JPS58154542A - Dimer of isopropenylphenyl maleamidic acid - Google Patents

Abstract

NEW MATERIAL:The dimer of isopropenylphenyl maleamide of formulaI(D is group of formula II or formula III). USE:Useful as an agricultural chemical, vulcanization accelerator, curing agent for thermosetting resin, paint, or adhesive. It can also be used as an intermediate of a maleimide compound useful as a raw material of a heat-resistant resin, by the dehydrative cyclization. PROCESS:The compound of formulaIcan be prepared by reacting the dimer of p-isopropenylaniline with maleic anhydride in the presence of a solvent (e.g. acetone) at 10-40 deg.C. The amount of the solvent is preferably 1.5-70pts.wt./1pt.wt. of the used primary amine, and that of the maleic anhydride is 1.0-2.0mol, preferably 1.05-1.2mol/1equiv. of the amino group of p-isopropenylaniline used as a starting material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diwarm body of isopropenylphenylmaleamic acid represented by formula (1) (wherein D is H3CH3).

The compound of the present invention is a new substance, which is a chemical agent, a vulcanization accelerator,
It is useful as a curing agent for thermosetting resins, paints, and adhesives, and since it has a carboxyl group and two or more double bonds in its molecule, it has extremely high utility value as a resin raw material that requires specific functions. It is something. A combination of these? ! Ij
Provides a resin with a high I'i melting point and excellent heat resistance,
The maleimide compound obtained by dehydrating these maleamic acid compounds is a raw material rich in layer functionality. In other words, resins containing maleimide compounds exhibit outstanding performance in electrical insulation, impact resistance, heat resistance, and dimensional stability of molded products, and are extremely widely used in industries such as electrical insulation materials, heat-resistant adhesives, and molding materials. It is something that is used.

For example, as an example of the heat resistance of the compound of the present invention, the thermal decomposition temperature (measured with a thermobalance) is as follows.

The compound of the present invention can be produced using various known methods for producing maleamic acid compounds, and specifically can be produced by the following method.

That is, p-isopropenyl aniline binomer is reacted with maleic anhydride in the presence of acetone at a temperature of 10 to 40°C.

This reaction proceeds in a temperature range of 0 to 120°C; it is preferably carried out under mild conditions in a temperature range of 10 to 40°C. Although the reaction time depends on the reaction temperature, it is usually 1
In a temperature range of 0 to 40°C, a time of 1 to 5 hours is sufficient. The solvent used in the reaction is often acetate, but in addition to this, chloroform, carbon tetrachloride, methyl ethyl ketone, tetrahydrofuran, formic acid, acetic acid, butyric acid, methyl acetate, ethyl acetate, methyl cellosolve, celonollev 0, ethenocyclohexane , cyclohexanone,
Dioxane, benzene, toluene, xylene, chlorobenzene, pyridine, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoramide, N-methylcaprolactam, methanol, ethanol, and propyl alcohol can be used. The amount of solvent used is preferably 15 to 70 times the weight of the primary amine used.

In addition, the amount of maleic anhydride used in the reaction is 10 to 20 mol, preferably 105 to 1 mol, per equivalent of the amino group of the starting material p-isopropenylaniline.
82 mol of maleic anhydride was used. The produced L&P-ingropenyl phenyl maleamide compound is precipitated as a precipitate, and the reaction solution becomes a slurry. This precipitate is filtered once, thoroughly washed with a solvent or water, and then dried.

The compound of the present invention can be obtained in high yield and in a sufficiently purified state under the above reaction conditions.

By dehydrating and cyclizing the compound of the present invention, it can also be used as an intermediate raw material for a maleimide compound, which has extremely high utility value as a raw material for a heat-resistant tape material. This maleimide compound is prepared by mixing the compound of the present invention with 1!1m acetic anhydride in an organic solvent in the presence of a catalyst such as sodium, nickel salt or cobalt salt, and a tertiary amine such as triethylamine, N,N-dimethylbenzylamine. , can be produced by applying a dehydrating agent such as butyric anhydride.

The present invention will be explained below with reference to Examples.

Example 1 Anhydrous maleic f118.69 was dissolved in 100xJ of acetone and 2,4-di(p-aminophenyl)-4-methyl-1-pentene IQ. 7f was gradually added dropwise. After the dropwise addition was completed, the mixture was stirred at a temperature of 20° C. for 2 hours. The reaction solution was a slurry with yellow precipitate. The precipitate was filtered, washed with acetone, and then dried.

The following bismaleamic acid was obtained in a yield of 98%. Based on infrared absorption spectra, nuclear magnetic resonance absorption spectra, and elemental analysis values, 2.4-bis(p-(2-
It was confirmed that it was carboxyvinylcarbonylamino)phenyl]-4-methyl-1-pentene.

Infrared absorption spectrum group Absorption position) C=0 1710cm-” ArNH1510~1580c〃+-1 Nuclear magnetic resonance absorption spectrum (D6-DMSO solvent) group
Attribution (δ value ppm) -CH21,15-0H2-2,78 =CH24,71,5,13 -CH=CH-6,26,6,51 (double line, J=12
c/5ec)-COOH10,45 Elemental analysis value (wt%) HN Calculated value 67.52 5,67 6.06 Theoretical value
67.40 5,79 5.92 Example 2 2,4-di(p-aminophenyl)- of the method of Example 1
2,4-di(p-
By the same method using (aminophenyl)-4-methyl-2-pe/tene, the following bismaleamic acid was obtained in 975% yield.

Based on the infrared absorption spectrum, nuclear magnetic resonance absorption spectrum, and elemental analysis values, 2゜4-bis[p
It was confirmed that it was -(2-carboxyvinylcarbonylamino)phenyl]4-methyl-2-pentene.

Infrared absorption spectrum group Absorption position) C=0 1705cm-1Al-Nl+-
1490-1580 cm-1 nuclear magnetic resonance spectrum (D
6-DMSO melting group belonging (δ value p
pm) -CH21,50 =CH-6,12 -CH=CH-6,25,6,55 (double line, J=1
2c/5ec)-coon 10.49 Elemental analysis value (wt%) CHN Calculated value 67.52 5,67 6.06 Analysis value
67.56 5,79 6.04 Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Scope of Claims] 1) A dimer of isopropenylphenylmaleamic acid represented by formula (1) (wherein D is indicated).