JPH0912878A - Method for producing wholly aromatic polyamide copolymer composite - Google Patents

Abstract

(57) [Abstract] [Purpose] Improving the solubility of wholly aromatic polyamide, which is a reinforcing polymer, in organic solvents, and dispersing it well in a matrix polymer to obtain a molded product with excellent mechanical strength. Provided is a method for producing a possible molecular composite material. [Structure] A matrix polymer and a wholly aromatic polyamide copolymer having side chains are dissolved in an organic solvent to prepare a solution containing 13-40
By preparing a solution of 1% by weight and charging it in a non-solvent such as alcohol, a molecular composite material comprising a matrix polymer and a wholly aromatic polyamide copolymer having side chains is obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a molecular composite material comprising a matrix polymer and a wholly aromatic polyamide copolymer having side chains, and is particularly excellent in mechanical properties and the like, and is used in aircraft, automobiles, space equipment, etc. The present invention relates to a molecular composite material suitable for use as a structural material of.

[0002]

2. Description of the Related Art In recent years, so-called engineering plastics having excellent mechanical properties and heat resistance have been widely used for the purpose of reducing the weight of aircraft and automobiles. Further, in order to improve strength and rigidity, development of composite materials such as FRP in which a plastic material and a high-strength and highly-elastic fiber such as carbon fiber are combined has been actively developed and widely used in practice. There is.

It is known that the strength of these composite materials is greatly influenced by the interfacial adhesion between the fiber and the matrix resin in addition to the strength of the plastic used as the matrix and the fiber itself used as the reinforcing material. . Further, whether the impregnability of the matrix resin into the fiber reinforced preform is good or bad affects not only the viewpoint of manufacturing but also the strength of the product. Under these circumstances, even if a fiber or resin having high strength and high elasticity is used as a material, it is not always possible to obtain a composite material having excellent strength.

Therefore, a so-called rigid polymer such as an aromatic polyamide is finely dispersed to a molecular level in a polymer serving as a matrix resin to overcome the above problems as a so-called polymer blend type composite material (molecular composite material). , An attempt to obtain a high-strength composite material has been proposed and researched.

The aromatic polymer preferably used as a reinforcing component of the molecular composite material is, for example, one having a hetero ring such as a thiazole ring, an imidazole ring, an oxazole ring or an oxazine ring in a repeating unit, or a wholly aromatic polyamide. and so on.

[0006]

However, even if a reinforcing polymer such as wholly aromatic polyamide is simply mixed with a matrix polymer to produce a molecular composite material, the wholly aromatic polyamide is generally dissolved in an organic solvent. However, the compatibility between the wholly aromatic polyamide and the matrix polymer is not generally good, and it is difficult to obtain a uniform dispersion of the wholly aromatic polyamide in the matrix polymer. Unless the reinforcing aromatic wholly aromatic polyamide is uniformly dispersed in the matrix polymer, a molecular composite material having excellent mechanical properties cannot be obtained. Further, in general, different kinds of polymers have poor compatibility, and even if they are subjected to molecular complexation, large phase separation occurs during melt molding.

The present invention has been made against the background of the above conventional technical problems, and solves the above problems and improves the solubility of wholly aromatic polyamide as a reinforcing polymer in organic solvents. To improve the physical properties of the molded product, such as obtaining a composite material that can be well dispersed in the matrix polymer, phase separation does not easily occur during melt molding, and thus a molded product excellent in mechanical strength can be obtained. An object of the present invention is to provide a method for producing a molecular composite material that can be manufactured.

[0008]

According to the present invention, a matrix polymer and side chains are introduced into a non-solvent by adding a 13-40% by weight organic solvent solution of a wholly aromatic polyamide copolymer having side chains. A method for producing a wholly aromatic polyamide copolymer composite material, which comprises obtaining a molecular composite material comprising the wholly aromatic polyamide copolymer.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, examples of the matrix polymer include polyamide, polyimide, polyamideimide, aramid resin (aromatic polyamide), polyether sulfone and polyether imide.
These resins have good compatibility with the wholly aromatic polyamide copolymer and can provide a molecular composite material having excellent mechanical strength. As the matrix polymer, an aromatic polyamide is particularly preferred.

Next, a wholly aromatic polyamide copolymer having a side chain will be described. In the present invention, as the wholly aromatic polyamide copolymer to be the reinforcing polymer of the molecular composite material, a polyamide obtained from an aromatic diaminodithiol compound in which a hydrogen atom of a thiol group is substituted with a substituted or unsubstituted alkyl group and a dicarboxylic acid is used. Examples thereof include random copolymers or block copolymers (hereinafter referred to as “dithiol-based copolymers”) including, random copolymers or block copolymers including polyamide obtained from an aromatic diaminodihydroxy compound and dicarboxylic acid (hereinafter referred to as “dihydroxy-based copolymer”), and the like. Among them, preferred are random copolymers containing a polyamide obtained from an aromatic diaminodithiol compound in which a hydrogen atom of a thiol group is substituted with a substituted or unsubstituted alkyl group and a dicarboxylic acid.

All of these wholly aromatic polyamide copolymers have side chains. Examples of the side chain include halogen, a lower alkyl group, a lower alkoxy group, a phenyl group and the like. By introducing such a side chain, the solubility in a solvent can be improved.

First, the dithiol random copolymer will be described. (1) Production of Dithiol Random Copolymer The dithiol random copolymer is represented by the following formula (Formula 1).

[0013]

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(Wherein Ar and Ar 'are aromatic residues, R is a substituted or unsubstituted alkyl group, and X is
Is a residue of a dicarboxylic acid derivative, m and n are both integers, and m: n is 0.01: 99.99 to 99.
It is 99: 0.01. ) If m is less than 0.01, there is no reinforcing effect, while 99.9.
If it exceeds 9, there is no effect as a composite material.

The dithiol-based random copolymer is
(A) an aromatic diaminodithiol compound in which a hydrogen atom of a thiol group is substituted with a substituted or unsubstituted alkyl group,
It can be produced from (b) an aromatic diamino compound and (c) a dicarboxylic acid derivative.

(A) Substituting a hydrogen atom of a thiol group or
Aromatic diaminodithio substituted with an unsubstituted alkyl group
In the present invention, the aromatic diaminodithiol compound (hereinafter referred to as “compound (a)”) in which the hydrogen atom of the (a) thiol group is substituted with a substituted or unsubstituted alkyl group is represented by the following general formula (Formula 2) It is represented by.

[0017]

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(However, Ar is an aromatic residue, and R is a substituted or unsubstituted alkyl group.) Here, the aromatic residue Ar is not limited to a benzene ring and is not limited to two or more benzene rings. It may be a condensed aromatic ring, or may be one in which two or more benzene rings are bonded, such as biphenyl. The positions of the amino group and the thioether group on both sides may be left-right symmetric or point-symmetric with respect to the aromatic residue. Specific examples of the compound (a) include the following (Chemical Formula 3).

[0019]

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The compound (a) can be synthesized from an aromatic diaminodithiol compound which is a compound having an amino group and a thiol group on both sides of an aromatic residue. As the aromatic diaminodithiol compound, those in which the alkyl group R of each compound shown in the above (formula 3) is replaced with a hydrogen atom can be used, but this aromatic diaminodithiol compound is used in order to prevent deterioration. It is used in the form of a salt such as hydrochloride.

The alkyl group R bonded to the thiol group of the aromatic diaminodithiol compound is a substituted or unsubstituted alkyl group. Examples of the unsubstituted alkyl group include isopropyl group, ethyl group, n-propyl group, n-butyl group,
Examples thereof include sec-butyl group and tert-butyl group. As the alkyl group, secondary and tertiary alkyl groups are particularly preferable.

The substituted alkyl group is preferably an alkyl group substituted with a carboxyl group, an ester group, a cyano group, a benzene group or the like. In addition, when it has such a substituent, the alkyl group does not need to be particularly secondary. Examples of the alkyl group having a substituent include the following (Chemical Formula 4).

[0023]

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In the above-mentioned 6 substituted alkyl groups in which the two ester groups shown above are substituted, the alkyl group bonded to the oxygen atom in the ester bond is not limited to the methyl group, but has 2 carbon atoms. It may be an alkyl group of 10 to 10.

Particularly, when the hydrogen atom of the thiol group of the aromatic diaminodithiol compound is replaced with an alkyl group having a cyano group or an alkyl group having an ester group, the wholly aromatic polyamide copolymer [the above-mentioned (formula 1)
Of the polymer of [1] to an organic solvent such as N-methyl-2-pyrrolidone is improved.

The above-mentioned alkyl group is used as an alkyl halide which is a halide thereof, and from this and the aromatic diaminodithiol compound (salt thereof) described above, a compound (a) is synthesized by the following method. . As the halide, a bromide of the above alkyl group,
Chlorides and iodides can be used.

In the synthesis of the compound (a), the salt of the aromatic diaminodithiol compound described above and the alkyl halide are reacted in an alkaline aqueous solution. The alkaline aqueous solvent used is water or a mixed solvent of water and alcohol (ethanol and / or methanol),
A solution in which a basic salt such as sodium hydroxide is dissolved can be used. By making the solvent alkaline, the salt of the aromatic diaminodithiol compound can be easily dissolved. It also increases the nucleophilicity of the thiol group and promotes the substitution reaction. The alkali concentration of the alkaline aqueous solvent is preferably 2 equivalents or more and 4 equivalents or less of the monomer.
The reaction is an equilibrium reaction. If the amount is less than 2 equivalents, the reaction does not proceed sufficiently.

This substitution reaction can be carried out in the range of 0 ° C to 100 ° C. If the temperature is lower than 0 ° C, the reaction rate becomes slow, which is not preferable. On the other hand, when the temperature exceeds 100 ° C,
Side reactions occur, which is not preferable. A more preferable reaction temperature is 0 to 95 ° C. Although the reaction time is not particularly limited, it is generally about 2 to 24 hours. It is preferable to stir the solution in order to increase the reaction rate. Moreover, the reaction rate can be increased by making the amount of the alkyl halide excessive.

Further, cetyltrimethylammonium chloride, n-butyltriphenylphosphonium bromide,
Tetraphenylphosphonium bromide, 18-crown-6
The reaction rate can be increased by adding such as a phase transfer catalyst. Such a phase transfer catalyst causes the reaction between the salt of the aromatic diaminodithiol compound and the alkyl halide to proceed rapidly.

By performing the substitution reaction under the above conditions,
A monomer [compound (a)] in which a hydrogen atom of a thiol group of a salt of an aromatic diaminodithiol compound is substituted with an alkyl group can be obtained.

In the reaction for synthesizing the compound (a), the reaction between the salt of the aromatic diaminodithiol compound and the alkyl halide proceeds as shown below (Chemical Formula 5). Here, as an example of the salt of the aromatic diaminodithiol compound, 2,5
-Diamino-1,4-benzenedithiol dihydrochloride is used. In addition, in the formula, X-R represents an alkyl halide.

[0032]

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(B) Aromatic Diamino Compound The aromatic diamino compound used in the present invention is preferably an aromatic diamino compound having a bendable structure, and a diamine having an aromatic residue such as diphenyl ether or biphenyl is preferably used. be able to. As the aromatic diamino compound, specifically, those having an aromatic residue represented by (Chemical Formula 6) can be used.

[0034]

[Chemical 6]

In order to improve the compatibility between the wholly aromatic polyamide copolymer and the matrix polymer, the compound (b) has the same or similar structure as a part of the matrix polymer to be mixed. It is better to choose.

(C) Dicarboxylic Acid Derivative Further , examples of the dicarboxylic acid derivative used in the present invention include those in which each carboxyl group is substituted as shown in the following (Chemical Formula 7).

[0037]

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Examples of the residue of the above dicarboxylic acid derivative include an alkylene group having a relatively short chain (having 2 to 10 carbon atoms) and an aromatic residue of the following (Chemical formula 8). In addition, as an example of the dicarboxylic acid, an aromatic dicarboxylic acid is preferable.

[0039]

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A halogen and / or a substituent such as a lower alkyl group, a lower alkoxyl group or a phenyl group may be added to the aromatic residue. In the present invention, the wholly aromatic polyamide copolymer must have a side chain, and the side chain can be introduced by using a dicarboxylic derivative having such a substituent added, and the solubility in a solvent can be improved. Can be improved.

Among such aromatic dicarboxylic acid derivatives, terephthalic acid dichloride or its halogen substitution product is particularly preferable, and specifically, terephthalic acid dichloride, 2-chloroterephthalic acid dichloride and 2,5-dichloroterephthalic acid. Dichloride and the like can be preferably used. In addition, these aromatic dicarboxylic acid derivatives may be used alone or in combination of two or more kinds.

Next, a method for producing the dithiol random copolymer will be described. In the case of producing a random copolymer, the compounds (a), (b) and (c) are dissolved in an organic solvent at a desired compounding ratio and the three are copolymerized.
Preferably, a homogeneous solution of the compound (a) and the compound (b) is first prepared, and the (c) dicarboxylic acid derivative is added thereto.

The ratio of the amount of the compound (a) to the amount of the compound (b) in the solution using the organic solvent is such that in the finally obtained dithiol-based random copolymer, the portion changed to a rigid linear portion and the flexible chain portion are The ratio (i.e., the ratio of m to n in (Chemical Formula 1) above) is determined, but the amounts of the compound (a) and the compound (b) are appropriately determined according to the purpose of use of the dithiol random copolymer. To do. In the present invention, m: n is 0.01: to 99.99 to 99.9.
The compound (a) and the compound (b) are blended so as to be 9: 0.01.

The amount of the (c) dicarboxylic acid derivative is
The amount is equal to or more than the total molar amount of the compound (a) and the compound (b). Further, the concentration of the total amount of the compound (a), the compound (b) and the compound (c) in the organic solvent is preferably about 0.1 to 2 mol / liter. If the concentration exceeds 2 mol / liter, it becomes difficult to dissolve each component, which is not preferable.

As the organic solvent, an amide type organic solvent can be preferably used. As the amide-based organic solvent,
Examples thereof include N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, N, N-dimethylacetamide and the like, and these can be used alone or as a mixed solution. Further, chloride such as LiCl or CaCl ₂ may be added in an amount of 5 to 20% by weight in order to improve the solubility.

The compounds (a), (b) and (c) are polymerized to produce a dithiol random copolymer.
The polymerization reaction temperature at this time is preferably -20 to 50 ° C. If the polymerization temperature is lower than -20 ° C, a sufficient polymerization reaction does not occur, and the dithiol-based random copolymer obtained has a low degree of polymerization. On the other hand, the thiazole ring-closing reaction may occur at a temperature of about 250 ° C. Therefore, the upper limit of the temperature of the polymerization reaction is set to 50 ° C. for safety. More preferably, it is in the range of -20 to 30 ° C.

In the above polymerization reaction, it is preferable to stir the solution in order to increase the reaction rate. Further, the reaction time is not particularly limited, but generally it may be about 1 to 24 hours. By carrying out the polymerization reaction under the above conditions, a dithiol random copolymer having a large degree of polymerization can be obtained without causing a thiazole ring closure reaction. Intrinsic viscosity η _inh (N
-Methyl-2-pyrrolidone, 30 ° C) is 0.4-2.
It is about 5.

This polymerization reaction is considered to proceed as follows. In the reaction formula (Formula 9) below, as an example of the compound (a), 2,5-diamino-1,
Using an alkyl group-substituted product of 4-benzenedithiol dihydrochloride, using 4,4′-diaminodiphenyl ether (4-amino-p-phenoxyaniline) as an example of compound (b), and (c) an example of a dicarboxylic derivative 2-chloroterephthalic acid dichloride is used. Note that m
And n represent the degree of polymerization.

[0049]

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The obtained dithiol random copolymer can be washed and dried by a known method.

(2) of dithiol block copolymer
Production In the present invention, the dithiol block copolymer is
An aromatic diaminodithiol compound represented by the above (Chemical formula 1) similar to the above random copolymer and having the same hydrogen atom as the above (a) thiol group substituted with a substituted or unsubstituted alkyl group, and (b) aromatic It can be produced from a group diamino compound and (c) dicarboxylic acid derivative.

Specifically, the dithiol block copolymer is prepared by reacting (i) the compounds (a) and (b) separately with the (c) dicarboxylic acid derivative in an organic solvent to prepare two kinds of oligomers. It can be produced by synthesizing and (ii) reacting the obtained two kinds of oligomers in an organic solvent.

Here, for the sake of simplicity, the oligomer obtained by reacting the compound (a) with the dicarboxylic acid derivative (c) is called an oligomer (I), and the compound (b) and the dicarboxylic acid (c) are referred to as an oligomer. The oligomer obtained by reacting with the derivative is called oligomer (II).

(2) -1 Dithiol block copolymer
Synthesis of oligomer (a) The aromatic diaminodithiol compound (a) and the dicarboxylic acid derivative (c) are dissolved in an organic solvent and stirred at a predetermined temperature to produce an oligomer (I). In the synthesis of the oligomer (I), the molar amount of the compound (a) and the molar amount of the dicarboxylic acid derivative (c) are basically the same, but the molecular weight of the oligomer (I) is appropriate, and In order to improve the reaction with the oligomer (II) described later, (c)
The amount of the dicarboxylic acid derivative may be adjusted to some extent.

Further, the concentration of the total amount of the compound (a) and the compound (c) dicarboxylic acid derivative in the organic solvent is 0.5 to
It is preferable that the amount is about 5 mol / liter. Concentration is 5 mol /
If it exceeds liter, it is not preferable because the dissolution of each component becomes difficult. Examples of the organic solvent include those similar to those used in the production of the random copolymer.

The polymerization reaction temperature when the oligomer (I) is synthesized by polymerizing the aromatic diaminodithiol compound (a) and the dicarboxylic acid derivative (c) is -20 to 200.
℃ is good. When the reaction temperature is less than -20 ° C,
Not enough polymerization reaction. On the other hand, at a temperature of about 250 ° C., a thiazole ring closure reaction may occur. More preferably, it is in the range of -10 to 50 ° C.

In the production of the above oligomer (I), it is preferable to stir the solution in order to increase the reaction rate. The reaction time is preferably about 1 to 120 minutes. The polymerization reaction of the compound (a) and the compound (c) is
It is considered that the process proceeds as shown in (Chemical Formula 10) below.
In the following reaction formula (Formula 10), the compound (a)
2,5-diamino-1,4-benzenedithiol dihydrochloride is used as an example, and 2-chloroterephthalic acid dichloride is used as an example of the (c) dicarboxylic acid derivative. In addition, m represents a polymerization degree. The intrinsic viscosity η _inh (N-methyl-2-pyrrolidone, 30 ° C.) of the oligomer (I) is about 0.2 to 0.8.

[0058]

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The oligomer (II) can also be synthesized in the same manner as the above-mentioned method for synthesizing the oligomer (I). Also in the case of synthesizing the oligomer (II), the amount of the (c) dicarboxylic acid derivative is basically the same as the molar amount of the compound (b). The oligomer (I
It is also preferable to adjust the amount of the (c) dicarboxylic acid derivative in the synthesis of I).

The concentration of the total amount of the compounds (b) and (c) dicarboxylic acid derivative in the organic solvent is 0.5 to
It is preferable that the amount is about 5 mol / liter. The polymerization reaction temperature is −20 ° C. to 300 ° C., preferably −20 to 20.
The temperature is preferably set to 0 ° C. If the temperature is lower than -20 ° C, a sufficient polymerization reaction does not occur. On the other hand, since thermal decomposition occurs at a temperature of about 400 ° C., the upper limit of the temperature of the polymerization reaction is 3
Set to 00 ° C. More preferably, it is in the range of -10 to 50 ° C.

As the organic solvent used in the synthesis of the oligomer (II), the same organic solvent as used in the synthesis of the oligomer (I) can be mentioned. The reaction time is
There is no particular limitation, but it is generally preferable that the time is 1 to 120 minutes.

The polymerization reaction of the compound (b) and the compound (c) is considered to proceed as shown in the following (Chemical Formula 11). In the reaction formula (Formula 11) below, 4,4′-diaminodiphenyl ether (4-amino-p-phenoxyaniline) is used as an example of the compound (b),
(C) 2-Chloroterephthalic acid dichloride is used as an example of the dicarboxylic acid derivative. Note that n represents the degree of polymerization. The intrinsic viscosity η _inh (N-methyl-2-pyrrolidone, 30 ° C.) of the oligomer (II) is about 0.1 to 0.6.

[0063]

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(2) -2 Dithiol block copolymer
Oligomers obtained by the process produced the aforementioned chromatography (I) and oligomers (II) are reacted in an organic solvent to synthesize a dithiol-based block copolymer. As the organic solvent, the one used in the synthesis of the above-mentioned oligomer (I) or (II) can be used.

Specifically, an organic solvent in which the oligomer (I) is dissolved and an organic solvent in which the oligomer (II) is dissolved are mixed and stirred at -10 to 50 ° C to synthesize a dithiol block copolymer. If it is lower than -10 ° C, the polymerization does not proceed. If the temperature exceeds 250 ° C, the thiazole ring-closing reaction will proceed.

By carrying out the polymerization reaction under the above conditions,
A dithiol-based block copolymer having a large degree of polymerization can be obtained without causing a thiazole reaction. Intrinsic viscosity η of the resulting dithiol block copolymer
_inh (N-methyl-2-pyrrolidone, 30 ° C.) was 0.
It is about 4 to 2.3.

The polymerization reaction of the oligomer (I) and the oligomer (II) proceeds as shown in the following (Chemical Formula 12) to obtain a dithiol block copolymer. Here, as the oligomer (I), the one obtained by the reaction shown in the above (Chemical formula 10) is used, and as the oligomer (II), the
Although the one shown in 1) is used, the present invention is not limited to this.

[0068]

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Incidentally, m and n indicate the degree of polymerization. In the present invention, the sum of m in one copolymer (the total degree of polymerization in the precursor copolymer of the sites bounded by m in the above formula) and the sum of n (n in the above formula)
The ratio of the total degree of polymerization in the copolymer of the site bounded by the ratio m: n is 0.01: to 99.99.
It takes a range of 99.99: 0.01.

The dithiol block copolymer obtained can be washed and dried by a known method.

Next, the dihydroxy copolymer will be described. In the present invention, the dihydroxy copolymer is represented by the following (Chemical Formula 13).

[0072]

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(However, Ar is an aromatic residue, both m and n are integers, and m: n is 0.01: 99.
It is 99-99.99: 0.01. )

The dihydroxy copolymer is (d)
Produced from aromatic diaminodihydroxy compound in which hydrogen atom of amino group and / or hydroxyl group is substituted or unsubstituted, (e) aromatic diamino compound in which hydrogen atom of amino group is substituted or unsubstituted, and (c) dicarboxylic acid derivative can do.

(D) Amino group and / or hydroxy
Aromatic diamino with or without substitution of hydrogen atom
Dihydroxy Compound The aromatic diaminohydroxy compound in the present invention is a compound having an amino group and a hydroxyl group on both sides of an aromatic residue, and the aromatic residue is not limited to a benzene ring, but two or more benzene rings are condensed. It may be an aromatic ring, or may be one in which two or more benzene rings are bonded, such as biphenyl. Further, the positional relationship between the amino group and the hydroxyl group on both sides may be symmetrical or point-symmetrical with respect to the aromatic residue. Examples of such an aromatic diaminodihydroxy compound include the following (Chemical Formula 14).

[0076]

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In the present invention, the aromatic diaminodihydroxy compound (d) may be one in which the hydrogen atom of the amino group and / or hydroxyl group is substituted. It is preferable to produce a dihydroxy copolymer by using a silylated product in which a hydrogen group is substituted with a silyl group, since a high molecular weight product can be obtained in a high yield.

Further, in the above-mentioned (d) aromatic diaminodihydroxy compound, the aromatic residue having a substituent such as Cl may be used. These aromatic diaminodihydroxy compounds are preferably used in the form of salts such as hydrochloride to prevent deterioration. As the aromatic diaminodihydroxy compound, especially 4,6-diamino-1,
3-dihydroxybenzene (or a salt thereof) and its silylated product are preferably used.

(E) The hydrogen atom of the amino group is substituted or not
Substituted aromatic diamino compound As the aromatic diamino compound used in the present invention, an aromatic diamino compound having a bendable structure is preferable, and a diamine having an aromatic residue such as diphenyl ether or biphenyl ether can be preferably used. . Specific examples of the aromatic diamino compound include the above (chemical formula 6)
Those having an aromatic residue represented by can be used, but the hydrogen atom of the amino group of these aromatic diamino compounds may be substituted. Particularly, silylated one is preferable. Among the aromatic residues in (Chemical Formula 6) described above, the diphenyl ether group and the triphenyl ether group shown in the upper order are preferable. By using such a diphenyl ether group, it is possible to impart sufficient flexibility to the resulting dihydroxy copolymer.

In order to improve the compatibility of the dihydroxy type copolymer with the matrix polymer, the compound (e) having the same or similar structure as a part of the matrix polymer to be mixed is used. Good to choose.

The dihydroxy type copolymer of the present invention is obtained from the above-mentioned compounds (d), (e) and (c), but the copolymer may be a block copolymer,
Either a random copolymer or both may be used. Below, these manufacturing methods are demonstrated.

(3) Dihydroxy random copolymer
In order to produce a dihydroxy random copolymer, an aromatic diaminodihydroxy compound in which an amino group and a hydroxyl group of an aromatic diaminodihydroxy compound are silylated is used as the compound (d), and an amino group is added as the compound (e). It is preferable to use a silylated aromatic diamino compound and react these with the (c) dicarboxylic acid derivative. As described above, the compound (d) is thus
When a copolymer is produced by using a silylated compound as (e), a high molecular weight product can be obtained in a high yield.

To silylate the amino group and hydroxyl group of an aromatic diaminodihydroxy compound, the aromatic diaminodihydroxy compound or a salt thereof, particularly a hydrochloride salt thereof is used with a nitrogen-containing silylating agent in an organic solvent or without a solvent. Then, the treatment is performed at 80 to 140 ° C. for 6 to 72 hours.

Examples of the nitrogen-containing silylating agent effective for such a silylation reaction include hexamethyldisilazane, N, N
-Diethylaminotrimethylsilane, N, O-bis (trimethylsilyl) carbamate, N-trimethylsilylimidazole and the like.

As the organic solvent for the silylation reaction, tetrahydrofuran, carbon tetrachloride, N, N-dimethylacetamide or the like can be used, but the organic solvent can be omitted. When the silylation temperature is lower than 80 ° C, the reactivity is insufficient, while when it is higher than 140 ° C, the amine hydrochloride is decomposed, which is not preferable.

Similarly, the aromatic diamino compound (e) can be silylated. When the silylated product is produced under the above conditions, the following compounds (d), (e)
And (c) are dissolved in an organic solvent at a desired mixing ratio, and -1
The 3 parts are copolymerized by stirring at 0-40 ° C for 2-12 hours. Preferably, a homogeneous solution of the compound (d) and the compound (e) is first prepared, and the (c) dicarboxylic acid derivative is added thereto. Further, if the polymerization temperature is lower than -20 ° C, the polymerization does not proceed, while if it exceeds 250 ° C, the oxazole ring-closing reaction proceeds.

By carrying out the polymerization reaction under the above conditions,
A dihydroxy random copolymer having a large degree of polymerization can be obtained without causing an oxazole reaction. Intrinsic viscosity η of the obtained dihydroxy random copolymer
_inh (N-methyl-2-pyrrolidone, 30 ° C.) was 0.
It is about 3 to 2.0.

The ratio of the amount of the compound (d) to the amount of the compound (e) in the solution using the organic solvent is such that in the finally obtained random copolymer, the portion that changes to the rigid linear portion and the portion that becomes the flexible chain portion. And the ratio [that is,
[Ratio of m to n in 3)], the compound (d) may be adjusted according to the purpose of use of the dihydroxy random copolymer.
And the amount of compound (e) are appropriately determined. In the present invention, m: n is 0.01: to 99.99 to 99.99:
It can take the range of 0.01.

The amount of the (c) dicarboxylic acid derivative is
The amount is equal to or more than the total molar amount of the compound (d) and the compound (e). The concentration of the total amount of compound (d), compound (e) and compound (c) in the organic solvent is preferably about 0.1 to 5 mol / liter.
If the concentration exceeds 5 mol / liter, it becomes difficult to dissolve each component, which is not preferable.

Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-
Amide solvents such as methyl-2-pyrrolidone, aromatic amine solvents such as pyridine, sulfur solvents such as dimethyl sulfoxide and tetramethyl sulfone, benzene solvents such as benzene, toluene, anisole, diphenyl ether, nitrobenzene and benzonitrile, Ether-based solvents such as tetrahydrofuran and 1,4-dioxane, neutral solvents such as halogenated hydrocarbons such as chloroform, trichloroethane, and carbon tetrachloride (aprotic)
solvent).

The random copolymer obtained can be washed and dried by a known method. When a silylated compound is used as the compounds (d) and (e),
Stir in alcohol such as methyl alcohol for several hours,
By repeating the alcohol cleaning, a desilylation reaction treatment is performed as illustrated in the following reaction formula (Formula 15). In the formula, Ar is an aromatic residue.

[0092]

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(4) Dihydroxy block copolymer
In the present invention, the dihydroxy block copolymer has the same formula (1) as the random copolymer.
3), which can be produced from a silylated (d) aromatic diaminodihydroxy compound, a silylated (e) aromatic diamino compound, and (c) a dicarboxylic acid derivative similar to the above.

Specifically, the dihydroxy block copolymer comprises (i) compounds (d) and (e),
Two kinds of oligomers are synthesized by separately reacting with (c) dicarboxylic acid derivative in an organic solvent, (ii)
It can be produced by reacting the obtained two kinds of oligomers in an organic solvent. Here, in order to simplify the explanation, the oligomer obtained by reacting the compound (d) with the (c) dicarboxylic acid derivative is referred to as an oligomer (III).
The oligomer obtained by reacting the compound (e) with the dicarboxylic acid derivative (c) is called an oligomer (IV).

(4) -1 Dihydroxy Block Copoly
Synthesis of oligomer for mer Once the silylated aromatic diaminodihydroxy compound is produced under the above-mentioned conditions, the silylated aromatic diaminohydroxy compound is then reacted with a dicarboxylic acid derivative to produce an oligomer (III). . The reaction between the silylated aromatic diaminodihydroxy compound and the dicarboxylic acid derivative is -20 ° C. in an organic solvent, under substantially anhydrous and oxygen-free conditions, under dry nitrogen or argon gas, depending on the solvent used. It may be carried out at -80 ° C for 5 minutes to 2 hours. When the reaction temperature is lower than -20 ° C, the reactivity is insufficient, while when it exceeds 100 ° C, the reaction product may be oxidized. Preferably, the reaction temperature is -10 to 3
Set to 0 ° C.

The molar amount of the compound (d) and the molar amount of the (c) dicarboxylic acid derivative are basically the same, but the molar amount of the (c) dicarboxylic acid derivative is appropriately increased or decreased with respect to the compound (d). Good to do. The adjustment of the amount of the compound (c) dicarboxylic acid derivative will be described later. The concentration of the total amount of the compound (d) and the dicarboxylic acid derivative (c) in the organic solvent is preferably about 0.1 to 5 mol / liter. When the concentration exceeds 5 mol / liter, it becomes difficult to dissolve each component, which is not preferable.

As the organic solvent, those similar to those used in the production of the random copolymer can be mentioned.
It is considered that the polymerization reaction of the compound (d) and the compound (c) proceeds as shown in (Chemical Formula 16) below. In addition,
In the following reaction formula (Formula 16), as the silylated aromatic diaminohydroxy compound, a compound obtained by silating diaminodihydroxybenzene is used.

[0098]

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(In the formula, Ar represents an aromatic residue, X represents a halogen, and Me represents a methyl group.) Oligomer (IV)
The synthesis of can also be carried out in the same manner as the synthesis of the above-mentioned oligomer (III), using a silylated aromatic diamino compound as the compound (e), and reacting this with the (c) dicarboxylic acid derivative.

Also in the case of the synthesis of the oligomer (IV), (c)
The amount of the dicarboxylic acid derivative is basically the same as the molar amount of the compound (e), but the oligomer (IV) is adjusted according to the adjustment of the amount of the (c) dicarboxylic acid derivative during the synthesis of the oligomer (III). The amount of the (c) dicarboxylic acid derivative in the synthesis of is also preferably adjusted. This will be described later.

The concentration of the total amount of the compounds (e) and (c) dicarboxylic acid derivative in the organic solvent is 0.1-0.1%.
It is preferably about 2 mol / liter. When the concentration exceeds 0.1 mol / liter, it becomes difficult to dissolve each component,
Not preferred. The polymerization reaction may be performed at -20 to 80 ° C for 2 to 12 hours. When the reaction temperature is lower than -20 ° C, the reactivity is insufficient, while when it exceeds 100 ° C, the reaction product may be oxidized. Preferably,
The reaction temperature is -20 to 30 ° C.

The organic solvent used for the synthesis of the oligomer (IV) may be the same as that used for the synthesis of the oligomer (III). The polymerization reaction of the compound (e) and the compound (c) is considered to proceed as shown in the following (Chemical Formula 17). In addition, the following reaction formula (Formula 1
In (7), as (e) silylated aromatic diamino compound, 3,4'-diaminodiphenyl ether silylated is used.

[0103]

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(In the formula, Ar is an aromatic residue, X is a halogen, and Me is a methyl group.) Next, in the synthesis of the oligomer (III) and the oligomer (IV), the (c) dicarboxylic acid derivative The adjustment of the amount will be described. In the synthesis of each oligomer, the molar amount of the compound (d) or the compound (e) and the molar amount of the (c) dicarboxylic acid derivative are basically the same, but the following reasons are given: The oligomer (III) and , Oligomer (IV), so that it can react well with oligomer (IV)
The end of one of the -COCl, the end of the other oligomer to a -NH _2, and to the molecular weight of the oligomer (III) or (IV) as appropriate, the compound (d) or the compound It is preferable to appropriately increase or decrease the molar amount of the (c) dicarboxylic acid derivative with respect to (e).

According to the studies conducted by the present inventors, when a relatively large amount of the oligomer (III) is used in the production of the copolymer described later (ie, the dihydroxy group block copolymer is finally obtained, the dihydroxyl group is used). In the case of introducing a large amount of rigid part of wholly aromatic polyamide having a), it is preferable that the amount of the dicarboxylic acid derivative (c) in the synthesis of the oligomer (III) is slightly larger than the number of moles of the compound (d). On the other hand, when the amount of the oligomer (III) is less than the amount of the oligomer (IV) in the production of the copolymer, the amount of the (c) dicarboxylic acid derivative in the synthesis of the oligomer (III) is the number of moles of the compound (d). It is better to make it slightly smaller. However, when the amount of the (c) dicarboxylic acid derivative is slightly reduced in the synthesis of one oligomer, the amount of the (c) dicarboxylic acid derivative is increased in the synthesis of the other oligomer by the reduced amount.

(4) -2 Dihydroxy Block Copoly
Production of mer The block copolymer is synthesized by reacting the oligomer (III) obtained by the above-mentioned method with the oligomer (IV) in an organic solvent. As the organic solvent, those used in the synthesis of the above-mentioned oligomer (III) or (IV) can be used.

Specifically, an organic solvent in which the oligomer (III) is dissolved and an organic solvent in which the oligomer (IV) is dissolved are mixed and stirred at -10 to 30 ° C for 2 to 12 hours to synthesize a block copolymer. Polymerization does not proceed below -20 ° C,
On the other hand, if the temperature exceeds 250 ° C., the oxazole ring-closing reaction proceeds.

By carrying out the polymerization reaction under the above conditions,
A block copolymer having a large degree of polymerization can be obtained without causing an oxazole reaction. The intrinsic viscosity η _inh (N-methyl-2-pyrrolidone, 30 ° C.) of the obtained dihydroxy block copolymer is about 0.3 to 2.0.

The polymerization reaction of the oligomer (III) and the oligomer (IV) proceeds as shown in the following (Chemical formula 18) to obtain a block copolymer. Here, as the oligomer (III), the one obtained by the reaction shown in (Chemical Formula 16) above is used, and as the oligomer (IV), the one shown in (Chemical Formula 17) is used. It is not limited to.

[0110]

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Incidentally, m and n represent the degree of polymerization. m: n is 0.01: to 99.99 to 99.99:
It can take the range of 0.01. The block copolymer obtained can be washed and dried by known methods.

In the present invention, when the silylated products are used as the compound (d) and the compound (e), the block copolymer obtained by the above reaction is stirred in an alcohol such as methyl alcohol for several hours and washed with alcohol. By repeating the above, the desilylation reaction treatment is performed in the same manner as the random copolymer.

Method for producing molecular composite material The above matrix polymer and the wholly aromatic polyamide copolymer obtained as described above are dissolved in an organic solvent in which both are well dissolved, and this is put into a non-solvent. By doing so, a molecular composite material comprising a matrix polymer and a wholly aromatic polyamide copolymer having side chains can be obtained.

Examples of such organic solvent include N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N
An amide-based organic solvent such as dimethylacetamide can be preferably used.

In the blending of the wholly aromatic polyamide copolymer and the matrix polymer, the reinforcing effect is obtained even if the blending amount of the wholly aromatic polyamide copolymer is extremely small, but the blending ratio of the wholly aromatic polyamide copolymer and the matrix polymer is finally obtained. Is 1:99 to 80: 2 by weight.
It is preferable to set it in the range of 0. If the compounding ratio of the wholly aromatic polyamide copolymer, which is a reinforced polymer, becomes too high, the presence of it will become too dense, and the wholly aromatic polyamide copolymers will agglomerate with each other, resulting in poor dispersion at the molecular level. It is considered to reduce the mechanical strength of the material. A more preferable compounding ratio depends on the kind of wholly aromatic polyamide copolymer, but is 5:95 by weight.
It is 60:40.

In order to obtain a molecular composite material, the wholly aromatic polyamide copolymer must have good solubility in the solvent used, but the copolymer of the present invention has a side chain and a molecular chain. It is possible to set a portion exhibiting flexibility in a part thereof to have a large solubility and further to set a portion composed of the compound (b) component or (e) component so as to have a high affinity for an organic solvent. Therefore, the solubility in an organic solvent is further increased, and it is very excellent as a reinforcing polymer for a molecular composite material.

The wholly aromatic polyamide copolymer and the matrix may be dissolved by any method as long as a homogeneous solution is obtained. For example, a solution of a wholly aromatic polyamide copolymer and a matrix polymer may be prepared and then mixed to form a homogeneous solution, or a matrix polymer may be added to a solution in which the wholly aromatic polyamide copolymer is dissolved to form a homogeneous solution. . Also, both may be dissolved in one kind of solvent at a time.

The mixing may be somewhat different depending on the matrix polymer and solvent used, but is preferably about 6 hours to 30 days. The mixing temperature is preferably -15 to 150 ° C. The solution of the wholly aromatic polyamide copolymer and the matrix polymer may be prepared and mixed in an atmosphere of an inert gas such as nitrogen gas or argon gas, or in vacuum.

In the method of the present invention, the mixed solution thus obtained is charged into a non-solvent of both polymers to form a molecule consisting of the matrix polymer and the wholly aromatic polyamide copolymer having side chains. Get a composite. Examples of the non-solvent include alcohols such as methanol and ethanol, distilled water and the like.

Any method may be used as a charging method, for example, a method of obtaining a powder by spraying or dropping a polymer solution into a non-solvent, or a method of pouring finely and continuously to obtain a fibrous coagulated product. However, the method is not limited to these. Of these, the method of spraying is preferable.

The concentration of the polymer solution when added to the non-solvent is 13 to 40% by weight. The powder of the composite material obtained from the solution of less than 13% by weight has a low mechanical strength of the molded product, while the powder of more than 40% by weight has a too high solution viscosity and is difficult to spray. The powder obtained by spraying with a concentration in the above range has a large mechanical strength. In particular, it is preferably set to 15 to 30% by weight. In the present invention, it has been found that the concentration of the polymer solution can be increased in this way, and the composite material obtained from the high concentration solution has high mechanical strength.

Therefore, an excellent molded article having a large mechanical strength can be obtained from the powder of the composite material obtained by the method of the present invention. Molding is done by hot pressing the mold,
It can be easily molded by general melt molding such as injection molding and autoclave.

[0123]

The wholly aromatic polyamide is generally poor in solubility due to its high rigidity and inferior in compatibility, and has problems in forming a matrix polymer and a composite material. In the present invention, as a means for solving such a drawback, a matrix polymer and a common fragment are introduced into a wholly aromatic polyamide copolymer to obtain a copolymer,
Further, the introduction of the side chain improves the solubility of the wholly aromatic polyamide copolymer in the organic solvent and also improves the compatibility with the matrix polymer. Therefore, the wholly aromatic polyamide, which is a reinforcing polymer, can be favorably and uniformly dispersed in the matrix polymer, and a molecular composite material having excellent mechanical properties can be obtained.

[0124]

The present invention will be described in more detail with reference to the following examples. Example 1 (1) Synthesis of thiol-based random copolymer 8 mmol of the compound (a) represented by the following formula (Formula 19) and 2 mmol of the compound (b) represented by the following formula (Formula 20) were replaced with argon. Under an atmosphere, it was dissolved in 15 ml of N-methyl-pyrrolidone (hereinafter referred to as "NMP") to prepare a uniform solution.

[0125]

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[0126]

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This solution, together with the container, was cooled with ice to obtain the compound (c).
Was added as 2-chloroterephthalic acid chloride (10 mmol). While stirring the solution, the temperature was gradually raised, and when the temperature reached room temperature, the temperature was maintained and the reaction was continued for 6 hours. The resulting emerald green solution was poured into a large amount of methanol. This operation was performed while stirring methanol.

After continuing stirring for 30 minutes, the mixture was filtered and further refluxed with a water-methanol solution overnight to remove the solvent.
The obtained polymer was dried in vacuum at 100 ° C. for 24 hours. The yield was 99.8%. The intrinsic viscosity η _inh of this polymer was 1.8 (dl / g). The intrinsic viscosity was measured in NMP at a polymer concentration of 0.5 g /
dl and performed at 30 ° C. by the Ubbelohde method. The structure of the obtained random copolymer is considered to be as shown in the following (Chemical Formula 21).

[0129]

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In this polymer, m: n is
8: 2. (2) Production of molecular composite material Random copolymer 3.67 obtained as described above
and an aromatic polyamide represented by the following formula (Formula 22) as a matrix polymer [TX-1 manufactured by Toray Industries, Inc.]
4.33 g was dissolved in NMP so as to have a concentration of 15, 20, 25, 30, 35, 40% by weight, and stirred at room temperature to 80 ° C for 1 week and mixed to obtain a uniform brown solution.

[0131]

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The solution viscosity of each solution is shown in FIG. All were values of 1,000 mPa · s or more. The solution viscosity was measured with an E-type viscometer manufactured by Tokyo Keiki Co., Ltd. This solution was sprayed into a large amount of ethanol to obtain a coagulated powder. This is filtered and the obtained coagulated powder is heated to 100 ° C.
And vacuum dried.

This vacuum-dried powder was filled in the mold shown in FIG. 6 and was subjected to a mold hot pressing method to obtain 15 × 50 × 2t.
A (mm) flat plate was molded. The mold heating program at this time is shown in FIG. Moreover, the bending elastic moduli of the molded products of the powders obtained from the solutions of the respective concentrations are shown in FIG.
The rigidity of the powder molded product obtained from the solution with high concentration was higher.

Comparative Example 1 A powder of a composite material was obtained in the same manner as in Example 1 except that the solution concentration in Example 1 was changed to 3, 10% by weight, and a molded product was obtained in the same manner as in Example 1. The bending elastic modulus of this molded product is shown in FIG. 3 together with the results of Example 1. Since the solution concentration is low, the flexural modulus is smaller than that in Example 1.

Comparative Example 2 Only the matrix polymer used in Example 1 was
The molding was performed in the same manner as in Example 1. The bending elastic modulus of this molded product is shown in FIG. 3 together with the results of Example 1 and Comparative Example 1.
Note that FIG. 3 is a graph showing the relationship between the solution concentration and the elastic modulus when the coagulated powder of the composite material is obtained. For convenience of comparison, the elastic modulus of only the matrix polymer is compared with the solution concentration of the molecular composite material of 0%. Indicated at the position.

Example 2 (1) Synthesis of Oligomer (I) and Oligomer (II) Under a dry argon stream, 5 ml of NMP was placed in a well-dried 50 ml flask, and the
8 mmol of the compound (a) represented by 9) (2.227)
g) was added and dissolved to prepare a uniform NMP solution.

With this container being ice-cooled together with the container, 8.2 mmol (1.947 g) of 2-chloroterephthalic acid chloride as compound (c) was further added and stirred for 5 minutes to synthesize oligomer (I). .

Simultaneously with the synthesis of the above-mentioned oligomer (I), 50 ml well dried under a stream of dry argon.
10 ml of NMP was placed in the flask of 2 and 2 mmol (0.400) of the compound (b) represented by the above
4 g) was added and dissolved to prepare a uniform NMP solution.

While this container was ice-cooled together with the container, 1.8 mmol (0.427 g) of 2-chloroterephthalic acid chloride as a compound (c) was further added and stirred for 5 minutes to synthesize an oligomer (II). .

(2) Combination of thiol block copolymer
The NMP solution of formed oligomer obtained in the above procedure (I), was added to the NMP solution of the oligomer (II). The NMP solution of the oligomer (I) was mixed with the NMP solution of the oligomer (II).
After addition to the MP solution, the flask of oligomer (I) NMP solution was further washed with 2 ml of NMP, and this washed NMP was also added to the oligomer (II) NMP solution.

While keeping the mixed oligomer solution on ice,
The mixture was stirred for an hour, the temperature was raised to room temperature with further stirring, the temperature was kept at room temperature, and the stirring was continued for another 4 hours. The resulting solution was poured into a large amount of methanol. This operation was performed while stirring methanol.

Next, this methanol solution was filtered, and the obtained precipitate (polymer) was dried in vacuum at 100 ° C. for 24 hours. The yield was 99.8%. The intrinsic viscosity η _inh of this polymer was 1.4 (dl / g). The intrinsic viscosity was measured by measuring the polymer concentration in NMP at 0.
It was 5 g / dl and was carried out by the Ubbelohde method at 30 ° C. The structure of the block copolymer obtained is believed to be similar to the copolymer obtained in Example 1.

In this polymer, the degree of polymerization m of the site which exhibits the rigidity due to the oligomer (I),
The ratio (m: n, where m and n are the totals in the entire polymer) of the degree of polymerization n of the site which is derived from the oligomer (II) and exhibits flexibility is 8: 2.
Met.

(3) Production of Molecular Composite Material 3.1 g of block copolymer obtained by the above method
And 3.54 g of the same polyamide as in Example 1 were dissolved in NMP to prepare a solution of 15, 20, 25, 30, and 35 wt%, and mixed by stirring at room temperature to 80 ° C. for 1 week, A homogeneous brown solution was obtained. The viscosity of each solution is shown in FIG. All were values of 1,000 mPa · s or more. In addition, the increase in viscosity was also rapid in this respect. The solution viscosity was measured with an E-type viscometer manufactured by Tokyo Keiki Co., Ltd.

Coagulated powder was obtained from the above solution in the same manner as in Example 1, dried in vacuum, and molded in the same manner as in Example 1. FIG. 5 shows the flexural modulus of the powder molded article obtained from the solutions having the respective concentrations. It can be seen that the molded product of the powder obtained from the one having a high solution concentration has high rigidity.

Comparative Example 3 A coagulated powder was obtained in the same manner as in Example 2 except that the concentration of the solution was changed to 10% by weight, and a molded product was manufactured. The bending elastic modulus of the obtained molded product is shown in the graph of FIG. 5 together with the results of Example 2. Further, for comparison, the result of Comparative Example 2 is also shown in FIG. 5 similarly to the above.

[0147]

According to the method of the present invention, since a fragment common to the matrix polymer is introduced into a wholly aromatic polyamide which is a reinforcing polymer to form a copolymer, and a side chain is introduced, the organic compound of the wholly aromatic polyamide copolymer is introduced. It is possible to obtain a composite material in which the solubility in a solvent is improved, the compatibility between the reinforcing polymer and the matrix polymer is improved, and the wholly aromatic polyamide copolymer is uniformly and well dispersed in the matrix polymer. It is also possible to obtain a high-concentration solution, and the powder obtained by spraying a solution having a concentration of 13 to 40% by weight has a large mechanical strength and can improve the physical properties of a molded product.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between solution viscosity and solution concentration in Example 1 and Comparative Example 1.

2 is a heating program for molding in Example 1. FIG.

FIG. 3 is a graph showing the relationship between flexural modulus and solution concentration in Example 1 and Comparative Example 1.

FIG. 4 is a graph showing the relationship between solution viscosity and solution concentration in Example 2 and Comparative Example 3.

5 is a graph showing the relationship between flexural modulus and solution concentration in Example 2 and Comparative Example 3. FIG.

FIG. 6 is a configuration diagram of a mold used in the embodiment,
(A) is an assembly block diagram, (b) is an exploded block diagram.

Claims (3)

[Claims] 1. A matrix polymer and a wholly aromatic polyamide copolymer having side chains are obtained by introducing a 13-40 wt% organic solvent solution of the wholly aromatic polyamide copolymer having side chains into a non-solvent. A method for producing a wholly aromatic polyamide copolymer composite material, comprising: 2. The matrix polymer is an aromatic polyamide, and the wholly aromatic polyamide copolymer is a random polyamide containing an aromatic diaminodithiol compound in which a hydrogen atom of a thiol group is substituted with a substituted or unsubstituted alkyl group and a polyamide obtained from a dicarboxylic acid. A copolymer 1
A method for producing the wholly aromatic polyamide copolymer composite described. 3. A molded article comprising the wholly aromatic polyamide copolymer composite material according to claim 1.