JPS6151050A - Production of electrically conductive polymer - Google Patents

Abstract

PURPOSE:To obtain an electrically conductive polymer whose manufacturing cost is low and which has high electrical conductivity and stability in a doped state, by polymerizing a cyclic compd. in the presence of an acetylenic high polymer and an oxidizing agent and doping the resulting polymer with a dopant. CONSTITUTION:A cyclic compd. is polymerized in the presence of an acetylenic high polymer and an oxidizing agent, and the resulting polymer is doped with a dopant. Examples of the acetylenic high polymers are polymers of acetylene, methylacetylene or chloroacetylene and copolymers of acetylene with ethynylbenzene and/or divinylbenzene. A composite material comprising the acetylenic high polymer and an electrically conductive material such as carbon black, metallic fiber or metallic powder may be used. As the oxidizing agent, catalysts for the Friedel-Crafts reaction can be used. Examples of such catalysts are aluminum chloride, zinc chloride and boron trifluoride.

Description

DETAILED DESCRIPTION OF THE INVENTION Acetylene polymers can be made to have an electrical conductivity of about 10 to 10 s/cm by doping with a suitable dopant, and are a material with extremely high industrial utility value. However, the doped acetylene-based polymer reacts with the dopant over time, and its properties may then rapidly change from a semiconductor to an insulator. In order to avoid such drawbacks, research has been carried out on conductive polymers that remain stable even when doped, and as a result, polymers with cyclic units, such as 4-lipyrrole and polythiophene, are useful. It has been known. However, the above-mentioned polymer with doped cyclic units t comparable to the conductive dust of doped acetylene-based polymers can only be obtained by electrolytic polymerization, which is a very unique polymerization method, resulting in high production costs and limited electrode area. It has the disadvantage that only a film with a size equal to that can be obtained.

As a result of intensive studies to overcome these difficulties, the inventors of the present invention have found that manufacturing costs can be reduced by polymerizing a cyclic compound in the presence of an acetylene polymer and an oxidizing agent, and then doping the compound. We discovered that it is possible to produce a conductive polymer that has low conductive dust, high conductive dust, and is stable in a doped state, and has completed the present invention. It can be applied to conductive materials or various devices.

The acetylene-based polymer in the present invention is at least one selected from acetylene, phenylacetylene, methylacetylene, hexylacetylene, butylacetylene, naphthylacetylene, chloroacetylene, chloromethylacetylene, acetylenecarpic acid, and acetylene dicarboxylic acid. and copolymers of acetylene and ethynylbenzene and/or novinylbenzene. It may also be a composite of an acetylene polymer and a conductive material such as carbon black, metal fiber, or metal powder.

Examples of the oxidizing agent in the present invention include catalysts used in a series of reactions called Friedel-Crafts reactions in organic chemistry.
Aluminum chloride, zinc chloride, tin chloride, copper chloride, iron trichloride,
Examples include boron trifluoride and iodine, and these may be used in combination.

Further, the cyclic compound in the present invention is represented by general formula (1).

(2) , (3) , (4) , (5) , (
6) and (where Xn (n is 1 to 1
(integer at 91) is RRO elementary atom, phenyl group, saturated hydrocarbon group having 6 or less carbon atoms,
Halodane, hydroxyl group. ) At least one selected from anthracene, phenanthorene, pyrene, quinone, and benzoquinone.

Representative examples of compounds represented by general formulas (1) to (6), benzene, chlorobenzene, brombenzene,
Phenol, pyridine, N-methylpyridine, pyrazone, naphthalene, quinoline, inquinoline, phthalazine,
Quinazoline, dinoline, quinoxaline, acridine, phenothiacin, pyrrole, thiophene, selenocene,
Pyrazole, anthracene, benzovirol, benzo [
b] Thiophene, benzo[C]thiophene, pe/sifurane, imidazole, benzimidazole, carbazole, thiazole, and benzothiazole. Also,
When the cyclic compound is solid at the polymerization temperature, it is desirable to use an appropriate solvent (eg, known solvents such as alcohols and ketones) in order to carry out the polymerization uniformly.

The soil used for the cyclic compound in the present invention is between 10 times the mole and 1/300 mole of the acetylene-based high polymer powder, and below this the effect of the present invention will not be exhibited, and above this there will be no cost advantage. There is no.

In addition, the amount of oxidizing agent varies depending on the polymerization performance of the cyclic compound, but generally it is from 3 times the mole to 1/3 of the cyclic compound.
Between moles is preferred.

The polymerization method in the present invention involves bringing an acetylene polymer into contact with a cyclic compound in the presence of an oxidizing agent while stirring. At this time, the oxidizing agent may be doped into the acetylene polymer in advance. The polymerization temperature is between -80°C and 120p, and the polymerization time is 24 hours or less. In order to increase the polymerization yield, the inside of the polymerization system is preferably substantially anhydrous and in an inert gas atmosphere.

Generally, a conductive polymer is obtained by removing unreacted oxidizing agents and cyclic compounds after polymerization, and then doping with a dopant.

For doping, either chemical doping or electrochemical doping may be used.

Chemically doping dopants include various conventionally known electron-accepting compounds and electron-donating compounds, such as (I) halodane such as iodine, bromine, and bromine iodide, (■) arsenic pentafluoride, antimony pentafluoride,
Metal halides such as silicon tetrafluoride, phosphorus pentachloride, pentafluoride, phosphorus fluoride, aluminum chloride, aluminum bromide and aluminum fluoride; (■) sulfuric acid, nitric acid, fluorosulfuric acid, trifluoromethanesulfuric acid and chlorosulfuric acid; protic acids such as (■) oxidizing agents such as sulfur trioxide, nitrogen dioxide, difluorosulfonyl e-oxide, (V
)AgClO4, (■) Tetracyanoethylene, Tetracyanoquinodimethane, Floranil, 2,3-fuchloro-5,6-cyano/mother lapenzoquinone, 2,3 dibromo-516-cyano/IP lapenzoquinone, (V[)
Li.

Examples include alkali metals such as Na and Ni.

On the other hand, as a dopant to be electrochemically doped, (i) pF'''6.5br2, A s Fp, 5bc
Halodanide anions of Va group elements such as t, tv,
Halodanides of group IIIa elements such as BF″'4 Anio7, I-(Ii), Kihalo r such as Br-1CL″″
(ii) Li”, N
a”, alkali metal ions such as K+, R4N” (R
Cation dopants such as quaternary ammonium ions such as (C1-C20 hydrocarbon group) can be mentioned, but are not necessarily limited to these.

A specific example of a compound that provides the above-mentioned anion donocent and cation donocent' is LiPF.
Li5bF LiAaF LiCtO4,N
aI, 6 x 6 islands
6) NaPF Na5bF NaAaF
NaClO4, KI, KPF6.6'
6% 6%KSbF6, KA
sF6, KCtO+, ((n-Bu)4N:l
+・(AsF6)−1((n −B u )a N)”
・(PFb)-1((n-Bu)4N
]” ・C104, Likl-CL −, LiBF4,
NO@A3F6, No 2 ・A s F b, No-
Examples include BF4, No-BF4, and No-PF6, but are not necessarily limited to these.

These dopants may be used alone or in combination of two or more.

The anion/dopant other than the above is an HF2 anion, and the cation/dopant other than the above is a pyrylium or pyridium cation represented by the following formula (II): (wherein, X is an oxygen atom or Nitrogen atom H/ is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, 6 to 15 carbon atoms
aryl group, R" is a rhodane atom or an alkyl group having 1 to 10 carbon atoms, and 6 to 15 carbon atoms.
In the aryl group, m is O when X is an oxygen atom, and 1 when x is a nitrogen atom. n is O
1 or 1 to 5. ) or a carbonium cation represented by the following formula (ill or (IV)): and R-C'' (IV) [in the above formula,
RlR, R is a hydrogen atom (R% R% R3 is not a hydrogen atom at the same time) an alkyl group having 1 to 15 carbon atoms, an allyl group having 6 to 15 carbon atoms, ary-/L/
(aryl) group or -OR5 group, where R represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R4 is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. group, and an aryl group having 6 to 15 carbon atoms. ] It is.

The I (F2 anion used) is usually represented by the following general formula % (): [However, in the above formula, R' and R'' are hydrogen atoms or carbon atoms having 1
~15 alkyl group, aryl having 6 to 15 carbon atoms/l/
(aryl) group, R'' is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, X is an oxygen atom or a nitrogen atom, and n is 0 or a positive integer of 5 or less. M is an alkali metal] by dissolving the compound (hydrogen fluoride salt) in an appropriate organic solvent.Specific examples of the compounds represented by the above formulas (V), (Vl) and (■) Examples include H2S-HF2,n
-B u 4N -HF 2 and Na -HF 2 are produced.

The pyrylium or girinonium cation represented by the above formula (1) is the cation represented by the formula (I) and ct
o″′4, BF;, Atct;, FeCt″4, S n
CL:, PF:, pct,, 5bir;, A s F
It can be obtained by dissolving a salt with an anion such as ;, cF3so;, HF;, etc. in an appropriate organic solvent. Specific examples of such salts include the following.

Specific examples of carbonylam cations represented by the above formula (I[[) or (IV) include (C6H5)3C+,
O0 These carzanium cations can be obtained by dissolving salts of them and anions (calzonium salts) in a suitable organic solvent. Representative examples of anions used here include BF:, htct;, AtBr CL",
FeCl-6n CL-PF-P CL-S b C
L'b, 5 4"l
3'6'61SbF'''', c
to;, cF3soH, etc., and specific examples of calzonium salts include (C6H5)3
C""'4, (CH,)3C-BF4, I(Co-Al
Cl2, )(Co-BF4, C6H5C0''S nct
I can give you 5th grade.

The electrically conductive composite thus obtained has high electrical conductivity and is stable in a doped state, so it can be used in various applications.

The details of the present invention will be described below with reference to Examples.

Example 1 Pyrrole 1.9 (15 mmol) and acetone IQm were added to a 300 ml container containing polyacetylene powder 511 acetone 100 In11 iron trichloride 2.9 (12.3 mmol).
1 of the solution was added dropwise at room temperature. After the dropwise addition, the mixture was reacted at 70°C for 8 hours, and then the liquid was removed and thoroughly washed with purified acetone. After drying under reduced pressure, weight measurement, infrared spectrometry, and elemental analysis revealed that polyacetylene contained 1 6 wt % of polypyrrole. Next, it was doped with iodine gas to form a conductive polymer with conductive dust of 335 s/crn. Even after being left in the air for 36 hours, there was no decrease in conductive dust.

Examples 2 to 6 Conductive polymers were obtained in the same manner as in Example 1, except that the cyclic compounds shown in Table 1 were used for the pyrrole fluff 9 in Example 1.

Example 7 A conductive polymer was obtained in the same manner as in Example 1 except that anhydrous aluminum chloride was used instead of iron trichloride. As a result of analysis, it was found that polypyrrole was contained at 13 wt%.395% of iodine-doped conductive dust was contained.
With s/crn, no reduction in conductive dust was observed after 36 hours.

Example 8 A polymer was obtained in the same manner as in Example 1 except that a copolymer powder of acetylene and phenylacetylene (phenylacetylene unit amount xo%) was used instead of polyacetylene powder. A conductive polymer was made by doping with arsenic pentafluoride. Conductive dust is 520 s/cm
Therefore, there was no reduction in conductive dust even after being left in the air for 36 hours.

Comparative Example 1 50 J of polyacetylene powder and 8 Fe polypyrrole powder were sufficiently mixed in a mixer to obtain a mixture of polyacetylene and polypyrrole. Conductive dust doped with iodine at 335 s/
z, and then left in the air for 36 hours. Conductive dust was reduced to 1.5 s/m.

Table 1

Claims (1)

[Claims] A method for producing a conductive polymer, comprising polymerizing a cyclic compound in the presence of an acetylene polymer and an oxidizing agent, and then doping with a dopant.