JPS6277376A - Novel glycidyl compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A novel glycidyl compound having >=2 glycidylamino groups directly bonded to the aromatic ring of a >=10C condensed aromatic hydrocarbon compound. EXAMPLE:N,N,N',N'-tetraglycidyl-1,5-diaminonaphthalene. USE:Raw material of coating material, adhesive, casting material and matrix resin for carbon fiber or glass fiber laminated sheet. PREPARATION:The objective novel glycidyl compound can be produced by (1) carrying out the addition reaction of an epihalohydrin with a compound having >=2 amino groups directly bonded to the aromatic ring of a >=10C con densed aromatic hydrocarbon compound preferably using water or an alcohol as a catalyst and (2) subjecting the addition reaction product to de hydrohalogenation reaction with an alkali in the presence of preferably a quater nary ammonium salt or quaternary phosphonium salt as a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a monovalent or polyvalent glycidylamine compound having a condensed ring and a method for producing the same.

More specifically, it was completed as a result of intensive research into a new epoxy resin that has condensed rings in its molecules and has high heat resistance and mechanical properties. In addition, it is expected to be used as a Mad IJx resin for carbon fiber and glass fiber laminates.

[Means and effects for solving the problems] The present invention provides that the glycycylaglycidylamino group directly bonded to the aromatic ring of the fused ring aromatic hydrocarbon compound having 10 or more carbon atoms is
New glycidyl compounds having two or more glycidyl compounds in the molecule, and fused ring aromatic compounds having 10 or more carbon atoms, such as compounds having two or more amine groups directly bonded to aromatic rings such as naphthalene, anthracene, phenanthrene, pyrene, and benzopyrene. After adding epihalohydrin, the content includes a manufacturing method in which a dehydrohalogenation reaction is performed with an alkali.

The chemical structural formula of the above novel glycidyl compound is, for example, as shown in the following formula (1).

(However, a and b are integers from 0 to 4 that are not 0 at the same time,
R1, 12, IL8. R and 4 are hydrogen atoms or glycidyl groups, and one or both of R1 and R2, and one or both of Ra and 4 are glycidyl groups. ) The novel glycidyl compound of the present invention can be produced by the following steps:
First, a compound having two or more amine groups directly bonded to the aromatic ring of a condensed ring aromatic hydrocarbon compound having 10 or more carbon atoms is subjected to an addition reaction with epihalohydrin. During the addition reaction, water or alcohol is used as a catalyst, It has been found that it is appropriate to use a quaternary ammonium salt or a quaternary phosphonium salt as a catalyst in the subsequent dehalogenation reaction.

The first step addition reaction is carried out by reacting the fused ring compound and epihalohydrin in the presence of water or alcohol. As the alcohol, methanol, ethanol, n-propertool, 1so-propertool, butanol, etc. can be used. The amount of the catalyst to be used can be arbitrarily selected within the range of 0.5 to 300 mol%, but preferably 1 to 200 mol%, based on the fused ring compound.

As the epihalohydrin, epichlorohydrin, epibromohydrin, and epiiodohydrin can be used, and the amount used is at least equimolar, preferably 1.0 to 20 times the molar amount, and more preferably is 1
．． 05 to 5 times the molar amount.

The reaction temperature and time are 30 to 150°C for 10 minutes to 10 hours, more preferably 60 to 120°C for 30 minutes to 7 hours. At this time, an aromatic solvent, a ketone solvent, or an alcohol solvent may be used.

In the second step, a dehydrohalogenation reaction is carried out using an alkali. As the alkali, sodium hydroxide, potassium hydroxide, etc. can be used. As the catalyst, quaternary ammonium salts such as tetrabutylammonium bromide, trioctylmethylammonium chloride, and benzyltriethylammonium chloride, and quaternary phosphonium salts such as tetraphenylphosphonium chloride and tetrabutylphosphonium chloride can be used.

The amount of ammonium salt or phosphonium salt to be used can be arbitrarily selected within the range of 0.001 to 100 mol%, based on the fused ring compound, but preferably 0.02 to 20 mol%. The amount of alkali to be used is equal to or more, preferably 1.05 to 2.0 times the mole per hydrogen atom of the amino group of the fused ring compound used. Note that, before performing the dehydrohalogenation reaction, the reaction may be performed in a solvent such as methyl isobutyl ketone, methyl ethyl ketone, toluene, xylene, or ethanolate. After the reaction is completed, the produced salt is removed by washing with water, and unreacted epichlorohydrin and the solvent are distilled off, whereby the desired glycidyl compound can be obtained with high purity and high yield.

〔Example〕

Synthesis examples of glycidyl compounds are shown below, but the present invention
It is not limited to this.

Example ■, 5-naphthalenediamine 15.8 g (0.1 mol), epichlorohydrin 55.51 (0.6 mol),
1.8 P (0.1 mol) of pure water was placed in a 300-shoulder Taro flask, the flask was purged with nitrogen, the temperature was raised to 80°C, and the reaction was allowed to proceed for 6 hours with stirring. Subsequently, 40 ml of methyl isobutyl ketone. Benzyltriethylammonium chloride 0.456. f (0,002 mol) was added to the temperature at 50°C, and to this was added 64 g (0,64
mol) was added dropwise over a period of 30 minutes, followed by a reaction at 50'C for 2 hours, 80 txl of water was added to dissolve the salt, and the aqueous layer was removed. After washing once with water five times, drying with sodium sulfate, distilling off the solvent, and adding N.N.

84.41 of Nl,Nr-tetraglycidyl-1,5-diaminonaphthalene was obtained. The yield was 90%.

The epoxy equivalent weight (according to the hydrochloric acid-pyridine method) of this product was 111.5, and the amount of hydrolyzed chlorine was 0.030% (according to ASTM D-1726-78).

Table 1 shows the physical properties of samples obtained by curing the glycidyl compounds obtained in Examples with methylhimic anhydride.

Table 1 Note) (1) Curing conditions are 140°C for 2 hours, then 170°C.
Heat at ゛°C for 15 hours.

(2) The methods for measuring HDT, bending strength, and bending modulus in Table 1 are all based on JIS K-6911.

Claims (4)

[Claims] (1) It has a glycidylamino group directly bonded to the aromatic ring of a fused ring aromatic hydrocarbon compound having 10 or more carbon atoms. A new glycidyl compound that exists in more than 100%. (2) A novel glycidyl compound according to claim 1, wherein the glycidyl compound is represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, a and b are integers from 0 to 4 that are not 0 at the same time, and R^1, R^2, R^3, and R^4 are hydrogen atoms. or a glycidyl group, and one or both of R^1 and R^2 and one or both of R^3 and R^4 are glycidyl groups.) (3) After adding epihalohydrin to a compound having two or more amino groups directly bonded to the aromatic ring of a condensed ring aromatic hydrocarbon compound having 10 or more carbon atoms, a dehydrohalogenation reaction is performed with an alkali. A method for producing a novel glycidyl compound. (4) The production method according to claim 3, in which water or alcohol is used as an addition catalyst for epihalohydrin and an amino group, and a quaternary ammonium salt or a quaternary phosphonium salt is used as a catalyst for the dehydrohalogenation reaction.