JP2566949B2 - Bismaleimide and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a bismaleimide compound useful as a monomer of a heat resistant polymer and a method for producing the same.

More specifically, the formula (I) And a bismaleimide represented by the formula (II): The present invention relates to a method for producing a diamine having an ether bond represented by and maleic anhydride.

(Prior Art) Conventionally, a resin having an imide structure has been widely used industrially because it exhibits excellent electrical insulation properties, heat resistance, and dimensional stability of molded products. For example, as the heat-resistant thermosetting resin used for the electric insulating material, a polyimide resin,
Polyamino bismaleimide resins and the like are known and widely used for impregnating varnishes, laminated plates, molded products and the like.

However, although these conventional resins are generally excellent in heat resistance, they have drawbacks in that molded products are brittle and are not practical for purposes as molding resins.

(Problems to be Solved by the Invention) An object of the present invention is to utilize the characteristics of a bismaleimide compound represented by N, N ′-(4,4′-methylenediphenylene) bismaleimide as a thermosetting resin. , And 4,4 ′
To provide a bismaleimide compound represented by the above formula (I), which is a raw material monomer of a resin having good heat resistance and flexibility in which a skeleton of -bis (4-aminophenoxy) benzophenone is incorporated into a maleimide structure. Is.

(Means for Solving Problems) The inventors of the present invention have earnestly studied to solve the problems of the present invention based on such an idea. As a result, the novel bismaleimide compound represented by the formula (I) has excellent heat resistance, and this compound is easily prepared by subjecting the diamine represented by (II) and maleic anhydride to condensation / dehydration reaction. The present invention has been completed and the present invention has been completed.

That is, the present invention provides the compound of formula (I) And 4,4'-bis (4-aminophenoxy) benzophenone represented by

This compound is a novel compound, and the 5% weight loss temperature is an example of a measure of the heat resistance of the compound, but in the case of the present compound (I), it is at a very high level of 460 ° C. in air.

The method for producing the compound of the present invention will be described.

The diamine used as a raw material is a compound represented by the formula (II). This diamine is 4,4'-bis (4-aminophenoxy) benzophenone. This diamine is, for example, the condensation of 4,4'-dichlorobenzophenone and p-aminophenol (Liebig's Analene.
Dare Chemie, Liebige Ann. Chem., 740,169 (197
According to (0)), it can be industrially advantageously produced with high purity and high yield.

The method for producing the compound of the present invention is not particularly limited, but usually, in the first step, diamino represented by the formula (II) and maleic anhydride are reacted in an organic solvent to give the compound represented by the formula (III) The bismaleamic acid represented by Known methods are applied for this purpose. Usually, reaction solvents used are halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane and trichloroethylene, ketones such as acetone, methyl ethyl ketone, cyclohexanone and diisopropyl ketone, ethers, ethers such as tetrahydrofuran, dioxane and β-oxyethyl methyl ether. , Aromatic compounds such as benzene, toluene, chlorobenzene, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidi An aprotic polar solvent such as non.

The amount of these solvents used is not particularly limited, but usually,
1 to 10 times the weight of the raw material is sufficient.

Next, in the second step, the bismaleamic acid is cyclized and dehydrated to produce the bismaleimide represented by the general formula (I). As this method, a known method in which acetic anhydride is used as a dehydrating agent and the reaction is carried out in an organic solvent in the presence of a base and a catalyst is used (Japanese Patent Publication Nos. 46-23250 and 49).
-40231, Japanese Patent Publication No. 59-52660).

At this time, the amount of acetic anhydride used is not particularly limited as to the upper limit, but it is usually in the range of 2 to 4 times the mol of bismaleamic acid.

The catalysts used are alkaline earth metal oxides, iron (II and III), nickel (II), manganese (II and III), copper (I and II) or cobalt (II and I).
II) carbonates, sulfates, phosphates, acetates, etc.
Particularly preferably, nickel (II) acetate, cobalt acetate (I
I), magnesium oxide. These catalysts alone exert a sufficient effect, but two or more kinds of them may be used in combination. The amount used is 5 × 10 ^-4 to bismaleamic acid
It is in the range of 0.1 mol.

The base used is an alkali metal acetate or a tertiary amine. Specific examples include sodium acetate, potassium acetate, trimethylamine, triethylamine and tributylamine. The amount used is in the range of 0.05 to 1.1 mol based on bismaleamic acid.

The embodiment of the method of the present invention is not particularly limited,
The intermediate bismaleamic acid produced in the step does not necessarily have to be isolated to produce the bismaleimide,
The second stage cyclization dehydration reaction can be carried out as it is in the same solvent. The reaction temperature is in the range of 20 to 80 ° C, and the reaction time is in the range of 0.5 to 9 hours.

After completion of the reaction, the precipitated crystals are filtered or discharged into water or methanol to obtain the desired crystals.

(Operation and Effect) The compound of the present invention is a compound useful as a polymaleimide resin and a polyamine-modified polymaleimide resin raw material having excellent heat resistance and flexibility.

Therefore, it has a wide range of applications as a material for resins that require unique functions, such as electrical and electronic insulating materials, heat resistant adhesives, and substrates for the aerospace industry.

(Examples) Hereinafter, the present invention will be described more specifically with reference to Examples.

Example 1 12.96 g (0.13 mol) of maleic anhydride and 39.0 g of acetone were charged into a reaction flask equipped with a stirrer and a thermometer and dissolved. A solution prepared by dissolving 23.79 g (0.06 mol) of 4,4'-bis (4-aminophenoxy) benzophenone in 11.90 g of acetone was added dropwise thereto at room temperature, and the mixture was further stirred at 23 to 27 ° C for 3 hours.

After the reaction was completed, the resulting crystals were filtered, washed with acetone and dried to obtain bismaleamic acid as pale yellow crystals.

Yield 35.0g (Yield 98.5%) mp.> 300 ℃ Elemental analysis (%) CHN Calculated 66.89 4.08 4.73 Analyzed 67.22 3.69 4.64 IR (KBr, cm ^-1 ): 3450 and 3280 (NH) 1730 (CO ₂ H group) 1640 (ketone) 1260 (ether bond) Bismaleamic acid thus obtained 11.85 (0.0
2 mol) in 35.5 g of acetone, and triethylamine
Add 0.96g and stir at room temperature for 30 minutes.

Magnesium oxide (II) 40 mg, cobalt acetate (II)
After adding 4 mg of 4H ₂ O, 5.2 g of acetic anhydride was added dropwise at 25 ° C. over 30 minutes, and the mixture was further stirred at room temperature for 2 hours. After the reaction was completed, the resulting crystals were filtered, washed and dried to obtain bismaleamide as pale yellow crystals.

Yield 8.4g (Yield 75.7%) mp. 175-177 ℃ Elemental analysis (%) CHN calculated value 71.72 3.60 5.03 Analytical value 70.69 3.34 4.97 IR (KBr, cm ^-1 ): 1785 and 1715 (imide bond) 1260 (Ether bond) 5% weight loss temperature (in air): 462 ° C Example 2 12.96 g (0.13 mol) of maleic anhydride and 39.0 g of acetone are charged and dissolved in a reaction flask equipped with a stirrer and a thermometer. A solution of 23.79 g (0.06 mol) of 4,4′-bis (4-aminophenoxy) benzophenone dissolved in 119.0 g of acetone was added dropwise at room temperature, and the mixture was further stirred at 23 to 27 ° C. for 3 hours to precipitate crystals. come.

To this, 2.88 g of triethylamine is added and stirred at room temperature for 30 minutes. After adding 120 mg of magnesium (II) oxide and 12 mg of cobalt (II) ・ 4H ₂ O, 15.6 g of acetic anhydride was added at 25 ° C.
The mixture is added dropwise over 30 minutes and further stirred at room temperature for 2 hours.

After the reaction was completed, the crystals formed were filtered, washed and dried to obtain bismaleimide as pale yellow crystals.

Yield 28.4g (Yield 85.2%) mp. 175-177 ℃

Claims (2)

(57) [Claims] 1. A formula (I) Bismaleimide represented by. 2. Formula (II) Represented by the formula (I), characterized by reacting a diamine having an ether bond with maleic anhydride. A method for producing a bismaleimide represented by: