JPH01152121A - Novel conductive or semiconductive polymer - Google Patents

Abstract

PURPOSE:To obtain an organic polymeric conductor or semiconductor useful for electronic devices, semiconductor junction elements and switching elements, by reducing a specified compound having linear double bonds. CONSTITUTION:This conductive or semiconductive polymer is obtained by reducing a compound of the formula (wherein X and X' are each Cl, Br or H, Y and Y' are each Cl or Br, and n is 1-4). This polymer can be formed by applying a specified electric field to a reaction solution formed by dissolving a monomer and an electrolyte in a solvent and is obtained in the form of a single film, a laminated film or a fibrous material on the surface of a cathode. A good result can be attained when the electrolyte salt is formed by combining a tetrabutylammonium salt as a cation with boron tetrafluoride or phosphorus hexafluoride as an anion. The polymerization solution is prepared by dissolving the monomer and the electrolyte salt by mixing them preferably at such a ratio that the concentration of the monomer is 0.01-1M and that of the electrolyte salt is 0.1-5M based on the solvent.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to various electronic devices such as batteries, semiconductor junction devices,
The present invention relates to a novel organic polymer conductor or semiconductor useful for switching elements.

[Prior Art] In recent years, research on electronic materials has been actively conducted, and among these, functional polymer materials using conjugated polymers are attracting attention as they have a wide variety of possibilities. When conjugated polymers are doped with impurities, they form complexes and change from insulators or semiconductors to having electrical conductivity comparable to that of metals, so they are expected to be used as functional materials. type, polypyrrole type, polyacetylene type (JP-A-81-4165, JP-A-56-13)
No. 6469, Journal of Polyyn+
erSclense,Polyier Chea+1c
Al Editlon, Vol. 12, pp. 11-20), and various other materials have been studied.・Although these polymers have a well-developed π-electron system, localization of π-electrons occurs due to bond alternation, so molecular design is being carried out to delocalize them.

[Objective] The object of the present invention is to provide a novel conductive or semiconductive polymer.

[Structure] The high molecular weight polymer of the present invention can be obtained by reducing a monomer represented by the following general formula.

y4cmc+, y'
A monomer containing a halogen selected from r, I, that is, a halide of a compound having a linear double bond represented by ethylene, butadiene, and hexatriene, and is a polymer obtained in particular by electrochemical reduction. Obtained as a black film on the cathode surface. In particular, the polymerization of butadiene compounds proceeds easily, and specific examples include tetrachlorobutadiene, hexachlorbutadiene, and hexabrombutadiene.

This electrochemical polymerization method is generally used, for example, in J, E1e
ctrochea+, Soc,, Vol. 130. No
, 7.1508-1509 (lH3), EIelectro
chem, Aeta, , Vol. 27, N
o, 1, 61-85 (1982), J. Chem.
Soc,,Chem,Coa+sun,,1199~(
+984), etc., are mainly shown for anodic oxidation polymerization.

In contrast, the present invention is realized by a cathodic reduction method in which the polymerization reaction proceeds by eliminating the reducing group simultaneously with the reduction of the monomer. There are few examples of polymer synthesis by cathodic reduction, and only polyphenylene, polyphenylene vinylene, and polyphenylene xylylene have been successful. The present invention is realized by applying a predetermined electric field to a reaction solution in which a monomer and an electrolyte are dissolved in a solvent, and a polymer is obtained on the surface of a cathode in the form of a single film, a laminated film, or a fibrous material.

Examples of electrolyte salts include tetramethylammonium perchlorate, tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, and perchlorate. Lithium acid, lithium tetrafluoroborate, tetramethylammonium hexafluoroarsenate, tetraethylammonium hexafluoroarsenate, tetrabutylammonium hexafluoroarsenate, sodium hexafluoroarsenate, tetramethylammonium hexafluorophosphate, hexafluorophosphoric acid Tetrabutylammonium, sodium hexafluorophosphate,
Examples include sulfuric acid, tetramethylammonium hydrogen sulfate, tetrabutylammonium hydrogen sulfate, sodium trifluoroacetate, and tetramethylammonium p-toluenesulfonate. Particularly good results are obtained when a tetrabutylammonium salt is used as the cation and boron tetrafluoride or phosphorus hexafluoride is used as the anion.

As the solvent, it is preferable to use a polar solvent that has undergone purification treatments such as dehydration and deaeration, such as tetrahydrofuran, hexamethylphosphoramide, dimethoxyethane, acetonitrile, propylene carbonate, nitrobenzene, benzonitrile, methylene chloride, and dimethylformamide. , dimethyl sulfoxide, acetonitrile, etc. are used, and tetrahydrofuran, dimethoxyethane, and propylene dicarbonate are particularly preferred for reductive polymerization.

The composition of the polymerization solution is preferably such that the monomer is omitted relative to the solvent.
, ot-IM, and electrolyte salts are adjusted by mixing and dissolving them in a range of 0.1 to 5M.

Copper, silver,
Metal electrodes such as gold, platinum, nickel, zinc, tin, aluminum, etc.; carbon electrodes such as glassy carbon, metal oxide electrodes such as ITO, etc. can also be used;
Carbon, ITO glass, 3n02 glass, and platinum electrodes are preferred. The reaction atmosphere is preferably an inert atmosphere such as dry nitrogen or argon.

Electrolysis proceeds using any of the constant current electrolysis method, constant potential electrolysis method, and constant voltage electrolysis method, but the constant potential electrolysis method is preferable.
Hereinafter, it is preferable to apply a potential of -2V to -10V to the working electrode.

A single or laminated film is thus obtained on the cathode. According to the characterization, this polymer has an internal humulene structure and a graphite structure, and in the case of hexachlorobutadiene, linear polymerization proceeds due to the elimination of chlorine at the α position, and at the same time, due to the elimination of the chlorine at the β position, 2
It is thought that it is a polymer with a dimensional or three-dimensional structure. Therefore, the obtained polymer is insoluble and infusible and it is impossible to measure the degree of polymerization, but based on the elemental analysis values, it is assumed that the polymerization proceeds in a linear manner, and the polymer has a carbon number of 12 to 100 units. It is thought that a polymer was obtained. (Actually, it is thought that it has a graphite structure from Figure 2, so the number of carbon atoms is estimated to be larger.) Its electrical conductivity (as-grown) is 1G-2 to 103s/c+e.
Met. This polymer has no characteristic absorption in the infrared spectrum, and absorption of carbon-carbon double bonds is seen in the Raman spectrum (Figure 1).

When cyclic voltammodalum was measured in an electrolyte solution using this polymer as a working electrode, oxidation and reduction waves were observed.
In particular, a strong reduction wave appears at −〇, 8 V vs A g /Ag0. This is a material that is stable to cation doping because the smaller the electrolyte cation, the larger the current, and is useful as a negative electrode for polymer secondary batteries. Second
From the figure or FIG. 3, an X-ray diffraction pattern considered to be the 002 plane of graphite was obtained.

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

Example 1 0.1M Bu4NBF+ methyl cyanide solution fo
Hexachloro-1,3-butadiene 0.25a+ in al
1 (0,18M) and immersed I To (2,42xlO's 2) as a working electrode, pt as a cathode, and A g/A g+ as a reference electrode in this solution, -3, OV vs Ag at room temperature. /Ag'', electrolytic reduction polymerization was performed for 1 hour.

0.5 layered dark brown polymer film on ITO electrode
3/lag was obtained. The electrical conductivity of this polymer film is 0.2X 1G-coS/ei, CI/C is 0.5
3. There was absorption at 1600cm-lightning (double bond) in the Raman spectrum, but there was no strong absorption in the IR.

Example 2 Electrolytic reduction polymerization was carried out in the same manner as in Example 1, except that the working electrode was replaced with GC and the polymerization time was 70 minutes. 1.482 mg of a black polymer film was obtained.

The electrical conductivity of this polymer film is 6.2X10'S
/crys elemental analysis value CI/C was 0.53, and the Raman spectrum showed absorption due to a double bond at 1600 cm-', and there was no strong absorption in IR.

Using this film as a working electrode, cyclic polkunmetry was measured in acetonitrile, and as shown in Figure 2, the smaller the electrolyte cation, the 0.6 to -1.8 relative to silver.
When scanning the potential of V, the oxidation-reduction wave becomes large, and it is considered that cations are doped into the film.

Figure 3 shows the X-ray diffraction of 2θ-53″
The diffraction is considered to be due to the 002 plane of the graphite structure.

Table 1 shows the elemental analysis values in each doped state, where a is -a and OV with respect to Ag, that is, as-grown
b is the elemental analysis value of the film dedoped to a potential of -'t, ov, and C is the elemental analysis value of the film completely dedoped with Ov. In C, the amount of N due to ammonium cations is 0, indicating that cations are present inside the film in alb.

Table 1 Example 3 Electrolytic reduction polymerization was carried out in the same manner as in Example 1 except that the Bu4NBF4 solution was replaced with propylene carbonate. 0.814 mg of a polymer film having a black periphery and a brown color was obtained. The electrical conductivity of this polymer film is 1.3X
to°2S / 81% elemental analysis value CI/C is 0.51
, the Raman spectrum had an absorption at 1600 cm"1 (double bond).

Example 4 0.1M Bu4NBF4 acetonitrile solution 10
Dissolve 0.2 ml of tetrachlorethylene in m1 and mix this solution with 5n02 glass (4Ω/mouth 2.4
X 10' rrr), pt as cathode.

Ag/Ag+ was immersed as a reference electrode, −3,
Electrolytic polymerization was carried out at 5V v, s, A g /A g+ for 1 hour.

Electrical conductivity 1.3X 10→S/amCI/C
O,1B Raman spectrum 1600 cm-'Example 5 0.1M Bu4NBF4 dissolved in acetonitrile iff
Dissolve 0.4 ml of octabromohexatriene in 110 ml, and add ITO (2,4
'b), PT as cathode, Ag/Ag+ as reference electrode
was immersed and electrolytically polymerized at room temperature in -3,OVu,s,Ag/Ag'' for 1 hour.

Electrical conductivity 3.2X 1O-3S/0mC
1/CO,77 Raman spectrum 1600 am-' [Effect] As explained above, the present invention provides a useful novel conductive or semiconductive polymer.

[Brief explanation of the drawing]

Fig. 1 is a graph showing the IR and Raman spectra of the polymer film of Example 2, Fig. 2 is a graph showing the steady-state cyclic portamogram of the same film, and Fig. 3 is a graph showing the X-ray diffraction of the same film. Graph showing.

Claims (1)

[Claims] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X and X' are selected from Cl, Br, and H, and Y and Y
' represents a halogen selected from Cl and Br, and n represents an integer from 1 to 4. conductive or semiconductive polymer obtained by reducing ).