JPH0359004A - Production of electronically conductive polymer and conductive material prepared therefrom - Google Patents

Abstract

PURPOSE:To obtain a filmlike electronically conductive polymer having excellent electronic conductivity mechanical strengths and moldability by polymerizing an aniline compound or a heterocyclic compound and a specified prepolymer on the same support in the presence of an oxidizing agent. CONSTITUTION:At least either an aniline compound or a heterocyclic compound and a prepolymer comprising repeating ethylene units and having a site with which the aniline compound or the heterocyclic compound can be polymerized as at least a side chain are polymerized in the presence of an oxidizing agent on the same support to obtain an electronically conductive polymer comprising repeating ethylene units and having repeating units of the aniline compound or the heterocyclic compound as an electronically conductive part in the side chain. It is desirable that the prepolymer further contains repeating ethylene units having an anionic group as the side chain.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to batteries,
Capacitors, antistatic materials, electricity! The present invention relates to a method for producing an electronically conductive polymer that can be applied as various materials such as wave shielding materials, electronic devices, and electrochromic elements, and to conductive materials using the same.

[Conventional technology]

In recent years, organic polymeric materials with electronic conductivity have been considered for application as pantries and various functional devices.

For example, polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polyphenylene acetylene, polyacetylene, etc. are promising, and West German Patent No. 3,223,
No. 544, No. 3,318,856, No. 3,318,8
No. 57, No. 3,325.892, No. 3.338°90
No. 4, No. 3,421.296, JP-A-58-1874
No. 32, No. 59-43060, No. 59-112583
No. 5B-209864, No. 59-207933
No. 60-120722, No. 60-67527,
No. 62-225518, No. 62-53328, No. 6
No. 3-199726, No. 60123817, No. 618
No. 3221, No. 59-31565, etc.

Conductive materials that combine these electronically conductive polymers and electrolytes as layers are used, but in order to function adequately as a device or battery, exchange of electrons and ions is required at the interface between the two. need to be done promptly.

As an electrolyte, polymer solid electrolytes are superior in terms of no leakage, high mechanical strength, and high flexibility of laminated materials, and various reports have been made.

Conductive electronic materials that combine such polymer solid electrolytes and electronically conductive polymers include POLYMER,
1981, vol, 22. November 14
An organic battery combining polyacetylene and a solid electrolyte has been proposed on pages 54 to 1455, but the polyacetylene film produced by this addition polymerization has poor oxidation stability and is resistant to oxidation at the interface with the solid polymer electrolyte. There were problems such as insufficient contact and poor conductivity, and slow response speed as a device material.

In addition, as a compound that aims to achieve both mechanical strength and conductivity, at the 37th Polymer Symposium 2HO4, a compound having a repeating unit of a carbazole group in the side chain by electrolytic polymerization method, such as (CZOae)- has been studied, but its conductivity is 10-4 to 10-'
S/cII and insufficient.

Furthermore, when polyaniline or polyheterocycle is used as an electrode material, anions are doped or dedoped as a result of the redox reaction. Takehara et al. reported at the 56th Electrochemical Society of Japan 3G24 that the diffusion of anions becomes rate-determining in this case. As a method for preventing diffusion of anions, Japanese Patent Laid-Open No. 63-215772 discloses a method using an anionic polymer as a doping agent. but,
In this method, as doping was repeated, a concentration gradient occurred due to diffusion of the anionic polymer, and it could not be a sufficient means of improvement.

On the other hand, known methods for producing these polymers include chemical oxidative polymerization using an oxidizing agent and electrochemical oxidative polymerization (electrolytic polymerization). In electrolytic polymerization, an electronically conductive polymer is produced in the form of a film on the anode, so the size of the product is regulated by the size of the electrode, and there are also disadvantages such as high costs due to the need to use expensive equipment. there were. In addition, chemical oxidative polymerization is easy to synthesize in large quantities, but since the resulting polymer is an insoluble and infusible powder or lump, its moldability is poor, and it is difficult to use it as a conductive material. There is an inconvenience in that after synthesis, it is necessary to disperse it in a suitable binder or process it by compression molding.

As a continuous manufacturing method for conductive sheets, Japanese Patent Application Laid-Open No. 61-25
No. 8830 discloses a method in which a solution of aniline or a derivative thereof is attached or impregnated onto a base sheet, and then brought into contact with an oxidizing agent to oxidatively polymerize aniline or a derivative thereof. The conductive organic polymers used in this study were significantly inferior in mechanical strength and charge/discharge suitability.

[Problem 8 to be solved by the invention] The first object of the present invention is to provide a film-like electronically conductive polymer that has excellent electronic conductivity, mechanical strength, and moldability. .

A second object of the present invention is to provide a film-like electron conductive polymer in which anion doping and dedoping reactions occur quickly in the redox reaction of the electron conductive polymer.

The third object of the present invention is to provide an electronically conductive polymer and solid polymer electrolyte that, when combined with a solid polymer electrolyte, has low resistance at the contact interface, excellent electrical conductivity, and has a fast response speed as a device material. The object of the present invention is to provide a conductive material for a laminate with a laminate.

A fourth object of the present invention is to provide an electrically conductive material in which an electronically conductive polymer has the function of a solid polymer electrolyte, thereby substantially eliminating the need for an electrolyte layer.

(Means for solving the problem) The above object could be achieved by the following method for producing an electron-conducting polymer or a conductive material using the electron-conducting polymer. Namely, an aniline compound or a heterocyclic compound. A prepolymer consisting of an ethylenic repeating unit having at least one of the following and a site capable of polymerizing an aniline compound or a heterocyclic compound in the side chain is polymerized on the same support in the presence of an oxidizing agent. Achieved by a method of producing an electron-conducting polymer consisting of an ethylenic repeating unit having a repeating unit of a compound or a heterocyclic compound as an electron-conducting moiety in the side chain, or by a conductive material using the electron-conducting polymer. I was able to do that.

The prepolymer composed of ethylenic repeating units having at least a site in the side chain capable of polymerizing the aniline compound or heterocyclic compound used in the production of the present invention will be explained in more detail.

The above-mentioned prepolymer can have ethylenic repeating units derived from the ethylenic compounds shown below, and can be obtained by generally known polymerization methods of ethylenic compounds (for example,
It can be synthesized by radical polymerization method).

An ethylenic compound capable of polymerizing a small amount of an aniline compound and a heterocyclic compound into a side chain is preferably represented by the following formula (1).

Preferably, the prepolymer of the present invention further has an ethylenic repeating unit having a repeating unit of an oxyalkylene group in its side chain and/or an ethylenic repeating unit having an anionic group in its side chain.

The compound inducing an ethylenic repeating unit having a repeating unit of an oxyalkylene group in its side chain is preferably represented by general formula (II).

The ethylenic compound that induces an ethylenic repeating unit having an anionic group in its side chain is preferably represented by the general formula (111
).

In general formulas (1), (II), (III), A1,
A2 and A3 may be the same or different and represent a hydrogen atom or a substituent on ethylene carbon, and L represents a divalent linking group. D represents an aniline compound or a heterocyclic compound. G represents a substituted or unsubstituted alkylene group, and M represents an integer of 1 to 30. However, when L≧2, G may be the same or different; A4 represents a substituted or unsubstituted alkyl group, aryl group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, or arylsulfonyl group; E represents an anionic group.

-a Formulas (1) to (III) will be explained in detail.

Preferred examples of substituents on ethylene carbon represented by AI, g*, and A3 include substituted or unsubstituted carbon atoms having 1 to 1 carbon atoms;
4 alkyl groups (e.g. methyl, ethyl, n-propyl, n-butyl, 1so-propyl, methoxyethyl,
carboxymethyl), cyano group, carboxy group (including alkali metal salts), carbamoyl group (which may be substituted with a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, e.g. , -CONHz
, -CON(Cll+)z, unsubstituted alkoxycarbonyl group having 1 to 4 carbon atoms (e.g., -C00CI+,
-cooczns, -COOCJ4N (C1b)!
, -COOCJq(n)) and halogen atoms (eg, fluorine, chlorine, bromine).

A1, A2 and A3 are particularly preferably a hydrogen atom, a chlorine atom, a methyl group or a carboxyl group.

Specifically, L is +-(L 斤HJ+
) r) r-TE, where C, J2, and J may be the same or different, 0-l-3-1-CO-1-SO,-1
-0CO-1-COO-1-CONRI-SOzNR'
--NR'-CO-1-NR'-50! --NR'-R
"--NR'-R"-NR3--NR--CO-NR'
--NR'-5o! -NR3關'co, - or -0C
Represents ONR'-. llI represents a hydrogen atom, an optionally substituted alkyl group, or a phenyl group; Rt represents an alkylene group having 1 to 4 carbon atoms; R5 represents a hydrogen atom, an optionally substituted alkyl group or a phenyl group; sJl representing an alkyl group, J! , J3 is preferably -CO-1-3
O! --CONH-1-3O! NH--N11-CO-
1-N1(-5Ot-1-〇-1-NlICOIIH-
1-5-1-CO□-10CO-1-NIICO□- or -〇C0)Jll-.

Xlz L and X may be the same or different,
Alkylene group, arylene group, aralkylene group or +G-0)7CHtCF1g-, each of which may be substituted
represents a group. Here, G has the same meaning as above.

N5, Xt, and N3 are preferably an alkylene group having 1 to 4 carbon atoms, an arylene group having 6 to 9 carbon atoms, a substituted arylene group, or a +G-0)TCII□CI+□- group.

p, q, r, s and U represent 0 or l.

In the above general 2N), D represents an aniline compound or a heterocyclic compound.

Preferred specific examples of the heterocyclic compound include ru, oxazole (including iso-form), thiazole (including iso-form)
, pyridine, diazine, riazole, benzoxazole, benzothiazole, purine, quinoline, isoquinoline, benzuzine, phenazine, phenoxazine, pyrazolotriazole, pyrazolodiazole, pyrazoloazole, benzopyrazoloazole, and the like.

Z represents -0--8- or .N-R (1?' has the same meaning as above).

Particularly preferred examples of D are aniline compounds, virol compounds, thiophene compounds, and furan compounds.

The aniline compound and heterocyclic compound represented by D may each be substituted with an arbitrary substituent. Examples of this substituent include halogen atom, nitro group, cyano group, alkyl group, alkokene group, -NIICOI? '
, Nll5O□R4, -5OR'~SO□R',
COR' = C0NR', -3o! Examples thereof include NR', an amino group (which may be further substituted with an alkyl Rk Rh group), a hydroxyl group, and a group that is hydrolyzed to form a hydroxyl group. R4 represents an alkyl group, a phenyl group, or an aralkyl group. R5 and Rh may be the same or different and represent a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group. Also,
Two substituents may be fused to form a carbocycle or a heterocycle.

Furthermore, among the substituents exemplified on D above and A1, A book,
Examples of substituents that may be substituted include alkyl groups, alkoxy groups, phenyl groups, aralkyl groups in the substituents of A3 and A4, and monosubstituted alkylene groups, substituted arylene groups, and substituted aralkylene groups of xl, xN, and xl. is a hydroxyl group, a nitro group, an alkoxy group having 1 to 4 carbon atoms, -N)IsO! R
', -NHCOI? '-3OtNR' -CO
NR'', R1R9 5OIR', -Coil', halogen atom, cyano group, amino group (may be further substituted with an alkyl group)
etc. R7 has the same meaning as R4. R3 and R
9 may be the same or different and has the same meaning as R5.

Specific examples of D are shown below, but of course the invention is not limited to these.

H3C-C-CH3 I l1z CH3, ■ l HH D is particularly preferably aniline, thiophene or pyrrole.

G represents a substituted or unsubstituted alkylene group having 1 to 9 carbon atoms, preferably -CHzC1h-1-CI1. C.I.
+-C++.

-CHzC1h-.

t represents an integer of 1 to 30, preferably 2 to 20, particularly preferably 3 to 15.

A4 is a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms (e.g., methyl, n-propyl), an aryl group (e.g., phenyl, tolyl), an alkylcarbonyl group (e.g., methylcarbonyl, ethylcarbonyl),
Arylcarbonyl groups (e.g. phenylcarbonyl,
4-a7doaminophenylcarbonyl), alkylsulfonyl groups (e.g., methylsulfonyl, ethylsulfonyl), and arylsulfonyl groups (e.g., phenylsulfonyl, tosyl), preferably having 1 to 3 carbon atoms.
is an alkyl group, particularly preferably a methyl group.

Preferred examples of the anionic group of E include carboxyl groups and salts thereof, sulfonic acid groups and salts thereof, sulfuric acid groups and salts thereof, and phosphoric acid groups and salts thereof.

Specific examples of the repeating unit derived from the ethylenic compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

+CHi C)- -1 Cl(3 +CII* C)- ■ -6 +CHt CHH -2 +cut　-CH)- ■ -3 CI3 -7 +CIb -C11)- +CHt　C)- -8 ■-12 9 ti3 ■-13 Hs +C1, -C)- ! -1O CH.

+CL-c)--14 ■ m is any integer from 1 to 30 (hereinafter the same meaning)-15 +C11x CI)-! -11 +C1, -CI)- (2) Specific examples of the repeating unit derived from the ethylenic compound represented by (n) below are shown below, but the present invention is not limited thereto.

-t +CH* -C11)-C00-(C)ItCIltO)rCHsHowever, t! −
t4 (average) II-2 At n-l, tζ7 (average) -3 tζ9 (average) ■-4 tζ12 (average) f-5 tζ16 (average) -6 tζ23 (average) -7 ■-8 ■-9 ■-1゜-11 ■-12 ■-13 l-14 ■-15 ■-16 CI +CH1-C)- COMCII□CH! O star CI+3 However, at tζ4 (average) n-7, t-7 (average) s t! = i9 (average) tζ12 (average) tζ16 (average) tζ23 (average) t=2 +cux cn)- C0O- (CHtCH寞0) E-1 madashi [! =i7 (average) -(-CIll -CHh COO-(CHzCHO)T-CHs H3 However, tζ4 (average) In II-15, tζ7 (average) "-17 +ct+t -CI)-Summer il However, tI!=f3( Average) t8ζ4 (average) ■-18 1h -fcut -C)- Specific examples of repeating units derived from the ethylenic compound represented by the general formula (■) are shown below, but the present invention is limited thereto. It's not a thing.

(M represents a hydrogen atom, an alkali metal, or an alkaline earth metal; hereinafter the same meaning) However, t, -3 (average) t! ζ4 (average) ■-19 H1 +co, -C)-COOmcH*cHto)T-OCOCHsHowever, tζ
7 (average) ■-20 +CI! co>- C00(CIIzCHtO)T-OSOICH3t-3 -4 C0NII CCH*5OJ CI! .

+CI+, -C1l)- COOCslliSOJ -+CH! -C11)- CONllC2HsSOJ However, t-7 (average) 111-6 +C1h cu)- ■-12 CH8 COOCJa00CCJhCOOM -1 +C)! , -C! ! >- COOCtHJl(COC3FaCOO1'1-8 +C! b CH)- COOCJaO5O3M 11-9 +CHx CH)- OOM ■-1O C11゜ +CHffi-C)- C0〇- C8゜ ■-15 CI+.

-(-C11! -C)- COOC41! asOJ-14 The prepolymer of the present invention has a general formula ([), (II), or (I) for the purpose of increasing mechanical strength or improving solubility.
II) In addition to the repeating unit represented by
repeating unit.

Specific examples of this include acrylic acid, α-chloroacrylic acid,
α-alkyl acrylic acid (such as methacrylic acid),
Itaconic acid, crotonic acid or citraconic acid, amides or esters derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n- Propyl acrylate, n-butyl acrylate, L-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-
Octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, β-hydroxy methacrylate, vinyl esters (e.g. Eva, vinyl acetate, vinyl propionate, vinyl laurate), acrylonitrile, methacrylate trile, aroma Group vinyl compounds (e.g. styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene)
, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic esters,
Examples include, but are not limited to, N-ruvinyl 2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. These repeating units are
It is preferably contained in the prepolymer of the present invention in an amount of 0 to 20 mol%.

The prepolymer of the present invention may have repeating units derived from the ethylenic compound represented by the above general formula (1) in any ratio in the polymer, preferably 1 to 5.
It contains 0 mol%, more preferably 1 to 20 mol%.

Further, in the prepolymer of the present invention, general formulas (II), (II
The repeating units derived from the ethylenic compound represented by I) are 5 to 99 mol% and 5 to 80 mol%, respectively.
The content is preferably mol%.

Further, the number average molecular weight of the prepolymer of the present invention is about 500
~too, ooo is preferred, particularly preferably about 1.0
00~so, ooo.

-a When the repeating unit derived from the ethylenic compound represented by formula (1) is too small, the conductivity will be low, and when it is too large, the charge/discharge suitability will be reduced.

It is preferable to have a repeating unit derived from an ethylenic compound represented by ([+) or (III)] because it has excellent charge/discharge suitability.

Specific examples of the prepolymer of the present invention are listed below, but the present invention is not limited thereto.

Prepolymer PI'-1 P-3 +CHx CHhs t'', 4 (average) COOCJaSOJ (M represents a hydrogen atom, an alkali metal, or an alkaline earth metal; hereinafter the same meaning) -7 (average) P CI+, + 5υ3j P- 5 P-7 H3 Hs -(-C11! -Ch +CHg C)we P P-8 C)].

-f　CHHz C11)1 +011□ hs L', 4 (average) +CHz CHh.

ti=i9 (average) COMM.

PP 9 PP-11 CH.

+011□-ch -(-co, CHh.

PP-12 +011□-CIlh (-C11゜CIl″h COOCJaSOlM t!:i? (Average) PP 0 ■ +Cl1z CHhs COO-(C)IzCHz031 CH3-7 (Average) PP-13 COOCJaSOfM OOC Jw tζ4 (average) mζ3 (Average) Lt7 (Average) PP-14 PP-16 CH3 mζ3 (Average) tζ4 (Average) PP-15 C11°CH3 tζ4 (Average) t' (Average) PP-17 mζ5 at PP-13 (Average) PP 8 m'i 5 for PP-14 (average) PP-19 m-7 for PP-13 (average) PP-20 mζ7 for PP-14 (average) Next, regarding the method for manufacturing the electronically conductive polymer of the present invention. ,
It will be explained in more detail.

The production of the electron conductive polymer of the present invention is characterized by polymerizing the following compounds on the same support.

(^) The above prepolymer (B) Aniline compound or heterocyclic compound (which may be the same as or different from that shown by D in the above-determination (1)) (C) Oxidizing agent Here, (^) , (B) and (c) may each be one type (or two or more types may be used).

Specifically, the aniline compound or heterocyclic compound represented by D in the prepolymer (^) and the aniline compound or heterocyclic compound (B) are brought into contact with each other in the step of coating and drying on the same support. , by chemically oxidatively polymerizing with the oxidizing agent (C), an electron conductive moiety made of at least one of an aniline compound or a heterocyclic compound is polymerized into a side chain as a repeating unit.

Application methods include roller coating, spin cord, Giesser coating, dip coating, spray coating,
Known coating methods such as extrusion molding can be used.

The drying method can be carried out at -10°C to 100°C, and known drying methods such as natural drying, ventilation drying, and reduced pressure drying can be used.

The above coating is carried out using (A), (B) and (C) together or separately dissolved or dispersed in water or any organic solvent (which may contain water). be exposed.

In this case, an appropriate dispersant (including a surfactant) or a conductive compound may be used. If (C) is applied separately, simultaneous multilayer coating may be performed, or each may be applied in sequence (
may also include a drying or semi-drying step).

Solvents used for coating include organic solvents (e.g. acetonitrile, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, sulfolane, formamide, dimethoxyethane, propylene carbonate, dioxane, methanol, ethanol, n
-propanol, isopropanol, n-butanol,
T-butylradokone, acetone, methyl ethyl ketone,
diethyl ketone, n-butyl acetate, ethyl acetate, dichloroethane, chloroethylene, tetrahydrofuran, etc.),
Mention may be made of water or a mixture of both.

As the conductive compound, inorganic acids (for example, HIJ, tt
, so, , HIJOi, HBFn), organic acids (e.g., sulfonic acids such as toluenesulfonic acid, trifluoromethylsulfonic acid, polystyrene sulfonic acid, formic acid,
carboxylic acids such as acetic acid polyacrylic acid), organic bases (such as
e.g. pyridine, triethanolamine) and conductive salts (e.g. alkali metal cations (Li., Na'
, K・, etc.), No・, No 0, cation, onium cation (Et, N・, Bu4N・, Bu, P・, etc.) and negative A: t 7 (BF4'% A9Pae−, ASF&e
% 5bFa', 5bC1b', PFh', ClO
s', AfP46.117F-1NiF4'', ZrF
6”.

TiF,”,B+oC!1゜”,H3O5”,So,
"Salt consisting of "5C1e, Bre, Fo, 10), sulfonic acid anion <Cll5CbHaSO2", CJs
salts containing carboxylic acid anions such as HCOOLi, sodium polyacrylate, Fe (chlorides such as J3, organic amine salts such as pyridine hydrochloride, etc.) ).

As the dispersant, cationic, anionic, nonionic, betaine polymers and surfactants (emulsifiers) can be used. Specific examples of these include polyvinyl alcohol, polyethylene oxide, polypropylene oxide, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, dextrin, polyvinylpyrrolidone, sodium polystyrene sulfonate, polyacrylic acid, polyacrylamide, gelatin, collagen, tertiary or quaternary Polymers having ammonium salt sites, polymers having oxonium salt sites, polymers having sulfonium salt sites, long chain alkyl compounds having quaternary ammonium salt sites, higher fatty acid alkali salts (e.g. ClzlltsCOONa)
, alkyl sulfates (e.g. sodium lauryl sulfate), alkyl sulfonates (e.g. sodium lauryl sulfonate), alkylaryl sulfonates (e.g. sodium dodecylbenzenesulfonate), sulfosuccinate ester salts, higher amine halogenates , halogenated alkylpyridinium (e.g. dodecylpyridinium chloride), quaternary ammonium salts (e.g. trimethylammonium chloride), polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride, amino acids and the like.

When a dispersant is used, it is used in an amount of 1 to 300% by weight, preferably 5 to 200% by weight, based on the dispersion. When using a surfactant, 0.01 to 50
It is used in weight percent, preferably 0.1 to 20 weight percent.

Examples of oxidizing agents include chlorides such as ferric chloride and cupric chloride, sulfates such as ferric sulfate and cupric sulfate, metal oxides such as lead dioxide and manganese dioxide, potassium persulfate, and persulfate. Examples include peroxides such as ammonium sulfate and hydrogen peroxide, quinones such as benzoquinone, halogens such as iodine and bromine, and potassium ferricyanide. Specific examples of these are disclosed in JP-A-63-213518 and JP-A-63-19.
No. 3926, No. 62-116665, No. 62-104
No. 832, No. 63-215717, No. 63-6982
It is also described in No. 3, No. 63-101415, No. 60-58430, etc.

The amount of oxidizing agent varies depending on the characteristics of the aniline compound or heterocyclic compound and the oxidizing agent used, but the molar ratio of oxidizing agent/aniline compound or heterocyclic compound is from 0.01 to
A range of 10 can be used.

Preferably it is 0.1-5.

The amount of prepolymer will vary depending on the properties of the aniline compound or heterocyclic compound and the prepolymer used;
The molar ratio of the aniline compound or heterocyclic compound represented by D to the aniline compound or heterocyclic compound in the prepolymer is 0. It can be used in the range of O1 to 1000. Preferably it is 0.1-500.

The supports used include, for example, polymer compound films such as polyethylene terephthalate film and cellulose triacetate film, metal plates such as aluminum foil and stainless thin plates, conductive nets such as stainless steel nets and polymer nets, or filters. When using the obtained electronically conductive polymer as a conductive material such as, but not limited to, a polymer battery, it is preferable to use an electrode, a current collector, a separator, etc. as a support.

Examples of manufacturing the @ chain electronically conductive polymer manufactured according to the present invention are shown below, but the invention is not limited thereto.

[Production Example 1] (Production of Compound P-1) While stirring 21.5 g of 0-nitrophenethyl alcohol, 100 g of acetonitrile, and 11.7 g of pyridine under water cooling, 15.3 g of methacryloyl chloride was added to 3 g of methacryloyl chloride.
It was dropped in 0 minutes. After further stirring for 1 hour, 200 In1 of ethyl acetate and 300 A+ffi of water were added, and the ethyl acetate layer was extracted. It was washed with 300 ml of water to obtain an ethyl acetate solution (1-A) of 0-nitrophenethyl methacrylate.

Reduced iron 50g, ammorum chloride Q, 5g, water 30d,
75° without stirring 200m ethanol and 1g vinegar M
The temperature was raised to C. After the above 1-A was added dropwise over 1 hour, the mixture was further stirred for 3 hours. The insoluble portion of the reaction solution was filtered, concentrated, and purified using a silica gel column using chloroform as a developing solvent.
23 g of 0-aminophenethyl methacrylate [Compound 1
Monomer (1-
1')) was obtained.

Its structure was confirmed by NMR1 elemental analysis.

0.005 mol of monomer N-1'), 0.005 mol of monomer (ff-2') capable of forming a repeating unit represented by compound n-2;
) and 0.095 mol of eta)-4100rnl 7
While stirring at 0°C, 0.5 g of 2.2'-azobisisobutyronitrile was added and stirred for 6 hours to obtain a prepolymer (PP-1). According to NMR1 elemental analysis, the prepolymer (PP-1) was +1-1)r-(II-2)yr-.

(PP-1) /aniline/LiCZO, /IIBF,
Dissolved in water at a weight ratio of 3/3/I/2, a thin stainless steel plate (with a stainless steel mesh on the coated surface) was added.
) to a coating amount of 20g/rrj,
After drying with ventilation at room temperature, FeC1, 6H2 is applied on top of this.
0 aqueous solution was applied at a coating amount of 20 g/po, and dried under ventilation at room temperature. Finally, the coating film on the stainless steel plate was washed with water to remove excess oxidizing agent.

Compound P-1 produced in this production example was found to have the following structure by elemental analysis.

-1 l13 Average n number 35.1 tζ7 (average) [Production Example 2] (Production of Compound '&P-2) Production Example 1 except that HBFa was not used in Production Example 1 and pyrrole was used instead of aniline. Go in the same way as
Compound P-2 was obtained.

Compound P-2 produced in this production example was found to have the following structure by elemental analysis.

-2 Cl+.

■ Average n number 48.5 tζ7 (average) [Production Example 3] (Production of Compound P-3) Compound obtained in Production Example 1! -1 0.006 mol, n-butyl acrylate 0.094 mol and ethyl acetate 100
While stirring m at 70°C, 0.5 g of azobisisobutyronitrile was added, stirred for 6 hours, and the prepolymer (
PP-2) was obtained.

Prepolymer (PP-2) dissolved in acetonitrile and aniline/LiCZ a/HIJO4
was dissolved in water at a weight ratio of 3/1/2, and then sequentially applied and dried on a thin stainless steel plate (with a stainless steel mesh fused to the coated surface) at a coating weight of 15 g/I.
Next, on top of this, add 30
g/Po and dried at 30"C.Finally, to remove excess oxidant,
The upper coating film was washed with water.

Compound P-3 produced in this production example was found to have the following structure by elemental analysis.

-5 C.I.

Average n number 26 [Production Example 4] (Production of compound P-4) 4-(2-hydroxyethoxy)methylthiophene 0.
1 mol, 0.1 mol of pyridine and 100 mol of acetonitrile
While stirring m at 10°C or lower, 0.1 mol of methacryloyl chloride was added dropwise over 30 minutes. After further stirring for 1 hour, 200 d of ethyl acetate and 200 d of water were added, and the ethyl acetate layer was extracted. After concentration 11, column purification was performed, and 4-
Thienyl methoxyethyl methacrylate [Compound 1-3
A monomer (1-3') that can form a repeating unit represented by
)) was obtained.

10 g of monomer (1-3'), monomer (II-1') capable of forming a repeating unit represented by compound 11-1
50 g of Up-styrene sulfonic acid, 10 g of Up-styrene sulfonic acid, 300 d of ethanol, and 0.6 g of 2,2'-azobismethylisoptyle) were stirred at 80°C for 5 hours under a nitrogen stream to obtain prepolymer (PP-3). I got it.

Prepolymer (PP-3>/thiophene-1/2 (weight ratio) dissolved in water was coated with 40e/r on a thin stainless steel plate (stainless steel mesh was fused to the coated surface).
It was coated and dried using an RF coating amount. Next, on top of this, FeC
1. Apply 6H20 aqueous solution at a coating amount of 40g/bo,
Air dried at room temperature. Finally, in order to remove excess oxidizing agent, the coating film on the stainless thin +H was washed with polymer water.

-5 Compound P-4 produced in this production example has an NMR1CI! Elemental analysis revealed a compound with the following structure.

CI! 3 +CHt C) Ts -6 Average n number 14.8 tζ4 (Average) Compounds P-5 to P-21 produced by the production method of the present invention according to Production Example 1 are listed below, but the present invention The invention is not limited to these.

-7- CH3 +CHg CHh Average number of n-34 T! :=4 (average) Average number of n-51 tζ9 (average) -8 0 1 Average n number = 48 tζ7 (average) +CHz CHh COOCsH*SOJ Average number of n = 33 -7 (average) P-11 P-13 (C11゜ CI+)( +CHx C11hs CooICHzCHzO)TC)I! Average number of n-66 Average number of n-26 tζ7 (average) tζ4 (average) -14 -12 CH3 +CL Chs +cHt CH)vy Coo-(cHtcHio)ycHs Average number of n-73 tζ9 (average) Hs ■ +CHi Chs C0O-(CH*CLO)ICHs Average number of n-69 tζ7 (average) mζ3 (average) -15 -16 +CH* Co), - C)I.

(CH1-Ch +CHt CHhs C00(CH*Cll0)IC■.

Ch +CHi Ch Average number of n-4O tζ4 (average) ) mζ3 (average) CH.

+CHg Cats Coo-(cutcHtQ)ICHs Average number of n-52 average n' Number = 52 T! :i4 (average) P-17 CH.

+CH2-Ch 113 -13 m-5 at P-14 (average) -19 m'' at P-15, 5 (average) -2O mζ7 at P-14 (average) -2l m at P-15: +7 ( Average) [Comparative Production Example 1: Production of Comparative Compound 1] Comparative Compound 1 was produced as follows.

Aniline / LiC70a / HBF4 = 3 /
l / 2 (weight ratio) dissolved in water was placed on a thin stainless steel plate (with a stainless steel mesh fused to the coated surface).
Next, an aqueous FeCl2.6HzO solution was applied on top of this at a coating amount of 25 g/n and dried.Finally, in order to remove the excess oxidizing agent, The coated film on the thin stainless steel plate was washed with water.

[Comparative Production Example 2: Production of Comparative Compound 2] Comparative Production Example 2 was prepared in the same manner as Comparative Production Example 1 except that 1 (HF) was not used and virol was used instead of aniline. Obtained.

The electron conductive polymer of the present invention can be laminated with a solid polymer electrolyte and used as a conductive material such as a polymer battery. At that time, the electron conductive polymer is 10g/rrT~1
It is preferable to use a film thickness of 00 g/rrf.

The electron conductive polymer of the present invention may form multiple layers,
Further, a plurality of layers may be formed together with a known electron conductive polymer, or a layer may be further formed with a salt of a metal ion of group Ia or group Ila of the periodic table. However, it is preferable that the solid polymer electrolyte and the electron conductive polymer of the present invention are in direct contact with each other because of low interfacial resistance.

Polymer solid electrolytes to obtain the laminated conductive material with the electron conductive polymer of the present invention include cationic polymer anionic polymers, polyacrylonitrile, polyalkylene oxide polymers (silicon compounds including polyethylene oxide, polypropylene oxide and polyethylene oxide, and phosphazene, etc.). ), polyvinyl alcohol, etc. in combination with salt. Specific examples of these are disclosed in Japanese Patent Application Laid-open No. 1983
-256573, 61-124001, 62-
No. 20263, No. 62-139266, No. 63-24
No. 1066, No. 63-241026, No. 63-135
No. 477, No. 63-142061, No. 63-1306
No. 13, No. 60-23974, No. 63-136409
No. 63-193954, No. 63-186766, No. 63-205364, "Macromolecules"
It is described in Volume 21, page 648.

Examples of the salt constituting the solid polymer electrolyte include the conductive salts used during the polymerization described above. Preferably, it is a salt of a metal ion of group Ia or group Ila of the periodic table, and more preferably a Li salt.

Laminated conductive materials are made by laminating a melted or molten polymer solid electrolyte in close contact with an electron conductive polymer film formed on electrodes, current collectors, separators, etc. by coating, etc. can do.

In addition, the compound produced by the present invention has the function of a solid polymer electrolyte, thereby making it possible to substantially eliminate the need for an electrolyte.

That is, the function as a battery can be expressed simply by using a separator between the positive electrode (the compound produced by the present invention) and the negative electrode.

The separator should be impregnated with any organic solvent (e.g., propylene carbonate, ethylene carbonate, T-butyl lactone, dimethoxyethane, methyltetrahydrofuran, etc.) so that ions (e.g., Li") of the negative electrode material can easily diffuse. is preferred.

As the separator material, any material such as polyolefin, polyester, polyvinyl chloride, fluororesin, polyamide, polysulfone, cellulose, BoIJ+''7 rethane, etc. can be used.

The evaluation methods and results of specific examples of compounds obtained by the production method of the present invention and conductive materials using the same are shown below; however, the conductive materials of the present invention are not limited to these.

[Electrical conductivity measurement]

Compound P-1,2,3,4,8 produced according to the present invention
, 11, 16, 17 and Comparative Compounds 1 and 2 were scraped off from the support to form powders, which were then pressure molded to obtain 200-mm pellets, respectively.

Table 1 shows the electrical conductivity measured by the four-terminal method.

(Scratch strength test) Compound p produced according to the invention obtained on a support
-t, 2.3.4.8.11.16.17 and comparative compound 1.2 as they are, using a 1 mm diameter sapphire needle,
A scratch resistance test was conducted, and the load applied by a needle when the film was destroyed and a scar remained was determined, which was defined as the scratch strength. Table 1 shows the results.

[Electrical conductivity measurement] Compound P produced according to the present invention obtained on a support
-1, 2, 3, 4, 8, 11, 16, 17 and comparative compound 1.2 were laminated as they were with a cast film (about 200 nm thick) of the polymer solid electrolyte shown below, and sandwiched between stainless steel plates. Laminated materials were prepared (stainless steel plates were also used on the polymer solid electrolyte side). The conductivities of these laminated materials were measured using the Cole-Cole plot method and are shown in Table 1.

(Polymer solid electrolyte film) CHtW=CI-C00(C!lIn0″)ICO-C
II=CHz 1 g, propylene carbonate 6
gSLiCZO41.5g, 2. 10 mg of 2'isobisisobutyronitrile was dissolved in acetone in 7 volumes, cast on a Teflon plate, and then polymerized at 80° for 4 hours to obtain a polymer solid electrolyte film. The electrical conductivity obtained by the Cole-Cole plot method was 3×10 −S/c+1.

[Charge/discharge test 1] The laminated material obtained above with a lithium sheet crimped was placed in a stainless steel can, the mouth was sealed with insulating synthetic rubber, and compression molded to create a battery as shown in Figure 1. . This battery was subjected to continuous charging and discharging tests as a secondary battery.
The average voltage after 0 cycles or the average voltage after 10 cycles was measured at 20°C and -25°C and is shown in Table 1.

[Charge/discharge test 2] Compound P produced according to the present invention obtained on a support
-1,2,3,4,8,1116,17 and comparative compound 1.2 were soaked in a 20% Li1JO4 acetonitrile/propylene carbonate (80/20 ICI ratio) solution, dried, and each was impregnated with propylene carbonate. The prepared polypropylene and lithium sheets were laminated and placed in a stainless steel can, the mouth of which was sealed with insulating synthetic rubber, and compression molded to produce a battery as shown in FIG.

This battery was subjected to continuous charging and discharging tests as a secondary battery.
The average voltage after 0 cycles was measured at 20'C and is shown in Table 2.

Table 2 It was found that the material had excellent charge and discharge characteristics as a pond material.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing the structure of a secondary battery prepared in charge/discharge test 1 of the present invention. FIG. 2 is a cross-sectional view showing the configuration of a secondary battery created in charge/discharge test 2 of the present invention. (Symbols in the figure) 1; Physical loss obtained from the compound of the present invention 2: Polymer solid electrolyte film 3: 9L electrode (lithium sheet) 4. Stainless steel case 5; Insulating synthetic rubber 6: Separate lake [Effects of the invention] ]

Claims (5)

[Claims] (1) A prepolymer consisting of at least one aniline compound or a heterocyclic compound and an ethylenic repeating unit having at least a site in the side chain that can polymerize the aniline compound or the heterocyclic compound in the presence of an oxidizing agent. A method for producing an electron-conductive polymer comprising an ethylenic repeating unit that is polymerized on the same support and has a repeating unit of an aniline compound or a heterocyclic compound in its side chain as an electron-conducting moiety. (2) The method for producing an electronically conductive polymer according to claim (1), wherein the prepolymer further has an ethylenic repeating unit having a repeating unit of an oxyalkylene group in a side chain. (3) The method for producing an electronically conductive polymer according to claim 1 or 2, wherein the prepolymer further contains an ethylenic repeating unit having an anionic group in a side chain. (4) An electrically conductive material comprising a laminate of an electronically conductive polymer and a solid polymer electrolyte produced by the production method according to claim (1), (2) or (3). (5) An electrically conductive material comprising a laminate of an electronically conductive polymer and a separator produced by the production method according to claim (1), (2) or (3).