JPS5817219B2 - Manufacturing method of condensation polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to formula C, where Ar is a diaminomonoamide compound a residue, R1 is a dibasic acid halide residue, Y is CO or SO□, R
is 1 selected from alkyl, cycloalkyl, and allyl groups
The purpose is to produce polymers with excellent heat resistance, abrasion resistance, and chemical resistance, and to be used as electrical insulation materials, molding materials, films, and reverse osmosis membranes. The object of the present invention is to provide polymers useful as alignment films, coating materials, adhesives, and the like.

The feature of the present invention is that two amine groups and one Y
-NHR group (where, Y represents CO or SO2, S
(represents a monovalent group selected from a cycloalkyl group, a chloroalkyl group, and an allyl group) in the aromatic nucleus, and among them, 1
A diaminomonoamide compound bonded to carbon atoms adjacent to the amino groups and Y-NHR groups and a dibasic acid...logenide are reacted in an inert solvent to synthesize a polyamide type intermediate. The purpose is to dehydrate the intermediate and cause ring closure.

The diaminomonoamide compound used in the present invention has the following general formulas ((I) to (I)), where Y represents SO□ or CO, and R is 1 selected from an alkyl group, a chloroalkyl group, and an ali group. Indicates a valence group.

Indicates XKe0, CH2°SO2,s or CO, etc.

As long as one amino group introduced to the aromatic nucleus and Y-NHR are bonded to adjacent carbon atoms, their positions are not restricted.

Furthermore, the hydrogen atom bonded to the aromatic nucleus may be substituted with other inert groups such as an alkyl group, an allyl group, a halogen atom, etc. ,4'-diaminodiphenyl ether-3-N
-Methylsulfonamide, 4.4'-diaminodiphenylsulfone-3-N-methylsulfonamide, 4.4'
-diaminodiphenyl sulfide-3-N-methylsulfonamide, 2,5-diaminobenzene-1-N-methylsulfonamide, 2,4-diaminobenzene-1-
N-methylsulfonamide, 2,4-diaminobenzene-1-N-ethylsulfonamide 2,4-diaminobenzene-IN-n-propylsulfonamide, 2,4-diaminobenzene-1-N-iso-propylsulfone Amide, 2,4-diaminobenzene-1-N-butylsulfonamide, 2,4-diaminobenzene-1-N-phenylsulfonamide, 4,4'-diaminodiphenyl ether-3-N-methylcarbonamide, 4,4 '-Diaminodiphenyl ether-3-N-ethyl carbonamide, 4,4'-diaminodiphenyl ether-3N
n-propylcarbonamide, 4,4'-diaminodiphenyl ether-3N-iso-propylcarbonamide, 4,4'-diaminodiphenyl ether-3N-
n-/'thylcarbonamide, 4.4'-diaminodiphenyl ether-3-N-phenylcarbonamide, 3
．． 4'-Diaminodiphenyl ether-4-N-methylcarbonamide, 3.4'-Diaminodiphenyl ether-3'-N-methylcarbonamide, 3.4'-Diaminodiphenyl ether-3'-N-ethylcarbonamide, 3. 4'-diaminodiphenyl ether-3'N
-n-propyl carbonamide, 3,4'-diaminodiphenyl ether-3'N 1so-propyl carbonamide, 3,4'-diaminodiphenyl ether-3'Nn-7'' thyl carbonamide 3,4'-diaminodiphenyl ether-3 '-N-phenylcarbonamide, 3,3'-diaminodiphenyl ether-4-N
-Methylcarbonamide 4.4'-Diaminodiphenylmethane-3'-N-methylcarbonamide, 3.4'-
Diaminodiphenylmethane-4-N-methylcarbonamide, 3.4'-diaminodiphenylmethane-3' -
N-ethyl carbonamide, 3,3'-diaminodiphenylmethane-4-N-methyl-carbonamide, 4.
4'-diaminodiphenylsulfone-3-N-methylcarbonamide, 4,4'-diaminodiphenylsulfone-3-N-ethylcarbonamide, 4,4'-diaminodiphenylsulfone-3N-n-propylcarbonamide, 4.4'-diaminodiphenylsulfone-3Ni
so-7''ropylcarbonamide, 4,4'-diaminodiphenylmene-3Nn-butylcarbonamide, 4,
4'-Sia; Minodiphenylsulfone-3-N-phenylcarbonamide, 3,4'-diaminodiphenylsulfone-3'-N-methylcarbonamide, 3,3'-diaminodiphenylsulfone-4N-ethylcarbonamide, 4,4'-diaminodiphenyl sulfide-3-
N-methylcarbonamide, 3j4'-diaminodiphenyl sulfide-4-N-methylcarbonamide, 3
, 3'-diaminodiphenyl sulfide-4-N-methylcarbonamide, 3,4'-diaminodiphenyl sulfide-.3-N-methylcarbonamide, 2,5
-Diamino-N-methylbenzamide, 2,4-diamino-N-methylbenzamide, 2,4-diamino-N-
Ethyl-benzamide, 2,4-diamino-N-n-propylbenzamide, 2,4-diamino-N-' 1
so-propylbenzamide, 2,4-diamino-N-
Examples include n-butylbenzamide and 2,4-diamino-N-phenylbenzamide.

Two or more of these diaminomonoamide compounds can also be used in combination.

In addition, examples of dicarboxylic acid halides include isophthalic acid halides, terephthalic acid halides, 4,
4'-diphenyl ether dicarboxylic acid halide,
4.4'-diphenylsulfonedicarboxylic acid halide, 2,6-naphthalenedicarboxylic acid halide,
malonic acid halide, malonic acid halide, succinic acid halide, glutaric acid halide, adipic acid halide, pimelic acid halide, speric acid halide, azelaic acid halide, sebatic acid halide, 1,10-decane Examples include dicarboxylic acid decogenide, 1,3-diclopentanedicarboxylic acid halide, and (1),4-diclohexanedicarboxylic acid halide.

Inert solvents are used in the practice of this invention.

As the inert solvent, for example, one or more of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, hexamethylsulfolamide, tetramethylenesulfone, etc. is used. It will be done.

Inorganic salts such as lithium chloride and magnesium chloride can also be added to these solvents to increase the solubility of the polymer.

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

An embodiment of the present invention is that when equivalent moles of a diaminomonoamide compound and a dicarboxylic acid halide are reacted in an inert solvent at room temperature or lower temperature, the reaction proceeds rapidly and the viscosity of the reaction system is extremely high. A type intermediate is obtained.

This polyamide-type intermediate undergoes ring closure by heating or treatment with chemicals, converting it into a polymer having heterocycles.

The present invention is represented by the following general formula.

(In the formula, Ar is a diaminomonoamide compound residue,
O or SO□, R represents a monovalent group selected from an alkyl group, a cycloalkyl group, and an allyl group, R1 represents a residue of a dicarboxylic acid halide, and Z represents a halogen.

) Next, examples will be shown and concretely explained.

Example 1 10 equipped with thermometer, stirrer and calcium chloride tube
2,4-diaminobenzene- in a 0 cc three-loaf flask.
2.01 g of 1-N-methylsulfonamide.

N-Methyl-2-pyrrolidone 30 CO1 lithium chloride is added, the contents are stirred and the flask is kept cooled in a water bath.

2.03 g of inphthalic acid dichloride was gradually added to the mixture, and after the addition was completed, a reaction was carried out at 10° C. for 3 hours.

The reaction product was poured into water to form a precipitate, filtered, washed with water,
It was dried under reduced pressure at room temperature.

The reduced viscosity η5p10 of the produced polyamide type intermediate is 1
．． 36. (Solvent: N-methyl-2-pyrrolidone, concentration: g/100 cc solution, temperature: 30°C, measurement conditions are the same below).

Dissolve 1 g of polyamide-type intermediate powder in 20 g of N-methyl-2-pyrrolidone, further add tri-n-butylamine, heat at 180 ° C. for 2 hours, and cast the solution on a glass plate to create a film. The ring was closed by heating to 250-350°C.

This film did not lose weight in air up to 410°C.

Example 2 In a flask similar to Example 1, 2.57 g of 4,4'-diaminodiphenyl ether-3-N-methylcarbonamide was added.
g, 30 cc of N-methyl-2-pyrrolidone, and 1.5 g of lithium chloride were added, the contents were stirred, and the flask was kept ice-cooled.

To this, 2.03 g of inphthalic acid dichloride was gradually added and reacted at 10° C. for 3 hours.

The reduced viscosity of the polyamide type intermediate produced is 1.56617g
Met.

Polyamide type intermediate N-methyl-2-pyrrolidone 10
% solution and cast it on a glass plate to create a film,
Heat treatment was performed at 250 to 350°C to close the ring.

This film did not lose weight in air up to 420°C.

Claims (1)

[Claims] 12 amino groups and one Y-NHK group (wherein, Y represents CO spanning SO2, and R represents a monovalent group selected from an alkyl group, a chloroalkyl group, and an allyl group) as an aromatic nucleus. Among them, one amino group and Y-NHR group are formed by reacting a diamino monoamide compound bonded to adjacent carbon atoms with a dibasic acid...loginide in an inert solvent to form a polyamide type. A method for producing a condensation polymer, which comprises synthesizing an intermediate and then ring-closing the intermediate.