JPS617266A - Novel glycidyl compound and preparation thereof - Google Patents

Abstract

NEW MATERIAL:A glycidyl compound expressed by formula I (R<1> and R<2> are 1- 20C aliphatic hydrocarbon group, 6-20C aromatic group or H; R<3> is 1-20C bifunctional hydrocarbon group or 6-20C bifunctional aromatic group; Ar<1> and Ar<1>' represent 6-20C aromatic group, and have respectively one or more glycidyl groups). EXAMPLE:Diglycidyl ether of ethylenediaminebissalicylamide. USE:A cured article having high heat resistance and mechanical strength which is in the form of a viscous liquid - solid and has expectable reinforcing effect further by compounding with glass fibers or carbon fibers. PREPARATION:A compound expressed by formula II (R<4> and R<5> are 1-20C aliphatic hydrocarbon group, etc.; R<6> is 1-20C bifunctional alphatic hydrocarbon group, etc.; Ar<2> and Ar<2>' are 6-20C aromatic group or either one or both have hydroxyl groups) is subjected to addition with an epihalohydrin, and the dehydrohalogenating reaction is carried out with an alkali to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel glycidyl ether compound of monohydric or polyhydric phenols containing an amide group 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 an amide group in its molecule and has high heat resistance and mechanical properties, and it has the general formula (I) (in the formula, NR2 represents the same or different group selected from the group consisting of a C0 to C2o aliphatic hydrocarbon group, a C6 to C2o aromatic group, and a hydrogen atom, and R is C1 to
Represents a C2o divalent hydrocarbon group or a C6-C2o divalent aromatic group.

AI! , A:' represents a C6-C2o aromatic group,
The present invention relates to novel glycidyl compounds, each having one or more glycidyloxy groups, and a method for producing the same.

[Structure of the invention]

The novel glycidyl compound (I) of the present invention has the following general formula f
f) (In the formula, R4 and R5 each independently represent a C1 to C2o aliphatic hydrocarbon group, a C6 to C2o aromatic group, or a hydrogen atom, and R6 is a C1 to C2o divalent aliphatic hydrocarbon group) Or represents a C6-C2o divalent aromatic group.

A>, A:' represents a C6 to C2o aromatic group, and Al1. A: It can be produced by adding a compound represented by (one or both of which have at least one hydroxyl group) and epihalohydrin, and then carrying out a dehydrohalogenation reaction with an alkali.

Compound (V) is an aromatic carboxylic acid ester having a phenolic hydroxyl group and a diamine compound heated at 100 to 150°C.
By reacting at a temperature of 3 to 6 hours, it can be easily synthesized by a dealcoholization reaction by amitrisis. Examples of aromatic carboxylic acid esters having a phenolic hydroxyl group include methyl p-hydroxybenzoate, and halogenated versions thereof.
Examples of diamine compounds include, but are not limited to, ethylene diamine, hexamethylene diamine, to+ m+ p-phenylene diamine, and the like.

As a result of studying a method for glycidylating the hydroxyl group of the compound represented by the general formula (■), we conducted an addition reaction between the compound (■) and epihalohydrin in the presence of a phase transfer catalyst, and then dehydrohalogenated it with an alkali. We have found that the method of doing this is appropriate.

According to this method, the hydroxyl group of compound (■) is glycidylated with good yield, and hydrolysis of the amide group does not substantially occur. The manufacturing method will be explained in detail below.

The first step addition reaction is carried out by reacting compound (V) with epihalohydrin in the presence of a phase transfer catalyst. The phase transfer catalyst is generally known, for example, tetrabutylammonium bromide.

Trioctylmethylammonium chloride.

Quaternary salts such as benzyltriethylammonium chloride
quaternary ammonium salts; quaternary ammonium salts such as tetraphenylphosphonium chloride and tetrabutylphosphonium chloride;
grade phosphonium salts can be used. The amount of the phase transfer catalyst to be used can be arbitrarily selected from 0 to 1 to 100 mol% of the compound (V), preferably 0.02 to 20 mol%.
amount can be used.

The amount of epihalohydrin used is equal to or more than 1 molar equivalent of hydroxyl group of compound (V), preferably 1.5 to 20 molar equivalents of hydroxyl group of compound (V).
This is twice the molar amount. At this time, a non-reactive solvent may be used. Epihalohydrin includes epichlorohydrin,
Shrimp bromohydrin and shrimp iodohydrin can be used. The reaction temperature and reaction time are 30 to 150°C for 10 minutes to 5 hours, preferably 60 to 120°C for 30 minutes to 2 hours.

In the second step, a dehydrogenation reaction is carried out using an alkali. As the alkali, sulfur hydroxide,
Potassium hydroxide, lithium hydroxide, sodium carbonate, etc. can be used. As a catalyst for dehydrohalogenation reaction,
The phase transfer catalyst used in the first step is used as is, but a phase transfer catalyst can be added if necessary. In addition to the above-mentioned phase transfer catalysts, additional phase transfer catalysts include ethylene glycol, diethylene glycol, tetraethylene glycol, polyethylene glycol, crown ethers, and the like. The amount of alkali to be used is equal to or more than the equivalent molar amount to the generated halohydrin ether. Preferably, 1.05 to 1.5 times the mole is used.

The reaction temperature and time are 20 to 100°C for 10 minutes to 5 hours, preferably 30 to 70'C for 30 minutes to 3 hours.

Before carrying out the dehydrohalogenation reaction, excess epihalohydrin is removed under reduced pressure, and a non-reactive solvent such as methyl isobutyl ketone or acetone is used.

The reaction may be carried out in a solvent such as chloroform or methylene chloride.

After completion of the reaction, the produced salt is removed by water washing, and unreacted epihalohydrin is distilled off, whereby the glycidyl compound represented by general formula (I) can be obtained with high purity and high yield.

〔Effect of the invention〕

The novel glycidyl compound represented by the general formula (I) of the present invention is in a viscous liquid to solid state at room temperature and can be cured using a common epoxy resin curing agent, and the cured product has high heat resistance,
It has mechanical strength and is expected to have a remarkable reinforcing effect when combined with glass fiber or carbon fiber.

〔Example〕

The present invention will be explained below using specific examples, but the present invention is not limited only to these examples.

Example 1 Ethylenediamine bissalicylamide 98y (0,32
7 mol), epichlorohydrin 242y (2.62 mol) and benzyltriethylammonium chloride 3.
72 y (0,016': 3 mol) at 90-1
After stirring for 1 hour at 00°C, the reaction mixture was heated to 45°C.
Cool to °C and 144 mi of 5N sodium hydroxide!
(0,720 mol) was added dropwise under stirring at 50°C over 245 minutes, followed by stirring at 50°C for 1 hour. After cooling to room temperature, add 300ml of methylene chloride (!) to separate the layers, wash the organic layer three times with 1,500ml of water, and dilute with sulfuric acid. After drying with IJum, methylene chloride and epichlorohydrin are distilled off under reduced pressure. A yellowish white solid of 9F/ was obtained. This solid was purified by recrystallization using methanol and the NMR spectrum (Figure 2) showed it to be the diglycidyl ether of ethylenediamine bissalicylamide. The elemental analysis value is C: 64.07%.

H: 5.87chi, N: 6.79% (calculated value C: 64.6
6%, H: 5.95%, N: 6.72%).

The epoxy equivalent weight determined by the hydrochloric acid-pyridine method was 236 (calculated value 206).

Example 2 Hexamethylenediamine bissalicylamide 183, .
1-(0,515 mol), epichlorohydrin 381y
(4.12 mol), benzyltriethylammonium chloride 5.87y (0.0258 mol)
After stirring for 45 minutes at 0-100°C, the reaction mixture was cooled to 45°C and added with 226 m
e (1.13 mol) was added dropwise to 508C over 145 minutes with complete stirring, followed by stirring at 50° C. for 1 hour. After cooling to room temperature, 300me of methylene chloride was added, the layers were separated, and the organic layer was diluted with 1.
After washing three times with 200ml of water and dehydrating with IJ sulfuric acid, methylene chloride and epichlorohydrin were distilled off under reduced pressure to obtain a yellowish white solid of 236.6y. This solid was purified by recrystallization using methanol to obtain a colorless solid with a melting point of 118-122°C.

The infrared absorption spectrum (Figure 3) and 'HN
The MR spectrum (Figure 4) showed it to be a diglycidyl ether of hexamethylene diamine bissalicylamide. The epoxy equivalent by the hydrochloric acid-pyridine method is 26
3 (calculated value 234).

Example 3 After heating and dissolving 100 parts of the glycidyl compound obtained in Example 1, 64 parts of methylhimic anhydride and 2 parts of benzyldimethylamine were added, and the mixture was poured into a mold.
The cured product obtained by heat curing at 00°C for 2 hours and 150°C for 15 hours has a heat distortion temperature (JIS-6911 bending stress of 18.5 to 9/cd) and a bending strength of 10.4 at 151°C.
7 Kg/+++a, flexural modulus 388.3 Kg/i
J (JIS-6911,230C), Izot impact strength (JIS-6911° notched) 2.2Kg.
cm/crA was shown.

Example 4 After heating and dissolving 100 parts of the glycidyl compound obtained in Example 2, 58 parts of methylhimic anhydride and 2 parts of benzyldimethylamine were added, and the mixture was poured into a mold.
The cured product obtained by heat curing at 00°C for 2 hours and 150°C for 15 hours has a heat distortion temperature (JIS-6911
Bending stress 1s, 5 Kgler&) 126°C 1 Bending strength 18.86 Kg/-, Bending modulus 329, 7
h/ma (23°C, JIS-6911), Izod impact strength (JIS-6911.notched) 3
, '3 Kg·cm/ci.

[Brief explanation of drawings]

Figures 1 and 2 are the infrared absorption spectrum (Nujol method) and HNMR spectrum (CDC18 solvent, TMS standard) of the novel glycidyl compound of the present invention obtained in Example 1, respectively. Figure 4 shows the infrared absorption spectrum (Nujol method) and 'HNMR spectrum (CDC13 solvent, TMS standard) of the glycidyl compound of the present invention obtained in Example 2, respectively.

Claims (6)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 and R^2 are aliphatic hydrocarbon groups of C_1 to C_2_0, aromatic groups of C_6 to C_2_0 represents the same or different groups selected from the group consisting of hydrogen atoms,
R^3 represents a divalent hydrocarbon group of C_1 to C_2_0 or a divalent aromatic group of C_6 to C_2_0. A＾１＿
r, A^1_r' represent an aromatic group of C_6 to C_2_0, each having one or more glycidyloxy groups) A novel glycidyl compound represented by: (2) The novel glycidyl compound according to claim 1, wherein the glycidyl compound is a compound represented by the following formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1 and R^2 represent C_1 to C_2_0 aliphatic hydrocarbon groups or C_6 to C_2_0 aromatic groups or hydrogen atoms, and R^ 3 represents a divalent aliphatic hydrocarbon group of C_1 to C_2_0 or a divalent aromatic group of C_6 to C_2_0, A, B, C, D, A', B', C',
D' represents the same or different group selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group of C_1 to C_2_0, an aromatic group, a halogen atom, and a glycidyloxy group). (3) The novel glycidyl compound according to claim 1, wherein the glycidyl compound is a compound represented by the following formula (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (4) The novel glycidyl compound according to claim 1, wherein the glycidyl compound is a compound represented by the following formula (IV). , ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (5) The following general formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, R^4 and R^5 are each independently C_1 to C_
2_0 represents an aliphatic hydrocarbon group or C_6 to C_2_0 aromatic group or hydrogen atom, and R^6 is C_1 to C
_2_0 divalent aliphatic hydrocarbon group or C_6 to C_
Represents a divalent aromatic group of 2_0. A^2_r, A^2_
r' represents an aromatic group of C_6 to C_2_0, and A^2
One or both of _r, A^2_r' have at least one hydroxyl group) and epihalohydrin are added, and then a dehydrohalogenation reaction is carried out with an alkali. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 and R^2 are C_1 to C_2_0 aliphatic hydrocarbon groups, C_6 to C_2_0 aromatic groups, and hydrogen atoms. represents the same or different groups selected from the group consisting of,
R^3 represents a divalent hydrocarbon group of C_1 to C_2_0 or a divalent aromatic group of C_6 to C_2_0. A_r^
1, A_r^1 represents an aromatic group of C_6 to C_2_0, each having one or more glycidyloxy groups) A method for producing a novel glycidyl compound represented by: (6) Quaternary ammonium salt or quaternary
6. The manufacturing method according to claim 5, which uses a class phosphonium salt.