JPS6254813B2 - - Google Patents

Description

[Detailed description of the invention]

(Technical field to which the invention relates) The present invention relates to a novel polyamide resin and a method for producing the same. (Prior Art) In the past, wholly aromatic polyamide resins have excellent heat resistance and excellent mechanical properties, and have been widely used as industrial materials. Among these polyamide resins, those having a high glass transition point and excellent heat resistance exhibit low solubility in organic solvents and have problems in moldability. On the other hand, those exhibiting high solubility have a low glass transition point and have problems in heat resistance. Therefore, the present inventors have developed a method that is soluble in various organic solvents.
In addition, we worked diligently to produce a polyamide resin with a high glass transition point, and completed the present invention. (Disclosure of the invention) The first invention of the present invention is based on the general formula (In the formula, R is one or two selected from the group consisting of a phenylene group and an oxydiphenylene group.
It is a divalent organic group of species, and Ar is a divalent tetraphenylthiophene group when Ar is one type, and Ar is a divalent tetraphenylthiophene group when Ar is one type.
In the case of a species, one type of Ar is a divalent tetraphenylthiophene group, and another type of Ar is a divalent oxydiphenylene group, and the other species of Ar may be the same as R or not. They may be different, and n is an integer representing the degree of polymerization. ), and when R is composed of two types of the divalent organic groups, the proportion of the various divalent organic groups that are R is arbitrary, and the arrangement order of those R is random, and Ar is two types, the divalent tetraphenylthiophene group accounts for 20 to 99 mol% of the Ar group, and the tetraphenylthiophene group and
Ar of the oxydiphenylene group which is another species of Ar
The sequence order for 30 in sulfuric acid is random.
Intrinsic viscosity measured at ℃, concentration of 0.5g/dl is 0.90~
1.75 is a polyamide resin. The second invention of the present invention is the general formula (In the formula, R is one or two selected from the group consisting of a phenylene group and an oxydiphenylene group.
It is a divalent organic group of species, and Ar is a divalent tetraphenylthiophene group when Ar is one type, and Ar is a divalent tetraphenylthiophene group when Ar is one type.
In the case of a species, one type of Ar is a divalent tetraphenylthiophene group, and another type of Ar is a divalent oxydiphenylene group, and the other species of Ar may be the same as R or not. They may be different, and n is an integer representing the degree of polymerization. ), and when R is composed of two types of the divalent organic groups, the proportion of the various divalent organic groups that are R is arbitrary, and the arrangement order of those R is random, and Ar is two types, the divalent tetraphenylthiophene group accounts for 20 to 99 mol% of the Ar group, and the tetraphenylthiophene group and
Ar of the oxydiphenylene group which is another species of Ar
The sequence order for 30 in sulfuric acid is random.
Intrinsic viscosity measured at ℃, concentration of 0.5g/dl is 0.90~
1.75, the general formula H ₂ N-Ar-NH ₂ () (in the formula, Ar is a divalent tetraphenylthiophene group when there is one type of Ar; If , then Ar
One type of Ar is a divalent tetraphenylthiophene group, and the other type of Ar is a divalent oxydiphenylene group. ) or Ar in the diamine
The diamine in which Ar is a divalent tetraphenylthiophene group is within the range of 20 to 99 mol%, and the remainder is a diamine in which Ar is a divalent oxydiphenylene group 2
Seed diamine mixture and general formula (In the formula, R is one or two selected from the group consisting of a phenylene group and an oxydiphenylene group.
is a divalent organic group of species, R may be the same or different from other species of Ar, and X is a halogen atom. ) One or two dicarboxylic acid dihalides represented by
This is a method for producing a polyamide resin, which is characterized by reacting the diamine and the dicarboxylic acid dihalide in an approximately equimolar ratio with a mixture of species in an arbitrary ratio in an organic solvent. The polyamide resin represented by the above general formula () is manufactured from the diamine represented by the above general formula () and the dicarboxylic acid dihalide represented by the above general formula (), but in the diamine, Ar in the above formula () is divalent. A diamine consisting of a tetraphenylthiophene group can be used alone, or 20 to 99 mol% of the above Ar may be added to a diamine consisting of a tetraphenylthiophene group by 80-1
It is also possible to use a diamine in which mol% of the above Ar is composed of an oxydiphenylene group. When using a mixture of diamines, if the diamine consisting of divalent tetraphenylthiophene groups is less than 20 mol%, the characteristics of the present invention, such as an increase in glass transition point and solubility in organic solvents, will not be sufficiently satisfied. . As the diamine represented by the above general formula (), a diamine consisting of a divalent tetraphenylthiophene group is used alone, and the above general formula ()
It is also possible to use a mixture of two types of dicarboxylic acid dihalides represented by: The copolymer thus produced is a copolymer with a random arrangement corresponding to the charging ratio of each component. Among the diamines represented by the above general formula (), the diamine in which Ar is a divalent tetraphenylthiophene group refers to 2,5-bis(4-aminophenyl)3,4-diphenylthiophene.
It is known that this diamine can be produced from benzyl chloride and sulfur, which are industrially available at low cost. For example, Ba Deilte et al. (W.
Dilthey in J.Prakt.Chem., Volume 2, pages 151 and 257 (1938). Among the diamines represented by the above general formula (),
Examples of diamines in which Ar is a divalent oxydiphenylene group include 3,3'-oxydianiline, 4,
Examples include 4'-oxydianiline and 3,4'-oxydianiline. Examples of the dicarboxylic acid dihalide represented by the above general formula () include dichloride, difluoride, and dibromide of the following dicarboxylic acids. That is, dichloride, difluoride, and dibromide such as terephthalic acid, isophthalic acid, 4,4'-diphenyl ether dicarboxylic acid, and 3,3'-diphenyl ether dicarboxylic acid can be exemplified. A method for producing a polyamide resin represented by the above general formula () is to mix a diamine compound represented by the above general formula () and a dicarboxylic acid dihalide represented by the above general formula () in an organic solvent at a temperature of -20° to
This is carried out by reacting at 200°C for several minutes to several days. In this method, the molecular weight of the polyamide resin represented by the general formula () is limited by the amount of the diamine compound represented by the general formula () and the dicarboxylic acid dihalide represented by the general formula (), and these reaction components are equated. When used in a molar amount, a high molecular weight polyamide resin represented by the above general formula () can be produced. The reason for limiting the intrinsic viscosity of the polyamide resin represented by the general formula () to 0.90 to 1.75 when measured in sulfuric acid at 30°C and a concentration of 0.5 g/dl is that if it is lower than 0.90, the mechanical Properties such as properties and heat resistance are insufficient, and the intrinsic viscosity is
This is because if it exceeds 1.75, the solubility in organic solvents etc. will deteriorate. Organic solvents that can be used in this method include N,
Amide solvents such as N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, chloroform, dichloromethane, 1 ,2-dichloroethane, 1,1,2,2-
Examples include halogenated solvents such as tetrachloroethane. It is effective to carry out the reaction by coexisting an acid acceptor such as pyridine or triethylmine with such an organic solvent, or by using a two-phase system with an alkaline aqueous solution in the case of a solvent that is immiscible with water. . In particular, when amide solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone are used, these solvents themselves become acid acceptors, and a high polymer polyamide resin can be obtained. The solubility of the thus produced polyamide resin represented by the general formula () changes depending on the diamine represented by the general formula () used and the type of dicarboxylic acid dihalide represented by the general formula () used. , chloroform, tetrachloroethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, and pyridine. In the polyamide resin represented by the above general formula (), no glass transition point is observed up to around 300°C, and no significant weight change is observed even when heated up to around 400°C. (Examples of the Invention) Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 2,5-bis(4-aminophenyl)-3,4
- 7.5 g (2.5 mmol) of diphenylthiophene
ml of dimethylacetamide and cooled at 0°C in an ice bath.
It was cooled to To this solution, 0.508 g (2.5 mmol) of isophthalic acid chloride was added all at once in its crystal form, and further 2 ml of dimethylacetamide was added. After stirring on an ice bath for 1.5 hours, the resulting solution was poured into 300 ml of methyl alcohol to obtain a polyamide. Yield 99% Intrinsic viscosity 0.99 (measured in sulfuric acid at 30°C at a concentration of 0.5 g/dl) Elemental analysis C H N S Calculated value (%) 78.83 4.37 5.10 5.83 Actual value (%) 77.46 4.35 4.71 5.73 Thermogravimetric measurement Temperature of 10% weight loss due to equipment: 490°C in air, 500°C in nitrogen Solubility in organic solvents is shown in Attached Table 1. Example 2 2,5-bis(4
-aminophenyl)-3,4-diphenylthiophene 1.045g (2.5mmol) and isophthalic acid chloride
0.406g (2mmol), terephthalic acid chloride 0.102g
A copolyamide was obtained from the combination with (0.5 mmol). Yield: 96% Intrinsic viscosity: 1.08 (measured in sulfuric acid at 30°C at a concentration of 0.5g/dl) 10% weight loss temperature: 490°C in air, 510°C in nitrogen Solubility in organic solvents is shown in Attached Table 1. Example 3 2,5-bis(4
-aminophenyl)-3,4-diphenylthiophene 1.045g (2.5mmol) and isophthalic acid chloride
0.305g (1.5mmol), terephthalic acid chloride
A copolyamide was obtained from the combination with 0.203 g (1 mmol). Yield: 96% Intrinsic viscosity: 1.10 (measured in sulfuric acid at 30°C at a concentration of 0.5g/dl) 10% weight loss temperature: 495°C in air, 515°C in nitrogen Solubility in organic solvents is shown in Attached Table 1. Example 4 2,5-bis(4
-aminophenyl)-3,4-diphenylthiophene 1.045g (2.5mmol) and isophthalic acid chloride
0.203g (1mmol), terephthalic acid chloride 0.305g
A copolyamide was obtained from the combination with (1.5 mmol). Yield: 96% Intrinsic viscosity: 1.60 (measured in sulfuric acid at 30°C at a concentration of 0.5g/dl) 10% weight loss temperature: 490°C in air, 510°C in nitrogen Solubility in organic solvents is shown in Attached Table 1. Example 5 2,5-bis(4
-aminophenyl)-3,4-diphenylthiophene 1.045g (2.5mmol) isophthalic acid chloride
0.102g (0.5mmol), terephthalic acid chloride
A copolyamide was obtained from the combination with 0.406 g (2 mmol). Yield: 94% Intrinsic viscosity: 1.44 (measured in sulfuric acid at 30°C at a concentration of 0.5g/dl) 10% weight loss temperature: 490°C in air, 510°C in nitrogen Solubility in organic solvents is shown in Attached Table 1. Example 6 2,5-bis(4
-aminophenyl)-3,4-diphenylthiophene 1.045g (2.5mmol) and terephthalic acid chloride
Polyamide was obtained from 0.508g (2.5mmol). Yield 98% Intrinsic viscosity 1.71 (measured in sulfuric acid at 30°C at a concentration of 0.5g/dl) 10% weight loss temperature 500°C in air, 530°C in nitrogen The polyamide obtained was N-methyl- containing 5% LiCl. It was dissolved in 2-pyrrolidone, but not in pyridine, cresol, etc. Example 7 2,5-bis(4
-Aminophenyl)-3,4-diphenylthiophene 0.523g (1.25mmol), 4,4'-oxydianiline 0.250g (1.25mmol) and isophthalic acid chloride 0.508g (2.5mmol). Obtained. Yield: 98% Intrinsic viscosity: 0.94 (measured in sulfuric acid at 30°C at a concentration of 0.5g/dl) 10% weight loss temperature: 480°C in air, 495°C in nitrogen Solubility in organic solvents is shown in Attached Table 1. Example 8 2,5-bis(4
-Aminophenyl)-3,4-diphenylthiophene 0.523g (1.25mmol), 4,4'-oxydianiline 0.250g (1.25mmol) and terephthalic acid chloride 0.508g (2.5mmol). Obtained. Yield: 99% Intrinsic viscosity: 1.53 (measured in sulfuric acid at 30°C, concentration of 0.5 g/dl) 10% weight loss temperature: 495°C in air, 500°C in nitrogen The copolyamide obtained is N-methyl-2-pyrrolidone, It was partially dissolved in N,N-dimethylacetamide. Example 9 2,5-bis(4
-aminophenyl)-3,4-diphenylthiophene 1.045 g (2.5 mmol) and 4,4'-diphenyl ether dicarboxylic acid dichloride 0.738 g
Polyamide was obtained from (2.5 mmol). Yield: 98% Intrinsic viscosity: 1.04 (measured in sulfuric acid at 30°C at a concentration of 0.5 g/dl) Solubility in organic solvents is shown in Attached Table 1.

[Table] (Effects of the Invention) The present invention provides a polyamide resin represented by the general formula () and an advantageous method for producing the polyamide resin. While many conventional polyamide resins have low solubility in organic solvents and are difficult to mold, the polyamide resin of the present invention is soluble in organic solvents, easy to mold, and has excellent properties. It has great value as an industrial material because of its heat resistance, electrical properties, and mechanical properties.

Claims (1)

[Claims] 1. General formula (In the formula, R is one or two selected from the group consisting of a phenylene group and an oxydiphenylene group.
It is a divalent organic group of species, and Ar is a divalent tetraphenylthiophene group when Ar is one type, and Ar is a divalent tetraphenylthiophene group when Ar is one type.
In the case of a species, one type of Ar is a divalent tetraphenylthiophene group, and another type of Ar is a divalent oxydiphenylene group, and the other species of Ar may be the same as R or not. They may be different, and n is an integer representing the degree of polymerization. ), and when R is composed of two types of the divalent organic groups, the proportion of the various divalent organic groups that are R is arbitrary, and the arrangement order of those R is random, and Ar is two types, the divalent tetraphenylthiophene group accounts for 20 to 99 mol% of the Ar group, and the tetraphenylthiophene group and
Ar of the oxydiphenylene group which is another species of Ar
The sequence order for 30 in sulfuric acid is random.
Intrinsic viscosity measured at ℃, concentration of 0.5g/dl is 0.90~
1.75 polyamide resin. 2 General formula (In the formula, R is one or two selected from the group consisting of a phenylene group and an oxydiphenylene group.
It is a divalent organic group of species, and Ar is a divalent tetraphenylthiophene group when Ar is one type, and Ar is a divalent tetraphenylthiophene group when Ar is one type.
In the case of a species, one type of Ar is a divalent tetraphenylthiophene group, and another type of Ar is a divalent oxydiphenylene group, and the other species of Ar may be the same as R or not. They may be different, and n is an integer representing the degree of polymerization. ), and when R is composed of two types of the divalent organic groups, the proportion of the various divalent organic groups that are R is arbitrary, and the arrangement order of those R is random, and Ar is two types, the divalent tetraphenylthiophene group accounts for 20 to 99 mol% of the Ar group, and the tetraphenylthiophene group and
Ar of the oxydiphenylene group which is another species of Ar
The sequence order for 30 in sulfuric acid is random.
Intrinsic viscosity measured at ℃, concentration of 0.5g/dl is 0.90~
1.75, the general formula H ₂ N-Ar-NH ₂ (wherein, Ar is a divalent tetraphenylthiophene group when there is one type of Ar, and a divalent tetraphenylthiophene group when there are two types of Ar). is Ar
One type of Ar is a divalent tetraphenylthiophene group, and the other type of Ar is a divalent oxydiphenylene group. ), or the diamine in which Ar is a divalent tetraphenylthiophene group is within the range of 20 to 99 mol%, and the remainder is an oxydiphenylene group where Ar is a divalent group. A mixture of two diamines and the general formula (In the formula, R is one or two selected from the group consisting of a phenylene group and an oxydiphenylene group.
is a divalent organic group of species, R may be the same or different from other species of Ar, and X is a halogen atom. ) One or two dicarboxylic acid dihalides represented by
A method for producing a polyamide resin, which comprises reacting a mixture of the diamine and the dicarboxylic acid dihalide in an approximately equimolar ratio in an organic solvent.