JPS6279221A - Method for producing conductive film-like pyrrole polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing a conductive film-like beer polymer.

1 Prior Art] Courbet, Mann J3 and Courbet Report [J, Poly
m, Sci: Polym, Chem, Ed, (Journal of Polymer Science: Polymer Chemistry Edition) Volume 20, 1089-10
95 pages.

(1982) reported that pyrrole can be polymerized in aqueous solution in the presence of potassium persulfate. There, the resulting polymer is in powder form. Furthermore, Japanese Patent Publication No. 1982-226020 describes a method of electrochemically polymerizing pyrrole in an aqueous organic solvent in the presence of aromatic sulfonic acids. There, at least 50,03% water is added to the organic solvent. Generally, from an engineering standpoint, it is better to use water than organic solvents from the viewpoint of economy and safety.

In addition, the Singer and Miller paper rJ, An.

Chew, Soc, (Journal of the American Chemical Society) Volume 106, 6861-6
863 pages.

1984, polypylicol was obtained by anodizing pyrrole in an aqueous solution using ferricyanide ions (Fc (CN) ) as a conductive salt.

Although there are several techniques for obtaining pyrrole polymers as described above, it has not yet been possible to obtain a self-supporting film that is easily peelable from the anode.

[Purpose] The present invention has been made in view of the above-mentioned current situation, and provides a film-like film that is dense and has sufficient mechanical strength for practical use.
An object of the present invention is to provide a method for manufacturing an electrically conductive cloth.

[Structure] The present invention uses a salt of an anion having a higher oxidation number #5 of a redox couple of a transition metal B anion as an 8B electrolytic salt, and electrochemically, preferably in an aqueous solution. This method is characterized by forming a film of Volivil oil on a flat anode.

Conductive salts act as charge carriers during the polymerization of electrical compounds in aqueous solutions (as well as being doped into the resulting polymers, influencing the properties of the polymers, in particular their electrical and mechanical properties). The electrical conductivity n structure of conductive polypyrrole is usually “
The hopping of charge carriers between the two polypyrrole mirrors in contact with the FIJ controls the electrical conductivity of the polypyrrole film.
This is explained by the hopping model. According to this popping model, if a conductive salt also has the function of giving and receiving electrons, that is, has the ability to act as a resistance-reducing couple, it is thought to have the effect of facilitating electrical conduction.

The present inventor electrochemically oxidizes and polymerizes pyrroles in an aqueous solution in the presence of a transition metal complex ion as a redox couple and a button ion consisting of an anion with a higher oxidation number. The present invention was achieved by discovering that even in an aqueous solution, a film-like polymer that can be easily peeled from an electrode and has self-supporting properties can be obtained.

The transition metal complex anions used in the present invention include cobalt(III)Ii ions and [1-me(III)
>83 anions and the like. As a representative example,
Go (edta) −, CO (pdta) +, G
o <cydta) −, Co (dtpa) 2−
1Cr (ox), Cr (edta)
(G120) - can be mentioned.

The concentration of the conductive salt used in the present invention is generally 0.001 to 1 mol, preferably 0.05 to 0.2 mol per mol of tS.
It is a mole. Cations for this illuminating salt include alkali metal cations, preferably K", Na
+ is used.

In the present invention, it is preferable to use unsubstituted pyrrole alone as the hexamer. However, mixtures with other rolls may also be used. Other pyrroles which can serve as comonomers include pyrroles having substituents on carbon atoms, in particular monoalkyl-, dialkyl-, monohalogen- or dihalogen-substituted pyrroles. An example of a replacement beer is 3
．． 4-dialkylpyrrole, especially 1-4 in the alkyl group
7 carbon atoms, such as 3,4-dimebrupyrrole and 3,4-dimebrupyrrole, and 3.4
-dihalogenpyrrole e.g. 3,4-dichlorbi[''-
It is le. These comonomers are 1 to 25 of the total monomers.
Used in M of Φ hanging %. In addition, the 7-mer Q degree is the solvent 1
Generally 0.001 to 0.05 molk per hour or 0.0
It is 1 to 0.2 mol.

The method of the invention can be carried out in a conventional electrolytic cell or electrolyzer. A diaphragm separating the anode and cathode may or may not be used. Electrolyzers with reference electrodes can also be used to define accurate potentials. The electrodes may be made of common inert electrode materials, in particular noble metals such as platinum or electrically conductive Nesa glass.

The method of the invention is normally carried out at room temperature. However, the reaction temperature can be varied between the freezing point and boiling point of the reaction solution used. Generally reaction temperature is +10~4-30
C is particularly preferred.

In the electrochemical polymerization reaction of the present invention, the degree difference between the anode and the cathode is 6 or less, preferably 3.0V or less.

This polymerization reaction can be carried out by any method such as a constant current method, a low potential method, or a constant voltage method.

The reaction time depends in particular on the conductive salt applied, the reaction conditions and especially on the desired film thickness.

Usually the time ranges from one hour to several hours.

The thickness of the film increases with polymerization time, for example, typically 50-60 μm after 3 hours of polymerization. These values do not provide an upper limit to the film thickness.

After the reaction is completed, the polypyrrole deposited on the anode is washed with water to remove unreacted substances. At this time, it can be easily peeled off from the frame (the rubbed film is dried at normal temperature and pressure. The film thus obtained is self-supporting, has good mechanical properties and a well-formed surface. Furthermore, it exhibits high electrical conductivity and generally has 56
Shows electrical conductivity of cIm-1 or higher.

The films obtained by the method of the invention can be used in many applications, such as electronic components, electrical openers, special electrode materials, shielding materials or solar cells.

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

[Implementation VA] Examples 1 to 2 The conductive salts listed in Table 1 were synthesized in advance by a conventional method.
1 mol of pyrrole and 0.061 mol of pyrrole were dissolved with stirring in a 200 d beaker to which 100 d of water was added. Add 3cm x 3 x 0.1c as an anode to this solution.
, 1 nanometer (8501-1) and 3ct as the cathode
rx x 3 cm x O,05cz Nl plate and forged ~ chloride I as a reference electrode! The electrodes were immersed, and the Nesaglass and N1 roots were connected to the positive and negative electrodes of the potentiostat with copper wires, respectively. The potential of the positive electrode is +1.4V from the reference electrode.
The electrochemical polymerization was carried out at room temperature with the current set at 100 mA and current was applied for 180 min. After the reaction was completed, the polypyrrole formed on the anode was peeled off, washed with water, and then dried at room temperature and normal pressure. A stable film with a smooth, homogeneous surface was thus obtained. The electrical conductivity measured by the four-terminal method is shown in the last column of Table 1.

Table 1 Examples 3-4 By repeating Examples 1-2 under exactly the same conditions except for using the conductive salts listed in Table 2, similarly excellent films were obtained. The electrical conductivity of the film is shown in the last column of the same table.

Table 2 [Effects] According to the method of the present invention, it is possible to easily and repeatedly produce polypyrrole films of any size, and the film-like polymer obtained at this time can be easily peeled off from the anode. It is self-supporting, stable, and exhibits high electrical conductivity. This film has the potential to be used in many different applications.

Procedural amendment November 27, 1985 Michibe Uga, Commissioner of the Patent Office, Case description 1985 Patent Application No. 219113 2 Title of invention Process for producing conductive film-like pyrrole polymer 3 Amendment Patent applicant address: 1-3-6 Nakamagome, Ota-ku, Tokyo Name: Ricoh Co., Ltd. 4, Agent 5, Date of amendment order (voluntary) Contents of Z amendment 1) Page 6 Correct "compound" in line 13 to "chemical".

2) Delete "Generally preferred." from lines 9 to 10 on page 6.

3) Correct "low potential" in line 16 of page 6 to "constant potential".

4) Change [85Ωcrn-'J in the third line of page 8 to “100Ω
crn-2”.

5) Replace rs--'J in Table 1 on page 8 with "5cyn-'
Correct it with J.

6) Change r 5cJn-I J in Table 2 on page 9 to [5cr
Correct it as n-' J.

that's all

Claims (1)

[Claims] A conductive film of pyrrole, which is characterized by anodizing and polymerizing pyrrole in an aqueous solution in the presence of a conductive salt consisting of an anion with a higher oxidation number among the redox couple of transition metal complex anions. Method for producing polymers.