JP3135011B2 - Method for producing bisimide compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved method for producing a bisimide compound.

[0002]

2. Description of the Related Art Conventionally, a general method for producing a bisimide compound has been obtained by reacting a diamine compound prepared by reducing a dinitro compound with an α, β-unsaturated dicarboxylic anhydride, for example, maleic anhydride. There is known a method of thermally dehydrating and ring closing bismaleamic acid in the presence of an acid catalyst, or a method of closing a ring using a carboxylic anhydride as a dehydrating agent in the presence of an alkali metal salt catalyst.
Regarding these production methods, many improved methods have been proposed for the purpose of improving purity, yield, and productivity.

For example, JP-A-3-14835 and JP-A-3-77865 disclose dehydration ring closure in the presence of an excess of α, β-unsaturated dicarboxylic acid or α, β-unsaturated dicarboxylic anhydride. A method for producing a bismaleimide with improved yield and purity is disclosed. Further, JP-A-1-226873 and JP-A-1-238568 disclose a bismaleimide compound obtained by dehydration and ring closure with a dehydrating agent, dissolving and washing with a halogen-substituted hydrocarbon solvent, and then washing with a methane-based hydrocarbon solvent. A method for improving the purity by reprecipitation is described. On the other hand, Japanese Patent Publication No. 2-58267 and Japanese Patent Application Laid-Open No. 1-211563 disclose that a diamine and maleic anhydride are reacted in the presence of a halogenated hydrocarbon solvent and an aprotic solvent to form bismaleamic acid. After that, a method for producing a high-purity bismaleimide by dehydration and ring closure in the presence of an acid catalyst without isolation is disclosed.

However, considering that a bisimide compound is industrially produced via a dinitro compound, it is not always possible to reach an advantageous production method by examining only the above-mentioned addition reaction step and dehydration ring closure reaction. Absent.

[0005]

In a production method comprising a number of reaction steps, improvements are made to improve the yield and purity of each reaction step. In this case, in order to carry out each reaction under the best conditions, an intermediate product is usually isolated and produced between each step.

The process for producing a bisimide compound via a dehydration ring closure reaction with a carboxylic anhydride, which is the subject of the present invention, comprises two different reactions, a step of reducing a dinitro compound and a dehydration ring closure reaction of a bisamic acid. However, the catalytic reduction reaction and the reaction with a carboxylic anhydride have remarkably different reaction properties, and it has been considered that it is preferable to perform the reaction in different environments to improve the yield and purity.

That is, in the reduction reaction step, methanol, ethanol, isopropyl alcohol, methyl cellosolve, N, N-dimethylformamide and the like which are inert to the reaction are considered to be preferable, while diamine and α, β-
The formation of bisamidic acid by the reaction of unsaturated dicarboxylic anhydride and the subsequent dehydration ring closure reaction can be performed in the same or different solvents, but usually it does not react with both components and is a good solvent. Since it is desirable to be able to dissolve the bisimide compound, ketones such as acetone have been used.

[0008] Therefore, when bismaleimide is produced by a reduction step and a dehydration ring-closure reaction step, it has been said that it is necessary to once isolate and purify in the middle, but such a purification operation is not suitable for improving the purity. Although preferred, it is pointed out that this is the cause of the decrease in yield.

Accordingly, an object of the present invention is to provide a method for producing a bisimide compound which solves the conflicting problem of obtaining a product of high purity while maintaining high productivity in a simple process.

[0010]

Means for Solving the Problems The present inventors have the general formula

[0011]

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(X is the same or different single bond, -C
_{H 2 -, - O -,} - SO 2 -, - C (CH 3) 2 -, - C (C
_{F 3) 2 -, - O} -C (CH 3) 2 -, - C (CH 3) 2 -O-,
_{-O-C (CF 3) 2} - and -C (CF ₃₎ divalent group selected from ₂ -O-, R ¹ are each the same or different halogen (fluorine, chlorine, bromine) or having 10 or less carbon Alkyl group, halogenated (fluorine, chlorine, bromine) alkyl group,
A substituent selected from a perfluoroalkyl group, n is 1 to
Integer of 6, 1 and m represent 0 or an integer of 4 or less. )) To reduce the dinitro compound represented by the general formula

[0013]

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A diamine compound represented by the formula (X, R ¹ , l, m, and n are the same as in the chemical formula 1) is obtained.

[0015]

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(D represents a divalent organic group having an ethylenically unsaturated bond), and reacted with an α, β-unsaturated dicarboxylic anhydride represented by the general formula:

[0017]

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(X, R ¹ , l, m, and n are the same as in Chemical Formula 1 and D is the same as in Chemical Formula 3), and this is further dehydrated with a carboxylic acid anhydride. General formula consisting of three steps

[0019]

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(Wherein X, R ¹ , l, m, and n are the same as in Chemical formula 1 and D is the same as Chemical formula 3). After examining ways to improve performance,
Surprisingly, they have found that the use of a specific solvent in common throughout each production step contributes not only to an improvement in productivity but also to an improvement in product purity, and has arrived at the present invention.

That is, in the present invention, when a fatty acid ester solvent is used, a common solvent can be used in any of the reduction reaction, the addition reaction, and the dehydration ring-closure reaction.
Intermediates can be transported in solution or slurry without the need for delivery in a purified solid state, as is commonly done between steps, and only intermediate removal of solids and moisture between steps This is based on the finding that the purification operation has no effect on the reaction in the step.

More specifically, in a first step, a nitro compound corresponding to a bisimide compound as a target product is dissolved in a fatty acid ester, and reduced by introducing a pressurized hydrogen gas in the presence of a metal catalyst such as Pd or Pt. Then, the catalyst is filtered off, and the resulting diamine compound is subjected to the next addition reaction in a state of a solution in which water generated by the reaction is dehydrated with a solid desiccant. The bisamide compound is obtained as a solution or slurry by adding an α, β-unsaturated dicarboxylic anhydride to the diamine compound in the ester solution, and without any treatment, the bisamide compound is further treated with a carboxylic anhydride in a third step. It comprises adding a metal salt as a catalyst and heating to complete the ring-closing condensation reaction.

In the fatty acid ester solution of the bisimide compound obtained here, the carboxylic acid generated by the dehydration reaction is dissolved and a metal salt as a dehydration aid is dispersed. Residue reduces purification efficiency in the purification step to obtain a higher purity bisimide compound, and it is particularly important to completely remove these in the quality of electronic materials. It is preferable to add a water, more preferably a warm water, to the fatty acid ester solution of the bisimide compound obtained and wash it with stirring to obtain a bisimide compound in which these are sufficiently reduced.

The fatty acid ester used in the present invention is represented by the general formula: R ² COOR ³ (R ² and R ³ are the same or different and may have a branched alkyl group having 1 to 5 carbon atoms), What can be at least partially separated when mixed with water, for example, butyl formate, isobutyl formate, t-butyl formate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate,
Examples thereof include t-butyl acetate, methyl propionate, and ethyl propionate. Ethyl acetate, butyl acetate, isobutyl acetate, and t-butyl acetate are most preferable.
Further, these can be used by appropriately mixing.

In the reduction step of the present invention, a nitro group is catalytically reduced to an amino group.
Pd, Pt and other metal catalysts or supported catalysts or Raney catalysts, preferably Pd or Pt activated carbon supported catalysts,
0.01% based on metal relative to nitro compound as reactant
This is performed using 10 to 10% by weight. The reaction temperature and reaction pressure are not particularly limited, but are generally 10 to 200 ° C, preferably 10 to 150 ° C, and normal pressure to 50 kg / cm ² . The dehydration treatment of the water generated at this time can be efficiently performed by using a zeolite or a solid drying agent such as anhydrous sodium sulfate and anhydrous magnesium sulfate.

At this time, the water content in the fatty acid ester solution of the diamine compound may be 0.5% or less. When the content is 0.5% or more, a large amount of carboxylic anhydride is required as a dehydrating agent when a bisimide compound is generated, and the generation of by-products is undesirably increased.

The adjustment of the bisamic acid in the second step is carried out by adding 1 part to the fatty acid ester solution of the diamine compound obtained in the first step.
It is carried out by gradually adding α, β-unsaturated dicarboxylic anhydride in a powdery, granular or solution state at 0 to 60 ° C., preferably 10 to 40 ° C., with stirring. At this time, α,
It is preferable that the charged amounts of the β-unsaturated dicarboxylic anhydride and the diamine compound are slightly excessive with respect to the diamine compound. Usually, 2.02 to 3.00 of α, β-unsaturated dicarboxylic anhydride is suitable for 1 mol of the diamine compound.

In the dehydration ring closure reaction in the third step, a carboxylic acid anhydride, preferably acetic anhydride, as a dehydrating agent is added to the bisamic acid solution obtained in the second step in an amount of 1.80 per mole of amic acid group.
0 to 3.0 mol is added, and although it depends on the boiling point of the solvent and the operating pressure, 20 to 100 ° C, preferably 20 to 80 ° C
For 1 to 30 hours to complete the reaction.

In the washing with water after the completion of the reaction in the third step, the separation of the interface is good, and the fatty acid ester layer is separated or not separated beforehand. Can be purified and precipitated. As the poor solvent, hydrocarbon compounds such as hexane, heptane, octane, cyclohexane, and petroleum ether are preferable.

The carboxylic anhydride used as the dehydrating agent is practically limited to acetic anhydride for economic reasons, but need not be particularly limited. Examples of the catalyst used in the dehydration ring closure reaction include alkali metal (sodium, potassium, and lithium) carbonates, hydrogencarbonates, sulfates, nitrates, phosphates, acetates, formates, higher fatty acid salts, and the like. Salts and halides of transition metals such as nickel, cobalt and manganese are used, but potassium acetate is preferred. The amount of these additives is 0.1 to 4.
0 mole is preferred.

Further, if necessary, a tertiary amine can be appropriately added for the purpose of accelerating the dehydration ring closure reaction. Examples of this are triethylamine,
Examples include tripropylamine, tributylamine, triphenylamine, pyridine and the like. The amount of these additives is about 0.1 to 2.0 mol per 1 mol of the amic acid group.

The general formula used in the present invention

[0033]

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(X is the same or different single bond, -C
_{H 2 -, - O -,} - SO 2 -, - C (CH 3) 2 -, - C (C
_{F 3) 2 -, - O} -C (CH 3) 2 -, - C (CH 3) 2 -O-,
R ¹ is a divalent group selected from —OC (CF ₃ ) ₂ — and —C (CF ₃ ) ₂ —O—
Substituents selected from the following alkyl groups, halogenated (fluorine, chlorine, bromine) alkyl groups and perfluoroalkyl groups, n represents an integer of 1 to 6, and l and m represent an integer of 0 or 4 or less. )), Specifically, 2,
2-bis (4-nitrophenyl) propane, 1,1,
1,3,3,3-hexafluoro-2,2-bis (3-
Nitrophenyl) propane, 4,4'-dinitrodiphenyl ether, 2-trifluoromethyl-4-nitrodiphenyl ether, 3,3'-dinitrodiphenylsulfone, 2-trifluoromethyl-4-nitrodiphenylsulfone , Bis (4- (4-nitrophenoxy) phenyl) sulfone, bis (4- (2-trifluoromethyl-4-nitrophenoxy) phenyl) sulfone, bis
(4- (4-nitrophenoxy) phenyl) methane, bis (4- (2-methyl-4-nitrophenoxy) phenyl) methane, bis (4- (2-trifluoromethyl-4)
-Nitrophenoxy) phenyl) methane, bis (4-
(2,6-dimethyl-4-nitrophenoxy) phenyl) methane, bis (4- (2,6-bistrifluoromethyl-4-nitrophenoxy) phenyl) methane, 2,
2-bis (4- (4-nitrophenoxy) phenyl) propane, 2,2-bis (4- (2-methyl-4-nitrophenoxy) phenyl) propane, 2,2-bis (4-
(2,6-dimethyl-4-nitrophenoxy) phenyl) propane, 2,2-bis (4- (2-trifluoromethyl-4-nitrophenoxy) phenyl) propane,
2,2-bis (4- (2,6-bistrifluoromethyl-4-nitrophenoxy) phenyl) propane,
1,1,3,3,3-hexafluoro-2,2-bis
(4- (4-nitrophenoxy) phenyl) propane,
1,1,1,3,3,3-hexafluoro-2,2-bis (4- (2-methyl-4-nitrophenoxy) phenyl) propane, 1,1,1,3,3,3-hexa Fluoro-2,2-bis (4- (2-trifluoromethyl-4
-Nitrophenoxy) phenyl) propane, 1,1,
1,3,3,3-hexafluoro-2,2-bis (4-
(2,6-dimethyl-4-nitrophenoxy) phenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4- (2,6-bistrifluoromethyl-4- Nitrophenoxy) phenyl) propane, bis (4- (4-nitrophenoxy) phenyl) ether, bis (4- (2-methyl-4-nitrophenoxy)
Phenyl) ether, bis (4- (2-trifluoromethyl-4-nitrophenoxy) phenyl) ether, bis (4- (2,6-dimethyl-4-nitrophenoxy)
Phenyl) ether, bis (4- (2,6-bistrifluoromethyl-4-nitrophenoxy) phenyl)-
Ter, 1,3- or 1,4-bis (2- (4-nitrophenoxy) isopropyl) benzene, 1,3- or 1,4-bis (1,1,1,3,3,3-hexafluoro -2- (4-nitrophenoxy) isopropyl) benzene, 1,3- or 1,4-bis (2- (2-methyl-4-nitrophenoxy) isopropyl) benzene,
1,3- or 1,4-bis (1,1,1,3,3,3
-Hexafluoro-2- (2-methyl-4-nitrophenoxy) isopropyl) benzene, 1,3- or 1,
4-bis (2- (2-trifluoromethyl-4-nitrophenoxy) isopropyl) benzene, 1,3- or 1,4-bis (1,1,1,3,3,3-hexafluoro-2- (2-trifluoromethyl-4-nitrophenoxy) isopropyl) benzene and the like.

The method of the present invention comprises the above exemplified compounds
General formula

[0036]

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(Ar is a general formula

[0038]

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(R ⁴ is the same or different and is a substituent selected from a halogen (fluorine, chlorine, bromine) or methyl group, a halogenated (fluorine, chlorine, bromine) methyl group and a trifluoromethyl group, and k is 0 or 4 The following integers are shown.)
Represents ), The most remarkable effect can be obtained when applied to a compound having 3 to 4 aromatic rings and / or two or more ether bonds.

The α, β-unsaturated dicarboxylic anhydride used in the present invention includes maleic acid, chloromaleic acid, dichloromaleic acid, citraconic acid, itaconic acid, mesaconic acid, and tetrahydrophthalic anhydride. Can be

[0041]

The present invention will be described below with reference to examples. In the examples, the analysis of organic substances is performed by high performance liquid chromatography, the analysis value is indicated by area%, and the analysis of moisture is indicated by wt% by Karl Fischer method. Example 1 1,1,1,3,1 was placed in a 1000 ml autoclave equipped with a thermometer, a pressure gauge, a hydrogen inlet tube and a hydrogen purge port.
3,3-hexafluoro-2,2-bis (4- (2-trifluoromethyl-4-nitrophenoxy) phenyl)
Propane (hereinafter abbreviated as BIS-AF-OFN) 25
0.0 g (0.35 mol), 600 ml of ethyl acetate and 5.0 g of 5% -Pd / C (50% wet product) as a catalyst
(1% by weight) and sealed, and the system was replaced twice with hydrogen. 100 ° C, pressure 5.0kg / c with stirring
The temperature was raised to m ² and the pressure was increased, and the conditions were maintained for 4 hours to perform a reduction reaction. After the reaction, dehydration was performed using 50 g of anhydrous magnesium sulfate, and the catalyst and magnesium sulfate were removed by filtration under reduced pressure. The obtained 1,1,1,3,3,3-hexafluoro-2,2-bis (4- (2-trifluoromethyl-4-aminophenoxy) phenyl) propane (hereinafter, referred to as
Abbreviated as BIS-AF-OFA. ) The ethyl acetate solution had a purity of 99.2% and a water content of 0.4%.

The BIS-A obtained in a 2000 ml four-necked flask equipped with a thermometer, a stirrer and a Dimroth condenser was used.
F-OFA ethyl acetate solution total amount and ethyl acetate 600ml
And 75.5 g of maleic anhydride (0.
(77 mol) were added in portions. Some time after the addition, bismaleamic acid was precipitated. Further stirring at room temperature for 2 hours gave a slurry of bismaleamic acid and ethyl acetate having a purity of 99.0%. Subsequently, 107.1 g (1.05 mol) of acetic anhydride and 13% of potassium acetate were added thereto.
7.2 g (1.40 mol) were added and the reaction temperature was raised to 60 ° C.
And the ring closure reaction was started. After stirring at 60 ° C. for 3 hours, the purity of bismaleimide was 96.7% at a reaction rate of 99.5%. After the reaction, 3000 ml
The solution was washed three times with warm water to remove excess acetic anhydride, potassium acetate, and acetic acid produced by the reaction. The washed bismaleimide ethyl acetate solution was placed in a 5000 ml beaker, and stirred with n. 2400 ml of hexane was added to precipitate bismaleimide crystals. These crystals were collected by filtration under reduced pressure, and dried to obtain 252.0 g of bismaleimide having a purity of 98.1%. The yield at this time is 8
It was 8.3%. Example 2 1,3-bis (1,1) was placed in a 1000 ml autoclave equipped with a thermometer, a pressure gauge, a hydrogen inlet tube and a hydrogen purge port.
157.6 g of 1,1,3,3,3-hexafluoro-2- (2-trifluoromethyl-4-nitrophenoxy) isopropyl) benzene (hereinafter abbreviated as 1,3-HFAB-OFN). 20 mol) and ethyl acetate 50
0 ml and 5% -Pd / C as catalyst (50% wet product)
3.2 g (1 wt%) was charged and sealed, and the inside of the system was replaced twice with hydrogen. While stirring, the temperature is 100 ° C. and the pressure is 5.
The temperature was raised to 0 kg / cm ² and the pressure was increased, and these conditions were maintained for 4 hours to perform a reduction reaction. After the reaction, anhydrous magnesium sulfate 5
Dehydration was performed using 0 g, and the catalyst and magnesium sulfate were removed by filtration under reduced pressure. The obtained 1,3-bis (1,1,
Ethyl 1,3,3,3-hexafluoro-2- (2-trifluoromethyl-4-aminophenoxy) isopropyl) benzene (hereinafter abbreviated as 1,3-HFAB-OFA) ethyl acetate solution has a purity of 99. 4% and moisture 0.5%.

The 1,3-H obtained in a 2000 ml four-necked flask equipped with a thermometer, a stirrer and a Dimroth condenser was used.
FAB-OFA Total amount of ethyl acetate solution and ethyl acetate 500
41.2 g of maleic anhydride while mixing and stirring.
(0.42 mol) was added in small portions. Some time after the addition, bismaleamic acid was precipitated. Further stirring at room temperature for 2 hours gave a slurry of bismaleamic acid and ethyl acetate having a purity of 99.1%. Subsequently, 61.2 g (0.6 mol) of acetic anhydride and potassium acetate 7
8.4 g (0.8 mol) was added, and the reaction temperature was raised to 60 ° C. to initiate a ring closure reaction. After stirring at 60 ° C. for 5 hours, the purity of the bismaleimide was 95.7% at a reaction rate of 99.3%. After the reaction, washing with warm water was performed three times using a 3000 ml separating funnel to remove excess acetic anhydride, potassium acetate, and acetic acid generated by the reaction, and the washed ethyl bismaleimide ethyl acetate solution was used as a 5000 ml beaker. −
2,000 ml of n-hexane was added with stirring to precipitate bismaleimide crystals. The crystals were collected by filtration under reduced pressure, and dried to obtain 155.7 g of bismaleimide having a purity of 97.3%. The yield at this time was 85.
3%. Example 3 1,1,1,3,1 was placed in a 1000 ml autoclave equipped with a thermometer, a pressure gauge, a hydrogen inlet tube and a hydrogen purge port.
3,3-hexafluoro-2,2-bis (4- (4-nitrophenoxy) phenyl) propane (hereinafter referred to as BIS-
Abbreviated as AF-N. ) 289.0 g (0.5 mol), 500 ml of ethyl acetate and 5% -Pd / C (50
5.8 g (1 wt%) was sealed and charged, and the inside of the system was replaced twice with hydrogen. 100 temperature with stirring
The temperature and pressure were increased to 5.0 ° C. and a pressure of 5.0 kg / cm ² , and these conditions were maintained for 4 hours to carry out a reduction reaction. After the reaction, dehydration was performed using 50 g of anhydrous magnesium sulfate, and the catalyst and magnesium sulfate were removed by filtration under reduced pressure. The resulting 1,1,
1,3,3,3-hexafluoro-2,2-bis (4-
(4-aminophenoxy) phenyl) propane (hereinafter, referred to as
Abbreviated as BIS-AF-A. ) Ethyl acetate solution has a purity of 9
9.7% and moisture 0.4%.

The BIS-A obtained in a 2000 ml four-necked flask equipped with a thermometer, a stirrer and a Dimroth condenser was used.
102.9 g (1.05 mol) of maleic anhydride was added little by little while stirring the whole amount of FA and 500 ml of ethyl acetate. Some time after the addition, bismaleamic acid was precipitated. Further stirring at room temperature for 2 hours, purity 9
A slurry of 9.6% bismaleamic acid and ethyl acetate was obtained. Subsequently, 112.2 g of acetic anhydride was added thereto.
(1.10 mol) and 196.0 g of potassium acetate (2.0
Mol) was added and the reaction temperature was raised to reflux (78 ° C.) to initiate the ring closure reaction. After stirring at reflux for 4 hours, the purity of the bismaleimide was 95.8% at a conversion of 99.1%. After the reaction, 3000 ml
The solution was washed three times with warm water to remove excess acetic anhydride, potassium acetate, and acetic acid produced by the reaction. The washed bismaleimide ethyl acetate solution was placed in a 5000 ml beaker, and stirred with n. -2000 ml of hexane was added to precipitate crystals of bismaleimide. The crystals were collected by filtration under reduced pressure, and dried to obtain 292.7 g of bismaleimide having a purity of 97.0%. The yield at this time is 8
It was 3.9%. Example 4 In a 1000 ml autoclave equipped with a thermometer, a pressure gauge, a hydrogen inlet tube and a hydrogen purge port, 2,2-bis (4-
(4-nitrophenoxy) phenyl) propane (hereinafter, referred to as
Abbreviated as BIS-AN. ) 235.0 g (0.5 mol)
And ethyl acetate 500 ml and 5% -Pd / C as a catalyst
(50% wet product) 4.7 g (1 wt%) was charged and sealed, and the inside of the system was replaced twice with hydrogen. Temperature 1 with stirring
The temperature was raised to 00 ° C. and the pressure to 5.0 kg / cm ² , and the pressure was increased. These conditions were maintained for 4 hours to perform a reduction reaction. After the reaction, dehydration was performed using 50 g of anhydrous magnesium sulfate, and the catalyst and magnesium sulfate were removed by filtration under reduced pressure. 2,2 obtained
The ethyl acetate solution of -bis (4- (4-aminophenoxy) phenyl) propane (hereinafter abbreviated as BIS-AA) had a purity of 99.5% and a water content of 0.4%.

The BIS-A obtained in a 2000 ml four-necked flask equipped with a thermometer, a stirrer and a Dimroth condenser was used.
-A total amount and 500 ml of ethyl acetate were charged, and 102.9 g (1.05 mol) of maleic anhydride was added little by little while stirring. Some time after the addition, bismaleamic acid was precipitated. Further stirring at room temperature for 2 hours, purity 9
A slurry of 9.3% bismaleamic acid and ethyl acetate was obtained. Subsequently, 112.2 g of acetic anhydride was added thereto.
(1.10 mol) and 196.0 g of potassium acetate (2.0
Mol) was added and the reaction temperature was raised to reflux (78 ° C.) to initiate the ring closure reaction. After stirring at reflux for 4 hours, the purity of the bismaleimide was 96.6% at a reaction rate of 99.1%. After the reaction, 3000 ml
The solution was washed three times with warm water to remove excess acetic anhydride, potassium acetate, and acetic acid produced by the reaction. The washed bismaleimide ethyl acetate solution was placed in a 5000 ml beaker, and stirred with n. -2000 ml of hexane was added to precipitate crystals of bismaleimide. The crystals were collected by filtration under reduced pressure and dried to obtain 266.0 g of bismaleimide having a purity of 97.9%. The yield at this time is 9
1.5%. Example 5 BIS-AF-OF was placed in a 1000 ml autoclave equipped with a thermometer, a pressure gauge, a hydrogen inlet tube and a hydrogen purge port.
N250.0g (0.35mol) and butyl acetate 600m
4. 5% -Pd / C (50% wet product) as a catalyst
0 g (1 wt%) was charged and sealed, and the inside of the system was replaced twice with hydrogen. 100 ° C, pressure 5.0kg with stirring
/ Cm ² , the pressure was increased, and the conditions were maintained for 4 hours to carry out a reduction reaction. After the reaction, dehydration was performed using 50 g of anhydrous magnesium sulfate, and the catalyst and magnesium sulfate were removed by filtration under reduced pressure. The obtained BIS-AF-OFA butyl acetate solution had a purity of 99.3% and a water content of 0.4%.

The BIS-A obtained in a 2000 ml four-necked flask equipped with a thermometer, a stirrer and a Dimroth condenser was used.
F-OFA butyl acetate solution total amount and ethyl acetate 600ml
And 75.5 g of maleic anhydride (0.
(77 mol) were added in portions. Some time after the addition, bismaleamic acid was precipitated. When the mixture was further stirred at room temperature for 2 hours, a slurry of bismaleamic acid and butyl acetate having a purity of 99.1% was obtained. Subsequently, 107.1 g (1.05 mol) of acetic anhydride and 13% of potassium acetate were added thereto.
7.2 g (1.40 mol) were added and the reaction temperature was raised to 60 ° C.
And the ring closure reaction was started. After stirring at 60 ° C. for 3 hours, the purity of bismaleimide was 96.1% at a reaction rate of 99.3%. After the reaction, 3000 ml
Washing was performed three times with hot water to remove excess acetic anhydride, potassium acetate, and acetic acid generated by the reaction. The washed bismaleimide butyl acetate solution was placed in a 5000 ml beaker, and stirred with n. 2400 ml of hexane was added to precipitate bismaleimide crystals. The crystals were collected by filtration under reduced pressure and dried to obtain 240.3 g of bismaleimide having a purity of 98.1%. The yield at this time is 8
4.3%.

[0047]

According to the method of the present invention, the bisimide compound can be obtained in a high yield and a high purity state, although the production process is greatly simplified mainly in the purification operation.

Continued on the front page (72) Inventor Junichi Bandai 2805 Imafukunakadai, Kawagoe-shi, Saitama Tokyo Central Research Laboratory (56) References JP-A-1-238568 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07D 207/452 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A compound of the general formula (X is the same or different single bond, —CH ₂ —, —O
_{-, - SO 2 -, -} C (CH 3) 2 -, - C (CF 3) 2 -, -
_{O-C (CH 3) 2} -, - C (CH 3) 2 -O -, - O-C (C
F _{3) 2} - and -C (CF _{3) 2} divalent group selected from -O-, R ¹ is different from the same or each halogen (fluorine, chlorine, bromine) or having 10 or less of the alkyl group carbon atoms, a halogen ( A substituent selected from a fluorine, chlorine, bromine) alkyl group and a perfluoroalkyl group, n represents an integer of 0 or 6 or less, and l and m represent an integer of 0 or 4 or less. ) Is reduced to give a compound of the general formula (Wherein X, R ¹ , l, m, and n are the same as those in Chemical Formula 1), and a diamine compound represented by Chemical Formula 2 and a general formula: (D represents a divalent organic group having an ethylenically unsaturated bond.) An α, β-unsaturated dicarboxylic anhydride represented by the general formula: (Where X, R ¹ , l, m, and n are the same as in Chemical Formula 1 and D is the same as in Chemical Formula 3), and three steps of dehydrating and cyclizing the bisamic acid with a carboxylic anhydride. A general formula consisting of (Where X, R ¹ , l, m, and n are the same as in Chemical Formula 1 and D is the same as Chemical Formula 3). In the method for producing a bisimide compound represented by the formula, the intermediate produced in each step is separated from the solution. And producing each bisimide compound in a fatty acid ester solvent. 2. A compound of the general formula (X is the same or different single bond, —CH ₂ —, —O
_{-, - SO 2 -, -} C (CH 3) 2 -, - C (CF 3) 2 -, -
_{O-C (CH 3) 2} -, - C (CH 3) 2 -O -, - O-C (C
F _{3) 2} - and -C (CF _{3) 2} divalent group selected from -O-, R ¹ is different from the same or each halogen (fluorine, chlorine, bromine) or having 10 or less of the alkyl group carbon atoms, a halogen ( A substituent selected from a fluorine, chlorine, bromine) alkyl group and a perfluoroalkyl group, n is an integer of 1 to 6,
l and m represent 0 or an integer of 4 or less. ) To reduce the dinitro compound represented by the general formula (Wherein X, R ¹ , l, m, and n are the same as in Chemical Formula 1), and a diamine compound represented by Chemical Formula 2 and a general formula: (D represents a divalent organic group having an ethylenically unsaturated bond.) An α, β-unsaturated dicarboxylic anhydride represented by the general formula: (Where X, R ¹ , l, m, and n are the same as in Chemical Formula 1 and D is the same as in Chemical Formula 3), and three steps of dehydrating and cyclizing the bisamic acid with a carboxylic anhydride. Wherein the intermediate formed in each step is separated from the solution and each step is carried out in a fatty acid ester solvent. (Wherein X, R ¹ , l, m, and n are the same as in Chemical Formula 1 and D is the same as Chemical Formula 3). The bisimide compound obtained as a solution is washed with water,
Next, a method for producing a bisimide compound, comprising depositing a solid by adding a poor solvent. 3. The method according to claim 1, wherein the fatty acid ester is an acetic acid ester. 4. The method for producing a bisimide compound according to claim 1, wherein the fatty acid ester is ethyl acetate or butyl acetate.