WO2018110670A1

WO2018110670A1 - Epoxy compound polymerization catalyst containing amidate compound

Info

Publication number: WO2018110670A1
Application number: PCT/JP2017/044976
Authority: WO
Inventors: 赳英川道; 元嘉宮城; 晋吾新田
Original assignee: 広栄化学工業株式会社
Priority date: 2016-12-15
Filing date: 2017-12-14
Publication date: 2018-06-21
Also published as: JPWO2018110670A1; JP7113758B2

Abstract

The present invention relates to: an epoxy compound polymerization catalyst which contains an amidate compound represented by formula (1); and a method for producing a polymer of an epoxy composition, which uses this epoxy compound polymerization catalyst. An epoxy compound polymerization catalyst which contains an amidate compound represented by formula (1) (wherein A represents a substituted or unsubstituted hydrocarbon group; n represents an integer of 1 or more; and D represents a nitrogen-containing organic group represented by formula (2) (wherein R¹, R², R³ and R⁴ may be the same or different, and each represents a hydrocarbon group having 1-20 carbon atoms, which may contain a heteroatom; or alternatively, some or all of the R¹, R², R³ and R⁴ moieties may combine with each other to form a ring structure; X represents a nitrogen atom, an oxygen atom or a sulfur atom; a represents 0 or 1; in cases where X represents a nitrogen atom, a represents 1; and in cases where X represents an oxygen atom or a sulfur atom, a represents 0)).

Description

Epoxy compound polymerization catalyst containing amidate compound

This application claims priority based on Japanese Patent Application No. 2016-243037 filed on December 15, 2016, the entire disclosure of which is incorporated herein by reference.

The present invention relates to an epoxy compound polymerization catalyst containing an amidate compound, and a method for producing a polymer of an epoxy composition using the same.

Among the coordinated unsaturated compounds collectively referred to as carbene species, heterocyclic carbene compounds (NHCs) have recently attracted attention for their catalytic action. As an example of using a heterocyclic carbene compound as a catalyst, it is known that it can be suitably used as a catalyst for producing a polymer having a polyether structure from an epoxy compound such as an alkylene oxide (Patent Document 1). 2).

In Patent Document 3, it is reported that a cured bisphenol A type epoxy resin produced using a heterocyclic carbene compound as a catalyst is useful as a sealing agent for electronic chips.

Generally, a heterocyclic carbene compound has a higher catalytic activity as the substituent on the nitrogen atom adjacent to the carbene is smaller, but it is unstable and storage stability is low. On the other hand, when the substituent on the nitrogen atom adjacent to the carbene of the heterocyclic carbene compound is made bulky, the catalytic activity is lowered. Therefore, as reported in Patent Documents 1, 4 and 5, a carbene precursor in which carbene is generated in a reaction system by heating is used as a catalyst instead of an unstable heterocyclic carbene compound having high catalytic activity. It is effective to use as.

Of the carbene precursors that can be used as a catalyst in the production of a polymer having a polyether structure, the most common one is a carbene carbonate adduct (Patent Documents 4 and 5). However, when the present inventors examined, the carbonic acid adduct of carbene had low catalytic activity at a low temperature of 100 ° C. (see the comparative example described later). Carbonate adducts of carbene generate CO ₂ gas when carbene is generated. From this, for example, when used as a curing catalyst for producing a cured epoxy resin, voids and the like are generated in the resulting cured epoxy resin, so that the airtightness of the cured product is expected to decrease. Carbonate adducts of carbene, such as low catalytic activity at low temperatures and CO ₂ gas generation when carbene is generated, are epoxy resin encapsulants for electronic components that require curing at low temperatures and high airtightness. It is unsuitable for use.

International Publication No. 2009/013344 Pamphlet Special table 2013-526630 gazette US Patent Application Publication No. 2007/0090532 JP-T-2015-511659 International Publication No. 2014/187782 Pamphlet

The present invention has been made in view of the above-mentioned background art, and does not generate CO ₂ gas when used as an epoxy compound polymerization catalyst, and it can be cured at a low temperature such as an epoxy resin sealing material for electronic parts. It is an object of the present invention to provide an epoxy compound polymerization catalyst that exhibits sufficient catalytic activity even in a necessary production process.

As a result of intensive studies conducted by the present inventors to solve the above problems, when the compound represented by the formula (1) is used as an epoxy compound polymerization catalyst, sufficient catalytic activity is obtained even at a curing temperature of 100 ° C. As a result, the present invention has been completed.

That is, the present invention relates to the following [1] to [6].

[1] Formula (1):

(In the formula, A is a substituted or unsubstituted hydrocarbon group. N is an integer of 1 or more. D is a formula (2):

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. In addition, R ¹ , R ² , R ³ and R ⁴ may be partially or all bonded to each other to form a ring structure, X represents a nitrogen atom, an oxygen atom or a sulfur atom, a represents 0 or 1, and X represents In the case of showing a nitrogen atom, a is 1, and when X is an oxygen atom or a sulfur atom, a is a nitrogen-containing organic group. )
The epoxy compound polymerization catalyst containing the amidate compound represented by these.

[2] The epoxy compound polymerization catalyst according to [1], wherein n is an integer of 1 to 6.

[3] The [1], wherein the amidate compound represented by the formula (1) is a compound represented by any one of the following formulas (1-1), (1-2), and (1-3) Epoxy compound polymerization catalyst.
Formula (1-1):

(Wherein R ⁵ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and D is the same as defined above.)
Formula (1-2):

(Wherein R ⁶ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and D is as defined above.)
Formula (1-3):

(In the formula, m is an integer of 0 to 4, and D is the same as above.)

[4] The nitrogen-containing organic group represented by the formula (2) is a nitrogen-containing organic group represented by any of the following formulas (2-1), (2-2), or (2-3) The epoxy compound polymerization catalyst according to any one of [1] to [3].
Formula (2-1):

(Wherein R ¹ , R ⁴ , X and a are the same as defined above, and R ⁷ and R ⁸ are the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom) .)
Formula (2-2):

(Wherein R ¹ , R ⁴ , X and a are the same as defined above; R ⁹ and R ¹⁰ are the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom; .)
Formula (2-3):

(In the formula, R ¹ , R ⁴ , X and a are the same as above; R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and each may contain a hydrogen atom or a hetero atom; To 6 hydrocarbon groups.)

[5] The epoxy compound polymerization catalyst according to any one of [1] to [4], wherein X is a nitrogen atom.

[6] A method for producing a polymer of an epoxy composition in which an epoxy composition is reacted in the presence of the epoxy compound polymerization catalyst according to any one of [1] to [5].

Epoxy compound polymerization catalyst that does not generate CO ₂ gas when used as an epoxy compound polymerization catalyst, and exhibits sufficient catalytic activity even in manufacturing processes that require curing at low temperatures, such as epoxy resin encapsulants for electronic parts. Can provide.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

In the formula (1), A is a substituted or unsubstituted hydrocarbon group. Preferably, it is a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. It is a hydrogen group.

When A is a hydrocarbon group having a substituent, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkylamino group such as a methylamino group, and a dimethylamino group. Dialkylamino group, alkoxy group such as methoxy group and ethoxy group, aryloxy group such as benzyloxy group, halogenated alkyl group such as trifluoromethyl group, nitro group, cyano group, sulfonyl group, (alkylamino) carbonylamino group , (Dialkylamino) carbonylamino group or isocyanate group. Further, the hydrocarbon group of A may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. When the hydrocarbon group of A is substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group has, for example, a group such as —O—, —NH—, and —S—. The hydrocarbon chain is interrupted by these groups.

Examples of the alkyl moiety of the alkylamino group, dialkylamino group, alkoxy group, halogenated alkyl group, (alkylamino) carbonylamino group and (dialkylamino) carbonylamino group include methyl, ethyl, n-propyl, isopropyl, n- Examples thereof include linear or branched alkyl groups having 1 to 6 carbon atoms such as butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. The alkyl group preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms.

Examples of the aryl moiety of the aryloxy group include aryl groups having 6 to 10 carbon atoms. Specific examples include a phenyl group and a naphthyl group.

The number of substituents can be 1 to 5, preferably 1 to 3, more preferably 1 or 2.

N is an integer of 1 or more, and is preferably 1 to 6, particularly preferably 1 to 4, from the viewpoint of availability. D is a nitrogen-containing organic group represented by the formula (2).

In the present invention, the amidate compound represented by formula (1) (hereinafter referred to as amidate compound (1)) is any one of formula (1-1), formula (1-2), or formula (1-3). The amidate compound represented is preferred.

In the formula (1-1), R ⁵ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group. An unsubstituted hydrocarbon group having 1 to 6 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, decyl group, dodecyl group, octadecyl group , Cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, tolyl group, allyl group and the like, preferably butyl group and phenyl group.

When R ⁵ is a substituted hydrocarbon group having 1 to 20 carbon atoms, examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and alkylamino groups such as methylamino group. Group, dialkylamino group such as dimethylamino group, alkoxy group such as methoxy group and ethoxy group, aryloxy group such as benzyloxy group, alkyl halide group such as trifluoromethyl group, nitro group, cyano group, sulfonyl group, (Alkylamino) carbonylamino group, (dialkylamino) carbonylamino group, isocyanate group and the like can be mentioned. Further, the hydrocarbon group of R ⁵ may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. When the hydrocarbon group of R ⁵ is substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group has, for example, a group such as —O—, —NH—, and —S—. However, the hydrocarbon chain is interrupted by these groups.

Examples of the alkyl moiety of the alkylamino group, dialkylamino group, alkoxy group, halogenated alkyl group, (alkylamino) carbonylamino group and (dialkylamino) carbonylamino group include methyl, ethyl, n-propyl, isopropyl, n- Examples thereof include linear or branched alkyl groups having 1 to 6 carbon atoms such as butyl, isobutyl, s-butyl, t-butyl and n-pentyl. The alkyl group preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms.

In formula (1-1), D is the same as described above.

In the formula (1-2), R ⁶ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Specifically, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dodecylene group, octadecylene group, cyclohexylene group, phenylene group, naphthylene group Among them, a phenylene group and a butylene group are preferable.

When R ⁶ is a substituted hydrocarbon group having 1 to 20 carbon atoms, examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and alkylamino groups such as methylamino group. Group, dialkylamino group such as dimethylamino group, alkoxy group such as methoxy group and ethoxy group, aryloxy group such as benzyloxy group, alkyl halide group such as trifluoromethyl group, nitro group, cyano group, sulfonyl group, (Alkylamino) carbonylamino group, (dialkylamino) carbonylamino group, isocyanate group and the like can be mentioned. Further, the hydrocarbon group of R ⁶ may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. When the hydrocarbon group of R ⁶ is substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group has, for example, a group such as —O—, —NH—, and —S—. However, the hydrocarbon chain is interrupted by these groups.

In formula (1-2), D is the same as above.

In the formula (1-3), m is an integer of 0 to 4. D is the same as above.

In the formula (2), R ¹ , R ² , R ³ and R ⁴ are the same or different and are hydrocarbon groups having 1 to 20 carbon atoms which may contain a hetero atom. R ¹ , R ² , R ³ and R ⁴ may be partly or all bonded to each other to form a ring structure. For example, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ² , R ³ and R ⁴ , or R ¹ , R ² , R ³ and R ⁴ are , May be bonded to each other to form a ring structure. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, and t-butyl. Group, pentyl group, hexyl group, allyl group, benzyl group, cyclohexyl group, adamantyl group, phenyl group, 2,6-diisopropylphenyl group, 2,4,6-trimethylphenyl group, 2-methoxyethyl group, 2-ethoxy Examples include an ethyl group and a 2- (dimethylamino) ethyl group. A methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, and a 2,4,6-trimethylphenyl group are preferable, and a methyl group or an ethyl group is particularly preferable. X is a nitrogen atom, oxygen atom or sulfur atom, preferably a nitrogen atom.

In formula (2), a represents 0 or 1. When X represents a nitrogen atom, a represents 1, and when X represents an oxygen atom or a sulfur atom, a represents 0. That is, the formula (2) is a nitrogen-containing organic group represented by any of the following formulas (2a), (2b), or (2c). In other words, when X represents an oxygen atom or a sulfur atom, a represents 0 and R ¹ is absent.

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above).

In the present invention, from the viewpoint of availability, it is preferable that R ² and R ³ of the nitrogen-containing organic group represented by the formula (2) are bonded to each other to form a ring structure. The nitrogen-containing organic group forming the ring is preferably a nitrogen-containing organic group represented by any one of the formulas (2-1), (2-2), or (2-3), and particularly preferably the formula This is a nitrogen-containing organic group represented by (2-1).

In the formula (2-1), R ¹ , R ⁴ , X and a are the same as described above. R ⁷ and R ⁸ are the same or different and each represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom, preferably a hydrogen atom. Examples of the hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, Examples include a hexyl group, a cyclohexyl group, a phenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2- (dimethylamino) ethyl group, and a methyl group is preferable.

Specific examples of the nitrogen-containing organic group represented by the formula (2-1) include 1,3-dimethylimidazolium group, 1-ethyl-3-methylimidazolium group, 1-methyl-3-propylimidazolium. 1-methyl-3-isopropylimidazolium group, 1-butyl-3-methylimidazolium group, 1-tert-butyl-3-methylimidazolium group, 1-methyl-3-pentylimidazolium group, 1- Hexyl-3-methylimidazolium group, 1-heptyl-3-methylimidazolium group, 1-methyl-3-octylimidazolium group, 1-methyl-3-nonylimidazolium group, 1-decyl-3-methylimidazole Rium group, 1-allyl-3-methylimidazolium group, 1-benzyl-3-methylimidazolium group, 1- (2-methoxyethyl)- -Methylimidazolium group, 1- (2-ethoxyethyl) -3-methylimidazolium group, 1- (2-dimethylaminoethyl) -3-methylimidazolium group, 1,3,4,5-tetramethylimidazole Lilium group,

3-methyloxazolium group, 3,5-dimethyloxazolium group, 3,4,5-trimethyloxazolium group,

Examples include 3-methylthiazolium group, 3,4-dimethylthiazolium group, 3,5-dimethylthiazolium group, 3,4,5-trimethylthiazolium group, and preferably 1,3 -Dimethylimidazolium group, 1-ethyl-3-methylimidazolium group, 1-methyl-3-propylimidazolium group, 1-butyl-3-methylimidazolium group, particularly preferably 1,3-dimethyl It is an imidazolium group.

In the formula (2-2), R ¹ , R ⁴ , X and a are the same as described above. R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom, preferably a hydrogen atom. Examples of the hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, Examples include a hexyl group, a cyclohexyl group, a phenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2- (dimethylamino) ethyl group, and a methyl group is preferable.

Specific examples of the nitrogen-containing organic group represented by the formula (2-2) include 1,3-dimethylimidazolinium group, 1-ethyl-3-methylimidazolinium group, and 1-methyl-3-propyl. Imidazolinium group, 1-butyl-3-methylimidazolinium group, 1-methyl-3-pentylimidazolinium group, 1-hexyl-3-methylimidazolinium group, 1-heptyl-3-methylimidazolium Nium group, 1-methyl-3-octylimidazolinium group, 1-methyl-3-nonylimidazolinium group, 1-decyl-3-methylimidazolinium group, 1-allyl-3-methylimidazolinium group 1-benzyl-3-methylimidazolinium group, 1- (2-methoxyethyl) -3-methylimidazolinium group, 1- (2-ethoxyethyl) -3-methylimid Zoriniumu group, 1- (2-dimethylaminoethyl) -3-methyl-imidazolinium group, 1,3,4,5-tetramethyl imidazolinium group,

3-methyloxazolinium group, 3,4-dimethyloxazolinium group, 3,5-dimethyloxazolinium group, 3,4,5-trimethyloxazolinium group,

Examples include 3-methylthiazolinium group, 3,4-dimethylthiazolinium group, 3,5-dimethylthiazolinium group, 3,4,5-trimethylthiazolinium group, and preferably 1,3 -Dimethylimidazolinium group, 1-ethyl-3-methylimidazolinium group, 1-methyl-3-propylimidazolinium group, 1-butyl-3-methylimidazolinium group, particularly preferably 1 , 3-dimethylimidazolinium group.

In the formula (2-3), R ¹ , R ⁴ , X and a are the same as described above. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom, preferably a hydrogen atom. Examples of the hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, Examples include a hexyl group, a cyclohexyl group, a phenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2- (dimethylamino) ethyl group, and a methyl group is preferable.

Specific examples of the nitrogen-containing organic group represented by the formula (2-3) include 1,3-dimethylbenzimidazolium group, 1-ethyl-3-methylbenzimidazolium group, and 1-methyl-3-propyl. Benzimidazolium group, 1-butyl-3-methylbenzimidazolium group, 1-methyl-3-pentylbenzimidazolium group, 1-hexyl-3-methylbenzimidazolium group, 1-heptyl-3-methylbenzimidazole 1-methyl-3-octylbenzimidazolium group, 1-methyl-3-nonylbenzimidazolium group, 1-decyl-3-methylbenzimidazolium group, 1-allyl-3-methylbenzimidazolium group 1-benzyl-3-methylbenzimidazolium group, 1,3,6-trimethylbenzimidazolium group, Chill-3,6-dimethyl-benzimidazolium group, 1,3,6,7- tetramethyl-benzimidazolium group, 1,3-dibenzyl-6,7-dimethyl-benzimidazolium group,

3-methylbenzoxazolium group,

A 3-methylbenzothiazolium group, etc., preferably 1,3-dimethylbenzimidazolium group, 1-ethyl-3-methylbenzimidazolium group, 1-methyl-3-propylbenzoimidazolium group, A 1-butyl-3-methylbenzimidazolium group, particularly preferably a 1,3-dimethylbenzimidazolium group.

In the present specification, unless otherwise specified, descriptions of propyl, butyl, pentyl, hexyl, hexyl, heptyl, octyl, nonyl, decyl and the like are n-propyl, n-butyl, n-pentyl, n- A linear alkyl group such as hexyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the like is shown.

Specific examples of the amidate compound (1) are shown below, but the present invention is not limited thereto. In the following specific examples, Et represents an ethyl group, Pr represents an n-propyl group, and Bu represents an n-butyl group.

(In formula (1-3-1), m is the same as above.)

The amidate compound (1) is preferably a compound represented by the formula (1-1-20) or (1-1-40).

When the amidate compound (1) of the present invention has an isomer such as an optical isomer, a stereoisomer, a positional isomer, etc., any mixture of isomers may be used unless specified. Included in the compounds of the present invention. For example, when the amidate compound (1) has an optical isomer, the optical isomer resolved from the racemate may also be included in the amidate compound (1). Each of these isomers can be obtained as a single compound by a known synthesis method or separation method (concentration, solvent extraction, column chromatography, recrystallization, etc.).

Moreover, it is considered that the amidate compound (1) is isomerized by resonance. For example, in the compound represented by the formula (1), when X is a nitrogen atom, it is considered that the following resonance structure can be taken.

(In the formula, A, n, R ¹ , R ² , R ³ and R ⁴ are the same as above.)

Although the manufacturing method of the amidate compound (1) of this invention is not specifically limited, For example, it can manufacture from the following process 1 and 2.

Step 1 Nitrogen-containing organic compound represented by the following formula (3) (hereinafter referred to as nitrogen-containing organic compound (3)) and dialkyl carbonate represented by formula (6) (hereinafter referred to as dialkyl carbonate (6)) The manufacturing process of the carboxylate compound (henceforth a carboxylate compound (4)) represented by following formula (4) with which is made to react.

Formula (3):

(Wherein R ¹ , R ² , R ³ , X and a are the same as above)

Formula (6):

(In the formula, R ⁴ is the same as above.)

Formula (4):

(Wherein R ¹ , R ² , R ³ , R ⁴ , X and a are the same as above)
Process 2 The process with which the carboxylate compound (4) and the isocyanate compound (henceforth an isocyanate compound (5)) represented by following formula (5) are made to react.

Formula (5):

(In the formula, A and n are the same as above.)

First, step 1 will be described.

In formula (3), R ¹ , R ² , R ³ , X and a are the same as described above. In the present invention, from the viewpoint of easy availability, R ² and R ³ in Formula (3) are preferably bonded to each other to form a ring structure. The nitrogen-containing organic group (3) forming a ring is preferably a group consisting of a nitrogen-containing organic group represented by any one of formula (3-1), formula (3-2) or formula (3-3) The nitrogen-containing organic compound represented by the formula (3-1) is particularly preferable.

Formula (3-1):

(Wherein R ¹ , R ⁷ , R ⁸ , X and a are the same as above)

Formula (3-2):

(Wherein R ¹ , R ⁹ , R ¹⁰ , X and a are the same as above)

Formula (3-3):

(Wherein R ¹ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , X and a are the same as above)

In formula (3-1), R ¹ , R ⁷ , R ⁸ , X and a are the same as above. Specific examples of the nitrogen-containing compound represented by the formula (3-1) include 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-isopropylimidazole, 1-butylimidazole, 1-tert-butylimidazole. 1-pentylimidazole, 1-hexylimidazole, 1-heptylimidazole, 1-octylimidazole, 1-nonylimidazole, 1-decylimidazole, 1-allylimidazole, 1-benzylimidazole, 1- (2-methoxyethyl) imidazole 1- (2-ethoxyethyl) -imidazole, 1- (2-dimethylaminoethyl) imidazole, 1,4,5-trimethylimidazole

Oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole,

Examples include thiazole, 4-methylthiazole, 5-methylthiazole, 4,5-dimethylthiazole, and the like, preferably 1-methylimidazole, 1-ethylimidazole, 1propylimidazole, 1-butylimidazole, particularly preferably. 1-methylimidazole.

In formula (3-2), R ¹ , R ⁹ , R ¹⁰ , X and a are the same as described above. Specific examples of the nitrogen-containing compound represented by the formula (3-2) include 1-methylimidazoline, 1-ethylimidazoline, 1-propylimidazoline, 1-isopropylimidazoline, 1-butylimidazoline, 1-tert-butylimidazoline. 1-pentylimidazoline, 1-hexyl imidazoline, 1-heptyl imidazoline, 1-octyl imidazoline, 1-nonyl imidazoline, 1-decyl imidazoline, 1-allyl imidazoline, 1-benzyl imidazoline, 1- (2-methoxyethyl) imidazoline 1- (2-ethoxyethyl) imidazoline, 1- (2-dimethylaminoethyl) imidazoline, 1,4,5-trimethylimidazoline

Oxazoline, 5-methyloxazoline, 4,5-dimethyloxazoline,

Examples include thiazoline, 4-methylthiazoline, 5-methylthiazoline, 4,5-dimethylthiazoline, preferably 1-methylimidazoline, 1-ethylimidazoline, 1-propylimidazoline, 1-butylimidazoline. Is 1-methylimidazoline.

In formula (3-3), R ¹ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , X and a are the same as described above. Specific examples of the nitrogen-containing compound represented by the formula (3-3) include 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-propylbenzimidazole, 1-butylbenzimidazole, 1-pentylbenzimidazole, 1 -Hexylbenzimidazole, 1-heptylbenzimidazole, 1-octylbenzimidazole, 1-nonylbenzimidazole, 1-decylbenzimidazole, 1-allylbenzimidazole, 1-benzylbenzimidazole, 1,6-dimethylbenzimidazole, 1 -Acetyl-6-methylbenzimidazole, 1,6,7-trimethylbenzimidazole,

Examples include benzoxazole, benzothiazole, and the like, preferably 1-methylbenzimidazole, 1-ethyllbenzimidazole, 1-propylbenzimidazole, 1-butylbenzimidazole, and particularly preferably 1-methylbenzimidazole. is there.

In the formula (4), R ¹ , R ² , R ³ , R ⁴ , X and a are the same as described above. In the present invention, it is preferable that R ² and R ³ of the carboxylate compound represented by the formula (4) are bonded to each other to form a ring structure. The carboxylate compound (4) forming a ring is preferably selected from the group consisting of carboxylate compounds represented by any one of formula (4-1), formula (4-2) or formula (4-3) And at least one carboxylate compound represented by formula (4-1) is particularly preferred.

Formula (4-1):

(Wherein R ¹ , R ⁴ , R ⁷ , R ⁸ , X and a are the same as above)

Formula (4-2):

(Wherein R ¹ , R ⁴ , R ⁹ , R ¹⁰ , X and a are the same as above)

Formula (4-3):

(Wherein R ¹ , R ⁴ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , X and a are the same as above)

In formula (4-1), R ¹ , R ⁴ , R ⁷ , R ⁸ , X and a are the same as described above. Specific examples of the carboxylate compound represented by the formula (4-1) include 1,3-dimethylimidazolium-2-carboxylate, 1-ethyl-3-methylimidazolium-2-carboxylate, 1-methyl -3-propylimidazolium-2-carboxylate, 1-methyl-3-isopropylimidazolium-2-carboxylate, 1-butyl-3-methylimidazolium-2-carboxylate, 1-tert-butyl-3- Methylimidazolium-2-carboxylate, 1-methyl-3-pentylimidazolium-2-carboxylate, 1-hexyl-3-methylimidazolium-2-carboxylate, 1-heptyl-3-methylimidazolium-2 -Carboxylate, 1-methyl-3-octylimidazolium-2-ca Boxylate, 1-methyl-3-nonylimidazolium-2-carboxylate, 1-decyl-3-methylimidazolium-2-carboxylate, 1-allyl-3-methylimidazolium-2-carboxylate, 1-benzyl -3-Methylimidazolium-2-carboxylate, 1- (2-methoxyethyl) -3-methylimidazolium-2-carboxylate, 1- (2-ethoxyethyl) -3-methylimidazolium-2-carboxylate 1- (2-dimethylaminoethyl) -3-methylimidazolium-2-carboxylate,

3-methyloxazolium-2-carboxylate, 3,5-dimethyloxazolium-2-carboxylate, 3,4,5-trimethyloxazolium-2-carboxylate,

3-methylthiazolium-2-carboxylate, 3,4-dimethylthiazolium-2-carboxylate, 3,5-dimethylthiazolium-2-carboxylate, 3,4,5-trimethylthiazolium -2-carboxylate, and the like, preferably 1,3-dimethylimidazolium-2-carboxylate, 1-ethyl-3-methylimidazolium-2-carboxylate, 1-methyl-3-propylimidazole Rium-2-carboxylate, 1-butyl-3-methylimidazolium-2-carboxylate, particularly preferably 1,3-dimethylimidazolium-2-carboxylate.

In formula (4-2), R ¹ , R ⁴ , R ⁹ , R ¹⁰ , X and a are the same as described above. Specific examples of the carboxylate compound represented by the formula (4-2) include 1,3-dimethylimidazolinium-2-carboxylate, 1-ethyl-3-methylimidazolinium-2-carboxylate, -Methyl-3-propylimidazolinium-2-carboxylate, 1-butyl-3-methylimidazolinium-2-carboxylate, 1-methyl-3-pentylimidazolinium-2-carboxylate, 1-hexyl -3-Methylimidazolinium-2-carboxylate, 1-heptyl-3-methylimidazolinium-2-carboxylate, 1-methyl-3-octylimidazolinium-2-carboxylate, 1-methyl-3 -Nonylimidazolinium-2-carboxylate, 1-decyl-3-methylimidazolinium-2 Carboxylate, 1-allyl-3-methylimidazolinium-2-carboxylate, 1-benzyl-3-methylimidazolinium-2-carboxylate, 1- (2-methoxyethyl) -3-methylimidazolinium -2-carboxylate, 1- (2-ethoxyethyl) -3-methylimidazolinium-2-carboxylate, 1- (2-dimethylaminoethyl) -3-methylimidazolinium-2-carboxylate,

3-methyloxazolinium-2-carboxylate, 3,4-dimethyloxazolinium-2-carboxylate, 3,5-dimethyloxazolinium-2-carboxylate, 3,4,5-trimethyloxazolinium -2-carboxylate,

3-methylthiazolinium-2-carboxylate, 3,4-dimethylthiazolinium-2-carboxylate, 3,5-dimethylthiazolinium-2-carboxylate, 3,4,5-trimethylthiazolinium -2-carboxylate and the like, preferably 1,3-dimethylimidazolinium-2-carboxylate, 1-ethyl-3-methylimidazolinium-2-carboxylate, 1-methyl-3-propyl Among them, imidazolinium-2-carboxylate and 1-butyl-3-methylimidazolinium-2-carboxylate are preferable, and 1,3-dimethylimidazolinium-2-carboxylate is particularly preferable.

In formula (4-3), R ¹ , R ⁴ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , X and a are the same as above. Specific examples of the carboxylate compound represented by the formula (4-3) include 1,3-dimethylbenzimidazolium-2-carboxylate, 1-ethyl-3-methylbenzimidazolium-2-carboxylate, -Methyl-3-propylbenzimidazolium-2-carboxylate, 1-butyl-3-methylbenzimidazolium-2-carboxylate, 1-methyl-3-pentylbenzimidazolium-2-carboxylate, 1-hexyl -3-Methylbenzimidazolium-2-carboxylate, 1-heptyl-3-methylbenzimidazolium-2-carboxylate, 1-methyl-3-octylbenzimidazolium-2-carboxylate, 1-methyl-3 -Nonylbenzimidazolium-2-carboxylate, 1-de 3-methylbenzimidazolium-2-carboxylate, 1-allyl-3-methylbenzimidazolium-2-carboxylate, 1-benzyl-3-methylbenzimidazolium-2-carboxylate, 1,3 6-trimethylbenzimidazolium-2-carboxylate, 1-acetyl-3,6-dimethylbenzimidazolium-2-carboxylate, 1,3,6,7-tetramethylbenzimidazolium-2-carboxylate, 1 , 3-dibenzyl-6,7-dimethylbenzimidazolium-2-carboxylate,

3-methylbenzoxazolium-2-carboxylate,

3-methylbenzothiazolium-2-carboxylate and the like, preferably 1,3-dimethylbenzimidazolium-2-carboxylate, 1-ethyl-3-methylbenzimidazolium-2-carboxylate, 1-methyl-3-propylbenzimidazolium-2-carboxylate, 1-butyl-3-methylbenzimidazolium-2-carboxylate, particularly preferably 1,3-dimethylbenzimidazolium-2-carboxylate Rate.

In formula (6), R ⁴ is the same as described above. Specific examples of the dialkyl carbonate (6) include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, etc., preferably dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, especially Preferred is dimethyl carbonate.

The amount of dialkyl carbonate (6) used is usually 1 mol or more, preferably 1 to 6 mol, per 1 mol of the nitrogen-containing organic compound (3).

In Step 1, the optimum reaction temperature varies depending on the raw materials and solvents used, but is usually room temperature or higher, preferably 20 to 200 ° C.

In step 1, a solvent may or may not be used. When a solvent is used, the solvent to be used is not particularly limited as long as it does not affect the reaction. Specific examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 1-methoxy-2-propanol and ethoxyethanol, polyol solvents such as ethylene glycol, propylene glycol and diethylene glycol, and dipropylene glycol. Mono n-butyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol mono n-propyl ether, dipropylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, tripropylene glycol mono n-butyl ether, propylene Glycol monomethyl ether, diethylene glycol monoethyl ether, etc. Ruki ether solvent and the like, preferably an alcohol solvent, particularly preferably methanol. The amount of the solvent used is usually 50 parts by weight or less, preferably 10 parts by weight or less, per 1 part by weight of the nitrogen-containing organic compound (3).

In step 1, if necessary, the reaction may be performed in an inert gas atmosphere that does not affect the reaction of nitrogen, argon, helium, or the like.

After completion of the reaction, the carboxylate compound (4) is isolated by removing the solvent, dialkyl carbonate (6), nitrogen-containing organic compound (3) and the like by a known method such as concentrating the reaction solution.

Next, step 2 will be described.

In formula (5), A and n are the same as described above. Isocyanate compound (5) is preferably at least one selected from the group consisting of isocyanate compounds represented by any of formula (5-1), formula (5-2) or formula (5-3), More preferred is an isocyanate compound represented by the formula (5-1).

Formula (5-1):

(Wherein R ⁵ is the same as defined above.)

Formula (5-2):

(Wherein R ⁶ is the same as described above.)

Formula (5-3):

(Wherein m is the same as above)

Specific examples of the isocyanate compound (5) are shown below, but the present invention is not limited thereto. In the following specific examples, Et represents an ethyl group, Pr represents an n-propyl group, and Bu represents an n-butyl group.

(Wherein m is the same as above)

The isocyanate compound (5) is preferably a compound represented by the formula (5-1-20) or (5-1-40).

In step 2, the carboxylate compound (4) is usually reacted in an amount of 0.8 mol or more, preferably 1 to 3 mol, per 1 mol of the isocyanate group contained in the isocyanate compound (5).

In step 2, a solvent may or may not be used. Examples of the solvent include aromatic hydrocarbons such as toluene, benzene, and xylene, and aliphatic hydrocarbons such as methylcyclohexane, cyclohexane, n-hexane, n-heptane, and octane, preferably aromatic hydrocarbons. Yes, particularly preferably toluene. Two or more kinds of solvents can be mixed and used as necessary. The usage-amount of a solvent is 50 parts weight or less normally with respect to 1 weight part of carboxylate compound (4), Preferably it is 10 parts weight or less.

Although the reaction temperature is not particularly limited, it may be not higher than the boiling point of the solvent, and is usually 10 ° C. or higher, preferably 40 to 140 ° C., particularly preferably 80 to 120 ° C.

After completion of the reaction, the amidate compound (1) can be obtained by concentrating the reaction solution and distilling off the solvent. The obtained amidate compound (1) can be purified by a method such as recrystallization.

The epoxy compound polymerization catalyst of the present invention comprises the amidate compound (1) as an active ingredient, and can be used alone as an epoxy compound polymerization catalyst, or two or more amidate compounds ( 1) can also be mixed and used. Moreover, it can also mix and use in combination with a well-known epoxy compound polymerization catalyst.

Known epoxy compound polymerization catalysts include, for example, amine compounds, polyamines, carboxylic acid-modified polyamines, epoxy-modified polyamines (epoxy adducts), Michael addition polyamines, amine-Mannich reactants, urea or thiourea and amine reactants, ketimines And other modified polyamines such as imidazoles, boron trifluoride-amine complexes, triphenylphosphine, phosphonium salts, dicyandiamide, acid hydrazide, dimethylurea derivatives, acid anhydrides, and novolacs. In particular, compounds such as aromatic amine compounds such as guanamines and melanin, dicyandiamide, acid hydrazide, acid anhydrides, phenols, and the like can be used as the activation accelerator for these polymerization catalysts by the amidate compound (1). In order to act, since it is thought that the polymerization reaction of an epoxy composition is accelerated | stimulated more as a result, it is preferable.

The polymer of the epoxy composition can be produced by reacting the epoxy composition in the presence of the epoxy compound polymerization catalyst of the present invention.

In the present invention, the epoxy composition contains at least one epoxy compound. Examples of the epoxy compound include, but are not limited to, alkylene oxide such as ethylene oxide and propylene oxide, monofunctional glycidyl ether such as phenyl glycidyl ether, allyl glycidyl ether, and butyl glycidyl ether, bisphenol A type epoxy resin, Bisphenol F type epoxy resin, polyphenols such as catechol and resorcin, polyglycidyl ether obtained by reacting a polyhydric alcohol such as glycerin and polyethylene glycol with epichlorohydrin, or 3,4-epoxycyclohexylmethyl-3,4 -Cycloaliphatic epoxy resin represented by epoxycyclohexanecarboxylate, or hydroxycarboxylic acid such as p-oxybenzoic acid and epichlorohydrin Glycidyl ether esters obtained by reaction, polyglycidyl esters obtained from polycarboxylic acids such as phthalic acid and terephthalic acid, or glycidyl amine type epoxy resins obtained from 4,4-diaminodiphenylmethane, m-aminophenol, etc. Furthermore, a phenol novolac type epoxy resin or the like is used. These epoxy compounds may be used alone or in combination of two or more.

The epoxy composition of the present invention can be blended with an inorganic filler, a coupling agent, a colorant and the like as required. Examples of the inorganic filler include calcium carbonate, barium sulfate, fused silica, crystalline silica, glass filler, aluminum hydroxide, magnesium hydroxide, and alumina. Examples of the coupling agent include 3-glycidoxypropyl. Examples include trimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane. Examples of the colorant include carbon black and titanium oxide.

Furthermore, the epoxy composition of the present invention can contain a thixotropic agent as necessary. Examples of the thixotropic agent include Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Dispalon C-308, Disparon 4110, Disparon 4300, Disparon 6500, Disparon 6600, and the like manufactured by Nippon Aerosil Co., Ltd.

As an epoxy composition, when two or more types of epoxy compounds are mixed and used together, or when an inorganic filler, a coupling agent, a colorant, or a thixotropic agent is blended, a general stirring method is used as a method for preparing an epoxy composition. Mixing equipment and mixing conditions apply. Examples of the apparatus used include a mixing roll, a dissolver, a planetary mixer, a kneader, and an extruder. As mixing conditions, epoxy resin or the like may be dissolved and / or reduced in viscosity, and heated to improve stirring and mixing efficiency. Further, cooling may be performed as necessary in order to remove frictional heat generation, reaction heat generation, and the like. The time for stirring and mixing may be determined if necessary, and is not particularly limited.

The amount of the epoxy compound polymerization catalyst of the present invention is such that the amidate compound (1) is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy compound contained in the epoxy composition. When only one kind or two or more kinds of amidate compounds (1) are used as an epoxy compound polymerization catalyst, 3 to 10 parts by weight of the amidate compound (1) is 100 parts by weight of the epoxy compound contained in the epoxy composition. It is preferable to do. When the amidate compound (1) and another known epoxy compound polymerization catalyst are used in combination as an epoxy compound polymerization catalyst, the amidate compound (1) is 0 with respect to 100 parts by weight of the epoxy compound contained in the epoxy composition. An amount of 5 to 5 parts by weight is preferred.

In the present invention, as a procedure for producing a polymer of an epoxy composition, polymerization is usually performed by mixing an epoxy compound polymerization catalyst and an epoxy composition and heating the resulting mixture. As a mixing method of the epoxy compound polymerization catalyst and the epoxy composition, a general stirring and mixing apparatus and mixing conditions are applied. Examples of the apparatus used include a mixing roll, a dissolver, a planetary mixer, a kneader, and an extruder. As mixing conditions, epoxy resin or the like may be dissolved and / or reduced in viscosity, and heated to improve stirring and mixing efficiency. Further, cooling may be performed as necessary in order to remove frictional heat generation, reaction heat generation, and the like. The time for stirring and mixing may be determined if necessary, and is not particularly limited.

When mixing two or more types of epoxy compounds as an epoxy composition, or when blending inorganic fillers, coupling agents, colorants, or thixotropic agents, an epoxy compound polymerization catalyst and a desired epoxy compound are necessary. Depending on the situation, an inorganic filler, a coupling agent, a colorant, etc. and a thixotropic agent are placed in a stirring and mixing device and stirred to simultaneously prepare the epoxy composition and mix the epoxy compound polymerization catalyst and the epoxy composition. It can also be done.

Since the amidate compound (1) used as the epoxy compound polymerization catalyst of the present invention is a heat-latent catalyst that is relatively stable at room temperature and functions by heating, the reaction according to the method for producing a polymer of an epoxy composition Is preferably carried out in the range of 80 ° C. to 180 ° C. More preferably, it is 100 ° C to 140 ° C.

The polymer of the epoxy composition can be obtained by the method described above. The polymer of the epoxy composition obtained by the method of the present invention can be used for paints, adhesives, sealing materials and the like.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these at all. In the examples, ¹ H-NMR was measured at 400 MHz using AV400 manufactured by Bruker Corporation.

[Synthesis Example 1] Synthesis of DMIm-CO ₂

A 500 mL autoclave purged with nitrogen was charged with 82.1 g (1.0 mol) of 1-methylimidazole, 119.8 g (1.0 mol) of dimethyl carbonate and 83.1 g of methanol, and the resulting mixture was heated at an internal temperature of 120 ° C. for 22 hours. Stir. The resulting reaction mixture was cooled to 25 ° C. and concentrated under reduced pressure to obtain a white solid. The obtained white solid was washed with toluene and dried under reduced pressure to obtain 47.8 g of the compound represented by the above formula (DMIm-CO ₂ ) (yield 34%). The results of ¹ H-NMR analysis of DMIm-CO ₂ are shown below.

¹ H-NMR (CD ₃ OD) δ (ppm) = 7.46 (s, 2H), 4.08 (s, 6H)

[Synthesis Example 2] Synthesis of DMIm-PI

A three-necked flask purged with nitrogen was charged with 3.0 g (21 mmol) of DMIm-CO ₂ obtained in Synthesis Example 1, 100 mL of toluene, and 2.5 g (21 mmol) of phenyl isocyanate, and the resulting mixture had an internal temperature of 110 ° C. For 3 hours. The obtained reaction mixture was cooled to 25 ° C. and concentrated under reduced pressure to obtain 5.3 g (pure content: 4.9 g) of the compound represented by the above formula (DMIm-PI) (yield 97%). The results of ¹ H-NMR analysis of DMIm-PI are shown below.

¹ H-NMR (CD ₃ OD) δ (ppm) = 7.45 (m, 2H), 7.35-7.27 (m, 4H), 7.00 (m, 1H), 3.98 (s , 6H)

[Synthesis Example 3] Synthesis of DMIm-pClPI

A three-necked flask purged with nitrogen was charged with 3.0 g (21 mmol) of DMIm-CO ₂ obtained in Synthesis Example 1, 100 mL of toluene, and 3.3 g (21 mmol) of p-chlorophenyl isocyanate, and the resulting mixture was cooled to an internal temperature. Stir at 110 ° C. for 3 hours. The obtained reaction mixture was cooled to 25 ° C. and filtered, and the resulting yellow solid was dried under reduced pressure to obtain 4.6 g of a compound represented by the above formula (DMIm-pClPI) (yield 88%). . The results of ¹ H-NMR analysis of DMIm-pClPI are shown below.

¹ H-NMR (CD ₃ OD) δ (ppm) = 7.47 (s, 2H), 7.39 (m, 2H), 7.25 (m, 2H), 3.99 (s, 6H)

Examples 1 and 2 and Comparative Example 1 [Evaluation of curability at each temperature]
As shown in Table 1, the degree of cure at 100 ° C., 120 ° C., and 140 ° C. of the epoxy composition in the presence of various epoxy compound polymerization catalysts was measured with a differential scanning calorimeter (DSC-7020 manufactured by Hitachi High-Tech Science Co., Ltd.). evaluated.
Measurement of calorific value A (J / g) 1 g of bisphenol A type epoxy resin (AER-260, manufactured by Asahi Kasei Co., Ltd.) was taken, and 5 parts by weight or 10 parts by weight of the epoxy compound polymerization catalyst shown in Table 1 was added thereto, Stirred uniformly. About 5 mg of the resulting mixture was weighed and heated from −30 ° C. to 300 ° C. at a heating rate of 10 ° C./min with a differential scanning calorimeter to measure the total calorific value. A calorific value per unit weight (denoted as calorific value A in Table 1) was calculated from the total calorific value obtained.
・ Measurement of calorific value B (J / g) About 5 mg of the mixture prepared in the same manner as the calorific value A was measured with a differential scanning calorimeter at temperatures from −30 ° C. to 100 ° C., 120 ° C. and 140 ° C. Was heated at a rate of temperature increase of 10 ° C./min until the predetermined temperature was reached, and held at that temperature for 1 hour. The calorific value per unit weight was calculated from the total calorific value while maintaining the temperature, and the calorific value per unit weight when cured for 1 hour at each temperature (referred to as calorific value B in Table 1). .
The degree of cure at each temperature was B / A × 100 (%). The results are shown in Table 1.

As shown in Table 1, when DMIm-PI and DMIm-pClPI were used as the epoxy compound polymerization catalyst, both showed a high degree of cure at 100 ° C. On the other hand, it was found that when DMIm-CO ₂ was used as an epoxy compound polymerization catalyst, the curability at 100 ° C. was low and it could not be cured sufficiently at a low temperature. Further, when DMIm-PI and DMIm-pClPI were used as the epoxy compound polymerization catalyst, a high degree of cure was exhibited even at 120 ° C. and 140 ° C.

Claims

Formula (1):

(In the formula, A is a substituted or unsubstituted hydrocarbon group. N is an integer of 1 or more. D is a formula (2):

(Wherein R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. In addition, R 1 , R 2 , R 3 and R 4 may be partially or all bonded to each other to form a ring structure, X represents a nitrogen atom, an oxygen atom or a sulfur atom, a represents 0 or 1, and X represents In the case of showing a nitrogen atom, a is 1, and when X is an oxygen atom or a sulfur atom, a is a nitrogen-containing organic group. )
The epoxy compound polymerization catalyst containing the amidate compound represented by these.
The epoxy compound polymerization catalyst according to claim 1, wherein n is an integer of 1 to 6.
The epoxy compound according to claim 1, wherein the amidate compound represented by the formula (1) is a compound represented by any one of the following formulas (1-1), (1-2), and (1-3): Polymerization catalyst.
Formula (1-1):

(Wherein R 5 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and D is the same as defined above.)
Formula (1-2):

(Wherein R 6 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and D is as defined above.)
Formula (1-3):

(In the formula, m is an integer of 0 to 4, and D is the same as above.)
The nitrogen-containing organic group represented by the formula (2) is a nitrogen-containing organic group represented by any one of the following formulas (2-1), (2-2), and (2-3) 4. The epoxy compound polymerization catalyst according to any one of 1 to 3.
Formula (2-1):

(Wherein R 1 , R 4 , X and a are the same as defined above, and R 7 and R 8 are the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom) .)
Formula (2-2):

(Wherein R 1 , R 4 , X and a are the same as defined above; R 9 and R 10 are the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom; .)
Formula (2-3):

(In the formula, R 1 , R 4 , X and a are the same as above; R 11 , R 12 , R 13 and R 14 are the same or different and each may contain a hydrogen atom or a hetero atom; To 6 hydrocarbon groups.)
The epoxy compound polymerization catalyst according to any one of claims 1 to 4, wherein X is a nitrogen atom.
A method for producing a polymer of an epoxy composition in which an epoxy composition is reacted in the presence of the epoxy compound polymerization catalyst according to any one of claims 1 to 5.