JPH1053650A - Production of polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer useful as an electroconductive polymer such as conductor without requiring any troublesome operation, process or apparatus by arranging a specific polymer solid in the neighborhood of a substrate containing a polymerization catalyst and carrying out vapor phase polymerization. SOLUTION: (B) A monomer is impregnated into (A) a polymer solid (e.g. chloroprene rubber sheet) and the impregnated component A is arranged in the neighborhood of a substrate (e.g. glass substrate) containing (C) a polymerization catalyst (e.g. ferric chloride) and the component B impregnated in the component A is subjected to vapor phase polymerization. Furthermore, the component B is preferably impregnated into the component A in vapor phase state and a polymer prepared from a compound selected from among pyrrole, a pyrrole substituent, aniline and an aniline substituent is preferably used as the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates particularly to conductors and contacts,
Various battery materials, transistors, diodes, display elements such as electrochromism, recording elements, electromagnetic wave shielding,
The present invention relates to a method for producing a conductive polymer such as various sensors and an antistatic material by gas phase polymerization.

[0002]

2. Description of the Related Art Conventionally, an electron conductive type conductive polymer has a semiconductor-like and insulator-like property from metal-level conductivity depending on its structure and composition, and has various interesting properties. Therefore, it is actively researched for various uses and some of them are put to practical use. Methods for producing these conductive polymers include a method by chemical polymerization using a catalyst, a method by electrolytic polymerization, and a method by post-treatment using a precursor. As one method of using a catalyst, a method of easily producing a conductive polymer by gas phase polymerization is disclosed in Japanese Patent Publication No. 2-24299 and Japanese Patent Publication No. 3-63.
No. 971 and Japanese Patent Publication No. 6-47631. In these gas phase polymerization methods, a monomer is supplied in a gas phase, and a conductive polymer is polymerized on the surface or inside of a substrate containing a polymerization catalyst.

[0003]

However, the conventional method of electrolytic polymerization requires an electrode having a required area in order to form a film on the electrode, and also requires an electrolyte. The method of manufacturing by a post-treatment using a precursor has a disadvantage that two steps of a manufacturing step of the precursor and a manufacturing step for the post-treatment are required. Among the chemical polymerization methods using a catalyst, the method by gas phase polymerization is attracting attention as a very simple production method for obtaining a large-area polymer film, but the gas phase polymerization method of a conductive polymer is, Raw material monomers that are usually liquid at room temperature are stored in a container such as a beaker or a tank, and the monomer is supplied in a gaseous state by piping in the container or at a place where the polymerization reaction is to be performed from the container. Therefore, facilities such as dedicated containers and piping are required,
In handling a liquid raw material monomer, processes such as replacement and recovery of the raw material monomer, and cleaning of containers and pipes become complicated. In addition, the method by chemical polymerization not by gas phase polymerization,
This is a method that is not too suitable for obtaining a film.

[0004]

According to the present invention, a polymer solid is impregnated with a monomer, and the impregnated polymer solid is disposed near a substrate containing a polymerization catalyst, and the polymer solid is impregnated with the monomer. Is a gas phase polymerization of a polymer.

Hereinafter, the present invention will be described in more detail.

Examples of the monomer used in the method for producing a polymer of the present invention include known monomers capable of performing gas phase polymerization to obtain a polymer. Specific monomers include, but are not limited to, pyrrole and pyrrole-substituted products, aniline and aniline-substituted products, thiophene and thiophene-substituted products, phenylenediamine and phenylenediamine-substituted products, furan and furan-substituted products, indole and indole Substituted, selenophene and selenophene substituted, fluorene and fluorene substituted,
There are acetylene and acetylene-substituted products.

The polymer of the present invention obtained by polymerizing these monomers is preferably a conductive polymer. As for the conductive polymer, various kinds of conductive polymers are known in which the conductivity changes widely or not so much depending on the presence of the dopant. In the present invention, the degree of the conductivity is not particularly limited.

The production method of the present invention is characterized in that another polymer solid is impregnated with these monomers in advance. As the type of the monomer, it is preferable to use a monomer selected from pyrrole, a pyrrole-substituted product, aniline, and an aniline-substituted product having a relatively high vapor pressure from the viewpoint of ease of impregnation and gas phase polymerization described later.

Specific examples of the substituted pyrrole include N-alkylpyrroles such as N-methylpyrrole and N-ethylpyrrole, N-arylpyrroles such as N-phenylpyrrole, 2-nitrophenylpyrrole, and 3-methylpyrrole. Pyrrole, 3-ethylpyrrole, 3-chloropyrrole, 3,
Examples of substituted anilines such as 4-dimethylpyrrole and 3,4-dichloropyrrole include N-methylaniline and N-methylaniline.
-Ethylaniline, N-dimethylaniline, N-diethylaniline, chloroaniline, dichloroaniline, chloro-N-methylaniline, chloro-N-dimethylaniline, dichloro-N-acetylaniline and the like can be used. In addition, the monomer selected from these is not limited to one type, and a copolymer can be produced by simultaneously using a plurality of monomers.

The method of impregnating a polymer solid with the above-mentioned monomer of the present invention is not particularly limited, but a method of impregnating a monomer with another polymer solid in a gaseous state, And a method in which a polymer solid and a monomer are heated and melted and mixed, and the like. Although it depends on the temperature and vapor pressure characteristics of the monomer to be used, a method of impregnating the polymer solid in a gaseous state by heating the monomer at room temperature or in a gaseous state is a particularly simple and preferable method.

Here, the impregnation of the monomer into the polymer solid means a phenomenon of adsorption or absorption, sorption, swelling, swelling and dissolving on the surface or inside of the polymer solid. In addition, as a method of impregnating these, another solvent or solution not involved in the subsequent gas phase polymerization reaction may be mixed in the monomer.

The polymer solid to be impregnated with the monomer of the present invention is a polymer solid such as a thermoplastic resin, a thermosetting resin, a thermoplastic elastomer, or a vulcanized rubber, and particularly has a composition, structure, shape, etc. Is not limited. Specifically, polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene, polyvinyl chloride,
Polyvinylidene chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetal, fluoropolymers such as polyvinylidene fluoride and polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, Polyacrylonitrile, styrene-acrylonitrile copolymer, ABS resin, polyphenylene ether and modified PPE resin, aliphatic and aromatic polyamides, polyimide, polyamideimide,
Polymethacrylic acid esters such as polymethacrylic acid and its methyl ester, polycarbonate, polyphenylene sulfide, polysulfone, polyether sulfone, polyether nitrile, polyether ketone, polyketone, liquid crystal polymer, silicone resin, thermoplastic resin such as ionomer and Crosslinked product, styrene-butadiene or styrene-isoprene block copolymer and its hydrogenated polymer and styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyurethane-based thermoplastic Elastomers, thermoplastic elastomers such as polyamide-based thermoplastic elastomers and their crosslinked products, natural rubber, butadiene rubber, isoprene rubber, styrene Vulcanized rubber such as tadiene copolymer rubber, nitrile rubber, chloroprene rubber, ethylene propylene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, butyl rubber and halogenated butyl rubber, fluoro rubber, urethane rubber, silicone rubber, epoxy resin, phenol resin, Unsaturated polyester resin, rayon, cellulose, casein, starch and the like.
Further, a polymer alloy composed of a plurality of polymers selected from these polymers may be used.

Regarding the shape of the above polymer solid, powder, pellet, film, plate, fiber, woven,
Although not particularly limited, such as a non-woven fabric, a plate-like foam, a shape obtained by finely cutting the foam, a powder-granular shape including a pellet shape, and a cloth-like material comprising fibers and fibers are preferable. Among them, from the viewpoint of significantly impregnating the monomer, a foamed polymer solid having a large surface area, specifically, a foamed plastic such as foamed polyethylene, polystyrene, and foamed polyurethane, and foamed rubber are preferable. The expansion ratio and the foaming prescription at this time are not limited at all, and a plurality of polymer solids may be selected.

The gas-phase polymerization catalyst used in the present invention is not specified. Commonly known ferric chloride, ferric bromide, ferric perchlorate, cupric chloride, molybdenum chloride, metal salts such as ruthenium chloride, metal oxides such as lead dioxide, potassium persulfate, Examples include peroxo salts such as ammonium sulfate, quinones such as benzoquinone, diazonium salts such as benzenediazonium chloride, potassium ferricyanide, and hexachloroplatinic acid. After the reaction, these catalysts themselves also function as dopants.

The polymerization catalyst used in the present invention can be applied to a target glass or resin substrate directly or as a solution or dispersion by a usual method. A polymer material as exemplified in the above polymer solid is heated and melted, or mixed in a solution state using an appropriate solvent such as water, acetone, alcohols, and toluene, and applied onto a substrate. It is known that the adhesion with the base material is improved by
The present invention is also applicable. Among them, a method of applying a solution mixed with another polymer material is simple and effective. The base material is a polyethylene terephthalate film (PE
In the case of a resin base material such as T film, the surface of the base material can be modified in advance with ultraviolet irradiation, plasma, corona, flame treatment, or the like to impart polarity to the resin surface and improve adhesion. It is known and can be used in the present invention as needed. A solution of a polymerization catalyst and a polymer is applied to one or both sides of the substrate by a known method such as brushing or dipping, spraying, roll coating, gravure printing, screen printing, and the like, and drying. Thus, a substrate containing a desired polymerization catalyst can be produced. In addition,
The material and shape of the substrate are not specified,
Metal, glass, ceramics, resin, rubber, fiber and cloth,
Films, sheets, papers or foams are used.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a conductive polymer according to the present invention, a polymer solid previously impregnated with a monomer is placed near a substrate containing the above-mentioned polymerization catalyst, and the monomer is subjected to gas phase polymerization. It is characterized by. The method for arranging the solid polymer in the vicinity of the substrate containing the polymerization catalyst is not particularly limited. The meaning of the vicinity of the base material may be in direct contact with the base material, or may be set at a distance of several cm to several tens of cm, and set arbitrarily in connection with the polymerization conditions and the characteristics of the target polymer. can do. The polymer solid may be filled in a specific container, or may be in a fluidized state in the case of a granular material or a strip. The temperature and the polymerization time of the gas phase polymerization can also be determined with reference to conventionally known materials. The reaction system may be a closed system or an open system, or may be an inert gas atmosphere such as nitrogen gas or argon gas, or an atmosphere circulating water vapor. Usually, it is not always necessary because the previous polymerization catalyst acts as a dopant, but for the purpose of obtaining a desired conductive polymer after gas phase polymerization, halogens such as iodine, boron fluorides, paratoluenesulfonic acid, etc. A dopant such as a sulfonic acid, a metal halide, or an alkyl ammonium may be added again. Further, in order to improve the abrasion resistance of the film, an acrylic resin, a urethane resin, a silicone resin, or the like can be overcoated on the surface of the conductive polymer of the present invention by a known method.

Hereinafter, examples of the method for producing a polymer according to the present invention will be described.

In the present embodiment, a method is adopted in which two kinds of monomers are exchanged for continuous polymerization so that the present invention can be better understood, but the present invention is not limited to this embodiment.

[0019]

Example 1 A foamed chloroprene rubber sheet having a thickness of 3 mm was cut into about 3 mm squares, vacuum-dried at 60 ° C. for 20 hours, and then placed in a stainless steel 60 mesh net basket. On the other hand, commercially available pyrrole (manufactured by Wako Pure Chemical Industries, Ltd.,
Dehydrated with magnesium sulfate all day and night, distilled under reduced pressure under a nitrogen atmosphere, put into a beaker, placed a net basket containing the cut foamed chloroprene rubber sheet piece on top of the beaker, and placed in a nitrogen atmosphere. The previously purified pyrrole was impregnated in the gas phase for 20 hours to obtain an impregnated polymer A (foamed chloroprene rubber sheet). From the weight change before and after the impregnation of the pyrrole-impregnated polymer A piece, impregnation with 12% by weight of pyrrole per unit weight was recognized.

Separately, an aqueous solution of 4% of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) and 6% of ferric chloride (manufactured by Wako Pure Chemical Industries, Ltd.) having an average degree of polymerization of 500 was prepared, and glass having a thickness of 1 mm was prepared. 5μm thick on the substrate with a bar coater
And dried in a normal state all day and night, followed by vacuum drying to prepare a glass substrate a containing a polymerization catalyst.

The impregnated polymer A obtained above is placed in a beaker, the prepared glass substrate a is placed on top of the beaker, and pyrrole is subjected to gas phase polymerization at a polymerization temperature of 0 ° C. for 20 hours in a nitrogen atmosphere to obtain polypyrrole. Obtained. The resistivity (JISK7194) of the obtained polypyrrole by the four-point probe method is as follows:
It was 80 Ω · cm.

[0022]

Example 2 A foamed polyurethane sheet having a thickness of 4 mm was
The pieces were cut into about 4 mm squares, vacuum-dried at 60 ° C. for 20 hours, and then placed in a stainless steel 60 mesh net basket.
On the other hand, commercially available aniline (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was dehydrated with magnesium sulfate for 24 hours, distilled under reduced pressure under a nitrogen atmosphere, and then put into a beaker. Was placed therein, and aniline previously purified was impregnated in a gaseous state for 30 hours in a nitrogen atmosphere to obtain an impregnated polymer B (foamed polyurethane sheet). The aniline-impregnated polymer B piece was found to be impregnated with aniline at 14% by weight per unit weight.

Next, the impregnated polymer A in the beaker was replaced with the impregnated polymer B in the same beaker as that for producing the polypyrrole in Example 1. Similarly, the glass substrate a was placed on top of the beaker, and nitrogen was added. 2 at polymerization temperature of 10 ° C under atmosphere
The aniline was subjected to gas phase polymerization for 0 hour to obtain polyaniline.
The resistivity of the obtained polyaniline by the four probe method (JIS
K7194) was 740 Ω · cm.

[0024]

Example 3 A biaxially oriented polystyrene sheet having a thickness of 0.2 mm was cut into approximately 3 mm squares, dried in a vacuum at 60 ° C. for 20 hours, and then placed in a stainless steel 60 mesh net basket and impregnated with a polymer. Similarly to A, it was placed on the top of a beaker containing purified pyrrole and impregnated with pyrrole in a gaseous state for 20 hours under a nitrogen atmosphere to obtain an impregnated polymer C (biaxially stretched polystyrene sheet). The resulting pyrrole-impregnated polymer C pieces were found to be impregnated with 21% by weight of pyrrole per unit weight.

Separately, an aqueous solution of 5% of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) and 5% of ferric chloride (manufactured by Wako Pure Chemical Industries, Ltd.) having an average degree of polymerization of 1500 is prepared, and irradiated with short-wavelength ultraviolet rays. 0.2mm thick P
It was applied to a thickness of 5 μm on an ET film by a bar coater, dried in a normal state all day and night, and further dried under vacuum to prepare a PET film substrate b containing a polymerization catalyst.

The impregnated polymer C obtained above is placed in a beaker, the prepared PET film substrate b is placed on top of the beaker, and pyrrole is subjected to gas phase polymerization at a polymerization temperature of 0 ° C. for 10 hours in a nitrogen atmosphere to obtain polypyrrole. I got The resistivity of the obtained polypyrrole by a four-point probe method (JIS K719)
4) was 230 Ω · cm.

Next, the impregnated polymer C in the same beaker
Is replaced with the impregnated polymer B obtained in Example 2, and PET
The film substrate b was placed on the top of the beaker, and aniline was subjected to gas phase polymerization at a polymerization temperature of 10 ° C. for 20 hours under a nitrogen atmosphere to obtain polyaniline. The resistivity (JIS K7194) of the obtained polyaniline by the four-point probe method is 1800Ω.
Cm.

Comparative Example 1 Purified pyrrole was placed in a beaker, the glass substrate a was placed on the beaker, and pyrrole was subjected to gas phase polymerization at a polymerization temperature of 0 ° C. for 20 hours in a nitrogen atmosphere to obtain polypyrrole. The resistivity (JIS K7194) of the obtained polypyrrole by the four-point probe method is 70 Ω.
Cm.

Next, the remaining pyrrole in the same beaker is collected, the beaker is washed with acetone and pure water, dried and then replaced with purified aniline, and the glass substrate a is placed on top of the beaker and polymerized under a nitrogen atmosphere. Aniline was vapor-phase polymerized at a temperature of 10 ° C. for 20 hours to obtain polyaniline. The resistivity (J
ISK7194) was 810 Ω · cm.

(Comparative Example 2) A purified pyrrole was put in a beaker, a PET film substrate b was placed on top of the beaker, and pyrrole was vapor-phase polymerized under a nitrogen atmosphere at a polymerization temperature of 0 ° C for 10 hours to obtain polypyrrole. . Resistivity of the obtained polypyrrole by a four-point probe method (JIS K7194)
Was 210 Ω · cm.

Next, the remaining pyrrole in the same beaker is collected, and the beaker is washed with acetone and pure water, dried and then exchanged for purified aniline, and the PET film substrate b
Was placed on the top of the beaker, and aniline was subjected to gas phase polymerization at a polymerization temperature of 10 ° C. for 20 hours to obtain polyaniline. The resistivity of the obtained polyaniline by the four probe method (JISK7
194) was 1900 Ω · cm.

[0032]

As described above, according to the present invention, a polymer solid is impregnated with a monomer in advance, and the impregnated polymer solid is placed near a base material containing a polymerization catalyst to perform gas phase polymerization. Since it is no longer necessary to directly handle liquid monomers during the polymerization reaction as in the past, an excellent high-performance process that eliminates the need for complicated operations, processes and equipment for washing and drying containers and piping with other solvents and pure water, etc. This is a method for producing a molecule.

Claims (4)

[Claims] 1. A polymer solid is impregnated with a monomer, the impregnated polymer solid is placed near a base material containing a polymerization catalyst, and the polymer impregnated monomer is subjected to gas phase polymerization. A method for producing a polymer. 2. The method for producing a polymer according to claim 1, wherein the polymer is a conductive polymer. 3. The method for producing a polymer according to claim 1, wherein the polymer solid is impregnated with the monomer in a gas phase. 4. The method for producing a polymer according to claim 1, wherein the monomer is a polymer selected from pyrrole, a substituted pyrrole, an aniline, and a substituted aniline.