JPH0670135B2 - Method for producing aromatic polythioether amide polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aromatic polyamide. The aromatic polyamide obtained by the method of the present invention has excellent heat resistance and moldability, and is useful as a fiber film or coating material.

[0002]

2. Description of the Related Art An aromatic polyamide resin synthesized from an aromatic diamine and an aromatic dicarboxylic acid or a chloride thereof has been actively researched and developed due to its excellent heat resistance and flame retardancy. However, aromatic polyamides generally have a high melting point, and many have a melting point above the thermal decomposition initiation temperature in air, making injection molding and extrusion molding difficult. Also, the solubility in ordinary organic solvents is poor,
It is extremely inconvenient when forming fibers, films or coatings. Therefore, the processability is improved by lowering the melting point of the copolymer or dissolving it in a solvent.

As such an aromatic polyamide having improved processability, (a) a method of copolymerizing an aliphatic component (JP-A-52-109592, JP-A-53-94397).
(B), a method of introducing a linking functional group into the main chain or imparting flexibility (US Pat. No. 3,505,288, JP-A-52-23198, JP-A-53-10469).
5) and (c) a method of randomly copolymerizing an aromatic component (JP-A-53-104697 and JP-A-56-88427).
Publication, U.S. Pat. No. 4,410,684) and the like are known.

[0004]

However, the polyamides obtained by these techniques are not sufficient in terms of balance between processability and heat resistance. The present invention provides a method for producing an aromatic polyamide in which molding processability and heat resistance are well balanced.

[0005]

That is, the present invention provides the following general formula (I)

[Chemical 2]

[Wherein, X is a divalent hydrocarbon group having 1 to 10 carbon atoms, —O—, —SO—, —SO ₂ — or —CO—
Indicates. a is 0 or 1, and when a is 0, X
None means that aromatic rings are bonded to each other. Y is an alkyl group having 1 to 20 carbon atoms, 3 to 2 carbon atoms
It represents a cycloalkyl group having 0, an aralkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen group or a nitro group, which may be the same or different from each other. b and c are the same or different from each other 0 to 4
Represents the integer. ] An aromatic polythioether amide polymer having a well-balanced molding processability and heat resistance, which is characterized by reacting an aromatic diamine containing 50 mol% or more of the diamine represented by the above with an aromatic dicarboxylic acid chloride. A method of manufacturing is provided.

(Aromatic Diamine) Specific examples of the aromatic diamine having a thioether bond represented by the general formula (I) used in the present invention are 2,2-bis (4- (4-aminophenylthio)). Phenyl) propane, 1,1,1,
3,3,3-hexafluoromethyl-2,2-bis [4
-(4-aminophenylthio) phenyl] propane,
4,4'-bis (4-aminophenylthio) diphenyl ether, 4,4'-bis (4-aminophenylthio)
Benzophenone, 4,4'-bis (4-aminophenylthio) diphenyl sulfoxide, 4,4'-bis (4-
Aminophenylthio) diphenyl sulfone, 3,3′-
Bis (4-aminophenylthio) diphenyl sulfone,
4,4'-bis (4-aminophenylthio) biphenyl, 2,2 ', 6,6'-tetramethyl-4,4'-bis (4-aminophenylthio) biphenyl and the like can be used.

Part of these aromatic diamines (50 mol%
Hereinafter, preferably 5 to 30 mol%) may be replaced with another aromatic diamine to improve the solubility and moldability of the resulting aromatic polyamide. As such an aromatic diamine, the following general formula (II)

[Chemical 3]

[In the formula, Y is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and 6 to 2 carbon atoms.
It represents an aralkyl group of 0, an aryl group of 6 to 20 carbon atoms, a halogen group or a nitro group, which may be the same or different from each other. d is a number between 0 and 20,
e and f represent the same or different integers of 0-4. Aromatic diamines or represented by], aromatic diamine _{H 2 N-Ar'-NH 2} (III) wherein represented by the following general formula (III), Ar 'is an aromatic ring having from 6 to 30 carbon atoms Is. ] Is mentioned.

As the aromatic diamine represented by the above formula (II), 4,4'-bis (4-aminophenylthio) diphenyl sulfide, 1,4-bis (4-aminophenylthio) benzene, 1 , 3-bis (4-aminophenylthio) benzene, α, ω-diaminopoly (1,4-phenylene) oligomer, and the like.

As the aromatic diamine represented by the formula (III), p-phenylenediamine, m-phenylenediamine, 4-methyl-1,3-phenylenediamine, 5
-Methyl-1,3-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,
4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, 2,
2-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,4-bis (4
-Aminobenzenesulfonyl) benzene, 4,4'-bis (4-aminophenoxy) diphenyl ether, 4,
4'-bis (4-aminophenoxy) diphenyl sulfide, 4,4'-bis (4-aminophenoxy) benzophenone, 4,4'-bis (4-aminophenoxy) diphenyl sulfone, 4,4'-bis (4-aminophenoxy) diphenylmethane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 4,4'-bis (4-aminobenzoyl) diphenyl ether, 4,
4'-bis (4-aminobenzoyl) benzophenone,
4,4'-bis (4-aminobenzoyl) diphenyl sulfoxide, 4,4'-bis (4-aminobenzoyl)
Diphenyl sulfone, 4,4'-bis (4-aminobenzoyl) diphenylmethane, 2,2-bis (4- (4-
Aminobenzoyl) phenyl) propane, 4,4'-bis (4-aminobenzenesulfonyl) diphenyl ether, 4,4'-bis (4-aminobenzenesulfonyl)
Diphenyl sulfide, 4,4'-bis (4-aminobenzenesulfonyl) benzophenone, 4,4'-bis (4-aminobenzenesulfonyl) diphenyl sulfoxide, 4,4'-bis (4-aminobenzenesulfonyl) diphenyl Examples thereof include sulfone, 4,4'-bis (4-aminobenzenesulfonyl) diphenylmethane, and 2,2-bis [4- (4-aminobenzenesulfonyl) phenyl] propane.

(Aromatic dicarboxylic acid chloride) Examples of the aromatic dicarboxylic acid chloride used in the present invention include terephthalic acid chloride, isophthalic acid chloride, 4,4'-biphenyldicarboxylic acid chloride,
4,4'-diphenyl ether dicarboxylic acid chloride, 4,4'-diphenyl sulfide dicarboxylic acid chloride, 4,4'-benzophenone dicarboxylic acid chloride, 4,4'-diphenyl sulfone dicarboxylic acid chloride, 4,4'-diphenylmethane Examples thereof include dicarboxylic acid chloride and 1,5-naphthalene dicarboxylic acid chloride.

(Production of Polyamide) In the present invention, the reaction between the aromatic diamine and the aromatic dicarboxylic acid chloride is carried out by an interfacial polycondensation method, a solution polycondensation method or the like.
For the interfacial polycondensation method, a known water-soluble neutralizing agent is used. For example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogen carbonate can be mentioned. The amount of alkali used is in the range of 0.3 to 3 equivalents relative to the number of moles of the reactive groups of the aromatic dicarboxylic acid chloride, preferably 0.5 to
It is 1.5 equivalents. Dispersing an aromatic diamine in a water solvent containing the above water-soluble neutralizing agent, and by adding a solution of an aromatic dicarboxylic acid chloride dissolved in an organic solvent to the reaction to produce an aromatic polythioether amide You can

Examples of the above organic solvent include ketone solvents such as cyclohexanone, diisobutyl ketone, acetophenone and p-methylacetophenone, or methylene chloride,
Examples thereof include halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, 1,1,1-trichloroethane and 1,1,2,2-tetrachloroethane. Cyclohexanone, p-methylacetophenone and the like are preferable for obtaining a high molecular weight product. The reaction temperature is in the range of 0 to 100 ° C, preferably 3 to 50 ° C. Reaction time is 1 minute to 1
It is 0 hour, preferably 5 minutes to 3 hours.

In the case of the solution polycondensation method, a known tertiary amine may be used as a neutralizing agent. Examples thereof include triethylamine, tributylamine, pyridine, quinoline, pyrimidine, and 2,6-lutidine.
However, these compounds are not necessarily added when the organic acid amide is used as the reaction solvent. When the neutralizing agent is used, it is preferably used in an amount of 0.3 to 3.0 equivalents based on the number of moles of the reactive groups of the aromatic dicarboxylic acid chloride. On the other hand, organic acid amides and organic sulfoxides are preferable as the reaction solvent. For example, N, N
-Dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-methyl-ε-caprolactam, hexamethylphosphoramide, tetramethylurea, dimethylsulfoxide and the like can be mentioned. An aromatic diamine is dissolved in the above reaction solvent, a neutralizing agent is added if necessary, and an aromatic dicarboxylic acid chloride is added to this solution and reacted to produce a polyamide having the following repeating unit. be able to.

[0016]

[Chemical 4]

This polyamide may have the following units in the polyamide molecule by using the aromatic diamine represented by the above formula (II) or formula (III).

[0018]

[Chemical 5]

When polyamide is produced by adding 5 to 10% by weight of lithium chloride, calcium chloride, calcium rhodanide and the like to the reaction system, the solubility is significantly increased, which may be advantageous. In this case, the reaction temperature is -30 to + 100 ° C,
It is preferably in the range of -20 ° C to + 30 ° C. The reaction time is in the range of 5 minutes to 10 hours, preferably 30 minutes to 5 hours.

(Purification) A solution containing the aromatic polythioether amide polymer produced by the above-mentioned method is diluted with a solvent which does not dissolve the polymer and is easily compatible with the reaction solvent, to precipitate the polymer. And the polyamide is isolated by filtering this. The glass transition temperature of the polyamide thus obtained is about 150 to about that of the homopolymer.
280 ° C, that of the copolymer is about 200-350 ° C.

(Processing and Use) When the polymer obtained by the method of the present invention is molded and processed, various known filler components may be contained. As typical examples of the filler component, (a) fibrous filler: glass fiber, carbon fiber, boron fiber, aramid fiber, alumina fiber, silicon = carbite fiber, etc., (b) inorganic filler: mica, Talc, clay, graphite, carbon black, silica, asbestos, molybdenum sulfide, magnesium oxide,
Calcium oxide etc. can be mentioned. The polymer obtained by the method of the present invention, various parts in the electrical and electronic fields, housings, automobile parts, aircraft interior materials, sliding parts, gears, insulating materials, heat resistant films, heat resistant varnishes,
It can be used in a wide range such as heat resistant fibers.

[0022]

EXAMPLES Next, the present invention will be described more specifically by way of examples. Example 1 A stirring rod, a thermometer, and a dropping funnel were set in a 1-liter three-necked flask, and 2.0 g of sodium hydroxide was dissolved in 40 ml of water and placed in the flask. Then 4,4'-
5.80 g of bis (4-aminophenylthio) diphenyl sulfone and 2.50 g of 4,4′-diaminodiphenyl ether were added, and the mixture was vigorously stirred at 5 ° C. and dispersed in an aqueous solution.

On the other hand, 2.54 g of terephthaloyl chloride
And 2.54 g of isophthalic acid chloride were dissolved in 120 ml of cyclohexanone, and this acid claroid solution was poured into the flask from a dropping funnel. At this time, the reaction temperature was kept at 15 ° C. or lower. After 20 minutes, water 10 was added to the reaction solution.
0 ml and 80 ml of cyclohexanone were added, and then 200 ml of acetone was poured in to precipitate the polymer.

The polymer was filtered off, washed with hot water and then dried in a vacuum oven (100 ° C., 8 hours). Yield 11.6g
(Yield 100%). The glass transition temperature of this polymer is 2
It was 08 ° C. The intrinsic viscosity is 0.89 dl / g
(0.5% DMSO solution, 30 ° C.). The infrared absorption spectrum of this polymer was measured and found to be 164
Absorption derived from amide 0,1515cm ^-1, 1240
absorption derived from ether cm ^-1, absorption derived from sulfone 1145cm ^-1, absorption derived from thioether to 1070 cm ^-1, the absorption derived from the aromatic ring 805cm ^-1 was observed.

Example 2 A raw material having the following composition was used and manufactured in the same manner as in Example 1. (1) Sodium hydroxide 2.0 g Water 40 ml 4,4'-bis (4-aminophenylthio) biphenyl 10.0 g (2) Terephthalic acid chloride 2.54 g Isophthalic acid chloride 2.54 g Cyclohexanone 120 ml Polymer yield 13.2 g (100%). Glass transition temperature 250 ° C. Intrinsic viscosity 0.45 dl / g (0.2% NMP
Solution, 30 ° C). IR spectrum: 1640, 1520 cm ^-1 (amide), 1080 cm ^-1 (thioether), 805 cm ^-1
(Aromatic ring).

Example 3 A stirring rod, a thermometer and a dropping funnel were set in a 500 ml three-necked flask, and 10.7 g of 4,4'-bis (4-aminophenylthio) benzophenone was added to 50 ml of dry N-methylpyrrolidone. Melted and placed in a flask. -5
A solution of 5.08 g of isophthalic acid chloride in 50 ml of dry N-methylpyrrolidone was poured into the flask from a dropping funnel while stirring at 0 ° C. At this time, the reaction temperature was kept at 0 ° C or lower. Stirring was continued at 0 ° C. for 2 hours, after which the reaction solution was poured into acetone to precipitate the polymer.

The polymer was filtered off, washed with hot water and then dried in a vacuum oven (100 ° C., 8 hours). Yield of polymer 14.0 g (100%). Glass transition temperature 231 ° C, softening point 310 ° C. Intrinsic viscosity 0.99 dl / g (0.5% D
MSO solution, 30 ° C). Infrared absorption IR spectrum: 1640, 1512 cm ^-1
(Amide), 1640 cm ^-1 (ketone), 1070 cm
^-1 (thioether), 810 cm ^-1 (aromatic ring).

Example 4 A polyamide was produced in the same manner as in Example 1, using the raw materials having the following composition. (1) Sodium hydroxide 2.0 g Water 40 ml 4,4'-bis (4-aminophenylthio) benzophenone 10.7 g (2) Terephthalic acid chloride 2.54 g Isophthalic acid chloride 2.54 g Cyclohexanone 120 ml Polymer yield 14.0 g (100%). Glass transition temperature 229 ° C, softening point 322 ° C. Intrinsic viscosity 0.45 dl / g
(0.5% DMSO solution, 30 ° C.). Intrinsic viscosity 0.45
dl / g (0.2% NMP solution, 30 ° C.). IR spectrum: 1645, 1520 cm ^-1 (amide), 1645 cm ^-1 (ketone), 1080 cm ^-1 (thioether), 825 cm ^-1 (aromatic ring).

Example 5 A raw material having the following composition was used, and the same apparatus and method as in Example 1 were used. (1) Sodium hydroxide 2.0 g Water 40 ml 4,4'-bis (4-aminophenylthio) benzophenone 10.7 g (2) Terephthalic acid chloride 1.02 g Isophthalic acid chloride 4.06 g Cyclohexanone 120 ml Yield 13.9 g ( 99%). Glass transition temperature 227 ° C,
Softening point 300 ° C. Intrinsic viscosity 0.88 dl / g (0.5%
DMSO solution, 30 ° C). IR spectrum: 1640,1510cm ^-1 (amide), 1640 cm ^-1 (ketone), 1070 cm ^-1 (thioether), 810 cm ^-1 (aromatic ring). When this polymer was compression molded at 320 ° C., a light yellow tough resin plate was obtained.

Example 6 A polyamide was produced in the same manner as in Example 1 by using the raw materials having the following compositions. (1) Sodium hydroxide 2.0 g Water 40 ml 4,4'-bis (4-aminophenylthio) diphenyl sulfone 11.6 g (2) Isophthalic acid chloride 5.08 g Cyclohexanone 120 ml Yield 14.7 g (99%). Glass transition temperature 188 ° C,
Softening point 262 ° C. Intrinsic viscosity 0.41 dl / g (0.5%
DMSO solution, 30 ° C). IR spectrum: 1650, 1510 cm ^-1 (amide), 1150 cm ^-1 (sulfone), 1070 cm
^-1 (thioether), 810 cm ^-1 (aromatic ring).

Example 7 A polyamide was produced in the same manner as in Example 1 by using the raw materials having the following compositions. (1) Sodium hydroxide 2.0 g Water 40 ml 4,4'-bis (4-aminophenylthio) diphenyl sulfone 11.6 g (2) Terephthalic acid chloride 2.54 g Isophthalic acid chloride 2.54 g Cyclohexanone 120 ml Yield 14.9 g (100%). Glass transition temperature 199
C., softening point 284.degree. Intrinsic viscosity 0.63 dl / g (0.
5% DMSO solution, 30 ° C). IR spectrum: 1640, 1510 cm ^-1 (amide), 1150 cm ^-1 (sulfone), 1070 cm
^-1 (thioether), 815 cm ^-1 (aromatic ring).

Example 8 A polyamide was produced in the same manner as in Example 1 by using the raw materials having the following compositions. (1) Sodium hydroxide 2.0 g Water 40 ml 4,4'-bis (4-aminophenylthio) diphenyl sulfone 5.80 g (50 mol%) 1,4-bis (4-aminophenylthio) benzene 4.05 g (50 mol%) (2) Isophthalic acid chloride 2.54 g Cyclohexanone 120 ml Yield 13.1 g (100%). Glass transition temperature 243
° C. Intrinsic viscosity 0.54 dl / g (0.5% DMSO solution, 30 ° C.). IR spectrum: 1640, 1510 cm ^-1 (amide), 1145 cm ^-1 (sulfone), 1070 cm
^-1 (thioether), 805 cm ^-1 (aromatic ring).

Example 9 A polyamide was produced in the same manner as in Example 1 by using the raw materials having the following compositions. (1) Sodium hydroxide 2.0 g Water 40 ml 4,4'-bis (4-aminophenylthio) diphenyl sulfone 5.80 g (50 mol%) 1,4-bis (4-aminophenylthio) diphenyl sulfide 5. 40 g (50 mol%) (2) Terephthalic acid chloride 2.54 g Isophthalic acid chloride 2.54 g Cyclohexanone 120 ml Yield 14.5 g (99%). Glass transition temperature 230 ° C.
Intrinsic viscosity 0.55 dl / g (0.5% DMSO solution, 3
0 ° C). IR spectrum: 1640, 1510 cm ^-1 (amide), 1145 cm ^-1 (sulfone), 1070 cm
^-1 (thioether), 805 cm ^-1 (aromatic ring).

Example 10 A polyamide was produced in the same manner as in Example 1, using the raw materials having the following compositions. (1) Sodium hydroxide 2.0 g Water 40 ml 4,4'-bis (4-aminophenylthio) benzophenone 5.35 g (50 mol%) 4,4'-diaminodiphenyl ether 2.50 g (50 mol%) (2 ) Terephthalic acid chloride 2.54 g Isophthalic acid chloride 2.54 g Cyclohexanone 120 ml Yield 11.2 g (100%). Glass transition temperature 241
° C. Intrinsic viscosity 0.88 dl / g (0.5% DMSO solution, 30 ° C.). IR spectrum: 1640,1510cm ^-1 (amide), 1640 cm ^-1 (ketone), 1240 cm ^-1 (ether), 1070 cm ^-1 (thioether), 805c
m ^-1 (aromatic ring).

Example 11 A polyamide was produced in the same manner as in Example 1 using the raw materials having the following compositions. (1) Sodium hydroxide 2.0 g Water 40 ml 4,4'-bis (4-aminophenylthio) benzophenone 5.35 g (50 mol%) 1,4-bis (4-aminophenylthio) benzene 4.05 g ( 50 mol%) (2) Terephthalic acid chloride 2.54 g Isophthalic acid chloride 2.54 g Cyclohexanone 120 ml Yield 12.7 g (100%). Glass transition temperature 232
° C. Intrinsic viscosity 0.61 dl / g (0.5% DMSO solution, 30 ° C.). When this polymer was compression-molded at 300 ° C., an ocher-colored tough resin plate was obtained. IR spectrum: 1640,1510cm ^-1 (amide), 1640 cm ^-1 (ketone), 1070 cm ^-1 (thioether), 805cm ^-1 (aromatic ring).

[0036]

INDUSTRIAL APPLICABILITY According to the method of the present invention, injection molding and extrusion molding can be carried out with well-balanced molding processability and heat resistance.
An aromatic polyamide having excellent heat resistance and useful as a fiber film or coating material can be obtained.

Claims (3)

[Claims] 1. A compound represented by the general formula (I): [In the Formula, X is a C1-C10 bivalent hydrocarbon group, -O.
-, - SO -, - shows or -CO- - SO _2. a is 0 or 1, and when a is 0, X means that the aromatic rings are bonded to each other. Y is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, and 6 to 2 carbon atoms.
0 represents an aryl group, a halogen group or a nitro group, which may be the same or different from each other. b and c represent the same or different integers of 0-4. ] The manufacturing method of the aromatic polythioether amide polymer characterized by making an aromatic diamine containing 50 mol% or more of the diamine shown by this, and an aromatic dicarboxylic acid chloride react. 2. The method according to claim 1, wherein the aromatic diamine is dispersed in an alkaline aqueous solution, a solution of aromatic dicarboxylic acid chloride in an organic solvent is added to the dispersion, and the reaction is carried out by an interfacial polycondensation method. Method. 3. The method according to claim 1, wherein the aromatic diamine is dissolved in an organic acid amide or an organic sulfoxide, and the aromatic dicarboxylic acid chloride is added thereto and the reaction is carried out by a solution polycondensation method.