JPS6197276A - Novel epoxy resin and its production - Google Patents

Abstract

NEW MATERIAL:An epoxy resin shown by the formula I (R and R' are H, or lower alkyl; n and m are 0, or 1; l is 0 or 1-4). USE:Useful as a raw material for a cured material showing improved curing physical properties. The epoxy resin is curable by using an aliphatic polyamine, alicyclic polyamine, aromatic polyamine, polybasic carboxylic acid, etc. as a curing agent, its cured material shows improved properties such as high- temperature flexural strength, Izot impact strength, boiling water absorption ratio, etc., suitable as a material for building and civil engineering works, poly mer alloy, etc. PREPARATION:A diamine compound shown by the formula II and an epihalohydrin compound shown by the formula II (R is H, or methyl; X is halogen) are subjected to ring closure addition reaction. Then, an alkali is added to the reaction mixture, and the reaction product is dehydrohalogenated and subjected to ring closure, to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel epoxy resin and a method for producing the same. More specifically, the present invention relates to a novel epoxy resin capable of producing a cured product exhibiting excellent cured physical properties and a method for producing the same.

[Conventional technology]

Composite materials, electrical equipment materials, adhesives, thermosetting resins,
Epoxy resins are widely used in paints and other applications.
For example, glycidyl ether type, glycidyl ester type,
Various types of epoxy resins, such as glycidylamine type, are known, but these known epoxy resins do not necessarily satisfy the above-mentioned uses in terms of various properties such as curing speed and cured physical properties. For example, in the case of bisphenol A-epichlorohydrin-based epoxy resin, the heat distortion temperature of the cured product is low, and the temperature of the cured product decreases in bending strength and weight when stored for a long period of time.

[Problem that the invention seeks to solve]

The present inventors focused on the fact that more polyfunctional, or more polycyclic, epoxy resins tend to give cured products with better heat resistance. As a result of various studies in search of an epoxy resin with low strength and excellent heat resistance, it was discovered that a glycidyl compound derived from a specific diamine compound effectively solves the above problems.

[Means for Solving the Problems] and [Operation] Accordingly, the present invention relates to a novel epoxy resin, which has the general formula (wherein R and R' are hydrogen atoms or lower alkyl groups, n and m are 0 or 1, and 1 is Ot or an integer from 1 to 4).

The present invention also relates to a method for producing such an epoxy resin, and the production of the epoxy resin is carried out using the following general formula (where Bl is a hydrogen atom or a lower alkyl group, and 1 is O or an integer from 1 to 4). A diamine compound is subjected to a ring-opening addition reaction with a shrimp halohydrin compound represented by the general formula (where R is a hydrogen atom or a methyl group, and X is a halogen atom), and then decomposed using an alkali metal. This is carried out by carrying out a ring-closing reaction using hydrogen halide.

As the diamine compound represented by the above general formula (It), the following compounds can be exemplified, and the compounds marked with 0 are particularly preferably used.

ol, 4-bis[α-(4-amino-2-methylphenyl)-α-methylethyl]benzene 1.4-bis[α-(4-amino-2-methylphenyl)-α-methylethyl]henzene 1.4 −Bis [α−(
4-amino-3-methylphenyl)-α-methylethyl]benzene 1,4-bis[α-(4-amino-3,5-
dimethylphenyl)-α-methylethyl]benzene 01
．． 3-bis[α-(4-aminophenyl)-α-methylethyl]benzene 1.3-bis[α-(4-amino-2-methylphenyl)-α-methylethyl]benzene 1.3-bis[ α−(
4-amino-3-methylphenyl)-α-methylethyl]benzene 1,3-bis[α-(4-amino-3,5-
(dimethylphenyl)-α-methylethyl]benzene. Examples of the epichlorohydrin compound represented by the above general formula [11] include epichlorohydrin, β-methylepichlorohydrin, ebibromhydrin, β-methylebibromhydrin, and mixtures thereof. Among them, epichlorohydrin is particularly preferred.

The reaction between a diamine compound and an epihalohydrin compound is
For example, it is carried out in the same manner as the known method for producing polyglycidylamine compounds as described in Japanese Patent Publication No. 49-14211, in which an epihalohydrin compound is added to a diamine compound to form a halohydrin compound as an intermediate. This is carried out by dehydrohalogenating this compound in the presence of an alkali and subjecting it to a ring-closing reaction.

Specifically, shrimp halohydrin is added to the diamine compound in an amount of about 5 to 10 times the molar amount relative to the amino group thereof, and preferably at the bottom right of a lithium compound catalyst such as lithium hydroxide, lithium oxide, or lithium chloride, After stirring in a water-containing organic solvent such as water-containing methanol, water-containing ethanol, or water-containing acetone to carry out a ring-opening addition reaction, about 2 to
Five times the molar amount of an alkali such as lithium hydroxide, sodium hydroxide, potassium hydroxide or an aqueous solution thereof is added, and the reaction is carried out at a temperature from room temperature to about 100 t. After a series of operations,
The above general formula [! ] An epoxy resin is obtained. The ring-opening addition reaction also proceeds efficiently using a Lewis acid such as a boron trifluoride ether complex.

The obtained epoxy resin generally has diglycidylamino groups at both ends, but by lowering the molar ratio of shrimp halohydrin to the diamine compound (1) K, it can be made into a compound having a monoglycidylamino group at both ends or at one end. You can also.

This new epoxy resin can be used by mixing it with other known epoxy resins within a range that does not impair its original properties.For the same purpose, a part of the diamine compound can be mixed with other suitable amine compounds, For example, the reaction can be carried out by substitution with Gf4.4'-diaminodiphenylmethane, p-phenylenediamine, p-aminophenol, m-aminophenol, or the like.

〔Effect of the invention〕

The epoxy resin according to the present invention is cured as a total curing agent, such as an aliphatic polyamine, an alicyclic polyamine, an aromatic polyamine, a polybasic carboxylic acid, or an acid anhydride thereof, in the same way as general bisphenol-based epoxy resins. Although the cured product does not show any particular improvement in terms of thermal deformation temperature, it shows improved properties in terms of bending strength at high temperatures, isot impact strength, evaporation water absorption, etc. By effectively utilizing these characteristics, it can be suitably used for the above-mentioned applications, as well as for construction and civil engineering materials, polymer alloys, and the like.

〔Example〕

Next, the present invention will be fully explained with reference to examples.

Example 1 1,4-bis[α-(4-aminophenyl)
-α-methylethyl]benzene 275g (0.8 mol)
, 888 g (9.6 mol) of evicrylhydrin and 1529 t of 95% ethanol were charged and stirred at room temperature for 12 hours. Thereafter, the temperature of the reaction mixture was raised to 55-60°C, and 48% sodium hydroxide aqueous solution 4009 (
4.8 mol) was added dropwise during t-2 hours. At this temperature 4
After stirring for a period of time, ethanol and unreacted epichlorohydrin were distilled off under reduced pressure at a temperature below 60°C to leave a residue. Extracted with toluene and washed twice with water. To this toluene solution was added 200% of a 7% aqueous solution of hydroxide, and the mixture was stirred at a temperature of 55 to 60°C for 30 minutes. The aqueous layer was removed, water in the toluene solution was azeotropically distilled off with toluene using a Digi-Stahl trap, and then inorganic salts in the resin were removed using a glass filter (G-4 type). This filtrate was concentrated under reduced pressure at a temperature below 60° C. to obtain 440 g of a pale yellow viscous product.

The nuclear magnetic resonance spectrum of the viscous product is shown in FIG. [α-(4-aminophenyl)-α-
It is thought to be a mixture of the tetraglycidyl form and lower glycidyl form of methylethyl]benzene.

Separation of the tetraglycidyl form from this mixture is performed by purification operations such as recrystallization or adsorption column separation.

The identified positions of the nuclear magnetic resonance spectrum are as follows.

Example 2 Using the same amount of 1,3-bis[α-(4-aminophenyl)-α-methylethyl]benzene as the diamine compound in Example 1, a yellow viscous product of 4309 was obtained. . The epoxy equivalent weight of this product was 173 (theoretical value as a tetraglycidyl compound: 142).

Example 3 In Example 1, when the diamine compound was added to 1,4-bis[α-(4-amino-2-methylphenyl)-α-methylethyl]benzene 2989 (0.8 mol), , 480 g of a yellow viscous product were obtained. The epoxy equivalent weight of this product was 179 (theoretical value as a tetraglycidyl compound: 149).

Reference Example: About 80% of the theoretical amount of 4,4'-diaminodiphenylmethane was blended as a curing agent into the epoxy resin obtained in each of the Examples above, and this blend was heated at t-80'c, 3 hours-15
Cured under the conditions of 0 ° C., 2 hours - 1800 °C, 2 hours,
Cured physical properties of cured product Measured according to T-J Engineering 5x-6911. For comparison, similar curing was performed using a tetraglycidyl form of 4,4'-diaminodiphenylmethane (MY-720, a product of Ciba Geigy Co., Ltd., epoxy equivalent (25), which is a typical commercially available glycidylamine-based epoxy resin. (Comparative Example) The results obtained are shown in the following table.

Epoxy resin Sword 11 Nyokyoku 2 To Cod 3 Heat deformation temperature (C) 223 159 213 213 Bending strength (25℃) (Kf/gl) 13.3 14
．． 4 1L8 1L71 (i■℃) ('#/d)
10.0 10.8 9.8 9.61 (
150C) ('f/1ul) &8 7.9 8
．． 1 6.2 Compressive strength (odor/-) 16.
4 17.8 18.3 16.4 Aisin H1
Sound hardness threshold [(Kf~) 0.98 1.02
1.10 0.89MM! #10 Ebisu, Sashi (To) (4) 0.37 0.29 0.31 0.58

[Brief explanation of the drawing]

FIG. 1 is a nuclear magnetic resonance spectrum of the epoxy resin obtained in Example 1.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] (Here, R and R' are hydrogen atoms or lower alkyl groups, and n and m are 0 or 1. , l is 0 or an integer of 1 to 4). 2. Diamine compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [II] (where R' is a hydrogen atom or a lower alkyl group, and l is 0 or an integer from 1 to 4) is subjected to a ring-opening addition reaction with an epihalohydrin compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] (where R is a hydrogen atom or a methyl group, and X is a halogen atom) There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (where R and R' are hydrogen atoms or lower alkyl n and m are 0 or 1, and l is 0 or an integer from 1 to 4).