CA2217378A1 - Method for producing soluble conductive polymer having acidic group - Google Patents
Method for producing soluble conductive polymer having acidic group Download PDFInfo
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- CA2217378A1 CA2217378A1 CA002217378A CA2217378A CA2217378A1 CA 2217378 A1 CA2217378 A1 CA 2217378A1 CA 002217378 A CA002217378 A CA 002217378A CA 2217378 A CA2217378 A CA 2217378A CA 2217378 A1 CA2217378 A1 CA 2217378A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G85/00—General processes for preparing compounds provided for in this subclass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
Abstract
A method for producing a soluble conductive polymer having acidic groups, which comprises subjecting to electrolytic polymerization (a) at least one compound selected from the group consisting of acidic group-substituted anilines, acidic group-substituted pyrroles, acidic group-substituted thiophenes, acidic group-substituted furans, acidic group-substituted selenophenes, acidic group-substituted tellurophenes, acidic group-substituted isothianaphthenes, acidic group-substituted isobenzofurans, acidic group-substituted isoindolines, acidic group-substituted isobenzoselenophenes, acidic group-substituted isobenzotellurophenes, and their metal salts, ammonium salts and substituted ammonium salts in a solution containing (b) a basic compound.
Description
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to a method for produc-ing a soluble conductive polymer which is soluble in a solvent.
A solution comprising this soluble conductive polymer as the main component can be used for forming a conductor by a simple method such as a spray coating method, a dip coating method, a roll coating method, a gravure coating method, a reverse roll coating method, an air-knife coating method, a curtain coating method or the like on various substrates. The above solution can also be used in admixture with a suitable binder polymer for increasing the adhesiveness of a conductive film and the strength of a coating film.
As the substrate to be coated, there are men-tioned various plastics, for example, polyester resins such as polyethylene terephthalate (PET), polyethylene-naphthalate (PEN) and the like, polyethylene, polypropyl-ene, polyvinyl chloride, nylon, polystyrene, polycarbo-nate, epoxy resins, fluoroplastics, polysulfone, polyim-ide, silicone resins, polyurethane, phenol resins, and the like; molded articles and films of these plastics such as synthetic papers and the like; paper; iron;
aluminum; copper; zinc; nickel; stainless steel; and the like. The coating step may be conducted in the course of the production of these substrates, for example, before or during a monoaxial stretching step, a biaxial stretch-ing step, a molding step, an embossing step or the like, or can be applied to a substrate which has been subjected to these treatment.
Moreover, a composition comprising the above soluble conductive polymer as the main component can be applied to various antistatic agents, condensers, bat-teries, EMI shields, chemical sensors, display devices,nonlinear molding materials, anticorrosive agents, adhe-sives, fibers, antistatic coating compositions, electro-coating compositions, plating primer, electrostatic coat-ing primer, electric prevention for corrosion, enhance-ment of the storing capacity of battery and the like.In addition, the above polymer is excellent in applica-bility to various antistatic uses because it has no mois-ture-dependency of conductivity, has a high transparency and can be subjected to stretching, molding, embossing and the like.
The application of the soluble conductive polymer to antistatic uses includes packaging materials, magnetic cards, magnetic tapes, magnetic discs, photo-graphic films, printing substrates, heat seal tapes and films, IC trays, IC carrier tapes, cover tapes and the like.
Description of the Related Art Doped polyaniline has been well known as a soluble conductive polymer; however, it is insoluble in almost all general solvents except some nonprotonic polar solvents and hence has a difficulty in molding.
Moreover, though a process for producing a polyaniline by electrolytic oxidation polymerization [JP-A-60-235,831 and J. Polymer Sci. Polymer Chem. Ed., 26, 1531 (1988)] can form a film of polyaniline on an elec-trode, but has such a problem that its isolation opera-tion becomes complicated and its mass production is dif-ficult.
Proposals have recently been made for an alka-li-soluble sulfonated polyaniline which develops conduc-tivity without adding a doping agent and its synthesis method and for a carboxylated polyaniline and its synthe-sis method.
As a method for the synthesis of a sulfonatedpolyaniline, there are known, for example, a method for the synthesis of a sulfonated polyaniline by electrochem-ically polymerizing aniline and m-aminobenzenesulfonic acid (Journal of The Chemical Society of Japan, 1985, 1124 and JA-A-2-166,165), a method for the synthesis of a sulfonated polyaniline by electrochemically polymerizing an o-, m- or p-aminobenzenesulfonic acid alone [Lecture Preprint II in the 64th Autumn Annual Convention of The Chemical Society of Japan, 706 (1992)], a method for the synthesis of a sulfonated polyaniline by chemically polymerizing aniline and an o- or m-aminobenzenesulfonic acid (JP-A-1-301,714), a method for the chemical oxida-tion polymerization of an aminobenzenesulfonic acid com-pound or monomers comprising an aminobenzenesulfonic acid compound and an aniline compound (JP-A-6-56,987), a meth-od for the sulfonation with conc. sulfuric acid of an emeraldine type polymer (polyaniline) obtained by chemi-cal or electrochemical polymerization (JP-A-58-210,902), a method for the sulfonation with sulfuric anhyd-ride/triethyl phosphate complex (JP-A-61-197,633), a method for the sulfonation with fuming sulfuric acid [J.
Am. Chem. Soc., (1991) 113, 2665-2671, J. Am. Chem. Soc., (1990) 112, 2800 and W091-06887], a method for the syn-thesis of a sulfonated polyaniline of the N-substitution type by chemically polymerizing diphenylamine-4-sulfonic acid (sodium salt) [Polymer, (1993) 34, 158-162] and the like.
In J. Am. Chem. Soc., (1991) 113, 2665-2671, it is reported that the chemical and electrochemical polymerization of o- or m-aminobenzenesulfonic acid was tried but was not successful.
Furthermore, JP-A-6-56,987 states that when an aminobenzenesulfonic acid compound is or an aminobenzene-sulfonic acid compound and an aniline compound are sub-jected to chemical oxidative polymerization in all of the acidic, neutral and alkaline solutions, a soluble conduc-tive polymer which is soluble in water is obtained, and shows polymerization examples in sulfuric acid-acidic solution. However, in said publication, there is no statement of the molecular weight and other physical properties of the polymer, and hence, it is not clear what physical properties the polymer has. According to the present inventors' duplication, no polymer having a sufficiently large molecular weight for forming a film was able to be obtained. Moreover, when the present inventors have tried polymerization in an aqueous solu-tion containing a protonic acid using sodium peroxodisul-fate as an oxidizing agent, a polymer soluble in water was obtained but the molecular weight of the polymer was low and no practicably usable polymer for forming a film was able to be obtained.
Furthermore, the present inventors have dupli-cated the method for chemically polymerizing aniline and m-aminobenzenesulfonic acid with ammonium peroxodisulfate stated in JP-A-1-301,714 and the method for chemically polymerizing aniline and m-aminobenzenesulfonic acid with potassium permanganate stated in JP-A-6-56,987, to find that the sulfonic acid group has been introduced only in a proportion of about one sulfonic acid group per 5 aro-matic rings in the polymer, and the polymer exhibitedhigh conductivity but was completely insoluble in neutral or acidic water and substantially insoluble in an alka-line aqueous solution such as ammonia water. Moreover, when the sulfonation has been effected according to the method of JP-A-1-97,633, the solubility of the polyanil-ine in the sulfonation solvent has not been sufficient and the sulfonation reaction has proceeded in the disper-sion state of the polymer, so that the sulfonic acid group has been introduced only in a proportion of about 1 group per 5 aromatic rings as described on page 7 of the same publication. The thus obtained sulfonated polyani-line in which the proportion of the sulfonic acid group introduced is small has such a problem that the conduc-tivity and solubility are not sufficient.
In addition, J. Am. Chem. Soc., 113, 2665-2671 (1991) and J. Am. Chem. Soc., 112, 2800 (1990) state that when polyaniline is sulfonated with fuming sulfuric acid, the sulfonic acid group is introduced in a proportion of about one sulfonic acid group per two aromatic rings.
However, when the polyaniline has been tried to be suffi-ciently sulfonated according to the above-mentioned method, a large excess of fuming sulfuric acid has become necessary because the solubility of the polyaniline in fuming sulfuric acid has not been sufficient. Moreover, there is also such a problem that when the polyaniline is added to fuming sulfuric acid, the polymer is easy to solidify. In addition, there is such a problem that the polymer synthesized by the above-mentioned method and its sulfonated product are dissolved in an aqueous solution containing a base such as ammonia, an alkylamine or the like but not dissolved in water alone.
Also, Polymer, 34, 158-162 (1993) describes that when diphenylamine-4-sulfonic acid (sodium salt) is polymerized, an N-position-substituted type sulfonated polyaniline in which the benzenesulfonic acid group has been introduced in a proportion of one group per aniline skeleton is obtained, and this is dissolved in water alone, but ultracentrifugal operation is required for the isolation of the polymer. According to the present inventors' duplication, the yield of the polymer taken out of the polymerization solvent has been low because of the high solubility of the polymer in the solvent, and when no high speed centrifugal operation has been effect-ed, it has been impossible to isolate the polymer.
Furthermore, since the polymer is of an N-position-sub-stituted type, it has been lower in conductivity than thepolymer synthesized by the method of J. Am. Chem. Soc., 113, 2665-2671 (1991).
As a method for the synthesis of a carboxylat-ed polyaniline, JP-A-4-268,331 proposes, for example, a production method in which 2- or 3-carboxyl group-substi-tuted aniline or its salt is subjected to oxidative poly-merization and then treated with a basic material to obtain a product in which the carboxyl group is in the form of a salt; however, the amount of the oxidizing agent used is required to be at least 2 equivalents per equivalent of the starting material and the electrical conductivity is low. From this fact, it is considered that the reactivity of monomer be low and a low molecular weight polymer have been produced.
JP-A-5-226,238 proposes a synthesis method in which methyl anthranilate (methyl ester of anthranilic acid) is polymerized in the presence of ammonium peroxo-disulfate in an aqueous acidic medium and thereafter the methyl ester is saponified with alcoholic potassium hy-droxide. However, since the reaction is effected two steps, the operation is very much complicated.
Further, the present inventors have tried to polymerize 2-carboxyl group-substituted aniline in an aqueous solution containing a protonic acid using ammoni-um peroxodisulfate as an oxidizing agent, but have not been able to obtain any product. They have also tried to polymerize aniline and a 2-carboxyl group-substituted aniline in an aqueous solution containing a protonic acid using ammonium peroxodisulfate as an oxidizing agent.
However, a copolymer has been obtained, but the solubili-ty and conductive thereof have been low. From this fact, it is considered that the copolymerization ratio of 2-carboxyl group-substituted aniline be low in the copoly-mer obtained.
When the moldability including film-formabili-ty by coating and the like are taken into consideration, particularly in order to make the polymer coatable on both hydrophilic and hydrophobic substrates, it is desir-ed that the polymer is soluble in both water and organic solvent. However, the sulfonation product of polyaniline is soluble in alkaline aqueous solutions but insoluble in neutral to acidic aqueous solutions, and it cannot be said that the solubility in an organic solvent is suf-ficient.
As a method for solving these various prob-lems, the present inventors have considered that in order to allow a polymer to exhibit conductivity without adding a doping agent and allow its solubility to be enhanced, it is necessary to introduce more acidic groups such as sulfonic acid groups or carboxyl groups into the main chain aromatic ring, and have proposed a process for producing a sulfonation product of an aniline copolymer by copolymerizing at least one compound selected from the group consisting of aniline, N-alkylanilines and phenylenediamines with aminobenzenesulfonic acid using an oxidizing agent in an acidic solvent and further sulfo-nating the resulting copolymer with a sulfonating agent (JP-A-5-178,989). However, the above process has had a problem of treatment of wasted acid because the sulfona-tion operation is effected in conc. sulfuric acid.
Incidentally, the copolymers synthesized are all inferred to have the structures represented by the general formula (7):
R' )x ~ ~ ~ )1- x R11 R12 R13 R14 n wherein each of R11 to R14 is a group selected from the group consisting of hydrogen and sulfonic acid group; R' is a group selected from the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms; the number of the sulfonic acid group is 40 to 80% of the number of the aromatic ring; x represents any number of 0 to 1 and n is a numeral of 2 to 1,500 showing the degree of poly-merization.
In addition, the present inventors have pro-posed a process for producing an aniline copolymer, char-acterized by copolymerizing at least one compound selec-ted from the group consisting of aniline, N-alkylanilines and phenylenediamines with an alkoxy group-substituted aminobenzenesulfonic acid. thereby omitting the sulfona-tion operation which causes a large amount of waste (JP-A-6-293,828). Incidentally, the copolymers synthesized are all inferred to have the structures represented by the general formula (8):
R /~
Rls R16 R17 R18 R19 R20 R21 R22 n wherein each of R15 to R22 is a group selected form the group consisting of hydrogen, alkoxy groups and sulfonic acid group; the number of the sulfonic acid group is 25 to 50~ of the number of the aromatic ring; the alkoxy group and the sulfonic acid group are contained in one and the same aromatic ring; R' is a group selected from the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms; x represents any number of 0 to 1 and n is a numeral of 2 to 1,500 which shows the degree of polymerization.
Furthermore, the present inventors have pro-posed a process for producing a soluble conductive poly-mer of the soluble aniline type by polymerizing an acidic group-substituted aniline such as a sulfonic acid group-substituted aniline, a carboxyl group-substituted aniline or the like in a solution containing a basic compound (JP-A-7-196,791 and JP-A-7-324,132). According to this process, contrary to the conventional established theory that it is difficult to polymerize alone anilines having sulfonic acid groups or carboxyl groups, it is possible to produce a high molecular weight polymer. In addition, the soluble conductive polymer obtained exhibits a high conductivity and also exhibits an excellent dissolvabili-ty in both acidic and alkaline aqueous solutions. How-ever, when the soluble conductive polymer is separated from the by-product salt of the oxidizing agent used in the oxidative polymerization, the operation thereof has not been easy on a commercial scale because the dissolv-ability of the soluble conductive polymer per se is very excellent. Incidentally, the copolymers synthesized by the above-mentioned processes are inferred to have the structures represented by the general formula (9):
H
~ ~ X ~ ~ 1 - X
A1 B1 A2 B2 A3 B3 A4 B4 n wherein each of A1 to A4 is a group selected from the group consisting of sulfonic group, carboxyl group and their alkali metal salts, ammonium salts and substituted ammonium salts; each of B1 to B4 is a group selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 4 carbon atoms;
straight chain or branched chain alkoxy groups having 1 to 4 carbon atoms, acidic groups, hydroxyl group, nitro group and halogen groups; x represents any number of O to 1; and n represents a numeral of 2 to 5,000 which shows the degree of polymerization.
On the other hand, there have been reported a process for synthesizing a sulfonated polyaniline by electrochemically polymerizing aniline and m-aminoben-zenesulfonic acid (Journal of The Chemical Society ofJapan, 1985, 1124 and JP-A-02-166,165) and a process for electrochemically polymerizing aminobenzenesulfonic acid [Preprint II of the 64th Autumn Annual Convention of The Chemical Society of Japan, 706 (1992)]. However, in these processes, an inorganic salt is added as an elec-trolyte, and hence, there is such a problem that the operation for separating the soluble conductive polymer from the electrolyte after the polymerization is compli-cated and the application of the processes to the mass production on a commercial scale is very difficult.
SUMMARY OF THE INVENTION
The object of this invention is to provide a soluble conductive polymer having a high molecular weight and having a high conductivity and solubility and also provide an industrially useful method for producing the same.
The present inventors have eagerly made re-search on a method for producing an acidic group-substi-tuted polyaniline in which the proportion of the acidic group introduced to the aromatic ring is large, such as a sulfonated polyaniline in which the proportion of the sulfonic acid group introduced to the aromatic ring is large, a carboxylated polyaniline in which the proportion of the carboxyl group introduced to the aromatic ring is large, or the like as a polyaniline having a high conduc-tivity and solubility, and have consequently found that when an acidic group-substituted aniline such as a sul-fonic acid group-substituted aniline, a carboxyl group-substituted aniline or the like is or this acidic group-substituted aniline and an aniline derivative are sub-jected as a monomer or monomers to electrolytic oxidation polymerization in a solution containing a basic compound, there is obtained a soluble conductive polymer having a high conductivity, a high solubility and a high molecular weight which has not been obtained by chemical oxidation polymerization.
In addition, the above monomers and polymer act as electrolytes and hence the electrolytes that have been necessary in the conventional electrolytic oxidation polymerization become unnecessary and hence the operation for separating the electrolytes from the soluble conduc-tive polymer can be omitted. Accordingly, the polymer-ization mixture per se can be used as a commercial arti-cle such as a coating agent or the like, and hence, theabove production method is industrially advantageous.
Furthermore, since the polymer formed by the polymerization is soluble in the reaction mixture, the mass production of a polymer on a commercial scale by polymerization in a continuous electrolysis system such as a flow through system or the like is possible. The flow through system is a system in which polymerization is conducted by circulating the reaction mixture to the cell between the acting electrode and the negative elec-trode by means of a liquid-transporting pump, and it is made possible to carry out the polymerization reaction under the optimum conditions by connecting the cells in series or in parallel. Moreover, the present inventors have found that the knowledge of the electrolytic poly-merization with regard to these acidic group-substituted anilines can also be applied in quite the same manner to acidic group-substituted pyrroles, thiophenes, furans, selenophenes, tellurophenes, isothianaphthenes, isoben-zofurans, isoindolines, isobenzoselenophenes and iso-benzotellurophenes. This invention has been achieved based on the above-mentioned knowledge.
That is to say, this invention relates to a method for producing a soluble conductive polymer having an acidic group which comprises subjecting to electro-lytic polymerization (a) at least one compound selected from the group consisting of acidic group-substituted anilines, acidic group-substituted pyrroles, acidic group-substituted thiophenes, acidic group-substituted furans, acidic group-substituted selenophenes, acidic group-substituted tellurophenes, acidic group-substituted isothianaphthenes, acidic group-substituted isobenzo-furans, acidic group-substituted isoindolines, acidic group-substituted isobenzoselenophenes, acidic group-substituted isobenzotellurophenes, and their metal salts, ammonium salts and substituted ammonium salts in a solu-tion containing (b) a basic compound.
The other embodiment of this invention relates to a method for producing a soluble conductive polymer having an acidic group which comprises subjecting to electrolytic polymerization (a) at least one compound selected from the group consisting of acidic group-sub-stituted anilines, acidic group-substituted pyrroles, acidic group-substituted thiophenes, acidic group-substi-tuted furans, acidic group-substituted selenophenes, acidic group-substituted tellurophenes, acidic group-substituted isothianaphthenes, acidic group-substituted isobenzofurans, acidic group-substituted isoindolines, acidic group-substituted isobenzoselenophenes, acidic group-substituted isobenzotellurophenes, and their metal salts, ammonium salts and substituted ammonium salts and (c) at least one compound selected from the group con-sisting of aniline derivatives, pyrrole derivatives, thiophene derivatives, furan derivatives, selenophene derivatives, tellurophene derivatives, isothianaphthene derivatives, isobenzofuran derivatives, isoindoline de-rivatives, isobenzoselenophene derivatives and isobenzo-tellurophene derivatives in a solution containing (b) a basic compound.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is an IR spectrum of the polymer in Example 1.
Fig. 2 is a GPC chart of the polymer in Exam-ple 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
An acidic group-substituted aniline polymer which is the most preferable example of this invention is used as an example below to explain this invention in more detail. However, this applies quite similarly to the cases of acidic group-substituted pyrroles, thio-phenes, furans, selenophenes, tellurophenes, isothia-naphthenes, isobenzofurans, isoindolines, isobenzosele-nophenes and isobenzotellurophenes.
The above-mentioned acidic group-substituted aniline represents at least one compound selected from - the group consisting of acidic group-substituted anilines represented by the general formula (1) and their metal salts, ammonium salts and substituted ammonium salts:
Rl R2 >=( H2N - ~ ) R3 (1) Rs R4 wherein R1, R2, R3, R4 and Rs are substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, acidic groups, hydroxyl group, nitro group and halogen groups and at least one of R1 to Rs represents an acidic group, the above acidic group mean-ing a sulfonic acid group or a carboxyl group. When the acidic group is bonded to the compound of the above gen-eral formula (1) in the o- or m-position to the amino group, the polymer obtained is superior in performance such as conductivity, solubility and the like.
As the above acidic group-substituted ani-lines, most typical are sulfonic acid group-substituted anilines and carboxyl group-substituted anilines. The sulfonic acid group-substituted anilines are preferably used and the conductivity of the polymer obtained tends to be higher than when the carboxyl group-substituted anilines are used.
The most typical sulfonic acid group-substi-tuted anilines are aminobenzenesulfonic acids, and spe-cifically, there are preferably used o-, m- and p-aminobenzenesulfonic acids, aniline-2,6-disulfonic acid, aniline-2,5-disulfonic acid, aniline-3,5-disulfonic acid, aniline-2,4-disulfonic acid and aniline-3,4-disulfonic acid.
As other sulfonic acid group-substituted ani-lines, there can be mentioned alkyl group-substituted aminobenzenesulfonic acids such as methylaminobenzenesul-fonic acid, ethylaminobenzenesulfonic acid, n-propyl-aminobenzenesulfonic acid, isopropylaminobenzenesulfonicacid, n-butylaminobenzenesulfonic acid, sec-butylamino-benzenesulfonic acid, t-butylaminobenzenesulfonic acid and the like; alkoxy group-substituted aminobenzenesulfo-nic acids such as methoxyaminobenzenesulfonic acid, etho-xyaminobenzenesulfonic acid, n-propoxyaminobenzenesulfo-nic acid, isopropoxyaminobenzenesulfonic acid, n-butoxy-aminobenzenesulfonic acid, sec-butoxyaminobenzenesulfonic acid, t-butoxyaminobenzenesulfonic acid and the like:
hydroxy group-substituted aminobenzenesulfonic acids;
nitro group-substituted aminobenzenesulfonic acids; halo-gen group-substituted aminobenzenesulfonic acids such as fluoroaminobenzenesulfonic acid, chloroaminobenzenesul-fonic acid, bromoaminobenzenesulfonic acid and the like;
etc. Among them, alkyl group-substituted aminobenzenesu-lfonic acids, alkoxy group-substituted aminobenzenesul-fonic acids and hydroxyl group-substituted aminobenzene-sulfonic acids are most preferable in practical use.
Incidentally, these sulfonic acid group-substituted ani-lines may be used alone or in admixture with any propor-tion of their isomers.
The most typical carboxyl group-substituted anilines are aminobenzenecarboxylic acids, and specifi-cally, there are preferably used o-, m- and p-aminoben-zenecarboxylic acids, aniline-2,6-dicarboxylic acid, aniline-2,5-dicarboxylic acid, aniline-3,5-dicarboxylic acid, aniline-2,4-dicarboxylic acid and aniline-3,4-di-carboxylic acid.
As other carboxyl group-substituted anilines, there can be mentioned alkyl group-substituted amino-benzenecarboxylic acids such as methylaminobenzenecarbox-ylic acid, ethylaminobenzenecarboxylic acid, n-propylami-nobenzenecarboxylic acid, isopropylaminobenzenecarboxylic acid, n-butylaminobenzenecarboxylic acid, sec-butylamino-benzenecarboxylic acid, t-butylaminobenzenecarboxylic acid and the like; alkoxy group-substituted aminobenzene-carboxylic acids such as methoxyaminobenzenecarboxylic acid, ethoxyaminobenzenecarboxylic acid, n-propoxyamino-benzenecarboxylic acid, isopropoxyaminobenzenecarboxylicacid, n-butoxyaminobenzenecarboxylic acid, sec-butoxy-aminobenzenecarboxylic acid, t-butoxyaminobenzenecarbox-ylic acid and the like; hydroxy group-substituted amino-benzenecarboxylic acids; nitro group-substituted amino-benzenecarboxylic acids, halogen group-substituted amino-benzenecarboxylic acids such as fluoroaminobenzenecarbox-ylic acid, chloroaminobenzenecarboxylic acid, bromoamino-benzenecarboxylic acid and the like; etc. Among them,alkyl group-substituted aminobenzenecarboxylic acids, alkoxy group-substituted aminobenzenecarboxylic acids and hydroxy group-substituted aminobenzenecarboxylic acids are most preferable in practical use. These carboxyl group-substituted anilines may be used alone or in admix-ture with any proportion of their isomers.
Specific examples of the acidic group-substi-tuted anilines of the general formula (l) include sulfon-ic acid group-substituted alkylanilines, carboxyl group-substituted alkylanilines, sulfonic acid group-substitut-ed alkoxyanilines, carboxyl group-substituted alkoxyani-lines, sulfonic acid group-substituted hydroxyanilines, carboxyl group-substituted hydroxyanilines, sulfonic acid group-substituted nitroanilines, carboxyl group-substi-tuted nitroanilines, sulfonic acid group-substituted flu-oroanilines, carboxyl group-substituted fluoroanilines, sulfonic acid group-substituted chloroanilines, carboxyl group-substituted chloroanilines, sulfonic acid group-substituted bromoanilines, carboxyl group-substituted bromoanilines and the like. Specific examples of the positions of these substituents and the combinations of the substituents are shown in Table 1.
Table 1 Rl R2 R3 R4 Rs A B H H H
A H B H H
A H H B H
A H H H B
H A B H H
H A H B H
H A H H B
B A H H H
H H A B H
H H A H B
B H A H H
H B A H H
H H H A B
H H B A H
H B H A H
B H H A H
H H H B A
H H B H A
H B H H A
B H H H A
In Table 1, A means at least one group selected from the group consisting of sulfonic acid group, carboxyl group and their alkali metal salts, ammonium salts and substi-tuted ammonium salts; B means at least one group selected from the group consisting of alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group and the like;
alkoxy groups such as methoxy group, ethoxy group, n-pro-poxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group and the like; hydroxyl group; nitro group; fluoro group; halogen groups such as fluoro group, chloro group, bromo group and the like; and H means hy-drogen.
The metals which form salts of these monomers include lithium, sodium, potassium and the like.
The substituted ammoniums include acyclic ammoniums, cyclic saturated ammoniums, cyclic unsaturated ammoniums and the like.
The above acyclic ammoniums include compounds represented by the general formula (10):
R24- 1 -R26 ( 10 ) wherein each of R23 to R26 is a group independently se-lected from the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms. There can be men-tioned, for example, methylammonium, dimethylammonium, trimethylammonium, ethylammonium, diethylammonium, triethylammonium, methylethylammonium, diethylmethylammonium, dimethylethylammonium, propylammonium, dipropylammonium, isopropylammonium, diisopropylammonium, butylammonium, dibutylammonium, methylpropylammonium, ethylpropylammonium, methylisopro-pylammonium, ethylisopropylammonium, methylbutylammonium, ethylbutylammonium, tetramethylammonium, tetramethylolam-monium, tetraethylammonium, tetra-n-butylammonium, tetra-sec-butylammonium, tetra-t-butylammonium and the like.
Among them, the case where one of R23 to R26 is hydrogen and the other three are alkyl groups having 1 to 4 carbon atoms is most preferable, and the case where two of R23 to R26 are hydrogens and the other two are alkyl groups having 1 to 4 carbon atoms are more preferable.
As the cyclic saturated ammoniums, there are mentioned piperidinium, pyrrolidinium, morpholinium, piperazinium and derivatives having these skeletons and the like.
As the cyclic unsaturated ammoniums, there are mentioned pyridinium, a-picolinium, ~-picolinium, ~-pico-linium, quinolinium, isoquinolinium, pyrrolinium and derivatives having these skeletons and the like.
The basic compound (b) used in this invention may be any compound as far as it is a compound forming salts with the above-mentioned acidic group-substituted anilines, and there are preferably used ammonia, acyclic amines, cyclic saturated amines, cyclic unsaturated amin-es, inorganic bases and the like. In particular, acyclic amines, cyclic saturated amines and cyclic unsaturated amines and the like are preferred.
The acyclic amines include compounds repre-sented by the general formula (11):
R28- 1 ( 11 ) Rz9 wherein each of R27 to R29 is a group selected indepen-dently from the group consisting of alkyl groups having 1 to 4 carbon atoms; and hydroxide compounds represented by the general formula ( 12):
Rl30 R3~ -R33-OH- ( 12) wherein each of R30 to R33 is a group selected indepen-dently from the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms.
As the cyclic saturated amines, there are preferably used piperidine, pyrrolidine, morpholine, piperazine, derivatives having these skeletons, ammonium hydroxy compounds of them and the like.
As the cyclic unsaturated amines, there are preferably used pyridine, a-picoline, ~-picoline, y-pico-line, quinoline, isoquinoline, pyrroline, derivatives having these skeletons, ammonium hydroxy compounds of them and the like.
As the inorganic base, hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are preferably used; however, the conductiv-ity of the polymer obtained tends to be inferior as com-pared with the above-mentioned acyclic amines, cyclic saturated amines and cyclic unsaturated amines.
The concentration of these basic compounds (b) is selected in the range of at least 0.1 mole/liter, preferably 0.1 to 10.0 moles/liter and more preferably 0.2 to 8.0 moles/liter. When the concentration is less than 0.1 mole/liter, the yield of the polymer obtained is decreased and when the concentration is more than 10.0 moles/liter, the conductivity shows a tendency to reduce.
The above basic compound (b) can be used in admixture of two or more in any proportion.
The aniline derivative (c) includes compounds represented by the general formula ( 4):
H2N F~ R8 ( ) Rlo Rg wherein R6 to Rlo represent substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, hydroxyl group, nitro group and halogen groups.
As the above-mentioned aniline derivative (c), aniline is most typical, and in addition to the same, there can be mentioned alkylanilines such as methylani-line, ethylaniline, n-propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline, t-butylaniline and the like; alkoxyanilines such as methoxyaniline, ethoxyani-line, n-propoxyaniline, isopropoxyaniline, n-butoxyani-line, sec-butoxyaniline, t-butoxyaniline and the like;
hydroxyaniline; nitroaniline; halogenoanilines such as fluoroaniline, chloroaniline, bromoaniline and the like.
The co-existence of the aniline derivative (c) exhibits an effective action to improve the conductivity, film-forming properties and the like of the conductive polymer obtained.
The weight ratio between the compound (a) in-cluding the above acidic group-substituted anilines and the like and the basic compound (b) is such that (a) :
(b) = 1 : 100 - 100 : 1, preferably 10 : 90 - 90 : 10.
Here, when the proportion of the basic compound is low, the reactivity is lowered and the conductivity is also lowered. On the contrary, when the proportion of the basic compound is high, the proportion of the acidic group of the polymer obtained forming a salt with the basic compound becomes high and the conductivity tends to be lowered.
The weight ratio between the compound (a) in-cluding the above-mentioned acidic group-substituted anilines and the like plus the aniline derivative (c) and the basic compound (b) is such that [(a) + (c)] : (b) = 1 : 100 - 100 : 1, preferably 10 : 90 - 90 : 10. Here, when the proportion of the basic compound is low, the reactivity is lowered and the conductivity is also low-ered. On the contrary, the proportion of the basic compound is high, the proportion of the acidic group of the polymer obtained forming a salt with the basic com-pound becomes high and the conductivity tends to be low-ered.
The molar proportion between the compound (a) including the above-mentioned acidic group-substituted anilines and the like and the aniline derivative (c) is in such a range that (a) : (c) = 100 : 0 - 30 : 70, pref-erably 99.999 : 0.001 - 50 : 50, more preferably 99.999 :
0.001 - 70 : 30. Here, the proportion of the aniline derivative is high (exceeding 70), the sulfonic acid group content in the polymer obtained is not sufficient and the solubility tends to be lowered.
The molar ratio between the acidic group (d) in the compound (a) including the above-mentioned acidic group-substituted anilines and the like and the basic compound (b) is such that (d) : (b) = 1 : 100 - 100 : 1, preferably 1 : 0.25 - 1 : 20, more preferably 1 : 0.5 - 1 : 15. Here, when the proportion of the basic compound is low, the reactivity is lowered and the conductivity is also lowered. On the contrary, when the proportion of the basic compound is high, the proportion of the acidic group of the polymer obtained forming a salt with the basic compound becomes high and the conductivity tends to be lowered.
The concentration of the compound (a) includ-ing the a acidic group-substituted anilines and the like and the concentration of the aniline derivatives (c) at the time of the electrolytic polymerization are at least 0.1~ by weight, preferably 0.5 to 50~ by weight and more preferably 1 to 30~ by weight, based on the weight of the solvent.
The polymerization or copolymerization is con-ducted by electrolytic oxidation polymerization in asolution containing the above basic compound. As the solvent, there are preferably used water, methanol, etha-nol, isopropanol, acetonitrile, methyl isobutyl ketone, methyl ethyl ketone, dimethylformamide, dimethylacetamide and the like.
As the electrode material in the electrolytic oxidation polymerization, there can be used metal plates and net electrodes of gold, silver, platinum, nickel, mercury, stainless steel, copper, zinc, tin, lead, iron, aluminum, titanium, ruthenium, iridium, oxides of them and the like; carbon electrodes such as glassy carbon and the like; glass electrodes to which a metal oxide such as IT0 glass, tin-indium oxide, tin oxide or the like is im-parted; and the like, and among them, silver, platinum, titanium, glassy carbon and IT0 glass are preferable.
As the electrolysis method, there can be used any method of electrolysis at constant current, control-led potential electrolysis and electrolysis at constant CA 022l7378 l997-lO-Ol voltage. The current density at the time of the electro-lytic polymerization at constant current is in the range of from 5 to 200 mA/cm2, preferably from 10 to 200 mA/-cm2, and more preferably from 15 to 150 mA/cm2. As to the potential in the electrolytic polymerization at con-stant potential, it is advantageous to apply to the work-ing electrode a potential of not more than -0. 5 V, pref-erably -1 V to -10 V and more preferably -1 V to -7 V, in relation to the standard electrode.
If necessary, an electrolyte, for example, LiBF4; a salt of HBF4, HCl04, HCl, H2S04 or the like; or the like can be added. However, in this invention, the compound (a) including the acidic group-substituted ani-lines and the like per se or the polymer per se serves as an electrolyte, so that the polymerization can be con-ducted without these electrolytes.
The reaction temperature is preferably -15~ to 70~C, more preferably -5~ to 60~C. Here, when the reac-tion temperature is lower than -1 5~C or higher than 70~C, the conductivity tends to be lowered.
All or some of the hydrogens of sulfonic acid groups or carboxyl groups in the polymer produced by the method of this invention, may be any member selected independently from the group consisting of alkali metals, ammonium and substituted ammoniums. Accordingly, these selected members may be present as one species or even in admixture of some species in the polymer.
Specifically, when the polymerization is ef-fected in the presence of sodium hydroxide, almost all the hydrogen atoms in the sulfonic acid groups or carbox-yl groups in the isolated polymer are in the sodium salt form. Similarly, when the polymerization is effected in the presence of ammonia, almost all the hydrogen atoms in the sulfonic acid groups or carboxyl groups of the poly-mer are in the ammonium form, and when the polymerization is effected in the presence of trimethylamine, almost all the hydrogen atoms of the sulfonic acid groups or carbox-yl groups of the polymer are in the triethylammoniumform. When the polymerization is effected in the pres-ence of quinoline, almost all the hydrogen atoms of the sulfonic acid groups or carboxyl groups of the polymer are in the quinolinium form. Moreover, when the basic compounds are used in admixture, the polymer is obtained in the same mixture form. Specifically, when the poly-merization is effected in the presence of sodium hydrox-ide and ammonia, it follows that a part of the hydrogen atoms in the sulfonic acid groups or carboxyl groups in the isolated polymer have been replaced with sodium and the other part thereof with ammonium. Moreover, when the polymer obtained is treated with a solution in which both sodium hydroxide and ammonia are present, similarly to the above case, a part of the hydrogen atoms of the sulfonic acid groups or carboxyl groups of the polymer have been replaced with sodium and the other part thereof with ammonia.
As described above, the polymer in which a part of the acidic groups are in the salt form can be converted to that having free acidic groups by treating the former polymer in an acidic solution and then isolat-ing the same. As the acidic solution, there can be men-tioned hydrochloric acid, sulfuric acid, p-toluenesulfo-nic acid, nitric acid and the like. However, it is difficult to render all the acidic groups completely free even when the acid-substitution has been sufficiently effected.
The weight average molecular weight of the soluble conductive polymer having sulfonic acid groups or carboxyl groups on the aromatic rings thus obtained is at least 3,000, preferably 3,000 to 1,000,000 and more pref-erably 5,000 to 500,000. Moreover, the proportion of acidic group introduced into the aromatic ring is at least 50%, preferably at least 70%, and more preferably at least 80%. Here, when the proportion of the acidic group introduced is less than 50%, the dissolvability of the polymer in water tends to be small, and it becomes difficult to appply the polymer in industry.
This conductive polymer can be dissolved, without being further subjected to sulfonation operation, in simple water; water containing a base such as ammonia, an alkylamine or the like or a basic salt such as ammo-nium acetate, ammonium oxalate or the like; water con-taining an acid such as hydrochloric acid, sulfuric acid or the like; a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol or the like; or a mixture thereof.
Explaining in detail the dissolvability, the soluble conductive polymer having acidic groups in this invention has such properties that it is dissolved in a proportion of at least 1~ by weight in an aqueous alkali solution such as 0.1 mole/liter ammonia water, dissolved in a proportion of at least 1~ by weight in an acidic solution such as 0.1 mole/liter aqueous sulfuric acid or the like, also dissolved in a proportion of at least 1 by weight in a neutral aqueous solution such as water alone or the like, and, in addition, dissolved in a pro-portion of at least 1~ by weight in an organic solvent such as a 0.1 mole/liter alcoholic ammonia solution or the like.
Incidentally, the polymers and copolymers syn-thesized according to the above-mentioned methods are all inferred to have the structures represented by the gener-al formula (13):
R34 R3s R38 R39 R42 R43 R4s R47 t H ~ ~ ~) ) ~N ~ N- ~
R37 R3s R41 R40 R45 R44 R4s R48 n (13) wherein R34 to R49 represent groups selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, acidic groups, hydroxyl group, nitro group and halogen groups; the number of the acidic groups introduced is at least 50~ of the number of the aromatic ring wherein the acidic groups mean sulfonic acid groups or carboxyl groups; x represents any number of 0 to 1;
and n represents a numeral of 2 to 1,500 which shows the degree of polymerization.
This invention is explained below in more de-tail by Examples and Comparative Examples; however, thisinvention should not be construed to be limited to the Examples.
[Measurement method]
IR spectrum was measured using an equipment manufactured by Perkin Elmer (Model 1600).
In the measurement of molecular weight distri-bution and molecular weight, as two GPC columns for aque-ous solution, TSK-GEL G-5000PWKL and TSK-GEL G-3000PWXL
(both of Toso K.K.) were connected in series and used to effect GPC-measurement (polyethylene oxide-reduced). As the column, three kinds of columns for aqueous solution were connected in series and used. Also, as the eluting solution, a 0.2 mole/liter phosphorate buffer solution was used.
As to conductivity, a four-probe method was used for the measurement of conductivity and a two-probe method was used for the measurement of surface resis-tance.
Example 1 In 150 ml of a pyridine solution having a con-centration of 0.05 mole/liter was dissolved 4.06 g of 2-aminoanisole-4-sulfonic acid, and in this solution were immersed glassy carbon as a working electrode and plati-num as a negative electrode, after which a constant volt-age of 1.5 V was applied with stirring at room tempera-ture and electrolytic polymerization was conducted for one hour. Just after the starting of the electrolytic polymerization, polymerization reaction was caused on the surface of the polymerization electrode, and after 5 minutes, the colorless, transparent reaction mixture was changed to brown. After completion of the polymerization reaction, the deposition of polymer on the polymeriza-tion electrode and the like were not observed and the polymerization mixture was uniform. Moreover, the elu-tion of a metal component from the polymerization elec-trode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ~um, a flat surface and a surface resistance value of 2 x 105 Q/~.
The result of measurement of molecular weight showed that the number average molecular weight (Mn) was 20,000, the weight average molecular weight (Mw) was 22,000, the Z average molecular weight (Mz) was 24,000, the degree of dispersion Mw/Mn was 1.1 and Mz/Mw was 1.1.
The polymerization mixture obtained was con-centrated under reduced pressure to isolate a polymer and the solubility of the polymer was measured. The solu-bility was determined by adding the polymer little by little to 10 ml of water, 10 ml of a 0.1 mole/liter aque-ous sulfuric acid or 10 ml of a 0.1 mole/liter aqueous ammonia water and filtering the mixture when the polymer became undissolved.
The solubilities of the soluble conductive polymer synthesized in the present Example were:
Water : 250 mg/ml Sulfuric acid: 245 mg/ml Ammonia water: 260 mg/ml.
Moreover, the IR spectrum of the soluble con-ductive polymer mentioned above is shown in Fig. 1, and the GPC chart of the polymer is shown in Fig. 2.
The assignment of IR spectrum is as follows:
Sulfone group: Absorption in the vicinity of 1,120, 1,020 cm~l Skeleton of polymer: Absorption in the vicinity of 1,500 cm~
Example 2 In 150 ml of an a-picoline solution having a concentration of 0.05 mole/liter was dissolved 3.7 g of 2-aminobenzenesulfonic acid, and in this solution were immersed glassy carbon as a working electrode and plati-num as a negative electrode, after which a constant volt-age of 2.0 V was applied with stirring at room tempera-ture and electrolytic polymerization was conducted for 0.5 hour. After completion of the polymerization reac-tion, the deposition of polymer on the polymerization electrode and the like were not observed and the polymer-ization mixture was uniform. Also, the elution of a metal component from the polymerization electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 80~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 5 x 106 Q/L.
Example 3 In 150 ml of a triethylamine solution (water/-isopropanol = 1/1) having a concentration of 0.05 mole/-liter were dissolved 3.6 g of 2-aminobenzenesulfonic acid and 0.1 g of aniline, and in this solution were immersed an IT0 electrode as a working electrode and platinum as a negative electrode, after which a constant voltage of 2.0 V was applied with stirring at room temperature, and electrolytic polymerization was conducted for 0.5 hour.
After completion of the polymerization reaction, the deposition of polymer on the polymerization electrode and the like were not observed and the polymerization mixture was uniform. Also, the elution of a metal component from the polymerization electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 1 x 107 Q/~, Example 4 In 100 parts by weight of water were stirred 50 parts by weight of the polymer solution obtained in Example 1 and 100 parts by weight of an aqueous acrylic emulsion resin (NIKAZOL RX-301C, a trade name of NIPPON
CARBIDE INDUSTRIES CO., INC.) at room temperature to prepare a conductive rough product. The solution thus obtained was coated on a PET film by a gravure coater of 40 ,um in depth and dried at 120~C, to obtain a film having a thickness of 0.2 ,um, a flat surface and a sur-face resistance value of 1 x 107 Q/~.
Example 5 100 parts by weight of the polymer solution obtained in Example 1 and 5 parts by weight of polyvinyl alcohol as a cross-linking agent were stirred and dis-solved at room temperature to prepare a cross-linkable conductive composition. The solution thus obtained was coated on a PET film by a gravure coater of 40 ,um in depth and dried at 150~C, to obtain a film having a thickness of 0.8 ,um, a flat surface and a surface resis-tance value of 5 x 106 n/~. This conductive film was immersed in water and acetone; however, since the film had been cross-linked, dissolution, peeling and the like were not observed.
Example 6 In 100 parts by weight of water were dissolved with stirring 100 parts by weight of the polymer solution obtained in Example 1, 5 parts by weight of polyvinyl alcohol as a cross-linking agent and 100 parts by weight of an aqueous acrylic emulsion resin (NIKAZOL RX-301C, a trade name of NIPPON CARBIDE INDUSTRIES CO., INC.) at room temperature to prepare a cross-linkable conductive composition. The solution thus obtained was coated on a zinc-plated steel plate (20 mm x 50 mm x 1 mm) by a dip coating method and dried at 150~C, to form a conductive layer having a thickness of 0.5 ~m. This zinc-plated steel plate provided with a conductive layer (No. l), a chromium compound-coated zinc-plated steel plate (the coating thickness: 5-6 ~m) (No. 2) as a comparison and a zinc-plated steel plate (No. 3) as another comparison were sprayed with an aqueous sodium chloride solution at 40~C (in accordance with the JIS-K-5400 method) and subjected to an anticorrosion test.
The results obtained are shown in Table 2.
Table 2 Zinc-plated steel Coated layer Corrosion length plate No.
1 Conductive layer 1 mm 2 Chromium compound 5 mm 3 None 6 mm Example 7 In 30 ml of an aqueous ammonia solution having a concentration of 0.5 mole/liter was dissolved 3.0 g of 2-aminoanisole-4-sulfonic acid, and in this solution were immersed platinum as a working electrode and glassy car-bon as a negative electrode, after which a constant volt-age of 2.5 V was applied at room temperature with stir-ring, and electrolytic polymerization was conducted for12 hours. Just after the application of the constant voltage, polymerization reaction was caused on the work-ing electrode, and the reaction mixture which was ini-tially colorless and transparent was changed to blackish green after 5 minutes. After completion of the polymer-ization reaction, the deposition of polymer on the work-ing electrode, and the like were not observed and the polymerization mixture was uniformed. In addition, the elution of a metal component from the working electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ~m, a flat surface and a surface resistance value of 2 x 105 Q/C~
Example 8 In 30 ml of an aqueous ammonia solution having a concentration of 0.5 mole/liter was dissolved 3.0 g of 2-aminoanisole-4-sulfonic acid. In this solution were immersed platinum as a working electrode and glassy car-bon as a negative electrode, and a constant voltage of2.0 V was applied at room temperature while the solution was circulated to a series flow through cell by a pump, and electrolytic polymerization was conducted. Just after the application of the constant voltage, polymer-ization reaction was caused on the working electrode andthe reaction mixture which was initially colorless and transparent was changed to blackish green after 5 min-utes. After completion of the polymerization reaction, the deposition of polymer on the working electrode, and the like were not observed and the polymerization mixture was uniform. In addition, the elution of a metal compo-nent from the working electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 80~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 5 x 106 Q/C.
Example 9 In 20 ml of an aqueous diethylamine solution having a concentration of 0.5 mole/liter was dissolved 3.0 g of 2-aminoanisole-4-sulfonic acid, and in this solution were immersed platinum as a working electrode and glassy carbon as a negative electrode, after which a constant voltage of 2.5 V was applied without stirring at room temperature and electrolytic polymerization was conducted for 5 hours. Just after the application of the constant voltage, polymerization reaction was caused on the surface of the working electrode and, after 3 hours, a blackish green film-like polymer adhered to the working electrode. After completion of the polymerization reac-tion, the peeling, falling-off and the like of the poly-mer from the working electrode were not caused.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 1 x 107 Q/~.
Example lO
In 30 ml of an aqueous ammonia solution having a concentration of 0.5 mole/liter was dissolved 2.5 g of o-aminobenzoic acid, and in this solution were immersed platinum as a working electrode and glassy carbon as a negative electrode, after which a constant voltage of 3.0 V was applied without stirring at room temperature and electrolytic polymerization was condcuted for 5 hours.
Just after the application of the constant voltage, poly-merization reaction was caused and, after 3 hours, ablackish green film-like polymer adhered to the working electrode. After completion of the polymerization reac-tion, the peeling, falling-off and the like of the poly-mer from the working electrode were not caused.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 5 x 10 Q/L.
Example 11 In 30 ml of an aqueous ammonia water having a concentration of 0.5 mole/liter was dissolved 2. 5 g of o-aminobenzoic acid and in this solution were immersed platinum as a working electrode and glassy carbon as a negative electrode, after which a constant voltage of 3.0 V was applied at room temperature while the solution was circulated to a series flow through cell by means of a pump, and electrolytic polymerization was conducted.
Just after the application of the constant voltage, poly-merization reaction was caused on the surface of theworking electrode and, after 5 minutes, the reaction mixture which was initially colorless and transparent was changed to blackish green. After completion of the polymerization reaction, the deposition of polymer on the working electrode, and the like were not observed and the polymerization mixture was uniform. In addition, the elution of a metal component from the working electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 7 x 106 Q/0.
Example 12 In 30 ml of an aqueous ammonia water having a concentration of 0.5 mole/liter was dissolved 3.0 g of o-aminobenzenesulfonic acid and in this solution were im-mersed platinum as a working electrode and glassy carbon as a negative electrode, after which a constant voltage of 2.0 V was applied at room temperature while the solut-ion was circulated to a series flow through cell by means of a pump, and electrolytic polymerization was conducted.
Just after the application of the constant voltage, poly-merization reaction was caused on the surface of the working electrode and, after 5 minutes, the reaction mixture which was initially colorless and transparent was changed to blackish green. After completion of the polymerization reaction, the deposition of polymer on the working electrode, and the like were not observed and the CA 022l7378 l997-lO-Ol polymerization mixture was uniform. In addition, the elution of a metal component from the working electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 80~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 7 x 106 Q/G.
Example 13 In 20 ml of an aqueous pyridine solution having a concentration of 0.5 mole/liter was dissolved l.0 g of thiophene-3-sulfonic acid, and in this solution were immersed platinum as a working electrode and glassy carbon as a negative electrode, after which a constant voltage of 2.0 V was applied without stirring at room temperature and electrolytic polymerization was conduted for 5 hours. Just after the application of the constant voltage, polymerization reaction was caused on the sur-face of the working electrode, and after 3 hours, a bla-ckish green film-like polymer adhered to the working electrode. After completion of the polymerization reac-tion, the peeling, falling-off and the like of polymer were not caused.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ~m, a flat surface and a surface resistance value of 1 x 105 CA 022l7378 l997-lO-Ol n/c.
Example 14 In 20 ml of an aqueous pyridine solution hav-ing a concentration of 0.5 mole/liter was dissolved 1.0 g of thiophene-3-sulfonic acid, and in this solution were immersed platinum as a working electrode and glassy car-bon as a negative electrode, after which a constant volt-age of 2.0 V was applied at room temperature while the solution was circulated to a series flow through cell by means of a pump and electrolytic polymerization was con-ducted. Just after the application of the constant volt-age, polymerization reaction was caused on the surface of the working electrode, and the reaction mixture which was colorless and transparent was changed to blackish green after 5 minutes. After completion of the polymerization reaction, the deposition of polymer on the working elec-trode, and the like were not observed and the polymeriza-tion mixture was uniform. In addition, the elution of a metal component from the working electrode, and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 7 x 105 Q/~-Comparative Example 1 2-Aminobenzenesulfonic acid was subjected to electrolytic polymerization according to the method de-scribed in Preprint II of the 64th Autumn Annual Conven-tion of The Chemical Society of Japan, 706 (1992).
The resulting polymerization mixture was coated on a glass substrate by a spin coating method and dried at 80~C. However, since the polymerization mixture contained sulfuric acid, its coatability was bad and no film was obtained.
Comparative Example 2 A soluble conductive polymer of the soluble aniline type was synthesized by subjecting 2-aminobenzen-esulfonic acid to chemical polymerization according to the method described in Example 1 of JP-A-7-324,132.
The resulting polymerization mixture was coated on a glass substrate by a spin coating method and dried at 80~C. The surface resistance value thereof was 1 x 107 Q/0. However, in the polymerization mixture, a large amount of sulfuric acid was contained, so that no flat film was obtained.
In addition, separation was conduted according to the method stated; however, the filterability was bad and the operation was very complicated.
Field of the Invention This invention relates to a method for produc-ing a soluble conductive polymer which is soluble in a solvent.
A solution comprising this soluble conductive polymer as the main component can be used for forming a conductor by a simple method such as a spray coating method, a dip coating method, a roll coating method, a gravure coating method, a reverse roll coating method, an air-knife coating method, a curtain coating method or the like on various substrates. The above solution can also be used in admixture with a suitable binder polymer for increasing the adhesiveness of a conductive film and the strength of a coating film.
As the substrate to be coated, there are men-tioned various plastics, for example, polyester resins such as polyethylene terephthalate (PET), polyethylene-naphthalate (PEN) and the like, polyethylene, polypropyl-ene, polyvinyl chloride, nylon, polystyrene, polycarbo-nate, epoxy resins, fluoroplastics, polysulfone, polyim-ide, silicone resins, polyurethane, phenol resins, and the like; molded articles and films of these plastics such as synthetic papers and the like; paper; iron;
aluminum; copper; zinc; nickel; stainless steel; and the like. The coating step may be conducted in the course of the production of these substrates, for example, before or during a monoaxial stretching step, a biaxial stretch-ing step, a molding step, an embossing step or the like, or can be applied to a substrate which has been subjected to these treatment.
Moreover, a composition comprising the above soluble conductive polymer as the main component can be applied to various antistatic agents, condensers, bat-teries, EMI shields, chemical sensors, display devices,nonlinear molding materials, anticorrosive agents, adhe-sives, fibers, antistatic coating compositions, electro-coating compositions, plating primer, electrostatic coat-ing primer, electric prevention for corrosion, enhance-ment of the storing capacity of battery and the like.In addition, the above polymer is excellent in applica-bility to various antistatic uses because it has no mois-ture-dependency of conductivity, has a high transparency and can be subjected to stretching, molding, embossing and the like.
The application of the soluble conductive polymer to antistatic uses includes packaging materials, magnetic cards, magnetic tapes, magnetic discs, photo-graphic films, printing substrates, heat seal tapes and films, IC trays, IC carrier tapes, cover tapes and the like.
Description of the Related Art Doped polyaniline has been well known as a soluble conductive polymer; however, it is insoluble in almost all general solvents except some nonprotonic polar solvents and hence has a difficulty in molding.
Moreover, though a process for producing a polyaniline by electrolytic oxidation polymerization [JP-A-60-235,831 and J. Polymer Sci. Polymer Chem. Ed., 26, 1531 (1988)] can form a film of polyaniline on an elec-trode, but has such a problem that its isolation opera-tion becomes complicated and its mass production is dif-ficult.
Proposals have recently been made for an alka-li-soluble sulfonated polyaniline which develops conduc-tivity without adding a doping agent and its synthesis method and for a carboxylated polyaniline and its synthe-sis method.
As a method for the synthesis of a sulfonatedpolyaniline, there are known, for example, a method for the synthesis of a sulfonated polyaniline by electrochem-ically polymerizing aniline and m-aminobenzenesulfonic acid (Journal of The Chemical Society of Japan, 1985, 1124 and JA-A-2-166,165), a method for the synthesis of a sulfonated polyaniline by electrochemically polymerizing an o-, m- or p-aminobenzenesulfonic acid alone [Lecture Preprint II in the 64th Autumn Annual Convention of The Chemical Society of Japan, 706 (1992)], a method for the synthesis of a sulfonated polyaniline by chemically polymerizing aniline and an o- or m-aminobenzenesulfonic acid (JP-A-1-301,714), a method for the chemical oxida-tion polymerization of an aminobenzenesulfonic acid com-pound or monomers comprising an aminobenzenesulfonic acid compound and an aniline compound (JP-A-6-56,987), a meth-od for the sulfonation with conc. sulfuric acid of an emeraldine type polymer (polyaniline) obtained by chemi-cal or electrochemical polymerization (JP-A-58-210,902), a method for the sulfonation with sulfuric anhyd-ride/triethyl phosphate complex (JP-A-61-197,633), a method for the sulfonation with fuming sulfuric acid [J.
Am. Chem. Soc., (1991) 113, 2665-2671, J. Am. Chem. Soc., (1990) 112, 2800 and W091-06887], a method for the syn-thesis of a sulfonated polyaniline of the N-substitution type by chemically polymerizing diphenylamine-4-sulfonic acid (sodium salt) [Polymer, (1993) 34, 158-162] and the like.
In J. Am. Chem. Soc., (1991) 113, 2665-2671, it is reported that the chemical and electrochemical polymerization of o- or m-aminobenzenesulfonic acid was tried but was not successful.
Furthermore, JP-A-6-56,987 states that when an aminobenzenesulfonic acid compound is or an aminobenzene-sulfonic acid compound and an aniline compound are sub-jected to chemical oxidative polymerization in all of the acidic, neutral and alkaline solutions, a soluble conduc-tive polymer which is soluble in water is obtained, and shows polymerization examples in sulfuric acid-acidic solution. However, in said publication, there is no statement of the molecular weight and other physical properties of the polymer, and hence, it is not clear what physical properties the polymer has. According to the present inventors' duplication, no polymer having a sufficiently large molecular weight for forming a film was able to be obtained. Moreover, when the present inventors have tried polymerization in an aqueous solu-tion containing a protonic acid using sodium peroxodisul-fate as an oxidizing agent, a polymer soluble in water was obtained but the molecular weight of the polymer was low and no practicably usable polymer for forming a film was able to be obtained.
Furthermore, the present inventors have dupli-cated the method for chemically polymerizing aniline and m-aminobenzenesulfonic acid with ammonium peroxodisulfate stated in JP-A-1-301,714 and the method for chemically polymerizing aniline and m-aminobenzenesulfonic acid with potassium permanganate stated in JP-A-6-56,987, to find that the sulfonic acid group has been introduced only in a proportion of about one sulfonic acid group per 5 aro-matic rings in the polymer, and the polymer exhibitedhigh conductivity but was completely insoluble in neutral or acidic water and substantially insoluble in an alka-line aqueous solution such as ammonia water. Moreover, when the sulfonation has been effected according to the method of JP-A-1-97,633, the solubility of the polyanil-ine in the sulfonation solvent has not been sufficient and the sulfonation reaction has proceeded in the disper-sion state of the polymer, so that the sulfonic acid group has been introduced only in a proportion of about 1 group per 5 aromatic rings as described on page 7 of the same publication. The thus obtained sulfonated polyani-line in which the proportion of the sulfonic acid group introduced is small has such a problem that the conduc-tivity and solubility are not sufficient.
In addition, J. Am. Chem. Soc., 113, 2665-2671 (1991) and J. Am. Chem. Soc., 112, 2800 (1990) state that when polyaniline is sulfonated with fuming sulfuric acid, the sulfonic acid group is introduced in a proportion of about one sulfonic acid group per two aromatic rings.
However, when the polyaniline has been tried to be suffi-ciently sulfonated according to the above-mentioned method, a large excess of fuming sulfuric acid has become necessary because the solubility of the polyaniline in fuming sulfuric acid has not been sufficient. Moreover, there is also such a problem that when the polyaniline is added to fuming sulfuric acid, the polymer is easy to solidify. In addition, there is such a problem that the polymer synthesized by the above-mentioned method and its sulfonated product are dissolved in an aqueous solution containing a base such as ammonia, an alkylamine or the like but not dissolved in water alone.
Also, Polymer, 34, 158-162 (1993) describes that when diphenylamine-4-sulfonic acid (sodium salt) is polymerized, an N-position-substituted type sulfonated polyaniline in which the benzenesulfonic acid group has been introduced in a proportion of one group per aniline skeleton is obtained, and this is dissolved in water alone, but ultracentrifugal operation is required for the isolation of the polymer. According to the present inventors' duplication, the yield of the polymer taken out of the polymerization solvent has been low because of the high solubility of the polymer in the solvent, and when no high speed centrifugal operation has been effect-ed, it has been impossible to isolate the polymer.
Furthermore, since the polymer is of an N-position-sub-stituted type, it has been lower in conductivity than thepolymer synthesized by the method of J. Am. Chem. Soc., 113, 2665-2671 (1991).
As a method for the synthesis of a carboxylat-ed polyaniline, JP-A-4-268,331 proposes, for example, a production method in which 2- or 3-carboxyl group-substi-tuted aniline or its salt is subjected to oxidative poly-merization and then treated with a basic material to obtain a product in which the carboxyl group is in the form of a salt; however, the amount of the oxidizing agent used is required to be at least 2 equivalents per equivalent of the starting material and the electrical conductivity is low. From this fact, it is considered that the reactivity of monomer be low and a low molecular weight polymer have been produced.
JP-A-5-226,238 proposes a synthesis method in which methyl anthranilate (methyl ester of anthranilic acid) is polymerized in the presence of ammonium peroxo-disulfate in an aqueous acidic medium and thereafter the methyl ester is saponified with alcoholic potassium hy-droxide. However, since the reaction is effected two steps, the operation is very much complicated.
Further, the present inventors have tried to polymerize 2-carboxyl group-substituted aniline in an aqueous solution containing a protonic acid using ammoni-um peroxodisulfate as an oxidizing agent, but have not been able to obtain any product. They have also tried to polymerize aniline and a 2-carboxyl group-substituted aniline in an aqueous solution containing a protonic acid using ammonium peroxodisulfate as an oxidizing agent.
However, a copolymer has been obtained, but the solubili-ty and conductive thereof have been low. From this fact, it is considered that the copolymerization ratio of 2-carboxyl group-substituted aniline be low in the copoly-mer obtained.
When the moldability including film-formabili-ty by coating and the like are taken into consideration, particularly in order to make the polymer coatable on both hydrophilic and hydrophobic substrates, it is desir-ed that the polymer is soluble in both water and organic solvent. However, the sulfonation product of polyaniline is soluble in alkaline aqueous solutions but insoluble in neutral to acidic aqueous solutions, and it cannot be said that the solubility in an organic solvent is suf-ficient.
As a method for solving these various prob-lems, the present inventors have considered that in order to allow a polymer to exhibit conductivity without adding a doping agent and allow its solubility to be enhanced, it is necessary to introduce more acidic groups such as sulfonic acid groups or carboxyl groups into the main chain aromatic ring, and have proposed a process for producing a sulfonation product of an aniline copolymer by copolymerizing at least one compound selected from the group consisting of aniline, N-alkylanilines and phenylenediamines with aminobenzenesulfonic acid using an oxidizing agent in an acidic solvent and further sulfo-nating the resulting copolymer with a sulfonating agent (JP-A-5-178,989). However, the above process has had a problem of treatment of wasted acid because the sulfona-tion operation is effected in conc. sulfuric acid.
Incidentally, the copolymers synthesized are all inferred to have the structures represented by the general formula (7):
R' )x ~ ~ ~ )1- x R11 R12 R13 R14 n wherein each of R11 to R14 is a group selected from the group consisting of hydrogen and sulfonic acid group; R' is a group selected from the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms; the number of the sulfonic acid group is 40 to 80% of the number of the aromatic ring; x represents any number of 0 to 1 and n is a numeral of 2 to 1,500 showing the degree of poly-merization.
In addition, the present inventors have pro-posed a process for producing an aniline copolymer, char-acterized by copolymerizing at least one compound selec-ted from the group consisting of aniline, N-alkylanilines and phenylenediamines with an alkoxy group-substituted aminobenzenesulfonic acid. thereby omitting the sulfona-tion operation which causes a large amount of waste (JP-A-6-293,828). Incidentally, the copolymers synthesized are all inferred to have the structures represented by the general formula (8):
R /~
Rls R16 R17 R18 R19 R20 R21 R22 n wherein each of R15 to R22 is a group selected form the group consisting of hydrogen, alkoxy groups and sulfonic acid group; the number of the sulfonic acid group is 25 to 50~ of the number of the aromatic ring; the alkoxy group and the sulfonic acid group are contained in one and the same aromatic ring; R' is a group selected from the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms; x represents any number of 0 to 1 and n is a numeral of 2 to 1,500 which shows the degree of polymerization.
Furthermore, the present inventors have pro-posed a process for producing a soluble conductive poly-mer of the soluble aniline type by polymerizing an acidic group-substituted aniline such as a sulfonic acid group-substituted aniline, a carboxyl group-substituted aniline or the like in a solution containing a basic compound (JP-A-7-196,791 and JP-A-7-324,132). According to this process, contrary to the conventional established theory that it is difficult to polymerize alone anilines having sulfonic acid groups or carboxyl groups, it is possible to produce a high molecular weight polymer. In addition, the soluble conductive polymer obtained exhibits a high conductivity and also exhibits an excellent dissolvabili-ty in both acidic and alkaline aqueous solutions. How-ever, when the soluble conductive polymer is separated from the by-product salt of the oxidizing agent used in the oxidative polymerization, the operation thereof has not been easy on a commercial scale because the dissolv-ability of the soluble conductive polymer per se is very excellent. Incidentally, the copolymers synthesized by the above-mentioned processes are inferred to have the structures represented by the general formula (9):
H
~ ~ X ~ ~ 1 - X
A1 B1 A2 B2 A3 B3 A4 B4 n wherein each of A1 to A4 is a group selected from the group consisting of sulfonic group, carboxyl group and their alkali metal salts, ammonium salts and substituted ammonium salts; each of B1 to B4 is a group selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 4 carbon atoms;
straight chain or branched chain alkoxy groups having 1 to 4 carbon atoms, acidic groups, hydroxyl group, nitro group and halogen groups; x represents any number of O to 1; and n represents a numeral of 2 to 5,000 which shows the degree of polymerization.
On the other hand, there have been reported a process for synthesizing a sulfonated polyaniline by electrochemically polymerizing aniline and m-aminoben-zenesulfonic acid (Journal of The Chemical Society ofJapan, 1985, 1124 and JP-A-02-166,165) and a process for electrochemically polymerizing aminobenzenesulfonic acid [Preprint II of the 64th Autumn Annual Convention of The Chemical Society of Japan, 706 (1992)]. However, in these processes, an inorganic salt is added as an elec-trolyte, and hence, there is such a problem that the operation for separating the soluble conductive polymer from the electrolyte after the polymerization is compli-cated and the application of the processes to the mass production on a commercial scale is very difficult.
SUMMARY OF THE INVENTION
The object of this invention is to provide a soluble conductive polymer having a high molecular weight and having a high conductivity and solubility and also provide an industrially useful method for producing the same.
The present inventors have eagerly made re-search on a method for producing an acidic group-substi-tuted polyaniline in which the proportion of the acidic group introduced to the aromatic ring is large, such as a sulfonated polyaniline in which the proportion of the sulfonic acid group introduced to the aromatic ring is large, a carboxylated polyaniline in which the proportion of the carboxyl group introduced to the aromatic ring is large, or the like as a polyaniline having a high conduc-tivity and solubility, and have consequently found that when an acidic group-substituted aniline such as a sul-fonic acid group-substituted aniline, a carboxyl group-substituted aniline or the like is or this acidic group-substituted aniline and an aniline derivative are sub-jected as a monomer or monomers to electrolytic oxidation polymerization in a solution containing a basic compound, there is obtained a soluble conductive polymer having a high conductivity, a high solubility and a high molecular weight which has not been obtained by chemical oxidation polymerization.
In addition, the above monomers and polymer act as electrolytes and hence the electrolytes that have been necessary in the conventional electrolytic oxidation polymerization become unnecessary and hence the operation for separating the electrolytes from the soluble conduc-tive polymer can be omitted. Accordingly, the polymer-ization mixture per se can be used as a commercial arti-cle such as a coating agent or the like, and hence, theabove production method is industrially advantageous.
Furthermore, since the polymer formed by the polymerization is soluble in the reaction mixture, the mass production of a polymer on a commercial scale by polymerization in a continuous electrolysis system such as a flow through system or the like is possible. The flow through system is a system in which polymerization is conducted by circulating the reaction mixture to the cell between the acting electrode and the negative elec-trode by means of a liquid-transporting pump, and it is made possible to carry out the polymerization reaction under the optimum conditions by connecting the cells in series or in parallel. Moreover, the present inventors have found that the knowledge of the electrolytic poly-merization with regard to these acidic group-substituted anilines can also be applied in quite the same manner to acidic group-substituted pyrroles, thiophenes, furans, selenophenes, tellurophenes, isothianaphthenes, isoben-zofurans, isoindolines, isobenzoselenophenes and iso-benzotellurophenes. This invention has been achieved based on the above-mentioned knowledge.
That is to say, this invention relates to a method for producing a soluble conductive polymer having an acidic group which comprises subjecting to electro-lytic polymerization (a) at least one compound selected from the group consisting of acidic group-substituted anilines, acidic group-substituted pyrroles, acidic group-substituted thiophenes, acidic group-substituted furans, acidic group-substituted selenophenes, acidic group-substituted tellurophenes, acidic group-substituted isothianaphthenes, acidic group-substituted isobenzo-furans, acidic group-substituted isoindolines, acidic group-substituted isobenzoselenophenes, acidic group-substituted isobenzotellurophenes, and their metal salts, ammonium salts and substituted ammonium salts in a solu-tion containing (b) a basic compound.
The other embodiment of this invention relates to a method for producing a soluble conductive polymer having an acidic group which comprises subjecting to electrolytic polymerization (a) at least one compound selected from the group consisting of acidic group-sub-stituted anilines, acidic group-substituted pyrroles, acidic group-substituted thiophenes, acidic group-substi-tuted furans, acidic group-substituted selenophenes, acidic group-substituted tellurophenes, acidic group-substituted isothianaphthenes, acidic group-substituted isobenzofurans, acidic group-substituted isoindolines, acidic group-substituted isobenzoselenophenes, acidic group-substituted isobenzotellurophenes, and their metal salts, ammonium salts and substituted ammonium salts and (c) at least one compound selected from the group con-sisting of aniline derivatives, pyrrole derivatives, thiophene derivatives, furan derivatives, selenophene derivatives, tellurophene derivatives, isothianaphthene derivatives, isobenzofuran derivatives, isoindoline de-rivatives, isobenzoselenophene derivatives and isobenzo-tellurophene derivatives in a solution containing (b) a basic compound.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is an IR spectrum of the polymer in Example 1.
Fig. 2 is a GPC chart of the polymer in Exam-ple 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
An acidic group-substituted aniline polymer which is the most preferable example of this invention is used as an example below to explain this invention in more detail. However, this applies quite similarly to the cases of acidic group-substituted pyrroles, thio-phenes, furans, selenophenes, tellurophenes, isothia-naphthenes, isobenzofurans, isoindolines, isobenzosele-nophenes and isobenzotellurophenes.
The above-mentioned acidic group-substituted aniline represents at least one compound selected from - the group consisting of acidic group-substituted anilines represented by the general formula (1) and their metal salts, ammonium salts and substituted ammonium salts:
Rl R2 >=( H2N - ~ ) R3 (1) Rs R4 wherein R1, R2, R3, R4 and Rs are substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, acidic groups, hydroxyl group, nitro group and halogen groups and at least one of R1 to Rs represents an acidic group, the above acidic group mean-ing a sulfonic acid group or a carboxyl group. When the acidic group is bonded to the compound of the above gen-eral formula (1) in the o- or m-position to the amino group, the polymer obtained is superior in performance such as conductivity, solubility and the like.
As the above acidic group-substituted ani-lines, most typical are sulfonic acid group-substituted anilines and carboxyl group-substituted anilines. The sulfonic acid group-substituted anilines are preferably used and the conductivity of the polymer obtained tends to be higher than when the carboxyl group-substituted anilines are used.
The most typical sulfonic acid group-substi-tuted anilines are aminobenzenesulfonic acids, and spe-cifically, there are preferably used o-, m- and p-aminobenzenesulfonic acids, aniline-2,6-disulfonic acid, aniline-2,5-disulfonic acid, aniline-3,5-disulfonic acid, aniline-2,4-disulfonic acid and aniline-3,4-disulfonic acid.
As other sulfonic acid group-substituted ani-lines, there can be mentioned alkyl group-substituted aminobenzenesulfonic acids such as methylaminobenzenesul-fonic acid, ethylaminobenzenesulfonic acid, n-propyl-aminobenzenesulfonic acid, isopropylaminobenzenesulfonicacid, n-butylaminobenzenesulfonic acid, sec-butylamino-benzenesulfonic acid, t-butylaminobenzenesulfonic acid and the like; alkoxy group-substituted aminobenzenesulfo-nic acids such as methoxyaminobenzenesulfonic acid, etho-xyaminobenzenesulfonic acid, n-propoxyaminobenzenesulfo-nic acid, isopropoxyaminobenzenesulfonic acid, n-butoxy-aminobenzenesulfonic acid, sec-butoxyaminobenzenesulfonic acid, t-butoxyaminobenzenesulfonic acid and the like:
hydroxy group-substituted aminobenzenesulfonic acids;
nitro group-substituted aminobenzenesulfonic acids; halo-gen group-substituted aminobenzenesulfonic acids such as fluoroaminobenzenesulfonic acid, chloroaminobenzenesul-fonic acid, bromoaminobenzenesulfonic acid and the like;
etc. Among them, alkyl group-substituted aminobenzenesu-lfonic acids, alkoxy group-substituted aminobenzenesul-fonic acids and hydroxyl group-substituted aminobenzene-sulfonic acids are most preferable in practical use.
Incidentally, these sulfonic acid group-substituted ani-lines may be used alone or in admixture with any propor-tion of their isomers.
The most typical carboxyl group-substituted anilines are aminobenzenecarboxylic acids, and specifi-cally, there are preferably used o-, m- and p-aminoben-zenecarboxylic acids, aniline-2,6-dicarboxylic acid, aniline-2,5-dicarboxylic acid, aniline-3,5-dicarboxylic acid, aniline-2,4-dicarboxylic acid and aniline-3,4-di-carboxylic acid.
As other carboxyl group-substituted anilines, there can be mentioned alkyl group-substituted amino-benzenecarboxylic acids such as methylaminobenzenecarbox-ylic acid, ethylaminobenzenecarboxylic acid, n-propylami-nobenzenecarboxylic acid, isopropylaminobenzenecarboxylic acid, n-butylaminobenzenecarboxylic acid, sec-butylamino-benzenecarboxylic acid, t-butylaminobenzenecarboxylic acid and the like; alkoxy group-substituted aminobenzene-carboxylic acids such as methoxyaminobenzenecarboxylic acid, ethoxyaminobenzenecarboxylic acid, n-propoxyamino-benzenecarboxylic acid, isopropoxyaminobenzenecarboxylicacid, n-butoxyaminobenzenecarboxylic acid, sec-butoxy-aminobenzenecarboxylic acid, t-butoxyaminobenzenecarbox-ylic acid and the like; hydroxy group-substituted amino-benzenecarboxylic acids; nitro group-substituted amino-benzenecarboxylic acids, halogen group-substituted amino-benzenecarboxylic acids such as fluoroaminobenzenecarbox-ylic acid, chloroaminobenzenecarboxylic acid, bromoamino-benzenecarboxylic acid and the like; etc. Among them,alkyl group-substituted aminobenzenecarboxylic acids, alkoxy group-substituted aminobenzenecarboxylic acids and hydroxy group-substituted aminobenzenecarboxylic acids are most preferable in practical use. These carboxyl group-substituted anilines may be used alone or in admix-ture with any proportion of their isomers.
Specific examples of the acidic group-substi-tuted anilines of the general formula (l) include sulfon-ic acid group-substituted alkylanilines, carboxyl group-substituted alkylanilines, sulfonic acid group-substitut-ed alkoxyanilines, carboxyl group-substituted alkoxyani-lines, sulfonic acid group-substituted hydroxyanilines, carboxyl group-substituted hydroxyanilines, sulfonic acid group-substituted nitroanilines, carboxyl group-substi-tuted nitroanilines, sulfonic acid group-substituted flu-oroanilines, carboxyl group-substituted fluoroanilines, sulfonic acid group-substituted chloroanilines, carboxyl group-substituted chloroanilines, sulfonic acid group-substituted bromoanilines, carboxyl group-substituted bromoanilines and the like. Specific examples of the positions of these substituents and the combinations of the substituents are shown in Table 1.
Table 1 Rl R2 R3 R4 Rs A B H H H
A H B H H
A H H B H
A H H H B
H A B H H
H A H B H
H A H H B
B A H H H
H H A B H
H H A H B
B H A H H
H B A H H
H H H A B
H H B A H
H B H A H
B H H A H
H H H B A
H H B H A
H B H H A
B H H H A
In Table 1, A means at least one group selected from the group consisting of sulfonic acid group, carboxyl group and their alkali metal salts, ammonium salts and substi-tuted ammonium salts; B means at least one group selected from the group consisting of alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group and the like;
alkoxy groups such as methoxy group, ethoxy group, n-pro-poxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group and the like; hydroxyl group; nitro group; fluoro group; halogen groups such as fluoro group, chloro group, bromo group and the like; and H means hy-drogen.
The metals which form salts of these monomers include lithium, sodium, potassium and the like.
The substituted ammoniums include acyclic ammoniums, cyclic saturated ammoniums, cyclic unsaturated ammoniums and the like.
The above acyclic ammoniums include compounds represented by the general formula (10):
R24- 1 -R26 ( 10 ) wherein each of R23 to R26 is a group independently se-lected from the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms. There can be men-tioned, for example, methylammonium, dimethylammonium, trimethylammonium, ethylammonium, diethylammonium, triethylammonium, methylethylammonium, diethylmethylammonium, dimethylethylammonium, propylammonium, dipropylammonium, isopropylammonium, diisopropylammonium, butylammonium, dibutylammonium, methylpropylammonium, ethylpropylammonium, methylisopro-pylammonium, ethylisopropylammonium, methylbutylammonium, ethylbutylammonium, tetramethylammonium, tetramethylolam-monium, tetraethylammonium, tetra-n-butylammonium, tetra-sec-butylammonium, tetra-t-butylammonium and the like.
Among them, the case where one of R23 to R26 is hydrogen and the other three are alkyl groups having 1 to 4 carbon atoms is most preferable, and the case where two of R23 to R26 are hydrogens and the other two are alkyl groups having 1 to 4 carbon atoms are more preferable.
As the cyclic saturated ammoniums, there are mentioned piperidinium, pyrrolidinium, morpholinium, piperazinium and derivatives having these skeletons and the like.
As the cyclic unsaturated ammoniums, there are mentioned pyridinium, a-picolinium, ~-picolinium, ~-pico-linium, quinolinium, isoquinolinium, pyrrolinium and derivatives having these skeletons and the like.
The basic compound (b) used in this invention may be any compound as far as it is a compound forming salts with the above-mentioned acidic group-substituted anilines, and there are preferably used ammonia, acyclic amines, cyclic saturated amines, cyclic unsaturated amin-es, inorganic bases and the like. In particular, acyclic amines, cyclic saturated amines and cyclic unsaturated amines and the like are preferred.
The acyclic amines include compounds repre-sented by the general formula (11):
R28- 1 ( 11 ) Rz9 wherein each of R27 to R29 is a group selected indepen-dently from the group consisting of alkyl groups having 1 to 4 carbon atoms; and hydroxide compounds represented by the general formula ( 12):
Rl30 R3~ -R33-OH- ( 12) wherein each of R30 to R33 is a group selected indepen-dently from the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms.
As the cyclic saturated amines, there are preferably used piperidine, pyrrolidine, morpholine, piperazine, derivatives having these skeletons, ammonium hydroxy compounds of them and the like.
As the cyclic unsaturated amines, there are preferably used pyridine, a-picoline, ~-picoline, y-pico-line, quinoline, isoquinoline, pyrroline, derivatives having these skeletons, ammonium hydroxy compounds of them and the like.
As the inorganic base, hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are preferably used; however, the conductiv-ity of the polymer obtained tends to be inferior as com-pared with the above-mentioned acyclic amines, cyclic saturated amines and cyclic unsaturated amines.
The concentration of these basic compounds (b) is selected in the range of at least 0.1 mole/liter, preferably 0.1 to 10.0 moles/liter and more preferably 0.2 to 8.0 moles/liter. When the concentration is less than 0.1 mole/liter, the yield of the polymer obtained is decreased and when the concentration is more than 10.0 moles/liter, the conductivity shows a tendency to reduce.
The above basic compound (b) can be used in admixture of two or more in any proportion.
The aniline derivative (c) includes compounds represented by the general formula ( 4):
H2N F~ R8 ( ) Rlo Rg wherein R6 to Rlo represent substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, hydroxyl group, nitro group and halogen groups.
As the above-mentioned aniline derivative (c), aniline is most typical, and in addition to the same, there can be mentioned alkylanilines such as methylani-line, ethylaniline, n-propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline, t-butylaniline and the like; alkoxyanilines such as methoxyaniline, ethoxyani-line, n-propoxyaniline, isopropoxyaniline, n-butoxyani-line, sec-butoxyaniline, t-butoxyaniline and the like;
hydroxyaniline; nitroaniline; halogenoanilines such as fluoroaniline, chloroaniline, bromoaniline and the like.
The co-existence of the aniline derivative (c) exhibits an effective action to improve the conductivity, film-forming properties and the like of the conductive polymer obtained.
The weight ratio between the compound (a) in-cluding the above acidic group-substituted anilines and the like and the basic compound (b) is such that (a) :
(b) = 1 : 100 - 100 : 1, preferably 10 : 90 - 90 : 10.
Here, when the proportion of the basic compound is low, the reactivity is lowered and the conductivity is also lowered. On the contrary, when the proportion of the basic compound is high, the proportion of the acidic group of the polymer obtained forming a salt with the basic compound becomes high and the conductivity tends to be lowered.
The weight ratio between the compound (a) in-cluding the above-mentioned acidic group-substituted anilines and the like plus the aniline derivative (c) and the basic compound (b) is such that [(a) + (c)] : (b) = 1 : 100 - 100 : 1, preferably 10 : 90 - 90 : 10. Here, when the proportion of the basic compound is low, the reactivity is lowered and the conductivity is also low-ered. On the contrary, the proportion of the basic compound is high, the proportion of the acidic group of the polymer obtained forming a salt with the basic com-pound becomes high and the conductivity tends to be low-ered.
The molar proportion between the compound (a) including the above-mentioned acidic group-substituted anilines and the like and the aniline derivative (c) is in such a range that (a) : (c) = 100 : 0 - 30 : 70, pref-erably 99.999 : 0.001 - 50 : 50, more preferably 99.999 :
0.001 - 70 : 30. Here, the proportion of the aniline derivative is high (exceeding 70), the sulfonic acid group content in the polymer obtained is not sufficient and the solubility tends to be lowered.
The molar ratio between the acidic group (d) in the compound (a) including the above-mentioned acidic group-substituted anilines and the like and the basic compound (b) is such that (d) : (b) = 1 : 100 - 100 : 1, preferably 1 : 0.25 - 1 : 20, more preferably 1 : 0.5 - 1 : 15. Here, when the proportion of the basic compound is low, the reactivity is lowered and the conductivity is also lowered. On the contrary, when the proportion of the basic compound is high, the proportion of the acidic group of the polymer obtained forming a salt with the basic compound becomes high and the conductivity tends to be lowered.
The concentration of the compound (a) includ-ing the a acidic group-substituted anilines and the like and the concentration of the aniline derivatives (c) at the time of the electrolytic polymerization are at least 0.1~ by weight, preferably 0.5 to 50~ by weight and more preferably 1 to 30~ by weight, based on the weight of the solvent.
The polymerization or copolymerization is con-ducted by electrolytic oxidation polymerization in asolution containing the above basic compound. As the solvent, there are preferably used water, methanol, etha-nol, isopropanol, acetonitrile, methyl isobutyl ketone, methyl ethyl ketone, dimethylformamide, dimethylacetamide and the like.
As the electrode material in the electrolytic oxidation polymerization, there can be used metal plates and net electrodes of gold, silver, platinum, nickel, mercury, stainless steel, copper, zinc, tin, lead, iron, aluminum, titanium, ruthenium, iridium, oxides of them and the like; carbon electrodes such as glassy carbon and the like; glass electrodes to which a metal oxide such as IT0 glass, tin-indium oxide, tin oxide or the like is im-parted; and the like, and among them, silver, platinum, titanium, glassy carbon and IT0 glass are preferable.
As the electrolysis method, there can be used any method of electrolysis at constant current, control-led potential electrolysis and electrolysis at constant CA 022l7378 l997-lO-Ol voltage. The current density at the time of the electro-lytic polymerization at constant current is in the range of from 5 to 200 mA/cm2, preferably from 10 to 200 mA/-cm2, and more preferably from 15 to 150 mA/cm2. As to the potential in the electrolytic polymerization at con-stant potential, it is advantageous to apply to the work-ing electrode a potential of not more than -0. 5 V, pref-erably -1 V to -10 V and more preferably -1 V to -7 V, in relation to the standard electrode.
If necessary, an electrolyte, for example, LiBF4; a salt of HBF4, HCl04, HCl, H2S04 or the like; or the like can be added. However, in this invention, the compound (a) including the acidic group-substituted ani-lines and the like per se or the polymer per se serves as an electrolyte, so that the polymerization can be con-ducted without these electrolytes.
The reaction temperature is preferably -15~ to 70~C, more preferably -5~ to 60~C. Here, when the reac-tion temperature is lower than -1 5~C or higher than 70~C, the conductivity tends to be lowered.
All or some of the hydrogens of sulfonic acid groups or carboxyl groups in the polymer produced by the method of this invention, may be any member selected independently from the group consisting of alkali metals, ammonium and substituted ammoniums. Accordingly, these selected members may be present as one species or even in admixture of some species in the polymer.
Specifically, when the polymerization is ef-fected in the presence of sodium hydroxide, almost all the hydrogen atoms in the sulfonic acid groups or carbox-yl groups in the isolated polymer are in the sodium salt form. Similarly, when the polymerization is effected in the presence of ammonia, almost all the hydrogen atoms in the sulfonic acid groups or carboxyl groups of the poly-mer are in the ammonium form, and when the polymerization is effected in the presence of trimethylamine, almost all the hydrogen atoms of the sulfonic acid groups or carbox-yl groups of the polymer are in the triethylammoniumform. When the polymerization is effected in the pres-ence of quinoline, almost all the hydrogen atoms of the sulfonic acid groups or carboxyl groups of the polymer are in the quinolinium form. Moreover, when the basic compounds are used in admixture, the polymer is obtained in the same mixture form. Specifically, when the poly-merization is effected in the presence of sodium hydrox-ide and ammonia, it follows that a part of the hydrogen atoms in the sulfonic acid groups or carboxyl groups in the isolated polymer have been replaced with sodium and the other part thereof with ammonium. Moreover, when the polymer obtained is treated with a solution in which both sodium hydroxide and ammonia are present, similarly to the above case, a part of the hydrogen atoms of the sulfonic acid groups or carboxyl groups of the polymer have been replaced with sodium and the other part thereof with ammonia.
As described above, the polymer in which a part of the acidic groups are in the salt form can be converted to that having free acidic groups by treating the former polymer in an acidic solution and then isolat-ing the same. As the acidic solution, there can be men-tioned hydrochloric acid, sulfuric acid, p-toluenesulfo-nic acid, nitric acid and the like. However, it is difficult to render all the acidic groups completely free even when the acid-substitution has been sufficiently effected.
The weight average molecular weight of the soluble conductive polymer having sulfonic acid groups or carboxyl groups on the aromatic rings thus obtained is at least 3,000, preferably 3,000 to 1,000,000 and more pref-erably 5,000 to 500,000. Moreover, the proportion of acidic group introduced into the aromatic ring is at least 50%, preferably at least 70%, and more preferably at least 80%. Here, when the proportion of the acidic group introduced is less than 50%, the dissolvability of the polymer in water tends to be small, and it becomes difficult to appply the polymer in industry.
This conductive polymer can be dissolved, without being further subjected to sulfonation operation, in simple water; water containing a base such as ammonia, an alkylamine or the like or a basic salt such as ammo-nium acetate, ammonium oxalate or the like; water con-taining an acid such as hydrochloric acid, sulfuric acid or the like; a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol or the like; or a mixture thereof.
Explaining in detail the dissolvability, the soluble conductive polymer having acidic groups in this invention has such properties that it is dissolved in a proportion of at least 1~ by weight in an aqueous alkali solution such as 0.1 mole/liter ammonia water, dissolved in a proportion of at least 1~ by weight in an acidic solution such as 0.1 mole/liter aqueous sulfuric acid or the like, also dissolved in a proportion of at least 1 by weight in a neutral aqueous solution such as water alone or the like, and, in addition, dissolved in a pro-portion of at least 1~ by weight in an organic solvent such as a 0.1 mole/liter alcoholic ammonia solution or the like.
Incidentally, the polymers and copolymers syn-thesized according to the above-mentioned methods are all inferred to have the structures represented by the gener-al formula (13):
R34 R3s R38 R39 R42 R43 R4s R47 t H ~ ~ ~) ) ~N ~ N- ~
R37 R3s R41 R40 R45 R44 R4s R48 n (13) wherein R34 to R49 represent groups selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, acidic groups, hydroxyl group, nitro group and halogen groups; the number of the acidic groups introduced is at least 50~ of the number of the aromatic ring wherein the acidic groups mean sulfonic acid groups or carboxyl groups; x represents any number of 0 to 1;
and n represents a numeral of 2 to 1,500 which shows the degree of polymerization.
This invention is explained below in more de-tail by Examples and Comparative Examples; however, thisinvention should not be construed to be limited to the Examples.
[Measurement method]
IR spectrum was measured using an equipment manufactured by Perkin Elmer (Model 1600).
In the measurement of molecular weight distri-bution and molecular weight, as two GPC columns for aque-ous solution, TSK-GEL G-5000PWKL and TSK-GEL G-3000PWXL
(both of Toso K.K.) were connected in series and used to effect GPC-measurement (polyethylene oxide-reduced). As the column, three kinds of columns for aqueous solution were connected in series and used. Also, as the eluting solution, a 0.2 mole/liter phosphorate buffer solution was used.
As to conductivity, a four-probe method was used for the measurement of conductivity and a two-probe method was used for the measurement of surface resis-tance.
Example 1 In 150 ml of a pyridine solution having a con-centration of 0.05 mole/liter was dissolved 4.06 g of 2-aminoanisole-4-sulfonic acid, and in this solution were immersed glassy carbon as a working electrode and plati-num as a negative electrode, after which a constant volt-age of 1.5 V was applied with stirring at room tempera-ture and electrolytic polymerization was conducted for one hour. Just after the starting of the electrolytic polymerization, polymerization reaction was caused on the surface of the polymerization electrode, and after 5 minutes, the colorless, transparent reaction mixture was changed to brown. After completion of the polymerization reaction, the deposition of polymer on the polymeriza-tion electrode and the like were not observed and the polymerization mixture was uniform. Moreover, the elu-tion of a metal component from the polymerization elec-trode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ~um, a flat surface and a surface resistance value of 2 x 105 Q/~.
The result of measurement of molecular weight showed that the number average molecular weight (Mn) was 20,000, the weight average molecular weight (Mw) was 22,000, the Z average molecular weight (Mz) was 24,000, the degree of dispersion Mw/Mn was 1.1 and Mz/Mw was 1.1.
The polymerization mixture obtained was con-centrated under reduced pressure to isolate a polymer and the solubility of the polymer was measured. The solu-bility was determined by adding the polymer little by little to 10 ml of water, 10 ml of a 0.1 mole/liter aque-ous sulfuric acid or 10 ml of a 0.1 mole/liter aqueous ammonia water and filtering the mixture when the polymer became undissolved.
The solubilities of the soluble conductive polymer synthesized in the present Example were:
Water : 250 mg/ml Sulfuric acid: 245 mg/ml Ammonia water: 260 mg/ml.
Moreover, the IR spectrum of the soluble con-ductive polymer mentioned above is shown in Fig. 1, and the GPC chart of the polymer is shown in Fig. 2.
The assignment of IR spectrum is as follows:
Sulfone group: Absorption in the vicinity of 1,120, 1,020 cm~l Skeleton of polymer: Absorption in the vicinity of 1,500 cm~
Example 2 In 150 ml of an a-picoline solution having a concentration of 0.05 mole/liter was dissolved 3.7 g of 2-aminobenzenesulfonic acid, and in this solution were immersed glassy carbon as a working electrode and plati-num as a negative electrode, after which a constant volt-age of 2.0 V was applied with stirring at room tempera-ture and electrolytic polymerization was conducted for 0.5 hour. After completion of the polymerization reac-tion, the deposition of polymer on the polymerization electrode and the like were not observed and the polymer-ization mixture was uniform. Also, the elution of a metal component from the polymerization electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 80~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 5 x 106 Q/L.
Example 3 In 150 ml of a triethylamine solution (water/-isopropanol = 1/1) having a concentration of 0.05 mole/-liter were dissolved 3.6 g of 2-aminobenzenesulfonic acid and 0.1 g of aniline, and in this solution were immersed an IT0 electrode as a working electrode and platinum as a negative electrode, after which a constant voltage of 2.0 V was applied with stirring at room temperature, and electrolytic polymerization was conducted for 0.5 hour.
After completion of the polymerization reaction, the deposition of polymer on the polymerization electrode and the like were not observed and the polymerization mixture was uniform. Also, the elution of a metal component from the polymerization electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 1 x 107 Q/~, Example 4 In 100 parts by weight of water were stirred 50 parts by weight of the polymer solution obtained in Example 1 and 100 parts by weight of an aqueous acrylic emulsion resin (NIKAZOL RX-301C, a trade name of NIPPON
CARBIDE INDUSTRIES CO., INC.) at room temperature to prepare a conductive rough product. The solution thus obtained was coated on a PET film by a gravure coater of 40 ,um in depth and dried at 120~C, to obtain a film having a thickness of 0.2 ,um, a flat surface and a sur-face resistance value of 1 x 107 Q/~.
Example 5 100 parts by weight of the polymer solution obtained in Example 1 and 5 parts by weight of polyvinyl alcohol as a cross-linking agent were stirred and dis-solved at room temperature to prepare a cross-linkable conductive composition. The solution thus obtained was coated on a PET film by a gravure coater of 40 ,um in depth and dried at 150~C, to obtain a film having a thickness of 0.8 ,um, a flat surface and a surface resis-tance value of 5 x 106 n/~. This conductive film was immersed in water and acetone; however, since the film had been cross-linked, dissolution, peeling and the like were not observed.
Example 6 In 100 parts by weight of water were dissolved with stirring 100 parts by weight of the polymer solution obtained in Example 1, 5 parts by weight of polyvinyl alcohol as a cross-linking agent and 100 parts by weight of an aqueous acrylic emulsion resin (NIKAZOL RX-301C, a trade name of NIPPON CARBIDE INDUSTRIES CO., INC.) at room temperature to prepare a cross-linkable conductive composition. The solution thus obtained was coated on a zinc-plated steel plate (20 mm x 50 mm x 1 mm) by a dip coating method and dried at 150~C, to form a conductive layer having a thickness of 0.5 ~m. This zinc-plated steel plate provided with a conductive layer (No. l), a chromium compound-coated zinc-plated steel plate (the coating thickness: 5-6 ~m) (No. 2) as a comparison and a zinc-plated steel plate (No. 3) as another comparison were sprayed with an aqueous sodium chloride solution at 40~C (in accordance with the JIS-K-5400 method) and subjected to an anticorrosion test.
The results obtained are shown in Table 2.
Table 2 Zinc-plated steel Coated layer Corrosion length plate No.
1 Conductive layer 1 mm 2 Chromium compound 5 mm 3 None 6 mm Example 7 In 30 ml of an aqueous ammonia solution having a concentration of 0.5 mole/liter was dissolved 3.0 g of 2-aminoanisole-4-sulfonic acid, and in this solution were immersed platinum as a working electrode and glassy car-bon as a negative electrode, after which a constant volt-age of 2.5 V was applied at room temperature with stir-ring, and electrolytic polymerization was conducted for12 hours. Just after the application of the constant voltage, polymerization reaction was caused on the work-ing electrode, and the reaction mixture which was ini-tially colorless and transparent was changed to blackish green after 5 minutes. After completion of the polymer-ization reaction, the deposition of polymer on the work-ing electrode, and the like were not observed and the polymerization mixture was uniformed. In addition, the elution of a metal component from the working electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ~m, a flat surface and a surface resistance value of 2 x 105 Q/C~
Example 8 In 30 ml of an aqueous ammonia solution having a concentration of 0.5 mole/liter was dissolved 3.0 g of 2-aminoanisole-4-sulfonic acid. In this solution were immersed platinum as a working electrode and glassy car-bon as a negative electrode, and a constant voltage of2.0 V was applied at room temperature while the solution was circulated to a series flow through cell by a pump, and electrolytic polymerization was conducted. Just after the application of the constant voltage, polymer-ization reaction was caused on the working electrode andthe reaction mixture which was initially colorless and transparent was changed to blackish green after 5 min-utes. After completion of the polymerization reaction, the deposition of polymer on the working electrode, and the like were not observed and the polymerization mixture was uniform. In addition, the elution of a metal compo-nent from the working electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 80~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 5 x 106 Q/C.
Example 9 In 20 ml of an aqueous diethylamine solution having a concentration of 0.5 mole/liter was dissolved 3.0 g of 2-aminoanisole-4-sulfonic acid, and in this solution were immersed platinum as a working electrode and glassy carbon as a negative electrode, after which a constant voltage of 2.5 V was applied without stirring at room temperature and electrolytic polymerization was conducted for 5 hours. Just after the application of the constant voltage, polymerization reaction was caused on the surface of the working electrode and, after 3 hours, a blackish green film-like polymer adhered to the working electrode. After completion of the polymerization reac-tion, the peeling, falling-off and the like of the poly-mer from the working electrode were not caused.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 1 x 107 Q/~.
Example lO
In 30 ml of an aqueous ammonia solution having a concentration of 0.5 mole/liter was dissolved 2.5 g of o-aminobenzoic acid, and in this solution were immersed platinum as a working electrode and glassy carbon as a negative electrode, after which a constant voltage of 3.0 V was applied without stirring at room temperature and electrolytic polymerization was condcuted for 5 hours.
Just after the application of the constant voltage, poly-merization reaction was caused and, after 3 hours, ablackish green film-like polymer adhered to the working electrode. After completion of the polymerization reac-tion, the peeling, falling-off and the like of the poly-mer from the working electrode were not caused.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 5 x 10 Q/L.
Example 11 In 30 ml of an aqueous ammonia water having a concentration of 0.5 mole/liter was dissolved 2. 5 g of o-aminobenzoic acid and in this solution were immersed platinum as a working electrode and glassy carbon as a negative electrode, after which a constant voltage of 3.0 V was applied at room temperature while the solution was circulated to a series flow through cell by means of a pump, and electrolytic polymerization was conducted.
Just after the application of the constant voltage, poly-merization reaction was caused on the surface of theworking electrode and, after 5 minutes, the reaction mixture which was initially colorless and transparent was changed to blackish green. After completion of the polymerization reaction, the deposition of polymer on the working electrode, and the like were not observed and the polymerization mixture was uniform. In addition, the elution of a metal component from the working electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 7 x 106 Q/0.
Example 12 In 30 ml of an aqueous ammonia water having a concentration of 0.5 mole/liter was dissolved 3.0 g of o-aminobenzenesulfonic acid and in this solution were im-mersed platinum as a working electrode and glassy carbon as a negative electrode, after which a constant voltage of 2.0 V was applied at room temperature while the solut-ion was circulated to a series flow through cell by means of a pump, and electrolytic polymerization was conducted.
Just after the application of the constant voltage, poly-merization reaction was caused on the surface of the working electrode and, after 5 minutes, the reaction mixture which was initially colorless and transparent was changed to blackish green. After completion of the polymerization reaction, the deposition of polymer on the working electrode, and the like were not observed and the CA 022l7378 l997-lO-Ol polymerization mixture was uniform. In addition, the elution of a metal component from the working electrode and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 80~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 7 x 106 Q/G.
Example 13 In 20 ml of an aqueous pyridine solution having a concentration of 0.5 mole/liter was dissolved l.0 g of thiophene-3-sulfonic acid, and in this solution were immersed platinum as a working electrode and glassy carbon as a negative electrode, after which a constant voltage of 2.0 V was applied without stirring at room temperature and electrolytic polymerization was conduted for 5 hours. Just after the application of the constant voltage, polymerization reaction was caused on the sur-face of the working electrode, and after 3 hours, a bla-ckish green film-like polymer adhered to the working electrode. After completion of the polymerization reac-tion, the peeling, falling-off and the like of polymer were not caused.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ~m, a flat surface and a surface resistance value of 1 x 105 CA 022l7378 l997-lO-Ol n/c.
Example 14 In 20 ml of an aqueous pyridine solution hav-ing a concentration of 0.5 mole/liter was dissolved 1.0 g of thiophene-3-sulfonic acid, and in this solution were immersed platinum as a working electrode and glassy car-bon as a negative electrode, after which a constant volt-age of 2.0 V was applied at room temperature while the solution was circulated to a series flow through cell by means of a pump and electrolytic polymerization was con-ducted. Just after the application of the constant volt-age, polymerization reaction was caused on the surface of the working electrode, and the reaction mixture which was colorless and transparent was changed to blackish green after 5 minutes. After completion of the polymerization reaction, the deposition of polymer on the working elec-trode, and the like were not observed and the polymeriza-tion mixture was uniform. In addition, the elution of a metal component from the working electrode, and oligomer and the like were hardly detected.
The polymerization mixture obtained was coated on a glass substrate by a spin coating method and dried at 100~C, to obtain a film having a thickness of 0.1 ,um, a flat surface and a surface resistance value of 7 x 105 Q/~-Comparative Example 1 2-Aminobenzenesulfonic acid was subjected to electrolytic polymerization according to the method de-scribed in Preprint II of the 64th Autumn Annual Conven-tion of The Chemical Society of Japan, 706 (1992).
The resulting polymerization mixture was coated on a glass substrate by a spin coating method and dried at 80~C. However, since the polymerization mixture contained sulfuric acid, its coatability was bad and no film was obtained.
Comparative Example 2 A soluble conductive polymer of the soluble aniline type was synthesized by subjecting 2-aminobenzen-esulfonic acid to chemical polymerization according to the method described in Example 1 of JP-A-7-324,132.
The resulting polymerization mixture was coated on a glass substrate by a spin coating method and dried at 80~C. The surface resistance value thereof was 1 x 107 Q/0. However, in the polymerization mixture, a large amount of sulfuric acid was contained, so that no flat film was obtained.
In addition, separation was conduted according to the method stated; however, the filterability was bad and the operation was very complicated.
Claims (7)
1. A method for producing a soluble conductive polymer having acidic groups, which comprises subjecting to electrolytic polymerization (a) at least one compound selected from the group consisting of acidic group-substituted anilines, acidic group-substituted pyrroles, acidic group-substituted thiophenes, acidic group-substituted furans, acidic group-substituted selenophenes, acidic group-substituted tellurophenes, acidic group-substituted isothianaphthenes, acidic group-substituted isobenzofurans, acidic group-substituted isoindolines, acidic group-substituted isobenzoselenophenes, acidic group-substituted isobenzotellurophenes, and their metal salts, ammonium salts and substituted ammonium salts in a solution containing (b) a basic compound.
2. The method according to Claim 1, wherein the electrolytic polymerization is continuously conducted using interconnected cells which are connected in series, in parallel or in combination of them.
3. The method according to Claim 1 or 2, wherein the above acidic group-substituted anilines are those represented by the general formula (1):
(1) wherein R1, R2, R3, R4 and R5 are substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, acidic groups, hydroxyl group, nitro group and halogen groups, and at least one of R1 to R5 is an acidic group wherein the acidic group means a sulfonic acid group or a carboxyl group; and the above acidic group-substituted pyrroles, acidic group-substituted thiophenes, acidic group-substituted furans, acidic group-substituted selenophenes, acidic group-substituted tellurophenes, acidic group-substituted isothianaphthenes, acidic group-substituted isobenzofurans, acidic group-substituted isoindolines, acidic group-substituted isobenzoselenophenes and acidic group-substituted isobenzotellurophenes are respectively acidic group-substituted pyrroles, acidic group-substituted thiophenes, acidic group-substituted furans, acidic group-substituted selenophenes, acidic group-substituted tellurophenes, acidic group-substituted isothianaphthenes, acidic group-substituted isobenzofurans, acidic group-substituted isoindolines, acidic group-substituted isobenzoselenophenes and acidic group-substituted isobenzotellurophenes represented by the general formulas (2) and (3):
(2) (3) wherein Z is any one of NH, S, O, Se and Te; R'1, R'2, R'3 and R'4 are substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, acidic groups, hydroxyl group, nitro group and halogen groups; and at least one of R'1 to R'4 is an acidic group, wherein the acidic group means a sulfonic acid group or carboxyl group.
(1) wherein R1, R2, R3, R4 and R5 are substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, acidic groups, hydroxyl group, nitro group and halogen groups, and at least one of R1 to R5 is an acidic group wherein the acidic group means a sulfonic acid group or a carboxyl group; and the above acidic group-substituted pyrroles, acidic group-substituted thiophenes, acidic group-substituted furans, acidic group-substituted selenophenes, acidic group-substituted tellurophenes, acidic group-substituted isothianaphthenes, acidic group-substituted isobenzofurans, acidic group-substituted isoindolines, acidic group-substituted isobenzoselenophenes and acidic group-substituted isobenzotellurophenes are respectively acidic group-substituted pyrroles, acidic group-substituted thiophenes, acidic group-substituted furans, acidic group-substituted selenophenes, acidic group-substituted tellurophenes, acidic group-substituted isothianaphthenes, acidic group-substituted isobenzofurans, acidic group-substituted isoindolines, acidic group-substituted isobenzoselenophenes and acidic group-substituted isobenzotellurophenes represented by the general formulas (2) and (3):
(2) (3) wherein Z is any one of NH, S, O, Se and Te; R'1, R'2, R'3 and R'4 are substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, acidic groups, hydroxyl group, nitro group and halogen groups; and at least one of R'1 to R'4 is an acidic group, wherein the acidic group means a sulfonic acid group or carboxyl group.
4. A method for producing a soluble conductive polymer having acidic groups, which comprises subjecting to electrolytic polymerization (a) at least one compound selected from the group consisting of acidic group-substituted anilines, acidic group-substituted pyrroles, acidic group-substituted thiophenes, acidic group-substituted furans, acidic group-substituted selenophenes, acidic group-substituted tellurophenes, acidic group-substituted isothianaphthenes, acidic group-substituted isobenzofurans, acidic group-substituted isoindolines, acidic group-substituted isobenzoselenophenes and acidic group-substituted isobenzotellurophenes and their metal salts, ammonium salts and substituted ammonium salts and (c) at least one compound selected from the group consisting of aniline derivatives, pyrrole derivatives, thiophene derivatives, furan derivatives, selenophene derivatives, tellurophene derivatives, isothianaphthene derivatives, isobenzofuran derivatives, isoindoline derivatives, isobenzoselenophene derivatives and isobenzotellurophene derivatives in a solution containing (c) a basic compound.
5. The method according to Claim 4, wherein the electrolytic polymerization is continuously effected using interconnected cells connected in series, in parallel or in combination thereof.
6. The method according to Claim 4 or 5, wherein the above aniline derivatives are aniline derivatives represented by the general formula (4):
(4) wherein R6, R7, R8, R9 and R10 are substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, hydroxyl group, nitro group and halogen groups; and the above pyrrole derivatives, thiophene derivatives, furan derivatives, selenophene derivatives, tellurophene derivatives, isothianaphthene derivatives, isobenzofuran derivatives, isoindoline derivatives, isobenzoselenophene derivatives and isobenzotellurophene derivatives are respectively pyrrole derivatives, thiophene derivatives, furan derivatives, selenophene derivatives, tellurophene derivatives, isothianaphthene derivatives, isobenzofuran derivatives, isoindoline derivatives, isobenzoselenophene derivatives and isobenzotellurophene derivatives represented by the general formulas (5) and (6):
(5) (6) wherein Z is any one of HN, S, O, Se and Te and R'6, R'7, R'8 and R'9 are substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, hydroxyl group, nitro group and halogen groups.
(4) wherein R6, R7, R8, R9 and R10 are substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, hydroxyl group, nitro group and halogen groups; and the above pyrrole derivatives, thiophene derivatives, furan derivatives, selenophene derivatives, tellurophene derivatives, isothianaphthene derivatives, isobenzofuran derivatives, isoindoline derivatives, isobenzoselenophene derivatives and isobenzotellurophene derivatives are respectively pyrrole derivatives, thiophene derivatives, furan derivatives, selenophene derivatives, tellurophene derivatives, isothianaphthene derivatives, isobenzofuran derivatives, isoindoline derivatives, isobenzoselenophene derivatives and isobenzotellurophene derivatives represented by the general formulas (5) and (6):
(5) (6) wherein Z is any one of HN, S, O, Se and Te and R'6, R'7, R'8 and R'9 are substituents selected from the group consisting of hydrogen, straight chain or branched chain alkyl groups having 1 to 24 carbon atoms, straight chain or branched chain alkoxy groups having 1 to 24 carbon atoms, hydroxyl group, nitro group and halogen groups.
7. The method according to Claim 4 or 5, wherein the molar proportion between the above compound (a) and the above compound (c) is in such a range that (a) : (c) = 100 : 0 to 30 : 70.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27987296 | 1996-10-02 | ||
| JP08-279872 | 1996-10-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2217378A1 true CA2217378A1 (en) | 1998-04-02 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002217378A Abandoned CA2217378A1 (en) | 1996-10-02 | 1997-10-01 | Method for producing soluble conductive polymer having acidic group |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5980784A (en) |
| EP (1) | EP0834885B1 (en) |
| KR (1) | KR19980032472A (en) |
| AU (1) | AU733376B2 (en) |
| CA (1) | CA2217378A1 (en) |
| DE (1) | DE69709819T2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432324B1 (en) * | 1999-08-25 | 2002-08-13 | Canon Kasei Kabushiki Kaisha | Semiconducting member, functional member for electrophotography, and process cartridge |
| WO2003018648A1 (en) * | 2001-08-31 | 2003-03-06 | Tda Research, Inc. | Poly(heteroaromatic) block copolymers with electrical conductivity |
| US7687582B1 (en) | 2001-08-31 | 2010-03-30 | Tda Research, Inc. | Methods of production, purification, and processing of poly(heteroaromatic) block copolymers with improved solubility or dispersability |
| TW200619301A (en) * | 2004-09-22 | 2006-06-16 | Showa Denko Kk | The water-soluable composition of antistatic agent, the antistatic agent, the method of forming antistatic film, coated products and pattern by using the same the agent |
| US7361728B1 (en) | 2004-09-30 | 2008-04-22 | Tda Research, Inc. | Electrically conducting materials from branched end-capping intermediates |
| DE102004047466A1 (en) * | 2004-09-30 | 2006-04-06 | Robert Bosch Gmbh | Method for the determination of acidic gases and sensor |
| CA2658181C (en) | 2006-07-21 | 2015-01-06 | Plextronics, Inc. | Sulfonation of conducting polymers and oled, photovoltaic, and esd devices |
| EP2291427B1 (en) | 2008-06-09 | 2016-03-30 | Solvay USA Inc. | Sulfonated polythiophenes comprising fused ring repeat units |
| BR112013002602A2 (en) * | 2010-08-02 | 2016-06-07 | Univ Florida | processing method for water soluble polymeric materials |
| WO2012145885A1 (en) * | 2011-04-25 | 2012-11-01 | Tongji University | Aniline copolymers and methods for their preparation and use |
| CN104211927A (en) | 2013-05-29 | 2014-12-17 | 纳米及先进材料研发院有限公司 | New conductive and photosensitive polymers |
| WO2015042971A1 (en) * | 2013-09-30 | 2015-04-02 | Tongji University | Lead ion sensors, methods of making and uses thereof |
| CN115490853B (en) * | 2022-06-29 | 2024-01-30 | 江西有泽新材料科技有限公司 | High-performance polyimide flexible copper-clad plate and preparation method thereof |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58210902A (en) * | 1982-05-31 | 1983-12-08 | Shin Etsu Chem Co Ltd | Polymerization of vinyl monomer |
| DE3318857A1 (en) * | 1983-05-25 | 1984-11-29 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING POLYPYROLES AND FILM-SHAPED PRODUCTS OBTAINED BY THIS METHOD |
| JPS60235831A (en) * | 1984-05-08 | 1985-11-22 | Matsushita Electric Ind Co Ltd | Synthesis of aniline polymer |
| JPH089662B2 (en) * | 1985-02-26 | 1996-01-31 | 日東電工株式会社 | Conductive material |
| GB8717458D0 (en) * | 1987-07-23 | 1987-08-26 | Cookson Group Plc | Electroconductive polymers |
| US5164465A (en) * | 1988-05-13 | 1992-11-17 | Ohio State University Research Foundation | Sulfonated polyaniline salt compositions, processes for their preparation and uses thereof |
| JP2699500B2 (en) * | 1988-12-21 | 1998-01-19 | 東ソー株式会社 | Conductive polymer composite |
| DE69013078T2 (en) * | 1989-07-04 | 1995-01-26 | Fuji Photo Film Co Ltd | Electrically conductive polymer and containing electroconductive material. |
| US5109070A (en) * | 1989-10-19 | 1992-04-28 | Ohio State University Research Foundation | Compositions of insulating polymers and sulfonated polyaniline compositions and uses thereof |
| JPH04268331A (en) * | 1991-02-25 | 1992-09-24 | Fuji Xerox Co Ltd | Production of self-doping conductive polymer |
| JPH05226238A (en) * | 1991-10-31 | 1993-09-03 | Internatl Business Mach Corp <Ibm> | Discharge top layer capable of being developed by base for e-beam resist use |
| JP3051244B2 (en) * | 1991-12-27 | 2000-06-12 | 三菱レイヨン株式会社 | Sulfonated aniline copolymers and their preparation |
| JP3112745B2 (en) * | 1992-06-17 | 2000-11-27 | 富士通株式会社 | Conductive composition for pattern formation and pattern forming method using the composition |
| JPH0656987A (en) * | 1992-08-11 | 1994-03-01 | Bridgestone Corp | Produciton of conductive polymer |
| JP2903038B2 (en) * | 1993-02-15 | 1999-06-07 | 三菱レイヨン株式会社 | Aniline-based conductive polymer and method for producing the same |
| JP2912123B2 (en) * | 1993-07-22 | 1999-06-28 | 新日本製鐵株式会社 | Manufacturing method of high-strength and high-toughness bainite-based rail with excellent surface damage resistance |
| JP2959968B2 (en) * | 1994-04-04 | 1999-10-06 | 三菱レイヨン株式会社 | Method for producing soluble aniline-based conductive polymer |
| US5589108A (en) * | 1993-12-29 | 1996-12-31 | Nitto Chemical Industry Co., Ltd. | Soluble alkoxy-group substituted aminobenzenesulfonic acid aniline conducting polymers |
| JP3154460B2 (en) * | 1993-12-29 | 2001-04-09 | 三菱レイヨン株式会社 | Water-soluble aniline-based conductive polymer and method for producing the same |
-
1997
- 1997-10-01 AU AU39877/97A patent/AU733376B2/en not_active Ceased
- 1997-10-01 US US08/941,742 patent/US5980784A/en not_active Expired - Lifetime
- 1997-10-01 KR KR1019970050785A patent/KR19980032472A/en not_active Application Discontinuation
- 1997-10-01 CA CA002217378A patent/CA2217378A1/en not_active Abandoned
- 1997-10-02 EP EP97117136A patent/EP0834885B1/en not_active Expired - Lifetime
- 1997-10-02 DE DE69709819T patent/DE69709819T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0834885B1 (en) | 2002-01-02 |
| AU3987797A (en) | 1999-04-22 |
| DE69709819D1 (en) | 2002-02-28 |
| US5980784A (en) | 1999-11-09 |
| KR19980032472A (en) | 1998-07-25 |
| EP0834885A2 (en) | 1998-04-08 |
| EP0834885A3 (en) | 1998-11-18 |
| DE69709819T2 (en) | 2002-08-14 |
| AU733376B2 (en) | 2001-05-10 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Discontinued |