JPS63128019A - Electrolytic polymer and organic semiconductor material - Google Patents

Abstract

PURPOSE:To obtain an electrolytic polymer, exhibiting electric conductivity within a semiconductor region and providing an organic semiconductor material capable of stably existing in air, by electrolytically polymerizing 1,2- dithienylethene monomer. CONSTITUTION:1,2-Dithienylethene monomer expressed by the formula and a supporting electrolyte are dissolved in a solvent, e.g. methylene chloride, etc., to form a solution and electrodes are put therein. A voltage is applied to afford the aimed polymer on the electrode surfaces. Furthermore, impurities are doped in the electrolytic polymerization to provide the polymer having properties as a semiconductor by doping impurities in electrolytic polymerization and the aimed organic semiconductor material can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an electrolytic monomer that becomes an organic semiconductor that can be applied to electrochronic materials, electromagnetic shielding materials, electrode materials, and the like. More specifically, the present invention relates to a novel electrolytic polymer that can be doped and dedoped with electrolyte ions by electrochemical techniques.

[Prior art]

In recent years, research on electronic materials has been actively conducted, and among these, mechanical polymer materials using conjugated polymer materials are attracting attention as they have a wide variety of possibilities.

It is known that when conjugated polymers are doped with impurities, a complex is formed and the polymer changes from insulating or semiconducting properties to having electrical conductivity comparable to that of gold, but the conduction mechanism is still unknown. However, many materials are being researched as they are expected to be functional materials.

Organic semiconductors that have been studied in the past include thiophene-based, virol-based, and acetylene-based (% open Wd56-1364).
No. 69, Journal Of Polymer8
cienas, Polymer Chemical E
dition Vol. 12, 11-20 (Negative)), but polyacetylene is not affected by oxygen and is unstable in air, and polythiophene is a dopant impurity or has problems such as shedding and stagnation in air. It has.

〔the purpose〕

The present invention has been made in view of the above-mentioned current situation, and
The purpose is to provide an organic semiconductor material that exhibits electrical conductivity in a semiconductor region and can exist stably in air.

[false]

The above object is achieved by an electrolytic polymer produced from a monomer represented by the formula by an electrolytic polymerization method.

The polymer of the present invention has semiconductor properties by being doped with impurities during electrolytic polymerization.

These impurities can create bottleneck ions that are taken in during electrolytic polymerization, and representative examples include tetrafluoroborate ions, perchlorate ions, hexafluorophosphate ions, hexafluorohydrophosphate ions, sulfate ions, and hydrogen sulfate ions. ion, trifluoroacetate ion, p-toluenesulfonate ion, etc. When a reverse voltage is applied to a polymer doped with the above-mentioned anions by electrolytic polymerization, the anions are separated from one another and become an insulating compound. This polymer can be made to have semiconducting properties again by contacting it with an electron acceptor such as iodine, trifluoride, arsenic pentafluoride, or antimony pentafluoride.

The polymer of the present invention can be produced by, for example, dissolving the 1,2-dithenylethene monomer represented by the formula and a supporting electrolyte in a solvent to form a solution, then inserting a pair of electrodes into this solution and applying a voltage. It can be manufactured by a so-called electrolytic polymerization method in which a polymer is deposited on the electrode surface.

Supporting electrolytes used in electrolysis method 1 include tetramethylammonium persalt xaate, tetraethylammonium perchlorate, tetrabutylammonium perchlorate, lithium perchlorate, tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate,
Tetrafluoro e-plated tetrabutylammonium, tetrafluoroCI lithium borate, tetramethylammonium hexafluoroarsenate, tetraethylammonium hexafluoroarsenate, tetramethylammonium hexafluorophosphate, sodium hexafluoroarsenate, tetramethylammonium hexafluorophosphate, hexa7 .11
/ O.

Tetrabutylammonium phosphate, hex? 7 /L, Oro? Sodium A acid, sulfuric acid, tetramethyhydrogen sulfate/l/
Examples include 7 ammonium hydrogen sulfate, tetrabutylammonium hydrogen sulfate, sodium trifluoroacetate, tetramethylammonium p-toluenesulfonate, and tetrabutylammonium p-toluenesulfonate. As the solvent used in the present invention, it is preferable to use a polar solvent,
Acetonitrile, benzonitrile, nitrobenzene, propylene carbonate, methylene chloride, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and the like are used, with acetonitrile and methylene chloride being particularly preferred.

In addition, the electrode materials used in the electrolytic polymerization method include fermented indicum, stannic oxide gold, glass electrodes with nitrogen and compounds deposited on the glass surface (Nesa Glass) 1 gold, and platinum gold metal. Although carbon electrodes such as Gratshi carbon or the like can be used, it is preferable to use Nesa glass.

As for the electrolytic method, the reaction proceeds no matter which method is used, such as constant current electrolysis, constant potential electrolysis, or constant voltage electrolysis, but 1,2-di(2,3'-chenyl)etheno is For electrolytic polymerization when used, constant potential electrolysis is preferred, and the reference electrode has a Q of 8 V to 2.0 V with respect to SOK. Ov
is preferable, and more preferably from tOV to 'L5
Preferably, a potential of V is applied.

When using 1,2-di(2,2'-chenyl)nitene as a monomer, polymerization proceeds no matter which electrolytic method is used, but it does not grow as a film but as a powder on the electrode. The color of the hexapolymer is blackish-purple, and when a reverse current is applied, the anion that is the dopant is desorbed, resulting in a red polymer. In contrast, for example, a polymer of 1,2-di(2,3'-chenyl)etheno is obtained as a blue-green film, and then by applying a reverse current, the dopant is desorbed from the film. It turns into a yellow polymer.

Although the structure of each polymer produced by the method of the present invention cannot be determined unambiguously, all of the polymers exhibit electrical conductivity in the semiconductor region, are insoluble in organic solvents, and have a chemical stability that is close to that of the other polymers. It's out of place. For example, 1,2 as a monomer
- When using di(2,2'-chenyl)etheno, there are two α-positions on the thiophene skeleton, and it is thought that polymerization proceeds from these positions to form a linear-dimensional polymer.
There are three similar α-positions for 2-di(2,5'-chenyl)ethene and four similar α-positions for 1,2-di(5,5'-chenyl)nitene, and these compounds α of
If five or more positions react, the polymer is considered to have a three-dimensional structure. Considering the transfer by bond exchange of polarons, which is currently proposed in the electrical conduction mechanism of conductive polymers, a polymer of 1,2-di(2,2'-cheni/I/)etheno, ie, 1 Dimensional structures are preferred; 1.
2-di(2,5'-chenyl)etheno, 1,2-di(3
, 5'-chenyl) etheno polymers are undesirable in this field because the free storage of polymer chains is further reduced. Therefore, in order to obtain high conductivity, which is one of the properties required for electrode materials and electromagnetic shielding materials. 1.2-di(2,2'
-thhenyl)etheno polymer structure is preferred; and since these polymers change color between doped and undoped states, they can also be used as electrochromic materials, and have a thiophene skeleton. It is possible to use monomers with different bonding positions to produce materials that exhibit different color changes upon polymerization.

〔effect〕

According to the present invention, when the electrolytic polymer is grown in the form of a film, the film thickness can be controlled by the amount of current applied, so there is no need for secondary molding. Further, since impurities are taken in during electrolytic polymerization, there is an advantage that impurity doping, which is a necessary step for developing conductivity in the semiconductor region, can be carried out substantially in one step.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these examples.

Example 1 1,2-di(2,2'-chenyl)etheno 144 (50 mmol) was placed in an electrolytic cell with TO glass and an anode (2 cm2) K and nickel as a cathode separated by 1 (NIL).
/Z) Tetrabutylammonium perchlorate 5201g
(0.1 moVt) After adding 15 sd of methylene chloride and dissolving it, blowing argon for 20 minutes and stirring for 5 minutes at a constant voltage of 267 V, a black-purple amalgam doped with perchlorate ions was formed. When the direction of the zero-order current generated in powder form on the anode was reversed, perchlorate ions were separated from the monomer, forming a red polymer. J after washing and drying!
Lii was α3q.

Example 2 The same operation as in Example 1 was performed except that acetonitrile was used instead of methylene chloride. When the mixture is allowed to proceed for 30 minutes at a constant voltage of 5.5 V, a black powder mixture is deposited on the anode. After washing this with acetonitrile, it was dried and formed into a pellet at 200 kgf/32, and the electrical conductivity '% was measured to be 42X10-2.
It was Bα-1.

Example 3 A 1.2-
Di(2,3'-chenyl)ethene 40M9C10nov
't＞Sodium hexafluorohypurate 360119 (
After adding and dissolving 85 mmol/Z) and 20 wIt of acetonitrile, argon was then bubbled in for 20 minutes. 1
A blue-green thin film polymer doped with hexafluorotetraarsenate ions on the anode was obtained with a constant potential of 250 m0Qt gas at a constant potential of .degree.V vaBOB. Next, when the direction of Kti was reversed, the hexafluoride arsenic ion separated from the polymer and changed to a yellow polymer.

Example 4 TO glass was used as an anode (2 cIL), nickel was used as a cathode (1 cIL).
1,2-di(2,5'-thienyl)ethene 50119 (10 mmol, /Z) was added to the electrolytic plates placed 3 apart.
, tetrabutylamsonium perchlorate 590QCα1
mol'l/l), acetonitrile 15- was added and dissolved, then argon was blown for 20 minutes, and polymerization was allowed to proceed for 7 hours at a constant voltage of When peeled off from the ta, a film-like substance was obtained.

This film-like material is stable in air and has an electrical conductivity of -11 at t7 x 10-48.

Patent applicant: Rico Co., Ltd. - 2 others

Claims (1)

[Claims] 1) An electrolytic polymer produced from a monomer represented by the formula ▲ Numerical formula, chemical formula, table, etc.▼ by an electrolytic polymerization method. 2) An organic semiconductor material consisting of an electrolytic polymer produced from the monomer shown by the formula ▲ Numerical formula, chemical formula, table, etc.▼ by electrolytic polymerization method.