JPH0341107A - New electronically conductive polymer and conductive material prepared by using the same - Google Patents

Abstract

PURPOSE:To provide the subject polymer excellent in electronic conductivity, strengths, etc., by constituting it from ethylenic repeating units each having a specified electronically conductive part as repeating units in the side chain and ethylenic repeating units each having repeating oxyalkylene group units in the side chain. CONSTITUTION:This electronically conductive polymer has ethylenic repeating units each having an electronically conductive part comprising at least either an aniline compound or a heterocyclic compound as repeating units in the side chain (e.g. formula I or II). This polymer further has ethylenic repeating units each having repeating oxyalkylene group units in the side chain (e.g. formula III or IV). By laminating this electronically conductive polymer with a solid-state polyelectrolyte (e.g. a combination of polyacrylonitrile with a salt), a conductive material which has excellent electric conductivity and can give an electronic device of a quick response can be produced.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is applicable to antistatic materials for plastics and the fields of electrical and electronic industries, such as electrodes or electrolyte materials for batteries, capacitors, electronic devices, and electrochromic devices. Alternatively, it can be applied as a wide range of conductive materials such as planar heating elements and electromagnetic shielding materials.

[Conventional technology]

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

For example, polyaniline, polythiophene, ho+)hyrol, polyphenylene vinylene, polyphenylene acetylene, polyacetylene, etc. are promising, and West German Patent No. 3.2.2
．． ! ,! ≠φ, 3゜3ir, tit, 3.31
1.137, J, 321, 192, J, 33
1.9011 No. J, F Co/, Kode G No. % Japanese Patent Publication No. 1983
”-117432, 11JO6O, 11JO6O, 2!13, ll-209rtlA, 207933, 207933, 20722, 2!

-67127, 7J-, 22jjIr, tcojJ32r, 63-/Tata 724, tO-22
31/7 issue, 7/-4322/ issue, Tatar 3164
It is stated in No. 1 etc. Although these polymers have excellent electronic conductivity, they have drawbacks such as poor mechanical strength, poor solubility in solvents, and poor moldability. Electron-conducting polymers with excellent properties have been desired.

Conductive materials that combine these electronically conductive polymers and electrolytes as layers are used, but in order to fully function as a device or battery, electrons and ions must be formed at the interface between the two. need to be replaced 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,
/91r/, vol 22, Novemb
Er.

lg! ≠〜lφj! An organic battery combining polyacetylene and a solid electrolyte has been proposed, but the polyacetylene film produced by this addition polymerization has poor oxidation stability and lacks contact with the solid polymer electrolyte at the interface. There were problems such as not being able to obtain sufficient and good conductivity, and having a slow response speed as a device material.

Japanese Patent Laid-Open No. 62-21177 describes a laminate conductive material that combines an electrolytically polymerized polymer with a conjugated double bond in its main chain and a polymer solid electrolyte, but There were problems such as insufficient adhesion at the interface between the molecule and the solid polymer electrolyte, resulting in high interfacial resistance, inability to obtain good conductivity, and poor mechanical strength.

However, as a compound that achieves both mechanical strength and conductivity, compounds having a repeating unit of a carbazole group in the side chain, such as the following, are being considered at the 37th Polymer Symposium 2H044. Electrical conductivity is 10-4 to 10-5
The length was 87 cm, which was insufficient.

When polyaniline or a polyheterocyclic ring is used as an electrode material, anions are doped or dedoped as a result of the redox reaction. In this case, Takehara et al. showed that the diffusion of anions becomes rate-determining! 6th Electrochemical Society JG,? ≠ is reported.

A specific example of a method for preventing the diffusion of anions is disclosed in Japanese Patent Application Laid-open No. Sho Jj-2/j772, in which an anionic compound is used as a doping agent. However, with this method, a concentration gradient occurs due to the diffusion of the anionic compound as doping is repeated, and it could not be a sufficient means for improvement.

[Problem to be solved by the invention]

A first object of the present invention is to provide an electronically conductive polymer having excellent % electronic conductivity, mechanical strength, and moldability.

A second object of the present invention is to provide an electron conductive polymer in which anion doping and dedoping reactions occur quickly in redox reactions of electron conductive polymers.

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 third object of the present invention is to provide an electrically conductive material that substantially eliminates the need for an electrolyte layer by providing an electronically conductive polymer with the function of a solid polymer electrolyte.

[Means to solve problems]

The above object could be achieved by the following electronically conductive polymer or conductive material using the same. That is,
At least an ethylenic repeating unit having in its side chain an electron conductive moiety consisting of at least seven anionic compounds or heterocyclic compounds, and an ethylenic repeating unit having a repeating unit of an oxyalkylene group in its side chain. It was possible to couple with an electronically conductive polymer or a conductive material using it.

The electron conductive polymer of the present invention will be explained in more detail.

At least 7 side chain aniline compounds, heterocyclic compounds
The electron conductive portion consisting of 2 may be /9, or may be more than or equal to 9. Furthermore, the repeating units of the electron conductive portions may be linked by a linking group.

The ethylenic compound that induces an ethylenic repeating unit having an electron-conductive moiety in its side chain as a repeating unit consisting of at least one of an aniline compound or a heterocyclic compound is a light or heavy compound having the following general formula % formula % oxyalkylene group in the side chain. An ethylenic compound that induces an ethylenic repeating unit having a repeating unit is represented by the general formula (I [I)].

In general formulas (I) to (III), A 11 , A
12A , A , A , A %A31
%A32A33 may be the same or different and represent a hydrogen atom or a substituent on ethylene carbon, Ll, L2,
L3 may be the same or different and represents a monovalent linking group. D
1, D2, D3, and D4 may be the same or different and represent an aniline compound or a heterocyclic compound. abaO or l
represents.

G represents a substituted or unsubstituted alkylene group, and tV
represents i/~3Q. However, when t≧2, G may be the same or different.

A34 is a substituted or unsubstituted alkyl group, aryl group, alkylcarbonyl group, arylcarbonyl group,
Represents an alkylsulfonyl group and a hyarylsulfonyl group.

General formulas (I) to (Ill) will be explained in detail.

A11, A12, A13, A", A, AA31
, A32, A33, the number of substituted or unsubstituted carbon atoms/
-4' alkyl group (e.g. methyl group, ethyl group, n
-propyl group, n-butyl group, is.

-propyl group, methoxyethyl group, carboxymethyl group), cyano group, carboxy group (including alkali metal salts)
, carbamoyl group (substituted or unsubstituted alkyl group having carbon number l-ψ, optionally substituted with substituted or unsubstituted phenyl group, e.g. -CON) (2, -CON(CH3)
2, -CONC2H40CH3, number/~g alkoxycarbonyl group (e.g. Eva C00C4H9(n -)),
Hao 'y' = z [child (e.g., th' 77 elements, chlorine,
Bromine).

A", A, A, A", A %AA", A
, A may be the same or different, and represent a hydrogen atom, a chlorine atom, a methyl group, a carboxyl group.

The electron conductive moiety and the oxyalkylene repeating unit are ethylene forming the main chain and Ll of the above general formula, respectively.
They are linked by linking groups represented by L2 and L3.

Ll, L2, and L3 may be the same or different. well%-o --s --co --so2--oc
I can say o--coo-. R1 represents a hydrogen atom, an optionally substituted alkyl group, or a phenyl group.

R2 represents an alkylene group having carbon number/-1.

R3 represents a hydrogen atom or an optionally substituted alkyl group having carbon number/~g. Jl, J2. J3 is preferably -
CO-1-so2-1-CONH--8O2NH-1-
NH-CO-1-NH-8O2-1-〇--NHCON
H--8-1-co2-1-OCO--NHCO2-1
and -0CONH-.

X1% I2 and I3 may be the same or different, and each represents an optionally substituted alkylene group, arylene group, aralkylene group, or (-G 1-0, CH2CH2- group. Here, G11t1 each represents G, It has the same meaning as t. Preferably, it is an alkylene group with carbon number/-4', an arylene group with a carbon number of ~5, a substituted arylene group, or a (-CH2CH20?CH2CH2- group. p, g
, r> and S represent θoutabar. I2 is synonymous with t.

In the general formula CI), [■], the electron conductive moieties represented by D1, Dl, D3, and D4 may be the same or different, and each represents an aniline compound or a heterocyclic compound. D
l, D3, and D4 are covalent, and Dl is trivalent.

Specific examples of the above heterocycles include monoru, oxazole (including iso), thiazole (including iso), pyridine, diazine, inzotriazole, and indioxazole.

Examples include benzothiazole, purine, quinoline, isoquinoline, penzdiazine, fluorene, enoxacin, pyrazolotriazole, pyrazolodiazole, pyrazoloazole, and benzopyrazoloazole.

Z represents O, S or -N-R3 (R3 has the same meaning as above).

Particularly preferred examples of Dl, Dl, D3, and D4 are aniline compounds, virol compounds, thiophene compounds, and 7-run compounds.

The aniline compound and heterocyclic compound represented by Dl, Dl, D3, and D4 may each be substituted with an arbitrary substituent. Examples of this substituent include halogen atom, nitro group, cyano group, alkyl group, alkoxy group, -NHCOR4, -NH802R4-8OR' -
802R4-COR4 (which may be further substituted with a kill 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 R6 may be the same or different,
Represents a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group. Furthermore, two substituents may be condensed to form a carbocycle or a heterocycle.

Furthermore, among the substituents exemplified by Dl, Dl, D3, and D4 above, and A 11 , A I2, A , AA , A
, A”, A32, A , A position 22
23 Examples of the optional substituents of the alkyl group, alkoxy group, phenyl group, aralkyl group, and the substituted alkylene group, substituted arylene group, and substituted aralkylene group in Xl, I2, and I3 include hydroxyl group, nitro Group, number of carbon atoms/-
4 alkoxy group, alkyl group with carbon number l-μ, -NH
8O2R7--NHCR7--COR7 halogen atom,
Examples include a cyano group and an amino group (which may be further substituted with an alkyl group).

R7 has the same meaning as R4. R8 and R9 may be the same or different and have the same meaning as R5.

Specific examples of the aniline compound and the heterocyclic compound are shown below, but the invention is not limited thereto.

H3C-C-CI(3 H3 Preferred are aniline, thiophene, and pyrrole.

G represents a substituted or unsubstituted alkylev group having 2 to 2 carbon atoms, preferably -CH2CH2-, particularly preferably -CH2CH□-.

t represents /~30, preferably 1 ~ 0;
Particularly preferred is 3-1! represents.

A34 is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms (e.g., methyl, ethyl, n-propyl),
Aryl groups (e.g. phenyl, tolyl), alkylcarbonyl groups (e.g. methylcarbonyl, ethylcarbonyl), 7-arylcarbonyl, IILt phenylcarbonyl, μm acetaminophenylcarbonyl), alkylsulfonyl groups (e.g. evamethylsulfonyl, ethylsulfonyl) ) and an arylsulfonyl group (eg, t, phenylsulfonyl, tosyl), preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group.

Specific examples of repeating units represented by general formulas (I) and (II) are shown below, but the present invention is not limited thereto.

n represents an arbitrary integer.

(hereinafter the same meaning) 1-. 2 ■-G +0(2C!(÷ ■-! a(3 / +CH2C-)- -G -7 1-1 cl(3 +CH2C)- ■－／／ 1-/ko +CH2CH÷ 1-/J T. (-CH2C-).

1-/F C) (3 amount 1-/! m is any integer from / to 30 (hereinafter the same meaning) ■-76 ÷cH2C) (÷ I-/7 )-/1 i-/ri CH3 MoCH2C-) -20 a(2 ■ I-2/ H3 ■-22 ■-23 It will be indicated by general 2■ below. Specific example of repeat unit is shown below, The present invention is not limited to this. It's not something you can do.

■-/ However, t Kiμ (average) ■-2 ffl -, J ■-g [1-j ■-4 l-7 Saw (average) 23 (average) -r ■-ta■-7゜l11-/i 1[[-iko[[-/J [[-/teiC00(-CH2CH20 -3, -CH3 but tmi4
L (average) 1[-7 t″F7 (average) Main 7 (average) Main/ko (average) tki/, < (average) Main 23 (average) t = 2 +c) (2cH+ ■ C00(-CH2CH20-)-H However, t soil 7 (average) ■-/! 1ll-/ ■-/! t=7 (average) ■-77 However, tl main 3 (average) t2:<<( Average) [[-/♂ However, t1 character 3 (average) t2 Kig (average) [i-/riCoo(cH2a-(0-i0cOcH3 However, 7 in t
(Average) ■-λQ However, 7 in t (average) ■-2/ The electronic conductive polymer of the present invention is light and heavy in that it further contains an ethylenic repeating unit having an anionic group in the side chain.

The ethylenic compound that induces an ethylenic repeating unit having an anionic group in its side chain preferably has the following general formula (
IV).

A", A and A may be the same or different and have the same meaning as A11. L4 has the same meaning as Ll. E represents an anionic group.

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

Specific examples of the repeating unit represented by the general formula (IV) are shown below, but the present invention is not limited thereto. (MH hydrogen atom, alkali metal (e.g. L
i%Na%K), alkaline earth metals (e.g. Mg, C
represents a). )■-/ ■-2 H3 -j +CH2c) (÷ CC00C3H6SO3 ■-g+CH2CH)- CON) (C2H4SO3M ■-t ■-+ +CH2a-r-)- ■ α) OC2H400CC3F6COOM■-7 +CH2CH÷ CC00C2H4N) ( COC3F6COO ■−r ÷CH2CH−)− COOC2H40S03M ■−ta+C)(2cH+ OOM ■−10 ■−// H3 ■−72 αphantom C4H8503M ■−73 ■−/lIt The compound of the present invention can increase mechanical strength or , for the purpose of improving solubility, general formula (1) or (If) and (II
I) may contain repeating units of arbitrary monomers in addition to the repeating units represented by (IV), if necessary.

Specific examples include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid (e.g. methacrylic acid, etc.)
, esters or amides derived from acrylic acids such as itaconic acid, crotonic acid or citraconic acid (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n- Propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-ethyl fuxyl acrylate, n-octyl acrylate, n-lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate ), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile,
methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, hinyl acetophenone buttons and sulphostyrene), hnylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic esters , N-vinyl-λ-pyrrolidone, N-vinylpyridine, and φ-vinylpyridine, but are not limited thereto.

The repeating unit having the electron conductive moiety of the present invention as a repeating unit in its side chain may be present in any ratio in the polymer. Good! S<ba/~! The number of θ moles is large.

The ethylenic repeating unit having a repeating oxyalkylene group in the side chain may be present in any proportion in the polymer, but preferably! ~22 moles in excess.

The ethylenic repeating unit having an anionic group in the side chain may be present in any proportion in the polymer, but preferably!
~ rO mole.

The synthesis method for obtaining the electron conductive polymer of the present invention uses commonly used synthesis methods, such as known polymerization methods, chemical oxidation polymerization methods, electrolytic oxidation polymerization methods, C-C coupling reactions, etc. be able to.

For example, after polymerizing the main chain so that the side chain has an electron conductive site, chemical oxidative polymerization, electrolytic oxidative polymerization, C
The compound of the present invention can be obtained by polymerizing the electron-conductive site by -C coupling reaction or the like. At this time, polymerization may be performed at different electron conductive sites. In addition, the polymerization of the electron conductive site can be carried out using chemical oxidation polymerization method, electrolytic oxidation polymerization method, C-
After the C-coupling reaction or the like, a side chain having a repeating unit of an electron conductive site may be introduced into the main chain polymer by a polymer reaction. Further, the main chain may be polymerized using a premonomer whose electron conductive site has been polymerized by a chemical oxidative polymerization method, an electrolytic oxidative polymerization method, a C--C coupling reaction, or the like. At this time, the premonomer that has undergone polymerization of the electron conductive site may be homopolymerized, or it may be copolymerized with any other monomer.

The above chemical oxidative polymerization method can be carried out in water or any organic solvent (
The monomer compound is dissolved or dispersed in a solution (which may contain water),
go 'C~-koQ0C (light and heavy Vi, zo'c-
o'c) by gradually dropping the catalyst (oxidizing agent) solution. In this case, an aqueous dispersion of the polymer can be obtained by using an appropriate dispersant or surfactant, which is preferable since it has excellent moldability.

The above electrolytic oxidation polymerization method involves dissolving or dispersing monomer compounds and conductive salts in water or an organic solvent capable of dissolving conductive salts, immersing the positive and negative electrodes in the ro 0c to -co 00C (preferably 1
or Jo'Co'C) by a constant voltage method, a constant potential method, or a constant current method.

Preferably, a constant voltage method is used.

The above C-C coupling reaction is mainly applied to thiophene compounds (it may also be applied to aniline compounds and pyrrole compounds), and a Grignard reagent or a metal halide is applied to a halogenated thiophene compound. can be obtained.

Specifically, 5ynthesis Metal, Coro,
2Z7(/Yl#') etc. In addition, the compounds of the present invention may be doped with any dopants (eg, halogens or salts used during the polymerization).

Catalysts that can be used in chemical oxidative polymerization methods include:
For example, 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, ammonium persulfate, and peroxide. Examples include peroxides such as hydrogen, quinones such as benzoquinone, halogens such as iodine and bromine, and potassium ferricyanide. Specific examples of these can be found in Japanese Patent Application Laid-Open No. 1997-3-. 2/J, Tlr issue, same 1. ! -/9! Octopus 6
No. 12-//J4At No. 44-1011?32
No. tJ-, 2/! 7/7 issue, same Aj-69Ir23
No. 1.3-10/It/! No. F, 6Q-yo 213
It is also written in No. 0 etc. The 1tVi of the catalyst varies depending on the characteristics of the monomer compound and the catalyst used, but the molar ratio of catalyst/monomer compound can be used in the range of O6O/ to /Q.

Electrode materials that can be used in the electrolytic oxidation polymerization method include metal electrodes (for example, Au, Pt, Ni, Cu, 8n%
(Zu, Ag, Ru, Y, stainless steel, etc.), carbon electrodes (e.g., Gratseeker ln), metal oxide-containing electrodes (e.g., S n 02, In2O3), and the like. Additionally, using a separate reference electrode is light and heavy.

Examples of solvents that can be used in the chemical oxidative polymerization method and the electrolytic oxidative polymerization method include organic solvents (e.g., acetonitrile, dimethyl sulfuric acid, N,N-dimethylacetamide, N,
N-dimethylformamide, dimethyl sulfoxide,
Examples include sulfuran, formamide, dimethoxyethane, propylene carbonate, dioxane, methanol, ethanol, r-butyl lactone, nitrobenzene, tetrahydrofuran, nitromethane, etc.), water, or a mixture of both.

Furthermore, a conductive compound may be added during chemical oxidative polymerization or electrolytic oxidative polymerization. As a conductive compound,
Inorganic rR (e.g. Hcl, H2BO3, Hα04, B
F4), organic acids (e.g. sulfonic acids such as toluenesulfonic acid, trifluoromethylsulfonic acid, polystyrene sulfonic acid, carboxylic acids such as formic acid, acetic acid, polyacrylic acid), organic bases (e.g. pyridine, triethanol amines) conductive salts (e.g. alkali metal cations, ten (L+, Na, K, etc.), NO, NO2 cations, onium (Et4N, Bu4N+Bu3P)
etc.) and negative io7 (BF4, AsF4AsF6
, SbF6. 5bC16, PF6, CtOa2 = AlF4, AlF6, N1F4, ZrF
6, TiF6, BIOC/! 10,
HSO3-,so4”-cl %Br %F
I), a salt consisting of a sulfonic acid anion (CH3C6H4
S03-1C, H5so3CF3S03, polystyrene sulfonic acid, etc.)! salts, HCOOLi, salts containing carboxylic acid anions such as sodium polyacrylate, Fe
Q! ! Examples include chlorides such as No. 3 and organic amine salts such as pyridine hydrochloride.

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, carboxymethyl-1zlulose, methylcellulose, dextrin, polyvinylpyrrolidone, sodium polystyrene sulfonate, polyacrylic acid, polyacrylamide, gelatin, collagen, tertiary Or a polymer having a secondary ammonium salt site, a polymer having an oquinnium salt site, a polymer having a sulfonium salt site, 4!
a long-chain alkyl compound having an ammonium salt site,
Higher fatty acid alkali salts (e.g. CH12H25COO
Na), 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 halogens Examples include acid salts, alkylpyridinium halides (e.g. dodecylpyridinium chloride), quaternary ammonium salts (e.g. trimethylammonium chloride), polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, nrubitan fatty acid esters, fatty acid monoglycerides, amino acids, etc. .

When using a dispersant, 1 to 3θO with respect to the monomer
It is used in heavy weights, light and heavy weights, and Fij to 200 weights. When using a surfactant, 0.0/
A large amount of -401J, preferably θ/~201J, is used at Keita.

These aqueous dispersions may be used after being subjected to treatment such as dialysis or ultrafiltration.

The above-mentioned conductive compound may be added to these aqueous dispersions, or a polymer compound such as polyvinyl acetate polymer may be blended therewith.

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. The electron conductive polymer of the present invention may form a plurality of layers, or may form a plurality of layers with a casing of a known electron conductive polymer. Moreover, it may further have a lamination with a salt of a metal ion of group 1a or fla group 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.

Polymer solid electrolytes for obtaining the laminated conductive material with the electron conductive polymer of the present invention include cation polymer anion polymer, polyacrylonitrile, polyalkylene oxide polymer (PEO, PPO, silicon compound containing PEO, 7-mole 7-azene, etc.). ), a combination of hollyhinyl alcohol, etc. and salt. Specific examples of these are disclosed in JP-A No. 7/-121tjt73 and AI-/2'AOO1.
No. 22-. 20jAJ issue, 4u-/JP, 2A7
No. 63-2111026, No. 63-211102
No. 6, No. 43-/jt4t77, No. 43-/4t20
t/issue, same A,? -/No. 30773, same tO-23
97← issue, same 43-/3tlAOY issue, same Jj-/93
2! No. 43-/fj7AA No. 63-20!3
4ψ issue, Macromolecules 27%tllt page.

Examples of the salt constituting the solid polymer electrolyte include conductive salts used during polymerization in the chemical oxidative polymerization method and electrolytic polymerization method described above.

It is a salt of a metal ion of group 1a or group Ⅰa of the periodic table, more preferably a Li salt.

When the electronically conductive polymer obtained by the chemical oxidation polymerization method of the present invention is in the form of powder or lumps, the laminate conductive material is produced by pressing a film processed by compression molding onto a solid polymer electrolyte membrane. can do. In addition, when the obtained electron conductive polymer is an aqueous dispersion, known coating methods such as roller coating, spin coating, keyer coating, dip coating, spray coating, extrusion molding, and known drying methods may be used. I can do it.

Applying a melted or melted solid polymer electrolyte onto an electron conductive polymer film formed on an electrode by an electrolytic oxidation polymerization method, or an electron conductive polymer film formed into a film by the above method, etc. They may be laminated in close contact.

In addition, the compound of the present invention can substantially eliminate the need for an electrolytic layer by having the function of a solid polymer electrolyte.

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

The laminated material may be laminated after each component is created independently, or the cathode material may be applied or pressed onto a separator in a housing, and then the negative electrode may be laminated.

The AV-ter is an ion of the negative electrode material (e.g. tdL+)
Any organic solvent that can be easily diffused (e.g., propylene carbonate, ethylene carbonate, γ-butyl lactone, dimethoxyethane, methyltetrahydro7rane, etc.)
A lithium salt may be added to the organic solvent which is preferably impregnated with.

As the separator material, any material such as polyolefin, polyester, vinyl chloride, fluororesin, polyamide, polysulfone, cellulose, polyurethane, etc. can be used. Further, these may be subjected to treatments such as plasma treatment, glow treatment, radiation treatment, plasma polymerization, plasma initiated polymerization, radiation gauze polymerization, and radiation initiated polymerization.

The compounds of the present invention and their synthesis examples are shown below, but the compounds of the present invention are not limited thereto.

[Synthesis Example 1; Synthesis of the compound of the present invention] O-nitrophenethyl alcohol 2/, jg.

13.3 g of methacryloyl chloride was added dropwise to iooml of acetonitrile and 7 g of pyridine over 30 minutes while stirring under water cooling. After further stirring for 1 hour, 200 ml of ethyl acetate and 300 ml of water were added to extract the ethyl acetate layer. Washing with 300 ml of water gave a solution of 0-nitrophenethyl methacrylate in ethyl acetate (/-A).

Reduced iron! Og1 ammonium chloride o, rg, water 30ml
．． x Tanol 2θOml and acetic acid/g without stirring 7
! The temperature was raised to 0C. The /-A ethyl acetate solution was added dropwise to the aqueous solution over 7 hours, and the mixture was further stirred for 3 hours. The insoluble matter of this reaction solution was concentrated by r and purified with a silica gel column using chloroform as a developing solvent to obtain 2 Jg (/-B) of O-aminophenethyl methacrylate. (Structure confirmed by NMR and elemental analysis) /-B, 0.00j mol, seven months -■ ~ 2.0°091
While stirring 100 ml of ethanol and 7,000 ml, 0.3 g of azoisobutyronitrile was added and stirred for 6 hours.
Prepolymer/-〇 was obtained.

NMR: According to elemental analysis, the structure of /-C is H3 Met.

t-Cx0g, 7 Nilin 20g, Licgo47
, jg, CF3COOH20g and hyacetonitrile 3
Electrolytic polymerization was carried out for 7 hours using a constant voltage method (3 V, 2 mA/cm 2 ) using Pt plates for both the positive and negative electrodes while stirring the 00 ml solution to obtain a polymer deposit on the negative electrode. From elemental analysis,
In the case of the compound of the present invention, the H3 average n number was 31r3.

[Synthesis Example: Synthesis of Compound λ of the Present Invention] 1-CJ012. obtained in Synthesis Example/. Feα3・AH2 while stirring pyrrolecoOg, Liα04/jg and water/l at xo 0C.
0/70y4 was added gradually. Stir for 7 hours after addition.
collected. Compound 2 of the present invention was obtained by washing with water and drying.

Compound 2If'i of the present invention was determined by elemental analysis.

The average n number was j/.

[Synthesis Example 3; Synthesis of Comparative Compound/] 7=S7.20 g%Li(llO4/Yg%CF
20g COOH and acetonitrile r o o ml
While stirring, Pt plates were used for both the positive and negative electrodes, and the constant voltage method (
Electrolytic polymerization was performed for 7 hours at JV 2 mA/cm2) to obtain a precipitate (comparative compound/) on the negative electrode.

[Synthesis example ≠; comparison comparison compound here synthesis]

/-Bo obtained in Synthesis Example 1, 0θ! mol, n-butyl acrylate o, oyr mol and 700 ml of ethyl acetate
While stirring at 0°C, add 4 g of azoisobutyronitrile O4.
was added and stirred for 6 hours to obtain a prepolymer (1A-C).

μmCx o g, aniline 20g%Liα04/
! M, 20 g of CF3COOH and acetonitrile! 00
Electrolytic polymerization was carried out for 7 hours using a constant voltage method (j V , 2 mA/cm 2 ) using Pt plates for both the positive and negative electrodes while stirring m1, and a precipitate (comparative compound, 2) was obtained on the negative electrode.

Elemental analysis revealed that in the comparative compound a''I3 formula, x/y = 1/9'tl (molar ratio), and the average n number was 2φ.

[Synthesis example! ; Synthesis of compound 3 of the present invention] 4-bromo 4
0.1 mol of 4-J-hydroxyethoxymethylthiophene, 0.1 mol of pyridine and 100 ml of acetonitrile
0.1 mol of methacryloyl chloride was added dropwise over 30 minutes while stirring the mixture at a temperature below /Q0C. After stirring for 1 hour,
After adding ethyl acetate, zooml and 200ml of water,
The ethyl acetate layer was extracted, concentrated, and purified using a column to obtain coprom-V-thienylmethoxyethyl methacrylate (1-
A: 1/g was obtained.

(1-A) 10g, ■-/J-Og, ■-31og
(M=)i), 300 ml of ethanol and 2゜λ'-azobismethylinbutyrate O, tgf under nitrogen stream ro
At 0c! Stir for hours. After ethanol concentration, nitrobenzene/l, silver trichloride/,! Add mole under nitrogen stream to
At o 0c, 2-chlorothiophene Q, Mamol, was added dropwise over 7 hours. After the dropwise addition, the mixture was stirred at 0c for 6 hours, and then the nitrobenzene was concentrated. Add 00ml of ethanol to this, heat extract the compound (1), and then purify it with a Sephadec column to obtain the compound of the present invention! ,! 3g was obtained.

From elemental analysis and NMR, compound 3 of the present invention, 0 (3rd X/)l/Z=/! /70//! Average number of n//
.

It was l.

[Synthesis example 1] Compound ψ~20 of the present invention was obtained according to Synthesis Example 1.

[Synthesis Example 7; Synthesis of Comparative Compound 3] Comparative Compound 3 was obtained by performing the same operation as in Synthesis Example 3 except that aniline was replaced with virol.

[Synthesis example r; comparative compound! synthesis]

Following Example 1 of JP-A No. 3-2/j772, p-
Polyinthianaphthene (comparative compound j) was synthesized using sodium styrene sulfonate and indianaphthene.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

〔Example〕

Electrical conductivity measurement Compounds of the present invention/, co,! %7.2, /! , /1.20
and Comparative Compounds /, 2.3 were made into powders and molded under pressure to give thicknesses of 0, . A 2 mm plate was obtained. The same operation was carried out on a mixture of the shredded comparative compound and polyethylene oxide (average molecular weight: 30,000) to obtain a comparative compound. Table 1 shows the electrical conductivity measured by the vprobe method.

Scratch strength test The obtained plate was subjected to a scratch resistance test using a sapphire needle with a diameter of 44/mm, and the load applied to the needle when the film was destroyed and a scar remained was determined, and the scratch strength was calculated as shown in Table 1. Indicated.

Measurement of electrical conductivity of laminated material The obtained plate was laminated with a cast film (approximately 200 μm thick) of a solid polymer electrolyte shown below, and a scissor S layer material was created using a stainless steel plate.

The conductivity of each of this laminated material (Co1e-Cole
The results of the measurements (plotting method) are shown in Table 1.

(Polymer solid electrolyte film) CH2=CH-Coo(-CzH40fCOCH=C)
12/g.

Propylene carbonate tg%Liα04/, tg
10 mg of azoisobutyronitrile was dissolved in acetone, cast on a Theon plate, and then polymerized for tθ001 hour to obtain a polymer solid electrolyte film.

(The electrical conductivity obtained by the Co1e-Cole plot method is 3 × 1
Ivy at 0-38/cm2. ) Continuous charge/discharge test/The obtained laminated material with lithium silt 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, and the Average Volta after 100 cycles or 10 cycles.
ge was measured at 20'C and -2!0C and is shown in Table/.

Continuous charge/discharge test 2 Obtained plate (dipped in 20% Liα04 acetonitrile-propylene carbonate solution (acetonitrile/propylene carbonate = 0/20) and then dried), separator (polypropylene) impregnated with propylene carbonate, and lithium The sheets were stacked, 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 Figure 2. Continuous charging and discharging tests were performed using this battery as a secondary battery, and the average voltage was measured at λθ0C after IO cycles. Table 2
It was shown to.

Table Comparison Compound 1 did not exhibit any function as a Vi battery. Table/Compounds of the present invention/,! ,7,/r,so and comparison compound/,ko,φ,! and compounds of the present invention, 2, 1
! Compare with Compound 3,! The comparison revealed that the compound of the present invention has excellent mechanical strength without impairing conductivity, has low interfacial resistance of the laminated material, and has excellent charge and discharge characteristics as a secondary battery material.

Further, among the compounds of the present invention, those having an ethylenic repeating unit having an oxyalkylene group repeating unit in the side chain and an ethylenic repeating unit having an anionic group in the side chain (compounds !, 7, ?, 20) It has become clear that this material has particularly excellent properties.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing the structure of a secondary battery produced in the continuous charge/discharge test of the present invention. FIG. 2 is a cross-sectional view showing the configuration of a secondary battery produced by the continuous charge/discharge tester of the present invention.

Claims (4)

[Claims] (1) At least an ethylenic repeating unit that has an electron-conductive moiety in its side chain as a repeating unit consisting of at least one of an aniline compound or a heterocyclic compound, and an ethylenic repeating unit that has a repeating unit of an oxyalkylene group in its side chain. An electronically conductive polymer characterized by having. (2) The electronically conductive polymer according to claim (1), further comprising an ethylenic repeating unit having an anionic group in a side chain. (3) A conductive material comprising a laminate of the electron conductive polymer according to claim (1) or (2) and a solid polymer electrolyte. (4) A conductive material comprising a laminate of the electron conductive polymer according to claim (1) or (2) and a separator.