JPH0827108A - Manufacture of heat-hardening compound and its intermediate - Google Patents

Abstract

PURPOSE:To obtain a bismaleimide compound by obtaining a bisphenol compound from isoprene and a phenolic compound, reacting the bisphenol compound with a nitrobenzene compound to obtain a dinitro compound, successively reducing the dinitro compound and finally reacting the reduced product with maleic anhydride. CONSTITUTION:A bisphenol compound of formula II (Q is a hydrocarbon derived from isoprene) is obtained by reacting isoprene with a phenolic compound of formula I [R1 and R2 are each a halogen, a (halogeno)hydrocarbon; c and d are each 0-4; c+d<=4]. A dinitro compound of formula IV is obtained by reacting the bisphenol compound with a nitrobenzene compound of formula III [X is F, Cl, Br, I or nitro; R1 and R2 are each a halogen or (halogeno)hydrocarbon; a and b are each 0-4; a+b<=4]. Successively, a diamino compound of formula V is obtained by reducing the dinitro compound. Finally, the objective bismaleimide is obtained by reacting the diamino compound of formula V with maleic anhydride. The bismaleimide compound has a low melting point, it is excellent in solubility in a widely used organic solvent, and it can produce a cured material having excellent heat resistance. Further, it is especially excellent in handleability and has wide applicability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting compound which is particularly useful as a sealing material for electronic parts and a laminate, and a method for producing an intermediate thereof.

[0002]

2. Description of the Related Art Conventionally, electrical and electronic parts such as semiconductors, which are molded and sealed with epoxy resin, have been widely used. This epoxy resin has been widely put into practical use because it is economically advantageous as compared with the hermetic sealing method using glass, metal, or ceramic. However,
In recent years, the usage conditions of electronic parts have tended to become severe. For example, as the mounting method shifts from conventional insertion mounting to surface mounting, the sealing material itself is exposed to the solder bath temperature. As a result, the heat resistance of the sealing material has become an important characteristic. Recently, thermosetting polyimide resin encapsulation has been proposed for the purpose of obtaining high heat resistance. Further, addition of a thermosetting polyimide to a resin component has been proposed for the purpose of improving heat resistance for electric / electronic parts such as a laminated board.

[0003]

However, although the electronic sealing component molded and sealed with the imide resin has excellent heat resistance, it has a major drawback in terms of moisture resistance which is a characteristic of the thermosetting imide resin. have. It is possible to reduce the moisture absorption rate by introducing a hydrophobic group into a compound such as N, N'-diphenylmethane bismaleimide, but since such a maleimide compound has a high melt viscosity and melting point,
It is difficult to add a resin component for high performance while ensuring sufficient flowability, and there is a problem that the degree of freedom of the resin composition is small. On the other hand, in the case of a laminated plate, a step of dissolving a resin component in a solvent to form a varnish and impregnating the base material is necessary, but a thermosetting polyimide is usually a high melting point, hardly soluble crystal and exhibits excellent physical properties. However, low workability is a problem. An object of the present invention is to provide a method for producing a bismaleimide compound having a low melting point and a low viscosity and having a high solubility in a general-purpose solvent and an intermediate thereof.

[0004]

As a result of intensive studies, the present inventors have found that a specific bismaleimide compound is suitable for the above purpose and completed the present invention. That is, the present invention is as follows. (A) (1) Isoprene and general formula (4)

[0005]

[Chemical 7] (In the formula, R ₁ and R ₂ are a halogen atom and a carbon number 1 respectively.
Represents a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and c and d each are an integer of 0 or more and 4 or less and satisfy c + d ≦ 4. ) Is reacted with one or more phenol compounds represented by the general formula (5)

[0006]

Embedded image (In the formula, Q represents a hydrocarbon group derived from isoprene. R ₁ , R ₂ , c, and d are defined by the general formula (4), respectively.
Is the same as in. ) A step of producing a bisphenol compound represented by the formula (2), the bisphenol compound obtained in the preceding step (2) and the general formula (6)

[0007]

[Chemical 9] (In the formula, X represents a fluorine, chlorine, bromine, iodine or nitro group, R _i and R _j are a halogen atom and a carbon number of 1 to 1 respectively.
Represents a hydrocarbon group having 6 or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a and b each are an integer of 0 or more and 4 or less;
+ B ≦ 4 is satisfied. ) By reacting with a nitrobenzene compound represented by the general formula (3)

[0008]

[Chemical 10] (Wherein, Q, R ₁ , R ₂ , R _i , R _j , a, b, c, d
Are the same as those in the general formula (4), the general formula (5) and the general formula (6), respectively. The manufacturing method of the dinitro compound characterized by performing sequentially the process of manufacturing the dinitro compound shown by these. (B) The dinitro compound obtained by the method described in the above item (A) is reduced to give the compound represented by the general formula (2):

[0009]

[Chemical 11] (In the formula, Q represents a hydrocarbon group derived from isoprene. R ₁ , R ₂ , Ri, and R _j are each a halogen atom,
It represents a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c and d are each an integer of 0 or more and 4 or less, and satisfy a + b ≦ 4 and c + d ≦ 4. )
A method for producing a diamino compound represented by: (C) The diamino compound obtained by the method described in (B) above is reacted with maleic anhydride to give a compound represented by the general formula (1):

[0010]

[Chemical 12] (In the formula, Q represents a hydrocarbon group derived from isoprene. R ₁ , R ₂ , R _i , and R _j are each a halogen atom,
It represents a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c and d are each an integer of 0 or more and 4 or less, and satisfy a + b ≦ 4 and c + d ≦ 4. )
A method for producing a bismaleimide compound represented by:

The present invention will be described in detail below. 1 of isoprene and the phenolic compound represented by the above general formula (4)
Regarding the reaction with one kind or two or more kinds, a known Friedel-Crafts reaction in which an olefin compound and a phenol are reacted in the presence of a catalyst such as a Lewis acid, a Bronsted acid, a heteropolyacid or an acidic ion exchange resin is used. .

Specific examples of the phenol compound include phenol, cresol, xylenol, trimethylphenol, ethylphenol, propylphenol, butylphenol, amylphenol, hexylphenol,
Methylpropylphenol, methylbutylphenol,
Examples thereof include methylphenylphenol, chlorophenol, chlorocresol, chloroxylenol, bromophenol, bromocresol, and bromoxylenol, with phenol, cresol, xylenol, and methylbutylphenol being preferred.

Depending on the reaction equivalence ratio between isoprene and the phenol compound, the reaction temperature, the type and amount of the catalyst, etc., in addition to isoprene, a dimer or trimer of isoprene ...
Etc. are produced, and these are reacted with the phenol compound to obtain the bisphenol compound represented by the general formula (5).
In the general formula (5), Q is a hydrocarbon group derived from isoprene as described above and has a natural number multiple of 5 (usually 1 to 5 times).

A bisphenol compound of the general formula (5),
The dinitro compound of the general formula (3) can be obtained by reacting the nitrobenzene compound of the general formula (6). Specific examples of the nitrobenzene compound of the general formula (6) include p-fluoronitrobenzene, p-chloronitrobenzene, p-bromochloronitrobenzene, p-iodonitrobenzene, m-dinitrobenzene and o-chloronitrobenzene. , P-chloronitrobenzene and m-dinitrobenzene are preferred.

The nitrobenzene compound is usually used in an amount of 0.8 times or more and 1.4 times or less, and preferably 0.9 times or more and 1.1 times or less, with respect to 1 mole of the hydroxyl group of the bisphenol compound. If the amount used exceeds 1.4 times, unreacted nitrobenzene derivative monomer is likely to remain in the product, which is not preferable. On the other hand, if the amount used is too low, the proportion of unreacted hydroxyl groups increases and the hygroscopicity of the product increases, which is not preferable.

Examples of the basic compound used in the coupling reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate. Alkali metal hydrogen carbonates, sodium methoxide, alkoxides such as potassium t-butoxide, hydrides such as lithium hydride and sodium hydride, and the like are used. These may be used alone, but there is no problem in using two or more kinds in combination. For dinitrobenzenes, it is preferable to use weak base compounds such as alkali metal carbonates such as sodium carbonate and potassium carbonate and alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate from the viewpoint of safety such as explosion avoidance.

A known catalyst can be used for the coupling reaction. Org.Synth., 445, (Vol II)
The active copper powder or copper salt prepared by the method described in can be used. Cyclic polyethers and chain polyethers such as quaternary ammonium salts, quaternary phosphorus salts, crown ethers and polyethylene glycols, and their terminal alkyl ethers, nitrogen-containing cyclic polyethers and nitrogen-containing chain polyethers, and their terminal alkyls. An interlayer transfer catalyst such as ether can be used. These may be used alone, but there is no problem in using two or more kinds in combination.

The solvent used is dimethylformamide, dimethylsulfoxide, dimethylacetamide, 1
An aprotic solvent such as -methyl-2-pyrrolidone, sulfolane, 1,3-dimethyl-2-imidazolidinone is used. The amount of these solvents used is not particularly limited, but usually 1 to 10 times by weight of the solvent is used with respect to the raw materials. When water is produced during the reaction, a method of azeotropic dehydration is used to add water such as toluene, xylene, chlorobenzene, and other hydrocarbons that are azeotropic with water, halogenated hydrocarbons, etc. You may.

The raw materials may be charged by preliminarily charging all the raw materials into a reaction kettle, by adding only the base component little by little at the end, by gradually preparing a phenolate salt and then gradually adding a nitrobenzene compound. Is typical. The coupling reaction is generally carried out at a constant temperature or in a stepwise manner between 50 and 200 ° C. and the coupling reaction is continued until the reaction is completed. After the reaction, the formed salt is removed by filtration. A solution of the dinitro compound represented by the general formula (3) is obtained by the above operation.

Next, a method for reducing the nitro compound will be described. Reduction of the dinitro compound represented by the general formula (3) to the corresponding diamino compound represented by the general formula (2) is carried out using hydrogen in the presence of a catalyst. If necessary, the solvent may be concentrated before the reaction. At this time, the dinitro compound may be dissolved in an aprotic solvent, or the reaction may be carried out in a suspended state even if it is not completely dissolved. Usually, the solvent is used in an amount of 1 to 30 times the weight of the raw material. The catalyst used is a metal such as palladium, nickel, platinum, cobalt, rhodium, ruthenium, or copper, or a supported catalyst, or a Raney catalyst, which is used in an amount of 0.001 to 20% by weight, preferably 0.05 to 5% by weight, based on the dinitro compound. The catalyst may be suspended in the solvent in advance, or may be gradually added to the reaction system as the reaction progresses. Alternatively, the catalyst may be suspended in an aprotic solvent in a hydrogen atmosphere, and a suspension or solution of the dinitro compound may be added dropwise thereto to carry out the reaction.
Activated carbon, metal oxides, carbonates, sulfates and the like are used for supporting the catalyst, and specifically, Celite, Florisil, alumina, silica gel, silica alumina, magnesium oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate. Etc. are used. If necessary, amines such as triethylamine and nitrogen-containing aromatic compounds such as quinoline and isoquinoline may be added to the reaction solvent to control the reaction.
It is also possible to add 1 ppm to 1% by weight. Regarding the reaction conditions, the reaction temperature is usually 0 to 200 ° C., the pressure is normal pressure to 25 atm, preferably the temperature is 0 to 150 ° C., and the pressure is normal pressure to 10 atm. The reaction time is usually about 4 to 24 hours.

After the reaction, the catalyst is filtered off. The catalyst used can be reused as it is or after being subjected to a regeneration treatment. Water in the solution is removed by a method such as azeotropic dehydration to obtain a diamino compound solution of the general formula (2).

Typical examples of the diamino compound represented by the general formula (2) are as follows. 2,3-Bis [4- (4
-Aminophenoxy) phenyl] -2-methylbutane,
2,3-bis [4- (3-aminophenoxy) phenyl]
-2-Methylbutane, 2,3-bis [4- (4-aminophenoxy) -3-methylphenyl] -2-methylbutane, 2,3-bis [4- (3-aminophenoxy) -3-
Methylphenyl] -2-methylbutane, 2,3-bis [4
-(4-Aminophenoxy) -3,5-dimethylphenyl] -2-methylbutane, 2,3-bis [3- (4-aminophenoxy) -3,5-dimethylphenyl] -2-methylbutane, 2,3 -Bis [4- (4-aminophenoxy)
-3-Butyl-6-methylphenyl] -2-methylbutane, 2,3-bis [4- (3-aminophenoxy) -3-
Butyl-6-methylphenyl] -2-methylbutane and the like.

The production method for synthesizing the maleimide compound represented by the general formula (1) of the present invention comprises preparing an amic acid of a diamino compound represented by the general formula (2) and maleic anhydride, followed by dehydration ring closure reaction. Is carried out to obtain the corresponding maleimide compound.

The amic acid is prepared by bringing an organic solution of the diamino compound represented by the general formula (2) into contact with a maleic anhydride solution. At this time, maleic anhydride is preferably used in an amount of 1 to 1.5 times equivalent to 1 equivalent of the amino group of the diamino compound. When it is less than 1 equivalent, amino groups that do not become amic acid remain, and even if it is used more than 1.5 times, there is no advantage due to being used in large amounts, and conversely unreacted maleic acid is mixed in the product. Not preferable. The usual addition method is to charge the organic solution of maleic anhydride with the solution of the diamino compound continuously or in a divided manner.
The time required for the addition is not particularly limited as long as the side reaction is not significant, but it is usually about 0.5 to 6 hours. The reaction temperature is -20 to 120 ° C, preferably room temperature to 60 ° C. If the temperature is too low, the reaction progresses slowly, and if it is too high, the purity of the target product is lowered due to by-products such as polymers.

As the solvent for dissolving maleic anhydride, aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, 1-methyl-2-pyrrolidone, sulfolane and 1,3-dimethyl-2-imidazolidinone are used. , One or more mixed solvents of aliphatic or alicyclic hydrocarbons such as hexane, heptane, decane and cyclohexane, hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene To use.

The total amount of the solvent used is 1 to 10 times by weight the total weight of the maleic anhydride and the diamino compound. Considering the yield per reaction, it is preferably 1 to 5 times by weight. . After the addition of the diamino compound is completed,
After about 0.5 to 4 hours, the corresponding amic acid is obtained.

Subsequently, a dehydration ring closure reaction of amic acid is carried out to produce a maleimide compound. In general, the dehydration ring closure reaction includes a chemical ring closure method in which acetic anhydride acts as a dehydrating agent in the presence of a catalyst such as sodium acetate, cobalt acetate, triethylamine and the like, and a thermal ring closure method in which it is dehydrated by heating in the presence of an acidic catalyst. However, the thermal cyclization method is preferable because the yield and product purity are high and the product removal step after the reaction is easy.

The solvent used in the thermal ring closure method may be basically the same as that used in the amide oxidation. Dimethylformamide, dimethylsulfoxide, dimethylacetamide, 1-methyl-2-pyrrolidone, sulfolane, 1,3-
Oxygen-containing and nitrogen-containing solvents such as dimethyl-2-imidazolidinone and mixtures thereof are used. Water is generated due to dehydration ring closure during the imidization reaction. Aliphatic or alicyclic hydrocarbons such as hexane, heptane, decane, and cyclohexane that are azeotropic with water in order to bring this water out of the system,
It is common to use a method of performing azeotropic dehydration using one or more mixed solvents of hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene. Is the way. The amount of these solvents used is 1 to 20 times by weight, preferably 2 to 10 times by weight, the amount of the solvent for azeotropic dehydration is 90% by weight or more based on the total amount of the solvent. It is preferable because it facilitates dehydration.

Examples of the acidic catalyst used for ring closure of amic acid include mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid and polyphosphoric acid, organic sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid, trichloroacetic acid and trifluoroacetic acid. Examples thereof include halogenated carboxylic acids, cation-type ion exchange resins, phosphotungstic acid, heteropolyacids such as phosphomolybdic acid, and solid acids such as silica-alumina. Among them, sulfuric acid, p
-Toluenesulfonic acid and sulfonic acid type ion exchange resins are preferred. When using a heteropolyacid, it is preferable to pretreat the catalyst at 150 to 200 ° C. to enhance the activity. These acids may be used by supporting them on activated carbon, silica gel, silica alumina, inorganic salts, or in the form of salts with diamino compounds. The amount of these acidic catalysts used depends on the type, but if the amount is a homogeneous system (system in which the catalyst cannot be separated by filtration), it is 0.1 to 10 relative to the total weight of the raw material diamino compound and maleic anhydride.
%, And 5 to 100% by weight is used for heterogeneous systems (systems in which the catalyst can be separated by filtration). If the amount used is less than the above range, the desired catalytic effect cannot be obtained, and even if it is used more than the above range, a certain result or more cannot be obtained, and on the contrary, the separation and removal operation of the catalyst becomes complicated. The heterogeneous catalyst can be reused as it is or after being subjected to a known regeneration treatment depending on the characteristics of the catalyst.

The thermal cyclization reaction may be carried out in the range of 60 to 200 ° C. and the reaction may be carried out at a constant temperature, but the reaction is preferably carried out in two steps. First, the preliminary ring-closing reaction, which is the first step, is performed.
The temperature of the preliminary reaction is 60 to 120 ° C., preferably 80 to 110 ° C. under reduced pressure reflux. The reaction time is 0.1 to 6 hours,
Especially 0.5 to 2 hours. During the reaction, water generated by ring closure is separated and removed to the outside of the system by using a device such as Dean-Stark azeotropic dehydration tube.

After the preliminary ring closure, the second step of the present reaction is carried out. Gradually return from reduced pressure to normal pressure while performing azeotropic dehydration 12
The temperature is raised to 0 ° C or higher and azeotropic dehydration is continued. At this time, it may be changed continuously or stepwise. Further, from the viewpoint of operation, the azeotropic dehydration may be interrupted for a short time, but it is preferable to continuously perform the azeotropic dehydration in order to suppress side reactions. The reaction temperature is preferably 120 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher and 160 ° C. or lower. 120 ° C
In the following, the significance of shortening the ring closure reaction time is small, and it is
In the above case, the product of sufficient purity cannot be obtained due to the polymerization of unsaturated imide. The reaction time is usually about 1 to 6 hours.

After the reaction, the azeotropic halogenated hydrocarbon solvent and the aprotic polar solvent are recovered under reduced pressure. At this time, it is preferable that 80% or more of the solvent is recovered to enhance the liquid separation property in the next water washing step.

Next, the concentrated reaction mixture is dissolved in an organic solvent which can be separated from water and has a specific gravity smaller than that of water. If an organic solvent having a higher specific gravity than water is selected as the organic solvent, it is necessary to take out the organic solution from the kettle at each washing step or to perform liquid separation from the top of the kettle, which is disadvantageous in terms of safety maintenance and production efficiency.

Specific examples of the organic solvent having a smaller specific gravity than water include ketone solvents such as methyl isobutyl ketone, ester solvents such as ethyl acetate, and hydrocarbon solvents such as toluene and xylene. Among them, methyl isobutyl is preferable. Ketone solvents such as ketones are preferred. Although the amount used depends on the solubility of the unsaturated imide, it is usually 2
~ 20 times the weight.

Next, washing at 20 to 90 ° C. and liquid separation are performed. The washing operation is preferably repeated twice or more. The water used is tap water, industrial water, ion-exchanged water, or saline, and it is preferable to neutralize and remove the acidic catalyst with a weak base such as sodium bicarbonate. The pH of the aqueous layer is finally 4-8, preferably
It is 5 to 7. The amount of cleaning liquid used is
0.5 to 20 times by weight.

After washing with water, water in the solution is removed by an operation such as azeotropic dehydration, and then an inorganic component is removed by filtration if necessary. At this time, a filter aid such as Celite or an ion adsorbent may be used. The solvent is distilled off under reduced pressure and atmospheric pressure to reduce the amount of residual solvent to 1% by weight or less based on the product, and after heating above the melting point or softening point of the unsaturated imide, it is discharged from the kettle and cooled to obtain the product. be able to.

[0037]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Example 1 A 2-liter four-necked flask equipped with a thermometer, a stirrer, and a condenser was placed under a trade name of bisphenol IPL (manufactured by Nippon Oil Co., Ltd., a hydrocarbon group derived from isoprene (carbon number).
5 / containing 10 carbon atoms in a ratio of 8/2) to which phenol is linked. Hydroxyl equivalent 140 g / eq.) 140.0 g
Then, 154.4 g of p-chloronitrobenzene and 495 g of dimethylacetamide (hereinafter abbreviated as DMAc) were charged and dissolved at 50 ° C. under a nitrogen stream. Sodium hydroxide 49.5 g
Was added, the temperature was raised to 80 ° C, the reaction was continued at 80-90 ° C for 3 hours,
After the internal temperature was raised to 100 ° C, the reaction was continued for 2 hours. Product name Kyoward 1000 after neutralization with carbon dioxide
(Filter aid, manufactured by Kyowa Chemical Industry Co., Ltd.) was added to 30 g of the reaction mixture to remove the salt generated by filtration. DMAc
It was washed with 200 g and combined with the filtrate. A part of this solution was concentrated under reduced pressure, dissolved in toluene, washed with water, and then the organic layer was dried over magnesium sulfate. After removing the desiccant by filtration, toluene was distilled off to obtain a standard product. From the infrared absorption spectrum, absorption by the nitro group was observed at 1340 and 1508 cm ^-1 . This compound is designated as NPL.

Example 2 The NPL obtained in Example 1 was placed in a 1 liter eggplant type flask.
DMAc solution (concentration adjusted to 23.3% by weight) 617.3 g
Then, 7.2 g of 5% palladium / activated carbon catalyst was charged. After the pressure was reduced, the pressure in the system was restored with nitrogen to remove oxygen in the system. Next, the operation of depressurizing again and then returning to pressure with hydrogen was repeated three times to replace the inside of the reaction vessel with hydrogen. Internal temperature under hydrogen atmosphere
The temperature was raised to 80 ± 5 ° C and the reaction was continued at the same temperature for 12 hours to complete the reduction reaction. After the pressure was reduced, the pressure was restored with nitrogen to remove hydrogen inside. Separately, the filter paper of the filter was coated with Radiolite (manufactured by Mizusawa Chemical Co., Ltd., a kind of filter aid), and the reaction solution was filtered at 80 ° C. and washed with 20 g of DMAc. Put the filtrate in a 1 liter flask and add D under reduced pressure.
The MAc was recovered. Chlorobenzene was added to dissolve the reaction mixture, followed by azeotropic dehydration under reduced pressure, and water in the system was separated and removed using a Dean-Stark dehydrator. Subsequently, insoluble components were removed by filtration. A part of the solution was concentrated under reduced pressure to obtain a standard product. This is a light brown glassy substance, and has an ether bond at 1226 cm ^-1 in the infrared absorption spectrum, 3210 ~
Absorption by an amino bond was observed at 3440 cm ^-1 . This compound is designated as APL.

EXAMPLE 3 Maleic anhydride 9.4 in a 300 ml four necked flask.
g, 55.1 g of chlorobenzene and 5.4 g of DMAc were charged, and they were dissolved by stirring under a nitrogen stream. 66.1 g of a chlorobenzene solution of APL obtained by the procedure of Example 2 (concentration adjusted to 27.8% by weight) was placed in a flask using a dropping funnel.
The solution was added dropwise at 25 ± 5 ° C over 2 hours. The reaction was continued at 35 ° C. for 2 hours to complete the amidation reaction. Subsequently, 0.76 g of p-toluenesulfonic acid monohydrate was added, and azeotropic dehydration was performed under reduced pressure at 100 ° C for 1 hour, 110 ° C for 1 hour, and then gradually returned to normal pressure at 131 ° C for 4 hours. The dehydration ring closure reaction was carried out for an hour. The produced water was separated from the system using a Dean-Stark azeotropic dehydrator to proceed the reaction. Then under reduced pressure,
A total of 90% recovery of chlorobenzene followed by DMAc was recovered.
Subsequently, 87 g of methyl isobutyl ketone (hereinafter abbreviated as MIBK) was added and dissolved. The solution was cooled to 60 ° C., and sodium bicarbonate and 300 g of water, which were weighed so that the pH of the aqueous layer was 5 to 7, were added to neutralize the solution, followed by washing and liquid separation. After further washing twice with 300 g of 15% saline at 60 ° C, liquid separation was performed, azeotropic dehydration was performed under reduced pressure, and salts were removed by filtration.
The filtrate was concentrated under reduced pressure, and after reaching the condition of 150 ° C / 5 Torr, the product was taken out from the flask in a molten state,
A light brown solid was obtained with a yield of 23.6 g (95.0% yield) (MP
Let L. ). Infrared absorption spectrum by an ether bond to 1237cm ^-1, absorption by imide bond at 1716 cm ^-1. It softens at 70 ° C and has a melt viscosity of 175 ° C.
It was 3.8 poise.

Example 4 and Comparative Example 1 MPL and N, N'-4,4'-diphenylmethane bismaleimide obtained in Example 3 (melting point 158 ° C., melt viscosity 2.4
Poise / 175 ° C., this compound is called Imide 1. )
Acetone, toluene, MIBK (methyl isobutyl ketone), PGM (propylene glycol monomethyl ether), and MEK (methyl ethyl ketone) are added to the above (amount of 30% by weight solution when each imide compound is dissolved), and solubility at room temperature Were compared. When dissolved, ○
The results are shown in Table 1 when the case of no dissolution was marked with x.

[0041]

[Table 1]

[0042]

EFFECT OF THE INVENTION N, N'-4,4'- which is a general-purpose maleimide
Compared to diphenylmethane bismaleimide, the maleimide compound obtained by the production method of the present invention shows a similar melt viscosity, but has a low melting point and excellent solubility in general-purpose organic solvents, and also has excellent heat resistance. Give things. Compared with imide compounds, which have conventionally had a high melting point, poor solubility, and poor workability, they are much easier to handle and can be used in a wider range of applications. Further, the diamino compound obtained by the production method of the present invention can be utilized as a raw material for a solvent-soluble polyimide in addition to the maleimide compound, and has a wide range of applications and is useful.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 73/10 C09K 3/10 L // C07B 61/00 300

Claims (3)

[Claims] 1. (1) Isoprene and the general formula (4): (In the formula, R ₁ and R ₂ are a halogen atom and a carbon number 1 respectively.
Represents a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and c and d each are an integer of 0 or more and 4 or less and satisfy c + d ≦ 4. ) Is reacted with one or more phenol compounds represented by the general formula (5) (In the formula, Q represents a hydrocarbon group derived from isoprene. R ₁ , R ₂ , c, and d are defined by the general formula (4), respectively.
Is the same as in. ) A step of producing a bisphenol compound represented by the formula (2), the bisphenol compound obtained in the previous step (2) and the general formula (6) (In the formula, X represents a fluorine, chlorine, bromine, iodine or nitro group, R _i and R _j are a halogen atom and a carbon number of 1 to 1 respectively.
Represents a hydrocarbon group having 6 or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, a and b are each an integer of 0 or more and 4 or less;
It satisfies + b ≤4. ) By reacting with a nitrobenzene compound represented by the general formula (3) (Wherein, Q, R ₁ , R ₂ , R _i , R _j , a, b, c, d
Are the same as those in the general formula (4), the general formula (5) and the general formula (6), respectively. The manufacturing method of the dinitro compound characterized by performing sequentially the process of manufacturing the dinitro compound shown by these. 2. The dinitro compound obtained by the method according to claim 1 is reduced to give a compound represented by the general formula (2): (In the formula, Q represents a hydrocarbon group derived from isoprene. R ₁ , R ₂ , Ri, and R _j are each a halogen atom,
It represents a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c and d are each an integer of 0 or more and 4 or less, and satisfy a + b ≦ 4 and c + d ≦ 4. )
A method for producing a diamino compound represented by: 3. A diamino compound obtained by the method according to claim 2 is reacted with maleic anhydride to obtain a compound represented by the general formula (1): (In the formula, Q represents a hydrocarbon group derived from isoprene. R ₁ , R ₂ , R _i , and R _j are each a halogen atom,
It represents a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c and d are each an integer of 0 or more and 4 or less, and satisfy a + b ≦ 4 and c + d ≦ 4. )
A method for producing a bismaleimide compound represented by: