JP3130362B2 - Molecular composite using aromatic heterocyclic copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a molecular composite comprising an aromatic heterocyclic block copolymer and a matrix polymer.
The present invention relates to a method for producing a molecular composite material suitable for use as a structural material for aircraft, automobiles, space devices, and the like.

[0002]

2. Description of the Related Art In recent years,
For the purpose of reducing the weight of aircraft and automobiles, so-called engineering plastics having excellent mechanical properties and heat resistance have been widely used. Also, in order to improve the strength and rigidity, the development of composite materials such as FRP, which is a combination of a plastic material and high-strength and high-elasticity fibers such as carbon fiber, has been actively conducted, and is widely used in practical use. .

It is known that the strength of these composite materials is greatly affected by the interfacial adhesion between the fibers and the matrix resin, in addition to the strength of the matrix plastic and the fibers used as the reinforcing material. . In addition, the poor impregnating property of the matrix resin into the reinforcing fiber preform affects not only the viewpoint of production but also the strength of the product.
Under such circumstances, even if a fiber or a resin exhibiting high strength and high elasticity is used as a material, it is not always possible to obtain a composite material having excellent strength.

[0004] Therefore, the above-mentioned problems can be overcome as a so-called polymer blend-type composite material (molecular composite material) by finely dispersing a so-called rigid polymer such as an aromatic polyamide to a molecular level in a polymer serving as a matrix resin. However, an attempt to obtain a high-strength composite material has been proposed, and research and development have been conducted.

Aromatic polymers suitably used in molecular composites include, for example, those having a heterocyclic ring such as a thiazole ring, an imidazole ring, an oxazole ring, or an oxazinone ring in a repeating unit. Aromatic polythiazoles are promising as reinforcing polymers for molecular composites due to their excellent mechanical strength.

By the way, even if an attempt is made to produce a molecular composite by simply mixing a reinforcing polymer such as aromatic polythiazole and a matrix polymer, the rigid polymer has a rigidity and a matrix polymer. Is generally 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. For this purpose, various attempts have been made so far.

For example, Japanese Patent Application Laid-Open No. 1-287167 discloses coagulation of a polymer solution mainly containing a reinforcing polymer (A) consisting essentially of a polyazole having a rod-like skeleton and a matrix polymer (B) having fusibility. A method for producing a polymer composite comprising introducing into a bath and forming a film, wherein the polymer solution exhibits optical anisotropy, and the polymer solution is apparently dipped in a coagulation bath. A method of solidifying after passing through an optically isotropic phase is disclosed.

Japanese Patent Publication No. 2-7976 discloses a reinforcing polymer A comprising a polyazole having a substantially rod-like skeleton,
A glass transition temperature of 500 ° C. or more and a flow onset temperature of 500 ° C. or less, and when it is kept at a temperature between the glass transition temperature and the flow onset temperature for any time within 5 hours,
A polymer composition comprising a matrix polymer B composed of a hardly crystalline aromatic copolyamide having an apparent crystal size of 25 or less and A / (A + B) = 0.15-0.70 (by weight). Disclosure.

However, in the method for producing a polymer composite disclosed in Japanese Patent Application Laid-Open No. 1-287167 and the production of a composite using the polymer composition disclosed in Japanese Patent Publication No. 2-7976, a reinforcing polymer and a matrix are used. Uniform dispersion with the polymer cannot be expected so much, and the mechanical strength and the like of the obtained molecular composite do not greatly improve. This is probably 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, instead of mixing the rigid aromatic polymer and the matrix polymer, the precursor of the rigid aromatic polymer and the matrix polymer or its precursor are uniformly mixed in an organic solvent to remove the organic solvent. A method in which the precursor is converted into a rigid aromatic polymer by subsequent heating has been proposed (JP-A-64-1760 and JP-A-64-1761).
.

According to the above method, a molecular composite material having relatively good mechanical strength and the like can be produced.

However, according to the research of the present inventors,
For example, using a thermoplastic resin as a matrix polymer for the purpose of hot pressing of a molecular composite material, and using an aromatic polythiazole precursor, the above-mentioned JP-A-64-1760
To produce a molecular composite material by the method disclosed in Japanese Patent Application Laid-Open No. HEI 6-17661 or Japanese Patent Application Laid-Open No. Sho 64-1761, an aromatic polythiazole formed by a thiazole ring-closing reaction in a step of heating a homogeneous mixture of a matrix polymer and a precursor. Were aggregated, and as a result, the mechanical properties of the molecular composite material were found to be reduced. In addition, aromatic polythiazole has poor interaction such as hydrogen bonding with matrix polymer,
The elongation of the resulting molecular composite is small. This is a disadvantage when used as a structural material or the like.

Accordingly, an object of the present invention is to solve the above-mentioned problems, and to provide a molecular composite material in which a rigid aromatic polymer as a reinforcing polymer is well dispersed in a matrix polymer and thus has excellent mechanical strength and the like. It is to provide a manufacturing method that can be used.

[0014]

Means for Solving the Problems In view of the above problems, as a result of intensive studies, the present inventors have found that, as a precursor copolymer of an aromatic heterocyclic polymer, a site which forms an aromatic heterocycle and exhibits rigidity, When a block copolymer having a main chain of a structure in which a matrix polymer and a site having a common or similar structure are alternately bonded to each other with an appropriate length is used, the precursor copolymer is well dispersed in the matrix polymer, In addition, even if this homogeneous mixture is heated, the rigid polymer does not agglomerate, and it has been discovered that a molecular composite material having excellent physical properties can be obtained,
The present invention has been completed.

That is, the molecular composite material of the present invention comprises an aromatic heterocyclic copolymer and a matrix polymer,
The aromatic heterocyclic copolymer and the matrix polymer at least partially have a common or similar structure.

Further, the method of the present invention for producing a molecular composite material comprising an aromatic heterocyclic block copolymer and a matrix polymer comprises the following steps:

Embedded image (Where Ar and Ar ′ are aromatic residues, R is a substituted or unsubstituted alkyl group, X is a residue of a dicarboxylic acid derivative, m and n are both integers, and m: n
Is 0.01: 99.99 to 99.99: 0.01. (2) preparing a homogeneous solution of an organic solvent with the precursor of the aromatic heterocyclic block copolymer represented by the formula (2) and a matrix polymer, and (2) removing the organic solvent, followed by heating. Causes a thiazole ring closure reaction of the following formula

Embedded image (However, Ar, Ar ', X, m and n are each
Same as in 4 . ), And a molecular composite comprising a matrix polymer and an aromatic heterocyclic block copolymer represented by the formula (1).

The present invention will be described in detail below. Precursor Copolymer In the present invention, a precursor of an aromatic heterocyclic block copolymer (hereinafter, referred to as a precursor copolymer) serving as a reinforcing polymer of a molecular composite is represented by the following formula:

Embedded image (Where Ar and Ar ′ are aromatic residues, R is a substituted or unsubstituted alkyl group, X is a residue of a dicarboxylic acid derivative, m and n are both integers, and m: n
Is 0.01: 99.99 to 99.99: 0.01. ).

This precursor copolymer comprises: (i) (a) an aromatic diaminodithiol compound in which a hydrogen atom of a thiol group is substituted by a substituted or unsubstituted alkyl group; and (b) an aromatic diamino compound. Two kinds of oligomers are synthesized by reacting with a dicarboxylic acid derivative (c) in an organic solvent, and (ii) the two kinds of obtained oligomers can be produced by reacting them in an organic solvent.

(A) An aromatic diaminodithiol compound in which a hydrogen atom of a thiol group is substituted with a substituted or unsubstituted alkyl group (hereinafter referred to as compound (a) for simplicity) is represented by the following general formula:

Embedded image (Where 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, or may be one in which two or more benzene rings are bonded, such as biphenyl. The positional relationship between the amino group and the thioether group on both sides may be left-right symmetric or point-symmetric about the aromatic residue. Examples of this compound (a) include:

Embedded image And the like.

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 Chemical formula 7 described above is replaced with a hydrogen atom can be used, and the aromatic diaminodithiol compound is preferably a hydrochloride or the like in order to prevent deterioration. Use in the form of salt.

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

As the substituted alkyl group, an alkyl group substituted by a carboxyl group, an ester group, a cyano group, a benzene group or the like is preferable. In addition, when it has such a substituent, the alkyl group does not need to be particularly secondary. As the alkyl group having a substituent,
For example,

Embedded image And the like.

In the above-mentioned six substituted alkyl groups, the alkyl group bonded to the oxygen atom in the ester bond is not limited to a methyl group, but is substituted with two higher ester groups. 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 substituted with an alkyl group having a cyano group or an alkyl group having an ester group,
Obtained precursor copolymer (polymer of the above formula 3)
Is preferred because the thiazole ring closure reaction in the above occurs at a relatively low temperature. Also, the N-methyl of these precursor copolymers
-2- Improves solubility in organic solvents such as pyrrolidone.

The above-mentioned alkyl group is used as an alkyl halide which is a halide thereof, and from the above-mentioned aromatic diaminodithiol compound (salt),
Compound (a) is synthesized by the method described below. As the halide, a bromide, chlorinated compound, iodide or the like of the above-mentioned alkyl group can be used.

In the synthesis of compound (a), the salt of the above-mentioned aromatic diaminodithiol compound and an alkyl halide are reacted in an alkaline aqueous solution. As the alkaline aqueous solvent to be used, one obtained by dissolving a basic salt such as sodium hydroxide in water or a mixed solvent of water and an alcohol (ethanol and / or methanol) 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 aqueous solvent preferably has an alkali concentration of 30% by weight or less.

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 is undesirably reduced. On the other hand, when the temperature exceeds 100 ° C., a side reaction occurs, which is not preferable. A more preferred reaction temperature is 0 ° C to 95 ° C.

The reaction time is not particularly limited, but generally ranges from 2 to
About 24 hours is fine.

It is preferable to stir the solution in order to increase the reaction rate. The reaction rate can be increased by increasing the amount of the alkyl halide.

Further, when cetyltrimethylammonium chloride, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, 18-crown-6 or the like is added as a phase transfer catalyst, the reaction rate can be increased. Such a phase transfer catalyst causes the reaction between the salt of the aromatic diaminodithiol compound and the alkyl halide to proceed rapidly.

By performing the substitution reaction under the above conditions,
Monomers in which the hydrogen atom of the thiol group of an aromatic diaminodithiol compound salt is substituted with an alkyl group (compound (a))
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 follows. Here, as an example of a salt of an aromatic diaminodithiol compound, 2,5-diamino-1,4-
Use benzenedithiol dihydrochloride. In the formula, XR represents an alkyl halide.

Embedded image

Next, (b) an aromatic diamino compound (hereinafter, referred to as an aromatic diamino compound)
As the compound (b) for simplicity), an aromatic diamino compound having a bendable structure is preferable, and a diamine having an aromatic residue such as diphenyl ether or biphenyl can be used. Specifically, the following equation

Embedded image Can be suitably used.

In order to improve the compatibility between the aromatic heterocyclic block copolymer and the matrix polymer, the compound (b) has the same or similar structure as a part of the matrix polymer to be mixed. It is good to choose what you have.

The dicarboxylic acid derivatives include those in which each carboxyl group is substituted as follows.

Embedded image

As the residue of the dicarboxylic acid derivative, an alkylene group having a relatively short chain (2 to 10 carbon atoms),
The following aromatic residues are exemplified. In addition, as an example of dicarboxylic acid, aromatic dicarboxylic acid is preferable, and terephthalic acid and isophthalic acid are particularly preferable.

Embedded image

The dicarboxylic acid derivative is not limited to one kind, and two or more kinds may be used in combination.

Next, a method for producing the precursor copolymer will be described. In the present invention, first, the compound (a) and the compound (b) described above are separately dicarboxylic acid derivatives (c)
To produce two types of oligomers. here,
For simplicity, compound (a) and a dicarboxylic acid derivative
(c) is reacted with
And the oligomer obtained by reacting the compound (b) with the dicarboxylic acid derivative (c) is referred to as oligomer II.

Compound (a) and dicarboxylic acid derivative (c) are dissolved in an organic solvent and stirred at a desired temperature to synthesize oligomer I.

In the synthesis of oligomer I, compound (a)
The molar amount of the dicarboxylic acid derivative (c) and the molar amount of the dicarboxylic acid derivative (c) are basically equivalent, but in order to make the molecular weight of the oligomer I appropriate and to improve the reactivity with the oligomer II described later, The amount of the dicarboxylic acid derivative (c) may be adjusted slightly.

The concentration of the total amount of the compound (a) and the dicarboxylic acid derivative (c) in the organic solvent is preferably about 0.5 to 5 mol / l. If the concentration exceeds 5 mol / l, it is difficult to dissolve each component, which is not preferable.

As the organic solvent, an amide organic solvent can be suitably used. Amide-based organic solvents include N-
Methyl-2-pyrrolidone, hexamethylphosphoric triamide, N, N-dimethylacetamide and the like,
A single or mixed solution thereof can be used. Further, in order to enhance the reactivity, a maximum of 5% of a chloride such as LiCl or CaCl ₂ may be added.

The polymerization reaction temperature when the compound (a) and the dicarboxylic acid derivative (c) are polymerized to synthesize the oligomer I is preferably -20 to 200 ° C. If the temperature is lower than -20 ° C, a sufficient polymerization reaction does not occur. On the other hand, a thiazole ring closure reaction may occur at a temperature of about 250 ° C., so the upper limit of the temperature of the polymerization reaction is set to 200 ° C. More preferably, the temperature is in the range of -10 to 50C.

In the production of the oligomer I, it is preferable to stir the solution in order to increase the reaction rate. The reaction time is preferably about 1 to 120 minutes.

The polymerization reaction of the compound (a) with the dicarboxylic acid derivative (c) is considered to proceed as follows. Here, an alkyl group-substituted product of 2,5-diamino-1,4-benzenedithiol dihydrochloride is used as an example of the compound (a), and terephthalic acid dichloride is used as an example of the dicarboxylic acid derivative (c). Here, m represents the degree of polymerization. The intrinsic viscosity of the oligomer I is about η _inh = 0.1 to 1.0 (N-methyl-2-pyrrolidone, 30 ° C.).

Embedded image

The oligomer II can also be synthesized in the same manner as the method for synthesizing the oligomer I described above.

In the synthesis of the oligomer II, the amount of the dicarboxylic acid derivative (c) is basically equal to the molar amount of the compound (b). The amount of the dicarboxylic acid derivative (c) in the synthesis of the oligomer II should be adjusted in accordance with the adjustment of the amount of

The concentration of the total amount of the compound (b) and the dicarboxylic acid derivative (c) in the organic solvent is preferably about 0.5 to 5 mol / l.

The polymerization temperature is preferably -20 to 300 ° C, more preferably -20 to 200 ° C. If the temperature is lower than -20 ° C, a sufficient polymerization reaction does not occur. On the other hand, 400 ℃
Since thermal decomposition occurs at about the temperature, the upper limit of the temperature of the polymerization reaction is set to 300 ° C. More preferably, the temperature is in the range of -10 to 50C.

The organic solvent used in the synthesis of the oligomer II may be the same as the organic solvent used in the synthesis of the oligomer I described above.

The reaction time is not particularly limited, but generally ranges from 1 to 1.
It takes about 120 minutes.

It is considered that the polymerization reaction to oligomer II proceeds as follows. Here, as an example of the compound (b), 4,4'-diaminodiphenyl ether (4-amino
dicarboxylic acid derivative using -p-phenoxyaniline)
As an example of (c), terephthalic acid dichloride is used. Here, n represents the degree of polymerization. The intrinsic viscosity of oligomer II is η
_inh = 0.1 to 1.0 (N-methyl-2-pyrrolidone, 30 ° C)
It is about.

Embedded image

Oligomer I obtained by the method described above
And oligomer II are reacted in an organic solvent to synthesize a precursor copolymer. As the organic solvent, those used in the synthesis of the above oligomer I (and oligomer 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 -1
The precursor copolymer is synthesized by stirring at 0 to 50 ° C. -20
If the temperature is lower than ℃, polymerization does not proceed. If the temperature exceeds 250 ° C., the thiazole ring closure reaction proceeds.

By conducting the polymerization reaction under the above conditions,
An aromatic heterocyclic block copolymer precursor having a large degree of polymerization can be obtained without causing a thiazole ring closure reaction. The intrinsic viscosity of the obtained aromatic heterocyclic block copolymer precursor is about η _inh = 0.5 to 2.0 (N-methyl-2-pyrrolidone, 30 ° C.).

The polymerization reaction between the oligomer I and the oligomer II proceeds as follows, and an aromatic heterocyclic block copolymer precursor (precursor copolymer) is obtained. here,
As the oligomer I, one obtained by the reaction shown in Chemical formula 9 above is used, and as the oligomer II, one obtained by the reaction shown in Chemical formula 10 is used, but the present invention is not limited to this. In addition, m and n represent the degree of polymerization. In the present invention, m in one precursor copolymer
The total (the total degree of polymerization in the precursor copolymer of the portion bounded by m in the following formula) and the total of n (the total degree of polymerization in the precursor copolymer of the portion bounded by n in the following formula) The ratio m: n is from 0.01: 99.99 to
99.99: Takes the range of 0.01.

Embedded image

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

Matrix polymer The matrix polymer used in the present invention is polyamide,
Small number selected from polyimide and polyamide imide
It is at least one kind of polymer . These resins have good compatibility with the precursor copolymer and can provide a molecular composite material having excellent mechanical strength. As the matrix polymer, an aromatic polyamide is particularly preferred.

Method for Producing Molecular Composite (1) First, the above precursor copolymer and matrix polymer are dissolved in an organic solvent in which both are well dissolved.
As such a solvent, an amide-based organic solvent such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide and the like can be suitably used.

In the blending of the precursor copolymer and the matrix polymer, even if the blending amount of the precursor copolymer is extremely small, there is a reinforcing effect, but finally, the aromatic heterocyclic block copolymer and the matrix polymer are mixed in a weight ratio of 1: 1: It is preferable to set the ratio in the range of 100 to 5: 1. If the compounding ratio of the aromatic heterocyclic block copolymer which is the reinforcing polymer is too large, its existence becomes too dense, the aromatic heterocyclic block copolymers aggregate and the dispersion at the molecular level becomes poor, and It is thought to reduce the mechanical strength of the molecular composite. A more preferred compounding ratio is 1:50 to 3.5: 1.

The dissolution of the precursor copolymer and the matrix polymer may be performed by any method as long as a homogeneous solution is obtained. For example, a solution of a precursor copolymer and a solution of a matrix polymer may be prepared and then mixed together to form a uniform solution, or a uniform solution may be obtained by adding a matrix polymer to a solution in which the precursor copolymer is dissolved. Alternatively, both may be dissolved in one kind of solvent at a time. The final solution concentration is preferably such that the sum of the precursor copolymer and the matrix polymer is 1 to 20% by weight.

The mixing is slightly different depending on the matrix polymer and the solvent used, but is preferably about 6 hours to 30 days. The temperature at the time of mixing is preferably -15 to 150 ° C.

The preparation and mixing of the solution of the precursor copolymer and the matrix polymer may be carried out in air, but more preferably in an atmosphere of an inert gas such as nitrogen gas or argon gas.

After preparing the homogeneous solution, the solvent is evaporated and dried. In practice, however, it is preferable to dry these after forming into a film or spinning by a casting method. Since the solution of the precursor copolymer obtained by substituting the alkyl group as described above has a high liquid crystallinity, it is easy to spin a composite of the precursor copolymer and the matrix polymer from an organic solvent. In addition, in order to increase the liquid crystallinity of the solution of the precursor copolymer, it is basically better to lengthen the alkyl group bonded to the thiol group. Length is good.

The drying of the composite by the precursor copolymer and the matrix polymer can be performed by a known method.

(2) Next, the composite of the precursor copolymer and the matrix polymer obtained above is heated to cause a thiazole ring closure reaction in the precursor copolymer to obtain a molecular composite.

By this heating, the alkyl group (R) of the precursor copolymer is eliminated, and a thiazole ring is formed at that site, whereby an aromatic heterocyclic block copolymer is formed. When the precursor copolymer obtained by the reaction formula shown in the above-mentioned chemical formula 16 is used , an aromatic heterocyclic block copolymer having the following structural formula is formed.

Embedded image

The heating temperature of the homogeneous mixture of the precursor copolymer and the matrix polymer depends on the type of the matrix polymer used, but is generally from 250 ° C. to 400 ° C.
And Heating at less than 250 ° C. results in less thiazole ring formation.

The heating is not limited to a constant heating temperature, but may be a heating program that changes the temperature stepwise. For example, a heating program may be adopted in which after heating at 120 ° C. for 30 minutes, the temperature is raised to 350 ° C. in 30 minutes and held at 350 ° C. for 30 minutes.

According to the above-described method, the precursor copolymer uniformly dispersed at the molecular level in the matrix polymer becomes the aromatic heterocyclic block copolymer as it is, so that the aromatic heterocyclic block copolymer is converted into the matrix polymer at the molecular level. This results in a uniform dispersion, which results in a molecular composite having good mechanical properties.

Further, in the aromatic heterocyclic block copolymer used in the present invention, a flexible structural site is arranged to have a certain length, and this site has an affinity for the matrix polymer. It can be set to be high (for example, a site capable of hydrogen bonding), so that the mechanical strength is reduced due to insufficient adhesion at the interface between the aromatic heterocyclic block copolymer molecule and the matrix polymer molecule, and the aromatic heterocyclic block is Aggregation of the copolymer can be prevented.

[0072]

The present invention will be described in detail with reference to the following specific examples. Synthesis Example 1 (1) Synthesis of Oligomer I and Oligomer II 5 ml of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was placed in a well-dried 50 ml flask under a stream of dry argon.
And the following equation

Embedded image 8 mmol (2.227 g) of the compound (a) represented by the formula was added and dissolved to prepare a uniform NMP solution.

The solution was cooled together with the whole container on ice, and the compound (c) was further converted to 2-chloroterephthalic acid chloride.
8.2 mmol (1.947 g) was added and the mixture was stirred for 5 minutes to synthesize an oligomer I.

Simultaneously with the synthesis of the above oligomer I, 10 ml of NMP was placed in a well-dried 50 ml flask under a stream of dry argon, and the following formula was added thereto.

Embedded image 2 mmol (0.4004 g) of the compound (b) represented by the formula was added and dissolved to prepare a uniform NMP solution.

The solution was cooled in an ice bath together with the container, and the compound (c) was further converted to 2-chloroterephthalic acid chloride.
1.8 mmol (0.427 g) was added and the mixture was stirred for 5 minutes to synthesize an oligomer II.

(2) Aromatic heterocyclic block copolymer precursor
Synthesis of a Compound The NMP solution of oligomer I obtained by the above operation was added to the NMP solution of oligomer II. In addition, oligomer I
Was added to the NMP solution of oligomer II,
A flask of the NMP solution of oligomer I was further filled with 2 ml of N
Washed with MP, this washed NMP is also oligomer II NMP
Added to the solution.

While the mixed oligomer solution was cooled on ice,
The mixture was stirred for another hour, and then the temperature was raised to room temperature while stirring.

The obtained 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 0.93. The intrinsic viscosity was measured in NMP at a polymer concentration of 0.5 g / dl at 30 ° C. by the Ubbelohde method.

The structure of the obtained polymer (precursor polymer) is considered to be as follows.

Embedded image In this polymer, derived from oligomer I,
The ratio of the degree of polymerization m of the portion exhibiting rigidity after heat treatment to the degree of polymerization n of the portion exhibiting flexibility derived from oligomer II in the whole molecule (m: n, where m and n are the entire polymer, respectively) Is 8: 2).

Synthesis Example 2 Using the same materials and the same method as in Synthesis Example 1,
An aromatic heterocyclic block copolymer precursor having an m: n ratio of 6: 4 in the formula shown in FIG. 9 was synthesized.

The yield was 99.8%. The intrinsic viscosity η _inh of this polymer was 0.86. The measurement of intrinsic viscosity is
In MP, the concentration of the polymer was set to 0.5 g / dl, and the reaction was carried out at 30 ° C. by the Ubbelohde method.

Example 1 The precursor copolymer obtained in the above Synthesis Example 1 was mixed with an aromatic polyamide (manufactured by Toray Industries, Inc.) as a matrix polymer.
TX-1) to produce a molecular composite (film) by the method shown below. Here, the amount of the precursor copolymer was changed, and a site having a thiazole ring showing rigidity in the aromatic heterocyclic block copolymer serving as a reinforcing molecule (the parenthesized portion enclosed by m in Chemical Formula 19 described above) A plurality of molecular composites (films) up to 17% by weight (relative to the sum of the aromatic heterocyclic block copolymer and the matrix polymer) at the corresponding sites, after the thiazole ring closure reaction has taken place. Was manufactured.

First, a desired amount of the precursor copolymer and TX-1 were taken, added to NMP so that the total amount became 5% by weight, and mixed at 80 ° C. for one week. Next, the homogenized NMP solution was cast on a glass plate,
Desolvation at ℃, a transparent isotropic film (thickness 30
μm).

These films were treated in vacuum with
Heat treatment was performed at 0 ° C. for 30 minutes. When the TG-DTA measurement and the IR spectrum were observed for the obtained film, the presence of a thiazole ring was confirmed. In addition, the tensile modulus and tensile strength of these films
It was measured according to K 7127. FIG. 1 shows the measurement results of the tensile modulus, and FIG. 2 shows the measurement results of the tensile strength. The horizontal axis of the graphs in FIGS. 1 and 2 is the ratio (wt%) of the rigid portion having a thiazole ring in the aromatic heterocyclic block copolymer in the molecular composite material, as described above.

Comparative Example 1 A film was prepared in the same manner as in Example 1 except that TX-1 alone was added to NMP without adding the precursor copolymer. This film was subjected to JISK 7127 in the same manner as in Example 1.
The tensile modulus and the tensile strength were measured in accordance with. FIG. 1 shows the measurement results of the tensile modulus, and FIG. 2 shows the measurement results of the tensile strength.
The results are shown together with the results of Example 1.

Comparative Example 2 Instead of the precursor copolymer of Example 1, the following formula:

Embedded image Using the ladder polymer obtained by the reaction formula represented by the following formula, and mixing it with TX-1 as a matrix, Example 1
A film was produced in the same manner as described above. The tensile modulus and tensile strength of this film were measured in the same manner as in Example 1 in accordance with JIS K 7127. Fig. 1 shows the measurement results of tensile modulus.
FIG. 2 shows the measurement results of the tensile strength together with the results of Example 1.

As is clear from FIGS. 1 and 2, Comparative Examples 1 and 2 in which no ladder polymer comprising a copolymer was used.
Is inferior to that of Example 1 in tensile strength.

Example 2 A plurality of composite films were produced in the same manner as in Example 1 except that the precursor copolymer obtained in Synthesis Example 2 was used.

For the plurality of films obtained above,
The tensile modulus and tensile strength were measured in the same manner as in Example 1. FIG. 1 shows the measurement results of the tensile modulus, and FIG. 2 shows the measurement results of the tensile strength.

As can be seen from FIGS. 1 and 2, the molecular composite according to the present invention has the same tensile modulus but a higher elongation than the molecular composite with the non-copolymerized reinforcing polymer. And the tensile strength is improved.

Examples 3 and 4 A composite film comprising a precursor copolymer and a matrix polymer in the same manner as in Example 1 except that the precursor copolymer obtained in Synthesis Example 1 and a polymer having the following skeleton were used. Was fabricated (Example 3).

Embedded image However, in Chemical formula 22 , x is an integer indicating the degree of polymerization.

Similarly, the precursor copolymer obtained in Synthesis Example 2 was used in the same manner as in Example 1 except that the polymer used in Example 3 (polymer having the structure shown in Chemical Formula 20) was used. A composite film composed of and a matrix polymer was produced (Example 4).

In the production of the above two types of films, the mixing ratio of the precursor copolymer and the matrix polymer depends on the inclusion of a portion exhibiting rigidity (a portion which forms a thiazole ring by heating to form a rigid structure). The rate was set so as to be 10% by weight.

For the plurality of films obtained above,
Heat treatment was performed so that the maximum temperature was 230 to 330 ° C., respectively, to obtain a molecular composite material (film). The tensile modulus of the obtained film was measured in the same manner as in Example 1. FIG. 3 shows the measurement results of the tensile modulus.

As can be seen from the graph shown in FIG. 3, in the molecular composite material according to the present invention, the heat treatment temperature of the film comprising the precursor copolymer and the matrix polymer was 2 ° C.
At around 50 ° C., the thiazole ring closure reaction is completed.
As the temperature rises to around ℃, the tensile modulus increases.

[0098]

As described in detail above, in the method of the present invention, (a) a portion having a thiazole ring exhibiting rigidity;
(B) using, as a reinforcing polymer, an aromatic heterocyclic block copolymer having a structure in which portions having flexibility and high compatibility with a matrix polymer are arranged alternately with a certain length. Therefore, the dispersion of the reinforcing polymer in the matrix polymer becomes good. Also,
Due to the increase in adhesion between the reinforcing polymer and the matrix polymer, physical properties are also improved. Furthermore, in the introduction of the aromatic heterocyclic block copolymer which is a reinforcing polymer, the aromatic heterocyclic block copolymer is well dispersed in the matrix polymer because it is mixed with the matrix polymer at the time of the precursor copolymer.

Therefore, in the molecular composite material according to the present invention, there is no aggregation of the reinforcing polymer as seen when polybenzothiazole is used as the reinforcing polymer, and the molecular composite material has excellent mechanical properties.

Since the molecular composite obtained by the method 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 the drawings]

FIG. 1 is a graph showing the measurement results of tensile modulus of the films manufactured in Example 1, Example 2, and Comparative Example 1.

FIG. 2 is a graph showing the measurement results of the tensile modulus of the films manufactured in Example 1, Example 2, and Comparative Example 1.

FIG. 3 is a graph showing the measurement results of the tensile modulus of the film in Examples 3 and 4.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C08L 79/08 C08L 79/08 Z 81/00 81/00 (72) Inventor Hiroto Kobayashi 1-4-4 Chuo, Wako-shi, Saitama No. 1 In Honda R & D Co., Ltd. (56) References JP-A 64-1761 (JP, A) JP-A 64-1760 (JP, A) JP-A 62-25158 (JP, A) -281077 (JP, A) JP-A-1-287167 (JP, A) JP-A-48-90352 (JP, A) JP-A-4-351637 (JP, A) (58) Fields investigated (Int. . ^7, DB name) C08L 1/00 - 101/16 C08G 75/32 C08G 69/00 C08G 73/10

Claims (6)

(57) [Claims] 1. A molecular composite material comprising an aromatic heterocyclic copolymer and a matrix polymer, wherein the aromatic composite is
The ring copolymer has the following formula : (Where Ar and Ar ′ are aromatic residues, and X is
M and n are both integers.
Yes, m: n is 0.01: 99.99 to 99.99: 0.01. )
And a block copolymer represented by
The matrix polymer is polyamide, polyimide,
At least one selected from the group consisting of polyamide imides
A molecular composite characterized by being a kind of polymer . 2. A method for producing a molecular composite comprising an aromatic heterocyclic block copolymer and a matrix polymer, comprising the steps of: (Where Ar and Ar ′ are aromatic residues, R is a substituted or unsubstituted alkyl group, X is a residue of a dicarboxylic acid derivative, m and n are both integers, and m: n
Is 0.01: 99.99 to 99.99: 0.01. (2) preparing a homogeneous solution of an organic solvent with the precursor of the aromatic heterocyclic block copolymer represented by (2) and a matrix polymer, and (2) removing the organic solvent, followed by heating. Which causes a thiazole ring closure reaction of the following formula: (However, Ar, Ar ', X, m and n are each
Same as in 2 . A) producing a molecular composite comprising an aromatic heterocyclic block copolymer represented by the formula (1) and a matrix polymer. 3. The method according to claim 2, wherein the aromatic residue Ar ′ is a diphenyl ether group. 4. The method according to claim 2, wherein
The method, wherein the dicarboxylic acid derivative is an aromatic dicarboxylic acid derivative. 5. The method according to claim 4, wherein the aromatic dicarboxylic acid derivative is a substituted or unsubstituted terephthalic acid dichloride or isophthalic acid dichloride. 6. The method according to claim 2, wherein the matrix polymer is a polyamide, a polyimide, or a polyamideimide.