JPH08176104A - Production of imide compound - Google Patents

Abstract

PURPOSE: To obtain an imide compound in a non-aqueous reaction system in a high yield by reacting a polycarboxylic acid anhydride derivative with at least one of the ketimine derivative of a compound having a primary amino group and the aldimine derivative of the compound and subsequently releasing a ketone or an aldehyde. CONSTITUTION: A polycarboxylic acid anhydride derivative is reacted with at least one of the ketimine derivative of a compound having a primary amino group and the aldimine derivative of the compound having the primary amino group. Subsequently, a ketone or an aldehyde is released to obtain the imide compound. Since water is not produced in the reaction system, and further since the ketone or the aldehyde not inhibiting the progress of the reaction is produced, the method does not require a special water-separating device in the production device. Thereby, a solvent can freely be selected, and a side reaction does not occur, because water does not exit in the reaction system. The polycarboxylic acid anhydride derivative is especially at least one of a maleic anhydride copolymer and a maleic anhydride graft copolymer. The other compound is preferably a compound having a formamide group in the molecule.

Description

Detailed Description of the Invention

[0001]

This invention relates to a method for producing an imide compound in a non-aqueous system.

[0002]

2. Description of the Related Art Conventionally, imide compounds have been useful compounds in various fields such as raw materials for chemical products, pharmaceuticals, agricultural chemicals, resin additives and the like. The following methods are known as methods for producing such imide compounds.

An imide compound is produced by reacting potassium succinimide with an alkyl chloride. An amide compound is produced by synthesizing an amic acid from a dicarboxylic acid anhydride and a primary diamine and then subjecting it to a dehydration reaction. The dicarboxylic acid anhydride is reacted with a lower alcohol to convert it into an ester acid, which is then reacted with a primary amine to dehydrate and dealcoholize to produce an imide compound. From primary amine salt of dicarboxylic acid, dehydration reaction,
Further, the amine is distilled off to produce an imide compound. An imide compound is produced by distilling an amine using a dicarboxylic acid diamide. An imide compound is produced by decarboxylation by reacting a dicarboxylic acid anhydride and an isocyanate compound.

[0004]

However, each of the above-mentioned conventional methods for producing an imide compound has the following problems.

Since the above-mentioned production method uses potassium succinimide, which is an expensive raw material, it is costly and economically disadvantageous. Further, in the above production method, a high temperature of 140 ° C. or higher is required for the dehydration reaction, and further it is necessary to remove water from the system. Therefore, it is required to use a solvent having a high boiling point, and it is necessary that the solvent is not compatible with water. In addition, the reactor also needs to be equipped with a device such as a water separator to separate and remove water. In the above production method, similarly to the above production method, it is necessary to separate water, and when the lower alcohol to be eliminated is miscible with water, such as methanol or ethanol, the separation from the reaction solvent becomes insufficient. , The reaction may not be completed. In the above production method, since dehydration reaction is required, in addition to the problems in the above production method, it is necessary to remove excess amine, so the amine used is limited to those having a low boiling point There are also restrictions on the device such as reducing the pressure. The above-mentioned production method also has the same problem as the above-mentioned production method due to the distillation of the amine. Furthermore, a higher reaction temperature is required than in the above-mentioned production method in order to cleave the amide bond to generate an imide bond.

In addition to these problems, in the above-mentioned processes (1) to (3), free primary amines are present at high temperature in the reaction system during the reaction. When it has a functional group, it may be damaged or further reacted with the above amine to generate many by-products.

Further, in the above-mentioned production method, the isocyanate compound is expensive, and like the above-mentioned production method, the cost is high and it is economically disadvantageous.

By the way, since the dicarboxylic acid anhydride used in the above-mentioned production method is a highly reactive compound, it reacts with active hydrogen compounds such as alcohols and amines and various compounds such as isocyanates to produce many products. . Therefore, if the desired imide compound is to be obtained in high yield, the compound to be reacted has 2 in 1 molecule.
Care must be taken to avoid those containing more than one functional group.

Further, it has been proposed to obtain a moisture-curable binder composition by using a polyamine ketimine and a maleic anhydride copolymer (Japanese Patent Publication No. 63-260947).
It is clear that in the above reaction, condensation occurs between a free amino group and an anhydrous group generated by water in the above reaction to generate an amic acid and no imide bond.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing an imide compound which can produce an imide compound in a non-aqueous reaction and at a high yield.

[0011]

In order to achieve the above object, the process for producing an imide compound according to the present invention comprises reacting the following (A) and (B) to eliminate a ketone or an aldehyde. . (A) Polycarboxylic anhydride derivative. (B) At least one of a ketimine derivative of a compound having a primary amino group and an aldimine derivative of a compound having a primary amino group.

[0012]

That is, the method for producing the imide compound of the present invention is
The imide bond-forming reaction is carried out by using the above polycarboxylic acid anhydride derivative (A) and at least one of the ketimine derivative of the compound having a primary amino group and the aldimine derivative of the compound having a primary amino group (B). Is carried out by eliminating the ketone or aldehyde to produce an imide compound without producing water in the reaction system. Therefore, it is not necessary to carry out the reaction system in a reaction device equipped with a special water diversion device, and it is possible to carry out the reaction under a lower temperature condition. In addition, it is not necessary to consider the separation of water or the like as the solvent to be used, only the solubility of the raw materials to be used may be considered, and a wide range of solvents can be used.

Next, the present invention will be described in detail.

In the method for producing an imide compound of the present invention, as a raw material, a polycarboxylic acid anhydride derivative (A) and at least one of a ketimine derivative of a compound having a primary amino group and an aldimine derivative of a compound having a primary amino group (B ) And are used.

The above polycarboxylic acid anhydride derivative (A)
Has a succinic anhydride ring structure represented by the following general formula in the molecule, and examples thereof include anhydrides of aliphatic, alicyclic and aromatic polycarboxylic acids and derivatives thereof.

[0016]

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Examples of the above-mentioned aliphatic polycarboxylic acid anhydride and alicyclic polycarboxylic acid anhydride include unsubstituted or substituted polycarboxylic acid anhydrides. Specifically, succinic anhydride, dimethyl succinic anhydride, maleic anhydride, itaconic anhydride, dimethyl maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydroanhydride. Phthalic acid, 3,6-endomethylene-1,2,3,6-
Examples thereof include tetrahydrophthalic anhydride, hexachloroendomethylene tetrahydrophthalic anhydride and the like.

Further, in the present invention, as the aliphatic polycarboxylic acid anhydride, a polymer compound having the above-mentioned succinic anhydride ring structure in the main chain or side chain of the polymer is also included, for example, maleic anhydride. And a copolymer of unsaturated monomer and a graft copolymer of maleic anhydride and an unsaturated monomer. Specifically, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, alkyl vinyl ether-maleic anhydride copolymer, ethylene-alkyl acrylate-maleic anhydride copolymer, propylene-maleic anhydride. Acid graft copolymer, ethylene-maleic anhydride graft copolymer, ethylene-propylene-maleic anhydride graft copolymer,
Styrene-butadiene-styrene block copolymer or hydrogenated maleic anhydride graft copolymer thereof,
Examples thereof include a styrene-isobutylene-styrene block copolymer or a hydrogenated maleic anhydride graft copolymer thereof.

The above-mentioned copolymer of maleic anhydride and an unsaturated monomer has a molecular weight of 1,000 to 20.
0000, the amount of maleic anhydride is 0.05 to 50% by weight
(Hereinafter abbreviated as “%”) is preferably used.
More preferably, the molecular weight is 4000 to 80,000, and the amount of maleic anhydride is 0.1 to 30%. On the other hand, in the graft copolymer of maleic anhydride and an unsaturated monomer, it is preferable to use one having a molecular weight of 1,000 to 200,000 and a maleic anhydride content of 0.05 to 50%. More preferably the molecular weight is 4000-8000
0, the amount of maleic anhydride is 0.1 to 30%.

Examples of the aromatic polycarboxylic acid anhydride and its derivative include unsubstituted or substituted aromatic polycarboxylic acid anhydride. Specifically, phthalic anhydride,
Naphthalene-2,3-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3',
4'-diphenylsulfone tetracarboxylic acid dianhydride,
Examples thereof include 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride and 2,3,4,5-tetrabromophthalic anhydride.

Among these polycarboxylic acid anhydrides and their derivatives, succinic anhydride, copolymers of maleic anhydride with other unsaturated monomers, and graft copolymers of maleic anhydride with other unsaturated monomers. It is preferable to use an aromatic dicarboxylic acid anhydride. Particularly preferred is
A copolymer of maleic anhydride and another unsaturated monomer, a graft copolymer of maleic anhydride and another unsaturated monomer, from the viewpoint of improving the reaction yield and easily separating the solvent and the unreacted product. It is a polymer.

Incidentally, some succinic anhydride rings are partially opened by water depending on the storage condition of the raw material to be dicarboxylic acids, so that they may be dehydrated and cyclized by a known method before use. It is preferable to set.

The ketimine derivative of a compound having a primary amino group and the aldimine derivative of a compound having a primary amino group (B) used together with the above (A) are prepared by using an amine and a ketone or an amine and an aldehyde. can get.

The above amines are represented by the general formula [R ₁ -NH ₂ ].
Is a compound containing one or more primary amino groups represented by. R ₁ in the above general formula is hydrogen atom or a carbon number of 1 to
20 alkyl group, cycloalkyl group, aryl group, arylalkyl group, and does not contain a hydroxyl group. further,
These molecules include those having a functional functional group having physiological activity, electric activity, and optical activity, and an ester group or an amide group. Specifically, ammonia, an aliphatic amine such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, laurylamine, oleylamine, stearylamine, cyclohexylamine, aminoethylmorpholine, aminoethylpiperazine, or an alicyclic ring. Formula amines and derivatives thereof include glycine, alanine and the like. In addition, aromatic amines such as aniline and diphenylaminomethane and their derivatives include tribromoaniline and the like. Furthermore, N, N-dimethylethylenediamine, N, N-dimethylpropylenediamine, N,
An amine having a tertiary amino group in R ₁ such as N-diethylenepropylenediamine, N-methyl-N-formylethylenediamine, N-formyl-N′-aminoethylpiperazine, N- (2-aminoethyl) -N Examples thereof include amines having an amide group in R ₁ , such as ′ -formylpiperazine and N-methyl-N-formyldiaminopropane.

When the desired imide compound is a diimide compound, the amines include ethylenediamine,
Ethylenediamines such as diethylenetriamine and triethylenetetramine, and diamines containing two primary amino groups such as propylenediamine can be used. In this case, a low molecular weight aliphatic, alicyclic or aromatic polycarboxylic acid anhydride is used, and specific examples thereof include succinic anhydride, phthalic anhydride, maleic anhydride, tetrabromophthalic anhydride and the like. In the unsaturated dicarboxylic acid anhydride copolymer and unsaturated dicarboxylic acid anhydride graft copolymer, the content of unsaturated dicarboxylic acid anhydride (weight ratio)
And a molecular weight product of 20,000 or less is used. That is, when a high molecular weight and high content of unsaturated dicarboxylic acid anhydride is used as (A), (A) is crosslinked with diamines to have a high molecular weight and a high viscosity diimide compound is obtained.

As described above, the amine can be appropriately selected according to the intended imide compound, regardless of whether it is aliphatic or aromatic.

Among the above amines, when an amine having a tertiary amino group is used, it can be used as an amino-modified polystyrene or the like which is used as an antistatic agent after quaternization after imidization reaction. . When the above-mentioned amine having an amide group (amine having a formyl group) is used, as an application thereof, after the imidization reaction, the amide group is hydrolyzed to contain an amino group without a crosslinking reaction. It has the advantage that it can be used for the synthesis of polymers. Furthermore, the use of the above-mentioned amine having an amide group is particularly preferable because the yield of the imide compound is improved.

The above-mentioned ketones and aldehydes contain at least one carbonyl group represented by the following general formula.

[0029]

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In the above general formula, at least one of R ₂ and R ₃ is a hydrogen atom, or both are C 1
To 12 alkyl groups, cycloalkyl groups or aryl groups. As such a compound, specifically,
Aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde, benzaldehyde, acetone, methyl ethyl ketone, methyl isopropyl ketone,
Examples include ketones such as methyl isobutyl ketone, diethyl ketone, diisopropyl ketone, dibutyl ketone, cyclohexanone, acetophenone and benzophenone. Particularly preferred are methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone and benzophenone.

Among the ketimine derivatives of compounds having a primary amino group and the aldimine derivatives (B) of compounds having a primary amino group obtained by using the above components,
In particular, it is preferable to use a ketimine derivative or an aldimine derivative having a formamide group in its molecule because the yield of the imide compound can be improved and the reaction time can be shortened.

The imide compound of the present invention is produced, for example, as follows using each of the above raw materials. That is,
First, a ketimine derivative of a compound having a primary amino group and an aldimine derivative (B) of a compound having a primary amino group are prepared in advance by dehydrating the above amines with a ketone or an aldehyde according to a known method. More specifically, amines, ketones or aldehydes, and a solvent are charged and heated to reflux until water is produced / separated. Then, the solvent and the unreacted material are distilled off to prepare a ketimine derivative and an aldimine derivative. The reaction temperature at this time varies depending on the dehydration method. For example, when a dehydrating agent such as a molecular sieve is used, the temperature is preferably set to 120 ° C or lower, more preferably 80 ° C or lower. Further, in the method by reflux dehydration, it is preferably set to 30 to 180 ° C, more preferably 50 to 140 ° C.

The mixing ratio of the amines (X) and the ketones or aldehydes (Y) in the dehydration reaction is (X) / (Y) = 1/1 in terms of the molar ratio to the functional group.
It is preferable to set in the range of ⅕ to ⅕, particularly preferably in the range of (X) / (Y) = 1 / 1.1 to ½.

Next, (B) prepared by the above reaction
An imide compound can be produced by reacting the polycarboxylic acid anhydride derivative (A) with the above.

The reaction between the above (A) and (B) will be described in detail. By reacting the above (A) and (B), an intermediate is first produced, and the imide compound is finally produced by elimination of ketones or aldehydes via the production of this intermediate. It The reaction temperature in the production of the above intermediate is not limited, but is preferably 10 ° C or higher, more preferably 30 to 70 ° C. And
The reaction temperature for elimination of ketones or aldehydes is preferably 70 ° C or higher, more preferably 90 to 180 ° C.
Is. Particularly preferably, it is 100 to 130 ° C. If the reaction temperature for the elimination of the above-mentioned ketones or aldehydes is less than 70 ° C., a large amount of intermediates will remain in the reaction product. Further, if it exceeds 180 ° C., problems such as coloring and deterioration of the produced imide compound occur.

In the reaction of the above (A) and (B), the mixing ratio of both is (A) / (molar ratio) to the functional group.
(B) = 1/1 to 1/2 is preferably set, and more preferably (A) / (B) = 1/1 to 1/1.
5, particularly preferably (A) / (B) = 1/1 to 1/1.
It is 3. That is, in the above blending ratio, (A) /
When the molar ratio of (B) is out of the above range, unreacted polycarboxylic acid anhydride derivative (A) remains and the reaction is not completed, or excess ketimine derivative and aldimine derivative remain, which is uneconomical in cost. It is because

In the above reaction, it is not always necessary to use a solvent, but it is preferable to use it for the purpose of carrying out the reaction more smoothly. Examples of the solvent used for this purpose include aromatic solvents such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and anisole. Hexane, octane,
Aliphatic solvents such as heptane, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO)
Aprotic polar solvent such as methyl isobutyl ketone,
Examples thereof include ketones such as cyclohexanone, esters such as butyl acetate and isoamyl acetate, and ethers such as butyl ether and diphenyl ether, but the type is not particularly limited as long as it is a non-aqueous solvent.

Further, during the above reaction, a Bronsted acid catalyst represented by mineral acids such as sulfuric acid and phosphoric acid, sulfonic acids such as paratoluenesulfonic acid, a Lewis acid catalyst such as BF ₃ , diazabicyclooctane, A basic catalyst typified by triethylamine may be added. The reaction time can be shortened by adding such a catalyst.

The reaction apparatus for carrying out the above reaction is required to have at least a stirring device and a heating device, and it is not necessary to separately provide a depressurizing device and a water dividing device.

Further, the reaction steps of (A) and (B) will be described in more detail. For example, as shown in the reaction below, (A) and (B) are reacted to form an intermediate, Further, the ketone (or aldehyde) is eliminated from the above intermediate to produce an imide compound.

[0041]

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[0042] The intermediates produced in the reaction step, in the infrared absorption (IR) spectrum, because the absorption of 1730 cm ^-1 and 1650～1680Cm ^-1 which is not observed in the starting materials and reaction products is observed, below It is considered that those having two kinds of structures are generated.

[0043]

[Chemical 4]

[0044]

INDUSTRIAL APPLICABILITY As described above, the method for producing the imide compound of the present invention comprises:
It is a method for producing an imide compound by reacting at least one (B) of a ketimine derivative of a compound having a primary amino group and an aldimine derivative of a compound having a primary amino group to eliminate a ketone or an aldehyde. Therefore, since water is not generated in the reaction system and a ketone or aldehyde that does not hinder the progress of the reaction is generated,
It is not necessary to equip the manufacturing apparatus with a special water diversion device. Further, the solvent used in the reaction system also does not need to consider separation of water and the like, so it is sufficient to consider only the solubility of the raw materials, etc., so that a solvent such as dimethylformamide that is miscible with water can be used. There is a large degree of freedom in selection. Furthermore, since water does not exist during the reaction, the target imide compound can be obtained in a high yield without causing a side reaction even from a raw material containing an unstable ester group or amide group with water, which is industrially possible. It is also an excellent manufacturing method. Moreover, since the water divider is not used as described above, it is not always necessary to set the reaction conditions under reflux (boiling point of the solvent), and different reaction temperatures can be selected even with the same solvent. In the production method of the present invention, it is particularly preferable to use a ketimine derivative having a formamide group or an aldimine derivative having a formamide group as (B) because the yield of the obtained imide compound is improved. And the imide compound thus obtained is
It can be used in various fields and is useful, for example, as a compatibilizing agent for different resins (polyester and polyolefin, etc.).

Next, examples will be described together with comparative examples.

Prior to the examples, first, a graft copolymer of maleic anhydride was prepared.

[Maleic anhydride graft copolymer M-1
Preparation] 100 parts by weight (hereinafter abbreviated as "part") of crystalline polypropylene powder having a weight average molecular weight (Mw) = 60,000 and a number average molecular weight (Mn) = 24,000, maleic anhydride 12 parts, dicumyl peroxide 4 Parts in advance,
Extruder [Screw diameter 30 mm, L (length) / D (width)
= 28] was set to a barrel temperature of 230 ° C., an extrusion reaction was performed at a screw rotation speed of 60 rpm, and the exfoliated graft compound was pulverized. Then, this crushed product was immersed in acetone to extract and remove unreacted maleic anhydride. Then, it was dried to prepare maleic anhydride grafted polypropylene M-1.

[Maleic anhydride graft copolymer M-2
Preparation of Maleic Anhydride Graft Copolymers M-2 to M-5 in the same manner as in Preparation of Maleic Anhydride Graft Copolymer M-1 using the raw materials shown in Table 1 below. It was made.

[0049]

[Table 1]

[Preparation of ketimine A-1] 1 mol of butylamine and 2 parts of methyl isobutyl ketone were placed in a 1000 ml flask equipped with a stirrer, a heating device, a dropping funnel, a thermometer, a Dean-Stark water divider, and a nitrogen inlet tube. Mol and hexane (500 ml) were charged, and the mixture was heated to 75 ° C. and refluxed until 1 mol of water was produced and separated. 50 reaction products
Hexane and unreacted methyl isobutyl ketone were distilled off under reduced pressure of 20 to 60 mmHg at -80 ° C, and as a result, ketiminated butylamine was produced.

[Ketimine or aldimine A-2 to A-
Production of 16] The raw materials shown in Table 2 below were prepared, and using these, ketimine or aldimine (A-2 to A-16) was produced according to the same production method as above.

[0052]

[Table 2]

[0053]

Example 1 A 1000 ml flask equipped with a stirrer, a heating device, a dropping funnel, a thermometer, and a reflux condenser was charged with 1 mol of succinic anhydride and 500 g of toluene.
The mixture was heated to 0 ° C., and 1.1 mol (1.1 times mol) of ketiminated butylamine (A-1) composed of butylamine and methyl isobutyl ketone was added dropwise to succinic anhydride. Was added dropwise, allowed to react for 1 hour, it was confirmed intermediates having a broad absorption at 1730 cm ^-1 and 1660 cm ^-1 on the IR spectrum. Subsequently, it was heated at 110 ° C. for 5 hours, and 1700 cm ⁻¹ and 177 on IR spectrum.
An imide compound having an absorption at 0 cm ^-1 was produced. The reaction product was further confirmed by a gas chromatograph equipped with a mass spectrometer for the presence of desorbed methyl isobutyl ketone, the reaction product N-butylsuccinimide, and the presence of a trace amount of unreacted succinic anhydride. did. In the gas chromatograph of the reaction product, the ratio of the peak of the imide compound (the yield of the imide compound) was 89 with respect to the sum of the peaks of the unreacted succinic anhydride and the peak of the imide compound.
%Met.

[0054]

Examples 2 to 10 Using a polycarboxylic acid anhydride shown in Table 3 below, ketimine or aldimine, a reaction catalyst and a reaction solvent, an imide compound was produced at the reaction temperature and time shown in the same table. The ratio (molar ratio) of the above polycarboxylic acid anhydride and ketimine or aldimine is also shown in Table 3 below. Then, the yield of the imide compound was determined as in Example 1 above.
It was determined by a gas chromatograph in the same manner as. Also,
For those that cannot be measured by gas chromatograph,
1775 due to the dicarboxylic acid anhydride group of the R spectrum
It was determined from the peak of 1700 cm ^-1 attributable to the peak and imide groups of cm ^-1. The results are also shown in Table 3 below.

[0055]

[Table 3]

[0056]

Examples 11 to 19 A 1000 ml flask equipped with a stirrer, a heating device, a dropping funnel, a thermometer and a reflux condenser was charged with a maleic anhydride graft copolymer shown in Table 4 below, a catalyst and a solvent. It was charged, heated to 80 ° C., and ketimine or aldimine shown in the same table was added dropwise thereto. After dropping, react for 1 hour, 1730 cm on IR spectrum
Intermediates with broad absorption at ^-1 and 1660 cm ^-1 were identified. Then, the mixture was heated at the temperature and reaction time shown in the same table, and the IR spectrum was measured at 1700 cm ⁻¹ and 17
An imide compound having an absorption at 70 cm ^-1 was produced. The ratio (molar ratio) of the above maleic anhydride graft copolymer and ketimine or aldehyde is also shown in Table 4 below.

Further, the imidation ratio (yield of imide compound) of the produced imide compound is similar to the above, the peak at 1775 cm ^-1 due to the dicarboxylic anhydride group in the IR spectrum and 1700 cm ^-1 due to the imide group. The imidization ratio (yield of imide compound) was determined from the peak of. The yield is also shown in Table 4 below.

[0058]

[Table 4]

[0059]

Examples 20 to 25 In a 1000 ml flask equipped with a stirrer, a heating device, a dropping funnel, a thermometer and a reflux condenser, a styrene-maleic anhydride copolymer [styrene: maleic anhydride = 3 is shown in Table 5 below. 1 (weight ratio)], a catalyst and a solvent were charged and heated to 80 ° C.,
Ketimine or aldimine shown in the same table was added dropwise thereto. After dropping, the mixture was reacted for 1 hour, and the IR spectrum was 173.
Intermediates with broad absorption at 0 cm ^-1 and 1660 cm ^-1 were identified. Subsequently, it was prepared imide compound having an absorption in the 1700 cm ^-1 and 1770 cm ^-1 on the IR spectrum was heated at a temperature and reaction time shown in Table. The ratio (molar ratio) of the maleic anhydride graft copolymer and ketimine or aldehyde is also shown in Table 5 below. Further, the imidization ratio (the yield of the imide compound) was obtained from each peak of the IR spectrum in the same manner as in Examples 11 to 19 above. The results are also shown in Table 5 below.

[0060]

[Table 5]

[0061]

[Comparative Example 1] 1 equipped with a stirrer, a heating device, a dropping funnel, a thermometer, a Dean-Stark water separator, and a nitrogen inlet pipe
A 000 ml flask was charged with 1 mol of succinic anhydride and 500 g of toluene, heated to 80 ° C., and 1.1 mol of butylamine was added dropwise to react for 1 hour. Then, 11
The reaction was carried out for 5 hours at 7 ° C. while removing the produced water with a water separator. In the gas chromatograph of the reaction product, the peak ratio of the imide compound was 71% with respect to the total of the peaks of the unreacted succinic anhydride and the peak of the imide compound. In addition, azeotropic removal of butylamine was observed in the reaction product water.

[0062]

[Comparative Examples 2 to 8] An imide compound was produced in the same manner as in Comparative Example 1 by setting the polycarboxylic acid anhydride, amine, reaction solvent, reaction temperature and time shown in Table 6 below. The imidization ratio (the yield of the imide compound) was determined by gas chromatography as in Comparative Example 1 above. For those which cannot be measured by gas chromatography, 1775 cm ^-1 due to dicarboxylic acid anhydride group in IR spectrum
And the peak at 1700 cm ⁻¹ due to the imide group. The results are also shown in Table 6 below as the yield of the imide compound.

[0063]

[Table 6]

[0064]

[Comparative Examples 9 to 18] In the flask used in Comparative Example 1,
Using a maleic anhydride graft copolymer or a styrene-maleic anhydride copolymer [styrene: maleic anhydride = 3: 1 (weight ratio)] shown in Table 7 below, an amine compound and a reaction solvent, the same table is used. An imide compound was produced under the reaction conditions of reaction temperature and time. In addition, the ratio of imidization ratio was determined to be 1700 cm due to the peak at 1775 cm ⁻¹ due to the carboxylic acid anhydride group on the IR spectrum and imide group.
It was determined from the peak at cm ^-1 . The results are also shown in Table 7 below.

[0065]

[Table 7]

The above Example 1, Comparative Example 1 and Tables 3 to 7
From the results, in all the examples, no water was generated in the reaction process of the imide compound, and the yield of the imide compound was high. In the examples, even when the monoformyl compound of diamine or triamine was used as the raw material of ketimine, the reaction did not occur as in Comparative examples 10, 15 and 18, and the reaction was performed without thickening or insolubilizing. On the other hand, in Comparative Example 1, since water produced was generated in the reaction,
It had to be removed by a water separator, and it was confirmed that butylamine as a raw material was azeotropically removed in the produced water. Moreover, the yield of the imide compound was low. Furthermore, Comparative Examples 2-18
However, the yield of the imide compound is low, or the reaction cannot be continued because the viscosity increases due to gelation during the reaction, or the reaction product becomes insoluble due to gelation.

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Claims (4)

[Claims] 1. The following (A) and (B) are reacted,
A process for producing an imide compound, which comprises removing a ketone or an aldehyde. (A) Polycarboxylic anhydride derivative. (B) At least one of a ketimine derivative of a compound having a primary amino group and an aldimine derivative of a compound having a primary amino group. 2. The method for producing an imide compound according to claim 1, wherein the polycarboxylic acid anhydride derivative (A) is at least one of a maleic anhydride copolymer and a maleic anhydride graft copolymer. 3. The method for producing an imide compound according to claim 1, wherein the ketimine derivative (B) is a ketimine derivative having a formamide group in the molecule. 4. The method for producing an imide compound according to claim 1, wherein the aldimine derivative (B) is an aldimine derivative having a formamide group in the molecule.