JPH01167254A - Electrically conductive polymer material composite - Google Patents

Abstract

PURPOSE:To obtain a glass/electrically conductive polymer material composite, having excellent electric conductivity and high functional properties and useful in the field of electronic devices, by compounding and laminating glass on an electrically conductive polymer material or homogeneously compounding both. CONSTITUTION:A metal alkoxide (e.g., FeCl3/C2H5OH), etc., is added to gelatinize a sol, such as silanol, and provide a glassy solid (A), which is then dipped, reacted with a liquid of an electrically conductive high polymer material (B), such as pyrrole monomer, subsequently washed and dried to prepare an electrically conductive polymer material composite in a composite laminated form, such as glass/polypyrrole.

Description

[Detailed description of the invention] [Technical field] The present invention relates to glass/conductive polymer material composites.

[Prior Art] In recent years, with the advancement of electronic devices, there has been a desire for highly functional abrasive materials, and many semiconducting and conductive materials have been developed, with the development of conductive polymer materials being particularly remarkable. Organic polymer materials such as polyacetylene, polypyrrole, and polythiophene can be doped with impurities to transform from insulating or semiconducting materials to conductive materials, so in addition to being applied as semiconductor materials and conductors, this transition can be utilized. A device has been proposed.

On the other hand, glass plays an important role as a structural material, and recently, high added value has been required for glass as well.

For example, ion-conductive glasses such as those known as NASICON and LISICON, and special glasses made of glass as a substrate and coated with metals or metal oxides (such as ITO) have been developed. is not currently developed.

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

[Structure] The present inventor has been conducting research to solve the above problems, and has discovered that it is effective to combine glass with a conductive polymer material, and has arrived at the present invention.

That is, the present invention is a glass/conductive polymer material composite characterized in that glass and a conductive polymer material are compositely laminated or homogeneously composited.

In this way, the present invention provides a conductive polymer material with the various workability and strength of glass, and also imparts conductivity to glass by making the conductive polymer material homogeneous or laminated into a composite. be.

This composite is useful for electromagnetic shielding, resistors, heating elements, nonlinear optical elements, memories, as well as sensors and electrochromic materials.

Conventionally, the compounding of conductive polymer materials into polymer matrices such as vinyl chloride, polyethylene oxide, methylcellulose, Nafion, etc. is described in Polymer Journal Vol. 18. No,
1 pp95-98 (198B), J, E Ia
ct rochcm.

Soc,, Vol., 133. No, 2 pp 310~
315 (1986), J.

Chcm, Soc, Chcm, Commun, pp 1
There are some research examples such as 293-1295 (198 [i)], but the present invention is a novel composite material in which a conductive polymer material is composited into glass.

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

This chemical glass production method includes a gelation method using D-silanol as a starting material, and a chemical production method using a so-called sol-gel method in which metal alkoxide is gelled. Gel method is preferred.

For the composite with conductive polymer material carried out in the above chemical manufacturing process, either 1) chemical oxidation method or 2) electrolytic oxidation method is adopted.
It is particularly preferred to polymerize the glass in the glass manufacturing process or to combine a sol-gel method with a chemical oxidation method.

In this way, the composite of the present invention can be used in a special glass manufacturing process to simultaneously utilize the reaction field of the glass manufacturing process as a reaction field for the polymerization of conductive polymers, which was not possible in conventional glass manufacturing processes. It is formed by

The composite of the present invention exhibits the conductivity of a semiconductor, a conductive region, and also has other functions of a conductive polymer material.

As mentioned above, chemical glass manufacturing methods are roughly divided into two methods, and the former is J and Po1m.

Sei, Polym, Chcm, Ed,, No. 21 (
1983) Silanol/
The reaction with THF solution is excellent, and it may be modified by adding an alcoholic polymer such as polyethylene oxide.

Also, the latter is H, 5hroeder; Physics o
rfilm, ed.

by G, Hass, R, E, Thum, Vol, 5
Academic Press.

New York, 1989 P87, the so-called sol-gel method involves a condensation reaction of metal alkoxide in an acidic solvent to form a gel and then vitrify it.
In this case as well, the organic polymer can be added within a range of 20%. Furthermore, by incorporating various fillers such as 5i02, it is possible to eliminate cracks caused by shrinkage during the glass production process.

Heat treatment is required in the process of producing glass from these gelled materials, but when compounding, it is possible to form a glassy solid at temperatures below 300°C.
When heated at 00°C or higher, the composite becomes ceramic vitrified, and the conductive polymer material is carbonized to form a new conductive composite. In addition, in the sol-gel method, by combining various alkali metal alkoxides, NASIC
It is also possible to use ion conductive glass such as ON or LISICON, and it is possible to impart a certain degree of ion conductivity without forming a gelatin.

Regarding the oxidizing property of the conductive polymer material in the present invention, monomers such as pyrrole, aniline, selfene, furan, thiophene, benzene, triphenylamine, diphenylbenzidine, carbazole, or their 3-methylthiophene, N-methylpyrrole, etc. Derivatives can be exemplified, and examples of reducing monomers include the general formula X2HC-A
r-CHX2, X3 C-Ar-CX3 (Ar is a heterocyclic compound or aromatic compound such as thiophene, pyrrole, benzene, anthracene, I can give you something like that. Special examples include thiophene and dimethylsulfonium salts of benzene.

In the present invention, good results can be obtained by chemical oxidative polymerization as a homogeneous composite of glass and conductive polymer material, but when reducing composite laminates or reducible monomers, electrolytic Polymerization method is suitable.

The former involves mixing an oxidizing agent and a reducing agent in a solution of silanol or metal alkoxide (glass conditioning solution), or mixing a monomer into the solution to form a gel or vitrify the oxidizing agent, reducing agent, and monomer. This is a method in which a conductive polymer is formed in a gel or glass by cleavage.The latter is a method in which electrolyte salts and monomers are mixed into a glass preparation solution and then electrolytically polymerized and vitrified, or electrolyte salts are mixed into a glass preparation solution. This is a method in which the mixture is mixed and vitrified, and then impregnated with a monomer and electrolytically polymerized. Examples of the oxidizing agent in the present invention include halogens such as iodine, fluorine, and borosiodide; metal halides such as arsenic pentafluoride, antimony pentafluoride, silicon tetrafluoride, and phosphorus pentachloride; sulfuric acid, nitric acid, and fluorine. Protonic acids such as sulfuric acid and chlorosulfuric acid; Oxygenated 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.

Materials constituting electrodes during electrolytic polymerization, working electrodes include amorphous carbon materials Au, Pt, Ni5Al, stainless steel, Fe%
Metals such as Cu, metal oxides such as 5n02 and In2O3, composite electrodes or coated electrodes thereof, and the like can be used, and a similar electrode can also be used as a counter electrode.

Electrolytic polymerization is carried out by constant voltage electrolysis, constant current electrolysis, or constant potential electrolysis, and in a glass conditioning solution, the entire glass can be made homogeneous or dispersed by stirring, but some parts of the glass near the electrodes By allowing the coalescence to precipitate, a laminated composite can be formed.

EXAMPLES The present invention will be explained in further detail by way of Examples below.

Example 1 S i (OC2Hs) < 25 parts by weight C
2H60H27.6 parts by weight H2023.5 parts by weight HCI 0.5 parts by weight A sol was prepared according to the above recipe. Add to this 5% FeC13/C
A glassy solid was prepared by adding 10 g of 2Hs OH solution and drying at room temperature for 24 hours.

This was immersed in 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 with a thickness of 1 mm. . Electric conductivity is 3
．． Ox 10' was 87cm.

Example 2 S i (OC2Hs) 4 20 parts by weight Glycerin 37.6 parts by weight H2023
, 5 parts by weight HCI 0.5 parts by weight A sol was prepared according to the above recipe. A 10% aqueous solution of 5% ammonium persulfate was added to this and dried at room temperature for 48 hours.
The reaction was further carried out at a temperature of 120°C for 24 hours. This was immersed in pyrrole monomer and reacted for 1 hour, washed with water and acetonitrile, and heated at 85°C for 48 hours to obtain a black, glossy polypyrrole/glass composite with a thickness of 0.5 mm. . Electrical type conductivity is 2, lX
It was l0-3.

Example 3 S i (OC2Hs) 4 20 parts by weight C2H50H37,6 parts by weight Polyethylene oxide (M W 5000) 5 parts by weight LiCl0+ 1 part by weight H20,2
3.5 parts by weight HCI 0.5 parts by weight A polypyrrole/glass composite was obtained in the same manner as in Example 1, except that a sol was prepared according to the above recipe. Electrical conductivity is 1. ]
X 10' s/cm.

Example 4 Ti (C4H90)4 17 parts by weight S i
(C2H50) 410.5 parts by weight PO (C4H
90) 3 34 parts by weight Li (C4H90)
8 parts by weight C2H5OH 50 parts by weight A polypyrrole/ion conductive glass composite was obtained in the same manner as in Example 2, except that a sol was prepared according to the above recipe.

The electrical conductivity was 2.2 x 10's/Qra.

Furthermore, this composite was heat-treated at 900° C. in an Ar gas atmosphere. The electrical conductivity was 1.6-]]-X 10'' 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 electrical conductivity is 1. BX was 10's/cm.

Example 6 Nesaglass was immersed as a working electrode and a platinum plate was immersed as a counter electrode in the sol of Example 2, 10ml of 0.5M aniline/2M HCl aqueous solution was added, and electropolymerization was carried out at a constant current of 2+nA/Cm2 (4C/cm2). 2) and then heat-treated under the same conditions as in Example 2 to reduce the thickness of polyaniline/glass.
A 1 mm composite laminate was obtained.

This composite exhibited electrochromic properties when subjected to a potential scan of -0.2 to 1.0 V with respect to SCE.

Example 7 3.6M HCI aqueous solution 50gNa2S
2020 g of io3.9H was mixed and stirred to prepare a first liquid.

Next, a solution of 30 g of NaCl in 50 ml of THF was added as a second solution to the first solution, stirred and allowed to stand, and the organic layer was separated and dried over anhydrous sodium sulfate to obtain 5i02/
It was made into a THF solution.

Further, 2 g of ammonium sulfate was added to this 5i02/THF solution and heated at 85° C. under a pressure of 11 g (80 mm) to obtain a glassy solid. This was brought into contact with pyrrole monomer vapor to obtain a polypyrrole/glass composite. Electrical conductivity is 3.
It was OX 10' s/cn+.

[Effect] As explained above, according to the configuration of the present invention, a conductive polymer material is reinforced with glass, and a novel composite body in which the glass is imparted with conductivity and is highly functional is provided. .

Claims (1)

[Claims] A glass/conductive polymer material composite characterized in that glass and a conductive polymer material are laminated or homogeneously composited.