JPS5818930B2 - Copolymer manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a copolymer with excellent heat resistance, and its purpose is to produce films, electrical insulating materials, adhesives, paints, semiconductor device stabilization materials, and alignment materials for liquid crystal displays. The purpose of the present invention is to provide polymers useful as membranes, solvent-solute separation membranes, and various molding materials.

The feature of the present invention is that the aromatic nucleus contains two amine groups and two alkoxycarbonylamino groups (-NHCOO
Aromatic diaminodialkoxycarbonylamino compounds 95 to 95, in which the amine group and the alkoxycarbonylamino group are bonded to adjacent carbon atoms of the aromatic nucleus. 5 mol%,
The method involves reacting 5 to 95 mol% of a diamine and a dicarboxylic acid halide in an inert solvent to obtain an intermediate, and then subjecting the intermediate to a heat treatment to cause ring closure.

Here, when the diaminodialkoxycarbonylamino compound is more than 95 mol%, the flexibility of the product decreases,
If it is less than 5 mol%, heat resistance will decrease.

It is preferable to react the dicarboxylic acid halide in an equivalent molar amount to the total mole of the aromatic diaminodialkoxycarbonylamino compound and the diamine, and the reaction proceeds quickly, the viscosity of the reaction system becomes significantly high, and an intermediate is obtained. .

The above-mentioned reaction can be expressed by the following general formula when the molar ratio of the diaminodialkoxycarbonylamino compound and the diaminedicarboxylic acid halokenide is 1:1:2.

Here, Ar is a residue of a diaminodialkoxycarbonylamino compound, R is an alkyl group, R1 is a diamine residue,
R2 is a dicarboxylic acid halide residue, X is a halogen atom, and n is a positive number.

The diaminodialkoxycarbonylamino compound used in the present invention has the following general formula (wherein, R is an alkyl group, Y is 0, S, SO□, CH
2. Indicates CO, etc.

Further, the amine group and the alkoxycarbonylamino group bonded to the aromatic nucleus may be substituted at any position as long as they are bonded to mutually adjacent carbon atoms.

Furthermore, the hydrogen atom bonded to the aromatic nucleus may be substituted with another inert group, such as an alkyl group, an allyl group, or a halogen.
'-Diamino-4,4'-jethoxycarbonylaminodiphenyl ether, 3,J-diamino-4,4'-diethoxycarbonylaminodiphenylmethane, 3,3'
-Diamino-4...4'-jethoxycarbonylaminodiphenyl, 3,3'-diamino-4,4'-jethoxycarbonylaminodiphenyl sulfone, 3,3'-diamino-4,4'-jethoxycarbonylamino Diphenylsulfide, 1,5-diamino-2,4-jethoxycarbonylaminobenzene, ■4-diamino-2,
Examples include 5-jethoxycarbonylaminobenzene.

Examples of diamines include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl ether.
4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone,
Metaphenylenecyamine, paraphenylenediamine,■
・5-diaminonaphthalene, 2,6-diaminonaphthalene, 4,4'-di(m-diaminophenoxy)diphenyl sulfone, 2,6-diamitupyridine, 4,47-di(p-aminobenzoyl)diphenyl ether, 4.4
'-di(p-aminophenoxy)diphenylsulfone,
■・4-di(p-aminophenoxy)benzene, 1.3
-di(p-aminophenoxy)benzene and the like.

Further, examples of dicarboxylic acid halides used in the present invention include isophthalic acid halides, terephthalic acid halides, phthalic acid halides, 4,4'-diphenyl ether dicarboxylic acid halides, and 4,4'-diphenylsulfonedicarboxylic acid halides. chemical compound, 2.6-
naphthalene dicarboxylic acid halide, oxalic acid halide, malonic acid halide, succinic acid halide, curtaric acid halide, adipic acid halide, pimelic acid halide, speric acid halide,
azelaic acid halide, sebacic acid halide,
■・10-decanedicarboxylic acid halide, 1・3-
Examples include cyclopentadicarboxylic acid halide and 1,4-cyclohexanedicarboxylic acid halide.

In the present invention, when reacting the above compounds, an inert solvent such as N-methyl-2-pyrrolidone, N-N-dimethylacetamide, N-N-dimethylformamide,
N-N-diethylformamide, hexamethylphosphoramide, pyridine, triethylamine, N-N-dimethylaniline, quinoline, inquinoline, N-ethylmorpholine, etc. are used.

Furthermore, the solubility of the polymer can be increased by adding lithium chloride, calcium chloride, magnesium chloride, or lithium bromide to these solvents.

Furthermore, it is advisable to add an epoxy compound in order to capture the generated hydrogen halide.

In an embodiment of the present invention, when a diaminodialkoxycarbonylamino compound, a diamine, and a dicarboxylic acid halide are reacted in an inert solvent at a temperature of 50°C or lower, the reaction proceeds rapidly and the viscosity of the solution becomes extremely high. Become.

Thereafter, when the product is heated to 250-350°C, it undergoes ring closure and is converted into polyamide imidacillin.

Next, the present invention will be described in more detail by showing examples.

Example 1 1 equipped with thermometer, stirrer and calcium chloride tube
In a 0Qcc four-day flask, add 3,3'-diamino-4.
4'-Jethoxycarbonylaminodiphenyl ether 3.74'? , 4,4'-diaminodiphenyl ether2. Add 60 cc of N-methyl-2-pyrrolidone and stir the contents well to dissolve.

The flask was cooled in a water bath, and 4.069 g of isophthalic acid chloride was gradually added thereto.
Stirring was continued for 2 hours at °C.

Pour the reaction solution into water, filter the resulting precipitate, wash with water,
Dry under reduced pressure.

The reduced viscosity ηSP/C of this polymer is 2.86 dl/g (solvent N-methyl-2-pyrrolidone, concentration 0.1-7
100 cc solution, temperature 30° C. (measurement conditions are the same below).

A solution of the polymer in N-methyl-2-pyrrolidone was cast onto a glass plate to form a film.

This film was heated to 250-300°C to close the ring.

This film did not lose weight in air up to 370°C.

Example 2 In a flask similar to Example 1, 3,3'-diamino-4.
4'-Jethoxycarbonylaminodiphenylmethane 3
．． 72° g, 4.32 f of 4,4'-di(m-aminophenoxy)diphenylsulfone and 60 cc of N-methyl-2-pyrrolidone were added, the contents were stirred, and the flask was cooled in a water bath.

5.91 of 4,4'-diphenyl ether-dicarboxylic acid chloride was gradually added to the mixture, and after the addition was completed, the mixture was heated to 10°C.
The mixture was stirred for 3 hours.

The reduced viscosity of the produced polymer was 1.20 dl/f.

A film was made from the polymer solution and heated to 200-300°C for ring closure.

This film did not lose weight in air up to 350°C.

Example 3 In a flask similar to Example 1, 3,3'-diamino-4.
4'-Jethoxycarbonylaminodiphenylmethane 3
．． 72'f! , 4,4'-diaminodiphenylmethane L
98P and 60 cc of N-methyl-2-pyrrolidone are added, the contents are stirred, and the flask is kept ice-cooled.

Gradually add adipyl chloride 3.661 to this,
After the addition was completed, the reaction was carried out at 10° C. for 3 hours.

The reduced viscosity of the produced polymer is 1.31 dl/f? Met.

A film was made from the polymer solution and heated to 200-300°C to close the ring.

This film did not lose weight in air up to 340°C.

Claims (1)

[Claims] 1 Two alkoxycarbonylamino groups (
-NHCOOR, where R is an alkyl group), and the amine group and the alkoxycarbonylamino group are mutually bonded to adjacent carbon atoms of the aromatic nucleus. Compound 95~
A method for producing a copolymer, which comprises reacting 5 mol % of a diamine, 5 to 95 mol % of a diamine, and a dicarboxylic acid halide in an inert solvent, and subjecting the reaction product to a heat treatment to cause ring closure.