Polyisocyanurate raw material composition and process for producing polyisocyanurate

文档序号：1249889 发布日期：2020-08-21 浏览：18次中文

阅读说明：本技术 聚异氰脲酸酯原料组合物及聚异氰脲酸酯的制造方法 (Polyisocyanurate raw material composition and process for producing polyisocyanurate ) 是由仓本拓树中西健一川口恭章西泽尚平奥野好成于 2019-11-13 设计创作，主要内容包括：一种聚异氰脲酸酯原料组合物,其包含多官能异氰酸酯、下述式(I)所示的化合物(I)、和环氧化合物。在式(I)中,R1和R2表示氢原子。R3～R5表示氢原子、碳原子数1～10的烷基、碳原子数6～12的芳基、碳原子数1～10的烷氧基、氨基、碳原子数1～10的单烷基氨基、碳原子数2～20的二烷基氨基、羧基、氰基、碳原子数1～10的氟代烷基、或卤原子。其中,各3个的R3～R5之中,至少1个基团为氨基、碳原子数1～10的单烷基氨基、或碳原子数2～20的二烷基氨基。<Image he="445" wi="700" file="DDA0002271567410000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(A polyisocyanurate raw material composition comprising a polyfunctional isocyanate, a compound (I) represented by the following formula (I), and an epoxy compound. In the formula (I), R 1 And R 2 Represents a hydrogen atom. R 3 ～R 5 Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a monoalkylamino group having 2 to 20 carbon atomsA dialkylamino group, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom. Wherein each 3 of R 3 ～R 5 Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.)

1. A polyisocyanurate raw material composition comprising a polyfunctional isocyanate, a compound (I) represented by the following general formula (I), and an epoxy compound,

in the general formula (I), R¹And R²Represents a hydrogen atom; r³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, an amino group, a carboxyl group,A cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom; 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵May be the same or different; wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

2. A polyisocyanurate raw material composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I),

in the general formula (I), R¹And R²Represents a hydrogen atom; r³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom; 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵May be the same or different; wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

3. The polyisocyanurate raw material composition according to claim 1 or 2, a ratio of the compound (I) to the polyfunctional isocyanate being 100/0.001 to 100/5 in terms of a molar ratio polyfunctional isocyanate/compound (I).

4. The polyisocyanurate raw material composition according to any one of claims 1 to 3, wherein the polyfunctional isocyanate is at least 1 selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, 1, 6-hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, and modified polyisocyanates thereof.

5. The polyisocyanurate raw material composition according to any one of claims 1 to 4, R in the general formula (I)¹And R²Each independently represents a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, wherein R is not included¹And R²Both are hydrogen atoms.

6. A kit for producing a polyisocyanurate comprising (a) a polyfunctional isocyanate, (b) a compound represented by the following general formula (I), and (c) an epoxy compound, wherein each of the above-mentioned (a) to (c) is contained in a different container,

in the general formula (I), R¹And R²Represents a hydrogen atom; r³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom; 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵May be the same or different; wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

7. A kit for producing a polyisocyanurate comprising (d) a composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (c) an epoxy compound, wherein the (d) and the (c) are contained in separate containers,

in the general formula (I), R¹And R²Represents a hydrogen atom; r³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom; 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵May be the same or different; wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

8. A kit for producing a polyisocyanurate comprising (d) a composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (e) a composition comprising a polyfunctional isocyanate and an epoxy compound, wherein the (d) and the (e) are contained in separate containers,

in the general formula (I), R¹And R²Represents a hydrogen atom; r³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom; 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵May be the same or different; wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

9. A kit for producing a polyisocyanurate comprising (e) a composition comprising a polyfunctional isocyanate and an epoxy compound and (b) a compound (I) represented by the following general formula (I), wherein the (e) and the (b) are contained in separate containers,

in the general formula (I), R¹And R²Represents a hydrogen atom; r³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom; 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵May be the same or different; wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

10. A cured polyisocyanurate raw material product obtained by heating the polyisocyanurate raw material composition according to any one of claims 1 to 5.

11. A polyisocyanurate raw material cured product comprising:

a polyisocyanurate; and

at least 1 compound selected from the group consisting of a compound (I) represented by the following general formula (I) and a compound (I ') represented by the following general formula (I'),

in the general formulae (I) and (I'), R¹And R²Represents a hydrogen atom; r³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom; 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵May be the same or different; wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

12. A process for producing a polyisocyanurate, comprising the steps of:

a mixing step of mixing a polyfunctional isocyanate, a compound (I) represented by the following general formula (I), and an epoxy compound; and

a heating step of heating the mixture obtained in the mixing step,

in the general formula (I), R¹And R²Represents a hydrogen atom; r³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom; 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵May be the same or different; wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

13. The process for producing a polyisocyanurate according to claim 12, wherein the mixing step is a step of mixing the epoxy compound in a mixture (d) of the polyfunctional isocyanate and the compound (I).

14. The process for producing a polyisocyanurate according to claim 12, wherein the mixing step is a step of mixing the compound (I) in a mixture (e) of the polyfunctional isocyanate and the epoxy compound.

15. The process for producing polyisocyanurate according to any one of claims 12 to 14, wherein the heating step is performed at a temperature of 40 to 240 ℃.

16. The process for producing polyisocyanurate according to claim 15, wherein the heating step is a step of heating at 60 to 120 ℃ for 1 to 180 minutes and then further heating at 120 to 240 ℃ for 1 to 180 minutes.

17. A catalyst for polyisocyanurate formation reaction comprising a combination of a compound (I) represented by the following general formula (I) and an epoxy compound,

in the general formula (I), R¹And R²Represents a hydrogen atom; r³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom; 3R³May be the same or different from each other,3R⁴Each of which may be the same or different, 3R⁵May be the same or different; wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

18. A kit for producing polyisocyanurate comprising a combination of a compound (I) represented by the following general formula (I) and an epoxy compound as a catalyst for a polyisocyanurate formation reaction,

in the general formula (I), R¹And R²Represents a hydrogen atom; r³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom; 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵May be the same or different; wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

Technical Field

The present invention relates to a polyisocyanurate raw material composition and a method for producing polyisocyanurate. The present invention also relates to a kit for producing polyisocyanurate, a cured polyisocyanurate raw material, and a catalyst for polyisocyanurate formation reaction.

This application claims priority based on Japanese application No. 2019-024875, filed on Japanese application on 2/14/2019, the contents of which are incorporated herein.

Background

The polyisocyanurate is a resin in which isocyanurate rings are optionally bonded. It is considered that introduction of an isocyanurate ring structure into a polyurethane foam improves heat resistance and flame retardancy, but industrial utilization of polyisocyanurate itself has not been advanced.

Polyisocyanurate is synthesized by trimerization reaction of polyfunctional isocyanate. Conventionally, tertiary amines, quaternary ammonium salts, metal salts, and the like have been used as catalysts for trimerization of isocyanates (for example, patent document 1).

Disclosure of Invention

Problems to be solved by the invention

However, catalysts such as tertiary amines, quaternary ammonium salts, and metal salts have high hygroscopicity and therefore cause foaming during heat curing.

On the other hand, as a catalyst having low hygroscopicity, a phosphorus catalyst is exemplified. However, with the phosphorus catalyst, the reaction efficiency of the trimerization reaction of the polyfunctional isocyanate is low, and an isocyanurate ring cannot be formed in an amount sufficient for thermal curing.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing polyisocyanurate having excellent curability with little foaming at the time of heat curing, and a polyisocyanurate raw material composition, a kit for producing polyisocyanurate, and a catalyst for a polyisocyanurate formation reaction which can be used in the above production method. Further, it is an object to provide a polyisocyanurate raw material cured product which is a polyisocyanurate and is produced by the above production method and is reduced in foaming.

Means for solving the problems

The present invention includes the following aspects.

[1] A polyisocyanurate raw material composition comprising a polyfunctional isocyanate, a compound (I) represented by the following general formula (I), and an epoxy compound.

[ in the general formula (I), R¹And R²Represents a hydrogen atom. R³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom. 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵The same or different. Wherein each 3 of R³～R⁵In which at least 1R³～R⁵The amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[2] A polyisocyanurate raw material composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I).

[ in the general formula (I), R¹And R²Represents a hydrogen atomAnd (4) adding the active ingredients. R³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom. 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵The same or different. Wherein each 3 of R³～R⁵In which at least 1R³～R⁵The amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[3] The polyisocyanurate raw material composition according to [1] or [2], wherein the ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate is 100/0.001 to 100/5.

[4] The polyisocyanurate raw material composition according to any one of [1] to [3], wherein the polyfunctional isocyanate is at least 1 selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, 1, 6-hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, and modified polyisocyanates thereof.

[5]According to [1]～[4]The polyisocyanurate raw material composition according to any one of the above general formula (I)³～R⁵Each independently represents a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms.

[6] A kit for producing a polyisocyanurate comprising (a) a polyfunctional isocyanate, (b) a compound represented by the following general formula (I), and (c) an epoxy compound, wherein each of the above-mentioned (a) to (c) is contained in a different container.

[7] A kit for producing a polyisocyanurate comprising (d) a composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (c) an epoxy compound, wherein the (d) and the (c) are contained in separate containers.

[8] The kit for producing a polyisocyanurate, according to item [7], wherein the ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate in the composition of item (d) is 100/0.001 to 100/5 polyfunctional isocyanate/compound (I).

[9] A kit for producing a polyisocyanurate comprising (d) a composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (e) a composition comprising a polyfunctional isocyanate and an epoxy compound, wherein the (d) and the (e) are contained in separate containers.

[10] A kit for producing a polyisocyanurate comprising (e) a composition comprising a polyfunctional isocyanate and an epoxy compound and (b) a compound (I) represented by the following general formula (I), wherein the (e) and the (b) are contained in separate containers.

[ in the general formula (I), R¹And R²Represents a hydrogen atom. R³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a carbon atomA dialkylamino group having a sub-number of 2 to 20, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom. 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵The same or different. Wherein each 3 of R³～R⁵In which at least 1R³～R⁵The amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[11] The kit for producing polyisocyanurate according to any one of [6] to [10], wherein the polyfunctional isocyanate is at least 1 selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, 1, 6-hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, and modified polyisocyanates thereof.

[12]According to [6]～[11]The kit for producing polyisocyanurate of any one of the above formulas (I), wherein R is R³～R⁵Each independently represents a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms (wherein R is not present)¹And R²Both are hydrogen atoms).

[13] A cured polyisocyanurate raw material product obtained by heating the polyisocyanurate raw material composition according to any one of [1] to [5 ].

[14] A polyisocyanurate raw material cured product comprising:

a polyisocyanurate; and

at least 1 compound selected from the group consisting of a compound (I) represented by the following general formula (I) and a compound (I ') represented by the following general formula (I').

[ in the general formulae (I) and (I'), R¹And R²Represents a hydrogen atom. R³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a carbon atomAlkoxy group having 1 to 10 atoms, amino group, monoalkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, carboxyl group, cyano group, fluoroalkyl group having 1 to 10 carbon atoms, or halogen atom. 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵The same or different. Wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[15] The polyisocyanurate raw material cured product according to [14], further comprising at least 1 compound selected from (I) an epoxy compound, (ii) a reactant of the epoxy compound and a polyfunctional isocyanate, (iii) a reactant of the epoxy compound and the above-mentioned compound (I), and (iv) a reactant of the epoxy compound and an epoxy compound.

[16]According to [ 14)]Or [15]]The cured polyisocyanurate raw material, R in the general formulae (I) and (I')³～R⁵Each independently represents a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms.

[17] A process for producing a polyisocyanurate, comprising the steps of: a mixing step of mixing a polyfunctional isocyanate, a compound (I) represented by the following general formula (I), and an epoxy compound; and a heating step of heating the mixture obtained in the mixing step.

[ in the general formula (I), R¹And R²Represents a hydrogen atom. R³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom. 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵The same or different. Wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[18] The process for producing a polyisocyanurate according to [17], wherein the mixing step is a step of mixing the epoxy compound in a mixture (d) of the polyfunctional isocyanate and the compound (I).

[19] The process for producing a polyisocyanurate according to [17], wherein the mixing step is a step of mixing the compound (I) in a mixture (e) of the polyfunctional isocyanate and the epoxy compound.

[20] The process for producing a polyisocyanurate according to [17], wherein the mixing step is a step of mixing a mixture (e) of the polyfunctional isocyanate and the epoxy compound with a mixture (d) of the polyfunctional isocyanate and the compound (I).

[21] The process for producing a polyisocyanurate according to any one of [17] to [20], wherein a mixing ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate is 100/0.001 to 100/5 polyfunctional isocyanate/compound (I).

[22] The process for producing a polyisocyanurate according to any one of [17] to [21], wherein the polyfunctional isocyanate is at least 1 selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, 1, 6-hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, and modified polyisocyanates thereof.

[23]According to [17]～[22]The process for producing polyisocyanurate of any one of the above-mentioned general formula (I), wherein R is³～R⁵Each independently represents a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms.

[24] The process for producing polyisocyanurate according to any one of [17] to [23], wherein the heating step is performed at a temperature of 40 to 240 ℃.

[25] The process for producing polyisocyanurate according to [24], wherein the heating step is a step of heating at 60 to 120 ℃ for 1 to 180 minutes, and then further heating at 120 to 240 ℃ for 1 to 180 minutes.

[26] A catalyst for polyisocyanurate formation reaction comprising a compound (I) represented by the following general formula (I) in combination with an epoxy compound.

[ in the general formula (I), R¹And R²Represents a hydrogen atom. R³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom. 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵The same or different. Wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[27] A kit for producing polyisocyanurate, comprising a combination of a compound (I) represented by the following general formula (I) and an epoxy compound as a catalyst for a polyisocyanurate formation reaction.

[ in the general formula (I), R¹And R²Represents a hydrogen atom. R³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a di-alkyl group having 2 to 20 carbon atomsAn alkylamino group, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom. 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵The same or different. Wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention provides a process for producing polyisocyanurate, which is less likely to foam during heat curing and has excellent curability, and a polyisocyanurate raw material composition, a kit for producing polyisocyanurate, and a catalyst for a polyisocyanurate formation reaction which can be used in the above-mentioned production process. Further, the polyisocyanurate and the polyisocyanurate raw material cured product produced by the above production method are provided which are less foamed.

Drawings

Fig. 1 is a dispersion diagram showing the relationship between the HOMO energy level and the average charge in the ortho position of the compounds shown in table 14.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described below.

In the present specification, the term "polyisocyanurate" refers to a compound having a structure in which a plurality of isocyanurate rings are optionally connected via a 2-valent organic group.

In the present specification, the "polyisocyanurate raw material composition" refers to a composition containing either or both of a raw material for polyisocyanurate (a reactant for polyisocyanurate formation reaction) and a catalyst for polyisocyanurate formation reaction, and is used for producing a polyisocyanurate or a cured polyisocyanurate raw material.

In the present specification, the "kit for producing polyisocyanurate" is a kit containing a raw material for polyisocyanurate and a catalyst for polyisocyanurate formation reaction, and is used for producing polyisocyanurate or a cured material of polyisocyanurate raw material.

In the present specification, the "polyisocyanurate raw material cured product" refers to a polyisocyanurate-containing cured product obtained by heating a polyisocyanurate raw material composition.

In the present specification, when the number of carbon atoms of an alkyl group, an alkoxy group, a fluoroalkyl group, and an aryl group is referred to, the number of carbon atoms in the substituents is not included in the number of carbon atoms.

[ polyisocyanurate raw Material composition ]

EXAMPLE 1 embodiment

In one embodiment, the present invention provides a polyisocyanurate raw material composition including a polyfunctional isocyanate, a compound represented by the following general formula (I) (hereinafter, also referred to as "compound (I)"), and an epoxy compound.

(polyfunctional isocyanate)

The "polyfunctional isocyanate" refers to a compound containing 2 or more isocyanate groups (— N ═ C ═ O). The polyfunctional isocyanate may be used without particular limitation as the polyfunctional isocyanate generally used for the production of polyisocyanurate. The number of the isocyanate group contained in the polyfunctional isocyanate is not particularly limited as long as it is 2 or more, and is preferably 2 to 5, more preferably 2 or 3, and further preferably 2. Examples of the polyfunctional isocyanate include aliphatic isocyanates and aromatic isocyanates.

The aliphatic isocyanate is a polyfunctional isocyanate containing an aliphatic hydrocarbon group and 2 or more isocyanate groups. The aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group having a ring in its structure. Examples of the aliphatic hydrocarbon group having a ring in its structure include an alicyclic group, a group in which the alicyclic group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which the alicyclic group is interposed in the linear or branched aliphatic hydrocarbon group, and the like. The aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 5 to 10 carbon atoms.

The aromatic isocyanate is a polyfunctional isocyanate containing at least 1 aromatic ring and 2 or more isocyanate groups. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n +2) pi electrons, and may be monocyclic or polycyclic. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of carbon atoms of the aromatic ring is preferably 6 to 15, more preferably 6 to 12. The number of aromatic rings in the aromatic isocyanate is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2. The aromatic isocyanate may contain an aliphatic hydrocarbon group in addition to the aromatic ring and the isocyanate group. Examples of the aliphatic hydrocarbon group include the same groups as those listed as the aliphatic hydrocarbon group in the aliphatic isocyanate.

Specific examples of the aliphatic isocyanate include tetramethylene-1, 4-diisocyanate, pentamethylene-1, 5-diisocyanate, hexamethylene-1, 6-diisocyanate, octamethylene-1, 8-diisocyanate, dodecamethylene-1, 12-diisocyanate, 2, 4-trimethylhexamethylene-1, 6-diisocyanate, 2,4, 4-trimethylhexamethylene-1, 6-diisocyanate, 1-isocyanato-3, 3, 5-trimethyl-5-iso-cyanateCyanate methylcyclohexane cis-cyclohexane-1, 4-diisocyanate, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane trans-cyclohexane-1, 4-diisocyanate, dicyclohexylmethane-4, 4 ' -diisocyanate, omega ' -diisocyanatomethyl-1, 4-cyclohexane, omega ' -diisocyanatomethyl-1, 3-cyclohexane, 3, 10-diisocyanatotricyclo [5, 2,1, 0]^2.6Decane, 2-bis (4-isocyanatocyclohexyl) propane, 6, 8-diisocyanatodicyclo [3, 3, 0] octene, undecane-1, 6, 10-triisocyanate, lysine diisocyanate methyl ester, N' -bis (. omega. -isocyanatopropyl)Diazinetrione, etc., but is not limited thereto.

Specific examples of the aromatic isocyanate include toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, diphenylmethane-2, 4 '-diisocyanate, diphenylmethane-4, 4' -diisocyanate, naphthylene-1, 5-diisocyanate, toluene diisocyanate, dimethylbiphenyl diisocyanate (bitolylene diisocyanate), anisidine diisocyanate, 3 '-dimethylbiphenyl-4, 4' -diisocyanate, diphenyl ether-4, 4 '-diisocyanate, triphenylmethane-4, 4', 4 "-triisocyanate, tris (4-isocyanatophenyl) thiophosphate, xylylene-1, 3-diisocyanate, xylylene-1, 4-diisocyanate, etc., but is not limited thereto.

The polyfunctional isocyanate may be a polyphenyl polymethylene polyisocyanate of the type obtained by condensing aniline and formaldehyde and then phosgenating the resulting product, diphenylmethane diisocyanates which are liquid at ordinary temperatures and contain carbodiimide groups or uretonimine groups as described in german patent No. 1092007, or modified polyisocyanates containing urethane bonds, allophanate bonds, isocyanurate ring structures, urea bonds, biuret bonds, uretdione ring structures, or the like.

The polyfunctional isocyanate may be an isocyanate-based prepolymer obtained by reacting an excess of the above-mentioned isocyanate with a polyol used in the urethane industry.

Among these, as the polyfunctional isocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, 1, 6-hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, modified polyisocyanates thereof, and the like are preferable.

The polyfunctional isocyanate may be any commercially available one. As commercially available products of polyfunctional isocyanates, there may be mentioned, for example, ミリオネート (registered trademark) MT (chinese character of imperial service ソー), コロネート (registered trademark) T-65 (chinese character of imperial service ソー), コロネート (registered trademark) T-80 (chinese character of imperial service ソー), コロネート (registered trademark) T-100 (chinese character of imperial service ソー), HDI (chinese character of imperial service ソー), デュラネート (registered trademark) 50M (asahi chemical corporation ケミカルズ), タケネート (registered trademark) 600 (three-well chemical corporation), コロネート (registered trademark) HX (chinese character of ソー), デュラネート (registered trademark) TPA-100 (asahi chemical corporation ケミカルズ), デュラネート (registered trademark) 24A-100 (asahi chemical corporation ケミカルズ), デュラネート (registered trademark) D201 (asahi chemical corporation ケミカルズ), and the like.

The polyfunctional isocyanate may be a polyfunctional isocyanate having a blocked isocyanate group. By "isocyanate group is blocked" is meant that the isocyanate group is protected by a protecting group. The blocked isocyanate group may be represented by the general formula — "N — C (═ O) -B (B is a protecting group)". As the protecting group, those generally used as a protecting group for an isocyanate group can be used without particular limitation. By using a polyfunctional isocyanate having a blocked isocyanate group (hereinafter, sometimes referred to as "blocked polyfunctional isocyanate"), it is possible to prevent an unexpected trimerization reaction from proceeding.

The polyfunctional isocyanate may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The proportion of the polyfunctional isocyanate in the polyisocyanurate raw material composition of the present embodiment is, for example, 80 mol% or more and less than 100 mol%. The proportion of the polyfunctional isocyanate in the polyisocyanurate raw material composition is preferably 85 mol% or more and 99.99 mol% or less, more preferably 90 mol% or more and 98 mol% or less, and further preferably 93 mol% or more and 97 mol% or less. When the ratio of the polyfunctional isocyanate is not less than the lower limit of the above range, good heat resistance can be achieved. Further, if the ratio of the polyfunctional isocyanate is not more than the upper limit of the above range, it is easy to achieve a balance with other components.

(Compound (I))

The compound (I) is a compound represented by the following general formula (I).

[ in the general formula (I), R¹And R²Represents a hydrogen atom. R³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom. 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵The same or different. Wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

In the above general formula (I), R¹And R²Represents a hydrogen atom.

In the above general formula (I), R³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom.

R³～R⁵The alkyl group having 1 to 10 carbon atoms in (A) may be linear or branched, or may have a structure containing a ring. R³～R⁵Of 1 to 10 carbon atomsThe alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 or 2 carbon atoms.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an isopentyl group, and a sec-pentyl group.

R³～R⁵The linear or branched alkyl group in (1) may have a substituent.

In the present specification, the phrase "may have a substituent" means that a hydrogen atom (-H) of a hydrocarbon group may be substituted with a 1-valent group. Examples of the substituent include an amino group, a carboxyl group, a cyano group, and a halogen atom. Examples of the halogen atom of the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As R³～R⁵The linear or branched alkyl group in (1) is more preferably an unsubstituted alkyl group.

Examples of the alkyl group having a structure containing a ring include a cycloalkyl group, a group in which a cycloalkane ring is bonded to the end of a linear or branched alkyl group, and a group in which a cycloalkane ring is interposed between linear or branched alkyl groups. In the above, the cycloalkane ring may be monocyclic or polycyclic, but is preferably monocyclic. Examples of the alkyl group having a structure containing a ring include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a group in which a linear or branched alkyl group is bonded to the cycloalkyl group, and the like.

R³～R⁵The alkyl group containing a ring in the structure (1) may have a substituent. Examples of the substituent include an amino group, a carboxyl group, a cyano group, and a halogen atom.

R³～R⁵The alkoxy group having 1 to 10 carbon atoms in (A) is preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 or 2 carbon atoms.

The alkoxy group is a group represented by-OR (R is an alkyl group). The alkyl group in the above R may be linear or branched, or may have a ring in the structure, but is preferably linear or branched. Examples of the alkyl group include the same groups as those listed for the alkyl group having 1 to 10 carbon atoms.

Specific examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group and the like. Wherein R is³～R⁵The alkoxy group having 1 to 10 carbon atoms in (A) is preferably a methoxy group or an ethoxy group, and more preferably a methoxy group.

R³～R⁵The aryl group having 6 to 12 carbon atoms in (A) is preferably 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a tolyl group, an o-xylyl group, a naphthyl group, and a biphenyl group.

R³～R⁵The aryl group having 6 to 12 carbon atoms in (A) may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an amino group, a carboxyl group, a cyano group, a halogen atom, and the like.

R³～R⁵The fluoroalkyl group having 1 to 10 carbon atoms in (A) is preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 or 2 carbon atoms. As R³～R⁵Specific examples of the fluoroalkyl group having 1 to 10 carbon atoms in (b) include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a group in which a part or all of hydrogen atoms of an alkyl group exemplified as the alkyl group having 1 to 10 carbon atoms is substituted with a fluorine atom.

As R³～R⁵Examples of the halogen atom in (2) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Wherein, as R³～R⁵The halogen atom in (2) is preferably a fluorine atom.

R³～R⁵In the (C1-C10) monoalkylamino group or C2-C20 dialkylamino group, each alkyl group is preferably C1-C10, preferably C1-C5, more preferably C1-C3, and still more preferably C1 or C2. The alkyl group may be linear or branched, or may have a ring in its structure. As R¹And R²Number of carbon atoms in (2)Specific examples of the monoalkylamino group having 1 to 10 carbon atoms or the dialkylamino group having 2 to 20 carbon atoms include a methylamino group, a dimethylamino group, and a group in which 1 or 2 of the hydrogen atoms of the amino group are substituted with an alkyl group exemplified as the alkyl group having 1 to 10 carbon atoms.

Wherein, as R³～R⁵From the viewpoint of reactivity, a hydrogen atom or an electron donating group is preferable. More specifically, R³～R⁵Preferably a hydrogen atom, an alkoxy group, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms, and more preferably a hydrogen atom, an alkoxy group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. As R³～R⁵Preferable examples of the (B) group include a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms, and a hydrogen atom, a methoxy group, a monomethylamino group, or a dimethylamino group is particularly preferable.

In the above general formula (I), 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵The same or different. With respect to 3R³3 of the groups may be different from each other, 2 of the 3 groups may be the same, 1 may be different, or 3 groups may all be the same, but 3R groups are preferable³All the same. With respect to 3R⁴3 of the groups may be different from each other, 2 of the 3 groups may be the same, 1 may be different, or 3 groups may all be the same, but 3R groups are preferable⁴All the same. With respect to 3R⁵3 of the groups may be different from each other, 2 of the 3 groups may be the same, 1 may be different, or 3 groups may all be the same, but 3R groups are preferable⁵All the same. Wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

Specific examples of the compound (I) include the compounds of phosphorus catalysts Nos. 13 to 59 described in tables 15 to 16, and DMAPDPP (phosphorus catalyst No.12) described below.

The compound (I) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The proportion of the compound (I) in the polyisocyanurate raw material composition of the present embodiment may be, for example, more than 0 mol% and 10 mol% or less. The proportion of the compound (I) in the polyisocyanurate raw material composition is preferably 0.001 mol% or more and 5 mol% or less, more preferably 0.01 mol% or more and 2 mol% or less, and further preferably 0.05 mol% or more and 2 mol% or less. If the ratio of the compound (I) is not less than the lower limit of the above range, good reaction efficiency can be achieved. Further, if the proportion of the compound (I) is not more than the upper limit of the above range, it is easy to achieve a balance with other components.

The ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate is preferably 100/0.001 to 100/5, more preferably 100/0.01 to 100/2, and still more preferably 100/0.05 to 100/2, based on the polyfunctional isocyanate/compound (I).

(epoxy compound)

The epoxy compound in the present embodiment is a compound containing 1 or more epoxy groups. The epoxy compound may be a compound generally used for a trimerization reaction of isocyanates without particular limitation. The epoxy equivalent of the epoxy compound is not particularly limited, but is preferably 50g/mol to 1000g/mol, more preferably 100g/mol to 500g/mol, and still more preferably 100g/mol to 300 g/mol.

Specific examples of the epoxy compound include monoepoxides such as allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, butylene oxide, propylene oxide, octylene oxide, styrene oxide, glycidol, and glycidyl esters of versatic acid;

1, 2-cyclohexanedicarboxylic acid diglycidyl ester, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, epoxidized butadiene, 3, 4-epoxycyclohexylmethyl- (3, 4-epoxy) cyclohexanecarboxylate, dicyclohexylene dioxide, 4 '-bis (1, 2-epoxyethyl) diphenyl ether, 4' -bis (1, 2-epoxyethyl) biphenyl, 2-bis (3, 4-epoxycyclohexyl) propane, m-phenylenediDiglycidyl ether of phenol, diglycidyl ether of methyltriphenol, bis (2, 3-epoxycyclopentyl) ether, 2- (3, 4-epoxy) cyclohexane-m-bisDiepoxides such as alkanes, bis (3, 4-epoxy-6-methylcyclohexyl) adipate, and N, N' -m-phenylenebis (4, 5-epoxy-1, 2-cyclohexane) dicarboximide;

and 3 or more functional epoxides such as triglycidyl isocyanurate, triglycidyl ether of p-aminophenol, polyallyl glycidyl ether, 1,3,5- (1, 2-epoxyethyl) benzene-2, 2 '-4, 4' -tetracyclooxypropoxy benzophenone, tetracyclooxypropoxy tetraphenylethane, polyglycidyl ether of phenol novolac, polyglycidyl ether of cresol novolac, triglycidyl ether of glycerin, and triglycidyl ether of trimethylolpropane.

Among the above, as the epoxy compound, phenyl glycidyl ether, styrene oxide, 1, 2-cyclohexanedicarboxylic acid diglycidyl ester, diglycidyl ether of bisphenol a, triglycidyl isocyanurate, polyglycidyl ether of phenol novolak, polyglycidyl ether of cresol novolak, and the like are preferable because they are industrially easily available.

The epoxy compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The proportion of the epoxy compound in the polyisocyanurate raw material composition of the present embodiment is, for example, more than 0 mol% and 20 mol% or less. The proportion of the compound (I) in the polyisocyanurate raw material composition is preferably 0.001 mol% or more and 15 mol% or less, more preferably 0.005 mol% or more and 10 mol% or less, and further preferably 0.1 mol% or more and 7 mol% or less. If the ratio of the compound (I) is not less than the lower limit of the above range, good reaction efficiency can be achieved. Further, if the proportion of the compound (I) is not more than the upper limit of the above range, it is easy to achieve a balance with other components.

The ratio (molar ratio) of the epoxy compound to the polyfunctional isocyanate is preferably 100/0.001 to 100/15, more preferably 100/0.005 to 100/10, and still more preferably 100/0.1 to 100/7.

(optional Components)

The polyisocyanurate raw material composition of the present embodiment may contain other components in addition to the above-mentioned polyfunctional isocyanate, compound (I) and epoxy compound. Examples of the other components include a solvent, a curing accelerator, a silane coupling agent, an antioxidant, a mold release agent, a defoaming agent, an emulsifier, a thixotropy imparting agent, a smoothing agent, a flame retardant, a pigment, a filler, and a shrinkage reducing agent.

By heating the polyisocyanurate raw material composition of the present embodiment, the trimerization reaction of the polyfunctional isocyanate proceeds to produce polyisocyanurate. The compound (I) and the epoxy compound mainly function as catalysts for the trimerization reaction of the polyfunctional isocyanate. Phosphorus catalysts generally have low hygroscopicity and are inhibited from foaming during heating, but when used as catalysts for the polyisocyanurate formation reaction, they have problems of low reactivity and insufficient curability (yield). However, as shown in examples described later, the compound (I) has a specific structure represented by the general formula (I) and exhibits high reactivity when used as a catalyst for a polyisocyanurate formation reaction, and can achieve sufficient curability (yield). That is, since the compound (I) has low hygroscopicity and high reactivity as a catalyst, foaming is suppressed and sufficient curability can be obtained at the time of thermal curing.

EXAMPLE 2 EXAMPLE

In one embodiment, the present invention provides a polyisocyanurate raw material composition comprising a polyfunctional isocyanate and a compound (I).

(polyfunctional isocyanate)

The polyfunctional isocyanate is the same as the polyfunctional isocyanate described in the description of embodiment 1. Preferred examples of the polyfunctional isocyanate include the same ones as those listed in embodiment 1 above.

The polyfunctional isocyanate may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The proportion of the polyfunctional isocyanate in the polyisocyanurate raw material composition of the present embodiment is, for example, 90 mol% or more and less than 100 mol%. The proportion of the polyfunctional isocyanate in the polyisocyanurate raw material composition is preferably 95 mol% or more and 99.99 mol% or less, more preferably 98 mol% or more and 99.99 mol% or less, and still more preferably 98 mol% or more and 99.95 mol% or less. When the ratio of the polyfunctional isocyanate is not less than the lower limit of the above range, good heat resistance can be achieved. Further, if the ratio of the polyfunctional isocyanate is not more than the upper limit of the above range, it is easy to achieve a balance with other components.

(Compound (I))

The compound (I) is the same as the compound (I) described in the description of embodiment 1. Preferred examples of the compound (I) include the same ones as those listed in embodiment 1 above.

Among them, as the compound (I), R in the above general formula (I) is preferable³～R⁵Each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms.

Furthermore, the compound (I) is preferably a compound represented by the above general formula (I-1), more preferably R in the above general formula (I-1)³～R⁵Each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms.

Among the above, the alkoxy group having 1 to 4 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, more preferably an ethoxy group or a methoxy group, and still more preferably a methoxy group. The alkyl group of the monoalkylamino group having 1 to 4 carbon atoms or the dialkylamino group having 2 to 8 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methylamino group or a dimethylamino group.

Specific examples of the compound (I) include the phosphorus catalysts Nos. 12 to 59 described in tables 14 to 16, which will be described later.

The compound (I) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(optional Components)

The polyisocyanurate raw material composition of the present embodiment may contain other components in addition to the polyfunctional isocyanate and the compound (I). As the other components, the same other components as those mentioned in embodiment 1 above can be mentioned.

The polyisocyanurate raw material composition of the present embodiment is mixed with an epoxy compound and heated to cause a trimerization reaction of a polyfunctional isocyanate to proceed, thereby producing polyisocyanurate. As the epoxy compound, the same epoxy compounds as those described in the description of embodiment 1 above can be used. Like the polyisocyanurate raw material composition of embodiment 1, the compound (I) and the epoxy compound mainly function as a catalyst for the trimerization reaction of the polyfunctional isocyanate. Since the compound (I) has low hygroscopicity and high reactivity as a catalyst, foaming is suppressed during heating, and sufficient curability (yield) can be obtained.

[ kit for producing polyisocyanurate ]

The kit for producing a polyisocyanurate of the present embodiment includes a polyfunctional isocyanate, a compound (I), and an epoxy compound.

Examples of the kit of the present embodiment include a kit comprising (a) a polyfunctional isocyanate, (b) a compound (I), (c) an epoxy compound, (d) a composition containing a polyfunctional isocyanate and a compound (I), and (e) a composition containing a polyfunctional isocyanate and an epoxy compound, each contained in a separate container, in an appropriate combination.

In the kit of the present embodiment, the amounts of the polyfunctional isocyanate, the compound (I), and the epoxy compound contained in the respective containers are not particularly limited, but are preferably amounts corresponding to a mixing ratio at which the respective components are mixed at the time of producing the polyisocyanurate.

For example, the molar ratio of the total molar amount of the polyfunctional isocyanates to the total molar amount of the compound (I) contained in the kit of the present embodiment is preferably 100/0.001 to 100/5, more preferably 100/0.01 to 100/2, and still more preferably 100/0.05 to 100/2, of the polyfunctional isocyanates/compound (I).

For example, the molar ratio of the total molar amount of polyfunctional isocyanates to the total molar amount of epoxy compounds contained in the kit of the present embodiment is preferably 100/0.001 to 100/15, more preferably 100/0.005 to 100/10, and still more preferably 100/0.1 to 100/7.

The container is not particularly limited, and may be any container. The material of the container may be any material as long as it is not corroded by the contents, and examples thereof include glass, resin, and metal.

EXAMPLE 1 (kit comprising (a), (b) and (c))

In one embodiment, the present invention provides a kit for producing polyisocyanurate comprising (a) a polyfunctional isocyanate, (b) a compound (I), and (c) an epoxy compound, wherein the above-mentioned (a) to (c) are contained in separate containers.

(polyfunctional isocyanate)

The polyfunctional isocyanate is the same as the polyfunctional isocyanate described in the description of embodiment 1 of the aforementioned "[ polyisocyanurate raw material composition ]. Preferable examples of the polyfunctional isocyanate include the same preferable examples as the preferable examples in embodiment 1 of the above-mentioned "[ polyisocyanurate raw material composition ].

(Compound (I))

The compound (I) is the same as the compound (I) described in the description of embodiment 1 of the aforementioned "[ polyisocyanurate raw material composition ]. Preferable examples of the compound (I) include the same preferable examples as those mentioned in embodiment 1 of the above-mentioned "[ polyisocyanurate raw material composition ]".

The compound (I) is preferably contained in a container in a state of being dissolved in a solvent. The solvent is not particularly limited as long as it can dissolve the compound (I), and a known organic solvent or the like can be used.

(epoxy compound)

The epoxy compound is the same as the epoxy compound described in the description of embodiment 1 of the aforementioned "[ polyisocyanurate raw material composition ]. Preferred examples of the epoxy compound include the same preferred examples as those mentioned in embodiment 1 of the above-mentioned "[ polyisocyanurate raw material composition ].

In the production of the polyisocyanurate, the polyfunctional isocyanate (a), the compound (b), and the epoxy compound (c) contained in the kit of the present embodiment may be mixed. By heating the above mixture, the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate can be obtained.

EXAMPLE 2 EXAMPLE (kit comprising (d) and (c))

In one embodiment, the present invention provides a kit for producing polyisocyanurate comprising (d) a composition comprising a polyfunctional isocyanate and a compound (I), and (c) an epoxy compound, wherein the (d) and the (c) are contained in separate containers.

(composition (d))

The kit of the present embodiment contains a composition (hereinafter referred to as "composition (d)") comprising a polyfunctional isocyanate and the compound (I).

The composition (d) is the same composition as the polyisocyanurate raw material composition according to embodiment 2 described in the section of "[ polyisocyanurate raw material composition ]".

(epoxy compound)

The epoxy compound is the same as that of the kit according to embodiment 1.

In the production of the polyisocyanurate, the composition (d) and the epoxy compound (c) contained in the kit of the present embodiment may be mixed. By heating the above mixture, the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate can be obtained.

EXAMPLE 3 EXAMPLE (kit comprising (d) and (e))

In one embodiment, the present invention provides a kit for producing a polyisocyanurate comprising (d) a composition comprising a polyfunctional isocyanate and a compound (I), and (e) a composition comprising a polyfunctional isocyanate and an epoxy compound, wherein the (d) and the (e) are contained in separate containers.

(composition (d))

The composition (d) is the same as the kit according to embodiment 2.

(composition (e))

The kit of the present embodiment contains a composition (hereinafter, referred to as "composition (e)") containing a polyfunctional isocyanate and an epoxy compound.

The polyfunctional isocyanate contained in the composition (e) is the same as the polyfunctional isocyanate described in the description of embodiment 1 of the aforementioned "[ polyisocyanurate raw material composition ]. Preferable examples of the polyfunctional isocyanate include the same preferable examples as the preferable examples in embodiment 1 of the above-mentioned "[ polyisocyanurate raw material composition ].

The polyfunctional isocyanate may be the same as or different from the polyfunctional isocyanate contained in the above-mentioned composition (d).

The epoxy compound contained in the composition (e) is the same as the epoxy compound described in the description of embodiment 1 of the aforementioned "[ polyisocyanurate raw material composition ]. Preferred examples of the epoxy compound include the same preferred examples as those mentioned in embodiment 1 of the above-mentioned "[ polyisocyanurate raw material composition ].

In the production of polyisocyanurate, the composition (d) and the composition (e) contained in the kit of the present embodiment may be mixed. By heating the above mixture, the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate can be obtained.

EXAMPLE 4 th embodiment (kit comprising (b) and (e))

In one embodiment, the present invention provides a kit for producing a polyisocyanurate comprising (e) a composition containing a polyfunctional isocyanate and an epoxy compound and (b) a compound (I), wherein the (e) and the (b) are contained in separate containers.

(composition (e))

The composition (e) is the same as the kit according to embodiment 3.

(Compound (I))

The compound (I) is the same as the kit according to embodiment 1.

In the production of the polyisocyanurate, the composition (e) and the compound (I) (b) contained in the kit of the present embodiment may be mixed. By heating the above mixture, the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate can be obtained.

The kits according to embodiments 1 to 4 may include any configuration in addition to the above-mentioned components. Examples of the optional structure include a description for producing polyisocyanurate, a mold for casting a polyisocyanurate raw material composition, and the like. In addition, when the polyfunctional isocyanate (a) contained in the kit of embodiment 1, or the polyfunctional isocyanate contained in the composition (d) or the composition (e) contained in the kit of embodiments 2 to 4 is a blocked polyfunctional isocyanate, the kit of embodiments 1 to 4 may contain a reagent for deprotecting the blocked polyfunctional isocyanate as an arbitrary configuration.

[ cured product of polyisocyanurate raw Material ]

In one embodiment, the present invention provides a cured polyisocyanurate raw material obtained by heating a polyisocyanurate raw material composition containing a polyfunctional isocyanate, a compound (I), and an epoxy compound. The cured polyisocyanurate raw material contains not only polyisocyanurate formed from polyfunctional isocyanate but also unreacted polyfunctional isocyanate, dimer, catalyst, modified catalyst, and other impurities.

The polyisocyanurate is not particularly limited as long as it has a structure in which a plurality of isocyanurate rings are optionally connected via a 2-valent organic group. The structure of the polyisocyanurate can be represented by, for example, the following general formula (II).

[ wherein R represents a 2-valent organic group, and n represents an integer of 2 or more. The plural R's may be the same or different. ]

In the general formula (II), R is a 2-valent organic group derived from a polyfunctional isocyanate.

In the case where the polyfunctional isocyanate used in the trimerization reaction is an aliphatic isocyanate, R is an aliphatic hydrocarbon group (e.g., alkylene group). When the polyfunctional isocyanate used in the trimerization reaction is an aromatic isocyanate, R is an aromatic hydrocarbon group (for example, an arylene group).

Polyisocyanurate has a structure in which isocyanurate rings are randomly bonded via a 2-valent organic group, and it is difficult to specify a whole structure. The polyisocyanurate raw material cured product according to the present embodiment can contain a plurality of types of polyisocyanurates having different structures and molecular weights. The polyisocyanurate raw material cured product according to the present embodiment may contain a compound (I) and an epoxy compound described later, and a reaction product (modified product) thereof.

The polyisocyanurate raw material cured product of the present embodiment can be obtained by mixing and heating a polyfunctional isocyanate, a compound (I), and an epoxy compound. The "heating" may be performed in the same manner as the heating step described in the section "production method of polyisocyanurate" to be described later.

The polyisocyanurate raw material cured product of the present embodiment may contain polyisocyanurate and at least 1 compound selected from the compounds represented by the above-mentioned compound (I) and the following general formula (I ') (hereinafter, also referred to as "compound (I')").

[ in the general formulae (I) and (I'), R¹And R²Represents a hydrogen atom. R³～R⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxyl group, a cyano group, a fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom. 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵The same or different. Wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

The proportion of the polyisocyanurate in the polyisocyanurate raw material cured product of the present embodiment is, for example, preferably 70 mass% or more and less than 100 mass%, and more preferably 80 to 99 mass%.

(Compound (I))

(Compound (I'))

The compound (I') is an oxide of the above-mentioned compound (I).

R in the above general formula (I')¹～R⁵And R in the above general formula (I)¹～R⁵The same is true. As R in the above formula (I')³～R⁵Preferable examples of (B) include R in the above general formula (I)³～R⁵Preferred examples of the present invention include the same preferred examples as the preferred examples. The compound (I') is preferably an oxide of the compound exemplified as a specific example of the compound (I).

The amount of the compound (I') contained in the cured polyisocyanurate raw material according to the present embodiment may be 1 or 2 or more.

The cured polyisocyanurate raw material according to the present embodiment may contain only the compound (I), only the compound (I '), or both the compound (I) and the compound (I'). When the polyisocyanurate raw material cured product of the present embodiment contains both the compound (I) and the compound (I '), the compound (I') is an oxide of the compound (I).

The total proportion of the compound (I) and the compound (I') in the polyisocyanurate raw material cured product of the present embodiment is, for example, preferably 0.001 to 5% by mass, and more preferably 0.001 to 1% by mass.

(epoxy Compound and reactant thereof)

The cured polyisocyanurate raw material according to the present embodiment may contain other components in addition to the polyisocyanurate and at least 1 compound selected from the group consisting of the compound (I) and the compound (I'). Examples of the other component include (I) an epoxy compound, (ii) a reactant of the epoxy compound and a polyfunctional isocyanate, (iii) a reactant of the epoxy compound and the above-mentioned compound (I), and (iv) a reactant of the epoxy compound and the epoxy compound (hereinafter, the components (I) to (iv) may be collectively referred to as "epoxy compounds" in some cases).

[ epoxy compound ]

[ reaction product of epoxy Compound with polyfunctional isocyanate ]

The reactant of the epoxy compound and the polyfunctional isocyanate is a compound produced by reacting the polyfunctional isocyanate with the epoxy compound upon heating reaction. The reactant of the epoxy compound and the polyfunctional isocyanate is not particularly limited as long as it is a compound produced by reacting the epoxy compound and the polyfunctional isocyanateThere are particular limitations. The reactant may, for example, compriseOxazolidone ring compounds.

[ reaction product of epoxy Compound with Compound (I) ]

The reactant of the epoxy compound and the compound (I) is a compound produced by reacting the epoxy compound and the compound (I) upon heating reaction. The reactant of the epoxy compound and the compound (I) is not particularly limited as long as it is a compound produced by reacting the epoxy compound and the compound (I). For example, in the case where the epoxy compound is a compound represented by the following general formula (E), a compound represented by the following general formula (E-1) can be exemplified as a reactant of the epoxy compound and the compound (I).

[ in the formula (E-1), R¹～R⁵And R in the general formula (I)¹～R⁵The same is true. 3R³Each of which may be the same or different, 3R⁴Each of which may be the same or different, 3R⁵The same or different. Wherein each 3 of R³～R⁵Wherein at least 1 group is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. In formulae (E) and (E-1), Re¹Is an organic radical.]

For example, in the case where the epoxy compound is phenyl glycidyl ether, Re in the above general formulae (E) and (E-1)¹Is phenoxymethyl.

[ reaction product of epoxy Compound with epoxy Compound ]

The reactant of the epoxy compound and the epoxy compound (reactant of the epoxy compounds) is a compound produced by reacting 2 or more epoxy compounds during the heating reaction. The reactant of the epoxy compounds is not particularly limited as long as it is a compound produced by reacting 2 or more epoxy compounds. For example, in the case where the epoxy compound is a compound represented by the above general formula (E), a polymer having a repeating unit represented by the following general formula (E-2) can be exemplified as a reactant of the epoxy compound and the epoxy compound.

[ in the formula (E-2), Re¹Is an organic radical.]

For example, in the case where the epoxy compound is phenyl glycidyl ether, Re in the above general formula (E-2)¹Is phenoxymethyl.

The total amount of the epoxy compounds and the like in the cured polyisocyanurate raw material according to the present embodiment is, for example, preferably 0.001 to 30% by mass, and more preferably 0.01 to 20% by mass.

Examples of the polyisocyanurate raw material cured product according to the present embodiment include, for example, polyisocyanurate containing 70% by mass or more and less than 100% by mass (preferably 79% by mass to 99.98% by mass); more than 0 mass% and 5 mass% or less (preferably 0.001 to 1 mass%) of the compound (I) and the compound (I') in total; and a cured product of a polyisocyanurate raw material such as an epoxy compound in an amount of more than 0 mass% and less than 30 mass% (preferably 0.01 to 20 mass%) in total.

The polyisocyanurate raw material cured product of the present embodiment is produced using the compound (I) as a catalyst, and therefore has little foaming and sufficient hardness. Therefore, the polyisocyanurate raw material cured product of the present embodiment can be used for various applications such as paints, adhesives, sealing materials, and optical members.

[ Process for producing polyisocyanurate ]

In one embodiment, the present invention provides a process for producing polyisocyanurate, comprising the steps of: a mixing step of mixing a polyfunctional isocyanate, a compound (I) represented by the general formula (I), and an epoxy compound; and a heating step of heating the mixture obtained in the mixing step.

(mixing procedure)

The mixing step is a step of mixing the polyfunctional isocyanate, the compound (I), and the epoxy compound.

(polyfunctional isocyanate)

(Compound (I))

(epoxy compound)

The mixing ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate is preferably 100/0.001 to 100/5, more preferably 100/0.01 to 100/2, and still more preferably 100/0.05 to 100/2.

The mixing ratio (molar ratio) of the epoxy compound to the polyfunctional isocyanate is preferably 100/0.001 to 100/15, more preferably 100/0.005 to 100/10, and still more preferably 100/0.1 to 100/7.

In the mixing step, the order of mixing the polyfunctional isocyanate, the compound (I), and the epoxy compound is not particularly limited, but it is preferable not to mix the compound (I) and the epoxy compound first from the viewpoint of suppressing the unexpected reaction from proceeding.

The mixing step may be, for example, a step of mixing an epoxy compound in the mixture (d) of the polyfunctional isocyanate and the compound (I). As the mixture (d), the polyisocyanurate raw material composition according to embodiment 2 explained in the section of "[ polyisocyanurate raw material composition ]" can be used.

The mixing step may be, for example, a step of mixing the compound (I) in a mixture (e) of a polyfunctional isocyanate and an epoxy compound. As the mixture (e), the same one as the composition (e) contained in the polyisocyanurate production kit according to embodiment 4 described in the section of "[ polyisocyanurate production kit ]", can be used.

The mixing step may be, for example, a step of mixing the mixture (e) of the polyfunctional isocyanate and the epoxy compound with the mixture (d) of the polyfunctional isocyanate and the compound (I). As the mixture (d), the same one as the composition (d) contained in the polyisocyanurate production kit according to embodiment 3 described in the section of "[ polyisocyanurate production kit ]", can be used. As the mixture (e), the same one as the composition (e) contained in the polyisocyanurate production kit according to embodiment 3 described in the section of "[ polyisocyanurate production kit ]", can be used.

When the polyfunctional isocyanate contains a blocked polyfunctional isocyanate, the deprotection reaction of the blocked isocyanate group may be performed before the mixing step, after the mixing step, or during the mixing step. The deprotection reaction can be appropriately selected depending on the kind of the protecting group for blocking the isocyanate group.

Heating Process

The heating step is a step of heating the mixture obtained in the mixing step.

After the mixing step, the mixture of the polyfunctional isocyanate, the compound (I) and the epoxy compound is appropriately stirred, poured into a mold or the like, and then heated to react. The heating temperature may be a temperature sufficient for the progress of the polyisocyanurate formation reaction, and may be, for example, 40 to 240 ℃ and preferably 60 to 200 ℃.

The heating time may be sufficient for the production of polyisocyanurate, and for example, 1 to 360 minutes, preferably 30 to 180 minutes, may be used.

The heating may be performed in 2 stages. For example, in stage 1, heating is performed at a relatively low temperature, and in stage 2, heating may be performed at a higher temperature than in stage 1. The heating temperature in the 1 st stage is, for example, 60 to 120 ℃ and preferably 70 to 110 ℃. The heating time in the 1 st stage is, for example, 1 to 180 minutes, and more preferably 30 to 150 minutes. The heating temperature in the 2 nd stage is, for example, 120 to 240 ℃ and preferably 150 to 210 ℃. The heating time in the 2 nd stage is, for example, 1 to 180 minutes, and more preferably 30 to 150 minutes. By performing the heating in 2 stages, warpage and cracking due to curing shrinkage can be suppressed.

By the above-mentioned operation, polyisocyanurate or a cured polyisocyanurate raw material can be produced. According to the production method of the present embodiment, the trimerization reaction of the polyfunctional isocyanate proceeds efficiently by using the compound (I) and the epoxy compound as catalysts. Further, since the compound (I) has low hygroscopicity, polyisocyanurate having little foaming or a cured polyisocyanurate raw material can be obtained.

[ catalyst for polyisocyanurate formation reaction ]

In one embodiment, the present invention provides a catalyst for a polyisocyanurate formation reaction comprising a combination of the compound (I) represented by the above general formula (I), and an epoxy compound.

In one embodiment, the present invention provides a kit for producing polyisocyanurate, comprising a combination of the compound (I) represented by the above general formula (I) and an epoxy compound as a catalyst for a polyisocyanurate formation reaction.

By using a combination of the compound (I) represented by the above general formula (I) and an epoxy compound as a catalyst for the polyisocyanurate formation reaction, foaming is suppressed and sufficient curability (yield) can be obtained upon heating.

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Polyisocyanurate raw material composition and process for producing polyisocyanurate

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