JPH0123489B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing polyamide resins, particularly polyamide resins that are soluble in various organic solvents and have a wide range of molding temperatures.

(Prior Art) Conventionally, N-phenyl-substituted polyamide resins have high glass transition points and high decomposition points, are soluble in various organic solvents, and are expected to be materials with high moldability. However, although conventionally produced N-phenyl substituted polyamide resins have good thermal properties, they do not have a sufficiently high molecular weight and still have problems with their mechanical properties.

(Problems to be Solved by the Invention) As mentioned above, conventional N-phenyl-substituted polyamide resins have a high glass transition temperature and a high decomposition temperature, and are soluble in various organic solvents. . As described above, N-phenyl substituted polyamide resin has both heat resistance and processability, but its low molecular weight has been a major problem in the commercial use of this resin.

Therefore, an object of the present invention is to provide a method for producing a high molecular weight N-phenyl substituted polyamide resin.

(Means for Solving the Problems) The present inventors have worked hard to produce a high molecular weight N-phenyl substituted polyamide resin and have completed the present invention.

The present invention is based on the general formula (In the formula, R ¹ and R ² are one or more divalent organic groups, R ¹ and R ² are the same or different, and n is 10 to
(representing an integer of 200) In producing polyamide resin,
general formula (In the formula, R ² is a divalent organic group, and X is a halogen atom.) One or two dicarboxylic acid dihalides represented by
More than species and general formula (In the formula, R ¹ represents a divalent organic group) is reacted with one or more N,N'-diphenyl-N,N'-bis(trimethylsilyl)diamines in an organic solvent. This is a method for producing a polyamide resin.

(Function) The polyamide resin represented by the above general formula () is produced from dicarboxylic acid dihalide represented by the above general formula () and N-phenyl-N-trimethylsilyldiamine represented by the above general formula (). As the dicarboxylic acid dihalide, one type or a mixture of two or more of the following dicarboxylic acid dichloride, difluoride, and dibromide can be used. That is, terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid,
1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 3,3'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 3 , 3'-diphenylmethanedicarboxylic acid,
4,4′-diphenylsulfonedicarboxylic acid, 3,
Examples include dichloride, difluoride and bromide such as 3'-diphenylsulfonedicarboxylic acid.

The N,N'-diphenyl-N,N'-bis(trimethylsilyl)diamine represented by the above general formula () includes the following N,N'-ditrimethylsilyl derivatives of N,N'-diphenyldiamine. can be exemplified. That is, N,N'-diphenyl-m-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-
Diphenyl-4,4'-diaminodiphenylmethane, N,N'-diphenyl-4,4'-diaminodiphenyl ether, N,N'-diphenyl-3,3'-
Diaminodiphenyl ether, N,N'-diphenyl-4,4'-diaminodiphenylbenzophenone, N,N'-diphenyl-3,3'-diaminodiphenylbenzoenone, N,N'-diphenyl-4 ，
4'-diaminodiphenyl sulfide, N,N'-diphenyl-3,3'-diaminodiphenyl sulfide, N,N'-diphenyl-4,4'-diaminodiphenylsulfone, N,N'-Diphenyl-3,3'-
Diaminodiphenyl sulfone, N,N'-diphenyl-2,2-bis(4-aminophenyl)propane, N,N'-diphenyl-4,4'-diaminobiphenyl, N,N'-diphenyl-3,3 '-diaminobiphenyl, N,N'-diphenyl-1,4-
Diaminonaphthalene, N,N'-diphenyl-1,
N, such as 5-diaminonaphthalene and N,N′-diphenyl-2,6-diaminonaphthalene,
An example is N'-diphenyl-N,N'-bis(trimethylsilyl)diamine.

The production of the polyamide resin represented by the above general formula () involves mixing dicarboxylic acid dihalide represented by the above general formula () with N,N'-diphenyl-N,N represented by the above general formula () in an organic solvent. It is carried out by reacting ′-bis(trimethylsilyl)diamine at 20 to 250°C for several minutes to several days. In this method, the molecular weight of the polyamide resin represented by the general formula () is the dicarboxylic acid dihalide represented by the above general formula () and the N,N'-diphenyl-N,N'-
It is limited by the amount of the bis(trimethylsilyl)diamine compound charged, and if equimolar amounts of these reaction components are used, a high molecular weight polyamide resin represented by the above general formula () can be produced.

The reason why n is limited to an integer between 10 and 200 in the polyamide resin represented by the above general formula () is that n is
If it is smaller than 10, the mechanical properties, heat resistance, etc. of the molded product formed into a film etc. will not be sufficient, and n will be
This is because if it exceeds 200, the solubility in organic solvents etc. will deteriorate.

Organic solvents that can be used in this method include hydrocarbon solvents such as hexane, octane, and decalin;
Aromatic solvents such as toluene, xylene, anisole, diphenyl ether, nitrobenzene, benzonitrile, chlorobenzene, o-dichlorobenzene, ketone solvents such as diethyl ketone, dibutyl ketone, and cyclohexanone, chloroform, 1,2-dichloroethane ,1,1,2,2
- Halogenated solvents such as tetrachloroethane and hexachloroethane, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, and diphenylsulfone and sulfolane. Examples include organic solvents such as sulfur-based solvents.

The thus produced polyamide resin represented by the above general formula () has an intrinsic viscosity of 1.5 or more,
A transparent and tough film can be obtained by solvent casting or hot pressing.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

Reference example 1 Add 13.0g (0.05g) to 200mL of tetrahydrofuran.
mol) of N,N'-diphenyl-p-phenylenediamine was dissolved, and 3.8 g (0.06 mol) of n-butyllithium was added dropwise thereto at 0°C, followed by stirring for 1 hour in a nitrogen atmosphere. Add 8.2 ml (0.065
mol) of trimethylsilichloride was added dropwise at 0°C, and the mixture was stirred for 1 hour. Similarly, 4.2 g (0.066 mol) of n-butyllithium was added dropwise at 0°C, stirred for 1 hour under nitrogen atmosphere, and then added to this solution with 9.5 mol of n-butyllithium.
ml (0.075 mol) of trimethylsilyl chloride was added dropwise at 0°C and stirred for 12 hours. The produced lithium chloride was filtered, and the solvent of the filtrate was distilled off under reduced pressure to obtain a crude product. This product was recrystallized from n-hexane to obtain pure N,N'-diphenyl-N,N'-bis(trimethylsilyl)-p-phenylenediamine.

Yield 65% Melting point 126-127℃ IR (KBr): 1260, 845, 750 Elemental analysis value C H N Calculated value (%) 71.23 7.97 6.92 Actual value (%) 71.00 8.05 6.87 Example 1 1.416 g (3.5 mmol) N,N'-diphenyl-N,N'-bis(trimethylsilyl)-p-phenylenediamine and 0.711 g (3.5 mmol) of isophthalic acid chloride were stirred in 5 ml of sulfolane under a nitrogen atmosphere at 160°C for 24 hours. I hung out. The resulting reaction solution was diluted with 20 ml of chloroform and poured into a large amount of methanol to obtain a white flaky polymer.

Yield: 93% Intrinsic viscosity: 1.65 dL/g (30°C in sulfuric acid, 0.5 g/d
) Elemental analysis value C H N Calculated value (%) 79.98 4.65 7.17 Actual value (%) 79.16 4.24 7.28 Example 2 1.416 g (3.5 mmol) of N,N'-diphenyl-N,N'-bis (Trimethylsilyl)-p-phenylenediamine and 0.711 g (3.5 mmol) of terephthalic acid chloride were stirred in 5 ml of sulfolane under a nitrogen stream at 200° C. for 24 hours. The resulting reaction solution was diluted with 20 ml of chloroform and poured into a large amount of methanol to obtain a white flaky polymer.

Yield: 92% Intrinsic viscosity: 2.21 dL/g (30°C in sulfuric acid, 0.5 g/g
Example 3 1.514 g (3.5 mmol) of N,N'-diphenyl-N,N'-bis(trimethylsilyl)-p-xylene diamine and 0.711 g (3.5 mmol) of isophthalic acid chloride, The mixture was stirred in 5 ml of sulfolane at 150° C. for 24 hours under a nitrogen stream. The resulting reaction solution was diluted with 20 ml of chloroform and poured into a large amount of methanol to obtain a white flaky polymer.

Yield 96% Intrinsic viscosity 1.53dL/g (30% in m-cresol
(measured at 0.5 g/d at a concentration of 0.5 g/d) (Effects of the Invention) The present invention provides an advantageous method for producing a polyamide resin represented by the above general formula (). The production method of the present invention has a high molecular weight, whereas the conventional polyamide resin represented by the above general formula () did not have a sufficiently high molecular weight even by the high temperature solution method. A polyamide resin is obtained. This makes it possible to improve moldability, which has been a problem in the past. The polyamide resin represented by the above general formula () is soluble in various organic solvents, can be solution molded, has a high decomposition point, and also has a high glass transition point unique to aromatic polyamides. It is an engineering plastic that can be heat molded. Therefore, the industrial value of the present invention, which can produce a polyamide resin represented by the above general formula () having a higher molecular weight, is great.

Claims (1)

[Claims] 1. General formula (In the formula, R ¹ and R ² are one or more divalent organic groups, R ¹ and R ² are the same or different, and n is 10 to
(representing an integer of 200) In producing polyamide resin,
general formula (In the formula, R ² is a divalent organic group, and X is a halogen atom.) One or two dicarboxylic acid dihalides represented by
More than species and general formula (In the formula, R ¹ represents a divalent organic group) is reacted with one or more N,N'-diphenyl-N,N'-bis(trimethylsilyl)diamines in an organic solvent. A method for producing a polyamide resin, characterized by: