JP2678679B2 - Reversible contraction / swelling body and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention has reversible shrinkage composed of polyamic acid, which is a polyimide precursor having excellent heat resistance and widely used in the fields of electronics, transportation equipment, aerospace, etc. Regarding a swollen body and a method for producing the same, a polymer gel having a structure in which a three-dimensional bond is formed by a specific monomer structure and having a self-supporting property in a state containing an organic solvent,
With the property of repeating contraction and swelling due to the entry and exit of solvent,
The present invention relates to a reversible shrinkage / swelling body composed of a polyamic acid polymer containing an organic solvent and a method for producing the same.

(Prior art)

With a precursor of polyamic acid obtained by polymerizing tetracarboxylic acid anhydride and aromatic diamine in an organic solvent,
A method for obtaining a polyimide resin having excellent heat resistance by dehydrating and ring-closing it by heating dehydration or a chemical reaction with a dehydrating agent is known.

Generally, the polymerization of polyamic acid, which is a precursor of polyimide resin, is carried out by a polyaddition reaction of tetracarboxylic dianhydride and aromatic diamine in an organic solvent so that the polymer concentration becomes 5 to 20% by weight. By this method, a high molecular weight polyamic acid solution uniformly dissolved in an organic solvent can be obtained. The solvent is removed from the polyamic acid solution to form a film or molded body. Further, it is a usual method to obtain a polyimide molded body by subjecting this molded body to a dehydration / ring-closing reaction by high temperature treatment or chemical treatment.

These techniques are disclosed in JP-A-61-78834 and JP-A-61-181828.
Nos. 61-250031, 63-254131 and the like.

However, regarding the polyamic acid that is the precursor of polyimide, it has a self-supporting property such that the specific monomer component is polymerized in an organic solvent and the polymer is three-dimensionally bonded in the solution, and the shape does not collapse due to its own weight. Few reports have been made on polyamic acid polymer gels containing organic solvents.

[Object of the invention]

An object of the present invention is to react a monomer having tetracarboxylic dianhydride, an aromatic diamine and a polyvalent amine as a main component in an organic solvent to obtain a multifunctional substance having a substance separation action, a stimulus-response action and the like. Another object of the present invention is to provide a reversible shrinkage / swelling body composed of the novel polyamic acid polymer gel, and to provide a method for producing the same. This polyamic acid polymer gel is useful as a precursor of a polyimide or a polyimide composite which gives a molded article having excellent heat resistance.

[Structure and effect of the invention]

 The present invention is as described below.

(1) Obtained by polymerizing a tetracarboxylic dianhydride, an aromatic diamine, and a tri- or tetraamino compound in an organic solvent, and the tetracarboxylic dianhydride, an aromatic diamine, and tri- or tetraamino. A shaped self-supporting organic solvent-containing organic polymer gel having a polyamic acid three-dimensional network molecular structure, wherein the compound mono ratio is (100) / (50-100) / (2-25) , The organic solvent-containing organic polymer gel has a property that contraction and swelling are reversibly performed by the contained organic solvent flowing out and the organic solvent entering from the outside into the organic solvent-containing organic polymer gel. And has a volume expansion coefficient of 2 to 50 when swollen.
A reversible shrinkage / swelling body consisting of an organic polymer gel containing an organic solvent, which is characterized by being doubled.

(2) In the reversible shrinkage / swelling body according to claim 1, at least one selected from a low molecular weight organic compound, an inorganic compound, a metal compound, and a high molecular weight organic compound is dispersed as a functional third component. A reversible shrinkage / swelling body characterized by being contained in a mixed state.

(3) The molar ratio of tetracarboxylic dianhydride, aromatic diamine, and tri- or tetraamino compound is (100) / (50
To 100) / (2 to 25) in an organic solvent for polymerization reaction to form a polyamic acid solution, and the polyamic acid solution is gelled and shaped at 0 ° C to 100 ° C.
A method for producing a reversible shrinkage / swelling body, which comprises obtaining a self-supporting organic solvent-containing organic polymer gel having a polyamic acid three-dimensional network molecular structure.

(4) In the method for producing a reversible shrinkage / swelling body according to claim 3, a low molecular weight organic compound or an inorganic compound is obtained at any time after the gelation after the polyamic acid is obtained by the polymerization reaction or after the gelation. A compound, a metal compound, a high-molecular organic compound and at least one kind of functional third component in a state of being dissolved or dispersed in a solvent, by adding to the polyamic acid, the third component is reversible A method for producing a reversible shrinkage / swelling body, which is characterized in that the shrinkage / swelling body is contained in a state of being dissolved, dispersed or mixed.

The reversible shrinkage / swelling body composed of the polyamic acid polymer gel containing the organic solvent has a volume swelling degree of 2 to 50 times in the organic solvent [(volume after swelling) / (solid volume without solvent before swelling). Volume)], which is a polymer gel having self-supporting property such that it does not flow even if it contains a large amount of organic solvent and can retain its shape.

In the present invention, the organic polymer gel, tetracarboxylic acid dianhydride 100 mol, aromatic diamine 50 to 100 mol, and a tri- or tetraamino compound in a ratio of 2 to 25 mol polymerization reaction in an organic solvent To form a solution of polyamic acid, and by gelling and shaping the solution of polyamic acid at 0 ° C. to 100 ° C., a three-dimensional cross-linking reaction proceeds due to the formation of an ionic salt and the formation of a covalent bond. , A network molecular structure was formed, and it was in a self-supporting gel state containing an organic solvent. This gel was not dehydrated and ring-closed, and was in a state of polyamic acid (polyamic acid). Does not mean.

In the present invention, a polyamic acid solution uniformly dissolved in an organic solvent is first obtained by polyaddition reaction of tetracarboxylic dianhydride, aromatic diamine and polyvalent amine. However, the state of this polyamic acid solution is intermediate, and the crosslinking reaction due to the unreacted functional groups contained in the polyamic acid gradually proceeds in the organic solvent, resulting in a three-dimensional network molecular structure of the polyamic acid component. Are formed to cause gelation, and finally an organic polymer gel composed of a polyamic acid containing an organic solvent is obtained.

The reversible shrinkage / swelling body of the present invention comprising an organic solvent or a polyamic acid polymer gel containing an organic solvent and a third component can be prepared according to the following procedure.

(1) A tetracarboxylic dianhydride, an aromatic diamine, and a polyvalent amine are mixed in an organic solvent, and a polyaddition reaction is performed to obtain a polyamic acid solution uniformly dissolved in the organic solvent.

(2) When the third component is combined with polyamic acid,
The third component is added to the polyamic acid solution obtained by the polyaddition reaction, which has not yet been gelled, to form a composite with the third component. Alternatively, polyamic acid is subjected to polyaddition reaction in a solution in which the third component is contained in an organic solvent in advance.

(3) In order to shape the polyamic acid solution or the mixed solution of the third component and the polyamic acid component before gelation occurs, the solution is poured into a mold having a specific shape or is formed on a film. Is cast on a substrate.

(4) A three-dimensional network molecular structure is obtained by allowing the above solution to stand at a temperature condition of 0 to 100 ° C. for at least 1 minute or more and allowing a crosslinking reaction by an unreacted functional group of polyamic acid to proceed in an organic solvent. A reversible shrinkage / swelling body of the present invention comprising an organic solvent or a polyamic acid polymer gel containing an organic solvent and a third component is obtained.

 The details of the preparation method will be described below.

First, a tetracarboxylic acid dianhydride, an aromatic diamine, and a polyvalent amine are mixed in an organic solvent, and a polyaddition reaction is performed to prepare a polyamic acid solution uniformly dissolved in the organic solvent.

The polyaddition reaction of tetracarboxylic acid dianhydride, aromatic diamine and polyvalent amine is, after all, a reaction of tetracarboxylic acid dianhydride and amines. Tetracarboxylic dianhydride may be added to a solution of an aromatic diamine and a polyvalent amine dissolved in an organic solvent under an active atmosphere. The tetracarboxylic acid dianhydride may be added in a solid form or in a liquid form dissolved in a solvent. A method of adding an aromatic diamine and a polyvalent amine to tetracarboxylic dianhydride may be used.

Typical examples of the tetracarboxylic dianhydride in the present invention, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-
Biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4'-
Biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3'-
Biphenyl tetracarboxylic dianhydride, 2,2 ', 6,6'-
Biphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4- Dicarboxyphenyl) propane dianhydride, diphenylsulfone-3,3 ', 4,4'-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,
4,9,10-Perylenetetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, benzene- 1,
2,3,4-tetracarboxylic dianhydride and the like can be mentioned. Further, tetracarboxylic dianhydride or fluorine having a relatively large molecular weight in which amide group, ester group, ether group, sulfone group, methylene group, propane group, phenylene group, imidazole group, thiazole group and the like are arbitrarily combined in the molecule. A tetracarboxylic dianhydride containing a halogen group in its structure can also be used. These can be used alone or in a mixture of two or more.

Representative examples of aromatic diamines include metaphenylenediamine, paraphenylenediamine, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfide. , 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4 '
-Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 2,2'- Bis (4-aminophenyl) propane, benzidine, 3,3'-diaminobiphenyl, 2,6-diaminopyridine, 2,5-diaminopyridine, 3,4-diaminopyridine, bis [4- (4-aminophenoxy) Phenyl]
Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- (3-aminophenoxy) phenyl] propane,
4,4'-bis (4-aminophenoxy) biphenyl, 1,4
-Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2'-bis [4
Examples include-(3-aminophenoxy) phenyl] hexafluoropropane, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene and derivatives thereof. Further, dihydrazide compounds such as isophthalic acid dihydrazide can also be used. These can be used alone or in a mixture of two or more.

In the present specification, the tri- or tetra-amino compound (polyvalent amine) refers to an amino compound having three or four substituents selected from an amino group and an ammonium base in one molecular structure.

As typical examples of polyvalent amino, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3'4,4'-tetraaminodiphenylmethane, 3,3', 4,4'-tetraaminobenzophenone, 3,3 ', 4,4'-tetraaminodiphenyl sulfone, 3,3', 4,4'-tetraaminobiphenyl, 1,2,4,5
-Tetraaminobenzene, 3,3 ', 4-triaminodiphenyl ether, 3,3', 4-triaminodiphenylmethane, 3,3 ', 4-triaminobenzophenone, 3,3', 4-triaminodiphenyl sulfone, 3,3 ', 4-triaminobiphenyl, 1,2,4-triaminobenzene and compounds in which the functional groups of these compounds are converted into the quaternary ammonium salt form, for example 3,3', 4,4 ′ -Tetraaminobiphenyl ・
Tetrahydrochloride and the like. The quaternary ammonium salt may be used in the form of sulfate or nitrate in addition to the hydrochloride. Among these compounds are also those in which all of the functional groups of the polyvalent amine are not in the form of quaternary ammonium salts. In addition, some of the above substances exist as hydrates, and these polyvalent amines can be used alone or as a mixture of two or more kinds. It is also possible to use aliphatic polyamines.

The organic solvent used in the polymerization of polyamic acid containing tetracarboxylic dianhydride, aromatic diamine and polyvalent amine as the main components is inert to the polymerization reaction and at the same time is formed by the monomers used and the reaction. It is capable of dissolving or swelling a high molecular weight substance containing the thus-obtained oligomer. As typical ones, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-
Diethylformamide, N, N-diethylacetamide,
Dimethyl sulfoxide, N-methyl-2-pyrrolidone,
N, N-dimethylmethoxyacetamide, hexamethylphosphoamide, pyridine, dimethyl sulfone, tetramethylene sulfone, cresol, phenol, phenols such as xylenol, benzene, toluene, xylene,
Examples thereof include benzonitrile, dioxane, cyclohexane and the like. These solvents are used alone or in combination of two or more.

The polymerization of polyamic acid mainly composed of tetracarboxylic dianhydride, aromatic diamine and polyvalent amine is carried out in an organic solvent at a temperature of -10 to 30 ° C, particularly preferably -5 to 20.
The reaction is performed in a temperature range of ° C. The reaction time is within 5 hours,
It is preferably within 2 hours.

If the reaction temperature is lower than -10 ° C, the reaction itself may not proceed sufficiently because the temperature is too low, in addition to the difficulty in handling and the reaction method, which is not preferable. If the reaction temperature is higher than 30 ° C, the reaction until gelation may be too fast to give a heterogeneous organic polymer gel. Therefore, the reaction temperature of the polyamic acid component is -10 to 30 ° C, particularly preferably -5 to 20 ° C.

Generally, when preparing a polyamic acid from tetracarboxylic dianhydride and aromatic diamine, it is preferable to react both components in equimolar amounts as much as possible in order to increase the molecular weight. In the present invention as well, in order to optimize the molecular weight between crosslinking points and the degree of crosslinking of the organic polymer gel, the molar ratio of tetracarboxylic acid dianhydride / aromatic diamine is (100) / (50 to 100), tetracarboxylic acid dianhydride. The molar ratio of compound / aromatic diamine / polyvalent amine is kept within the range of (100) / (50-100) / (2-25), and tetracarboxylic dianhydride and amines (aromatic diamine In order to obtain a polyamic acid polymer gel having self-supporting property, it is preferable to adjust the equivalent ratio (acid value / amine value ratio) of the reactive groups of the polyamine and the polyamine to within the range of 0.95 to 1.05.

When monomers are mixed and reacted in a composition outside this range, the degree of polymerization of the polyamic acid does not rise, and the resulting polyamic acid polymer gel properties, such as the tensile strength and elastic modulus of the organic polymer gel film. The mechanical properties such as are also low. The molar ratio of tetracarboxylic acid dianhydride / polyvalent amine to be reacted is preferably (100) / (2-25), and particularly preferably (100) / (4-1
Although it is within the range of 5), the suitable composition range may be slightly shifted depending on the kind of the monomer used.

The polyvalent amine functions as a cross-linking point of the polyamic acid polymer gel, and changes the network concentration (crosslinking density) existing in the polyamic acid polymer gel depending on its blending ratio. The number of moles of polyvalent amine compounded is 100% tetracarboxylic acid dianhydride.
If it is less than 2 mols per mol, the number of cross-linking points of the polyamic acid component in the solution will be small, the three-dimensional network molecular structure will be incomplete, and a self-supporting organic polymer gel will be difficult to form. If the blending number of moles of polyvalent amine is greater than 25 moles,
This leads to an increase in the number of cross-linking points in the three-dimensional network molecular structure and a decrease in the molecular weight between cross-linking points, which lowers the volume swelling degree of the polyamic acid polymer gel and tends to make it brittle. Therefore, the number of moles of the polyvalent amine compounded is preferably in the range of 2 to 25 moles per 100 moles of the tetracarboxylic dianhydride.

These tetracarboxylic acid dianhydrides, aromatic diamines and polyvalent amine components are used alone or as a mixture of two or more kinds, and thus the obtained polyamic acid includes a copolymer. It also includes a mixture of polyamic acids obtained by mixing a polyamic acid composed of a specific component and a polyamic acid in which at least one kind of constituent components of the polyamic acid is different.

The polyamic acid solution thus obtained is an intermediate until reaching the polyamic acid polymer gel as described above, and the crosslinking reaction by the unreacted functional group contained in the polyamic acid is performed in the organic solvent. By gradually advancing, a three-dimensional network molecular structure of the polyamic acid component is formed to cause gelation, and finally a polyamic acid polymer gel containing an organic solvent is provided. Further, among the polymers produced by the polyaddition reaction mainly composed of tetracarboxylic acid dianhydride, aromatic diamine and polyvalent amine component, linear high molecular weight substances not involved in the three-dimensional network molecular structure are also included. Be done. Their existence is confirmed by extraction with an organic solvent.

When the polyamic acid is combined with the third component, the third component is dissolved or dispersed in an organic solvent and added to the polyamic acid solution composed of the specific monomer of the present invention to form a complex.

As a third component, for example, when containing a low molecular weight organic compound, an inorganic substance, a metal compound, a high molecular weight organic compound,
The polycarboxylic acid dianhydride, the aromatic diamine and the polyvalent amine component are subjected to a polyaddition reaction in a solution containing a third component in an organic solvent in advance, or the organic solvent obtained by the polyaddition reaction is added to the organic solvent. The third component is mixed with the uniformly dissolved polyamic acid solution by a method such as adding the third component.

In the present specification, the low molecular weight organic compound means an organic compound having a molecular weight of less than 10,000, and the high molecular weight organic compound means an organic compound having a molecular weight of 10,000 or more.

Examples of the third component used in the complex include the following substances.

As the low molecular weight organic compound, there is a substance having a function such as stimulus-response action, and for example, a liquid crystal substance such as a Schiff liquid crystal, an azoxy liquid crystal, a cyanobiphenyl liquid crystal, a cyanophenyl liquid crystal, or the like, which has an optical functionality Having naphthalene derivative, spiropyran compound, azobenzene compound, phthalocyanine compound, porphyrin compound,
Dyes such as cyanine dyes, quinizarin compounds, stilbene compounds, hemicyanine compounds, crown ethers, electron donors tetrathiafulvalene, bisethylenedithiotetrathiafulvalene, electron acceptors tetracyanoquinodimethane, tetra Examples include cyanoethylene, other pyrene derivatives, pyrrole, acetylene compounds, and acetracene derivatives. These are used alone or as a mixture of two or more kinds.

The inorganic substance is preferably contained in the polyamic acid polymer gel as a fine powder, and alumina, tin oxide, lead zirconate titanate, zirconia, indium oxide, yttrium oxide, ceramics represented by ferrite and the like, Graphite, which can be used alone or in combination.

In the present specification, an inorganic substance means a substance having no C—H bond and excluding a metal compound.

The metal compound is also preferably contained as fine powder in the polyamic acid polymer gel, and representative examples thereof include Ag, Cu, Pt and the like, or these compounds.

As the high molecular weight organic compound, those soluble in an organic solvent are preferable, and polyamic acid, polyimide, polyamideimide, polyetherimide, polyethersulfone,
Examples thereof include polysulfone, polybenzimidazole, polybenzoxazole, polybenzothiazole, polyamide, polypeptide, polyester, polycarbonate and polyacrylonitrile. These high molecular weight organic compounds include modified products, precursors and oligomers of various polymers and can be contained in the polyamic acid high molecular weight gel.

In addition to the above, as a curable resin, a reactive monomer or oligomer component that eventually becomes a high molecular weight by an addition reaction can also be contained in the polyamic acid polymer gel. Maleimide resin, polyfunctional maleimide resin, phenol resin, unsaturated polyester resin, diallyl phthalate resin, dicyclopentadiene resin, cyanate resin, acetylene terminal compound, condensed polycyclic polynuclear aromatic (copna) resin, oligoacrylate resin, urea Examples thereof include resins, furan resins, melamine resins, guanamine resins, xylene resins, vinylstyrylpyridine resins, and the like, and these are often used as resin compositions containing a curing agent and additives.

In addition, carbonaceous fibers having an aspect ratio (fiber length / fiber diameter) of 2 or more, ceramic fibers such as alumina fibers, metal fibers, fiber materials such as organic fibers may be included in the polyamic acid polymer gel. it can.

These substances may be used alone or in combination of two or more.

When mixing the third component to the polyamic acid solution, as a solvent to dissolve or disperse the third component, as a representative, N, N-dimethylformamide, N, N-dimethylacetamide amide solvent such as, Phenols such as cresol, phenol and xylenol, sulfone solvents such as dimethyl sulfone, tetramethylene sulfone and dimethyl sulfoxide, hydrocarbons such as benzene, toluene, xylene and cyclohexane, chlorine solvents such as methylene chloride and dichloroethane, ketones , Alcohols, N-
Methyl-2-pyrrolidone, benzonitrile, pyridine,
Dioxane, polyphosphoric acid, N, N-diethylaniline and the like can be mentioned. These solvents are used alone or in combination of two or more. The organic solvent finally contained in the polyamic acid polymer gel contains these solvents and the solvent used for the polymerization of the above polyamic acid.

The amount of the third component added depends on the use of the organic polymer gel, but if the amount of the third component exceeds 80% by weight, the solution in which the polyamic acid and the third component are combined becomes a three-dimensional network molecule. It may not form a structure and may not cause gelation, which is not preferable. By the above operation, a polyamic acid solution uniformly dissolved in an organic solvent or a polyamic acid mixed solution mixed with a third component can be obtained.

The polyamic acid solution uniformly dissolved in an organic solvent or the mixed solution of the polyamic acid complexed with the third component is
By allowing the polyamic acid solution to stand under the temperature condition of 0 to 100 ° C., the three-dimensional crosslinking reaction by the functional group contained in the polyamic acid proceeds in the organic solvent, and the gelation phenomenon occurs, and the organic solvent is contained. An organic polymer gel in which a polyamic acid and a third component are combined is produced.

At this time, the polyamic acid solution or the mixed solution with the third component is cast into a shape such as a film by a method such as casting into a mold having a specific shape or casting on a substrate. A polyamic acid polymer gel or an organic polymer gel in which a polyamic acid and a third component are combined is obtained.

In order to obtain an organic polymer gel in which a third component is uniformly mixed with polyamic acid, tetracarboxylic acid dianhydride,
It is desirable that the third component is blended before polyamic acid, which is a polymer of aromatic diamine and polyvalent amine, forms a three-dimensional network molecular structure, so-called gelation.
As another method of combining the polyamic acid and the third component, to the gelled polyamic acid polymer gel prepared in advance, contact the solution in which the third component is dissolved or dispersed, the polyamic acid polymer gel of There is also a method of obtaining an organic polymer gel in which both are combined by a method of infiltrating a solution containing a third component into the three-dimensional network molecular structure.

Such a method for preparing a polymer gel of polyamic acid or an organic polymer gel complexed with a third component is a novel one, and a polymer gel of the obtained polyamic acid or, by removing a solvent from this, The obtained molded product is a unique polymer structure having a three-dimensional network molecular structure with a polyvalent amine as a cross-linking point.

In the organic solvent obtained in the present invention, or in a polyamic acid polymer gel containing an organic solvent and a third component, the polyamic acid component has a polyvalent amine as a cross-linking point, mainly a covalent bond and a hydrogen-bonded three-dimensional network. It is a self-supporting organic polymer gel that forms a molecular structure and contains a large amount of organic solvent.

Further, in the polyamic acid organic polymer gel containing the organic solvent and the third component, the mixed solution containing the third component is gelated to form a polymer gel, so that the three-dimensional network molecular structure of the polyamic acid is formed. The third component is dispersed and mixed relatively uniformly.

In particular, when the third component is a solvent-soluble substance, the polyamic acid component forms a three-dimensional network molecular structure and gels after both the polyamic acid and the third component are complexed in the solvent, It is presumed that the third component is dispersed and mixed in a state close to the molecular shape. At least in such an organic polymer gel, the component containing the polyamic acid forms a continuous phase that is three-dimensionally connected.
This structure is a complex system having an aggregate structure that is completely different from the system in which the polyamic acid and the third component are simply mixed, and is a specific polymer structure.

The polyamic acid polymer gel obtained by such a preparation method is an organic polymer gel with a new structure that exhibits a volume swelling degree of 2 to 50 times in an organic solvent, and reversibly contracts and swells due to the entry and exit of the solvent. Is a structure that repeats. The volume swelling degree of the polyamic acid polymer gel is within a range of 2 to 50 times depending on the change of the crosslink density depending on the type and mixing ratio of the monomer components forming the polyamic acid and the type of the organic solvent contained in the organic polymer gel. It is also possible to prepare a polyamic acid polymer gel having a constant volume swelling degree by changing the density and controlling the crosslinking density.

In the polyamic acid polymer gel of the present invention containing the organic solvent or the organic solvent and the third component, the phenomenon of contraction / swelling due to the ingress / egress of the solvent is reversible, and therefore the present invention utilizes this mechanical energy. And then a chemical sensor,
It can be effectively used as a switch or actuator.

Further, the swelled body having a three-dimensional network molecular structure of which the crosslink density is changed is imparted with substance separation ability and is used as a separation membrane, a separation carrier, or the like.

In a polyamic acid polymer gel containing an organic solvent and a third component, a functional substance such as a low molecular weight organic compound, an inorganic substance, a metal compound or a high molecular weight organic compound is used as the third component in the polyamic acid polymer gel. Therefore, the polyamic acid polymer gel is provided with the functionality of the third component.

A low molecular weight organic compound or a high molecular weight organic compound exhibiting a catalytic action, optical anisotropy, conductivity, piezoelectricity, ferromagnetism, or non-linear optical characteristics is compounded as a third component with a polyamic acid polymer gel or a molded body. In the case, it is still a polyamic acid polymer gel or a molded body to which functionalities such as catalytic action, optical anisotropy, conductivity, piezoelectricity, ferromagnetism or nonlinear optical characteristics are imparted, and the shape of a film or the like is mainly used. It is applied to semiconductor devices, electrodes, separation films, displays, photoconductors, conversion devices, etc.

The inorganic substances and metal compounds used as the third component are
Conductivity, ionic conductivity, electron emission, piezoelectricity, pyroelectricity,
Since many exhibit ferromagnetism, fluorescence, etc., a polyamic acid polymer gel containing an organic solvent and a third component is also a material having the same functionality.

The polyamic acid polymer gel of the present invention is an organic polymer gel having a new structure obtained by reacting a specific monomer component in an organic solvent, and because of the specificity of the structure as described above, it has a substance separation action. , Is a multifunctional functional polymer material with stimulus-responsive action. In addition, a complex of a polyamic acid and a third component, which is complexed with a functional substance by a specific method, is also new, and depending on the properties of the substance to be combined, catalytic action, optical anisotropy, conductivity, piezoelectricity, It becomes an excellent functional material exhibiting properties, ferromagnetism, or nonlinear optical characteristics.

(Examples and Comparative Examples)

Example 1 In a 300 ml four-neck separable flask, 1.816 g (0.0
168 mol) of purified paraphenylenediamine (abbreviation: PP)
D) and 0.634 g (0.0016 mol) of 3,3 ', 4,4'-tetraaminobiphenyl tetrahydrochloride dihydrate (abbreviation: TABT) were collected, and 50 g of distilled N, N- Dimethylacetamide (abbreviation DMAc) was added and stirred to dissolve.

Under a nitrogen atmosphere, the temperature of the external water tank was controlled to 5 ° C., and while stirring the above solution, 4.366 g (0.02 mol) of purified anhydrous pyromellitic dianhydride (abbreviation: PMDA) remained as a solid solution. The solution was gradually added while being careful not to raise the temperature, and after all the additions were completed, stirring was continued to prepare a uniform polyamic acid solution.

This polyamic acid solution was cast on a glass plate. The coating amount of the solution is controlled by a spacer and is about 0.
The thickness is 4mm. When left standing for a while, the cast polyamic acid solution caused gelation, and an organic solvent-containing polyamic acid polymer gel film was obtained.

This polyamic acid polymer gel film was self-supporting without forming change due to its own weight.

This polyamic acid polymer gel was vacuum dried at 30 ° C. to disperse the solvent in the organic polymer gel and then released from the glass plate in the form of a film. DM this film
When immersed in an Ac solvent, the film swelled and the volume swelling degree was 18.5 times. Further, it was confirmed that when the solvent in the swollen body was scattered and dried at 30 ° C. under vacuum, the original film-like shape was restored, and the shrinkage and swelling were repeated due to the inflow and outflow of the solvent.

This film is 400 ℃ for 1 hour, 300 ℃ for 1 hour, 400
When treated at 1 ° C for 1 hour, the infrared absorption spectrum of the film showed characteristic absorption bands of imide groups at 1780 cm ^-1 and 1720 ^-1 . This film is a polyimide, and the one before heat treatment is a polyimide precursor. Was confirmed to be a polyamic acid.

Comparative Example 1 In a 300 ml four-neck separable flask, 2.162 g (0.0
2 mol) of purified paraphenylenediamine
0 g of distilled N, N-dimethylacetamide was added and stirred to dissolve.

Under a nitrogen atmosphere, control the temperature of the external water bath at 5 ° C and stir the above solution while keeping 4.366 g (0.02 mol) of purified anhydrous pyromellitic dianhydride as a solid and raising the temperature of the solution. Add gradually while being careful not to
After all the additions were completed, stirring was continued to prepare a uniform polyamic acid solution.

As in Example 1, the polyamic acid solution was cast on a glass plate and allowed to stand still, but the solution did not form an organic molecular gel even after standing at room temperature for 5 hours, and the solution flowed by its own weight. A film prepared by removing the solvent from this polyamic acid solution in the same manner as in Example 1 was immersed in a DMAc solvent, and the film was dissolved in DMAc.

Example 2 In a 300 ml four-neck separable flask, 1.124 g (0.0
104 mol) of purified paraphenylenediamine and 0.961 g
(0.0048 mol) of 4,4′-diaminodiphenyl ether (abbreviation: 4.4′-DPE) and 0.950 g (0.0024 mol) of 3,
3 ', 4,4'-Tetraaminobiphenyl tetrahydrochloride dihydrate was collected, and 50 g of distilled N-methyl-2-pyrrolidone (abbreviation: NMP) was added and dissolved by stirring.

Under a nitrogen atmosphere, control the temperature of the external water bath at 5 ° C and stir the above solution while keeping 4.366 g (0.02 mol) of purified anhydrous pyromellitic dianhydride as a solid and raising the temperature of the solution. Add gradually while being careful not to
After all the additions were completed, stirring was continued to prepare a uniform polyamic acid solution.

In the same manner as in Example 1, when this polyamic acid solution was cast on a glass plate and allowed to stand, the solution gelled,
An organic solvent-containing polyamic acid polymer gel film was obtained. This product was self-supporting and did not change its shape due to its own weight.

This polyamic acid polymer gel was vacuum dried at 30 ° C. to disperse the solvent in the organic polymer gel and then released from the glass plate in the form of a film. This film,
When immersed in a DMAc solvent, the film swelled and the degree of volume swelling was 8.0 times. Further, when this film swollen body was dipped in benzene, the volume swelling degree was reduced by 1.5 times, and when it was dipped again in the DMAc solvent, the film was swollen and the volume swelling degree returned to 8.0 times. As described above, it was confirmed that the film repeatedly contracts and swells as the solvent flows in and out.

Example 3 In a 300 ml four-neck separable flask, 2.480 g (0.0
(1239 mol) of purified 4,4'-diaminodiphenyl ether and 0.396 g (0.001 mol) of 3,3 ', 4,4'-tetraaminobiphenyl tetrahydrochloride dihydrate were collected and distilled to give 40 g of The N, N-dimethylacetamide thus prepared was added and stirred to dissolve it.

Under a nitrogen atmosphere, the temperature of the external water tank was controlled to 5 ° C., and while stirring the above solution, 3.056 g (0.014 mol) of purified anhydrous pyromellitic dianhydride remained solid,
The solution was added slowly, being careful not to raise the temperature of the solution.

In another 300ml four-neck separable flask, this time
1.754 g (0.006 mol) of purified 1.4-bis (4-aminophenoxy) benzene (abbreviation: TPE-Q) was collected, and 30 g
Distilled N, N-dimethylformamide (abbreviation: DMF)
Was added and stirred to dissolve.

Similarly, under a nitrogen atmosphere, the temperature of the external water tank was controlled at 5 ° C, and the solution was stirred at 1.764 g (0.006
(Mol) of purified 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (abbreviation: BPDA) was gradually added while keeping the temperature of the solution solid.

The two types of reaction solutions were mixed and stirred while controlling the temperature at 5 ° C. to prepare a uniform polyamic acid solution.

Furthermore, 9.450 g of a commercially available polyether sulfone resin (ICCI's Victorex PES) was sampled, and a polymer solution dissolved in 70 g of distilled DMF in a 300 ml beaker was added to the polyamic acid solution to give a polyamic acid. A mixed solution of / polyether sulfone resin was obtained.

As in Example 1, when the mixed solution of the polyamic acid / polyether sulfone resin was cast on a glass plate and allowed to stand, the solution gelled, and the polyamic acid / polyether sulfone resin composite organic A solvent-containing organic polymer gel film was obtained. This product was self-supporting and did not change its shape due to its own weight.

The polyamic acid / polyether sulfone resin organic polymer gel was vacuum dried at 30 ° C. to disperse the solvent in the organic polymer gel and then released from the glass plate in a film form. When this film was dipped in a DMF solvent, the film swelled and the degree of volume swelling was 24.0 times. This product repeatedly contracted and swelled as the solvent came in and out.

Examples 4 to 10 and Comparative Example 2 A 300 ml four-neck separable flask was charged with various monomers and solvents of the types and amounts shown in Table 1, and a polymer solution and a polyamic acid polymer gel were prepared in the same manner. Then, the characteristics were investigated.

In Examples 4 to 10, after the prepared polymer solution was cast on a glass plate and allowed to stand, the polymer solution caused gelation, and organic polymer gel films having self-supporting properties were obtained.

 ─────────────────────────────────────────────────── --Continued from the front page (56) References JP-A-47-42995 (JP, A) JP-A-62-190227 (JP, A) JP-B-44-19878 (JP, B1) JP-B-45- 6555 (JP, B1) JP 45-3396 (JP, B1) JP 46-30499 (JP, B2) JP 48-11826 (JP, B2)

Claims (4)

(57) [Claims] 1. A tetracarboxylic dianhydride, an aromatic diamine, and a tri- or tetraamino compound are obtained by polymerizing in an organic solvent, and the tetracarboxylic dianhydride, aromatic diamine, and tri or The mono ratio of the tetraamino compound is (100) / (50-100) / (2-25),
A polyamic acid shaped organic solvent-containing organic polymer gel having a self-supporting organic solvent having a three-dimensional network molecular structure, wherein the organic solvent-containing organic polymer gel flows out from the outside and The organic solvent has a property that contraction and swelling are reversibly performed by infiltrating the organic solvent-containing organic polymer gel, and the volume expansion rate at the time of swelling is 2 to 50 times. A reversible shrinkage / swelling body composed of an organic polymer gel containing an organic solvent. 2. The reversible shrinkage / swelling body according to claim 1, wherein
Reversible shrinkage characterized by containing at least one selected from a low molecular weight organic compound, an inorganic compound, a metal compound, and a high molecular weight organic compound as a third functional component in a dispersed / mixed state -Swelling body. 3. A tetracarboxylic dianhydride, an aromatic diamine, and a tri- or tetraamino compound in a molar ratio (100).
By polymerizing in an organic solvent at a ratio of / (50 to 100) / (2 to 25) to give a solution of polyamic acid, and gelling and shaping the solution of polyamic acid at 0 ° C to 100 ° C, A method for producing a reversible shrinkage / swelling body, which comprises obtaining a self-supporting organic solvent-containing organic polymer gel having a polyamic acid three-dimensional network molecular structure. 4. The method for producing a reversible shrinkage / swelling body according to claim 3, wherein the low molecular weight organic compound is present at any time before or after gelation after the polyamic acid is obtained by the polymerization reaction. , An inorganic compound, a metal compound, a third component having at least one kind of functionality selected from high molecular weight organic compounds in a state of being dissolved or dispersed in a solvent, by adding to the polyamic acid, the third component A method for producing a reversible shrinkage / swelling body, which is characterized in that it is contained in the reversible shrinkage / swelling body in a dissolved, dispersed or mixed state.