JPS6079930A - Manufacture of oriented conductive polypyrrole - Google Patents

Abstract

PURPOSE:To obtain the titled molding with a high orientation as well as a high electric conductivity by stretching a non- or low-oriented conductive polypyrrole molding at least in one direction with the presence of a solvent. CONSTITUTION:A non- or low-oriented molding comprising conductive polypyrrole containing a dopant such as Cl<-> is stretched at least in one direction with the presence of a solvent (preferably, n-hexane or the like) to obtain the desired molding. The stretching of the non-oriented molding may be done by dipping and stretching the molding in the solvent or other methods. Polypyrrole can be obtained, for example, by a reaction of pyrrole in an electrolytic liquid using a platinum electrode.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing oriented conductive polypyrrole moldings.

Organic polymer compounds are generally classified as nonwoven materials, but it has become clear that when certain compounds are added to them, they become conductive organic polymer compounds that can be used as semiconductors or conductors. It has become clear that these conductive polymers can be used as p-type or n-type semiconductors depending on the type of additives used, and can be applied to applications such as scales, deafness, engineering, and aesthetics. An example of such an organic polymer compound is polyacetylene.

Examples include polypyrrole and poly-p-phenylene. However, conductive polymers made from these organic polymer compounds are insoluble and infusible, and it is difficult to obtain products in the desired form, which poses an obstacle in terms of application. Among the above-mentioned polymers, polypeel is a conductive polymer that is noteworthy because of its high conductivity and stability in air.

This highly conductive polypyrrole can be produced by electrolytic oxidation using platinum or gold (A, F, Dinzan 4).
K Kanazawa, J, C, 8, Chem, Cor.
+un,, 19)9゜635) insoluble on the anode surface,
Cells obtained by precipitation of infusible polymer moldings are known.

The present inventors have conducted extensive research into ways to improve the conductivity of the round conductive polypyrrole film, which is an example of a conductive polypyrrole molded product obtained as described above.
The present invention was achieved by discovering that the conductivity of these conductive polypyrrole molded products can be greatly improved by stretching them at least in the -direction in the presence of a solvent.

Therefore, the object of the present invention is to provide a stretched conductive, electrically conductive polypyrrole molded product, and furthermore, to provide a conductive polypyrrole molded product having a high degree of orientation, especially a film-like molded product. Specifically, it is desirable to provide a conductive polypyrrole molded product, particularly a film, having high electrical conductivity.

As described above, this object of the present invention is achieved by stretching a non-oriented or low-oriented conductive polypyrrole film in at least one direction in the presence of a solvent. This can be achieved by stretching in one direction with a small amount (K) in the presence of an aqueous solvent and/or an organic solvent that does not have an adverse effect.

In the present invention, the conductive polypyrrole molded product is one in which the polypyrrole itself is doped to exhibit a certain degree of conductivity, and there are various shapes such as thread-like, rod-like, and film-like shapes. The polypyrrole that makes up the above-mentioned conductive polypyrrole is pyrrole and its derivatives! Refers to homopolymers and copolymers obtained from hemorrhoidal KN-alkyl derivatives, preferably homopolymers from virol.

□ The dopant that exhibits electrical conductivity in cooperation with the polypyrrole is a compound that is electron-accepting to the polypyrrole, and specifically includes the following. namely, halogen anions such as CI-, Br- and I-; peracid anions such as cgo, -; anions of protonic acids such as sulfate, nitrate and phosphate anions; BF4-.

Anions formed from Lewis acids such as PF, -, AsF6-, 5bFs-: ) ICOO-, cnscoo-,
HOOC-COO-.

cutcl-coo-,cnc71. coo, cc
anions formed from organic carboxylic acids such as g, coo-'' and CF, COO-; ccg, go, -, CF,
SO, −, cHaSOl− and HCHs −<φ)−so
, - include anions formed from organic sulfonic acids such as -.

In the present invention, doping or doping refers to a phenomenon in which the above-mentioned compounds are added to polypyrrole and they work together to develop higher conductivity. It is not particularly limited. Therefore, in most cases, the polypyrrole and the compound form a chemical bond such as a complex, but in other cases, a mere mixed state may be included.

The conductive polypyrrole formed from such a polypyrrole and a dopant can be said to be non-oriented immediately after being formed. Although it shows a certain degree of conductivity even in a non-oriented state, by stretching the non-oriented or low-oriented conductive polypyrrole molded product according to the present invention, it can be highly oriented in at least one direction. Electrically conductive polypyrrole moldings are obtained, and thus conductive polypyrrole moldings with significantly increased conductivity.

The above-mentioned stretching is carried out in a state where the polypyrrole contains a dopant, that is, in a state where it is a conductive polypyrrole molded product.

Furthermore, the above-mentioned stretching is carried out in a gas phase of water, an aqueous solvent, and an organic solvent, or in a wet state in which they are present in liquid form.

Preferred substances for forming a wet state have a boiling point of, for example, 0°C to 250°C, preferably lO°C to 200°C.
It is a liquid substance in the temperature range of 0.degree. C., and it does not impair the conductivity of the conductive polypyrrole. Conductivity may be impaired if the dopant acts on the dopant, for example, if it chemically reacts with the dopant and the dopant is no longer able to perform its original function (for example, if the dopant is unable to perform its original function (for example, if a highly basic substance such as an aliphatic compound or an alkaline solution) solvent) and polypyrrole,
For example, there are cases where polypyrrole is no longer able to perform its original function due to chemical bonding or chemical separation of Pr"l (?Ma acid, *nitric acid).

The substances that form the gas phase or form a wet state include (11n-hexane, cyclohexane, heptane).

Hydrocarbon compounds such as benzene, toluene and xylene (Ill dichloromethane, 1,1.1-) Chlorinated hydrocarbon compounds such as dichloroethane and chlorobenzene (ffl) 7 Nitriles such as setonitrile, propionitrile and benzonitrile Middle class compounds (lv) Ketone compounds such as 7 setone, methyl ethyl leuton, methyl isobutyl ketone, cyclohexane (v) Anisole, tetrahydrofuran, dioxane, butyl ether, butyl cellosolve type ether compounds (vil nitromethane, nido-benzene) Nitro compounds such as 1- Ester compounds such as ethyl acetate, n-butylacetic acid, probin carbonate, propiolactone, etc. Alcohol compounds such as methanol, -1-tanol, butanol, ethylene glycol (trans)acetic acid , organic acid compounds such as boupionic acid (x), aromatic amine compounds with low basicity such as pyridine and aniline (xD), aprotic polar organic compounds such as N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, etc. Examples include water and aqueous solvents containing neutral salts and alcohols. These solvents may be used alone or in combination.

Among these, preferred are the group (11 to 0x) and the group (xli).

The most convenient way to stretch the conductive polypyrrole molded product in the gas phase of these substances or in a state moistened by it is to immerse the conductive polypyrrole molded product in the liquid of these substances and stretch it while it is immersed. Furthermore, although not in a liquid, it may be stretched under the protection of these materials.

The temperature during stretching varies depending on the type of dopant and the amount of wetting material, but is usually 0°C to 300°C, preferably 10°C to 200°C, and preferably 20°C to 150°C.

The stretching ratio is preferably as high as possible, but is usually 50 inches or more, preferably 6θ degrees or more, and more preferably 8θ degrees or more. In addition, from the viewpoint of manufacturing stability, the stretching ratio is 300 inches or less, preferably 200 inches or less, particularly preferably 150 inches.
less than or equal to

The stretching speed is between o,s4/sec and xoool/sec, preferably between 5 inches/sec and xooeA/sec.

The conductive polypyrrole molded product stretched at such a magnification is
80°C to 300°C, preferably 100°C to
At a temperature of 250°C, 1 minute to 1 hour, preferably 5 minutes to 0
．． Heat set for 5 hours. Heat fixation may be carried out under no tension, but it is preferably carried out under tension.

Thus, the half value of the intensity distribution adjusted to 2θ of the orientation peak by xlIs diffraction is taken as Ho, and the conventionally known synthesis method for polypyrrole used to obtain the highly oriented conductive polypyrrole molded product of the present invention is expressed by the following formula: The method is that f
For example, pyrrole and/or its derivatives can be applied to a working electrode (hereinafter referred to as WE) in an electrolytic solution consisting of an electrolyte, a solvent, and optionally a small amount of water, and a platinum plate as a counter electrode (hereinafter referred to as CE). A and F using a platinum plate or a conventionally known general-purpose material.

Dias and K., Kanazawa, J.C.
,S,Chem,Comm.

1979.635 and in, Kanazawa et al.
5ynth, *tlcMetals, 1 (1979/
80) can be obtained by reacting under conditions such as those described in 329-336.

The raw materials virole and its derivatives used in the above reaction preferably have high purity, and are preferably purified by distillation before use.

Examples of hylorno derivatives include N-alkyl impurities at C1~, N-phenyl derivatives, C1~ at the β-position of the beer ring,
Examples include alkyl-substituted products, alkoxy-substituted products, and phenyl derivative-substituted products.

When preparing polymers from these pyrrole derivatives, salts such as lamb salt and alkali metal salts may be used.

For example, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium perchlorate, tetrafluoroborate,
p-) Tetraethylammonium luenesulfonate, Tetra n-methylammonium bromide, Tetra n-butylammonium iodide, Tetra n-butylammonium perchlorate, Tetra n-butylammonium tetrafluoroborate, p-) Luenesulfone Tetra n-butylammonium acid, tetra n-butylammonium hydrogen sulfate, lithium perchlorate, lithium nitrate, lithium tetrafluoropolymer, sodium perchlorate, tetraz acetate n-
There are ammonium etc.

The required amount of these electrolytes is that the solution (2) is dissolved and that the electric current necessary for the reaction to proceed is obtained, and the minimum is 0.1 molar equivalent to pyrrole, preferably is 0.3 molar equivalent or more, and the maximum amount as an electrolytic solution varies depending on the type of electrolyte and the water envoy used if desired, but usually Q, 11 II IRk'/(mol/l) to 2 M
/ /, preferably 0.05M/l or 0.5
M/g Te, %, R0 The solvent used in the reaction is stable under the voltage required for polymerization of pyrrole compounds, and is 1! High solubility in solutes and water is required. Examples of such solvents are 7cetonitrile, benzonitrile, hexahydrofuran.

Examples include, but are not limited to, nitrobenzene, propylene carbonate, hexamethylphosphoramide, etc., and as long as the above conditions are met, general 1c! Conventionally known reactions are used in the reaction.

The role of water, which may be used as desired, is 'r! This improves the LH quality effect and improves the form in which polypyrrole is precipitated. The amount used varies depending on the type of electrolyte used, and the concentration of water in the MM solution ranges from o, IM/l to 5M/l.
, preferably from 0.3 M/l to 3 M/l.

The cathode material used in the reaction is deficient in the electrode reaction,
If there is no alteration in quality, the precipitation state of general-purpose Livirol is good. The ratio of cathode to anode surface area is 1
．． It is used at least 1 time, preferably at least 1.5 times, preferably at least 2 times, and particularly preferably at least 3 times.

The electrolytic voltage and drop current are not constant depending on the reaction conditions, but in general, the electrolytic voltage fI! F is allowed, the river is 1.0 volt or more,
Preferably it is 1.5 volts or more, particularly preferably 2 ports or more F, and the stability of the electrolytic reaction solvent is preferably 1 to 3.0 volts or less. The electrolytic current is 0.0 as the current density at the anode.
01 mA 7cm to 5 rnA/cd, preferably 0.01 mA/CrI to 3 mA/cl.

Particularly preferably o, s mA / d ~ 1 mA, /
It is al.

Preferably, the temperature of the entire reactor can be controlled.

The reaction temperature is not particularly limited, but should be below 100°C, preferably below 50°C! 1! ? preferably at 0°C
It is carried out at a temperature of -50°C or higher.

In particular, the polypyrrole molded product obtained from the reaction process at low temperature has a high stretching ratio in the above-mentioned stretching.
avmI”11 (JPS, Po1y, LettJdd, 19
82, 187)). That is, Pill 2
d and ethanol 103117 in a Petri dish.
．． 9 Pour into N-sulfuric acid with stirring and leave to stand for 15 hours to form polypyrrole as a film on the surface. In this case as well, since the polypyrrole contains sulfate ions as a dopant, it becomes a conductive polypyrrole molded product as it is.

The conductive polypeel molded product thus obtained may be subjected to the above-mentioned stretching treatment as it is, but in some cases, the dopant contained during the reaction may be replaced with a desired dopant.

In particular, when a halogen atom or the like is used as a dopant, stretching can be carried out after dopant substitution. Dopant substitution was performed using MBaGO-79930 (
5) The object of the present invention is achieved by first removing the dopant in polypyrrole electrochemically, that is, by electrolytic reduction of polypyrrole.

The present invention will be further explained below using specific examples.

The electrical conductivity in the example was calculated using the four-terminal method.
It was calculated from the voltage measured using a digital voltmeter 3456A manufactured by Tsukado.

The degree of orientation is determined by the above formula, and unless otherwise specified, the value is 2.0=0.4475.

For example, a platinum plate with a length of 5 cR and a width of 41 mm as an anode, and a platinum plate with a width of 5 aR and a length of 40 mm as a counter electrode in a separable ao-o-at glass electrolyte chamber equipped with an electrode inlet, a nitrogen inlet pipe, and an exhaust port. A protective copper foil was installed.

The entire electrolytic cell was immersed in a bath cooled to -2θ°C so that the temperature could be controlled.

Next, a propylene carbonate solution containing 0.06 mol/l of pyrrole and 0.1 mol/l of tetraethylammonium perchlorate and a bupylene carbonate solution cooled to -20°C containing 20.1 mol/l of water (
(hereinafter referred to as the holding solution), and after returning to room temperature, it was peeled off from the electrode.

The obtained film had a thickness of 100 μm and an electrical conductivity of 280 S/p.

This film was slit into strips with a width of 5B, gripped with a distance of 20cm between chucks, immersed in a holding solution heated to 70°C, preheated for 1 minute, and then stretched for 90 minutes at a speed of 50/sec. .

Then, it was transferred to a hot air dryer at 150°C and heat-set for 5 minutes.

The electrical conductivity of the obtained film in the stretching direction is 105087
It was cm. This film showed an orientation peak in its X-ray diffraction pattern, and the degree of orientation was 75.4.

Example 2 The electrolyte p-)luenesulfone degraded tetraethylammonium salt was reacted at -20°C in the same manner as in Example 1 using 77 tonitrile as the solvent.Examples 3 to 5 Same equipment and procedure as in Example 1. A polypyrrole film was prepared by This film was immersed in the solvent shown in the table below at room temperature for 3 days, and then stretched in this solvent for 1.20 inches at 40'C and a stretching speed of 2 f/sec.

The electrical conductivity and orientation degree of the polypyrrole film in the stretching direction after stretching were as shown in the table below.

Examples 6-19 Polypyrrole films were made using the same equipment and operations as in Example 1. This film was immersed in the stretching solvent specified in the table below at room temperature for 3 days.

The degree was measured.

Example 26 Except for changing the reaction for 20 hours instead of 60 hours: l is
A polypyrrole film was prepared by carrying out the same synthesis reaction as in Example 1. Tetraethylammonium bromide 0.0
Propylene carbonate containing 3 mol/e, t, zv was applied for 20 hours for de-dopant treatment. As a result of fluorescent X-ray analysis, only a trace amount of barchlorate was detected in 7'; and the conductivity was less than xo-'S/cm.

New tetraethylammonium bromide (0,03
In an electrolytic cell solution containing a mol/l)-propylene carbonate solution, the electrodes were connected again in the same manner as in the film-forming layer, and 3V was applied to react for 20 hours. The conductive polypyrrole film thus obtained has a thickness of 35 μm and a conductivity of 23 S/c.
It was m.

This film was prepared in the same manner as in Example 1 (however, the temperature was 4
The film obtained by stretching 100% (0°C) and heat setting had an electrical conductivity of 10 RtlS/cm in the stretching direction and a degree of orientation of 74.2%.

Example 27 A conductive polypyrrole film was obtained by the same synthesis reaction as in Example 1. This film is xoo'
Z) was carried out. The electrical conductivity of the stretched film is shown in the table below.

Procedures Amendment Written December 12, 1982 Commissioner of the Japan Patent Office 1, Case of a certain % petition AS-1SS4SS Name of the invention Process for manufacturing oriented conductive Bo-V-pyrrole molded product 3 Amendment. Relationship with the case of the person who did the following: Patent applicant: 1-3-1-5 Kasumigaseki, Chiyoda-ku, Tokyo Contents of Supplementary iE (1) “Gyo Hikareru.” in the fifth line of page 6 of Specification 4B was changed to “
rows appear. Note that the solvent used in the present invention is not meant to dissolve the conductive polypyrrole. ” he corrected. .

+21 Add the following between the 5th line from the bottom of 1JI thin lf page 16 and the 4th line of the same page.

[In the example, X-ray measurement is performed by Rigakuden RL! X-ray diffraction system made by A r?
CuKa l'a as a source at t(Nh4osaA3)
The transmitted X-rays of a sample having a thickness of about 500 μm were measured using a scintillation counter according to a conventional method. ” On top of that

Claims (1)

[Claims] 1. A method for producing an oriented conductive polypyrrole molded product, which comprises stretching a non-oriented or slightly oriented conductive polypyrrole molded product in at least one direction in the presence of a solvent.