JP6159238B2 - Method for producing imide compound - Google Patents

Description

The present invention relates to a method for producing an imide compound. More specifically, the present invention relates to a method for producing an imide compound that can be suitably used for various uses including electronic component materials.

Currently, imide compounds having various structures are used in various fields such as the electric / electronic field, the transportation equipment field such as aircraft / vehicles, and as a synthetic intermediate for agricultural medicine and natural products.
As a method for synthesizing such an imide compound, an amine compound and an acid anhydride are subjected to a ring-opening addition reaction in an organic solvent at room temperature to form an amic acid. A method of imidizing by dehydration condensation in the presence is widely known, and as an example of producing an imide compound using this method, for example, silylation of an amic acid, followed by imidation with desilanol under heating, imide silane A synthesis method is disclosed (see Patent Document 1).

JP 2001-72690 A

As described above, as a method for synthesizing an imide compound, a method of synthesizing an imide compound by using an amine as a catalyst and then dehydrating and condensing in the presence of acetic anhydride in an amount equal to that of an amic acid using an amine as a catalyst is known. This method has a problem that a large amount of acetic acid as a by-product is generated, and it is very difficult to remove acetic acid having a high polarity and a high boiling point. In addition, as the use of imide compounds has expanded, the demand for lowering the production cost of imide compounds has increased, and a method capable of producing imide compounds at a lower cost than conventional production methods is required. ing.

The present invention has been made in view of the above-described situation, and provides a method by which by-products can be removed more easily than conventional methods, and an imide compound can be produced at a low production cost. Objective.

The inventor has studied various methods for producing an imide compound at a lower cost than a conventional method for producing an imide compound, and a first step for reacting a primary amine compound with a ketone compound, and a first step. The process which manufactures an imide compound by the 2nd process of making a carboxylic acid anhydride react with the compound obtained by 1 was discovered. By using this method, it is possible to produce an imide compound without generating acetic acid that is difficult to remove, and there is no change in the amount of ketone compound in the reaction system, and the ketone progresses as the reaction proceeds. Since it is not necessary to replenish the compound and the ketone compound used for the reaction with the amine compound in the first step can also be used as a reaction solvent, it is possible to produce an imide compound at a lower cost than conventional production methods. As a result, the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.

That is, the present invention is a method for producing an imide compound from an amine compound, and the production method comprises the following formula (1);
_R-NH 2 (1)
(In the formula, R represents a monovalent organic group.) A first step in which a ketone compound is reacted with an amine compound represented by the formula, and a carboxylic acid anhydride is reacted with the compound obtained in the first step. A method for producing an imide compound, comprising a second step.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The reaction scheme in the method for producing an imide compound of the present invention is shown as an example in which a compound having one carboxylic acid anhydride structure (—CO—O—CO—) in the structure is used as the carboxylic acid anhydride. It is as follows.

As described above, the ketone compound that has reacted with the amine compound in the first step is eliminated during the reaction with the acid anhydride in the second step. For this reason, the amount of the ketone compound in the reaction system is constant. In the method of synthesizing an imide compound via an amic acid using an amine compound as a raw material described in Patent Document 1 and the like, both maleic anhydride used in the first step and acetic anhydride used in the second step are reacted. However, in the method of the present invention, it is only necessary to supply the acid anhydride used in the second step, while it is necessary to supply both of these into the reaction system. A silane compound can be produced at a lower production cost than conventional methods. In addition, in the method disclosed in Patent Document 1, an imide compound is produced by imidation reaction with desilanol after heating after silylation of the amic acid. In this method, silylation of the amic acid is performed. For this reason, it is necessary to use a silylating agent, leading to an increase in cost, whereas in the production method of the present invention, it is not necessary to use a silylating agent. This is more advantageous in terms of manufacturing cost. This method is also advantageous in that acetic acid that is difficult to remove is not by-produced.
The method for producing an imide compound of the present invention includes a first step in which a ketone compound is reacted with an amine compound represented by the above formula (1), and a first step in which a compound obtained in the first step is reacted with a carboxylic acid anhydride. As long as two steps are included, other steps may be included. The other steps include a step of purifying the product obtained in the second step.

In addition to the above reasons, the production method of the present invention is advantageous in terms of production cost in that the ketone compound used in the first step can also be used as a reaction solvent, and the ketone compound is also used as a reaction solvent. It is preferable.
That is, it is one of the preferred embodiments of the present invention that the ketone compound is also used as a solvent for the reaction in the first step and / or the second step.

R in the formula (1) represents a monovalent organic group, and examples of the monovalent organic group include a silicon atom-containing group. Among these, as a monovalent organic group, following formula (2);
_{-Ra-Si-X 3 (2} )
(In the formula, Ra represents an alkylene group having 1 to 6 carbon atoms. X is the same or different and represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 10 carbon atoms). Silicon atom-containing groups are preferred.
When a compound in which R in formula (1) has a structure as in formula (2) is used as the amide compound, an imidosilane compound is produced by the method for producing an imide compound of the present invention.
In the method of Patent Document 1, an imide silane compound is produced by silylation of an amic acid and then imidation accompanied by desilanol. When an imidosilane compound having an alkoxysilyl group is produced by this method, the hydrolysis reaction of the alkoxysilyl group proceeds at the same time during the desilanol, and the yield of the product is lowered.
On the other hand, in the production method of the present invention, since no dehydration reaction is involved in imidization, R in formula (1) has a structure as shown in formula (2) as an amine compound, and formula (2) Even when a compound in which at least one of X is an alkoxy group having 1 to 10 carbon atoms is used, the hydrolysis reaction of the alkoxysilyl group does not proceed, and the required imidosilane compound is obtained in a high yield. Can be obtained. Thus, in the production method of the present invention, as the amine compound, R in the formula (1) has a structure as shown in the formula (2), and at least one X in the formula (2) has 1 to 1 carbon atoms. It can be said that this is a particularly preferable production method as a method for producing an imidosilane compound using a compound having 10 alkoxy groups.
Thus, as an amine compound, it is one of the suitable embodiments of the present invention that R in formula (1) is a group having an alkoxysilane.

It does not restrict | limit especially as a ketone compound used for the manufacturing method of this invention, following formula (3);
R ¹ —CO—R ² (3)
(Wherein R ¹ and R ² are the same or different and each represents a hydrocarbon group, and R ¹ and R ² may form a bond), and any compound having a structure represented by Can be used and includes aromatic (aliphatic), aliphatic and cycloaliphatic ketones. The ^R 1, ^{R 2} in the formula (3), a hydrocarbon group having 1 to 20 carbon atoms, an aromatic group are preferred. More preferably, it is a C1-C4 hydrocarbon group. As the hydrocarbon group, an alkyl group is preferable. When R ¹ and R ² are bonded to form a ring structure, the ring structure is preferably a cycloalkyl group having 3 to 8 carbon atoms.
One type of ketone compound may be used, or two or more types may be used.

Specific examples of the ketone compound include aromatic ketones including C8-24 (preferably 8-18) mono- and poly-ketones. Examples of monoketones include acetophenone, propiophenone, and benzophenone; examples of polyketones include diketones (such as o- and p-diacetylbenzene) and triketones (such as 1,3,5-triacetylbenzene). Aliphatic ketones include saturated and unsaturated C3-24 (preferably 3-18) mono- and poly-ketones. Examples of monoketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-octanone, di-n-octyl ketone, and methyl vinyl ketone; examples of polyketones include diketones (acetylacetone, 3,5-pentanedione, and the like). Cycloaliphatic ketones include saturated and unsaturated C4-20 (preferably 4-10) mono- and poly-ketones. Examples of monoketones include cyclobutanone, cyclopentanone, and cyclohexanone; examples of polyketones include diketones (1,3-cyclopentanedione, 1,3-, and 1,4-cyclohexanedione, etc.). Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, or cyclohexanone is preferable because it is inexpensive and can be easily removed by a drying process.

The carboxylic acid anhydride used in the production method of the present invention is not particularly limited, and the following formula (4);

(Wherein R ³ and R ⁴ are the same or different and each represents an organic group, and R ³ and R ⁴ may form a bond), any compound having a structure represented by be able to. As R < ³ >, R < ⁴ > in Formula (4), a C1-C30 hydrocarbon group, an oxygen atom containing group, a sulfur atom containing group, etc. are mentioned. More preferably, they are a C1-C25 hydrocarbon group, an oxygen atom containing group, a sulfur atom containing group, etc. The oxygen atom-containing group is preferably a group having 1 to 5 oxygen atoms, and the sulfur atom-containing group is preferably a group having 1 to 3 sulfur atoms.
Further, it is preferable that R ³ and R ⁴ form a bond. More preferably, R ³ and R ⁴ form a bond containing an unsaturated double bond, more preferably a bond containing a polymerizable unsaturated double bond. .
When the site formed by R ³ and R ⁴ has a ring structure, examples of the ring structure include a cycloalkyl ring, a cycloalkenyl ring, an aromatic ring, an oxygen atom-containing heterocycle, a sulfur atom-containing heterocycle, and the like.

The acid anhydride represented by the above formula (4) includes not only a compound having one carboxylic anhydride structure (—CO—O—CO—) in the structure, but also the following formula (5);

(Wherein R ⁵ and R ⁶ may be the same or different and each represents an organic group, and R ⁵ and R ⁶ may form a bond to form a structure including a ring structure). Also included are compounds having two carboxylic anhydride structures (—CO—O—CO—) in the structure. In formula (5), examples of R ⁵ and R ⁶ include a hydrocarbon group having 1 to 30 carbon atoms, an oxygen atom-containing group, and a sulfur atom-containing group. More preferably, they are a C1-C25 hydrocarbon group, an oxygen atom containing group, a sulfur atom containing group, etc. The oxygen atom-containing group is preferably a group having 1 to 5 oxygen atoms, and the sulfur atom-containing group is preferably a group having 1 to 3 sulfur atoms. Moreover, it is preferable that R ⁵ and R ⁶ are bonded to form a structure including a ring structure.
If site formed by R ⁵ and R ⁶ have the ring structure, the ring structure, the same ring structure formed by R ³ and R ⁴ in the formula (4) below.
As the carboxylic acid anhydride, one type may be used, or two or more types may be used.

Specific examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 5-norbornene-2,3- Dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, exo-3,6-epoxy-1, 2,3,6-tetrahydrophthalic anhydride, endo-bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, 2,3-diethyl maleic anhydride, 4-ethynyl phthalic anhydride Compound having one carboxylic acid anhydride structure in the structure of acid, 4-phenylethynyl phthalic anhydride, etc .; pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracar Acid dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide Dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane Anhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) ) Benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [ ( Include 4-dicarboxyphenoxy) phenyl] propane dianhydride and the like. Among them, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , 3,4,9,10-perylenetetracarboxylic dianhydride and the like, a compound having two carboxylic anhydride structures in the structure. Among these, heating of carboxylic acid anhydrides having a polymerizable unsaturated double bond in the structure such as maleic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, etc. Acid anhydrides with very low solvent solubility, such as carboxylic acid anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride Any of these is preferred.

In the method of Patent Document 1, heating is required when silylation of an amic acid and then imidation with desilanol is performed. This method is used to prepare an imide compound having a polymerizable unsaturated double bond. When applied to, the polymerization reaction of the unsaturated double bond portion occurs in the heating step, the gelation proceeds, and the yield of the product may be lowered. On the other hand, in the production method of the present invention, since the reaction in the second step proceeds even at a temperature near room temperature, it has a polymerizable unsaturated double bond using a compound having a polymerizable unsaturated group as an acid anhydride. Even in the case of producing an imide compound, the unsaturated imide compound can be produced in a high yield without causing gelation by polymerization of the unsaturated imide compound. Thus, it can be said that the production method of the present invention is a production method particularly suitable as a method for producing an imide compound having a polymerizable unsaturated double bond.
Thus, it is one of the preferred embodiments of the present invention to use a compound having a polymerizable unsaturated double bond as the carboxylic acid anhydride.
Among the above-mentioned carboxylic acid anhydrides, maleic anhydride is preferable.

The production method of the present invention comprises a polymerizable unsaturated double bond using a compound having a group having an alkoxysilane in the structure as an amide compound and a compound having a polymerizable unsaturated double bond as a carboxylic acid anhydride. This method is particularly suitable as a method for producing an imide compound having a bond. In this case, when an amide compound having a group having an alkoxysilane in the structure is used (R in Formula (1) is an alkoxysilane. Both of the effects obtained when the compound has a polymerizable unsaturated double bond as the carboxylic acid anhydride and the effects obtained when the compound has a polymerizable unsaturated double bond can be obtained. In particular, the polymerization reaction of the polymerizable unsaturated double bond portion in the heating step in performing imidization with desilanol by the method of Patent Document 1 described above produces an imidosilane compound having an unsaturated double bond. In particular, the effect of suppressing the gelation due to the polymerization of the unsaturated imide compound by using the production method of the present invention is more noticeable in the case of producing an imide silane compound having a polymerizable unsaturated double bond. Demonstrated.
Therefore, the production method of the present invention is particularly suitable as a method for producing an imidosilane compound having a polymerizable unsaturated double bond and an alkoxysilyl group.
As an imidosilane compound having a polymerizable unsaturated double bond and an alkoxysilyl group, for example, the following formula (6);

(Wherein, R _a represents an alkylene group having 1 to 6 carbon atoms, and R _b represents an alkyl group having 1 to 10 carbon atoms).

In the method for producing an imide compound of the present invention, the ketone compound is preferably used at a ratio of 1 mol or more with respect to 1 mol of the amide compound represented by the above formula (1) as a reaction raw material. More preferably, it is used in a ratio of 1.5 mol or more with respect to 1 mol of the amide compound. Particularly preferably, as described above, it is also used in combination with a solvent. In this case, a large excess of ketone compound is used with respect to the amide compound.

In the method for producing an imide compound of the present invention, the carboxylic acid anhydride is used in a ratio of 1.0 to 1.5 mol with respect to 1.0 mol of the amide compound represented by the above formula (1) as a reaction raw material. preferable. More preferably, it is used in the ratio of 1.0-1.4 mol with respect to 1.0 mol of amide compounds, More preferably, it is used in the ratio of 1.0-1.2 mol.

It is preferable to perform reaction of the 1st process of the manufacturing method of the imide compound of this invention at the temperature below 60 degreeC and the boiling point of the ketone compound to be used. More preferably, it is carried out at 100 ° C. or higher and below the boiling point of the ketone compound used, and more preferably 120 ° C. or higher and below the boiling point of the ketone compound used.
In addition, the reaction in the first step may be performed under any conditions of normal pressure, reduced pressure, and increased pressure, but is preferably performed at normal pressure.

In the reaction of the first step, since water is generated as a by-product, it is preferable to proceed the reaction while removing by-produced water in order to increase the yield of the product. A method for removing water is not particularly limited, and a method of removing by azeotropic distillation together with a solvent can be used.

It is preferable to perform reaction of the 2nd process of the manufacturing method of the imide compound of this invention at the temperature of 60 degrees C or less. The reaction in the second step proceeds even at such a relatively low temperature, and by carrying out the reaction at such a temperature, the polymerization of the imide compound is also carried out when producing an imide compound having an unsaturated double bond. It can suppress and can manufacture the imide compound which has the target unsaturated double bond with a high yield. The reaction in the second step is more preferably performed at 50 ° C. or lower, and further preferably performed at 40 ° C.
In addition, the reaction in the second step may be performed under any conditions of normal pressure, reduced pressure, and increased pressure, but is preferably performed at normal pressure.

The imide compound produced by the method for producing an imide compound of the present invention can be suitably used in various fields including the electric, mechanical and automotive fields, but is particularly used in the electric / electronic field. Preferably, it is more preferably used as a material for forming a composition for a sealing material used for a substrate on which an electronic component, a semiconductor chip or the like is mounted.
Such an imide compound produced by the method for producing an imide compound of the present invention is also one aspect of the present invention, and a composition for a sealing material produced using the imide compound of the present invention as a material is also included. This is one of the present inventions.

The method for producing an imide compound of the present invention comprises the above-described structure, and is a method that makes it possible to produce an imide compound at a lower cost than a conventional method for producing an imide compound. This is a particularly preferred production method for producing an imidosilane compound having an alkoxysilyl group.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

Example 1
To a 500 mL four-necked flask equipped with a stirrer, temperature sensor, Dean-Stark trap, dropping funnel, and condenser tube, 175 g of cyclohexanone and 102 g of xylene were added, and the temperature was raised to 150 ° C. under nitrogen flow while stirring. When the temperature exceeds 110 ° C, dry distillation begins inside the flask, and the temperature rise rate is controlled so that the Dean-Stark trap top temperature does not exceed 100 ° C.・ Recovered in Stark trap. Next, 233 g of 3-aminopropyltriethoxysilane was added from the dropping funnel over 1 hour while maintaining the temperature of the reaction solution at 150 ° C. During this time, water and xylene as by-products were collected in the Dean-Stark trap by azeotropy, and stirring was continued at 150 ° C. for 6 hours until the azeotropy was completed after completion of the dropwise addition. Thereafter, while maintaining the temperature inside the flask, the pressure was reduced to 2.6 KPa while stirring, and the volatile matter was recovered to obtain the following compound (1). The compound was identified by ¹ H-NMR, ¹³ C-NMR, and GC-MS. The yield was 233 g, which was 98% of the theoretical yield.

Subsequently, 20 mL of cyclohexanone was put into a 100 mL four-necked flask equipped with a stirrer, a temperature sensor, a Dean Stark trap, a dropping funnel, and a condenser, and stirring was continued while dry distillation at 150 ° C. to remove moisture. After recovering in the trap, 8.2 g of maleic anhydride was dissolved by cooling to room temperature, and 23.8 g of the compound (1) was added from the dropping funnel over 1 hour while maintaining the flask at 40 ° C. or lower.
After the addition, stirring was continued for 3 hours while maintaining the flask at 40 ° C. or lower to obtain a reaction product. When the reaction product was identified by ¹ H-NMR, ¹³ C-NMR, and GC-MS, the following compound (2) was obtained. The reaction solution had a nonvolatile content of 46%, volatile content of cyclohexanone, and the reaction product yield was 23 g, which was 98% of the theoretical yield.

Example 2
A 500 mL four-necked flask equipped with a stirrer, temperature sensor, Dean-Stark trap, dropping funnel, and condenser tube was charged with 178 g of methyl isobutyl ketone and 102 g of xylene, and heated to 120 ° C. under nitrogen flow while stirring. . When the temperature exceeds 105 ° C, dry distillation begins inside the flask, and the temperature rise rate is controlled so that the temperature at the top of the Dean-Stark trap does not exceed 100 ° C.・ Recovered in Stark trap. Next, 233 g of 3-aminopropyltriethoxysilane was added from the dropping funnel over 1 hour while maintaining the reaction liquid temperature at 120 ° C. During this time, water and xylene as by-products were collected in the Dean-Stark trap by azeotropy, and stirring was continued at 150 ° C. for 6 hours until the azeotropy was completed after completion of the dropwise addition. Thereafter, while maintaining the temperature inside the flask, the pressure was reduced to 2.6 KPa while stirring, and the volatile matter was recovered to obtain the following compound (3). The compound was identified by ¹ H-NMR, ¹³ C-NMR, and GC-MS. The yield was 232 g, which was 98% of the theoretical yield.

Subsequently, 20 mL of methyl isobutyl ketone was put into a 100 mL four-necked flask equipped with a stirrer, a temperature sensor, a Dean-Stark trap, a dropping funnel and a condenser, and stirring was continued at 120 ° C. while dehydrating. After recovering in a Stark trap, it was cooled to room temperature to dissolve 8.2 g of maleic anhydride, and 23.8 g of the above compound (3) was added from the dropping funnel over 1 hour while maintaining the flask at 40 ° C. or lower. .
After the addition, stirring was continued for 3 hours while maintaining the flask at 40 ° C. or lower to obtain a reaction product. When the reaction product was identified by ¹ H-NMR, ¹³ C-NMR, and GC-MS, it was Compound (2). The reaction solution had a non-volatile content of 46%, volatile content of methyl isobutyl ketone, and the reaction product yield was 23 g, which was 98% of the theoretical yield.

Example 3
A reaction product was obtained in the same manner as in Example 1 except that 12.8 g of 3,4,5,6-tetrahydrophthalic anhydride was used in place of 8.2 g of maleic anhydride of Example 1. When the reaction product was identified by ¹ H-NMR, ¹³ C-NMR, and GC-MS, the following compound (4) was obtained. The reaction solution had a non-volatile content of 50%, volatile content of cyclohexanone, and the reaction product yield was 28 g, which was 98% of the theoretical yield.

Example 4
In the same manner as in Example 1 except that 13.9 g of exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride was used in place of 8.2 g of maleic anhydride of Example 1. I got a thing. When the reaction product was identified by ¹ H-NMR, ¹³ C-NMR, and GC-MS, the following compound (5) was obtained. The reaction solution had a non-volatile content of 50%, volatile content of cyclohexanone, and the reaction product yield was 28 g, which was 97% of the theoretical yield.

Example 5
To a 500 mL four-necked flask equipped with a stirrer, temperature sensor, Dean-Stark trap, dropping funnel, and condenser tube, 175 g of cyclohexanone and 102 g of xylene were added, and the temperature was raised to 150 ° C. under nitrogen flow while stirring. When the temperature exceeds 110 ° C, dry distillation begins inside the flask, and the temperature rise rate is controlled so that the Dean-Stark trap top temperature does not exceed 100 ° C.・ Recovered in Stark trap. Next, 233 g of 3-aminopropyltriethoxysilane was added from the dropping funnel over 1 hour while maintaining the temperature of the reaction solution at 150 ° C. During this time, water and xylene as by-products were collected in the Dean-Stark trap by azeotropy, and stirring was continued at 150 ° C. for 6 hours until the azeotropy was completed after completion of the dropwise addition. Thereafter, while maintaining the temperature inside the flask, the pressure was reduced to 2.6 KPa while stirring, and the volatile matter was recovered to obtain Compound (1). The compound was identified by ¹ H-NMR, ¹³ C-NMR, and GC-MS. The yield was 233 g, which was 98% of the theoretical yield.

Subsequently, 60 mL of N, N′-dimethylacetamide was introduced into a 100 mL four-necked flask equipped with a stirrer, temperature sensor, Dean Stark trap, dropping funnel, and condenser, and stirring was continued while dry distillation at 150 ° C. After collecting the water in a Dean-Stark trap, the mixture was cooled to room temperature to dissolve 11.2 g of 1,4,5,8-naphthalenetetracarboxylic dianhydride, and the above compound was maintained while maintaining the flask at 40 ° C. or lower. (1) 23.8 g was charged from the dropping funnel over 1 hour.
After the addition, stirring was continued for 3 hours while maintaining the flask at 40 ° C. or lower to obtain a reaction product. When the reaction product was identified by ¹ H-NMR, ¹³ C-NMR, and GC-MS, the following compound (6) was obtained. The reaction solution had a nonvolatile content of 26% and contained volatile components of cyclohexanone and N, N′-dimethylacetamide. The yield of the reaction product was 25 g, which was 98% of the theoretical yield.

Example 6
N-methylpyrrolidone was used in place of N, N′-dimethylacetamide in Example 5, and 3,4,9,10- in place of 11.2 g of 1,4,5,8-naphthalenetetracarboxylic dianhydride 16.4 g of perylenetetracarboxylic dianhydride was used. When the reaction product was identified by ¹ H-NMR, ¹³ C-NMR, and GC-MS, the following compound (7) was obtained. The reaction solution had a nonvolatile content of 30% and contained volatile components of cyclohexanone and N, N′-dimethylacetamide. The yield of the reaction product was 29 g, which was 96% of the theoretical yield.

Comparative Example 1
To a 500 mL four-necked flask equipped with a stirrer, temperature sensor, Dean-Stark trap, dropping funnel, and condenser, add 35.2 g of maleic anhydride and 58 g of methylene chloride, and warm to 60 ° C to homogeneity. The solution was cooled to room temperature, and 79.6 g of 3-aminopropyltriethoxysilane was added from the dropping funnel over 1 hour while maintaining the reaction temperature at 25 ° C., and 73 g of triethylamine was added all at once to the reaction solution. I put it in. Subsequently, while maintaining the reaction liquid temperature at 25 ° C., 77.7 g of trimethylsilyl chloride was added from the dropping funnel over 1 hour, and after completion of the addition, 300 g of methylene chloride was added and left overnight. A white precipitate was removed from the reaction solution by filtration, and methylene chloride was distilled off from the filtrate with a rotary evaporator to obtain a final product of a highly viscous fluid. ^When identified by ¹ H-NMR, ¹³ C-NMR, and GC-MS, it was a mixture of the compound (2) and the following compound (8), and the mixing ratio was 65/35.

Comparative Example 2
To a 500 mL four-necked flask equipped with a stirrer, a temperature sensor, a dropping funnel, and a condenser tube, 250 mL of toluene, 49.1 g of maleic anhydride, 123.6 g of 3-isocyanatopropyltriethoxysilane, and 0.92 g of tributylamine were added. When stirring was continued at 5 ° C. for 5 hours, the reaction solution gelled and the desired product could not be obtained.

Claims (4)

A method for producing an imide compound from an amine compound,
The production method comprises the following formula (1);
_R-NH 2 (1)
(Wherein R represents a monovalent organic group having an alkoxysilyl group ), a first step of reacting a ketone compound with an amine compound represented by:
And a second step of reacting the compound obtained in the first step with a carboxylic acid anhydride. The method for producing an imide compound according to claim 1, wherein the second step is performed at a temperature of 60 ° C. or less. The method for producing an imide compound according to claim 1 or 2 , wherein the ketone compound is also used as a solvent for the reaction in the first step and / or the second step. The method for producing an imide compound according to any one of claims 1 to 3, wherein the carboxylic acid anhydride is maleic anhydride.