JPH0757699B2 - Method for producing composite of conductive polymer material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a glass / conductive polymer material composite.

[Prior Art] In recent years, with the progress of electronic devices, it has been desired that materials have high functionality, and a large number of semiconducting and conductive materials have been developed. In particular, there are remarkable developments of conductive polymer materials. Courageous polymer materials such as polyacetylene, polypyrrole, and polythiophene can be used as semiconductor materials and conductors as well as semiconductor materials and conductors because they transfer from insulating or semiconducting materials to conductive materials by doping impurities. A device that has been proposed is proposed.

On the other hand, glass has an important position as a structural material, but recently, high added value is required for glass.

For example, ion-conducting glass known by NASICON, LISICON, etc., special glass (for example, ITO) on which glass or a metal oxide is coated on a glass substrate have been developed, but the glass itself has conductivity. Is not currently developed.

[Objective] In view of such circumstances, an object of the present invention is to provide a method for producing a novel glass / conductive polymer material composite having conductivity.

[Structure] The inventor of the present invention has conducted extensive research to solve the above problems, but has found that compounding a conductive polymer material with glass is effective, and has reached the present invention.

That is, the present invention is characterized in that in a method for producing glass from silanol or a metal alkoxide by a gelation method or a sol-gel method, glass and a conductive polymer material are composite laminated or homogeneously composited. It is a method for producing a hydrophilic polymer material composite.

As described above, the present invention provides the conductive polymer material with various workability and strength of glass, and also imparts the conductivity to the glass by uniformly or layer-compositing the conductive polymer material. is there.

The composite is useful for electromagnetic wave shields, low antibodies, heating elements, non-linear optical elements, memories, etc., as well as sensors and electrochromic materials.

Regarding the conventional compounding of a conductive polymer material in a polymer matrix such as vinyl chloride or polyethylene oxide, methyl cellulose, or Nafion, Polymer Journal Vol 18, No.1 pp95-98 (1986), J.
Elecotrochem.Soc., Vol.133, No.2 pp310-315 (198
6), J.Chem.Soc.Chem.Commun.pp 1293 ~ 1295 (1986)
Although there are some research examples such as the above, the present invention is a novel composite material in which a conductive polymer material is composited in glass.

The composite of the glass and the conductive polymer material in the composite of the present invention is realized in the chemical glass manufacturing process.

This chemical glass manufacturing method includes a gelling method using D silanol as a starting material, 2) a chemical manufacturing method prepared by a so-called sol-gel method in which a gel is formed from a metal alkoxide, and particularly, the sol of (2)- The gel method is preferred.

Any one of 1) a chemical oxidation method and 2) an electrolytic oxidation method is adopted for forming a composite with a conductive polymer material, which is carried out in the above chemical production process, and a monomer is produced into glass by these methods. Polymerization is carried out in the process, but it is particularly preferable to combine the sol-gel method and the chemical oxidation method.

As described above, the composite of the present invention was impossible in the conventional glass manufacturing process, but in the special glass manufacturing process, the reaction field of the glass manufacturing method was also used for the reaction field of the polymerization of the conductive polymer at the same time. It is formed by doing.

The composite of the present invention exhibits conductivity in the semiconductor and conductor regions and also has the function of a conductive polymer material.

The chemical glass manufacturing method is roughly divided into two methods as described above, the former is J. Polm.Sci.Polym.Chem.Ed.,
No. 21 (1983) P41 ~ Silanol / T
The reaction with the HF solution is excellent, and it may be modified by adding an alcoholic polymer such as polyethylene oxide.

The latter is H. Shroeder; Physics of film, ed. By G. Hass,
REThum.Vol.5 Academic Press, New York, 1969 P87, the so-called sol-gel method is used to vitrify via a gel by a condensation reaction of a metal alkoxide in an acidic solvent. The organic polymer can be added within the range of%. Further, by mixing various fillers such as SiO _2, cracks and the like due to shrinkage in the glass formation process can be eliminated.

Heat treatment is required in the process of producing glass from these gels, but in the case of compounding, it can be compounded as a glassy solid at 300 ° C or lower,
By heat treatment above ℃, the composite becomes a ceramic glass,
The conductive polymer material is carbonized to form a new conductive composite. In the sol-gel method, various alkali metal alkoxides are combined to produce NASICON and LISICON.
It is also possible to use an ion-conductive glass such as, for example, and it is possible to impart a certain degree of ion-conductivity without making it into a ceramic.

The oxidizing property of the conductive polymer material in the present invention, as the monomer, pyrrole, aniline, selenophene, furan, thiophene, benzene, triphenylamine, diphenylbenzidine, carbazole or 3-methylthiophene, N-methylpyrrole, etc. Derivatives can be exemplified, and the reducing monomer can be represented by the general formula X ₂ HC-Ar.
_{-CHX 2, X 3 C-Ar} -CX 3 (Ar is thiophene, pyrrole, benzene, heterocyclic compounds such as anthracene or aromatic compound, X is Cl, halogen such as Br), hexa-chloro-butadiene, hexa bromo butadiene And so on. Specific examples include thiophene and dimethyl sulfonium salt of benzene.

As a method for forming a homogeneous composite of glass and a conductive polymer material in the present invention, good results can be obtained in a chemical oxidative polymerization method, but in the case of reducing a composite laminate or a reducing monomer, electrolysis is performed. Polymerization methods are suitable.

In the glass manufacturing process, the former is a solution of silanol or metal alkoxide (glass adjusting solution), and is mixed with an oxidizing agent and a reducing agent, or is mixed with a monomer and gelated or vitrified, and then the oxidizing agent, the reducing agent and the monomer. Is a method of forming a conductive high-molecular polymer in a gel or glass by contacting, and the latter is a vitrification by electrolytic polymerization after mixing an electrolyte salt and a monomer in a glass preparation solution, or an electrolyte salt is added. This is a method of mixing and vitrifying, then impregnating a monomer and electrolytically polymerizing. Examples of the oxidizing agent in the present invention include halogens such as iodine, arsenic, and iodide; metal halides such as arsenic pentafluoride, antimony pentafluoride, silicon tetrafluoride, phosphorus pentachloride; sulfuric acid, nitric acid, fluoro Protic acids such as sulfuric acid and chlorosulfuric acid; oxygen-containing compounds such as sulfur trioxide and nitrogen dioxide; persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; hydrogen peroxide, peracetic acid, difluorosulfonyl peroxide, etc. Examples include peroxides.

Amorphous carbon bodies such as Au, Pt, Ni, Al, stainless steel, Fe, Cu, and Sn, Sn
A metal oxide such as O ₂ or In ₂ O ₃ , a composite electrode or coating electrode of these can be used, and a similar electrode can be used as the counter electrode.

Electrolytic polymerization is electrolyzed by any of constant voltage electrolysis, constant current electrolysis, and constant potential electrolysis, and the whole glass can be homogenized and dispersed by stirring in the glass-adjusted solution, but the partial weight in the vicinity of the electrode is increased. A laminated composite can be formed by precipitating the coalescence.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 Si (OC ₂ H ₅ ) ₄ 25 parts by weight C ₂ H ₅ OH 27.6 parts by weight H ₂ O 23.5 parts by weight HCl 0.5 parts by weight A sol was prepared according to the above formulation. 5% FeCl ₃ / C ₂
A glassy solid was prepared by adding 10 g of H ₅ OH solution and drying at room temperature for 24 hours.

This was immersed in a pyrrole monomer, reacted for 1 hour, washed with water and acetonitrile, and heated at a temperature of 85 ° C. for 48 hours to obtain a black glossy polypyrrole / glass composite having a thickness of 1 mm. Electrical conductivity is 3.0 × 10 ^-4 S
It was / cm.

Example 2 Si (OC ₂ H ₅ ) ₄ 20 parts by weight Glycerin 37.6 parts by weight H ₂ O 23.5 parts by weight HCl 0.5 parts by weight A sol was prepared according to the above formulation. A 5% ammonium persulfate 10% aqueous solution was added thereto, dried at room temperature for 48 hours, and further reacted at a temperature of 120 ° C. for 24 hours. This was immersed in a pyrrole monomer, reacted for 1 hour, washed with water and acetonitrile, and heated at 85 ° C. for 48 hours to obtain a black and glossy polypyrrole / glass composite having a thickness of 0.5 mm. The electric conductivity was 2.1 × 10 ^-3 .

Example 3 Si (OC ₂ H ₅ ) ₄ 20 parts by weight C ₂ H ₅ OH 37.6 parts by weight Polyethylene oxide (MW5000) 5 parts by weight LiClO ₄ 1 part by weight H ₂ O 23.5 parts by weight HCl 0.5 parts by weight A polypyrrole / glass composite was obtained in the same manner as in Example 1 except for the preparation. Electric conductivity
It was 1.1 × 10 ^-3 s / cm.

Example 4 Ti (C ₄ H ₉ O) ₄ 17 parts by weight Si (C ₂ H ₅ O) ₄ 10.5 parts by weight PO (C ₄ H ₉ O) ₃ 34 parts by weight Li (C ₄ H ₉ O) 8 parts by weight C ₂ H ₅ OH 50 parts by weight A polypyrrole / ion conductive glass composite was obtained by the same method as in Example 2 except that a sol was prepared according to the above formulation.
The electric conductivity was 2.2 × 10 ^-2 s / cm.

Furthermore, this composite was heat-treated at 900 ° C. in an Ar gas atmosphere. The electric conductivity was 1.6 × 10 ^-1 s / cm.

Example 5 A polypyrrole / glass composite was obtained in the same manner as in Example 2 except that the monomer in Example 2 was changed from pyrrole to 3-methylthiophene.

The electric conductivity was 1.6 × 10 ^-4 s / cm.

Example 6 Nesa glass was immersed in the sol of Example 2 as a working electrode and a platinum plate as a counter electrode, and 10 ml of 0.5 M aniline / 2M HCl aqueous solution was added.
Electropolymerization (4 C / cm ² ) was performed at a constant current of ² mA / cm ² , and heat treatment was performed as it was under the same conditions as in Example 2 to obtain a polyaniline / glass composite layer having a thickness of 1 mm.

This complex showed electrochromic property when subjected to -0.2 to 1.0 V potential scanning with respect to SCE.

Example 7 3.6M HCl aqueous solution 50 g Na ₂ SiO ₃ .9H ₂ O 20 g was mixed and stirred to prepare a first liquid.

Then, a solution prepared by adding 30 g of NaCl to 50 ml of THF was added to the first solution as the second solution, stirred and left to stand, and the organic layer was separated and dried over anhydrous sodium sulfate to obtain a SiO ₂ / THF solution.

Add 2 g of ammonium sulfate to this SiO ₂ / THF solution.
A glassy solid was obtained by heating at 85 ° C. under a pressure of 80 mmHg. This was brought into contact with pyrrole monomer vapor to obtain a polypyrrole / glass composite. The electric conductivity was 3.0 × 10 ^-5 s / cm.

[Effect] As described above, according to the constitution of the present invention, the conductive polymer material is reinforced by the glass, and the glass is provided with the conductivity to provide a highly functionalized novel composite. .

Continuation of the front page (56) Reference JP 62-181325 (JP, A) JP 62-17905 (JP, A) JP 61-97332 (JP, A) JP 63-10685 (JP , A) JP 63-125696 (JP, A)

Claims (1)

[Claims] 1. A method of producing glass from silanol or a metal alkoxide by a gelation method or a sol-gel method, wherein glass and a conductive polymer material are composite-laminated or homogeneously composited. A method for producing a polymer material composite.