, diglycidyl ether of bisphenol S and tetraglycidyl ether of diaminodiphenylmethane, etc.
A cured product with a heat distortion temperature of about 190°C is produced, but in the former case, the melting point of the polyepoxy compound before curing is about 140°C.
Since the temperature is 0 to 160°C, there is a problem that dilution with a suitable solvent is required during curing, and in the latter case, a colored cured product is obtained.

(Means for Solving the Problems) As a result of intensive study on methods for obtaining an epoxy resin that produces cured physical properties such as heat resistance and an almost colorless cured product, the present inventors discovered that It has been found that the novel epoxy resins derived effectively satisfy the above requirements.

That is, according to the present invention, the following formula (1), R1 00) I R9 In the formula, R1 and R2 are hydrogen or an alkyl group having 1 to 5 carbon atoms, and these may be the same or different. Provided is a novel epoxy resin characterized by the following:

According to the present invention, furthermore, in the following formula (II), H, R+ and R2 are hydrogen or an alkyl group having 1 to 5 carbon atoms, and these may be the same or different. A dihydric phenol compound represented by the following formula (I
TI), in which X represents a halogen atom, an epoxy resin characterized by carrying out a ring-opening addition reaction with a shrimp helohydrin compound represented by the following, and then dehydrohalogenating it by acting with an alkali metal hydroxide. A manufacturing method is provided.

(Function) The epoxy resin of the present invention has the above-mentioned formula (
It is novel in that it is derived from 1,3-bis(hydroxyphenoxy)-2-propatol represented by II) or its nuclear lower alkyl substituted product.

That is, when such an epoxy resin is cured using an aliphatic polyamine, aromatic polyamine, dicyandiamide, polybasic carboxylic acid or its acid anhydride, etc. as a curing agent in the same way as a normal bisphenol-based epoxy resin, it can be cured in the Examples described below. As shown in the figure, the cured product has excellent heat distortion temperature and other cured physical properties, and moreover, it produces a cured product with almost no coloration during curing.

(Preferred embodiment of the invention) Raw material dihydric phenol In the present invention, the raw material dihydric phenol that forms an ether bond with a glycidyl group is represented by the above-mentioned formula (II), and specifically, 1. 3-bis(hydroxyphenoxy)-2-propatol, and its benzene nucleus is substituted with a lower alkyl group having a carbon number of 1 to 5, such as a methyl group or an engineered methyl group.

Production of Epoxy Resin The epoxy resin of the present invention is produced in the same manner as conventionally known epoxy resins, except that the above-mentioned raw material dihydric phenol compound is used.

That is, the above-mentioned raw material dihydric phenol compound and epihalohydrin represented by the following formula (III), in which X represents a halogen atom, are reacted in the presence of a catalyst to perform ring-opening addition, and then an alkali metal Obtained by ring closure by dehydrohalogenation using hydroxide.

As the epihalohydrin represented by the above formula (III), epichlorohydrin, epibromohydrin, and mixtures thereof are commonly used, and epichlorohydrin is particularly preferred.

Further, as the catalyst, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, etc. are preferably used.

Further, as the alkali metal hydroxide used as the dehydrohalogenating agent, sodium hydroxide, potassium hydroxide, etc. are used, and these can also be used as a catalyst for carrying out the ring-opening addition reaction.

In this case, when a quaternary ammonium salt is used as a catalyst, the reaction stops at the ring-opening addition reaction stage, so the alkali metal hydroxide is reacted in the next step, but from the beginning the alkali metal hydroxide When a substance is used as a catalyst,
This method has the advantage that the epoxy resin can be produced in one step because it proceeds not only with ring-opening addition but also with ring-closing reaction.

Further, the epihalohydrin used is usually used in excess with respect to the raw material dihydric phenol compound, and the alkali metal hydroxide may be used in a solid state or as an aqueous solution.

In producing the above-mentioned epoxy resin, other suitable polyhydric phenols such as bisphenol A1 bisphenol S1 novolak resin may be used in combination with the raw dihydric phenol compound.

Thereby, it is possible to manufacture a series of epoxy resin compositions to be used depending on the application.

The novel epoxy resin of the present invention thus obtained has the characteristics that its cured product has excellent properties such as heat distortion temperature, and almost no coloring. It can be used for various purposes in combination with epoxy resin.

(Example) The excellent effects of the present invention will be explained with the following example.

Example 1 According to the following recipe, these were charged into a round bottom flask with a capacity of 200 mA equipped with a stirrer, a thermometer, and a condenser.
The ring-opening addition reaction was carried out at a temperature of .degree. C. for 5 hours.

1) Epichlorohydrin 85.1g (0.92 mol)
Next, the reaction mixture was cooled to 50° C., a water removal device was attached to the flask, and 15.33 g (0,184 mol) of a 48% by weight aqueous sodium hydroxide solution was added dropwise over 2 hours. During dropping, the reaction temperature was 70°C and the pressure was 150-1
The dehydrochlorination reaction was allowed to proceed by continuously azeotropically removing the produced water and the water accompanying the sodium hydroxide aqueous solution under conditions of 80+vnHg.

After removing excess unreacted epichlorohydrin under reduced pressure, 30 g of methyl isobutyl ketone was added and the mixture was washed twice with 40 g of warm water. After washing the methyl isobutyl ketone layer with a 15% by weight NaH, PO4 aqueous solution, water remaining in the layer was azeotropically distilled with methyl isobutyl ketone and removed from the system. After passing the remaining methyl isobutyl ketone layer through a glass filter (type 04), methyl isobutyl ketone was distilled off from the oral fluid under reduced pressure to obtain a pale yellow viscous Y4 liquid 29.
7g was obtained.

The properties of the obtained viscous liquid were as follows.

Epoxy equivalent, 221 (theoretical value 194) Hydrolyzable chlorine amount, 0.03% by weight Infrared absorption spectrum;
Shown in Figure 1.

From this result, the above viscous liquid has the following formula, Q
It is recognized that it is an epoxy resin represented by OH.

In Example 1, the same molar amount of 1.3-bis(4-hydroxyphenoxy)-2-propanol was used instead of 1.3-bis(4-hydroxyphenoxy)-2-propanol.
-bis(4-hydroxy-2-methylphenoxy)-2
-Property tools were used. 31.8 g of a pale yellow viscous liquid was obtained, and based on the epoxy equivalent of 230 (theoretical value 208), etc., this material was identified as an epoxy resin represented by the following formula: 0 0H.

Reference Example A theoretical amount of methyltetrahydrophthalic anhydride [trade name H
N-2200 (Hitachi Chemical Product)] and 0.5% curing accelerator [trade name U-cat] per the epoxy resin.
SA (manufactured by SunApollo Co., Ltd.)] and heat curing was performed at room temperature for 10 hours, at 120°C for 2 hours, and at 150°C for 3 hours.

The cured physical properties of this cured product were measured according to JIS K-6911. The measurement results are shown in Table 1.

For comparison, Table 1 also shows the cured physical properties of a cured product cured in the same manner using diglycidyl ether of bisphenol A [epoxy equivalent: 189 (abbreviated as EPX-1)].

Table 1

[Brief explanation of the drawing]

FIG. 1 shows an infrared absorption spectrum of the epoxy resin of Example 1.

Claims (2)

[Claims] (1) There are general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) In the formula, R_1 and R_2 are hydrogen or an alkyl group having 1 to 5 carbon atoms, and these may be the same or different. Epoxy resin. (2) The following general formula, ▲Mathematical formula, chemical formula, table, etc.▼・・・・・・(II) In the formula, R_1 and R_2 are hydrogen or an alkyl group having 1 to 5 carbon atoms, and these are mutually The raw dihydric phenol compound represented by can be the same or different, and can be expressed by the following general formula, ▲Mathematical formula, chemical formula, table, etc.▼・・・・・・・・・
・(III) An epoxy resin characterized by carrying out a ring-opening addition reaction with an epihalohydrin compound represented by the following formula, in which X represents a halogen atom, and then dehydrohalogenating it by acting with an alkali metal hydroxide. Production method.