JPH0925419A - Fine particle dispersion type molecular composite material - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: A rigid aromatic polymer, which is a reinforcing polymer, is finely and uniformly dispersed in a matrix polymer, and there is no agglomeration of the reinforcing polymer in the heat molding stage, which is mechanical. Provide a molecular composite material having excellent strength and the like. A fine particle-dispersed molecular composite material comprising a matrix polymer and an aromatic heterocyclic copolymer forming a fine particle-dispersed 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. The present invention relates to a fine particle-dispersed type 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. 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 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 fine particle dispersion type molecular composite material comprising a matrix polymer and an aromatic heterocyclic copolymer having a fine particle dispersion type structure. In addition, the present invention provides a method in which a matrix polymer and a precursor of an aromatic heterocyclic copolymer are made compatible with each other in an organic solvent, desolvated and solidified to obtain a composite material thereof, and then heat treatment is performed to heat the aromatic heterocyclic ring. Provided is a method for producing a fine particle-dispersed molecular composite material, which comprises subjecting a precursor of a copolymer to a ring-closing reaction to obtain a composite material of a matrix polymer and an aromatic heterocyclic copolymer, and subjecting the composite material to hot press molding of a mold. There is something to do.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The fine particle-dispersed type molecular composite material of the present invention is a two-phase composite material in which a matrix-rich phase is an island and a reinforced polymer (aromatic heterocyclic copolymer) -rich phase is a sea, and is a reinforced polymer-rich material. The reinforcing material is uniformly dispersed as fine particles in the phase.

In the present invention, examples of the matrix polymer include polyamide, polyimide, polyamideimide, 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 a matrix polymer,
Aromatic polyamide is particularly preferable.

Next, the aromatic heterocyclic copolymer will be described. In the present invention, the aromatic heterocyclic copolymer serving as the reinforcing polymer of the molecular composite material forms a fine particle dispersed structure in the composite material. The maximum diameter (φ) of fine particles is 1
Even if it is less than 00 nm, it is uniformly dispersed, and thus the composite material of the present invention has excellent mechanical properties. Such aromatic heterocyclic copolymers include polybenzothiazole (PBT) or polybenzoxazole (PB).
The random or block copolymer of O) is mentioned.

In the present invention, the matrix polymer and the aromatic heterocyclic copolymer are compounded by mixing the matrix polymer and the precursor of the aromatic heterocyclic copolymer into a composite material, which is heated at a predetermined temperature to close the ring. A reaction is allowed to occur, and finally a composite material of the matrix polymer and the aromatic heterocyclic copolymer is obtained. Then, the composite material molded article 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 has 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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(Wherein 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 may be an aromatic ring in which two or more benzene rings are condensed,
Further, it may be one having two or more benzene rings bonded to each other 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 alkali concentration of the alkaline aqueous solvent is preferably 2 equivalents or more and 4 equivalents or less of the monomer.
It is an equilibrium reaction, and if it is less than 2 equivalents, the reaction does not proceed sufficiently. On the other hand, if it exceeds 4 equivalents, it is troublesome to remove the alkaline aqueous solvent and the workability deteriorates.

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. 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. In addition, 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, the compound (b) having a structure similar to or similar to a part of the matrix polymer to be mixed is selected. Is good.

(C) Dicarboxylic Acid Derivative In addition, 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).

[0043]

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

[0045]

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In addition, 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 99.9.
Compound (a) and compound (b) so as to be 9: 0.01
Is blended.

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 enhance the solubility, 3 to 20% by weight of chloride such as LiCl or CaCl ₂ may be added.

The compounds (a), (b) and (c) are polymerized to produce a precursor random copolymer, and the polymerization reaction temperature at this time is preferably -20 to 50 ° 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 set to 50 ° C. More preferably, -2
It is in the range of 0 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 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 1.6.

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 form 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 acid derivative As 2-
Chloroterephthalic acid dichloride is used. Also,
m and n represent the degree of polymerization.

[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. 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 (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). 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.

The total concentration of the compounds (a) 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 /
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., the thiazole ring closure reaction may occur, so the upper limit of the temperature of the polymerization reaction is set to 200 ° C. Preferably, it is -20 to 80 ° C, more preferably -10 to 50 ° C.
Range.

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 follows. In the following reaction formula (Formula 10), as an example of the compound (a), an alkyl group-substituted product of 2,5-diamino-1,4-benzenedithiol dihydrochloride is used,
(C) 2-Chloroterephthalic acid dichloride is used as an example of the dicarboxylic acid derivative. In addition, m represents a polymerization degree. The intrinsic viscosity η _inh (N-methyl-2-pyrrolidone, 30 ° C., 0.5 g / dl) of the oligomer (I) is
It is about 0.1 to 0.7.

[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 0.5-5.
It is preferable to set it to about mol / liter. The polymerization reaction temperature is −20 ° C. to 400 ° C., preferably −20 to 200.
℃ is good. 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. More preferably, -10 to 50 ° C
Range.

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 not particularly limited, but it is generally good to set it to about 1 to 120 minutes.

The polymerization reaction of the compound (b) and the dicarboxylic acid derivative (c) is considered to proceed as follows. 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., 0.5 g / dl) of the oligomer (II) is 0.
It is about 1 to 0.4.

[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 0.4 to 1.5.

The polymerization reaction of the oligomer (I) and the oligomer (II) proceeds as shown in (Chemical Formula 12) below 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]

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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 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 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 the same or similar structure as part of the matrix polymer to be mixed is used. Good to choose.

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,
Decomposition of amine hydrochloride occurs, 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. If the polymerization temperature is lower than -20 ° C, the polymerization will not proceed, while if it exceeds 250 ° C, the oxazole ring-closing reaction will proceed.

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 0.4 to 1.2.

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). Further, the concentration of the total amount of the compound (d), the compound (e) and the compound (c) in the organic solvent is preferably about 0.5 to 5 mol / liter.
If the concentration is less than 0.5 mol / liter, the polymerization reaction is difficult to proceed, while if the concentration exceeds 5 mol / liter, it is 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 comprises (i) compounds (d) and (e), respectively.
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 PBO precursor block copolymer
Synthesis of oligomer for use in the production of silylated aromatic diaminodihydroxy compound under the above-mentioned conditions. Next, the silylated aromatic diaminohydroxy compound (d) is reacted with (c) dicarboxylic acid derivative to produce an oligomer. (III) is produced. The reaction between the (d) silylated aromatic diaminodihydroxy compound and the (c) dicarboxylic acid derivative is carried out in an organic solvent under substantially anhydrous and oxygen-free conditions under dry nitrogen or argon gas and the solvent used. -10 ℃ to 80
It may be carried out at 5 ° C. for 5 minutes to 2 hours. The reaction temperature is -20
If the temperature is lower than 0 ° C, the reactivity is insufficient, whereas if the temperature exceeds 100 ° C, the above reaction product may be oxidized. The reaction temperature is preferably -10 to 30 ° 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 relative to the compound (d) is appropriately set. It is better to increase or decrease. The adjustment of the amount of the compound (c) dicarboxylic acid derivative will be described later. Further, the concentration of the total amount of the compound (d) and the dicarboxylic acid derivative (c) in the organic solvent is preferably about 0.5 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 dicarboxylic derivative (c) is considered to proceed as follows. In addition, in the following reaction formula (Formula 15), as (d) 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 compound (e) and the dicarboxylic acid derivative (c) in the organic solvent is from 0.5 to
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 is carried out at -10 to 80 ° C for 5 minutes.
It may be done for a minute to two hours. If the reaction temperature is less than -20 ° C, the reactivity is insufficient, while if it exceeds 100 ° C, the reaction product may be oxidized. Preferably,
The reaction temperature is -10 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 dicarboxylic derivative (c) is considered to proceed as follows. In addition, the following reaction formula (Formula 1
In (6), as (e) silylated aromatic diamino compound, 3,4'-diaminodiphenyl ether silylated is used.

[0107]

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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 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 -10 to 40 ° C for 2 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 0.4 to 1.5.

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 to.

[0114]

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Here, 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.

Method for Producing Molecular Composite Material In order to obtain the fine particle-dispersed molecular composite material of the present invention, first of all, the above matrix polymer and the aromatic heterocyclic copolymer precursor obtained as described above are favorably used. After being dissolved and dissolved in an organic solvent to be dissolved, the solvent is removed and solidified to obtain a molecular composite material including 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. Also, both may be dissolved in one kind 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. 1% by weight
If it is less than the above range, it is too thin to be practical, and if it exceeds 40% by weight, the solubility is lowered.

The mixing time varies somewhat 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. The solution of the precursor 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.

As the method for removing the solvent, a compatible solution of the matrix polymer and the aromatic heterocyclic copolymer precursor is prepared.
There is a method in which the both polymers are put in a non-solvent or dried to form a cast film.

Examples of the non-solvent include alcohols such as methanol and ethanol, distilled water and the like. The charging method may be any method, such as spraying the polymer solution,
Examples of the method include, but are not limited to, dropping, pouring into fibers, spreading on a plate in a non-solvent, or desolvating by heating or decompression to solidify. Of these, the method of spraying is preferable.

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 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.

[0124]

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Next, the composite of the precursor copolymer and the matrix polymer obtained above is heated to cause a thiazole or oxazole cyclization reaction in the precursor copolymer to obtain a composite material of an aromatic heterocyclic copolymer.

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.

[0127]

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

[0129]

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The heating temperature of the homogeneous mixture of the precursor copolymer and the matrix polymer varies depending on the kind of the matrix polymer used, but is generally 250 ° C to 40 ° C.
Set to 0 ° C. At temperatures below 250 ° C, formation of thiazole or oxazole rings is not seen. On the other hand, 40
If it exceeds 0 ° C, decomposition of the polymer starts and it is not preferable. In the case of PBT, it takes about 30 minutes at 330 ℃,
Optimal. Further, in the case of PBO, it is optimal to carry out at 350 ° C. for about 30 minutes. The heating may be performed not only by a constant heating temperature but also by a heating program in which the temperature is changed stepwise. Further, the heating is preferably performed in vacuum.

The composite material of the present invention can be obtained by molding the composite material of the matrix polymer thus obtained and the aromatic heterocyclic copolymer by a mold hot pressing method. The molding temperature is preferably 200 to 400 ° C. If it is less than 200 ° C, the molding fluidity is low, while if it exceeds 400 ° C, the polymer starts to decompose, which is not preferable. Further, the pressure is preferably 60 to 300 kgf / cm ² , and more preferably 80 to 150 kgf / cm ² . If it is less than 60 kgf / cm ² , voids are likely to occur in the molded product, while if it exceeds 300 kgf / cm ² , the problem of residual stress tends to occur. The mold hot press molding is preferably performed in an argon atmosphere glove box.

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.

The composite material of the present invention thus obtained is finely composited in nanometer units. FIG.
A schematic diagram showing the state of the composite material of the present invention is shown in FIG. The matrix-rich phase is an island and the aromatic heterocyclic copolymer, which is a reinforcing material, is the sea. The reinforcing material is uniformly dispersed in the reinforcing material-rich phase as fine particles having a maximum diameter (φ) of 100 nm or less. This is clear from the electron micrograph (magnification: 40,000 times) of the composite material of the present invention shown in FIG. In the composite material of the present invention, the aromatic heterocyclic copolymer that is the reinforcing material thus forms a fine particle dispersed structure,
General melt molding is possible, and during molding, there is no agglomeration of the reinforcing polymer and no large phase separation occurs. Therefore, the composite material of the present invention has excellent mechanical properties.

[0134]

[Function] Aromatic heterocyclic polymers generally have poor solubility due to their high rigidity, are soluble only in strong acids, do not melt by heat, and have poor compatibility, making molding difficult. Therefore, there is a problem in forming a composite material with the matrix polymer.

In the present invention, as a means for solving such a drawback, a compound in which a fragment which is the same as or similar to the matrix polymer is introduced into an aromatic heterocyclic polymer to form a copolymer to improve the compatibility with the matrix polymer. Is. Then, the aromatic heterocyclic copolymer, which is the reinforcing material, is finely and finely dispersed in the matrix polymer in the unit of nanometer, and is composited. Thus, general melt molding becomes possible, a large phase separation does not occur during molding, and the aromatic heterocyclic copolymer does not aggregate, so that a molecular composite material having excellent mechanical properties can be obtained.

[0136]

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

[0137]

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

[0138]

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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 presumed to be as shown below.

[0141]

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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 an aromatic polyamide represented by the following formula (Formula 24) as a matrix polymer [Tray Co., Ltd., T
X-1] 21.64 g was dissolved in 160 ml of NMP and mixed by stirring at room temperature to 80 ° C. for 1 week to obtain a uniform brown solution.

[0143]

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This solution was sprayed into a large amount of ethanol to obtain a coagulated powder. This was filtered, and the obtained coagulated powder was vacuum dried at 100 ° C. This vacuum-dried powder was heat-treated in vacuum at 330 ° C. for 30 minutes to ring-close the precursor random copolymer to obtain a PBT copolymer. The content of PBT is 30% by weight.

The composite material thus obtained was filled in a mold shown in FIG. 14 and was subjected to 15 × 5 by a mold hot pressing method.
A molded product T / P of 0 × 2t (mm) was obtained. The mold heating program at this time is shown in FIG. Pressure is 100k
gf / cm ² .

The bending property of the obtained molded product has an elastic modulus of 6
The strength was 44 kgf / mm ² and the strength was 6.8 kgf / mm ² . Further, a transmission electron microscope (ultra thin section method) photograph of the molded product is shown in FIG. From this photograph, the molded product consists of two phases, an island-shaped portion and a sea-shaped portion containing the same, and particles having a maximum diameter (φ) of 10 to 50 nm are uniformly dispersed in the sea-shaped portion. I understand that.

FIG. 1 is a schematic representation of this photograph. EDX spectra of the sea-shaped portion and the island-shaped portion in this figure are taken and shown in FIGS. 4 to 5, respectively. It can be seen that the sea-shaped portion contains S and Cl, but the island-shaped portion does not contain these, and the sea-shaped portion is the polybenzothiazole-rich phase and the island-shaped portion is the matrix-rich phase.

As described above, the composite material of the present invention is a two-phase composite material in which the matrix-rich phase is an island and the reinforced polymer-rich phase is the sea.
The reinforcing material is uniformly dispersed as fine particles.

Comparative Example 1 100 kgf / cm ² was obtained from only the matrix polymer used in Example 1 by a die hot pressing method.
Under the conditions described above, a molded product T / P of 50 × 15 × 2t (mm) was obtained. The heating program is shown in FIG. The bending properties of the obtained molded product were an elastic modulus of 479 kgf / mm ² and a strength of 20.4 kgf / mm ² . Table 1 shows a comparison of the physical properties of Example 1 and Comparative Example 1.

[0150]

[Table 1]

In the table, the Izod impact was measured at room temperature without notches. Further, the bending elastic moduli of Example 1 and Comparative Example 1 at high temperature are shown in FIG. From the above, it can be seen that, even if a small amount of the reinforcing component was added, the rigidity, impact resistance, hardness, and high-temperature physical properties were significantly improved and the thermal expansion was decreased by the fine composite formation.

Example 2 Varying the mixing ratio of the precursor random copolymer and the matrix polymer, the resulting PBT content was 6-5.
Molded products were obtained in the same manner as in Example 1 except that the range was 0% by weight, and the flexural modulus of these molded products was investigated. PB
FIG. 8 shows the relationship between the T content and the flexural modulus.

Examples 3 to 8 Precursor random copolymers were obtained in the same manner as in Example 1 except that m was 6 and n was 4. The intrinsic viscosity η _inh of this polymer was 1.2. The intrinsic viscosity was measured in NMP at a polymer concentration of 0.5 g / d.
1 and performed at 30 ° C. by the Ubbelohde method. 6.5 g of the precursor random copolymer thus obtained and 4.34 g of the same matrix polymer as in Example 1 were
It was dissolved in the amount of NMP shown in Table 2 and a molded product was obtained in the same manner as in Example 1. The content of PBT in these molded products is
All were 30% by weight.

[0154]

[Table 2]

The bending properties of these molded products are shown in Table 3 below together with the results of Comparative Example 1. A graph showing the relationship between the polymer solution concentration and the flexural modulus at the time of compatibility is shown in FIG.

[0156]

[Table 3]

Examples 9 to 13 Precursor block copolymers having the same structural formula as the precursor copolymer of Example 1 were prepared as follows. (1) Synthesis of Oligomer (I) and Oligomer (II) Under a dry stream of argon, 5 ml of NMP was placed in a well-dried 50 ml flask, and the
1 mmol of the compound (a) represented by 1) (2.227)
g) was added and dissolved to prepare a uniform NMP solution.

With this container being ice-cooled together with the solution, 8.2 mmol (1.947 g) of 2-chloroterephthalic acid dichloride as compound (c) was 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 solution was cooled in ice with the container, 1.8 mmol (0.427 g) of 2-chloroterephthalic acid dichloride as compound (c) was added and stirred for 5 minutes to synthesize oligomer (II). .

(2) PBT precursor block copolymer
Synthesis The NMP solution of the oligomer (I) obtained by the above operation 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 the mixed oligomer solution was cooled with ice, 1
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 1.2. The intrinsic viscosity was measured by setting the polymer concentration in NMP to 0.5 g / dl,
It was carried out by the Ubbelohde method at 30 ° C.

In this polymer, the degree of polymerization m of the site which is derived from the oligomer (I) and exhibits rigidity is
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.
Becomes

(3) Production of Molecular Composite Material 5.0 g of the precursor block copolymer obtained by the above method and the same matrix polymer as in Example 1.
71 g was dissolved in the amount of NMP shown in Table 4, and a molded product was obtained by the same method as in Example 1. The content of PBT in each of these molded products was 30% by weight.

[0166]

[Table 4]

The bending properties of the molded product are shown in Table 5 below together with the results of Comparative Example 1. Further, a graph showing the relationship between the polymer solution concentration and the flexural modulus at the time of compatibility is shown in FIG.

[0168]

[Table 5]

Examples 14 to 15 Precursor random copolymers were obtained in the same manner as in Example 1 except that isophthalic acid dichloride was used as the compound (c). The intrinsic viscosity η _inh was 1.4. In addition,
Intrinsic viscosity was measured in NMP at a polymer concentration of 0.5.
g / dl and the Ubbelohde method at 30 ° C.
The structure of the obtained random copolymer is
It is presumed to be as in 5).

[0170]

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The obtained random copolymer and the same matrix polymer as in Example 1 were used in the amounts shown in Table 6, NMP4.
It was dissolved in 00 ml and a molded product was obtained in the same manner as in Example 1. Table 6 shows the PBT content of these molded products.

[0172]

[Table 6]

The bending properties of the molded product are shown in Table 7 below together with the result of Comparative Example 1. Further, a graph showing the relationship between the PBT content and the flexural modulus is shown in FIG.

[0174]

[Table 7]

Examples 16 to 18 and Comparative Example 2 Compound (b) represented by the following formula (Formula 26)

[0176]

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A precursor random copolymer was obtained in the same manner as in Example 1 except that the compound shown in was used. The intrinsic viscosity η _inh of this polymer was 0.88. 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 obtained random copolymer is presumed to be as shown below.

[0178]

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In this polymer, m: n is
It is 8: 2. Compound 40 represented by the above (Chemical Formula 26)
The mmol was dissolved in 60 ml of NMP to prepare a uniform NMP solution. In a state where this solution was ice-cooled together with a container, 40 mmol of 2-chloroterephthalic acid dichloride was added,
The mixture was stirred for 12 hours to synthesize a matrix polymer. The intrinsic viscosity η _inh of this polymer was 0.55. 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 obtained polymer is presumed to be as follows.

[0180]

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The precursor random copolymer obtained by the above method and the matrix polymer were added in the amounts shown in Table 8,
Dissolved in 400 ml of NMP, a molded product was obtained in the same manner as in Example 1. Table 8 shows the PBT content of these molded products.

[0182]

[Table 8]

As Comparative Example 2, only the matrix polymer was molded. The molding temperature at this time was according to the heating program shown in FIG. Pressure is 10kgf / c
m ² . The bending properties of these molded products are shown in Table 9 below. Further, a graph showing the relationship between the PBT content and the elastic modulus is shown in FIG.

[0184]

[Table 9]

Example 19 (1) Monomer Synthesis i) The following formula (Formula 29)

[0186]

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4,6-diaminoresorcinol 2 represented by
50 g (0.357 mol) of the hydrochloride was mixed with 123 ml (0.58 mol) of 1,1,1,3,3,3-hexamethyldisilazane in an argon atmosphere. 6 at 130 ° C
Reflux for a period of time to react. Then, vacuum distillation is performed to
A fraction having an oil bath temperature of 200 to 210 ° C. was obtained at 0 Torr. Thus, the following formula (Formula 30)

[0188]

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A monomer A represented by is obtained. Yield is 60
%Met. In addition, Me is a methyl group. ii) 10 g of the compound (b) represented by the above (formula 22)
(0.05 mol) in an argon atmosphere, 1, 1, 1,
50 ml of 3,3,3-hexamethyldisilazane (0.2
4 mol). The mixture was refluxed at 130 ° C. for 6 hours to be reacted. Then, vacuum distillation was performed to obtain a fraction having an oil bath temperature of 200 ° C. at 10 Torr. Thus, the following formula (Formula 31)

[0190]

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A monomer B represented by is obtained. Yield is 7
It was 0%. In addition, Me is a methyl group. (2) Synthesis of PBO Precursor Random Copolymer 16 mmol of the monomer A and 4 mmol of the monomer B obtained as described above were subjected to NMP2 under an argon atmosphere.
It was dissolved in 0 ml. While stirring this while cooling with ice,
20 mmol of 2-chloroterephthaloyl dichloride was added, and the mixture was stirred at 0 ° C to room temperature for 6 hours. The solvent was removed under reduced pressure at 80 ° C. to obtain a precursor random copolymer represented by the following (Chemical Formula 32). The intrinsic viscosity η _inh of this polymer is
It was 0.98. The intrinsic viscosity was measured by the Ubbelohde method at 30 ° C. with a polymer concentration of 0.5 g / dl in NMP. In this polymer,
m: n is 8: 2.

[0192]

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5.56 g of the PBO precursor random copolymer thus obtained and 6.14 g of the same matrix polymer as in Example 1 were dissolved in 46.8 ml of NMP and stirred at room temperature for 1 week. Then, this solution was sprayed into a large amount of ethanol to obtain a rapidly solidified powder. This coagulated powder was desilylated by refluxing it in a mixed solution of methanol / water (1: 1) for 2 hours, and dried under vacuum at 100 ° C. The structural formula of the polymer after desilylation is shown in Chemical formula 33.

[0194]

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The desilylated coagulated powder was heated at 350 ° C. in vacuum.
At 30 minutes, it heat-treated and the ring-closing reaction was performed, and it was set as the PBO copolymer. In the same manner as in Example 1, a 50 × 15 × 2t molded product was obtained by the die hot pressing method. The bending property of this molded product is such that the elastic modulus is 604 kgf / mm ² and the strength is 2.5 k.
gf / mm ² .

[0196]

INDUSTRIAL APPLICABILITY According to the method of the present invention, the compatibility between the reinforcing polymer and the matrix polymer is improved by introducing a fragment, which is the same as or similar to the matrix polymer, into the aromatic heterocyclic polymer which is the reinforcing polymer to form a copolymer. Can be made. Then, the aromatic heterocyclic copolymer that is the reinforcing material can be finely and uniformly dispersed in the matrix polymer in the unit of nanometer to form a composite.
Thus, general melt molding becomes possible, a large phase separation does not occur during molding, and the aromatic heterocyclic copolymer does not aggregate, so that a molecular composite material having excellent mechanical properties can be obtained.

With such a fine composite structure, rigidity, impact resistance, hardness, high temperature physical properties can be significantly improved and thermal expansion can be reduced even if a small amount of reinforcing component is added. Since the molecular composite material of the present invention has good mechanical strength,
It can be widely used for automobile parts, aviation parts, and space equipment.

[Brief description of drawings]

FIG. 1 is a schematic view showing a composite state of a fine particle dispersion type molecular composite material of the present invention.

2 is an electron micrograph (particle structure,
Magnification = 40,000 times).

3 is a heating program in Example 1. FIG.

FIG. 4 is an EDX of a sea-like portion in the molded article of Example 1.
It is a spectrum.

5 is an EDX of an island-shaped portion in the molded article of Example 1. FIG.
It is a spectrum.

6 is a heating program in Comparative Example 1. FIG.

FIG. 7 is a graph showing the relationship between temperature and flexural modulus in Example 1 and Comparative Example 1.

8 is a graph showing the relationship between PBT content and flexural modulus in Example 2. FIG.

FIG. 9 is a graph showing the relationship between solution concentration and flexural modulus in Examples 3 to 8.

FIG. 10 is a graph showing the relationship between solution concentration and flexural modulus in Examples 9 to 13.

11 is a graph showing the relationship between PBT content and flexural modulus in Examples 14 to 15. FIG.

12 is a heating program in Comparative Example 2. FIG.

FIG. 13 is a graph showing the relationship between PBT content and flexural modulus in Examples 16-18.

FIG. 14 is a configuration diagram of a mold used in an example,
(A) is an assembly block diagram, (b) is an exploded block diagram.

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[Procedure amendment]

[Submission date] October 9, 1995

[Procedure amendment 2]

[Document name to be amended] Drawing

[Name of item to be corrected] Figure 7

[Correction method] Change

[Correction contents]

FIG. 7

Claims (5)

[Claims] 1. A fine particle-dispersed molecular composite material comprising a matrix polymer and an aromatic heterocyclic copolymer having a fine particle-dispersed structure. 2. The 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 aromatic heterocyclic copolymer is obtained by compatibilizing the matrix polymer and the precursor of the aromatic heterocyclic copolymer in an organic solvent, desolvating and coagulating them to obtain a composite material thereof, and then heat treating the composite material. 2. A method for producing a fine particle dispersion type molecular composite material, which comprises subjecting the precursor of step 1 to a ring closure reaction to obtain a composite material of a matrix polymer and an aromatic heterocyclic copolymer, and subjecting the composite material to hot press molding with a die. 4. The method for producing a fine particle dispersed molecular composite material according to claim 3, wherein the matrix polymer is an aromatic polyamide and the aromatic heterocyclic copolymer is a polybenzothiazole copolymer. 5. A fine particle-dispersed type molecular composite material molded article obtained by the manufacturing method according to claim 1.