JPH06211789A - Imide compound, its production intermediate and production thereof - Google Patents

Abstract

PURPOSE:To provide a novel compound having the same moldability as conventional addition type bismaleimide resins, giving cured products good in flexural strength and heat resistance and excellent in low stress property, and useful for electronic part-sealing materials, resist materials, etc. CONSTITUTION:The compound of formula I (R1, R2 are <=6C alkyl, phenyl, etc.; R3 is H, <=6C alkyl, etc.; (m), (n) are 0-4; D is polymerizable 2-24C unsaturated double bond-containing organic group). This compound is obtained by reacting a trisphenol compound such as 1,1,1-tris(p-hydroxyphenyl)ethane with a nitrobenzene such as p-nitrochlorobenzene usually in the presence of a basic compound such as NaOH, catalytically reducing the produced new nitro compound of formula II with hydrogen, and subsequently reacting the produced new amine compound of formula III with an unsaturated dicarboxylic acid anhydride such as maleic acid anhydride.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel imide compound,
The present invention relates to an amine compound and a nitro compound which are intermediates in its production. By curing this imide compound, a cured product having high heat resistance can be obtained. More specifically, it is an imide compound that gives a cured product, which is useful as a resin material for laminated plates, fiber-reinforced composite materials, sliding materials, molding materials, electronic component sealing materials and protective paints, resist materials, etc. It relates to certain amine compounds and nitro compounds.

[0002]

2. Description of the Related Art In recent years, in the fields of electric / electronics, transportation equipment such as airplanes / vehicles, etc., materials having higher heat resistance have been demanded as the performance of the equipment has been improved and the size and weight have been reduced.
Conventionally, epoxy resins, maleimide resins and polyimide resins have been used in this field. However, although the epoxy resin has excellent mechanical properties and electrical properties, it does not necessarily have sufficient heat resistance. Further, although the polyimide resin has excellent heat resistance, it is often insoluble and infusible so that molding is often difficult. Various addition type bismaleimide resins are known as polyimides having improved moldability.

[0003]

DISCLOSURE OF THE INVENTION The present invention has molding processability similar to that of conventional addition type bismaleimide resin, and compared with that, the cured product is comparable in flexural strength and heat resistance and low. The present invention provides an imide compound having excellent properties of a cured product having excellent stress properties, a method for producing the same, an amine compound as a raw material in that case, and a nitro compound as a raw material.

[0004]

The present invention comprises the following inventions. (1) General formula (a)

[Chemical 5] (In the formula, R ₁ and R ₂ represent an alkyl group or cycloalkyl group having 6 or less carbon atoms, a phenyl group or an alkoxy group having 4 or less carbon atoms. R ₃ is a hydrogen atom or an alkyl group or cycloalkyl group having 6 or less carbon atoms. Indicates an alkyl group.
m and n are integers from 0 to 4, and when m + n ≧ 2, R ₁ and R ₂ may be the same or different. When R ₁ or R ₂ is plural, they may be the same or different. D represents an organic group having a polymerizable unsaturated double bond having 2 to 24 carbon atoms. )
An imide compound represented by.

(2) General formula (b)

[Chemical 6] (In the formula, the definitions of R ₁ , R ₂ , R ₃ , m and n are the same as in the case of the general formula (a).).

(3) General formula (c) (In the formula, the definitions of R ₁ , R ₂ , R ₃ , m and n are the same as in the case of the general formula (a).) A nitro compound represented by the formula.

(4) General formula (d) (In the formulae, R ₁ , R ₂ , m and n are defined by the general formula (a)
Is the same as in. ) An imide compound represented by:

(5) The trisphenol compound and nitrobenzenes are reacted to synthesize the nitro compound described in (3) above, and then the nitro compound is reduced to (2) above.
The method for producing an imide compound according to (1) above, which comprises synthesizing the amino compound described above and then reacting the amino compound with an unsaturated dicarboxylic acid anhydride.

(6) The method for producing an imide compound according to (1) above, which comprises reacting the amino compound according to (2) with an unsaturated dicarboxylic acid anhydride.

The imide compound of the first invention can be obtained by imidizing the amine compound of the second invention and an unsaturated dicarboxylic acid anhydride by a known method.
For example, a method of imidizing using a dehydrating agent such as acetic anhydride or an imidizing method using an azeotropic dehydrating solvent described in JP-B-2-58267 can be applied.

The unsaturated dicarboxylic acid anhydrides used in the present invention include maleic anhydride, itaconic anhydride, citraconic anhydride, dichloromaleic anhydride, and Diels-Alder reaction products of these unsaturated dicarboxylic anhydrides and dienes. Examples thereof include Diels-Alder reaction products of maleic anhydride with cyclopentadiene, furan and terpinene.

The amine compound of the second invention is obtained by reducing the nitro compound of the third invention by a known method. For example, the catalytic reduction method described in Industrial Organic Chemistry (Tokyo Kagaku Dojin) and ferric chloride described in Chem. Lett., 259, (1975).
Examples include a method of treating with hydrazine in the presence of hexahydrate. These methods will be described below.

(1) Catalytic Reduction Method Using Hydrogen The reaction solvent is not particularly limited as long as it does not participate in the reaction, and for example, water such as ion-exchanged water and industrial water,
Alcohols such as methanol, ethanol, isopropyl alcohol and butanol, glycols such as ethylene glycol, diethylene glycol and propylene glycol, ethers such as diethyl ether, tetrahydrofuran, dioxane, methoxyethanol and cellosolve acetate, methylene chloride, chloroform and carbon tetrachloride. , Halogenated hydrocarbons such as chlorobenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylene chloride, chloroform, carbon tetrachloride,
Halogenated hydrocarbons such as chlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene, ethyl acetate,
Chain or cyclic esters such as butyl acetate and butyl lactone, and aprotic polar solvents such as dimethylformamide and 1-methyl-2-pyrrolidone are used. These may be used alone, but there is no problem in using two or more kinds in combination. The amount of the solvent used may be an amount that completely dissolves the raw material or an amount that is less than that, and the reaction may proceed while the raw material is suspended. Usually, the solvent is used in an amount of 1 to 30 times the weight of the raw material.

The catalyst used is palladium, nickel,
A metal such as platinum, cobalt or copper, or a supported catalyst or Raney catalyst is used as a metal in an amount of 0.001 to 20% by weight, preferably 0.05 to 5% by weight, based on the nitro compound. The catalyst may be suspended in the solvent in advance, or may be gradually added to the reaction system as the reaction progresses. If necessary, amines such as triethylamine and nitrogen-containing aromatic compounds such as quinoline and isoquinoline may be added in an amount of 1 ppm to 1% by weight to the reaction solvent for controlling the reaction. Usually the reaction temperature is 0 to 150
The temperature and pressure are in the range of atmospheric pressure to 30 kg / cm ² , preferably the temperature is 0 to 100 ° C., and the pressure is in the range of atmospheric pressure to 10 kg / cm ² . The reaction time is usually about 4 to 24 hours.

(2) Reduction method using hydrazine It is possible to use ferric chloride / hexahydrate supported on activated carbon, celite, alumina, silica gel, etc., platinum, palladium or Raney nickel as a catalyst. Among these, the method of using ferric chloride hexahydrate as a catalyst is preferable in that the production rate of by-products is low and a large excess of hydrazine is not required. The amount of ferric chloride hexahydrate used as a catalyst is 1 m of nitro group of nitro compound.
It is about 0.00005 to 0.05 mol with respect to ol, and preferably 0.
It is 0005 to 0.005 mol. The amount of activated carbon used is 1 to 20% by weight, preferably 5 to 15% by weight, based on the nitro compound. Due to the reduction, hydrazine monohydrate is required to be 1.5 times mol or more based on stoichiometry with respect to 1 mol of the nitro group of the nitro compound. Usually, it is in the range of 1.5 to 3 times mol, preferably 1.75 to 2.5 times mol. If the amount is less than these ranges, unreduced nitro groups remain. On the other hand, if the amount is excessive, when recovering the solvent, hydrazine is likely to be mixed in the recovered solvent or high concentration of hydrazine is easily mixed in the wash water, which is not preferable. The reaction temperature is usually 40 to 120 ° C., but the range of 60 to 90 ° C. is preferable in terms of reaction time and reaction control.

Hydrazine monohydrate at a temperature of 60 to 90 ° C
Add dropwise within 1-10 hours. When the reaction scale exceeds 3000 ml, it is preferable to add dropwise over 2 to 5 hours to control the reaction because the heat generation is intense. After the completion of dropping, keep the temperature at the same temperature until the reaction is completed. The reaction usually ends in about 2 to 10 hours. The end point of the reaction is thin layer chromatography,
It can be easily confirmed with a measuring device such as high performance liquid chromatography or GPC. Subsequently, activated carbon is filtered off by a filtration operation, and the solvent of the filtrate is distilled off under reduced pressure to recover the solvent. The reaction solution concentrated to such an extent that the fluidity is not impaired is discharged into a poor solvent such as water or alcohol, or conversely, the poor solvent is dropped into the concentrating pot to filter the crystals formed, or the solvent is removed. After recovery, the amine compound can be obtained as crude crystals. After washing the crystals with water, a poor solvent such as an alcohol solvent is added and the mixture is heated with stirring, and then filtered while hot to obtain high-purity crystals. When a higher degree of purification is required, it can be purified by recrystallization by using the amine as it is or a salt of an acidic compound such as a hydrochloride. The amine compound of the present invention can be obtained by the above method.

The nitro compound of the third invention is obtained by a coupling reaction between nitrobenzenes and a trisphenol compound. Examples of nitrobenzenes used in the present invention include various isomers and derivatives such as chloronitrobenzene, bromonitrobenzene, chloronitrotoluene, bromonitrotoluene, chlorophenylnitrobenzene, chloronitroanisole, bromonitroanisole and dinitrobenzene. These nitrobenzenes can be used not only alone but also as a mixture of two or more kinds.

The trisphenol compound used in the present invention has a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a sec-butyl group as a substituent corresponding to R ₂ in the general formula (c). Having 6 carbon atoms such as tert-butyl group, n-hexyl group and cyclohexyl group
The following alkyl groups or cycloalkyl groups, phenyl groups or alkoxy groups having 4 or less carbon atoms such as a methoxy group, an ethoxy group and an n-butoxy group, and a substituent corresponding to R ₃ is also a hydrogen atom or a methyl group. A compound having an alkyl group having 6 or less carbon atoms such as an ethyl group, a propyl group, a cyclohexyl group or a cycloalkyl group.

Regarding the coupling reaction of the trisphenol compound and the nitrobenzene, in the presence of a basic compound,
A known method of reacting a phenol with a nitrobenzene derivative can be applied. Org.Synt
h., 445, (Vol II), US Pat. No. 4,538,006,
J.Org.Chem., 33,1245 (1968), J.Org.Chem., 50 (20), 371
7 (1985), J. Org. Chem., 50 (17), 3091 (1985), JP-A-61.
-194055, JP 62-70347, Macrolecul
es, 25, 64 (1992) and the like.

Nitrobenzenes are usually 0.8 mol to 1.4 mol per 1 mol of hydroxyl group of trisphenol compound.
Is used, preferably in an amount of 0.95 mol to 1.1 mol, more preferably 0.975 mol to 1.
An amount of 025 mol is used. If this amount is less than 0.8 mol, the ratio of the nitro compound in which hydroxyl groups remain in addition to the target trisphenols becomes large and the purity of the product decreases. Further, if the amount used exceeds 1.4 mol, unreacted nitrobenzenes tend to remain in the product, which is not preferable.

As the basic compound used in the coupling reaction, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like. 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. When using halogenated nitrobenzenes, it is preferable to use a strongly basic alkali metal hydroxide such as sodium hydroxide or potassium hydroxide because the reaction time is shortened and water-soluble impurities are less likely to be generated. In the class, it is preferable to use a weak base compound such as an alkali metal carbonate such as sodium carbonate or potassium carbonate or an alkali metal hydrogen carbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate from the viewpoint of safety such as explosion avoidance.

A known catalyst can be used for the coupling reaction. For example Org.Synth., 445, (Vol I
Activated copper powder or copper salt prepared by the method described in I) can be used. Quaternary ammonium salts; quaternary phosphorus salts; cyclic polyethers and chain polyethers such as crown ether and polyethylene glycol, 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.

An example of the method for producing the nitro compound of the present invention is as follows. Nitrobenzenes and trisphenols are used in an aprotic polar solvent such as dimethyl sulfoxide in the presence of an alkali such as sodium hydroxide or potassium hydroxide.
After conducting a condensation reaction at a reaction temperature of 40 to 110 ° C., after the reaction, the reaction solution is poured into a precipitable solvent such as water or alcohol to precipitate a target product, which is separated by filtration and then washed and filtered repeatedly,
Examples thereof include a method of obtaining the target product by drying.

The imide compound of the first invention can be cured by a known method. Specifically, a tough cured product is provided by heating and melting alone. Further, during curing, various polymerization initiators and catalysts may be added for the purpose of promoting the crosslinking reaction. It is also possible to use other maleimide compounds in combination. Curing by addition reaction with amines and allylphenols, epoxy resins, vinyl compounds, acrylates, methacrylates, cyanates, polyimides, polyethersulfones, polyetherketones, polyetheretherketones, polyesters, silicone elastomers, acrylonitrile- It is also possible to modify according to the purpose by blending a butadiene copolymer or the like. Further, it is possible to use a filler such as silica or a reinforcing material such as carbon fiber or glass fiber depending on the application.

[0026]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Example 1 Synthesis of nitro compound In a 1 liter four-necked flask equipped with a stirrer, a thermometer and a condenser, 1,1,1-tris (p-hydroxyphenyl) ethane 122.6 g (0.40 mol), p -Nitrochlorobenzene 226.9 g (1.44 mol) and dimethyl sulfoxide 210 g were charged, and the internal temperature was 8
Stirred and dissolved at 0 ° C. To this solution, 60 g (1.44 mol) of 96% sodium hydroxide was added, and the mixture was kept at 100 ° C. for 5 hours. After the reaction was completed, this solution was poured into 2500 g of water which was stirred at high speed to precipitate crystals. After separating the crystals by filtration, the crystals were washed twice each with 1000 g of water and methanol,
By drying under reduced pressure at 80 ° C., 265 g of yellow crystals (referred to as PNTP) were obtained. IR (KBr lock) is 134
0 cm ^-1 and 1580~1600cm ^-1 (nitro group)
A characteristic absorption was observed.

Example 2 Synthesis of amine compound In a 2 liter four-necked flask equipped with a stirrer, thermometer and condenser, PNTP 247.8 g (0.370 mol), activated carbon 25 g, ferric chloride hexahydrate. Thing 1.8
g (6.66 mmol) and methyl cellosolve 124
After charging 0 g and stirring at an internal temperature of 120 ° C. for 30 minutes, 80
The temperature was lowered to ℃. Hydrazine monohydrate 111g
(2.22 mol) was added dropwise over 2 hours, and the mixture was kept at 80 ° C. for 3 hours, then hot filtered and washed with 200 g of methyl cellosolve to remove activated carbon. The filtrate was concentrated under reduced pressure at 80 ° C,
Crystals were precipitated by pouring the concentrated liquid into a large amount of water.
The crystals are separated by filtration, washed with water and methanol, and dried under reduced pressure at 80 ° C. to give white crystals (referred to as PATP) 1.
96 g were obtained. IR (KBr tablet) is 3350-345
Characteristic absorption was observed at 0 cm ^-1 (amino group).

Example 3 Synthesis of Imide Compound A maleic anhydride (103.6 g, 1.056) was placed in a 2-liter four-necked flask equipped with a stirrer, a thermometer and a condenser.
Mol) and 1036 g of monochlorobenzene were charged and stirred.
Dissolved. PATP185.5 was previously added to this solution.
g (0.320 mol) 371 g of N-methylpyrrolidone
The solution dissolved in was added dropwise at an internal temperature of 35 ° C over 2 hours, and 4
It was kept warm at 0 ° C for 2 hours. Charge 3.04 g (0.016 mol) of p-toluenesulfonic acid monohydrate, 140 ° C
After azeotropic dehydration reaction for 5 hours (distilled water 17.3 g), distilling off monochlorobenzene under reduced pressure, injecting into ethanol to precipitate crystals, and repeating washing and filtration several times, By drying under reduced pressure at 80 ° C, yellow crystals (PATP-
Let M. ) 247 g were obtained. IR (KBr tablet) is 1
Characteristic absorption was observed at 710 cm ^-1 (derived from the imide ring).

Application Example 1 Imide compound PATP-M obtained in Example 1, o-cresol novolak glycidyl ether compound (trade name Sumiepoxy ESCN-195XL, manufactured by Sumitomo Chemical Co., Ltd.), and phenol novolak (trade name Tamanol) as a curing agent. 759, manufactured by Arakawa Chemical Industry Co., Ltd.), triphenylphosphine, triethylammonium tetraphenylborate as a curing accelerator, fused silica (trade name FS-891, manufactured by Denki Kagaku Kogyo) as a filler, carnauba wax as a release agent, coupling. Agent (trade name SH-6040,
Toray Dow Corning Silicone; trade name KBM-57
3, manufactured by Shin-Etsu Chemical Co., Ltd.) in an amount (g) shown in Table 1, kneaded by heating with a roll, and transfer molding was performed under the conditions of 175 ° C. × 70 kg / cm ² × 2 minutes. In addition, 200
Post-curing was carried out in an oven at ℃ for 5 hours to obtain a cured molded product. Bending strength (20 ° C, 24
0 ° C.), flexural modulus (20 ° C., 240 ° C.) and glass transition temperature were measured. The results are shown in Table 2.

Comparative Application Example 1 The same procedure as in Application Example 1 except that PATP-M was changed to N, N'-diphenylmethane bismaleimide (see Table 1 for the composition), and the results are shown in Table 2.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

INDUSTRIAL APPLICABILITY The imide compound of the present invention has molding processability similar to that of the conventional addition type bismaleimide, and compared with that, the cured product has bending strength and heat resistance (glass transition temperature).
In the case of (1), a cured product having the same physical properties and excellent physical properties as low stress (low flexural modulus) is provided. The amine compound and nitro compound of the present invention are important as intermediates for producing the imide compound of the present invention.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical indication location C08G 59/40 NKG 8416-4J (72) Inventor Shuichi Kanagawa 6 Kitahara, Tsukuba-shi, Ibaraki Sumitomo Chemical Co., Ltd.

Claims (6)

[Claims] 1. A compound represented by the general formula (a): (In the formula, R ₁ and R ₂ are each an alkyl group having 6 or less carbon atoms, a cycloalkyl group, a phenyl group, or a carbon atom having 4 carbon atoms.
The following alkoxy groups are shown. R ₃ represents a hydrogen atom or an alkyl group having 6 or less carbon atoms or a cycloalkyl group. m and n are integers from 0 to 4, and when m + n ≧ 2, R ₁ and R ₂ may be the same or different. When R ₁ or R ₂ is plural, they may be the same or different. D represents an organic group having a polymerizable unsaturated double bond having 2 to 24 carbon atoms. ) An imide compound represented by: 2. A general formula (b): (In the formula, the definitions of R ₁ , R ₂ , R ₃ , m and n are the same as in the case of the general formula (a).). 3. A compound represented by the general formula (c): (In the formula, the definitions of R ₁ , R ₂ , R ₃ , m and n are the same as in the case of the general formula (a).) A nitro compound represented by the formula. 4. A general formula (d): (In the formulae, R ₁ , R ₂ , m and n are defined by the general formula (a)
Is the same as in. ) An imide compound represented by: 5. A trisphenol compound is reacted with a nitrobenzene to synthesize the nitro compound according to claim 3, then the nitro compound is reduced to synthesize the amino compound according to claim 2, and then the amino compound. The method for producing an imide compound according to claim 1, wherein the reaction is carried out with an unsaturated dicarboxylic acid anhydride. 6. The method for producing an imide compound according to claim 1, which comprises reacting the amino compound according to claim 2 with an unsaturated dicarboxylic acid anhydride.