JP7005254B2 - Amidate polymer and a catalyst for producing polyurethane containing the amidate polymer - Google Patents

Description

The present invention relates to an amidate polymer, a catalyst for producing polyurethane containing the amidate polymer, and a method for producing polyurethane using the same.

Polyurethane is produced by reacting a polyol and an organic polyisocyanate in the presence of a catalyst and, if necessary, additives such as a foaming agent, a surfactant and a cross-linking agent. Polyurethane is widely used in automobiles, construction, home appliances, heavy-duty anticorrosion, plastic paints, adhesives, etc. because it has excellent adhesion to a base material, flexibility, and weather resistance. As the catalyst used in the production of polyurethane, an organic tin catalyst such as dibutyltin dilaurate or tin octanate is used (Non-Patent Document 1). However, the organotin catalyst is highly toxic, and its harmfulness to the environment and the human body has become a problem. There is already a movement to regulate the use of organotin catalysts in the production of polyurethane, mainly in Europe, and there is a strong demand for alternative catalysts for organotin catalysts.

In order to solve this problem, a method of using N-heterocyclic carbene (NHC) as a catalyst in the polymerization reaction of an aliphatic diisocyanate and an aliphatic diol has been reported (Non-Patent Document 2). However, carbene is generally a compound that is unstable to oxygen and water, and needs to be handled in a special facility such as a glove box, so that it is not satisfactory in terms of practical use. As a method for solving this problem, a method using an NHC CO ₂ adduct as a catalyst for producing polyurethane is known (Non-Patent Document 3).

When the present inventors investigated the CO ₂ adduct of NHC, the CO ₂ adduct of NHC is soluble in a protonic solvent such as chloroform, water, and methanol, but when producing polyurethane such as ethyl acetate and toluene. It was found that it does not dissolve in commonly used solvents. Here, chloroform is generally a highly toxic solvent and cannot be suitably used. Further, a protonic solvent such as water or methanol reacts with an isocyanate compound which is a raw material of polyurethane, and therefore cannot be used for producing polyurethane. Further, it was found that the CO ₂ adduct of NHC has a very high hygroscopicity in the air (see Example 7). Further, when the CO ₂ adduct of NHC acts as a catalyst, CO ₂ gas is generated as a decomposition product thereof, so that there is a problem that voids are generated especially when used for paint applications (see Comparative Example 2 described later). ). From these facts, when NHC is used as a catalyst for polyurethane production, there are still problems to be improved.

"Structure / Physical Characteristics of Polyurethane, Higher Functionality and Application Development", Published by Technical Information Association, 1998, p. 325 The Journal of Organic Chemistry 2008 Vol. 73, pp. 8039-8044 Chemistry A European Journal 2009 Vol. 15, pp. 3103-3109

The present invention has been made in view of the above background techniques, and when used as a catalyst for polyurethane production, CO ₂ gas is not generated, it is dissolved in various aprotic solvents, and polyurethane production having low hygroscopicity is produced. The subject is to provide a catalyst for use.

When the present inventor diligently studied to solve the above problems, when the compound represented by the formula (1) was used as a catalyst for producing polyurethane, CO ₂ gas was not generated and various aprotices were not generated. It was found that it was soluble in a sex solvent and had low hygroscopicity, and the present invention was completed.

That is, the present invention relates to the following [1] to [13].

[1] An amidate polymer having a structure represented by the following formula (1).
Equation (1):

（式中、Ｒ^１は結合手又は炭素数１～３のアルキレン基、Ｒ^２は水素原子又はメチル基であり、ｙは１以上の整数である。Ｄは式（２）：

(In the formula, R ¹ is a bond or an alkylene group having 1 to 3 carbon atoms, R ² is a hydrogen atom or a methyl group, and y is an integer of 1 or more. D is the formula (2) :.

（式中、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、同一又は異なって、ヘテロ原子を含んでいてもよい炭化水素基であり、一部または全てが相互に結合して環構造を形成していてもよい。Ｘは窒素原子、酸素原子又は硫黄原子を示す。ａは０又は１を示す。Ｘが窒素原子を示す場合は、ａは１を示し、Ｘが酸素原子又は硫黄原子を示す場合、ａは０を示す。））

(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrocarbon groups that are the same or different and may contain heteroatoms, and some or all of them are bonded to each other to form a ring structure. X indicates a nitrogen atom, an oxygen atom or a sulfur atom. A indicates 0 or 1. When X indicates a nitrogen atom, a indicates 1 and X indicates an oxygen atom or a sulfur atom. When indicated, a indicates 0.)))

[2] An amidate polymer having a structure represented by the following formula (1-1).
Equation (1-1):

（式中、Ｒ^１、Ｒ^２、Ｄ及びｙは前記に同じ、ｘは１以上の整数である。Ｒ^１５は水素原子又はメチル基である。Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９及びＲ^２０は、同一又は異なって、水素原子、炭素数１～１０の炭化水素基、炭素数１～１０のアルコキシ基、ハロゲン原子、トリフルオロメチル基、シアノ基、シアノメチル基又はアルコキシシリル基である。）

(In the formula, R ¹ , R ² , D and y are the same as above, x is an integer of 1 or more. R ¹⁵ is a hydrogen atom or a methyl group. R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ is the same or different, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a trifluoromethyl group, a cyano group, a cyanomethyl group or an alkoxysilyl group. .)

[3] 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 amidate polymer according to [1] or [2].
Equation (2-1):

（式中、Ｒ^３、Ｒ^６、ａ及びＸは前記に同じ、Ｒ^７及びＲ^８は、同一又は異なって、水素原子又はヘテロ原子を含んでいても良い炭素数１～６の炭化水素基を示す。）
式（２－２）：

(In the formula, R ³ , R ⁶ , a and X are the same as described above, and R ⁷ and R ⁸ are the same or different hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom. Shows.)
Equation (2-2):

（式中、Ｒ^３、Ｒ^６、ａ及びＸは前記に同じ、Ｒ^９及びＲ^１０は、同一又は異なって、水素原子又はヘテロ原子を含んでいても良い炭素数１～６の炭化水素基を示す。）
式（２－３）：

(In the formula, R ³ , R ⁶ , a and X are the same as described above, and R ⁹ and R ¹⁰ are the same or different hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom. Shows.)
Equation (2-3):

（式中、Ｒ^３、Ｒ^６、ａ及びＸは前記に同じ、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は、同一又は異なって、水素原子又はヘテロ原子を含んでいても良い炭素数１～６の炭化水素基を示す。）

(In the formula, R ³ , R ⁶ , a and X are the same as described above, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and may contain a hydrogen atom or a hetero atom. Shows 6 hydrocarbon groups.)

[4] The amidate polymer according to any one of [1] to [3], wherein X is a nitrogen atom.

[5] A catalyst for producing polyurethane containing the amidate polymer according to any one of [1] to [4].

[6] A method for producing polyurethane in which a polyol and a polyisocyanate are reacted in the presence of the catalyst for producing polyurethane according to [5].

[7] A polymer having a structure represented by the formula (4) is obtained by polymerizing a urethane compound represented by the following formula (3) and an ethylenically unsaturated monomer as needed, and the polymer and the following formula ( 5. The method for producing an amidate polymer according to [1] to [4], wherein the carboxylate compound represented by 5) is reacted.
Equation (3):

（式中、Ｒ^１及びＲ^２は前記に同じ、Ｒ^２１はヘテロ原子を含んでいてもよい炭化水素基である。）
式（４）：

（式中、ｙ、Ｒ^１、Ｒ^２、及びＲ^２１は前記に同じである。）
式（５）：

(In the formula, R ¹ and R ² are the same as described above, and R ²¹ is a hydrocarbon group which may contain a hetero atom.)
Equation (4):

(In the formula, y, R ¹ , R ² , and R ²¹ are the same as described above.)
Equation (5):

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、ａ及びＸは前記に同じである。）

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , a and X are the same as described above.)

[8] The urethane compound represented by the formula (3) and the ethylenically unsaturated monomer are copolymerized to obtain a polymer having a structure represented by the formula (4), and the polymer and the formula (5) are obtained. The method for producing an amidate polymer according to any one of [1] to [4], wherein the carboxylate compound represented by (1) is reacted.

[9] The method for producing an amidate polymer according to [7] or [8], wherein the ethylenically unsaturated monomer is a vinyl-based monomer.

[10] The method for producing an amidate polymer according to [7] or [8], wherein the ethylenically unsaturated monomer is a monomer represented by the following formula (8).
Equation (8):

（式中、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９及びＲ^２０は前記に同じである。）

(In the formula, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same as described above.)

[11] The method for producing an amidate polymer according to [7] or [8], wherein the ethylenically unsaturated monomer is styrene.

[12] The carboxylate compound represented by the formula (4) is a carboxylate compound represented by any of the following formulas (5-1), (5-2) or (5-3) [ 7] The method for producing an amidate polymer according to any one of [11].
Equation (5-1):

（式中、Ｒ^３、Ｒ^６、Ｒ^７、Ｒ^８、ａ及びＸは前記に同じ。）
式（５－２）：

(In the formula, R ³ , R ⁶ , R ⁷ , R ⁸ , a and X are the same as described above.)
Equation (5-2):

（式中、Ｒ^３、Ｒ^６、Ｒ^９、Ｒ^１０、ａ及びＸは前記に同じ。）
式（５－３）：

(In the formula, R ³ , R ⁶ , R ⁹ , R ¹⁰ , a and X are the same as described above.)
Equation (5-3):

（式中、Ｒ^３、Ｒ^６、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４、ａ及びＸは前記に同じ。）

(In the formula, R ³ , R ⁶ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , a and X are the same as described above.)

[13] The method for producing an amidate polymer according to any one of [7] to [11], wherein the carboxylate compound represented by the formula (5) is 1,3-dimethylimidazolium-2-carboxylate.

It is possible to provide a polyurethane production catalyst that does not generate CO ₂ gas when used as a polyurethane production catalyst, dissolves in various aprotic solvents, and has low hygroscopicity.

The analysis result of ^{1 1} H-NMR in Example 3 in the Example of this application is shown. The analysis result of ^{1 1} H-NMR in Example 4 in the Example of this application is shown.

Hereinafter, the present invention will be specifically described.

In the formula (1), R ¹ is a bond or an alkylene group having 1 to 3 carbon atoms, and is preferably a bond. When R ¹ is a bond, in other words, the formula (1) is an amidate polymer having a structure represented by the formula (1a).

Equation (1a):

（式中、ｙ、Ｒ^２及びＤは前記に同じ。）

(In the formula, y, R ² and D are the same as above.)

^R2 is a hydrogen atom or a methyl group, preferably a hydrogen atom. y is an integer of 1 or more. D is a nitrogen-containing organic group represented by the formula (2).

In formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ are hydrocarbon groups that may contain heteroatoms, even if some or all of them are bonded to each other to form a ring structure. good. The hydrocarbon group which may contain a hetero atom includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group and an n-hexyl group. , N-octyl group, n-decyl group, n-dodecyl group, allyl group, benzyl group, cyclohexyl group, adamantyl group, phenyl group, 2,6-diisopropylphenyl group, 2,4,6-trimethylphenyl group, 2 -Examples include a methoxyethyl group, a 2-ethoxyethyl group, a 2- (dimethylamino) ethyl group and the like. Preferred are a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, an n-octyl group, a cyclopentyl group, a cyclohexyl group and a 2,4,6-trimethylphenyl group, and more particularly preferably a methyl group and an ethyl group. Groups, isopropyl groups, t-butyl groups, n-octyl groups, phenyl groups, particularly preferably methyl groups, isopropyl groups, t-butyl groups, n-octyl groups and phenyl groups. X is a nitrogen atom, an oxygen atom or a sulfur atom, preferably a nitrogen atom. a indicates 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, if X is an oxygen atom or a sulfur atom, then R ³ is absent.

Equation (2a):

Equation (2b):

Equation (2c):

In the present invention, it is preferable that R ⁴ and R ⁵ 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 represented by the formula (2) forming the ring is preferably a nitrogen-containing organic group represented by any of the formulas (2-1) to (2-3), and is particularly preferable. It is a nitrogen-containing organic group represented by the formula (2-1).

In equation (2-1), R ³ , R ⁶ and X are the same as described above. R ⁷ and R ⁸ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom, which may be the same or different, and are preferably hydrogen atoms. Examples of the hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group and a pentyl group. Examples thereof include a hexyl group, a cyclohexyl group, a phenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2- (dimethylamino) ethyl group, and the like, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, and n-. It is a butyl group, particularly preferably a methyl group.

Specific examples represented by the formula (2-1) include a 1,3-dimethylimidazolium group, a 1-ethyl-3-methylimidazolium group, a 1-methyl-3-propylimidazolium group, and a 1-methyl-. 3-Isopropylimidazolium group, 1-butyl-3-methylimidazolium group, 1-t-butyl-3-methylimidazolium group, 1-methyl-3-pentylimidazolium group, 1-hexyl-3-methylimidazolium group Rium group, 1-heptyl-3-methylimidazolium group, 1-methyl-3-octylimidazolium group, 1-methyl-3-nonylimidazolium group, 1-decyl-3-methylimidazolium group, 1-allyl -3-Methylimidazolium group, 1-benzyl-3-methylimidazolium group, 1- (2-methoxyethyl) -3-methylimidazolium group, 1- (2-ethoxyethyl) -3-methylimidazolium group , 1- (2-dimethylaminoethyl) -3-methylimidazolium group, 1,3,4,5-tetramethylimidazolium group,

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

Examples thereof include a 3-methylthiazolium group, a 3,4-dimethylthiazolium group, a 3,5-dimethylthiazolium group, a 3,4,5-trimethylthiazolium group, and the like, preferably 1,3. -Dimethylimidazolium group, 1-ethyl-3-methylimidazolium group, 1-methyl-3-propylimidazolium group, 1-butyl-3-methylimidazolium group, 1-methyl-3-octylimidazolium group Yes, particularly preferred are a 1,3-dimethylimidazolium group, a 1-butyl-3-methylimidazolium group, and a 1-methyl-3-octylimidazolium group.

In equation (2-2), R ³ , R ⁶ and X are the same as described above. R ⁹ and R ¹⁰ are hydrocarbon groups having 1 to 6 carbon atoms which may contain a hydrogen atom or a hetero atom, which may be the same or different, and are preferably hydrogen atoms. Examples of the hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group and a pentyl group. Examples thereof include a hexyl group, a cyclohexyl group, a phenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2- (dimethylamino) ethyl group, and the like, and a methyl group is preferable.

Specific examples represented by the formula (2-2) include 1,3-dimethylimidazolinium group, 1-ethyl-3-methylimidazolinium group, 1-methyl-3-propylimidazolinium group, 1 -Butyl-3-methylimidazolinium group, 1-methyl-3-pentylimidazolinium group, 1-hexyl-3-methylimidazolinium group, 1-heptyl-3-methylimidazolinium 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-methylimidazolinium group, 1- (2-dimethylaminoethyl) -3-Methylimidazolinium group, 1,3,4,5-tetramethylimidazolinium group,

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

Examples thereof include a 3-methylthiazolinium group, a 3,4-dimethylthiazolinium group, a 3,5-dimethylthiazolinium group, a 3,4,5-trimethylthiazolinium group, and the like, preferably 1,3. -Dimethylimidazolinium group, 1-ethyl-3-methylimidazolinium group, 1-methyl-3-propylimidazolinium group, 1-butyl-3-methylimidazolinium group, 1-methyl-3-octyl It is an imidazolinium group, and particularly preferably a 1,3-dimethylimidazolinium group, a 1-butyl-3-methylimidazolinium group, and a 1-methyl-3-octylimidazolinium group.

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

Specific examples represented by the formula (2-3) include 1,3-dimethylbenzoimidazolium group, 1-ethyl-3-methylbenzoimidazolium group, 1-methyl-3-propylbenzoimidazolium group, 1 -Butyl-3-methylbenzoimidazolium group, 1-methyl-3-pentylbenzoimidazolium group, 1-hexyl-3-methylbenzoimidazolium group, 1-heptyl-3-methylbenzoimidazolium group, 1-methyl -3-octylbenzoimidazolium group, 1-methyl-3-nonylbenzoimidazolium group, 1-decyl-3-methylbenzoimidazolium group, 1-allyl-3-methylbenzoimidazolium group, 1-benzyl-3 -Methylbenzoimidazolium group, 1,3,6-trimethylbenzoimidazolium group, 1-acetyl-3,6-dimethylbenzoimidazolium group, 1,3,6,7-tetramethylbenzoimidazolium group, 1, 3-Dibenzyl-6,7-dimethylbenzoimidazolium group,

3-Methylbenzoxazolium group,

3-Methylbenzothiazolium group Preferredly, 1,3-dimethylbenzoimidazolium group, 1-ethyl-3-methylbenzoimidazolium group, 1-methyl-3-propylbenzoimidazolium group, 1-butyl-3. -Methylbenzoimidazolium group, particularly preferably 1,3-dimethylbenzoimidazolium group.

Unless otherwise specified, the description of propyl, butyl, pentyl, hexyl, hexyl, heptyl, octyl, nonyl, decyl and the like is described in this specification as n-propyl, n-butyl, n-pentyl, n-. It shows a linear alkyl group such as hexyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the like.

In the present invention, the molecular weight of the amidate polymer (1) is not particularly limited.

The structure of the amidate polymer (1) of the present invention is not particularly limited as long as it contains at least one structure represented by the formula (1), but for example, (I): only from the structure represented by the formula (1). It may be a polymer composed, and has a structure represented by (II): formula (1), and further has a structure derived from a monomer other than the urethane compound (3) such as an ethylenically unsaturated monomer. It may be a copolymer having. Preferably, it is a copolymer having a structure represented by the formula (1) and further having a structure derived from an ethylenically unsaturated monomer.

When the amidate polymer (1) is a copolymer, as the structure of the amidate polymer (1), for example, an amidate polymer having a structure represented by the formula (1-1) is preferable.
Equation (1-1):

（式中、Ｒ^１、Ｒ^２、Ｄ、及びｙは前記に同じ、ｘは１以上の整数である。Ｒ^１５は水素原子又はメチル基である。Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９及びＲ^２０は、同一又は異なって、水素原子、炭素数１～１０の炭化水素基、炭素数１～１０のアルコキシ基、ハロゲン原子、トリフルオロメチル基、シアノ基、シアノメチル基又はアルコキシシリル基である。）

(In the formula, R ¹ , R ² , D, and y are the same as above, x is an integer of 1 or more. R ¹⁵ is a hydrogen atom or a methyl group. R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ And R ²⁰ are the same or different, with a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a trifluoromethyl group, a cyano group, a cyanomethyl group or an alkoxysilyl group. be.)

In equation (1-1), R ¹ , R ² , D, and y are the same as described above. x is an integer of 1 or more. ^R15 is a hydrogen atom or a methyl group, preferably a hydrogen atom. R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same or different, and have a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom and a trifluoromethyl group. , Cyano group, cyanomethyl group or alkoxysilyl group, preferably a hydrogen atom.

The method for producing the amidate polymer (1) of the present invention will be described.

In the amidate polymer (1) of the present invention, the urethane compound represented by the formula (3) (hereinafter referred to as urethane compound (3)) is, if necessary, other than the urethane compound (3) such as an ethylenically unsaturated monomer. A polymer having a structure represented by the formula (4) (hereinafter referred to as a polymer (4)) is obtained by polymerizing with a monomer, and a carboxylate compound represented by the polymer (4) and the formula (5) (hereinafter referred to as a carboxylate compound). It can be produced by reacting with a carboxylate compound (5).

In formula (3), R ¹ and R ² are the same as described above, and R ²¹ is a hydrocarbon group which may contain a hetero atom. The hydrocarbon group which may contain a heteroatom is preferably a hydrocarbon group having 1 to 50 carbon atoms which may contain a heteroatom, more preferably a hydrocarbon group having 1 to 30 carbon atoms, and particularly preferably. It is a hydrocarbon group having 1 to 8 carbon atoms. The hydrocarbon group which may contain a hetero atom includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group and an n-hexyl group. , N-octyl group, n-decyl group, n-dodecyl group, allyl group, benzyl group, cyclohexyl group, adamantyl group, phenyl group, 2,6-diisopropylphenyl group, 2,4,6-trimethylphenyl group, 2 -Examples include a methoxyethyl group, a 2-ethoxyethyl group, a 2- (dimethylamino) ethyl group and the like. It is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, an n-octyl group, a cyclopentyl group, a cyclohexyl group, a 2,4,6-trimethylphenyl group, and more preferably a methyl group or an ethyl group. , An isopropyl group, a t-butyl group, an n-octyl group and a phenyl group, particularly preferably a methyl group, an isopropyl group, a t-butyl group, an n-octyl group and a phenyl group.

Specific examples of the urethane compound (3) include p-vinyl-N-methoxycarbonylaniline, p-vinyl-N-ethoxycarbonylaniline, p-vinyl-N-propoxycarbonylaniline, and p-vinyl-N-iso. Propoxycarbonylaniline, p-vinyl-Nn-butoxycarbonylaniline, p-vinyl-N-s-butoxycarbonylaniline, p-vinyl-Nt-butoxycarbonylaniline, p-vinyl-Nn-pentyloxy Carbonyl aniline, p-vinyl-Nn-hexyloxycarbonylaniline, p-vinyl-Nn-octyloxycarbonylaniline, p-vinyl-Nn-decyloxycarbonylaniline, p-vinyl-Nn- Dodecyloxycarbonylaniline, p-vinyl-N-allyloxycarbonylaniline, p-vinyl-N-benzyloxycarbonylaniline, p-vinyl-N-cyclohexyloxycarbonylaniline, p-vinyl-N-adamantyloxycarbonylaniline, p -Vinyl-N-phenoxycarbonylaniline, p-vinyl-N- (2,6-diisopropylphenoxy) carbonylaniline, p-vinyl-N- (2,4,6-trimethylphenoxy) carbonylaniline, p-vinyl-N -(2-methoxyethoxy) carbonyl aniline, p-vinyl-N- (2-ethoxyethoxy) carbonyl aniline, p-vinyl-N- (2- (dimethylamino) ethoxy) carbonyl aniline, p-vinyl-N-methoxy Carbonylbenzylamine, p-vinyl-N-ethoxycarbonylbenzylamine, p-vinyl-N-propoxycarbonylbenzylamine, p-vinyl-N-isopropoxycarbonylbenzylamine, p-vinyl-Nn-butoxycarbonylbenzylamine , P-vinyl-Ns-butoxycarbonylbenzylamine, p-vinyl-Nt-butoxycarbonylbenzylamine, p-vinyl-Nn-pentyloxycarbonylbenzylamine, p-vinyl-Nn-hexyl Oxycarbonylbenzylamine, p-vinyl-Nn-octyloxycarbonylbenzylamine, p-vinyl-Nn-decyloxycarbonylbenzylamine, p-vinyl-Nn-dodecyloxycarbonylbenzylamine, p-vinyl -N-allyloxycarbonylbenzylamine, p-vinyl-N-benzyloxycarbonylbenzylami , P-vinyl-N-cyclohexyloxycarbonylbenzylamine, p-vinyl-N-adamantyloxycarbonylbenzylamine, p-vinyl-N-phenoxycarbonylbenzylamine, p-vinyl-N- (2,6-diisopropylphenoxy) ) Carbonylbenzylamine, p-vinyl-N- (2,4,6-trimethylphenoxy) carbonylbenzylamine, p-vinyl-N- (2-methoxyethoxy) carbonylbenzylamine, p-vinyl-N- (2-) Examples thereof include ethoxyethoxy) carbonylbenzylamine and p-vinyl-N- (2- (dimethylamino) ethoxy) carbonylbenzylamine, preferably p-vinyl-Nt-butoxycarbonylaniline and p-vinyl-Nt. -Butoxycarbonylbenzylamine, particularly preferably p-vinyl-Nt-butoxycarbonylaniline.

The urethane compound (3) is, for example, an amine compound represented by the following formula (6) (hereinafter referred to as an amine compound (6)) and a carbonyl compound represented by the following formulas (7a) to (7c) (hereinafter referred to as a carbonyl compound). , A carbonyl compound (7)) can be reacted.

Equation (6):

（式中、Ｒ^１、Ｒ^２は前記に同じである。）

(In the formula, R ¹ and R ² are the same as described above.)

Equation (7a):

（式中、Ｒ^２１は前記に同じである。）

(In the formula, R ²¹ is the same as above.)

Equation (7b):

（式中、Ｒ^２１は前記に同じである。）

(In the formula, R ²¹ is the same as above.)

Equation (7c):

（式中、Ｒ^２１は前記に同じ、Ｙはハロゲン原子を示す。）

(In the formula, R ²¹ is the same as above, and Y is a halogen atom.)

In formula (6), R ¹ and R ² are the same as described above. Examples of the amine compound represented by the formula (6) include 4-aminostyrene and 4-vinylbenzylamine, and 4-aminostyrene is preferable.

In formula (7a), R ²¹ is the same as described above. Examples of the carbonyl compound represented by the formula (7a) include di-t-butyl dicarbonate, dibenzyl dicarbonate, di-t-amyl dicarbonate, and diallyl dicarbonate, and di-t-butyl dicarbonate is preferable. , Dibenzyl dicarbonate.

In formula (7b), R ²¹ is the same as described above. Examples of the carbonyl compound represented by the formula (7b) include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, diphenyl carbonate, dibenzyl carbonate and the like, and dimethyl carbonate, diethyl carbonate, etc. are preferable. Dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, dibenzyl carbonate.

In formula (7c), R ²¹ is the same as above, and Y represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. Examples of the carbonyl compound represented by the formula (7c) include methyl chloroate, ethyl chloroate, propyl chlororate, isopropyl chlororate, 2-methoxyethyl chlororate, butyl chloroate, isobutyl chlororate, amyl chloroate and chloro. Heptyl formic acid, hexyl chloro formic acid, nonyl chloro formic acid, n-octyl chloro formic acid, decyl chloro formic acid, dodecyl chloro formic acid, hexadecyl chloro formic acid, phenyl formic acid, 2-naphthyl formic acid, benzyl chloro formic acid and the like are preferable. Methyl formic acid, ethyl chloro formic acid, propyl chloro formic acid, isopropyl chloro formic acid, butyl chloro formic acid, n-octyl chloro formic acid, phenyl chloro formic acid, benzyl chloro formic acid.

Of the carbonyl compounds represented by the formulas (7a) to (7c), the carbonyl compound represented by the formula (7a) or the formula (7b) is preferably used from the viewpoint of availability and ease of reaction. The carbonyl compound represented by the formula (7a) is particularly preferably used.

The amount of the carbonyl compound (7) used is usually 1 mol or more, preferably 1 to 6 mol, relative to 1 mol of the amino group in the amine compound (6).

When the amine compound (6) and the carbonyl compound (7) are reacted, a base catalyst may be used if necessary. Examples of the base catalyst include organic bases such as triethylamine and dimethylaminopyridine, and inorganic bases such as potassium hydroxide, sodium hydroxide and sodium hydrogencarbonate, and triethylamine is preferable.

The optimum temperature of the reaction varies depending on the raw materials used, the solvent and the like, but is usually room temperature or higher, preferably 20 to 250 ° C.

The solvent may or may not be used. When a solvent is used, the solvent used is not particularly limited as long as it does not affect the reaction. Specific examples of the solvent include aromatic hydrocarbon solvents such as toluene, benzene and xylene, hydrocarbon solvents such as methylcyclohexane, cyclohexane, n-hexane, n-heptane and octane, and halogenated hydrocarbon solvents such as dichloromethane and chloroform. , Diethyl ether, tetrahydrofuran, ether solvent such as 1,4-dioxane, alcohol solvent such as methanol and ethanol, N, N-dimethylformamide, acetonitrile and the like, preferably an ether solvent and an alcohol solvent, and particularly preferably. Solvent and methanol. The amount of the solvent used is usually 50 parts by weight or less, preferably 0.1 to 10 parts by weight, based on 1 part by weight of the amine compound (6).

If necessary, the reaction may be carried out in an inert gas atmosphere that does not affect the reaction of nitrogen, argon, helium or the like.

After completion of the reaction, the urethane compound (5) can be isolated by treating the unreacted carbonyl compound (7) with an amine compound such as diethanolamine, washing with water or a weakly acidic aqueous solution, and concentrating the reaction solution. If necessary, purification such as recrystallization may be performed.

The polymer (4) will be described. In the present invention, the polymer (4) is not particularly limited in structure as long as it contains at least one structure represented by the formula (4), but for example, the formula (I): a formula obtained by polymerizing only the urethane compound (3). It may be a polymer composed only of the structure represented by (4), or (II): a monomer different from the urethane compound (3) such as an ethylenically unsaturated monomer and the urethane compound (3). It may be a copolymer of. Preferably (IIa): a copolymer with the urethane compound (3) and an ethylenically unsaturated monomer.

In formula (4), y, R ¹ , R ² and R ²¹ are the same as described above. When the polymer (4) is a copolymer of the urethane compound (3) and the ethylenically unsaturated monomer, the structure of the polymer (4) is, for example, a structure represented by the formula (4-1). The polymer having is preferable.

Equation (4-1):

（式中、Ｒ^１、Ｒ^２、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、ｘ及びｙは前記に同じである。）

(In the formula, R ¹ , R ² , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , x and y are the same as described above.)

In formula (4-1), R ¹ , R ² , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , x and y are the same as described above.

When the polymer (4) is a copolymer with an ethylenically unsaturated monomer, the polymer (4) is a monomer different from the urethane compound (3) such as an ethylenically unsaturated monomer (3). In the case of the copolymer with, the sequence of the repeating unit derived from the monomer in the polymer (4) may be random, alternate, block or the like, but is not particularly limited. The branched structure is not particularly limited, and may be a star shape, a graft, a multi-branched structure, or a mixture thereof, as well as a straight chain.

In the present invention, the ethylenically unsaturated monomer means a substance containing at least one polymerizable carbon-carbon double bond which can be mono-, di-, tri- or tetra-substituted. Examples of the ethylenically unsaturated monomer include a vinyl-based monomer, an acrylate-based monomer, a methacrylate-based monomer, and the like, and a vinyl-based monomer is preferable. Examples of the vinyl-based monomer include the formula (8):

（式中、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９及びＲ^２０は前記に同じである。）
で表されるモノマーなどが好適に使用される。

(In the formula, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same as described above.)
The monomer represented by is preferably used.

In formula (8), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same as described above.

Specific examples of the vinyl-based monomer include styrene, α-methylstyrene, 4-t-butylstyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, and 3,5-bis (trifluoromethyl). Styrene, 4-chloro-α-methyl styrene, 2-chloro styrene, 3-chloro styrene, 4-chloro styrene, vinyl benzyl cyanide, 4- (chloromethyl) styrene, 4-fluoro-α-methyl styrene, 3- Fluorostyrene, 4-fluorostyrene, 4-isopropenyltoluene, 4-methoxystyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-n-octylstyrene, 2,3,4,5,6 -Pentafluorostyrene, 2,4,6-trimethylstyrene, 3- (trifluoromethyl) styrene, 4- (trifluoromethyl) styrene, 1-vinylnaphthalene, 2-vinylpyridine, acrylonitrile and the like are preferable. Styrene and acrylonitrile, particularly preferably styrene. Examples of the acrylate-based monomer include methyl acrylate and the like. Examples of the methacrylate-based monomer include methyl methacrylate and glycidyl methacrylate. Two or more kinds of ethylenically unsaturated monomers can be used in combination. When the urethane compound (3) and the ethylenically unsaturated monomer are polymerized to form the polymer (4), the amount of the ethylenically unsaturated monomer used is not particularly limited, but is based on 100 parts by weight of the urethane compound (3). It is in the range of 1 to 10000 parts by weight, preferably in the range of 50 to 5000 parts by weight.

The method for polymerizing the monomer when producing the polymer (4) is not particularly limited, but examples thereof include radical polymerization, anion polymerization, cationic polymerization, and addition polymerization of coordination polymerization, and radical polymerization is preferable from the viewpoint of ease of operation.

When producing the polymer (4), a radical initiator can be used as an initiator of the polymerization reaction, if necessary. Radical initiators include benzoyl peroxide, acetyl peroxide, t-butyl hydroperoxide, dibenzoyl disulfide, ammonium persulfate, azobisisobutyronitrile, 2,2'-azobisisobutyrate dimethyl, 2,2'-azobis. (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile) or dimethyl-2,2'-azobis (2-methylpropionate) and the like can be mentioned. Azobisisobutyronitrile and other azo-based initiators are preferred.

When the radical initiator is used, the amount of the radical initiator used is not particularly limited, but the total amount of the monomers other than the urethane compound (3) and the optionally used ethylenically unsaturated monomer (3) other than the urethane compound (3) is 100. It is usually in the range of 0.1 to 10 parts by weight, preferably in the range of 0.5 to 5 parts by weight with respect to parts by weight. The initiator may be added to the polymerization system in a total amount at a time at the start of the polymerization reaction, or may be added in portions during the polymerization.

The polymerization temperature is not particularly limited, but is usually in the range of 20 to 150 ° C, preferably in the range of 50 to 110 ° C. The polymerization time is usually in the range of 5 minutes to 48 hours.

In the present invention, the polymerization reaction may be bulk polymerization without using a solvent, or solution polymerization using a solvent. Further, a suspension agent can be further used for suspension polymerization.

When a solvent is used in the polymerization reaction, the solvent used is not particularly limited as long as it does not affect the reaction. Specific examples of the solvent include aromatic hydrocarbon solvents such as toluene, benzene and xylene, hydrocarbon solvents such as methylcyclohexane, cyclohexane, n-hexane, n-heptane and octane, and halogenated hydrocarbon solvents such as dichloromethane and chloroform. , Diethyl ether, tetrahydrofuran, ether solvents such as 1,4-dioxane, alcohol solvents such as methanol and ethanol, dimethylsulfoxide, N, N-dimethylformamide, acetonitrile and the like, and dimethylsulfoxide is preferable. The amount of the solvent used is in the range of 0.1 to 100 parts by weight, preferably in the range of 1 to 10 parts by weight, based on 1 part by weight of the total amount of the urethane compound (3) and the ethylenically unsaturated monomer. ..

When the polymer (4) is produced by suspension polymerization, the suspending agent is not particularly limited as long as it does not affect the reaction. Specific examples of the suspending agent include polyvinyl alcohol, polyvinylpyrrolidone and the like.

The polymerization products obtained by the above-mentioned various polymerization methods are washed with a polar solvent such as water or methanol, and subjected to a solvent reprecipitation method, a thin film evaporation method, or the like to obtain an unreacted urethane compound (3) or optionally used ethylenic. The target polymer (4) can be obtained by removing monomers other than the urethane compound (3) such as unsaturated monomers, solvents and the like.

Next, the reaction between the polymer (4) and the carboxylate compound represented by the above formula (5) will be described.

In formula (5), R ³ , R ⁴ , R ⁵ , R ⁶ , a and X are the same as described above. From the viewpoint of availability, it is preferable that ^R4 and R5 are bonded to each other to form a ring structure in the carboxylate compound of the formula ( ⁵ ). The carboxylate compound (5) forming the ring is preferably a carboxylate compound represented by any of the above formulas (5-1) to (5-3), and is particularly preferably the formula (5-1). ) Is a carboxylate compound.

In formula (5-1), R ³ , R ⁶ , R ⁷ , R ⁸ , a and X are the same as described above.

Specific examples of the carboxylate compound represented by the formula (5-1) include 1,3-dimethylimidazolium-2-carboxylate, 1-ethyl-3-methylimidazolium-2-carboxylate, and 1-methyl. -3-propylimidazolium-2-carboxylate, 1-methyl-3-isopropylimidazolium-2-carboxylate, 1-butyl-3-methylimidazolium-2-carboxylate, 1-t-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-carboxylate, 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, etc., preferably 1,3-dimethylimidazolium-2-carboxylate, 1-ethyl-3-methylimidazolium-2-carboxylate, 1-methyl-3-propylimidazole, etc. Rium-2-carboxylate, 1-butyl-3-methylimidazolium-2-carboxylate, 1-methyl-3-octylimidazolium-2-carboxylate, and particularly preferably 1,3-dimethylimidazolium. -2-carboxylate, 1-butyl-3-methylimidazolium carboxylate, 1-methyl-3-octylimidazolium-2-carboxylate.

In formula (5-2), R ³ , R ⁶ , R ⁹ , R ¹⁰ , a and X are the same as described above.

Specific examples of the carboxylate compound represented by the formula (5-2) include 1,3-dimethylimidazolinium-2-carboxylate, 1-ethyl-3-methylimidazolinium-2-carboxylate, and 1 -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 -Nonyl imidazolinium-2-carboxylate, 1-decyl-3-methyl imidazolinium-2-carboxylate, 1-allyl-3-methyl imidazolinium-2-carboxylate, 1-benzyl-3-methyl Imidazolinium-2-carboxylate, 1- (2-methoxyethyl) -3-methylimidazolinium-2-carboxylate, 1- (2-ethoxyethyl) -3-methylimidazolinium-2-carboxylate , 1- (2-dimethylaminoethyl) -3-methylimidazolinium-2-carboxylate, 1,3,4,5-tetramethylimidazolinium-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. It is imidazolinium-2-carboxylate, 1-butyl-3-methylimidazolinium-2-carboxylate, and particularly preferably 1,3-dimethylimidazolinium-2-carboxylate.

In formula (5-3), R ³ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ , a, and X are the same as described above.

Specific examples of the carboxylate compound represented by the formula (5-3) include 1,3-dimethylbenzoimidazolium-2-carboxylate, 1-ethyl-3-methylbenzoimidazolium-2-carboxylate, and 1 -Methyl-3-propylbenzoimidazolium-2-carboxylate, 1-butyl-3-methylbenzoimidazolium-2-carboxylate, 1-methyl-3-pentylbenzoimidazolium-2-carboxylate, 1-hexyl -3-Methylbenzoimidazolium-2-carboxylate, 1-heptyl-3-methylbenzoimidazolium-2-carboxylate, 1-methyl-3-octylbenzoimidazolium-2-carboxylate, 1-methyl-3 -Nonylbenzoimidazolium-2-carboxylate, 1-decyl-3-methylbenzoimidazolium-2-carboxylate, 1-allyl-3-methylbenzoimidazolium-2-carboxylate, 1-benzyl-3-methyl Benzoimidazolium-2-carboxylate, 1,3,6-trimethylbenzoimidazolium-2-carboxylate, 1-acetyl-3,6-dimethylbenzoimidazolium-2-carboxylate, 1,3,6,7 -Tetramethylbenzoimidazolium-2-carboxylate, 1,3-dibenzyl-6,7-dimethylbenzoimidazolium-2-carboxylate,

3-Methylbenzoxadiazole-2-carboxylate,

3-Methylbenzothiazolium-2-carboxylate is preferably 1,3-dimethylbenzoimidazolium-2-carboxylate, 1-ethyl-3-methylbenzoimidazolium-2-carboxylate, 1-methyl-3. -Propylbenzoimidazolium-2-carboxylate, 1-butyl-3-methylbenzoimidazolium-2-carboxylate, and particularly preferably 1,3-dimethylbenzoimidazolium-2-carboxylate.

As the carboxylate compound (5), a compound produced by a conventionally known method can be used, and the production method thereof is not particularly limited, but for example, Chemical Communications (Cambridge, United Kingdom) 2003 1 The method for reacting a nitrogen-containing organic compound described in No. 28-29 with dialkyl carbonate, and the N-heterocyclic carbene and carbon dioxide described in Chemcomm Communications (Cambridge, United Kingdom) 2004 No. 1, pp. 112-113. Examples thereof include a method of reacting. The method for producing the carboxylate compound (5) by reacting the nitrogen-containing organic compound with the dialkyl carbonate will be described below.

A carboxylate compound obtained by reacting a nitrogen-containing organic compound represented by the following formula (9) (hereinafter referred to as a nitrogen-containing organic compound (9)) with a dialkyl carbonate (10) (hereinafter referred to as a dialkyl carbonate (10)). (5) is manufactured.

Equation (9):

（式中、Ｒ^３、Ｒ^４、Ｒ^５、ａ及びＸは前記に同じ。）

(In the formula, R ³ , R ⁴ , R ⁵ , a and X are the same as above.)

Equation (10):

（式中、Ｒ^６は前記に同じ。）

(In the formula, R ⁶ is the same as above.)

In the present invention, from the viewpoint of availability, it is preferable that R ⁴ and R ⁵ are bonded to each other in the formula (9) to form a ring structure. The nitrogen-containing organic compound (9) forming the ring is preferably a nitrogen-containing organic compound represented by any of the following formulas (9-1), (9-2) or (9-3), and particularly. It is preferably a nitrogen-containing organic compound represented by the formula (9-1).

Equation (9-1):

(In the formula, R ³ , R ⁷ , R ⁸ , a and X are the same as above.)

Equation (9-2):

(In the formula, R ³ , R ⁹ , R ¹⁰ , a and X are the same as above.)

Equation (9-3):

(In the formula, R ³ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , a and X are the same as above.)

In equation (9-1), R ³ , R ⁷ , R ⁸ , a and X are the same as described above. Specific examples of the nitrogen-containing organic compound represented by the formula (9-1) include 1-methylimidazole, 1-ethyl imidazole, 1-propyl imidazole, 1-isopropyl imidazole, 1-butyl imidazole and 1-t-butyl. Imidazole, 1-hexyl imidazole, 1-octyl imidazole, 1- (2-ethylhexyl) imidazole, 1-dodecyl imidazole, 1-allyl imidazole, 1-benzyl imidazole, 1-phenyl imidazole, 1- (2,6-diisopropyl) Imidazole, 1-mesityl imidazole, 1,4,5-trimethylimidazole

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

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

In formula (9-2), R ³ , R ⁹ , R ¹⁰ , a and X are the same as described above. Specific examples of the nitrogen-containing organic compound represented by the formula (9-2) include 1-methylimidazoline, 1-ethyl imidazoline, 1-propyl imidazoline, 1-isopropyl imidazoline, 1-butyl imidazoline, and 1-t-butyl. Imidazolines, 1-hexyl imidazoline, 1-octyl imidazoline, 1- (2-ethylhexyl) imidazoline, 1-dodecyl imidazoline, 1-allyl imidazoline, 1-benzyl imidazoline, 1-phenyl imidazoline, 1,4,5-trimethyl imidazoline

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

Examples thereof include thiazolin, 4-methylthiazolin, 5-methylthiazolin, 4,5-dimethylthiazolin, and the like, preferably 1-methylimidazoline, 1-ethylimidazoline, 1-propylimidazoline, 1-butylimidazoline, and particularly preferably. Is 1-methylimidazoline.

In equation (9-3), R ³ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , a and X are the same as described above. Specific examples of the nitrogen-containing organic compound represented by the formula (9-3) include 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-propylbenzimidazole, 1-isopropylbenzimidazole, 1-butylbenzimidazole. 1-t-propylbenzimidazole, 1-hexylbenzimidazole, 1-octylbenzoimidazole, 1- (2-ethylhexyl) benzimidazole, 1-dodecylbenzimidazole, 1-allylbenzoimidazole, 1-benzylbenzoimidazole, 1- Benzimidazole, 1,6-dimethylbenzimidazole, 1,6,7-trimethylbenzimidazole,

Examples thereof include benzoxazole and benzothiazole, preferably 1-methylbenzimidazole, 1-ethylbenzoimidazole, 1-propylbenzimidazole and 1-butylbenzimidazole, and particularly preferably 1-methylbenzimidazole. ..

In formula (10), R ⁶ is the same as described above. Specific examples of the dialkyl carbonate (10) include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate and the like, preferably dimethyl carbonate, diethyl carbonate, dipropyl carbonate and dibutyl carbonate, in particular. Dimethyl carbonate is preferred.

In the reaction between the nitrogen-containing organic compound (9) and the dialkyl carbonate (10), the amount of the dialkyl carbonate (10) used is usually 1 mol or more, preferably 1 to 6 mol, per 1 mol of the nitrogen-containing organic compound (9). Is.

The solvent may or may not be used in the reaction of the nitrogen-containing organic compound (9) with the dialkyl carbonate (10). When a solvent is used, the solvent used is not particularly limited as long as it does not affect the reaction. Specific examples of the solvent include monohydric alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 1-methoxy-2-propanol and ethoxyethanol, and polyol solvents such as ethylene glycol, propylene glycol and diethylene glycol. 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- Examples thereof include glycol monoalkyl ether solvents such as butyl ether, propylene glycol monomethyl ether and diethylene glycol monoethyl ether, preferably a monohydric alcohol solvent, and particularly preferably methanol. The amount of the solvent used is usually 50 parts by weight or less, preferably 10 parts by weight or less, based on 1 part by weight of the nitrogen-containing organic compound (9).

In the reaction of the nitrogen-containing organic compound (9) and the dialkyl carbonate (10), the optimum temperature varies depending on the raw materials used, the solvent and the like, but is usually room temperature or higher, preferably 20 to 200 ° C. .. In this specification, room temperature means about 20 ° C.

In the reaction of the nitrogen-containing organic compound (9) and the dialkyl carbonate (10), if necessary, the reaction may be carried out in an inert gas atmosphere that does not affect the reaction of nitrogen, argon, helium or the like.

After completion of the reaction, the reaction solution can be concentrated and the solvent can be removed to isolate the carboxylate compound (5). If the unreacted nitrogen-containing organic compound (9) and dialkyl carbonate (10) remain in the reaction solution, they can be removed by concentrating the reaction solution.

In the reaction between the polymer (4) and the carboxylate compound (5), the amount of the carboxylate compound (5) is usually 0.8 mol or more, preferably 1 mol, with respect to 1 mol of the carbamate group contained in the polymer (4). React in an amount of up to 3 mol.

The reaction temperature is not particularly limited as long as it is equal to or lower than the boiling point of the solvent, and is usually 10 ° C. or higher, preferably 40 to 200 ° C., and particularly preferably 80 to 150 ° C.

In the reaction between the polymer (4) and the carboxylate compound (5), a solvent may or may not be used. Examples of the solvent include aromatic hydrocarbon solvents such as toluene, benzene and xylene, aliphatic hydrocarbon solvents such as methylcyclohexane, cyclohexane, n-hexane, n-heptane and octane, butyl chloride, 1,2-dichloroethane and the like. Examples thereof include a halogenated hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent such as chlorobenzene, and the like, preferably an aromatic hydrocarbon solvent and a halogenated aromatic hydrocarbon solvent, and particularly preferably toluene, xylene, and chlorobenzene. .. If necessary, two or more kinds of solvents may be mixed and used.

The amount of the solvent used is usually 500 parts by weight or less, preferably 0.1 parts by weight or more and 35 parts by weight or less, based on 1 part by weight of the carboxylate compound (5).

In the reaction of the polymer (4) and the carboxylate compound (5), if necessary, the reaction may be carried out in an inert gas atmosphere that does not affect the reaction of nitrogen, argon, helium or the like.

After completion of the reaction, the amidate polymer (1) can be obtained by concentrating the reaction solution or removing the solvent by filtration. Further, the obtained amidate polymer (1) can be purified by a method such as recrystallization.

Next, the catalyst for producing polyurethane of the present invention will be described.

The catalyst for producing polyurethane of the present invention contains the amidate polymer (1) as an active ingredient, and even one kind of amidate polymer (1) alone can be used as a catalyst for producing polyurethane. It can also be used as a mixture of two or more. Further, if necessary, a solvent or the like can be mixed and used. Further, a known catalyst for polyurethane production can be combined and mixed and used.

When the amidate polymer (1) is mixed with a solvent or the like and / or mixed with a known polyurethane production catalyst to obtain a polyurethane production catalyst, it is a polyurethane production catalyst composition. In this case, a person skilled in the art can appropriately set the blending ratio of the amidate polymer (1) and the solvent or the like, and the blending ratio of the amidate polymer (1) and the known catalyst for polyurethane production.

Known catalysts for producing polyurethane include, for example, triethylamine, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N', N. ", N" -pentamethyldiethylenetriamine, N, N, N', N ", N" -pentamethyldipropylenetriamine, N, N, N', N'-tetramethylguanidine, 1,3,5-tris ( N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholin, N -Ethylmorpholin, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole and other tertiary amine catalysts , Tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide salt, tetramethylammonium-2-ethylhexanate, 2-hydroxypropyltrimethylammonium formate, 2- Examples thereof include quaternary ammonium salt compounds such as tetraalkylammonium organic acid salts such as hydroxypropyltrimethylammonium-2-ethylhexanate, preferably 1,4-diazabicyclo [2.2.2] octane (DABCO). .. Known catalysts for producing polyurethane can be used alone or in combination of two or more.

Polyurethane can be produced by reacting a polyol with a polyisocyanate in the presence of the catalyst for producing polyurethane of the present invention.

As for the amount of the catalyst for producing polyurethane of the present invention to be used, the amidate polymer (1) is usually in the range of 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the polyol used. It is an amount that becomes a part by weight.

In the method for producing polyurethane of the present invention, the polyol is not particularly limited, and for example, conventionally known polyether polyols, polyester polyols, polymer polyols, vegetable oil polyols, phosphorus-containing polyols, halogen-containing polyols and the like can be used. Flame-retardant polyols and the like are used. These polyols may be used alone or may be appropriately mixed and used in combination.

The polyether polyol is not particularly limited, and is, for example, a polyvalent compound having at least two or more active hydrogen groups (specifically, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like). Alcohols, amines such as ethylene diamine, alkanol amines such as ethanolamine and diethanolamine are exemplified, and alkylene oxides (specifically, ethylene oxide and propylene oxide) are exemplified as starting materials. ) (See, for example, Gunter Ether, Propylene Handbook (1985) Hanser Publishers (Germany), pp. 42-53].

The polyester polyol is not particularly limited, and for example, a polyhydric carboxylic acid such as adipic acid and phthalic acid and a polyhydric alcohol such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol. Condensation reactants, waste from nylon production, trimethylolpropane, pentaeristol waste, phthalic acid polyester waste, polyester polyols treated and derived from waste, etc. [For example, Keiji Iwata "Polyurethane Resin Handbook" (1987) Nikkan Kogyo Shimbun, Inc., p. 117].

The polymer polyol is not particularly limited, and for example, the above-mentioned polyether polyol is reacted with an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst. Examples include polymer polyols. The polymer polyol having a molecular weight of about 5000 to 12000 is particularly preferable.

The vegetable oil polyol is not particularly limited, and examples thereof include hydroxyl group-containing vegetable oils such as castor oil and coconut oil. Further, a castor oil derivative polyol obtained from castor oil or hydrogenated castor oil as a raw material can also be preferably used. Examples of the castor oil derivative polyol include castor oil, castor oil polyester obtained by the reaction of polyvalent carboxylic acid and short chain diol, and alkylene oxide adducts of castor oil and castor oil polyester.

The flame-retardant polyol is not particularly limited, and is, for example, a phosphorus-containing polyol obtained by adding an alkylene oxide to a phosphoric acid compound, a halogen-containing polyol obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, and an aromatic. Examples thereof include aromatic ether polyols obtained by adding an alkylene oxide to an active hydrogen compound having a ring, aromatic ester polyols obtained by a condensation reaction between a polyvalent carboxylic acid having an aromatic ring and a polyhydric alcohol, and the like.

The hydroxyl value of the polyol is preferably 5 to 300 mgKOH / g, more preferably 10 to 250 mgKOH / g. The hydroxyl value can be measured by the method specified in JIS-K0070.

The polyisocyanate is not particularly limited, and examples thereof include aromatic-based, alicyclic-based, and aliphatic-based polyisocyanates having two or more isocyanate groups, and modified polyisocyanates thereof. Specifically, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, phenylenedi isocyanate and xylylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyldiisocyanate and isophorone diisocyanate, hexamethylene diisocyanate and the like. Examples thereof include the aliphatic polyisocyanate of the above, prepolymer-type modified products, nurate-modified products, and urea-modified products of each of the above-mentioned polyisocyanates. These polyisocyanates may be used alone or may be appropriately mixed and used in combination.

The amount of the polyisocyanate used is not particularly limited, and the isocyanate index (NCO concentration / active hydrogen group concentration × 100) is usually 70 to 140, preferably 75 to 130, and more preferably 80 to 120. The quantity.

In the present invention, a colorant such as a pigment or a dye, an antioxidant, a stabilizer, an ultraviolet absorber, a flame retardant, or an inorganic filler for increasing mechanical strength can be used for the reaction between a polyol and a polyisocyanate, if necessary. Adhesion-imparting agents such as organic solvents, silane coupling agents, antifoaming agents, and leveling agents used for lowering the viscosity, and other additives can be added.

The amidate polymer (1), which is the main component of the polyurethane production catalyst of the present invention, functions as a thermal latent catalyst as shown in Examples described later. Therefore, it is preferable to carry out the reaction according to the method for producing polyurethane in the range of 120 ° C to 250 ° C. More preferably, it is 120 ° C to 200 ° C.

Polyurethane can be obtained by the method described above. The polyurethane obtained by the method of the present invention can be used for various purposes such as paints, adhesives and sealants.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto. In the examples, ^{1 1} H-NMR was measured at 400 MHz using AV400 manufactured by Bruker Co., Ltd. As GPC, HLC-8320GPC manufactured by Tosoh Corporation was used, and the polystyrene-equivalent number average molecular weight was calculated using N, N-dimethylformamide as an eluent. Moisture was analyzed using a Karl Fischer Moisture Meter (MKC-510N) manufactured by Kyoto Electronics Manufacturing Co., Ltd.

[Example 1] Synthesis of 1,3-dimethylimidazolium-2-carboxylate

窒素置換した５００ｍＬのオートクレーブに１－メチルイミダゾール８２．１ｇ（１．０ｍｏｌ）、炭酸ジメチル１１９．８ｇ（１．０ｍｏｌ）、メタノール８３．１ｇを仕込み、得られた混合物を内温１２０℃で２２時間撹拌した。得られた反応混合物を２５℃に冷却し、減圧濃縮を行い、白色固体を得た。得られた白色固体をトルエンで洗浄後、減圧乾燥を行い、上記式で表される化合物（ＤＭＩｍ－ＣＯ_２）を４７．８ｇ得た（収率３４％）。ＤＭＩｍ－ＣＯ_２の^１Ｈ－ＮＭＲ分析結果を以下に示す。

82.1 g (1.0 mol) of 1-methylimidazole, 119.8 g (1.0 mol) of dimethyl carbonate, and 83.1 g of methanol were charged in a 500 mL autoclave substituted with nitrogen, and the obtained mixture was charged at an internal temperature of 120 ° C. for 22 hours. Stirred. The obtained 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 then dried under reduced pressure to obtain 47.8 g of the compound (DMIm-CO ₂ ) represented by the above formula (yield 34%). The results of ¹ H-NMR analysis of DMIm-CO ₂ are shown below.

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

[Example 2] Synthesis of p-vinyl-Nt-butoxycarbonylaniline

窒素置換した５０ｍＬ試験管にｐ－ビニルアニリン１．０ｇ（８．５ｍｍｏｌ）、トリエチルアミン０．９ｇ（９．２ｍｍｏｌ）、ＴＨＦ１０ｍＬを仕込み、０℃に冷却し、混合物を撹拌しながら二炭酸ジ－ｔ－ブチル２．０ｇ（９．３ｍｍｏｌ）／ＴＨＦ１０ｍＬ溶液を滴下し、０℃で９０時間撹拌後、３０℃で２１．５時間撹拌した。得られた混合物にジエタノールアミン０．４ｇ（４．２ｍｍｏｌ）を滴下し、１時間撹拌後、得られた反応混合物を減圧乾燥した。得られた濃縮残にトルエン２０ｍＬ、水１０ｍＬを添加し、分液を行った。得られた有機層を減圧乾燥し、上記式で表される化合物（ｐ－ビニル－Ｎ－ｔ－ブトキシカルボニルアニリン）を１．８ｇ得た（収率９６％）。上記式で表される化合物の^１Ｈ－ＮＭＲ分析結果を以下に示す。

Add 1.0 g (8.5 mmol) of p-vinylaniline, 0.9 g (9.2 mmol) of triethylamine, and 10 mL of THF in a 50 mL test tube substituted with nitrogen, cool to 0 ° C., and stir the mixture to di-t dicarbonate. -A solution of 2.0 g (9.3 mmol) of butyl / 10 mL of THF was added dropwise, and the mixture was stirred at 0 ° C. for 90 hours and then at 30 ° C. for 21.5 hours. 0.4 g (4.2 mmol) of diethanolamine was added dropwise to the obtained mixture, and the mixture was stirred for 1 hour, and then the obtained reaction mixture was dried under reduced pressure. Toluene (20 mL) and water (10 mL) were added to the obtained concentrated residue, and liquid separation was performed. The obtained organic layer was dried under reduced pressure to obtain 1.8 g of the compound represented by the above formula (p-vinyl-Nt-butoxycarbonylaniline) (yield 96%). The results of ¹ H-NMR analysis of the compound represented by the above formula are shown below.

^{1 1} H-NMR (DMSO-d6) δ (ppm) = 9.42 (s, 1H), 7.44-7.34 (m, 4H), 6.67-6.60 (m, 1H), 5 .71-5.66 (m, 1H), 5.14-5.11 (m, 1H), 1.47 (s, 9H)

[Example 3] Copolymerization of styrene and p-vinyl-Nt-butoxycarbonylaniline

５０ｍＬ試験管に実施例２で得られたｐ－ビニル－Ｎ－ｔ－ブトキシカルボニルアニリン０．２９ｇ（１．３ｍｍｏｌ）、２，２－アゾビス(イソブチロニトリル)０．０３ｇ（０．２ｍｍｏｌ）、スチレン３．０３ｇ（２９．１ｍｍｏｌ）、ジメチルスルホキシド２７．８ｇを仕込み、窒素で１０分間バブリング後、７０℃で２２．５時間反応を行った。反応液をメタノール２５０ｍＬに滴下し、再沈殿により精製して上記式で表される共重合体を１．７ｇ得た。共重合体の^１Ｈ－ＮＭＲ分析結果を図１に示す。１．５ｐｐｍ付近にｔ－ブトキシカルボニル基由来のピークが観察できた。ＧＰＣ分析の結果、得られた共重合体のポリスチレン換算数平均分子量Ｍｎは１７０００であった。

0.29 g (1.3 mmol) of p-vinyl-Nt-butoxycarbonylaniline obtained in Example 2 and 0.03 g (0.2 mmol) of 2,2-azobis (isobutyronitrile) in a 50 mL test tube. , 3.03 g (29.1 mmol) of styrene and 27.8 g of dimethyl sulfoxide were charged, and after bubbling with nitrogen for 10 minutes, the reaction was carried out at 70 ° C. for 22.5 hours. The reaction solution was added dropwise to 250 mL of methanol and purified by reprecipitation to obtain 1.7 g of the copolymer represented by the above formula. The results of ¹ H-NMR analysis of the copolymer are shown in FIG. A peak derived from the t-butoxycarbonyl group was observed around 1.5 ppm. As a result of GPC analysis, the polystyrene-equivalent number average molecular weight Mn of the obtained copolymer was 17,000.

[Example 4] Synthesis of amidate polymer from a copolymer of p-vinyl-Nt-butoxycarbonylaniline and styrene

５０ｍＬ試験管に実施例３で得られた共重合体０．５０ｇ、実施例１で得られたＤＭＩｍ－ＣＯ_２０．０８７ｇ（０．６ｍｍｏｌ）、トルエン３５ｇを仕込み、窒素置換後、１１０℃で９．３時間撹拌した。得られた反応混合物を２５℃に冷却後、濾過を行い、濾液を減圧乾燥し、メタノールで洗浄後再度乾燥して、上記式で表されるアミデートポリマーを０．５０ｇ得た。アミデートポリマーの^１Ｈ－ＮＭＲ分析結果を図２に示す。１．５ｐｐｍ付近のｔ－ブトキシカルボニル基由来のピークが消失した代わりに、４．０ｐｐｍ付近にジメチルイミダゾリウム由来のピークが観察できた。ＧＰＣ分析の結果、得られたアミデートポリマーのポリスチレン換算数平均分子量Ｍｎは１２０００であった。

0.50 g of the copolymer obtained in Example 3, 0.087 g (0.6 mmol) of DMIm-CO ₂ obtained in Example 1, and 35 g of toluene were charged in a 50 mL test tube, and after nitrogen substitution, at 110 ° C. The mixture was stirred for 9.3 hours. The obtained reaction mixture was cooled to 25 ° C., filtered, the filtrate was dried under reduced pressure, washed with methanol and dried again to obtain 0.50 g of amidate polymer represented by the above formula. The results of ¹ H-NMR analysis of the amidate polymer are shown in FIG. Instead of the peak derived from the t-butoxycarbonyl group near 1.5 ppm disappearing, the peak derived from dimethylimidazolium was observed around 4.0 ppm. As a result of GPC analysis, the polystyrene-equivalent number average molecular weight Mn of the obtained amidate polymer was 12000.

[Example 5]
In a test tube, 1.8 g of polyol (SANIX GP3000, manufactured by Sanyo Chemical Industries, Ltd.), 0.2 g of isophorone diisocyanate (manufactured by Tokyo Chemical Industries, Ltd.) (NCO index 100%), amidate polymer 0 obtained in Example 4. .1 g was blended to prepare a urethane resin composition. The obtained urethane resin composition was heated and the curing temperature was measured. In addition, the appearance of the cured resin was confirmed, and the presence or absence of voids was confirmed. The results are shown in Table 1.

[Comparative Example 1]
The same procedure as in Example 5 was carried out except that the urethane resin composition was prepared in Example 5 without adding the amidate polymer. The results are shown in Table 1.

[Comparative Example 2]
It was carried out in the same manner as in Example 5 except that the amidate polymer was replaced with DMIm-CO ₂ in Example 5. The results are shown in Table 1.

The results of Example 5 and Comparative Examples 1 and 2 are shown in Table 1. In Table 1, in the "appearance of the resin composition", ◯ indicates that the resin composition was uniform, and × indicates that the resin composition was non-uniform.

As shown in Table 1, DMIm-CO ₂ had low solubility in the paint, and voids were observed in the cured product. On the other hand, the urethane resin composition to which the amidate polymer of the present invention was added had good solubility in paints, and no void was observed in the cured product. Therefore, the compound of the present invention is for polyurethane production. It was found that it can be suitably used as a catalyst.

[Example 6]
To 12 mg of the amidate polymer obtained in Example 4 was added 1 mL of the solvent shown in Table 2 to a test tube, and the solubility in various solvents at room temperature was evaluated. The results are shown in Table 2.

[Comparative Example 3]
It was carried out in the same manner as in Example 6 except that the amidate polymer was replaced with DMIm-CO ₂ in Example 6. The results are shown in Table 2.

The results of Example 6 and Comparative Example 3 are shown in Table 2. In Table 2, ◯ indicates dissolved and × indicates insoluble.

As shown in Table 2, it was found that the compound of the present invention is soluble in a wide variety of solvents as compared with DMIm-CO ₂ .

[Example 7]
6.4 mg of the amidate polymer obtained in Example 4 was charged in a test tube, opened in the air and allowed to stand. Table 3 shows the results of measuring the water content immediately after charging (after 0 hours) and after 74 hours.

[Comparative Example 4]
It was carried out in the same manner as in Example 7 except that the amidate polymer was replaced with DMIm-CO ₂ in Example 7. The results are shown in Table 3.

As shown in Table 3, the compound of the present invention was found to have lower hygroscopicity as compared with DMIm-CO ₂ .

Claims (11)

An amidate polymer having a structure represented by the following formula (1).
Equation (1):

(In the formula, R ¹ is a bond or an alkylene group having 1 to 3 carbon atoms, R ² is a hydrogen atom or a methyl group, and y is an integer of 1 or more. D is the formula (2-1) :.

(In the formula, R ³ and R ⁶ are a methyl group, an ethyl group, an isopropyl group, a t-butyl group, or an n-octyl group, R ⁷ and R ⁸ are hydrogen atoms, and X is a nitrogen atom and a. Indicates 1.)) ) An amidate polymer having a structure represented by the following formula (1-1).
Equation (1-1):

(In the formula, R ¹ is a bond or an alkylene having 1 to 3 carbon atoms, R ² is a hydrogen atom or a methyl group, and D is the formula (2-1) :.

(In the formula, R ³ and R ⁶ are a methyl group, an ethyl group, an isopropyl group, a t-butyl group, or an n-octyl group, R ⁷ and R ⁸ are hydrogen atoms, and X is a nitrogen atom and a. Indicates 1), y is an integer of 1 or more, and x is an integer of 1 or more. ^R15 is a hydrogen atom or a methyl group. R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same or different, and have a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom and a trifluoromethyl group. , Cyano group, cyanomethyl group or alkoxysilyl group. ) R ³ And R ⁶ The amidate polymer according to claim 1 or 2, wherein is a methyl group. A catalyst for producing polyurethane containing the amidate polymer according to any one of claims 1 to 3 . The method for producing polyurethane by reacting a polyol with polyisocyanate in the presence of the catalyst for producing polyurethane according to claim 4 . The urethane compound represented by the following formula (3) and the ethylenically unsaturated monomer are polymerized as needed to obtain a polymer having a structure represented by the formula (4), and the polymer and the following formula (5-1 ) are obtained. The method for producing an amidate polymer according to claim 1 to 3 , wherein the carboxylate compound represented by ) is reacted.
Equation (3):

(In the formula, R ¹ is a bond or an alkylene having 1 to 3 carbon atoms, R ² is a hydrogen atom or a methyl group , and R ²¹ is a hydrocarbon group which may contain a hetero atom.)
Equation (4):

(In the equation, R ¹ , R ² , and R ²¹ are the same as described above. Y is an integer of 1 or more. )
Equation (5-1):

(In the formula, R ³ and R ⁶ are a methyl group, an ethyl group, an isopropyl group, a t-butyl group, or an n-octyl group, R ⁷ and R ⁸ are hydrogen atoms, and X is a nitrogen atom and a. Indicates 1.) The urethane compound represented by the following formula (3) and the ethylenically unsaturated monomer are copolymerized to obtain a polymer having a structure represented by the following formula (4) , and the polymer and the following formula (5-1) are used. The method for producing an amidate polymer according to any one of claims 1 to 3 , wherein the represented carboxylate compound is reacted.
Equation (3):

(In the formula, R ¹ is a bond or an alkylene having 1 to 3 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ²¹ is a hydrocarbon group which may contain a hetero atom.)
Equation (4):

(In the equation, R ¹ , R ² , and R ²¹ are the same as described above. Y is an integer of 1 or more. )
Equation (5-1):

(In the formula, R ³ and R ⁶ are a methyl group, an ethyl group, an isopropyl group, a t-butyl group, or an n-octyl group, R ⁷ and R ⁸ are hydrogen atoms, and X is a nitrogen atom and a. Indicates 1.) The method for producing an amidate polymer according to claim 6 or 7 , wherein the ethylenically unsaturated monomer is a vinyl-based monomer. The method for producing an amidate polymer according to claim 6 or 7 , wherein the ethylenically unsaturated monomer is a monomer represented by the following formula (8).
Equation (8):

(In the formula, R ¹⁵ is a hydrogen atom or a methyl group. R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are the same or different, hydrogen atom, hydrocarbon group having 1 to 10 carbon atoms, carbon. Alkoxy group, halogen atom, trifluoromethyl group, cyano group, cyanomethyl group or alkoxysilyl group of number 1 to 10). The method for producing an amidate polymer according to claim 6 or 7 , wherein the ethylenically unsaturated monomer is styrene. The method for producing an amidate polymer according to any one of claims 6 to 10 , wherein the carboxylate compound represented by the formula (5-1) is 1,3-dimethylimidazolium-2-carboxylate.

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