KR940006438B1 - Thermosetting resin compositions and method for their preparation - Google Patents

Abstract

No content.

Description

Thermosetting resin composition and its manufacturing method

1 is a mass spectrum of the bismaleimide compound of Synthesis Example B1.

2 is its IR spectrum.

3 and 4 are IR spectra of the bismaleimide compounds of Synthesis Examples B3 and B4, respectively.

The present invention relates to a thermosetting resin composition obtained from an aromatic diamine compound and a bismaleimide compound and a method for producing the same.

Background Art Conventionally, thermosetting resins having an imide structure have been widely used industrially because they have excellent performance in electrical insulation, heat resistance, and dimensional stability of molded articles.

However, the thermosetting resin obtained by thermally polymerizing aromatic bismaleimide alone has a drawback that it is a material excellent in heat resistance but very soft and lacks flexibility. As a method of improving such a crystal, there has been an attempt to use a thermosetting resin composition composed of an aromatic bismaleimide and an aromatic diamine. For example, N, N-4, 4'-diphenylmethane bismaleimide And polyaminobismaleimide resins (manufactured by Tonu Co., Ltd., trade name catimide) comprising 4,4'-diaminodiphenylmethane and are widely used in impregnating varnishes, red plates, and molded articles. -23250).

However, these thermosetting resin compositions were not satisfactory for impact resistance and flexibility.

Moreover, when using these thermosetting resin compositions as a base material of an electrical / electronic component, etc., it has a drawback that the moldability and the water absorption which adversely affects the electrical characteristics are high.

It is an object of the present invention to provide a low absorption thermosetting resin composition excellent in mechanical strength, particularly impact resistance, and a method for producing the same.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the present inventors discovered that the thermosetting resin composition which consists of a novel bismaleimide compound and a specific aromatic diamine compound was especially effective, and completed this invention.

That is, the present invention,

(1) Formula (I)

Wherein R means H or CH ₃

An aromatic diamine compound represented by the formula and formula (IV)

Wherein R means H or CH ₃

It is a thermosetting resin composition containing a bismaleimide compound represented by "

The bismaleimide compound represented by the formula (IV),

Formula (I)

(Wherein R means H or CH ₃ group)

It is manufactured by the condensation and dehydration reaction of the diamine compound and the anhydride anhydrous represented by

Such diamine compounds are novel compounds filed by the present inventors and include 1, 4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1, 3-bis [4- ( 4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1, 4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1, 3-bis [4- ( 3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1, 4-bis [4- (4-aminophenoxy) -3, 5-dimethyl-α, α-dimethylbenzyl] benzene, 1, 3 -Bis [4- (4-aminophenoxy) -3, 5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -3, 5-dimethyl- α, α-dimethylbenzyl] benzene, 1, 2-bis [4- (3-aminophenoxy) -3, 5-dimethyl-α, α-dimethylbenzyl] benzene and reaction of these diamine compounds with maleic anhydride Bismaleimide compounds obtained by the present invention are also novel compounds filed by the present inventors.

In order to obtain the thermosetting resin composition of the present invention from these bismaleimide compounds and diamine compounds, the bismaleimide compound represented by Formula IV and the aromatic diamine compound represented by Formula I are mixed in the absence of solvent or in the presence of an organic solvent. It is preferable to carry out prepolymerization by heat-processing at the temperature of 70-220 degreeC.

More specifically, the following are preferably used.

(1) The bismaleimide compound and the aromatic diamine compound are pulverized and mixed in a solid-solid form, or they are heated to form a prepolymer, and then pulverized and pelletized or powdered. In this case, the heating conditions are preferably partially cured up to the stage of the prepolymer, and in general, the heat treatment is preferably performed at a temperature of 70 to 220 ° C for 5 to 240 minutes, preferably at 80 to 200 ° C for 10 to 180 minutes. .

(2) The bismaleimide compound and the aromatic diamine compound are dissolved in an organic solvent, and then discharged into a poor solvent, filtered and filtered, dried and pelletized or powdered, or dissolved in an organic solvent. After partially curing to the stage of the prepolymer by heat treatment, it is discharged into a poor solvent, and the precipitate is filtered off, dried, and then pelletized or powdered. The heat treatment conditions vary somewhat depending on the type of organic solvent, but essentially conform to the heat treatment conditions of ①.

The organic solvent that can be used is limited in that it is a solvent that does not substantially react with the cationic component. However, a good solvent for the cationic component is desired. Usually, solvents used are ketones such as halogenated hydrocarbons such as methylene chloride, dichloroethane and trichloroethylene, acetone, methyl ethyl ketone, cyclohexanone and diisopropyl ketone, tetrahydrofuran, dioxane, methyl cellosolve and the like. Ethers, aromatic compounds such as benzene, toluene, chlorobenzene, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, 1 And aprotic polar solvents such as 3-dimethyl-2-imidazolidinone.

The use ratio of the bismaleimide compound and the diamine compound is 0.1 to 1.2 moles, preferably 0.2 to 0.8 moles of the diamine compound, with respect to 1 mole of the bismaleimide compound. In this case, it is not preferable to obtain a product having good impact resistance and flexibility, and on the contrary, too much has an adverse effect on the heat resistance of the cured product.

The following components can be added to the thermosetting resin composition of this invention as needed in the range which does not impair the objective of this invention.

(A) Curing accelerators such as azo compounds, radical polymerization initiators of organic peroxides, tertiary amines, quaternary ammonium salts, imidazoles, boron trifluoride, amine salts and the like.

(B) powder reinforcing agents or fillers, for example, metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, basic magnesium silicate, calcined clay, Fine powder silica, molten silica, crystalline silica, carbon black, kaolin, fine powder mica, quartz powder graphite, asbestos, molybdenum sulfide, antimony trioxide and the like.

Further, fibrous reinforcing agents and fillers such as glass fibers and green mineral fibers such as ceramic fibers, alumina fibers and potassium titanate fibers and organic fibers such as carbon fibers and aromatic polyamides.

(C) Various synthetic resins may be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, resin molded article and the like. For example, thermosetting resins such as phenol resins, epoxy resins, melamine resins, silicone resins, polyamides, polycarbonates, polysulfones, polyethersulfones, polyetherethercatones, modified polyphenylene oxides, and polyphenylene salts , Polyetherimide, fluororesin and the like.

The thermosetting resin composition of this invention is shape | molded by well-known shaping | molding methods, such as a compression molding method, the transfer molding method, the extrusion molding method, and the injection molding method, and it is provided at room temperature.

The following describes the method of the present invention in detail by way of examples, but the present invention is by no means limited thereto. First, the synthesis example of the diamine compound represented by Formula (1) used in the present invention is as follows.

Synthesis Example A1

1410 g, 1,4-bis (4-hydroxy-α, N, N-dimethylformamide, which was subjected to water removal treatment in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a Dane stark water separator, and a nitrogen introduction tube. 207.6 g (0.6 mol) of α-dimethylbenzyl) benzene, 193.7 g (1.23 mol) of 4-chloronitrobenzene, and 248.8 g (1.8 mol) of potassium carbonate are charged, and 50 g of toluene is added.

Subsequently, this mixed liquid was heated and stirring was continued for 5 hours, maintaining the temperature of 140-150 degreeC.

Water produced by the reaction was sequentially removed by azeotroping with toluene.

After completion of the reaction, thermal filtration was performed to remove the inorganic salts, and then the liquid was heated again, and 210 g of water was added dropwise over 2 hours while maintaining the temperature at 90 to 95 ° C, and 1,4-bis [4- (4-nitrophenoxy) -α, α-dimethylbenzyl] benzene was crystallized. After slowly cooling the solution, the pale yellow crystals were filtered off, washed with a mixed solvent of N, N-dimethylformamide and methanol, and then 1 The slurry was washed with methanol, filtered and dried to obtain 335 g of pale yellow powder.

The purity by high performance liquid chromatography was 99.3%.

Melting Point 186.5 ~ 188.5 ℃

Elemental analysis

Calculated value (%); C: 73.47, H: 5.44, N: 4.76

Analysis value (%); C: 73.28, H; 5.56, N: 4.96

IR (KBr Purification Method)

1330, 1500cm ^-1 (Nitro)

1240cm ^-1 (ether bond)

294 g (0.5 mol) of 1, 4-bis [4- (4-nitrophenoxy) -α, α-dimethylbenzyl] benzene obtained above, 1175 g of dimethylformamide, and 17.5 g of 5% Pd / C catalyst were stirred, A closed reduction with a thermometer was inserted into the reactor and hydrogen gas was introduced with vigorous stirring.

The reaction was continued for 4 hours at a reaction temperature of 30 to 40 캜. 67.2 Hydrogen was absorbed and the reaction was terminated because no further absorption was recognized.

After completion of the reaction, filtration was carried out at room temperature, and the Pd / C catalyst was filtered off.

The obtained reaction solution was heated to 80-90 ° C., and 500 g of water was added dropwise over 2.5 hours while maintaining the same temperature, to thereby obtain 1, 4-bis [4- (4-aminophenoxy) -α and α-dimethylbenzyl. ] Benzene was crystallized. After slowly cooling the reaction solution, the obtained white crystals were filtered off, washed with a mixed solution of N, N-dimethylformamide and methanol, and then washed with methanol to dry 242.9 g of 1,4-bis [4-. The purity of (4-aminophenoxy) -α and α-dimethylbenzyl] benzene by high performance liquid chromatography was 99.2% (88.3% in total yield), and the analysis results are shown below.

Melting Point 189-190.5 ℃

Elemental analysis

Calculated value (%); C: 81.82, H: 6.82, N: 5.30

Analysis value (%); C: 81.90, H; 6.75, N: 5.21

IR (KBr Purification Method)

1620, 3320cm ^-1 (amino group)

1230cm ^-1 (ether bond)

Synthesis Example A2

N, N-dimethylformamide 600 g, 1, 3-bis (4-hydroxy) -α, which was subjected to water removal treatment in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a drain and stark water separator, and a nitrogen introduction tube. 207.6 g (0.6 mol) of α-dimethylbenzyl) benzene, 193.7 g (1.23 mol) of 4-chloronitrobenzene, and 248.8 g (1.8 mol) of potassium carbonate were charged and 50 g of toluene was added.

Subsequently, this mixed liquid was heated and stirring was continued for 5 hours, maintaining the temperature of 140-150 degreeC. The water produced by the reaction was sequentially removed by azeotroping with toluene.

After completion of the reaction, thermal filtration was performed to remove the inorganic salts, and then the solution was heated again and 260 g of water was added dropwise over 2 hours while maintaining the temperature at 90-95 ° C. 1, 3-bis [4- (4-nitrophenoxy) -α, α-dimentylbenzyl] benzene was crystallized. After slowly cooling the solution, the pale yellow crystals were filtered off and washed with a mixed solvent of N, N-dimethylformamide and methanol, followed by 1 The slurry was washed with methanol, filtered and dried to obtain 328 g of a pale yellow powder.

Purity by high performance liquid chromatography was 99.1%.

Expression results are shown below.

Melting Point 154.5 ~ 156.0 ℃

Elemental analysis

Calculated value (%); C: 73.47, H: 5.44, N: 4.76

Analysis value (%); C: 73.34, H: 5.20, N: 4.79

IR (KBr Purification Method)

1330, 1490cm ^-1 (Nitro)

1230cm ^-1 (ether bond)

294 g (0.5 mol) of 1, 3-bis [4- (4-nitrophenoxy) -α, α-dimethylbenzyl] benzene obtained above were inserted into a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler and a dropping funnel. And it mixed with 1500 g of methyl cellosolves, 29.4 g of activated carbon, ferric chloride, and 2.9 g of hexahydrates, stirring was continued for 3 hours, maintaining 100-105 degreeC.

Subsequently, 150.2 g of 80% hydrazine monohydrate was added dropwise over 3 hours while maintaining the same temperature.

Furthermore, after 1 hour of actuation at the same temperature, the solids were removed by thermal filtration, and the liquid was concentrated and recrystallized with isopropyl alcohol. The target product was 1, 3-bis [4- (4- White crystals of aminophenoxy) -α and α-dimethylbenzyl) benzene were obtained.

The white crystals were filtered off, washed with isopropyl alcohol, and dried to obtain 228.5 g of 1, 3-bis [4- (4-aminophenoxy) -α and α-dimethylbenzyl] benzene.

The purity by high performance liquid chromatography was 99.0% (81.4% in total yield).

The analysis results are shown below.

Melting Point 103 ~ 105.5 ℃

Elemental analysis

Calculated value (%); C: 81.82, H: 6.82, N: 5.30

Analysis value (%); C: 81.86, H: 6.46, N: 5.22

IR (KBr Purification Method)

1620, 2340 ~ 3440cm ^-1 (amino group)

1240cm ^-1 (ether bond)

Synthesis Example A3

400 g, 1, 4-bis (4-hydroxy-3.5-dimethyl) N, N-dimethylformamide subjected to water removal treatment in a reaction vessel equipped with a stirrer, a reflux cooler, a thermometer, a drain and stark water separator, and a nitrogen inlet tube. Charge 161.0 g (0.4 mol) of -α, alpha -dimethylbenzyl) benzene, 138.7 g (0.88 mol) of 4-chloronitrobenzene, and 66.3 g (0.48 mol) of potassium carbonate, and add 50 g of toluene.

Subsequently, stirring was continued for 5 hours, heating this liquid mixture and keeping it at the temperature of 140-150 degreeC.

Water produced by the reaction was sequentially removed by azeotroping with toluene.

After completion of the reaction, thermal filtration was performed to remove the inorganic salts, and then the liquid was cooled to crystallize 1,4-bis [4- (4-nitrophenoxy) -3.5-dimethyl-α and α-dimethylbenzyl) benzene. I was.

The pale yellow crystals were filtered off, washed with 500 ml of methanol and dried to obtain 245 g of pale yellow powder.

Purity by high performance liquid chromatography was 99.5%.

The analysis results are shown below.

Melting Point 224 ~ 226 ℃

Elemental analysis

Calculated value (%); C: 74.51, H: 6.25, N: 4.34

Analysis value (%); C: 73.94, H; 5.92, N: 4.54

IR (KBr Purification Method)

1345, 1515cm ^-1 (Nitro)

1250cm ^-1 (ether bond)

129.0 g (0.2 mol) of 1, 4-bis [4- (4-nitrophenoxy) -3, 5-dimethyl-α, α-dimethylbenzyl] benzene obtained above, 322 g of N, N-dimethylformamide, 2.6 g of 5% Pd / C catalyst was charged to a closed reduction reactor equipped with a stirrer and a thermometer, and hydrogen gas was introduced with vigorous stirring.

The reaction was continued for 4 hours at a reaction temperature of 30 to 40 캜. 26.9 Of hydrogen was absorbed and the reaction was terminated because no further absorption was recognized.

After completion of the reaction, filtration was carried out at room temperature, and the Pd / C catalyst was filtered off.

The obtained reaction solution was heated to 80-90 ° C., and 80 g of water was added dropwise over 2 hours while maintaining the same temperature. Then, 1, 4-bis [4- (4-aminophenoxy) -3.5-dimethyl-α, α-dimethylbenzyl) benzene was crystallized.

After slowly cooling the reaction solution, the obtained pale yellow crystals were filtered off, washed with 200 ml of methanol, dried and then 104.7 g of 1, 4-bis [4- (4-aminophenoxy) -3.5-dimethyl-α, α-dimethylbenzyl] benzene was obtained.

Purity by high performance liquid chromatography was 99.2% (85.0% yield)

The analysis results are shown below.

Melting Point 228 ~ 230 ℃

Elemental analysis

Calculated value (%); C: 82.15, H: 7.58, N: 4.79

Analytical Value (%): C: 82.09, H: 7.13. N: 4.84

IR (KBr Purification Method)

1630, 3320-3430 cm ^-1 (amino group)

1240cm ^-1 (ether bond)

Synthesis Example A4

N, N-dimethylformamide 400 g, 1, 4-bis (4-hydroxy-α, α) subjected to water removal treatment in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a drain and stark water separator, and a nitrogen inlet tube. Charge 138.6 g (0.4 mol) of dimethylbenzyl) benzene, 147.8 g (0,88 mol) of m-dinitrobenzene, 66.3 g (0.48 mol) of potassium carbonate and add 50 g of toluene.

Subsequently, this mixed liquid was heated and stirring was continued for 5 hours, maintaining at the temperature of 140-1500 degreeC. The water produced by the reaction was sequentially removed by azeotroping with toluene.

After the completion of the reaction, the mixture was filtered, the inorganic salts were removed, the filtrate was heated again, and 112 g of water was added dropwise over 2 hours while maintaining the temperature at 90 to 95 ° C, and 1,4-bis [4- (3 -Nitrophenoxy) -α, α-dimethylbenzyl) benzene was crystallized. After slowly cooling the solution, the slightly brown crystals were filtered off, and 500 ml of methanol was washed and dried to obtain 220 g of slightly brown powder.

Purity by high performance liquid chromatography was 99.3%.

The analysis results are shown below.

Melting point 123-125 ℃

Elemental analysis

Calculated value (%); C: 73.45, H: 5.48, N: 4.76

Analysis value (%); C: 73.53, H: 5.39, N: 4.74

IR (KBr Purification Method)

1355, 1525cm ^-1 (Nitro)

1240cm ^-1 (ether bond)

118 g (0.2 mol) of 1, 4-bis [4- (3-nitrophenoxy) -α, α-dimethylbenzyl] benzene obtained above, 295 g of N, N-dimethylformamide, 5% Pd / C catalyst, 2.4 g was charged into a closed reduction reactor equipped with a stirrer and a thermometer, and hydrogen gas was introduced with vigorous stirring.

The reaction was continued at a reaction temperature of 30 to 40 ° C. for 4 hours. 26.9 Hydrogen was absorbed and the reaction was terminated because no further absorption was recognized.

After completion of the reaction, filtration was carried out at room temperature, and the Pd / C catalyst was filtered off.

The obtained reaction solution was heated to 80-90 ° C. and maintained at the same temperature, and 126 g of water was added dropwise over 2 hours, thereby obtaining 1, 4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] Benzene was crystallized. After slowly cooling the reaction solution, the obtained pale yellow crystals were filtered off, washed with 200 ml of methanol, dried and 90.3 g of 1, 4-bis [4- (3-aminophenoxy) -α and α-dimethyl. Benzyl) benzene.

Purity by high performance liquid chromatography was 99.2% (80.0% in total yield)

The analysis results are shown below.

Melting Point 138 ~ 140 ℃

Elemental analysis

Calculated value (%); C: 81.79, H: 6.86, N: 5.30

Analysis value (%); C: 81.43, H: 6.79, N: 5.27

IR (KBr Purification Method)

1630, 3320-3430 cm ^-1 (amino group)

1240cm ^-1 (ether bond)

Synthesis Example A5

N, N-dimethylformamide 400 g, 1, 3-bis (4-hydroxy-α, α Charge 138.6 g (0.4 mol) of dimethylbenzyl] benzene, 147.8 g (0.88 mol) of m-dinitrobenzene, and 66.3 g (0.48 mol) of potassium carbonate, and add 50 g of toluene.

Subsequently, this mixed liquid was heated and stirring was continued for 5 hours, maintaining at the temperature of 140-1500 degreeC. Water produced by the reaction was sequentially removed by azeotroping with toluene.

After completion of the reaction, the mixture was filtered, and after removing the inorganic salt, the liquid was heated again, and 112 g of water was added dropwise over 2 hours while maintaining the temperature of 90 to 95 ° C, and 1, 3-bis [4- ( 3-nitrophenoxy) -α, α-dimethylbenzyl] benzene was crystallized. After cooling the solution slowly, the slightly brown crystals were filtered off, washed with 200 ml of methane, and dried to obtain 215 g of a slightly brown powder.

Purity by high performance liquid chromatography was 99.1%.

The analysis results are shown below.

Melting point 84 ~ 86 ℃

Elemental analysis

Calculated value (%); C: 73.45, H: 5.48, N: 4.76

Analysis value (%); C: 73.70, H; 5.40, N: 4.46

IR (KBr Purification Method)

1330, 2510cm ^-1 (Nitro)

1245cm ^-1 (ether bond)

1, 3-bis [4- (3-nitrophenoxy) -α, α-dimethylbenzyl) benzene obtained above, 118 g (0.2 mol), N, N-dimethylformamide 295 g, 5% Pd / C catalyst 2.4 g was charged into a closed reduction reactor equipped with a stirrer and a thermometer, and hydrogen gas was introduced with vigorous stirring.

The reaction was continued for 5 hours at a reaction temperature of 30 to 40 캜. 26.9 Hydrogen was absorbed and the reaction was terminated because no further absorption was recognized. After completion of the reaction, filtration was carried out at room temperature, and the Pd / C catalyst was filtered off.

The obtained reaction solution was heated to 80-90 ° C., and 126 g of water was added dropwise over 2 hours while maintaining the same temperature. 1,3-bis [4- (3-aminophenoxy) -α, α-dimethyl Benzyl] benzene was crystallized. After the reaction solution was slowly cooled, the obtained pale yellow crystals were filtered off, recrystallized from methanol, and dried to give 86,6 g of 1, 3-bis [4- (3-aminophenoxy) -α and α-dimethylbenzyl. ] Benzene was obtained.

Purity by high performance liquid chromatography was 99.0% (gross yield 75.0%)

The analysis results are shown below.

Melting Point 96 ~ 96 ℃

Elemental analysis

Calculated value (%); C: 81.82, H: 6.82, N: 5.30

Analysis value (%); C: 81.35, H: 6-96, N: 5.44

IR (KBr Purification Method)

1625, 3340-3440cm ^-1 (amino group)

1235cm ^-1 (ether bond)

In addition, the synthesis example of the bismaleimide compound represented by said Formula (IV) used for this invention is as follows.

Synthesis Example B1

Into a reactor equipped with a stirrer, a thermometer, a reflux condenser with a water separator, and a dropping funnel, 26.5 g (0.27 mol) of maleic anhydride, 1.6 g of P-toluenesulfonic acid, and 150 ml of toluene were charged and heated to maintain a reflux state of toluene. To this was first added a solution in which 52.8 g (0.1 mol) of 1, 3-bis [4- (4-aminophenoxy) -α, α-diethylbenzyl] benzene prepared according to Synthesis Example A2 was dissolved in 100 ml of toluene. It was dripped from the funnel. The whole quantity was dripped over 7 hours, and it fully aged 2 hours after completion | finish of dripping. From the start of dropping to the end of aging, the water produced by the reaction was held by a water separator equipped with a reflux condenser. After completion | finish of reaction, after cooling to 70 degreeC, 100 ml of warm water was added, and it stirred at the same temperature for 30 minutes. After standing still, the lower layer part (water layer) separated into two layers was wiped off, and 100 ml of warm water was added again, and it wash | cleaned and liquid-separated similarly.

The toluene solution of the upper layer was finally concentrated in a vacuum at a temperature not exceeding 130 ° C. to give a reddish brown transparent resin-like crude 1, 3-bis [4- (4-maleimidephenoxy) -α, 68 g of alpha -dimethylbenzyl] benzene was obtained. The yield was quantitative and the purity by HLC was 91%.

This was purified by recrystallization to obtain a pure yellow powdery product.

Melting Point 172 ~ 175 ℃

Elemental Analysis Value (C ₄₄ H ₃₆ N ₂ O ₆ )

Calculated value (%); C: 76.70, H: 5.27, N: 4.07

Measured value (%); C: 76.20, H; 5.43, N: 4.22

In addition, the mass spectrum is shown in FIG. 1, and the IR spectrum is shown in FIG.

Synthesis Example B2

Into a reactor similar to Synthesis Example B1, 26.5 g (0.27 mol) of maleic anhydride, 0.7 g of phosphoric acid, and 150 ml of mixed xylene were charged, and 1, 4-bis [4- first prepared according to Synthesis Example A1 under reflux of xylene. A solution in which 52.8 g (0.1 mol) of (4-aminophenoxy) -α and α-dimethylbenzyl] benzene were dissolved by heating and dissolving 100 ml of mixed xylene and 50 ml of N and N-dimethylformamide was added dropwise. The reaction was terminated by dropping time 5 hours and ripening time 2 hours. The reaction solution was concentrated to about 1/2 the amount, and 50 g of water was added at the time of cooling to 80 ° C. Then, crystallization precipitated when it cooled slowly with stirring. After cooling to room temperature and filtration and washing with cold methanol, 66.5 g of crude 1, 4-bis [4- (4-maleimidephenoxy) -α and α-dimethylbenzyl) benzene as the desired product were obtained. The yield was 96.7%, the purity by HLC was 97.5%.

This was refine | purified by recrystallization with toluene, and the pure yellow powdery pure product was obtained.

Melting Point 214 ~ 216 ℃

Elemental Analysis Value (C ₄₄ H ₃₆ N ₂ O ₆ )

Calculated value (%); C: 76.70, H: 5.27, N: 4.07

Measured value (%); C: 76.02, H: 5.51, N: 4.18

The mass spectrum was similar to the compound of Synthesis Example B1 (M / Z; M ⁺ 688, 673, 408).

Experimental Example 1

The result which presumed the solubility to the solvent of the bismaleimide obtained by the synthesis examples B1 and B2 is shown in a table | surface.

TABLE 1

Solvent Solubility of Bismaleimide Compound (g / 100ml)

*) 25 ℃ measurement

Synthesis Example B3

Into a reactor equipped with a stirrer, a thermometer, a reflux condenser with a water separator, and a dropping funnel, 26.5 g (0.27 mol) of maleic anhydride, 1.6 g of P-toluenesulfonic acid, and 150 ml of toluene were charged and heated to maintain a reflux state of toluene. First, 58.8 g (0.1 mol) of 1,4-bis [4- (4-aminophenoxy) -3, 5-dimethyl-α, α-dimethylbenzyl] benzene prepared according to Synthesis Example A3 was first added to 100 ml of toluene. The dissolved solution was added dropwise from the dropping funnel.

The whole quantity was dripped over 7 hours, and after completion | finish of dripping, it aged for 2 hours again. During the dropping from the start of dropping to the end of aging, the water produced by the reaction was collected by a water separator equipped with a reflux condenser. After completion | finish of reaction, after cooling to 70 degreeC, 100 ml of warm water was added, and it stirred at the same temperature for 30 minutes. After leaving still, the lower part (water layer) separated into two layers was wiped off, and 100 ml of warm water was added again, and washing and liquid separation were performed similarly.

When the upper toluene solution was cooled, a pale yellow precipitate was precipitated. This was crude 1, 4-bis [4- (4-maleimidephenoxy) -3, 5-dimethyl- alpha, alpha -dimethylbenzyl] benzene, and filtered and dried to obtain 65.2 g.

The yield was 87.5%, the purity by HLC was 96.4%.

This was purified by recrystallization to obtain a pure yellow powdery product.

Melting Point 232.5 ~ 235 ℃

Elemental Analysis Value (C ₄₈ H ₄₄ N ₂ O ₆ )

Calculated value (%); C: 77.38, H: 5.96, N: 3.76

Measured value (%); C: 77.05, H: 6.08, N: 3.66

In addition, the IR spectrum is shown in FIG.

Synthesis Example B4

Into a reactor equipped with a stirrer, a thermometer, a reflux condenser with a water separator, and a dropping funnel, 26.5 g (0.27 mol) of maleic anhydride, 1.6 g of P-toluenesulfonic acid, and 150 ml of toluene were charged and heated to maintain a reflux state of toluene. First, a solution in which 52.8 g (0.1 mol) of 1, 3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene prepared according to Synthesis Example A5 was dissolved in 150 ml of toluene was added dropwise It was dripped from. The whole quantity was dripped over 7 hours, and it fully aged 2 hours after completion | finish of dripping. From the start of dropping to the end of aging, the water purified by the reaction was collected by a water separator hooked to the reflux condenser. After completion | finish of reaction, after cooling to 70 degreeC, 100 ml of warm water was added, and it stirred at the same temperature for 30 minutes. After standing, the lower part (water layer) separated into two layers was wiped off, and 100 ml of warm water was added again, and the same washing | cleaning and liquid separation were performed.

The toluene solution of the upper layer was finally concentrated in vacuo at a temperature not exceeding 130 ° C. to give a reddish-brown transparent resin-like crude 1, 3-bis [4- (3-maleimidephenoxy) -α as a target product. , 68.2 g of α-dimethylbenzyl) benzene was obtained.

The yield was quantitative and the purity by HLC was 96.3%.

This was purified by column chromatography to obtain a pure yellow resin product.

Elemental Analysis Value (C ₄₄ H ₃₆ N ₂ O ₆ )

Toluene ＞ 50 8 <1

Tetrahydrofuran> 50 12 6

Methylene Chloride ＞ 50 15 8

───────────────────────────────────

*) 25 ℃ measurement

Synthesis Example B3

Into a reactor equipped with a stirrer, a thermometer, a reflux condenser with a water separator, and a dropping funnel, 26.5 g (0.27 mol) of maleic anhydride, 1.6 g of P-toluenesulfonic acid, and 150 ml of toluene were charged and heated to maintain a reflux state of toluene. First, 58.8 g (0.1 mol) of 1,4-bis [4- (4-aminophenoxy) -3, 5-dimethyl-α, α-dimethylbenzyl] benzene prepared according to Synthesis Example A3 was first added to 100 ml of toluene. The dissolved solution was added dropwise from the dropping funnel.

The whole quantity was dripped over 7 hours, and after completion | finish of dripping, it aged for 2 hours again. During the dropping from the start of dropping to the end of aging, the water produced by the reaction was collected by a water separator equipped with a reflux condenser. After completion | finish of reaction, after cooling to 70 degreeC, 100 ml of warm water was added, and it stirred at the same temperature for 30 minutes. After leaving still, the lower part (water layer) separated into two layers was wiped off, and 100 ml of warm water was added again, and washing and liquid separation were performed similarly.

When the upper toluene solution was cooled, a pale yellow precipitate was precipitated. This was crude 1, 4-bis [4- (4-maleimidephenoxy) -3, 5-dimethyl- alpha, alpha -dimethylbenzyl] benzene, and filtered and dried to obtain 65.2 g.

The yield was 87.5%, the purity by HLC was 96.4%.

This was purified by recrystallization to obtain a pure yellow powdery product.

Melting Point 232.5 ~ 235 ℃

Elemental Analysis Value (C ₄₈ H ₄₄ N ₂ O ₆ )

Calculated value (%); C: 77.38, H: 5.96, N: 3.76

Measured value (%); C: 77.05, H: 6.08, N: 3.66

In addition, the IR spectrum is shown in FIG.

Synthesis Example B4

Into a reactor equipped with a stirrer, a thermometer, a reflux condenser with a water separator, and a dropping funnel, 26.5 g (0.27 mol) of maleic anhydride, 1.6 g of P-toluenesulfonic acid, and 150 ml of toluene were charged and heated to maintain a reflux state of toluene. First, a solution in which 52.8 g (0.1 mol) of 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene prepared according to Synthesis Example A5 was dissolved in 150 ml of toluene was added dropwise to the funnel. It was dripped from. The whole quantity was dripped over 7 hours, and it fully aged 2 hours after completion | finish of dripping. From the start of dropping to the end of aging, the water purified by the reaction was collected by a water separator hooked to the reflux condenser. After completion | finish of reaction, after cooling to 70 degreeC, 100 ml of warm water was added, and it stirred at the same temperature for 30 minutes. After standing, the lower part (water layer) separated into two layers was wiped off, and 100 ml of warm water was added again, and the same washing | cleaning and liquid separation were performed.

The toluene solution of this conflict is finally concentrated in vacuo at a temperature not exceeding 130 ° C. to give a reddish-brown transparent resin-like crude 1, 3-bis [4- (3-maleimidephenoxy) -α as a target product. , 68.2 g of α-dimethylbenzyl) benzene was obtained.

The yield was quantitative and the temperature by HLC was 96.3%.

This was purified by column chromatography to obtain a pure yellow resin product.

Elemental Analysis Value (C ₄₄ H ₃₆ N ₂ O ₆ )

Calculated value (%); C: 76.70, H: 5.27, N: 4.07

Measured value (%); C: 76.41, H; 5.44, N: 4.01

Mass Spectrum

M / Z; M ⁺ 688,673,408

IR spectrum is also shown in FIG.

Synthesis Example B5

Into a reactor similar to Synthesis Example B4, 26.5 g (0.27 mol) of maleic anhydride, 0.7 g of phosphoric acid, and 150 ml of mixed xylene were charged, and 1, 4-bis [4 prepared according to A ₄ for synthesis first under reflux of xylene. 52.8 g (0.1 mol) of-(3-aminophenoxy) -α-α-dimethylbenzyl) benzene was dissolved in 100 ml of mixed xylene and 50 ml of N and N-dimethylformamide. The reaction was completed by dropping time 5 hours and ripening time 2 hours. The reaction solution was concentrated to about 1/2 the amount, and then 50 g was added at the time of cooling to 80 ° C. Then, crystallization precipitated when it cooled slowly with stirring. 67.1 g of crude 1, 4-bis [4- (3-maleimidephenoxy)-[alpha], [alpha] -dimethylbenzyl] benzene as the desired product was obtained by cooling to room temperature and filtration and washing with cold ethanol.

The yield was 94.8% and the purity by MLC was 92.0%.

This was refine | purified by recrystallization with toluene, and the pure yellow powdery pure product was obtained.

Melting Point 192 ~ 193 ℃

Elemental Analysis Value (C ₄₄ H ₃₆ N ₂ O ₆ )

Calculated value (%); C: 76.70, H: 5.27, N: 4.07

Measured value (%); C: 76.66, H: 5.33, N: 4.18

The result of the mass spectrum was the same as that of the compound of Synthesis Example B4.

(M / Z; M ⁺ 88,673,408)

[Examples C1 to C3 Comparative Examples C1 and C2]

Synthesis Example with 1, 3-bis [4- (4-maleimidephenoxy) -α, α-dimethylbenzyl] -benzene obtained in B1 for synthesis in a stainless reactor equipped with a stirrer, a reflux condenser and a nitrogen introduction tube 1, 3-bis [4- (4-aminophenoxy) -α and α-dimethylbenzyl) benzene prepared according to A2 were charged at the molar ratios shown in Table 2, respectively, and were heated and melted at 180 ° C. for 20 minutes. Furthermore, after degassing for 30 minutes at 150 degreeC under reduced pressure (10-15 mmHg), it cooled to room temperature and obtained the resin composition which solidified to the brown transparent glass form. The resin composition was filled into a mold heated to 180 ° C. while being heated and melted, and then held at 50 kg / cm ² and 200 ° C. for 30 minutes, and compression molded to take out the molded product, and the postcure was performed for 4 hours in an oven at 250 ° C. Thus, a test piece (127 mm long, 12.7 mm wide, and 6.4 mm thick) of the cured product was obtained.

The bending strength, the bending elastic modulus, the thermal decomposition initiation temperature and the moisture absorption of the test piece were measured, and the results are shown in Table 2.

Comparative Example C3

N, N ', 4, 4'-diphenylmethanebismaleimide and 4, 4'-diaminodiphenylmethane were used in the compositions (molar ratio 2/1) shown in Table 2, respectively, Examples C1 to C3 below The same operation as described above was performed to obtain the results shown in Table 2.

[Comparative Example C4]

Using Catimide-601 (manufactured by Nippon Polyimide Co., Ltd.) as a resin composition, the same operations as in Examples C1 to C3 were performed to obtain the results in Table 2.

[Examples C4 to C7]

Table 2 shows a bismaleimide compound prepared according to Synthesis Examples B1, B4, B3 and B5 and a diamine compound prepared according to Synthesis Examples A1, A3 and A2 in a stainless container equipped with a stirrer, a reflux cooler and a nitrogen introduction tube. Charged at the molar ratio indicated in 3, N-methyl-2pyrrolidone in an amount such that the resin concentration was 55% by weight was injected, and heated at 150 ° C for 50 minutes. The varnish solution obtained was discharged in water, and the precipitate was filtered off, washed with water and dried with hot air at 80 ° C. for 15 hours. After drying at 110 degreeC for 20 minutes and 130 degreeC for 30 minutes, it grind | pulverized in the mortar and the polyamino bismaleimide type thermosetting resin composition was obtained through 60 sieves. The results in Table 3 were obtained in the same manner as in Examples C1 to C3 below.

In addition, in these examples, physical properties, such as a thermosetting resin, were measured by the following method.

Flexural strength, flexural modulus: in accordance with ASTM-D-790

Pyrolysis start temperature: Measure the onset temperature of weight loss at the air speed and the temperature increase rate of 10 ℃ / min by TAG method.

Izod impact value: According to ASTM-D256.

Water absorption rate: According to ASTM D-570-63.

TABLE 2

TABLE 3

Claims (4)

Equation I Where R is H or CH ₃ Aromatic diamine compound represented by. Equation IV A thermosetting resin composition comprising a bismaleimide compound represented by (where R means H or CH ₃ ), wherein the aromatic diamine compound is in a ratio of 0.1 to 1.2 moles with respect to 1 mole of the bismaleimide compound. A curing accelerator according to claim 1; Reinforcing agent; A thermosetting resin composition comprising an additive selected from the group consisting of fillers and synthetic resins. After mixing the bismaleimide compound represented by the formula (IV) and the aromatic diamine compound represented by the formula (I) in the absence of a solvent or in the presence of an organic solvent, the prepolymer is heated at a temperature of 70 to 220 캜. A method for producing a thermosetting resin composition according to claim 1, wherein the resin is cured. The organic solvent of claim 3, wherein the organic solvent is halogenated hydrocarbon; Caron; Ether; Aromatic compounds; And an aprotic solvent.