JPS6217608B2 - - Google Patents

Description

Detailed Description of the Invention The present invention relates to a method for producing heat-resistant polymers, and its purpose is to produce films, electrical insulating materials, paints, semiconductor element protective films, alignment films for liquid crystal displays, solvent solute separation films, and various moldings. Our objective is to provide polymers that are useful as materials.

The feature of the present invention is that the aromatic nucleus has two amino groups and one alkoxycarbonylamino group (-NHCOOR, R is a monovalent organic group such as an alkyl group or an allyl group). and 95 to 5 mol% of a diaminoalkoxycarbonylamino compound in which one amino group and an alkoxycarbonylamino group are bonded to adjacent carbon atoms of an aromatic nucleus, 5 to 95 mol% of a diamine, and a dicarboxylic acid halide. The purpose is to carry out the reaction in an inert solvent and then perform a heat treatment to close the ring.

The above reaction can be expressed as a general formula as follows.

Here, Ar is a residue of a diaminomonoalkoxycarbonylamino compound, R is a monovalent organic group such as an alkyl group or an allyl group, R ₁ is a residue of a diamine, R ₂ is a residue of a dicarboxylic acid halide,
indicates a halogen atom. n represents a positive number.

The diaminomonoalkoxycarbonylamino compound used in the present invention has the following general formula: (In the formula, R represents a monovalent group such as an alkyl group or an allyl group, and Y represents O, CH ₂ , SO ₂ , S, CO, etc.) Furthermore, one amino group bonded to the aromatic nucleus and An alkoxycarbonylamino group may be bonded at any position as long as it is bonded to an adjacent carbon atom.Also, the hydrogen atom of the aromatic nucleus may be bonded to other inert groups such as an alkyl group, an allyl group, or a halogen atom. 2,4-diaminophenyl urethane, 2,4-diamino-6-methylphenyl urethane, 2,4-diamino-5-methyl Phenyl urethane, 2,6-diamino-3-methylphenyl urethane, 2,4-diamino-3-methyl phenyl urethane, 2,6-diamino-4-methyl phenyl urethane, 2,4-diamino-1 -Naphthyl urethane, 1,6-diamino-2-naphthyl urethane, 4,4-diamino-3-ethoxycarbonylaminodiphenyl ether, 5-(m-aminophenoxy)-2-aminophenyl urethane, 4
-(p-aminophenyl)-2-aminophenyl urethane, etc.

Examples of diamines include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenymethane, 4,4'-diaminodiphenylpropane, 4,
4'-Aminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, metaphenylenediamine, paraphenylenediamine, 1,5-diaminonaphthalene, 2,6 -diaminonaphthalene, 4,4'-di(m-aminophenoxy)diphenylsulfone,
2,6-diaminopyridine, 4,4'-di(P-aminobenzoyl) diphenyl ether, 4,4'-
Examples include di(P-aminophenoxy)diphenylsulfone, 1,4-di(P-aminophenoxy)benzene, and 1,3-di(P-aminophenoxy)benzene.

Examples of dicarboxylic acid halides include isophthalic acid halides, terephthalic acid halides, phthalic acid halides, 4,4'-diphenyl ether dicarboxylic acid halides, and 4,4'-
diphenylsulfonedicarboxylic acid halide 2,6-naphthalenedicarboxylic acid halide,
oxalic acid halide, malonic acid halide,
Succinic acid halide, glutaric acid halide, adipic acid halide, pimelic acid halide, suberic acid halide, azelaic acid halide, sebacic acid halide, 1,10
-decanedicarboxylic acid halide, 1,3-cyclopentanedicarboxylic acid halide, 1,4
- Examples include cyclohexanedicarboxylic acid halide.

In the present invention, when reacting the compound with the above, an inert solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, hexamethylphosphoramide is used. , pyridine,
Triethyleneamine, N,N-dimethylaniline, quinoline, isoquinoline, N-ethylmorpholine, etc. are used.

Furthermore, the solubility of the polymer can be increased by adding lithium chloride, calcium chloride, magnesium chloride, lithium bromide, etc. to these solvents. Furthermore, it is advisable to add an epoxy compound in order to capture the generated hydrogen halide.

When x moles of the above-mentioned diaminomonoalkoxycarbonylamino compound, y moles of diamine, and z moles of dicarboxylic acid halide (x+y=z) are reacted in an inert solvent at room temperature or a temperature lower than that, the reaction proceeds rapidly. The viscosity of the system increases significantly and a polyamide urethane intermediate is obtained. The diaminomonoalkoxycarbonyl compound and the diamine are used in a ratio of 95 to 5 mol% of the former and 5 to 95 mol% of the latter. If the amount of the diaminomonoalkoxycarbonyl compound is more than 95 mol %, the flexibility will be decreased, and if it is less than 5 mol %, the heat resistance will be decreased.

Next, the obtained intermediate solution can be separated from the solvent by coating and drying to form a film or by precipitating it and turning it into a powder. The obtained polyamide urethane can be made into any form such as powder, film, or coating.
It is converted into polyamide imidazolinone by heat treatment at 250-350°C.

Next, examples will be shown and concretely explained.

Example 1 1.95 g of 2,4-diaminophenyl urethane, 2.00 g of 4,4'-diaminodiphenyl ether and N-methyl- Add 60 g of 2-pyrrolidone, cool the flask in an ice bath, and stir the contents to dissolve.

Next, 4.06 g of isophthalic acid chloride was gradually added, and the mixture was stirred at 10°C for 3 hours. The reaction product was poured into water, and the resulting precipitate was crushed, filtered, washed with water, and dried under reduced pressure at room temperature. The reduced viscosity ηsp/c of the produced polyamide urethane is 1.37 dl/g (solvent dimethylacetamide, concentration 0.1 g/100 c.c. solution, temperature 30°C,
(Measurement conditions are the same below). The solution was cast onto a glass plate to form a film and heated to 250-350°C to convert it into polyamideimidazolinone.
This film did not lose weight in air up to 370°C.

Example 2 In a flask similar to Example 1, 2.09 g of 2,4-diamino-6-methylphenyl urethane and 4,4'-
Add 1.98 g of diaminodiphenylmethane and 60 g of N-methyl-2-pyrrolidone, cool the flask with ice, and stir the contents. Next, 5.9 g of 4,4'-diphenyl ether dicarboxylic acid dichloride was gradually added, and after the addition was completed, the reaction was carried out at 10°C for 3 hours. Reduced viscosity η of the polyamide urethane produced
sp/c was 1.22 dl/g. A film was made from the resulting solution and heated to 250-320°C for ring closure.
This film did not lose weight in air up to 350°C.

Example 3 Into a flask similar to Example 1, 1.95 g of 2,4-diaminophenyl urethane, 4.32 g of 4,4'-di(m-aminophenoxy)diphenyl sulfone, and 60 g of N-methyl-2-pyrrolidone were placed. Stir the contents.

Next, 3.66 g of diapic acid chloride was gradually added, and after the addition was completed, the reaction was carried out at 10° C. for 3 hours. The reduced viscosity ηsp/c of the produced polyamide urethane is 0.87
It was dl/g. A film was made and heated at 250-300°C to close the ring. This film is 330 in the air
The weight did not decrease to ℃.

Claims (1)

[Claims] 1 The aromatic nucleus has two amino groups and one alkoxycarbonylamino group (-NHCOOR, R is a monovalent organic group such as an alkyl group or an allyl group), and one amino group and 95 to 5 mol% of a diaminomonoalkoxycarbonylamino compound in which an alkoxycarbonylamino group is bonded to an adjacent carbon atom of an aromatic nucleus, 5 to 95 mol% of a diamine, and a dicarboxylic acid halide are reacted in an inert solvent. , followed by ring closure by heat treatment.