JPH0149414B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a polyamide resin, particularly a novel polyamide resin that is soluble in various organic solvents and has a high glass transition temperature, and a method for producing the same. (Prior Art) In the past, wholly aromatic polyamide resins have been expected to be materials with high glass transition points and high decomposition points. However, many conventionally produced aromatic polyamides are insoluble in organic solvents and have a glass transition point of 300° C. or higher, so there are still problems with their moldability. (Problems to be solved by the invention) As mentioned above, although conventional wholly aromatic polyamide resins have high thermal stability, they have poor moldability, and heat resistance The fact that there is no wholly aromatic polyamide resin that also has
This was a major problem in the commercial use of this resin. Therefore, the present invention aims to solve the problem of providing a new polyamide resin that is soluble in organic solvents, has a high glass transition point, and at the same time has a high decomposition point, and has excellent processability, and a method for producing the same. do. (Means for Solving the Problems) The present inventors have produced a new polyamide resin that is soluble in organic solvents, has a high glass transition point, and has a high decomposition point, and has excellent processability. We have worked diligently to accomplish this invention. The first invention of the present invention is based on the general formula (wherein R is at least one arylene group,
Ar contains at least 20 mol% of 1-phenoxy-2,
Arylene group consisting of 4-phenylene group, n is 10
(indicates an integer between 200 and 200). The second invention of the present invention has the general formula H ₂ N—Ar—NH ₂ () (in the formula, Ar represents an arylene group in which at least 20 mol% is a 1-phenoxy-2,4-phenylene group). At least one diamine represented by the general formula (In the formula, R represents an arylene group and X represents a halogen atom.) A polyamide resin represented by the general formula () obtained by reacting in an organic solvent with at least one dicarboxylic acid dihalide represented by This is the manufacturing method. The third invention of the present invention has the general formula H ₂ N—Ar—NH ₂ () (in the formula, Ar represents an arylene group in which at least 20 mol% is a 1-phenoxy-2,4-phenylene group). At least one diamine represented by the general formula (wherein, R represents an arylene group) is reacted with at least one dicarboxylic acid represented by the above general formula () in the presence of an aromatic phosphite and a pyridine derivative in an organic solvent. This is a method for manufacturing the polyamide resin. The polyamide resin represented by the above general formula is produced by reacting the diamine represented by the above general formula with the dicarboxylic acid dihalide represented by the above general formula, or the dicarboxylic acid represented by the above general formula, but the diamine is substituted with Ar. A diamine consisting of a phenylene group, that is, a 1-phenoxy-2,4-phenylene group, can be used alone, or at least one arylene diamine different from the above may be used at most of the total amount of diamine.
They can also be used in a mixture of up to 80 mol%. When using a mixture of diamines, if the diamine whose Ar is a 1-phenoxy-2,4-phenylene group is less than 20 mol% of the total diamines, the solubility in organic solvents and thermoformability, which are the characteristics of the present invention, will be reduced. I'm no longer fully satisfied with sex. As the diamine represented by the above general formula, Ar is 1-phenoxy-2,
A diamine consisting of a 4-phenylene group may be used alone, and one or more dicarboxylic acid dihalides represented by the above general formula or dicarboxylic acids represented by the above general formula may be used in combination. Among the diamines represented by the above general formula,
A diamine in which Ar is a 1-phenoxy-2,4-phenylene group has the structure of the following formula:
It is a diamine consisting of a 1-phenoxy-2,4-phenylene group. This diamine can be obtained by reducing 2,4-dinitrodiphenyl ether, which can be produced from 2,4-dinitrochlorobenzene and phenol, which are industrially available at low cost, using various conventional reduction methods. Among the diamines represented by the above general formula, 1
Examples of arylene diamines other than phenoxy-2,4-phenylene diamine include metaphenylene diamine, paraphenylene diamine,
4,4'-diaminobiphenyl, 3,3'-methylene dianiline, 4,4'-methylene dianiline, 4,
4'-ethylene dianiline, 4,4'-isopropylidene dianiline, 3,4'-oxydianiline,
4,4'-oxydianiline, 4,4'-thiodianiline, 3,3'-carbonyldianiline, 4,4'-
Carbonyl dianiline, 3,3'-sulfonyl dianiline, 4,4'-sulfonyl dianiline, 1,4
-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, etc. Examples of the dicarboxylic acid dihalide represented by the above general formula in which R is a divalent aromatic group include dichloride, difluoride, and dibromide of the following dicarboxylic acids. 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'-diphenylmethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 3,3'-diphenylsulfone dicarboxylic acid, etc. Examples include dichloride, difluoride and dibromide. The arylene dicarboxylic acids represented by the above general formula include 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′-diphenylmethanedicarboxylic acid, 3,
Examples include 3'-diphenylmethanedicarboxylic acid, 4,4'diphenylsulfonedicarboxylic acid, and 3,3'-diphenylsulfonedicarboxylic acid. The polyamide resin represented by the above general formula is produced by reacting a diamine 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 200°C for several minutes to several days. This is done by letting the In this method, the molecular weight of the polyamide resin represented by the general formula is limited by the amount of the diamine represented by the above general formula and the dicarboxylic acid dihalide represented by the above general formula, 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 if n is smaller than 10, the mechanical properties and heat resistance of the molded product, such as a film, will not be sufficient. This is because when n exceeds 200, the solubility in organic solvents etc. deteriorates. Organic solvents that can be used in this method include N,
Amide solvents such as N-dimethylacetamide and N-methyl-2-pyrrolidone, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, and benzonitrile, and chloroform, dichloromethane, 1,2-dichloroethane, 1 , 1,2,2-tetrachloroethane, and other halogenated solvents. Pyridine along with such organic solvents,
It is effective to carry out the reaction in the presence of an acid acceptor such as triethylamine, or in the case of a solvent that is immiscible with water, in a two-phase system with an alkaline aqueous solution. In particular, when an amide solvent such as N,N-dimethylacetamide or N-methyl-2-pyrrolidone is used, these solvents themselves become acid acceptors, and a high polymer polyamide resin can be obtained. Separately, the production of the polyamide resin represented by the above general formula involves combining a diamine represented by the above general formula and a dicarboxylic acid represented by the above general formula in the presence of an aromatic phosphite and a pyridine derivative. This can be carried out by reacting at a temperature of 20 to 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 amounts of the diamine represented by the above general formula and the dicarboxylic acid represented by the above general formula, and when equimolar amounts of these reaction components are used, the molecular weight becomes high. A polyamide resin having a molecular weight represented by the above general formula can be produced. Aromatic phosphites used in the present invention include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, and tri-m-tolyl phosphite. , di-m-tolyl phosphite, tri-p-tolyl phosphite, di-p-tolyl phosphite, tri-o phosphite
-chlorophenyl, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, di-p-chlorophenyl phosphite, and the like. The pyridine derivatives used in the present invention include pyridine, 2-picoline, 3-picoline, 4-picoline,
-Picoline, 2,4-lutidine, 2,6-lutidine, 3,5-lutidine, etc. can be mentioned. Typical organic solvents that can be used in this method are amide solvents such as N-methylpyrrolidone and N,N-dimethylacetamide. In order to obtain a polyamide resin with a high degree of polymerization, inorganic salts such as lithium chloride and calcium chloride,
Organic salts such as triethylamine hydrochloride, tetrabutylammonium chloride, cetyltrimethylammonium chloride, etc. can also be added to this reaction system. The polyamide resin represented by the above general formula produced in this manner is particularly sensitive to the type of the diamine represented by the above general formula used, the dicarboxylic acid dihalide represented by the above general formula used, or the dicarboxylic acid represented by the above general formula. Although the solubility changes, chloroform, tetrachloroethane, N,N-dimethylformamide, N,
It becomes soluble in all or part of solvents such as N-dimethylacetamide, dimethylsulfoxide, cresol, chlorobenzene, o-chlorophenol, and pyridine. The polyamide resin represented by the above general formula shows no significant weight change even when heated to around 400°C. (Example) Hereinafter, the present invention will be explained in more detail by reference examples and examples. Reference example 1 30.24 g (0.54 mol) of KOH in 200 ml of ethanol,
Dissolve 56.5g (0.6mol) of phenol, 2,4-
121.2 g (0.6 mol) of dinitrochlorobenzene was added and stirred at 75°C for 8 hours. After the reaction, the mixture was filtered while hot, and ethanol was distilled off under reduced pressure to obtain a product. The resulting pure 2,4-dinitrodiphenyl ether was obtained by recrystallization from ethanol. Yield: 108.6g (70%). Melting point 70-71°C (literature value 69-70°C). Reference Example 2 10.4 g (0.04 mol) of 2,4-dinitrodiphenyl ether was dissolved in 100 ml of ethanol, and a reduction reaction was carried out by hydrogenation using 1.3 g of 10% palladium activated carbon as a catalyst. After the reaction, the palladium activated carbon was filtered, 20 ml of concentrated hydrochloric acid was added to the filtrate, and the solvent was distilled off under reduced pressure. The obtained 2,4-diaminodiphenyl ether hydrochloride was recrystallized from a benzene-ethanol system. Yield 7.53g (69%). Next, 7.08 g (0.03 mol) of 2,4-diaminodiphenyl ether hydrochloride was dissolved in 100 ml of water containing hydrosulfite, and 2.8 g of sodium hydroxide was added.
An alkaline aqueous solution prepared from g (0.07 mol) and 25 ml of water was added dropwise. The precipitated 2,4-diaminodiphenyl ether was filtered, dried, and then recrystallized from benzene. Yield 12.47g (42%). Melting point 65-67°C (literature value 67°C). Example 1 Isophthalic acid 0.83g (5mmol), 2,4-diaminodiphenyl ether 1.00g (5mmol), triphenyl phosphite 3.10g (10mmol), pyridine
2.5ml, lithium chloride 1.00g and N-methyl-
10 ml of 2-pyrrolidone was stirred at 100° C. for 3 hours under a nitrogen atmosphere. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Yield 1.65g
(100%). Intrinsic viscosity 0.63 (concentration of 0.5 g/dL in sulfuric acid,
(measured at 30°C). 10% weight loss temperature by thermogravimetry, 435°C Glass transition temperature, 220°C by thermomechanical measurement The solubility of the produced polymer is shown in Table 1. Example 2 2,4-diaminodiphenyl ether 1.00g
(5 mmol) was dissolved in 10 ml of N,N-dimethylacetamide and completely frozen on a dry ice-acetone bath. 1.02 g (5 mmol) of isophthalic acid chloride was added to the generated solid, and the mixture was stirred at 0° C. under a nitrogen atmosphere for 3 hours. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Yield 1.59g (96
%). Intrinsic viscosity 0.30 (concentration of 0.5 g/dL in sulfuric acid, 30
(measured in °C). Example 3 Terephthalic acid 0.83g (5mmol), 2,4-diaminodiphenyl ether 1.00g (5mmol), triphenyl phosphite 3.10g (10mmol), pyridine
2.5ml, lithium chloride 1.00g and N-methyl-
10 ml of 2-pyrrolidone was stirred at 100° C. for 3 hours under a nitrogen atmosphere. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Yield 1.65g (100
%). Intrinsic viscosity 0.84 (concentration of 0.5 g/dL in sulfuric acid, 30
(measured in °C). 10% weight loss temperature by thermogravimetry, 400°C Glass transition temperature, 265°C by thermomechanical measurement The solubility of the produced polymer is shown in Table 1. Example 4 2,4-diaminodiphenyl ether 1.00g
(5 mmol) was dissolved in 10 ml of N,N-dimethylacetamide and completely frozen on a dry ice-acetone bath. 1.02 g (5 mmol) of terephthalic acid chloride was added to the generated solid, and the mixture was stirred at 0° C. under a nitrogen atmosphere for 3 hours. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Yield 1.65g (100
%). Intrinsic viscosity 0.74 (concentration of 0.5 g/dL in sulfuric acid, 30
(measured in °C). Example 5 1.08 g of 2,6-naphthalene dicarboxylic acid
(5mmol), 2,4-diaminodiphenyl ether 1.00g (5mmol), triphenyl phosphite 3.10
g (10 mmol), pyridine 2.5 ml, lithium chloride
1.00g and 10ml N-methyl-2-pyrrolidone
was stirred at 100°C for 3 hours under a nitrogen atmosphere.
After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Yield 1.90g (97%). Intrinsic viscosity 0.99 (measured at a concentration of 0.5 g/dL in sulfuric acid at 30°C). 10% weight loss temperature by thermogravimetry, 414°C Glass transition temperature, 251°C by thermomechanical measurement The solubility of the produced polymer is shown in Table 1. Example 6 Terephthalic acid 0.83g (5mmol), 2,4-diaminodiphenyl ether 0.40g (2mmol), 4,
4′-oxydianiline 0.60g (3mmol), triphenyl phosphite 3.10g (10mmol), pyridine 2.5
ml, 1.00 g of lithium chloride and N-methyl-2-
10 ml of pyrrolidone was stirred at 100° C. for 3 hours under a nitrogen atmosphere. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Yield 1.61g (97%).
Intrinsic viscosity 1.17 (measured at a concentration of 0.5 g/dL in sulfuric acid at 30°C). 10% weight loss temperature by thermogravimetry, 425°C Glass transition temperature, 255°C by thermomechanical measurement The solubility of the produced polymer is shown in Table 1. Example 7 Terephthalic acid 0.83g (5mmol), 2,4-diaminodiphenyl ether 0.60g (3mmol), 4,
4′-oxydianiline 0.40g (2mmol), triphenyl phosphite 3.10g (10mmol), pyridine 2.5
ml, 1.00 g of lithium chloride and N-methyl-2-
10 ml of pyrrolidone was stirred at 100° C. for 3 hours under a nitrogen atmosphere. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Yield 1.65g (100%).
Intrinsic viscosity 1.13 (measured at a concentration of 0.5 g/dL in sulfuric acid at 30°C). 10% weight loss temperature by thermogravimetry, 410°C Glass transition temperature, 255°C by thermomechanical measurement The solubility of the produced polymer is shown in Table 1. Example 8 Terephthalic acid 0.83g (5mmol), 2,4-diaminodiphenyl ether 0.80g (4mmol), 4,
4′-oxydianiline 0.20g (1mmol), triphenyl phosphite 3.10g (10mmol), pyridine 2.5
ml, 1.00 g of lithium chloride and N-methyl-2-
10 ml of pyrrolidone was stirred at 100° C. for 3 hours under a nitrogen atmosphere. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Yield 1.61g (98%).
Intrinsic viscosity 0.96 (measured at a concentration of 0.5 g/dL in sulfuric acid at 30°C). 10% weight loss temperature by thermogravimetry, 400°C Glass transition temperature, 250°C by thermomechanical measurement The solubility of the produced polymer is shown in Table 1. Example 9 Terephthalic acid 0.415g (2.5mmol), isophthalic acid 0.415g (2.5mmol), 2,4-diaminodiphenyl ether 1.00g (5mmol), triphenyl phosphite 3.10g (10mmol), pyridine 2.5ml, chloride 1.00 g of lithium and 10 ml of N-methyl-2-pyrrolidone were stirred at 100° C. for 3 hours under a nitrogen atmosphere. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Yield 1.65g (100%). intrinsic viscosity
0.66 (concentration of 0.5 g/dL in sulfuric acid, measured at 30°C). 10% weight loss temperature by thermogravimetry, 430°C Glass transition temperature, 230°C by thermomechanical measurement The solubility of the produced polymer is shown in Table 1.

【table】

[Table] (Effects of the Invention) The present invention provides a polyamide resin represented by the above general formula and an advantageous method for producing this polyamide resin. The polyamide resin of the present invention is different from conventional aromatic polyamide resins in that it is insoluble in organic solvents,
Whereas it was thermally infusible and had problems with moldability, it has a high glass transition temperature, is soluble in various organic solvents, can be solution molded, and can be heat molded. It has high industrial value as an engineering plastic.

Claims (1)

[Claims] 1. General formula (wherein R is at least one arylene group,
Ar contains at least 20 mol% of 1-phenoxy-2,
Arylene group consisting of 4-phenylene group, n is 10
(denoting an integer of ~200). 2 At least one diamine represented by the general formula H ₂ N-Ar-NH ₂ (in the formula, Ar represents an arylene group in which at least 20 mol% is a 1-phenoxy-2,4-phenylene group); formula (wherein, R represents an arylene group and X represents a halogen atom) is reacted with at least one dicarboxylic acid dihalide represented by the general formula (In the formula, R and Ar have the same meanings as above, and n
represents an integer from 10 to 200) A method for producing a polyamide resin, characterized in that a polyamide resin is obtained. 3 At least one diamine represented by the general formula H ₂ N-Ar-NH ₂ (in the formula, Ar represents an arylene group in which at least 20 mol% is a 1-phenoxy-2,4-phenylene group); formula (In the formula, R represents an arylene group) is reacted with at least one dicarboxylic acid represented by the following in the presence of an aromatic phosphite and a pyridine derivative in an organic solvent to form the general formula (In the formula, R and Ar have the same meanings as above, and n
represents an integer from 10 to 200) A method for producing a polyamide resin, characterized in that a polyamide resin is obtained.