JPH0931338A - Molecular composite of three-dimensionally networked fine particle dispersion type, its production, and its molded item - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molecular composite excellent in mechanical strengths, etc., by finely and homogeneously dispersing an arom. heterocyclic copolymer having a three-dimensionally networked fine particle dispersion structure in a matrix polymer. SOLUTION: A matrix polymer and an arom. heterocyclic polymer precursor are dissolved in an org. solvent and then subjected to solvent removal in a nonsolvent to thereby be solidified into a fibrous form, giving a fibrous composite. The composite is thermally treated under tension and/or stretching to cause cyclization of the precursor, giving a composite of the matrix polymer with an rom. heterocyclic copolymer. This composite is hot-press molded with a metal mold to give the objective molecular composite, which comprises the matrix polymer and the arom. heterocyclic copolymer with a three-dimensionally networked fine particle dispersion structure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molecular composite material comprising a matrix polymer and an aromatic heterocyclic copolymer, which is particularly excellent in mechanical properties and is used as a structural material for aircraft, automobiles, space equipment and the like. A molecular composite material suitable for use.

[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. In addition, in order to improve strength and rigidity, development of composite materials such as FRP, which is a combination of plastic materials and high-strength, high-elasticity fibers such as carbon fibers, has become brisk and widely put to practical use. ing.

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 such circumstances, even if a fiber or resin exhibiting high strength and high elasticity is used as a material, it is not always possible to obtain a composite material excellent in strength and rigidity.

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 for the molecular composite material includes, for example, those having a heterocyclic ring such as a thiazole ring, an imidazole ring, an oxazole ring and an oxazinone ring in a repeating unit, and particularly, a thiazole ring. Due to its excellent mechanical strength, polythiazole is regarded as a promising polymer for reinforcing a molecular composite material.

By the way, even if an attempt is made to simply mix a reinforcing polymer such as aromatic thiazole and a matrix polymer to manufacture a molecular composite material, due to the rigidity of the reinforcing polymer, the reinforcing polymer and the matrix polymer are combined. In general, the compatibility is not good, and it is difficult to obtain a uniform dispersion of the reinforcing polymer in the matrix polymer. Unless the reinforcing polymer is uniformly dispersed in the matrix polymer, a molecular composite material having excellent mechanical properties cannot be obtained. Therefore, various attempts have been made so far.

For example, JP-A-1-287167 discloses a polymer solution mainly containing a reinforcing polymer (A) consisting of polythiazole having a substantially rod-like skeleton and a matrix polymer (B) having a fusion property. Is introduced into a coagulation bath, a method for producing a polymer composite comprising film formation, wherein the polymer solution exhibits optical anisotropy, and the polymer solution is immersed in the coagulation bath, It discloses a method of apparently passing through an optically isotropic phase and then solidifying.

Further, Japanese Patent Publication No. 2-7976 discloses a reinforcing polymer (A) consisting essentially of polythiazole having a rod-like skeleton, a glass transition temperature of 200 ° C. or higher, and a glass transition temperature of 50.
It has a flow starting temperature of 0 ° C. or less, and when it is held at a temperature between the glass transition temperature and the flow starting temperature for any time within 5 hours, the apparent crystal size formed is 25 Å or less. The matrix polymer (B) made of a hardly crystalline aromatic copolyamide is (A) / [(A) +
(B)] = 0.15 to 0.70 (weight basis) is disclosed.

However, in the method for producing a polymer composite disclosed in JP-A-1-287167 and the production of a composite material using the polymer composition disclosed in JP-B-2-7976, a reinforcing polymer is used. The uniform dispersion of the matrix polymer with the matrix polymer cannot be expected so much, and the mechanical strength of the obtained molecular composite material is not significantly improved. It is considered that this is because the compatibility between the reinforcing polymer exhibiting rigidity and the matrix is not good and the reinforcing polymer is not sufficiently dispersed in the matrix polymer.

Therefore, the rigid aromatic polymer and the matrix polymer are not mixed, but the rigid aromatic polymer precursor and the matrix polymer or the precursor thereof are uniformly mixed in an organic solvent to remove the organic solvent. A method of heating the precursor to form a rigid aromatic polymer afterwards has been proposed (Japanese Patent Laid-Open Nos. 64-1760 and 64-1761). According to the above method, it becomes possible to manufacture a molecular composite material having relatively good mechanical strength and the like.

However, according to the research conducted by the present inventors, a thermoplastic resin is used as a matrix polymer for the purpose of, for example, thermocompression molding of a molecular composite material, and this is used together with an aromatic polythiazole precursor. Japanese Patent Laid-Open No. 64-1
In order to produce a molecular composite material by the method disclosed in Japanese Patent Laid-Open No. 760 or 64-1761, an aromatic compound formed by a thiazole ring closure reaction in a step of thermoforming a homogeneous mixture of a matrix polymer and a precursor. It has been found that the group polythiazole aggregates, resulting in poor mechanical properties of the molecular composite. Further, since aromatic polythiazole is poor in interaction with the matrix polymer such as hydrogen bond, the elongation of the obtained molecular composite material is small. This is a drawback when used as a structural material or the like.

[0012]

The present invention has been made against the background of the above-mentioned conventional technical problems, and an object of the present invention is to solve the above problems and provide a rigid polymer which is a reinforced polymer. It is an object of the present invention to provide a molecular composite material in which an aromatic polymer is finely and uniformly dispersed in a matrix polymer, and the reinforcing polymer is not agglomerated in the heat molding step, and thus has excellent mechanical strength.

[0013]

The present invention provides a three-dimensional network fine particle dispersion type molecular composite material comprising a matrix polymer and an aromatic heterocyclic copolymer forming a three-dimensional network fine particle dispersion type structure. It is a thing. Further, according to the present invention, a matrix polymer and a precursor of an aromatic heterocyclic copolymer are made compatible with each other in an organic solvent, and this solution is desolvated in a non-solvent and coagulated into a fibrous form to obtain these composite materials. By heat-treating the fibrous composite material under tension and / or stretching, a ring-closing reaction of the precursor of the aromatic heterocyclic copolymer is caused to obtain a composite material of the matrix polymer and the aromatic heterocyclic copolymer. The present invention provides a method for producing a three-dimensional network fine particle-dispersed type molecular composite material, which comprises subjecting a metal mold to hot press molding, and a molded article obtained by this production method.

[0014]

According to the present invention, since the precursor copolymer uniformly dispersed in the matrix polymer at the molecular level becomes an aromatic heterocyclic copolymer as it is, the aromatic heterocyclic copolymer is finely dispersed in the matrix polymer. It will be evenly dispersed, resulting in a molecular composite material having good mechanical properties. Further, due to the tension applied to the fiber during the ring-closing reaction, the reinforcing material molecules do not aggregate into particles, and the subsequent heating in melt molding causes the mesh to be subdivided into a group of particles, resulting in a uniform three-dimensional structure. It has a network fine particle dispersion structure.

In the present invention, as the matrix polymer, polyamide, polyimide, polyamideimide,
Examples include aramid resin (aromatic polyamide), polyether sulfone, polyether imide, and the like. These matrix polymers have good compatibility with the aromatic heterocyclic copolymer and can provide a molecular composite material having excellent mechanical strength. As the matrix polymer, an aromatic polyamide is particularly preferred.

Next, the aromatic heterocyclic copolymer will be described. In the present invention, the aromatic heterocyclic copolymer, which serves as the reinforcing polymer of the molecular composite material, is uniformly dispersed in the matrix polymer as fine particles in the composite material with a three-dimensional mesh-like distribution. The material has excellent mechanical properties. The aromatic heterocyclic copolymer is preferably one having a fragment containing at least a part of the matrix polymer. Such aromatic heterocyclic copolymers include polybenzothiazole (PBT) or polybenzoxazole (PBO).
, Random or block copolymers.

In the present invention, the matrix polymer and the aromatic heterocyclic copolymer are composited by first mixing the matrix polymer and the aromatic heterocyclic copolymer precursor into a composite material, and then subjecting it to tension and / or stretching. While heating at a predetermined temperature to cause a ring-closing reaction, a composite material of a matrix polymer and an aromatic heterocyclic copolymer is finally obtained. Then, the composite material of the present invention can be obtained by further molding this with a die hot press.

Therefore, the precursor of the PBT copolymer will be described first. Production of PBT Precursor Copolymer In the present invention, PBT serving as a reinforcing polymer for a molecular composite material
The precursor of the copolymer is represented by the following formula (Formula 1).

[0019]

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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. )

This precursor copolymer comprises (a) an aromatic diaminodithiol compound obtained by substituting a hydrogen atom of a thiol group with a substituted or unsubstituted alkyl group, (b) an aromatic diamino compound and (c) a dicarboxylic acid derivative. Can be manufactured from.

(A) The hydrogen atom of the thiol group is replaced or
Is an aromatic diaminodithio substituted with an unsubstituted alkyl group
In the present invention, an 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: 2).

[0023]

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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 (Chemical Formula 3).

[0025]

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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 (Chemical Formula 4).

[0029]

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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 and has 2 carbon atoms. It may be an alkyl group of 10 to 10.

In particular, 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, a precursor copolymer [polymer of the above-mentioned (formula 1)] ]
, The solubility in organic solvents such as N-methyl-2-pyrrolidone is improved.

The above-mentioned alkyl group is used as an alkyl halide which is a halide thereof. From this and the aromatic diaminodithiol compound (salt) described above,
Compound (a) is synthesized by the method shown below. In addition,
As the halide, the bromide, chloride or iodide of the above alkyl group 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 alkaline concentration of the alkaline aqueous solvent is preferably not less than 2 equivalents and not more than 6 equivalents of the monomer. It is an equilibrium reaction, and if it is less than 2 equivalents, the reaction does not proceed sufficiently, while if it exceeds 6 equivalents, the removal treatment of unreacted alkali becomes complicated.

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, if the temperature exceeds 100 ° C., a side reaction occurs, which is not preferable. A more preferable reaction temperature is 0 to 95 ° C. The reaction time is not particularly limited, but generally may be about 2 to 24 hours. It is preferable to stir the solution in order to increase the reaction rate. Further, 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 carrying out 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,
Examples of salts of aromatic diaminodithiol compounds include 2,
5-Diamino-1,4-benzenedithiol dihydrochloride is used. Further, in the formula, X-R represents an alkyl halide.

[0038]

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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.

[0040]

[Chemical 6]

Of the aromatic residues in (Chemical Formula 6) above,
The diphenyl ether group and the triphenyl ether group shown above are preferred. By using such a diphenyl ether group, it is possible to impart sufficient flexibility to the obtained precursor copolymer. In order to improve the compatibility between the aromatic heterocyclic copolymer and the matrix polymer, it is preferable to select, as the compound (b), a compound having a structure containing at least a part of the matrix polymer to be mixed. .

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

[0043]

[Chemical 7]

Further, 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 represented by the following chemical formula (8). In addition, as an example of the dicarboxylic acid, an aromatic dicarboxylic acid is preferable.

[0045]

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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. By introducing such a substituent, reactivity and solubility in a solvent can be improved.

Among such aromatic dicarboxylic acid derivatives, terephthalic acid dichloride, its halogen-substituted product, and isophthalic acid dichloride are preferable, and specifically, 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.

(1) of PBT precursor random copolymer
Production Next, a method for producing the precursor 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 PBT precursor random copolymer, the portion changing to the rigid linear portion and the flexible chain portion are obtained. The ratio of the PBT to the portion that becomes [that is, the ratio of m to n in (Chemical formula 1) above]
The amounts of the compound (a) and the compound (b) are appropriately determined according to the intended use of the precursor random copolymer. In the present invention, m: n is 0.01: to 99.99 to 99.
The compound (a) and the compound (b) are blended so as to be 99: 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 5 mol / liter.
If the concentration exceeds 5 mol / liter, it becomes difficult to dissolve each component, which is not preferable.

As the organic solvent, an amide 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, in order to increase the reactivity, chlorides such as LiCl and CaCl ₂ may be added in a maximum amount of 5% by weight.

The precursor random copolymer is produced by polymerizing the compounds (a), (b) and (c), and the polymerization reaction temperature at this time is preferably -20 to 250 ° C. When the polymerization temperature is lower than -20 ° C, a sufficient polymerization reaction does not occur, and the degree of polymerization of the obtained precursor random copolymer becomes low. On the other hand, at a temperature of about 250 ° C., a thiazole ring-closing reaction may occur, so for safety, the upper limit of the temperature of the polymerization reaction is 200 ° C. More preferably,
It is in the range of -20 to 50 ° 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 precursor 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, 0.5 g / dl) is preferably 0.4 or more, more preferably about 0.8 to 1.2.

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

[0055]

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

(2) PBT precursor block copolymer
Manufacture In the present invention, the precursor block copolymer is represented by the above (Chemical formula 1) in the same manner as the above random copolymer,
It can be produced from the same aromatic diaminodithiol compound (a) in which the hydrogen atom of the thiol group is substituted with a substituted or unsubstituted alkyl group, (b) an aromatic diamino compound and (c) a dicarboxylic acid derivative as described above. .

Specifically, the precursor 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 (c) dicarboxylic acid derivative is referred to as an oligomer (I), and the compound (b) and the (c) dicarboxylic acid derivative are referred to. The oligomer obtained by reacting with the derivative is called oligomer (II).

(2) -1 PBT precursor 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). Oligomer ((a)
In the synthesis, 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 the oligomer (II ), In order to improve the reaction with (c)
The amount of the dicarboxylic acid derivative may be adjusted to some extent.

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 250.
℃ is good. When the reaction temperature is less than -20 ° C,
Not enough polymerization reaction. On the other hand, a thiazole ring-closing reaction may occur at a temperature of about 250 ° C.,
The upper limit of the temperature of the polymerization reaction is preferably 200 ° C. 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 between the compound (a) and the (c) dicarboxylic acid derivative is considered to proceed as shown in (Chemical Formula 10) below. In the following reaction formula (Formula 10), 2,5-diamino-1,4 is used as an example of the compound (a).
-The alkyl group-substituted product of benzenedithiol dihydrochloride is used, 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 of the oligomer (I) is η _inh (N
-Methyl-2-pyrrolidone, 30 ° C, 0.5 g / dl)
Is about 0.1 to 0.8.

[0064]

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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, at a temperature of about 400 ° C., thermal decomposition occurs, so 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 solvents as those 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 about 1 to 120 minutes.

The polymerization reaction of the compound (b) and the dicarboxylic acid derivative (c) is considered to proceed as shown in the following (Chemical Formula 11). In the following reaction formula (Formula 11), as an example of the compound (b), 4,4′-diaminodiphenyl ether (4-amino-p-phenoxyaniline)
And 2-chloroterephthalic acid dichloride is used as an example of the (c) dicarboxylic acid derivative. Note that n
Represents the degree of polymerization. Intrinsic viscosity of oligomer (II) η _inh
(N-methyl-2-pyrrolidone, 30 ° C., 0.5 g / d
l) is about 0.1 to 0.6.

[0069]

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(2) -2PBT precursor block copolymer
Oligomers obtained by the process produced the aforementioned chromatography (I) and oligomers (II) are reacted in an organic solvent, to synthesize a precursor 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 precursor block copolymer. If it is lower than -10 ° C, the polymerization does not proceed.
If the temperature exceeds 250 ° C, the thiazole ring closure reaction will proceed.

By carrying out the polymerization reaction under the above conditions,
A precursor block copolymer having a large degree of polymerization can be obtained without causing a thiazole ring closure reaction. Intrinsic viscosity of obtained PBT precursor block copolymer η _inh (N
-Methyl-2-pyrrolidone, 30 ° C, 0.5 g / dl)
Is about 0.8 to 2.0.

The polymerization reaction of the oligomer (I) and the oligomer (II) proceeds as shown in the following (Chemical formula 12) to obtain a precursor block copolymer. Here, as the oligomer (I), the one obtained by the reaction shown in (Chemical Formula 10) above is used, and as the oligomer (II), the one shown in (Chemical Formula 11) is used. It is not limited to.

[0074]

[Chemical 12]

Incidentally, m and n represent 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 m: n of the portion surrounded by the total copolymerization degree in the precursor copolymer) is 0.01: to 99.
It is in the range of 99 to 99.99: 0.01.

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

Production of PBO Precursor Copolymer In the present invention, the PBO precursor copolymer is represented by the following formula (Formula 13).

[0078]

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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. )

This PBO precursor copolymer is (d) an aromatic diaminodihydroxy compound in which a hydrogen atom of an amino group and / or a hydroxyl group is substituted or unsubstituted,
It can be produced from (e) an aromatic diamino compound in which a hydrogen atom of an amino group is substituted or unsubstituted and (c) a dicarboxylic acid derivative.

(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 aromatic diaminodihydroxy compound include (Chemical Formula 14).

[0082]

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In the present invention, the aromatic diaminodihydroxy compound (d) may be a compound in which the hydrogen atom of its amino group and / or hydroxyl group is substituted. It is preferable to produce a precursor copolymer from a silylated product in which a hydrogen group is replaced 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 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 can be preferably used. As the aromatic diamino compound, specifically, those having an aromatic residue represented by the above (Chemical Formula 6) can be used.
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 obtained precursor copolymer.

In order to improve the compatibility between the precursor copolymer and the matrix polymer, the compound (e) having a structure containing at least a part of the matrix polymer as the mixing partner is selected. Is good.

The PBO precursor copolymer of the present invention is obtained from the above-mentioned compounds (d), (e) and (c), and the copolymer may be a block copolymer or a random copolymer. But it doesn't matter. Below, these manufacturing methods are demonstrated.

(3) PBO precursor random copolymer
Production In order to produce a PBO precursor 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 obtained 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 in a solvent or in a solvent using a nitrogen-containing silylating agent. Without, treat at 80 ° C-140 ° C for 6-72 hours.

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

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. If the silylation temperature is lower than 80 ° C, the reactivity is insufficient, while if 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 three are copolymerized by stirring at 0-40 ° C for 6-24 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. When the polymerization temperature is lower than -20 ° C, the polymerization does not proceed, while when the temperature exceeds 250 ° C, the oxazole ring-closing reaction proceeds.

By carrying out the polymerization reaction under the above conditions,
A precursor random copolymer having a large degree of polymerization can be obtained without causing an oxazole ring-closing reaction. Intrinsic viscosity η of the resulting PBO precursor random copolymer
_inh (N-methyl-2-pyrrolidone, 30 ° C., 0.5 g
/ Dl) is about 0.6 to 2.0.

The ratio of the amounts of the compound (d) and the compound (e) in the solution using an organic solvent is such that in the finally obtained random copolymer, the portion that changes to a rigid linear portion and the portion that becomes a flexible chain portion. And the ratio [that is,
The ratio of m to n in 3)], but the amounts of the compound (d) and the compound (e) are appropriately determined according to the intended use of the precursor random copolymer. In the present invention, m: n
Can range from 0.01: to 99.99 to 99.99: 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 obtained random copolymer can be washed and dried by a known method.

(4) of the PBO precursor block copolymer
Production In the present invention, the PBO precursor block copolymer is
The same silylated (d) aromatic diaminodihydroxy compound, silylated (e) aromatic diamino compound, and (c) dicarboxylic acid represented by the above (Chemical Formula 13) similar to the above random copolymer, It can be produced from a derivative.

Specifically, the PBO precursor block copolymer is prepared by reacting (i) the compounds (d) and (e) separately with the (c) dicarboxylic acid derivative in an organic solvent to obtain two kinds of oligomers. Can be produced by reacting (ii) the obtained two kinds of oligomers in an organic solvent. Here, for the sake of simplicity, the oligomer obtained by reacting the compound (d) with the (c) dicarboxylic acid derivative is referred to as an oligomer (III), and the compound (e) and the (c) dicarboxylic acid derivative are referred to as The oligomer obtained by the reaction is called oligomer (IV).

(4) -1 PBO precursor block copolymer
Synthesis of oligomer for use in the production of silylated aromatic diaminodihydroxy compound under the above-mentioned conditions, and then the silylated aromatic diaminohydroxy compound is reacted with dicarboxylic acid derivative to produce oligomer (III). . The reaction between the silylated aromatic diaminodihydroxy compound and the dicarboxylic acid derivative is slightly different depending on the solvent used in an organic solvent, under substantially anhydrous and oxygen-free conditions, under dry nitrogen or argon gas, but -20 It may be carried out at a temperature of 100 ° C to 100 ° 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. The reaction temperature is preferably -10.
-40 degreeC.

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 (c) dicarboxylic acid derivative will be described later. Further, the concentration of the total amount of the compound (a) 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.
The polymerization reaction between the compound (d) and the (c) dicarboxylic derivative is considered to proceed as shown in the following (Chemical Formula 15). In the following reaction formula (Formula 15), as the silylated aromatic diaminohydroxy compound, a compound obtained by silating diaminodihydroxybenzene is used.

[0102]

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

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 preferable that the amount is about 5 mol / liter. Concentration is 5 mol /
When it exceeds liter, it becomes difficult to dissolve each component, which is not preferable. The polymerization reaction may be performed at -20 ° C to 100 ° 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 40 ° 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 between the compound (e) and the (c) dicarboxylic derivative is performed by
It is considered that the process proceeds as described in 6). In the following reaction formula (Formula 16), as the (e) silylated aromatic diamino compound, 3,4'-diaminodiphenyl ether silylated is used.

[0107]

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(Wherein Ar represents an aromatic residue, X represents a halogen, and Me represents 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 the respective oligomers, the molar amount of the compound (d) or the compound (e) and the molar amount of the dicarboxylic acid derivative are basically the same, but the following reasons are mentioned: the oligomer (III) and the oligomer (IV ), Oligomer (III), 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 research conducted by the present inventors, when a relatively large amount of the oligomer (III) is used in the production of the precursor copolymer described later (that is, P
In the case where many rigid sites having dihydroxyl groups are introduced into the BO copolymer), the amount of the (c) dicarboxylic acid derivative in the synthesis of the oligomer (III) is set to the compound (d).
It is better to add a little more than the number of moles of. On the other hand, when the amount of the oligomer (III) is smaller than that of the oligomer (IV) in the production of the precursor copolymer, the amount of the (c) dicarboxylic acid derivative in the synthesis of the oligomer (III) is less than that of the compound (d). It is better to be slightly less than the number of moles. However, in the synthesis of one oligomer, (c)
When the amount of the dicarboxylic acid derivative is slightly reduced, the amount of the (c) dicarboxylic acid derivative is increased in the synthesis of the other oligomer by the reduced amount.

(4) Preparation of 2PBO Block Copolymer
The oligomer (III) and the oligomer (IV) obtained by the above - mentioned method are reacted in an organic solvent to synthesize a block copolymer. 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 -20 to 250 ° C. for 6 to 24 hours to synthesize a block copolymer. . If the temperature is lower than -20 ° C, the polymerization does not proceed. 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 ring-closing reaction. PB obtained
The intrinsic viscosity η _inh (N-methyl-2-pyrrolidone, 30 ° C., 0.5 g / dl) of the O precursor block copolymer is
It is about 0.6 to 2.0.

The polymerization reaction of the oligomer (III) and the oligomer (IV) proceeds as shown in the following (Chemical formula 17) to obtain a block copolymer. Here, as the oligomer (III), the one obtained by the reaction shown in (Chemical Formula 15) above is used, and as the oligomer (IV), the one shown in (Chemical Formula 16) is used. It is not limited.

[0114]

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Note that m and n indicate the degree of polymerization. Moreover, m: n is 0.01: -99.99-99.
It can be in the range of 99: 0.01. The block copolymer obtained can be washed and dried by known methods.

Method for Producing Molecular Composite Material In order to obtain the three-dimensional network fine particle-dispersed molecular composite material of the present invention, first, the above matrix polymer and the aromatic heterocyclic copolymer precursor obtained as described above are used. After they are dissolved in an organic solvent in which both are well dissolved and are made compatible with each other, they are desolvated in a non-solvent and coagulated into fibers to obtain fibers of a molecular composite material composed of a matrix polymer and a precursor copolymer.

Examples of such an 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 precursor copolymer and the matrix polymer, the reinforcing effect can be obtained even if the blending amount of the precursor copolymer is extremely small, but finally the blending ratio of the aromatic heterocyclic copolymer and the matrix polymer is a weight ratio. It is preferable to set it in the range of 1:99 to 90:10. If the compounding ratio of the aromatic heterocyclic copolymer, which is a reinforcing polymer, becomes too large, its existence becomes too dense,
It is considered that the aromatic heterocyclic copolymers aggregate with each other to cause poor dispersion at the molecular level, which lowers the mechanical strength of the molecular composite material. A more preferable mixing ratio is 3: 9.
It is 7 to 80:20.

The precursor copolymer and the matrix polymer may be dissolved by any method as long as a homogeneous solution is obtained. For example, a solution of the precursor copolymer and a matrix polymer may be prepared and then mixed to form a uniform solution, or the solution of the precursor copolymer may be added with the matrix polymer to form a uniform solution. Alternatively, both may be dissolved in one type of solvent at a time. The final concentration of the solution is preferably 1 to 40% by weight. More preferably, it is 3 to 30% by weight. If the final concentration of the solution is less than 1% by weight, it is too thin to be practical, while if it exceeds 40% by weight, the solubility decreases.

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., preferably room temperature to 80 ° C., more preferably room temperature to 60 ° C. If the temperature is lower than -15 ° C, the solubility is low. On the other hand, if the temperature exceeds 150 ° C, decomposition proceeds, which is not preferable. The preparation and mixing of the solution of the precursor copolymer and the matrix polymer is preferably performed in an atmosphere of an inert gas such as nitrogen gas or argon gas.

For the fibrous solidification, the solution may be poured into a coagulation bath. The pouring may be performed by simply pouring it into a coagulation bath, but it is more preferable to blow it out from a die of 0.1 to 1 mmφ. The fibers in the coagulation bath should be wound up continuously. Examples of the non-solvent used for desolvation include alcohols such as methanol and ethanol, and distilled water.

In the case of using the PBO precursor copolymer, in the case of using a silylated compound as the compounds (d) and (e), the mixture is agitated in an alcohol such as methyl alcohol for several hours, and the alcohol washing is repeated. As illustrated in the following reaction formula (Formula 18), desilylation reaction treatment is performed. In the formula, Ar is an aromatic residue.

[0123]

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Next, the fibers of the composite of the precursor copolymer and the matrix polymer obtained above are heat treated under tension and / or stretching to cause a thiazole or oxazole ring-closing reaction in the precursor copolymer to give an aromatic compound. A composite fiber of group heterocyclic copolymer is obtained.

In this heating, the alkyl group R is released in the case of the PBT precursor copolymer, and hydrogen is released in the case of the PBO precursor copolymer, and the thiazole ring or the oxazole ring is formed at that site, and the aromatic heterocyclic copolymer is formed. It is formed. When the precursor copolymer (PBT precursor copolymer) obtained by the reaction formula shown in (Formula 12) is used as the precursor copolymer, an aromatic heterocyclic copolymer having the following structural formula (Formula 19) is formed.

[0126]

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If the precursor copolymer (PBO precursor copolymer) obtained by the above reaction formula (Chemical formula 18) is used, an aromatic heterocyclic copolymer having the following structural formula (Chemical formula 20) is formed. It

[0128]

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In the present invention, such heat treatment is carried out under tension and / or stretching. That is, the heat treatment is carried out while maintaining a fixed length or stretching. You may do both of these. When the fiber is held at a constant length (tensile heat treatment), it is preferable to use a jig that can clamp both ends of the fiber. In the case of stretching, 1.1 to
It is preferable to stretch the film about 2.0 times. Since the precursor copolymer used in the present invention contracts due to a ring-closing reaction or the like, a contraction tension is applied at the time of heating, and when it is held at a constant length, it self-stretches, and thus is in the same state as the stretching. Therefore, by heating under such a tensioned condition, aggregation of the aromatic heterocyclic copolymer molecules can be prevented, and the rigid polymer can be well uniaxially oriented.

The heat treatment temperature of the composite fiber of the precursor copolymer and the matrix polymer varies depending on the type of the matrix polymer used, the tension, the stretching method and the like, but is generally 250 to 400 ° C. At temperatures lower than 250 ° C, formation of thiazole ring or oxazole ring is not observed. On the other hand, when the temperature exceeds 400 ° C, decomposition proceeds. In the case of heating while maintaining a constant length, in the case of PBT, it is heated at 250 ° C for 1 hour, then heated to 275 ° C and heated for 1 hour, and further heated to 300 ° C and heated for 1 hour while stretching. Best to do. 25 for PBO
It is optimal to perform heating at 0 to 400 ° C. for 30 minutes to 1 hour. When stretching, it is performed at 250 ° C. for 1 hour at 275
The temperature was raised to ℃ and stretched for 1 hour.
It is preferable to raise the temperature to ° C and heat for 1 hour. The heating may be performed by such a heating program in which the temperature is changed stepwise or by a constant heating temperature. The heating may be performed in the air, but is preferably performed in vacuum or in an inert atmosphere.

The composite material of the present invention can be obtained by molding the composite fiber of the matrix polymer and the aromatic heterocyclic copolymer thus obtained by the mold hot pressing method. At the time of molding, the fiber thus obtained has a length of 1 to 30 mm and a diameter of 0.3 to 1.
It is preferable to make short fibers of 0 mm, put them in a mold, and hot press the mold.

The molding temperature is preferably 250 to 400 ° C. If it is less than 250 ° C, melting does not occur, while if it exceeds 400 ° C, decomposition of the matrix component is not preferable. Further, the pressure is preferably 50 to 500 kgf / cm ² ,
More preferably, it is 100 to 300 kgf / cm ² .
If it is less than 50 kgf / cm ² , voids remain in the molded product, while if it exceeds 500 kgf / cm ² , the residual stress increases. The molding may be performed in the air, but an inert atmosphere is preferable.

According to the above-mentioned method, since the precursor copolymer uniformly dispersed in the matrix polymer at the molecular level becomes the aromatic heterocyclic copolymer as it is, the aromatic heterocyclic copolymer is finely and uniformly dispersed in the matrix polymer. As a result, a molecular composite material having good mechanical properties is obtained. Further, due to the tension applied to the fiber during the ring-closing reaction, the reinforcing material molecules do not aggregate into particles, and the subsequent heating in melt molding causes the mesh to be subdivided into a group of particles, resulting in a uniform three-dimensional structure. It has a network fine particle dispersion structure.

FIG. 1 is a schematic diagram showing the state of the composite material of the present invention. In the molded article, the aromatic heterocyclic copolymer-rich phase, which is a reinforcing material, is distributed in a three-dimensional network in the matrix polymer, and the fine particles are dispersed in the PBT copolymer-rich phase. This is an electron micrograph (magnification: 34,000) of the PBT copolymer composite material of the present invention shown in FIG.
Times). The average diameter of the mesh is preferably 2 μm or less, and the average particle diameter (φ) of the aromatic heterocyclic copolymer fine particles is preferably 60 nm or less.

In the composite material of the present invention, the aromatic heterocyclic copolymer which is the reinforcing material thus forms a three-dimensional network fine particle dispersion structure, and is extremely finely and uniformly dispersed in the matrix polymer. In addition, general melt molding is possible, and during molding, there is no agglomeration of the reinforcing material polymer, and large phase separation does not occur. Thereby, the composite material of the present invention,
It has excellent mechanical properties.

As described above, the aromatic heterocyclic polymer is
Due to its high rigidity, it generally has poor solubility, is soluble only in strong acids, does not melt by heat, and also has poor compatibility, making it difficult to mold and form it as a matrix polymer and composite material. There are also problems.

In the present invention, as a means for solving such a drawback, a fragment which is the same as or similar to the matrix polymer is introduced into the aromatic heterocyclic polymer to form a copolymer to improve the compatibility with the matrix polymer. . Then, during the ring-closing reaction, by applying tension to the fiber, it is possible to prevent the reinforcing material molecules from agglomerating into particles, and to subdivide the mesh into a group of particles by heating in the subsequent melt molding,
It is possible to form a three-dimensional network fine particle dispersion structure in the aromatic heterocyclic copolymer which is a reinforcing material and finely and uniformly disperse it in the matrix polymer to form a composite. Therefore, general melt molding becomes possible, a large phase separation does not occur at the time of molding, an aromatic heterocyclic copolymer does not aggregate, and a molecular composite material having excellent mechanical properties can be obtained.

[0138]

The present invention will be described in more detail with reference to the following examples. Example 1 (1) Synthesis of PBT precursor random copolymer

[0139]

[Chemical 21] And 8 mmol of the compound (a) represented by
2)

[0140]

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2 mmol of the compound (b) represented by
Under an argon atmosphere, N-methyl-pyrrolidone (hereinafter "N
(Referred to as “MP”) and dissolved in 15 ml to prepare a uniform solution. This solution was ice-cooled together with the container to obtain 2 as the compound (c).
10 ml of chloroterephthalic acid dichloride was added. 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 1.4. The intrinsic viscosity was measured in NMP with a polymer concentration of 0.5 g / dl,
It was carried out by the Ubbelohde method at 30 ° C. The structure of the obtained random copolymer is believed to be as follows.

[0143]

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In this polymer, m: n is
It is 8: 2. (2) Production of molecular composite material Precursor random copolymer 1 obtained as described above
8.35 g and 21.64 g of an aromatic polyamide represented by the following formula (Formula 24) as a matrix polymer were dissolved in 100 ml of NMP and mixed by stirring at room temperature to 80 ° C. for 1 week to obtain a uniform brown solution. Got

[0145]

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This solution was poured into a large amount of ethanol in a thread form and solidified to obtain a precursor random copolymer and a matrix polymer composite fiber. 100 fibers obtained
Vacuum dried at ℃. The vacuum dried fiber was clamped and held at a constant length for heat treatment to close the precursor random copolymer. The heating program at this time is shown in Fig. 3.
Shown in

The heat-treated fiber thus obtained was
Cut into 0.5 to 5 mm, put this in the mold shown in FIG. 8, and perform hot press molding of the mold to obtain 15 × 50 × 2t.
A (mm) flat plate molded product was obtained. The mold heating program at this time is shown in FIG. The molding was performed in an argon atmosphere. The bending properties of this molded product are shown in Table 1.

Further, a transmission electron micrograph (ultra thin section method) of the molded product is shown in FIG. From the photograph, it can be seen that in the molded product, the PBT copolymer-rich phase is distributed in the matrix polymer in a three-dimensional network, and moreover, it is dispersed as fine particles in the PBT copolymer-rich phase. The average diameter of the mesh was 0.5 μm or less, and the average diameter (φ) of the PBT copolymer fine particles was about 50 nm.

Example 2 In the same manner as in Example 1, a composite fiber of the matrix polymer and the precursor random copolymer was obtained and vacuum dried. This fiber was held at a constant length while the temperature was raised to 250 ° C., and stretched 1.5 times while the temperature was further raised to 330 ° C.
A heat treatment was performed at 0 ° C. for 30 minutes while maintaining a constant length. The heating program is shown in FIG.

The heat-treated fiber thus obtained was
Cut into 0.5 to 5 mm, put this in the mold shown in FIG. 8, and perform hot press molding of the mold to obtain 15 × 50 × 2t.
A (mm) flat plate molded product was obtained. The mold heating program at this time is shown in FIG. The molding was performed in an argon atmosphere. The bending properties of this molded product are shown in Table 1.

Comparative Example 1 Only the matrix polymer used in Example 1 was subjected to a die hot pressing method to obtain 50 × 15 × 2t (m).
m) was obtained. The heating program is shown in FIG. 7. The bending properties of the obtained molded product are shown in Table 1.

[0152]

[Table 1]

[0153]

INDUSTRIAL APPLICABILITY In the method of the present invention, a fragment containing at least a part of the matrix polymer is introduced into an aromatic heterocyclic polymer which is a reinforcing polymer to prepare a copolymer.
The compatibility between the reinforcing polymer and the matrix polymer is improved. When the aromatic heterocyclic copolymer that is the reinforcing material has a three-dimensional network fine particle dispersion structure, it becomes possible to disperse well and uniformly in the matrix polymer. Therefore, general melt molding becomes possible, a large phase separation does not occur at the time of molding, an aromatic heterocyclic copolymer does not aggregate, and a molecular composite material having excellent mechanical properties can be obtained.

With such a fine composite structure, the mechanical properties can be greatly improved without impairing the moldability. Since the molecular composite material of the present invention has good mechanical strength, it can be widely used in automobile parts, aviation parts, space equipment and the like.

[Brief description of drawings]

FIG. 1 is a schematic view showing a composite state of a three-dimensional network fine particle dispersed type molecular composite material of the present invention.

2 is an electron micrograph (particle structure,
Magnification = 34,000 times).

3 is a heating program for heat treatment in Example 1. FIG.

FIG. 4 is a heating program for molding in Example 1.

FIG. 5 is a heating program for heat treatment in Example 2.

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

7 is a heating program for molding in Comparative Example 1. FIG.

FIG. 8 is a configuration diagram of a mold used in an example,
(A) is an assembly block diagram, (b) is an exploded block diagram.

Claims (7)

[Claims] 1. A three-dimensional network fine particle dispersion type molecular composite material comprising a matrix polymer and an aromatic heterocyclic copolymer having a three-dimensional network fine particle dispersion type structure. 2. The three-dimensional network fine particle-dispersed molecular composite material according to claim 1, wherein the matrix polymer is an aromatic polyamide and the aromatic heterocyclic copolymer is a polybenzothiazole copolymer. 3. The three-dimensional network fine particle-dispersed molecular composite material according to claim 2, wherein a fragment containing at least a part of the matrix polymer is introduced into the polybenzothiazole copolymer to form a copolymer. 4. A matrix polymer and a precursor of an aromatic heterocyclic copolymer are made compatible with each other in an organic solvent, and the solution is desolvated in a non-solvent to coagulate into a fibrous form to obtain a composite material thereof, By subjecting this fibrous composite material to heat treatment under tension and / or stretching, a ring-closing reaction of the precursor of the aromatic heterocyclic copolymer occurs, and a composite material of the matrix polymer and the aromatic heterocyclic copolymer is obtained. A method for producing a three-dimensional network fine particle-dispersed molecular composite material, characterized by performing hot press molding of a mold. 5. The method for producing a three-dimensional network fine particle dispersed type molecular composite material according to claim 3, wherein the matrix polymer is an aromatic polyamide and the aromatic heterocyclic copolymer is a polybenzothiazole copolymer. 6. The method for producing a three-dimensional network fine particle-dispersed molecular composite material according to claim 5, wherein a fragment containing at least a part of a matrix polymer is introduced into a polybenzothiazole copolymer to form a copolymer. 7. A molded product obtained by the manufacturing method according to claim 4.