JPH0559031A - Diepoxy compound, its production and its cured product - Google Patents

Abstract

PURPOSE:To obtain a new diepoxy compound widely utilizable as an epoxy resin material, further as a biodegradable or bio-compatible polymer raw material, etc., having epoxy groups at both ends and having an amino acid structure in the molecule. CONSTITUTION:A diepoxy compound expressed by formula I or formula II (R is l-6C alkylene or 6-14C arylene; X is H, methyl, isopropyl, 2-methyl-propyl, 3-methylpropyl, 1-methylthioethyl ether or benzyl) such as adipoylbis-L-alanine glycidylester. The compound expressed by formula I or formula II is obtained by reacting a diamino compound expressed by formula III or formula IV with glycidol expressed by formula V in the presence of dimethylaminopyridine using dicyclohexylcarbodiimide.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention can be widely used as an epoxy resin material and further as a raw material for biodegradable or biocompatible polymers. It has epoxy groups at both ends and has an amino acid structure in the molecule. And a method for producing the same, and a cured product of the diamine compound.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
The epoxy compound used as a raw material for the epoxy resin is produced by reacting epichlorohydrin with a polyalcohol, an organic acid, an amine, an amide, or the like, or by oxidizing a double bond. Is synthesized in this way. (A) An epoxy ether is obtained by reacting a phenolic OH group with epichlorohydrin.

[0003]

[Chemical 4] (B) A glycidyl ester is obtained by reacting an organic acid with epichlorohydrin.

[0004]

[Chemical 5]

The epoxy compound thus obtained can be used as various materials, for example, as an epoxy resin in the fields of paints, electricity, civil engineering, and the like, and further expansion of its applications is expected.

[0006]

Means for Solving the Problems In view of the above circumstances, the present inventor has conducted extensive studies in order to obtain an epoxy compound having a wide range of use. As a result, for example, as shown in the following reaction formula, formula (3) or ( 3 ′) diamino compound is reacted with dicyclohexylcarbodiimide (DCC) of formula (5), and then 4-dimethylaminopyridine of formula (6) is used as a catalyst to react with glycidol of formula (4). It was found that the novel diepoxy compound represented by the following general formula (1) or (2) that can be synthesized has excellent properties.

[0007]

[Chemical 6] (In the formula, R is an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 14 carbon atoms, and X is a hydrogen atom, a methyl group, an isopropyl group, a 2-methyl-propyl group, 3-
It is a methyl-propyl group, a 1-methylthioethyl ether group or a benzyl group. )

The diepoxy compound of the formula (1) or (2) has an amino acid structure in the molecule and has epoxy groups at both ends, and exhibits the same reactivity as general epoxy compounds, and it has amine and acid. When it reacts with a curing agent such as anhydride, it hardens easily to give a cured product, which can be used as various materials in the same applications as conventional epoxy resins, for example, in the fields of paints, electricity, civil engineering and construction, etc. Since it has an amino acid structure, this cured product can be applied to various fields utilizing functions such as optical activity derived from the amino acid structure. For example, biodegradability, biocompatibility, liquid crystallinity, and optical resolution material. It was found that it can be used for such purposes. Further, the conventional method for producing an epoxy compound is often carried out under severe conditions such as high basicity and high temperature conditions, but according to the above method, the formula (1) or (2) can be used under mild conditions.
The present inventors have found that the diepoxy compound can be synthesized and completed the present invention.

Accordingly, the present invention provides a diepoxy compound represented by the following general formula (1) or (2) having an epoxy group at both ends and an amino acid structure in the molecule.

[0010]

[Chemical 7] (In the formula, R is an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 14 carbon atoms, and X is a hydrogen atom, a methyl group, an isopropyl group, a 2-methyl-propyl group, 3-
It is a methyl-propyl group, a 1-methylthioethyl ether group or a benzyl group. )

The present invention is also characterized by reacting a diamino compound represented by the following general formula (3) or (3 ') with a glycidol of the following formula (4) using dicyclohexylcarbodiimide in the presence of dimethylaminopyridine. A method for producing the diepoxy compound represented by the general formula (1) or (2), and a cured product obtained by curing the diepoxy compound are provided.

[0012]

[Chemical 8] (In the formula, R is an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 14 carbon atoms, and X is a hydrogen atom, a methyl group, an isopropyl group, a 2-methyl-propyl group, 3-
It is a methyl-propyl group, a 1-methylthioethyl ether group or a benzyl group. )

[0013]

[Chemical 9]

The present invention will be described in more detail below. The diepoxy compound of the present invention is represented by the following general formula (1) or (2).

[0015]

[Chemical 10]

[0016]

[Chemical 11]

Here, -COCO- and -CORCO- are dicarboxylic acid residues, and depending on the type of R, oxalyl, malonyl, succinyl, glutaryl, adipoyl,
It represents a suberoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthylenoyl, anthrenoyl or phenanthrenoyl group.

[0018]

[Chemical formula 12]

The diepoxy compound of the formula (1) or (2) is obtained by the reaction of dicarboxylic acid or dicarboxylic acid chloride with an amino acid, and is represented by the following formula (3) or (3 ').
The diamino compound of formula (5) is reacted with dicyclohexylcarbodiimide (DCC) of formula (5), and then glycidol of formula (4) is added and reacted in the presence of 4-dimethylaminopyridine of formula (6). be able to.

[0020]

[Chemical 13]

Here, the diamino compound of the formula (3) or (3 ′) is a known compound that is easily available. For example, when these diamino compounds are synthesized according to the following reaction formula, racemization can be prevented.

[0022]

[Chemical 14]

Further, the reaction of the compound of formula (3) or (3 ') with the DCC of formula (4) is preferably carried out in an organic solvent, for example, dry dimethylacetamide and methylene chloride in a volume ratio. A solvent or the like mixed at a ratio of 1/2 is preferably used. The mixing ratio of the compound of formula (3) or (3 ′) and the DCC of formula (5) is 1: 1.5 by molar ratio.
It can be 1: 2.5, and the reaction is preferably carried out at -20 to 30 ° C for 0.2 to 1 hour. Further, when 4-dimethylaminopyridine of the formula (6) and glycidol of the formula (4) as a catalyst are added to the reaction solution and reacted, the addition amount of 4-dimethylaminopyridine of the formula (6) is ) Or (3 ') in an amount of 1 to 5 mol% and the addition amount of the glycidol of the formula (4) can be equivalent to those of the formula (3) or (3'). Furthermore, although the reaction conditions are not particularly limited,
It is preferable to proceed the reaction at 0 to 30 ° C. for 3 to 24 hours.

After completion of the reaction, by-products such as dicyclohexylurea and the like are filtered, concentrated under reduced pressure using an evaporator and recrystallized by a usual method.
The desired diepoxy compound can be obtained.

The thus obtained diepoxy compound of the formula (1) or (2) is compounded with a curing agent as an epoxy resin component, other additives and the like to be polymerized or three-dimensionalized and cured when heated. ..

In this case, as the curing agent, those used in ordinary epoxy resin compositions can be used, and specifically, piperazine, ethylenediamine, diethylenetriamine,
Various amine curing agents such as triethylenetetramine, xylylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, guanidine, adipic acid dihydrazide, oxalic acid, phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride Various acid anhydride curing agents such as The compounding amount of the curing agent can be a usual amount. Further, the curing conditions can be adjusted appropriately, but it is 20 to 180.
A temperature of 1 to 24 hours is suitable.

The diepoxy compound of the formula (1) or (2) of the present invention is prepared as an epoxy resin as described above,
Similar to conventional epoxy resins, for example, in the paint field, beverages, lacquer on the inside and outside of food cans, cationic electrodeposition primers for automobiles, ship and heavy-duty anticorrosion paints, etc. (Reinforcing glass fiber), encapsulating material (insulating material), etc. In the field of civil engineering and construction, it can be used as a floor material, adhesive / grout material, etc. Furthermore, since the diepoxy compound of formula (1) has an amino acid structure in the molecule,
Utilizing properties such as optical activity derived from amino acid structure, for example, splints for plants, biodegradable polymer raw materials such as medical support materials, raw materials for optical resolution column resins, medical materials such as biocompatible polymer raw materials, and liquid crystals It can also be used as a polymer or the like.

[0028]

EFFECT OF THE INVENTION The diepoxy compound of the present invention has an amino acid structure in the molecule and epoxy groups at both ends, and exhibits the same reactivity as general epoxy compounds, and is easily reacted with a curing agent or the like. To give a cured product. Therefore, the diepoxy compound of the present invention can be used as an epoxy resin in the same applications as conventional epoxy resins, for example, as various materials in the fields of coating, electricity, civil engineering, and the like, and its cured product is derived from an amino acid structure. It can be applied to various fields using functions such as optical activity, and can be used for applications such as biodegradability, biocompatibility, liquid crystallinity, and optical resolution materials, and it has a very wide range of applications. It is applicable.

Further, according to the method for producing a diepoxy compound of the present invention, the diepoxy compound can be produced in a good yield under mild conditions.

[0030]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

Example 1 2.9 g of adipoylbis-L-alanine (ABA) was dried in a 100 ml three-necked flask equipped with a dropping funnel and a calcium chloride tube. Dimethylacetamide-methylene chloride (1/2 = V /
V) It was dissolved in 30 ml of the mixed solution, cooled to 0 ° C., 4.54 g of dicyclohexylcarbodiimide (DCC) was further added, and the mixture was reacted for 30 minutes. Then, after adding 0.02 g of 4-dimethylaminopyridine, glycidol 1.4
After 8 g was added dropwise and the reaction was performed for 3 hours, the reaction was performed at room temperature for 12 hours.

After the reaction was completed, the by-produced dicyclohexylurea (DCU) was filtered and the DCU was washed with methylene chloride. The filtrate was concentrated under reduced pressure with an evaporator and then concentrated to 200
When poured into ml of ether, 3.1 g of a white solid was obtained (crude yield 78%). Further, when this was recrystallized from ethyl acetate, the desired adipoylbis-L-alanine diglycidyl ester (melting point 9% was obtained with a yield of 70%
4-98 ° C) was obtained.

The analytical results of the obtained adipoyl bis-L-alanine diglycidyl ester are as follows. The infrared absorption spectrum of the raw material adipoylbis-L-alanine is shown in FIG. Further, the infrared absorption spectrum and the nuclear magnetic resonance spectrum of the obtained adipoylbis-L-alanine diglycidyl ester are shown in FIGS. 2 and 3, respectively. Infrared absorption spectrum [IR (KBr)]: 1745c
m ^-1 (ester group) 908 cm ^-1 (epoxy group) elemental analysis (%): measured value C: 53.92, H: 7.06, N: 6.97 calculated value C: 53.99, H: 7 .05, N: 7.00 Nuclear magnetic resonance spectrum [ ¹ H NMR (CDCL ₃ )]: δppm 1.42: d 6H J = 7.25 (d) 1.69 to 1.76: m 4H (a) 2 .20 to 2.27: m4H (b) 2.61 to 2.72: m2H (i) 2.80 to 2.91: m2H (j) 3.16 to 3.27: m2H (h ) 3.87 to 4.10: m2H (f) 4.38 to 4.44: m2H (e) 4.52 to 4.77: m2H (g) 6.60: d2H J = 7. 04 (c)

[0034]

[Chemical 15] Specific rotation: [α] ²⁵ _D = -31.1 ° (C = 1, methanol)

[Example 2]

[0036]

[Chemical 16]

In a 20 ml round-bottomed flask, 4.00 g of adipoylbis-L-alanine diglycidyl ester (ABADGE) represented by the above formula (7) and 1.7 of piperazine.
23 g (1 mol) was taken, 10 ml of dimethylacetamide was added as a solvent, and the mixture was reacted at 50 ° C. for 24 hours while stirring. After the reaction is completed, the reaction solution is poured into acetone,
A polymer represented by the above formula (8) having a molecular weight of 14800 (gel permeation chromatography, converted to polystyrene) was obtained with a yield of 81%.

The obtained polymer of the formula (8) is soluble in a solvent such as water, ethanol, dimethylformamide and dimethylsulfoxide, but insoluble in other organic solvents and is amphipathic. confirmed. The optical rotation was [α] ²⁵ _D = -25.6 ° (C = 1.0, methanol).

[Brief description of drawings]

FIG. 1 shows the raw material adipoylbis-L- used in the examples.
It is an infrared absorption spectrum of alanine.

FIG. 2 is an infrared absorption spectrum of adipoylbis-L-alanine diglycidyl ester obtained in the example.

FIG. 3 is a nuclear magnetic resonance spectrum of adipoylbis-L-alanine diglycidyl ester obtained in the example.

Claims (3)

[Claims] 1. A diepoxy compound represented by the following general formula (1) or (2). [Chemical 1] (In the formula, R is an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 14 carbon atoms, and X is a hydrogen atom, a methyl group, an isopropyl group, a 2-methyl-propyl group, 3-
It is a methyl-propyl group, a 1-methylthioethyl ether group or a benzyl group. ) 2. A diamino compound represented by the following general formula (3) or (3 ′): (In the formula, R is an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 14 carbon atoms, and X is a hydrogen atom, a methyl group, an isopropyl group, a 2-methyl-propyl group, 3-
It is a methyl-propyl group, a 1-methylthioethyl ether group or a benzyl group. ) And glycidol of the following formula (4): Is reacted with dicyclohexylcarbodiimide in the presence of dimethylaminopyridine, the method for producing a diepoxy compound of the general formula (1) or (2) according to claim 1. 3. A cured product obtained by curing the diepoxy compound according to claim 1 with a diamine compound.