JP2005132852A - Dopant for preparing conductive polymeric material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dopant for preparing a conductive polymeric material which has excellent conductivity and can obtain a conductive polymeric material capable of sufficiently maintaining its conductivity even under severe conditions, for example, even on exposure to high temperature and high humidity. <P>SOLUTION: The dopant for preparing the conductive polymeric material used is formed of a perfluoroalkylnaphthalenesulfonate ion represented by the formula (wherein a is an integer of 1-7; p and q are each an integer of 1-3; and X is a residue of naphthalene from which (p+q) hydrogen atoms are removed) and a counter anion of a lithium ion, a sodium ion, a potassium ion or a trivalent iron ion. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a dopant agent for preparing a conductive polymer material. Conductive polymer materials obtained by doping electron conjugated polymers such as polyacetylene, polyparaphenylene, polypyrrole, polyaniline, and polythiophene with an electron-accepting compound as a dopant agent include, for example, electronic materials such as capacitor electrode materials and the like. It is attracting attention as a battery electrode material. Such conductive polymer materials are required to have excellent conductivity due to their properties, and to maintain the conductivity sufficiently even under severe conditions, for example, even when exposed to high temperature and high humidity. The The present invention relates to a dopant agent capable of obtaining a conductive polymer material that meets such requirements.

Conventionally, as a dopant agent as described above, a benzenesulfonic acid derivative (see, for example, Patent Document 1), an m-fluorobenzenesulfonic acid derivative (see, for example, Patent Document 2), a sulfanilic acid derivative (see, for example, Patent Document 3), an alkoxy group Aromatic sulfonated products (see, for example, Patent Document 4) and the like are known. However, with these conventional dopant agents, it is not possible to obtain a conductive polymer material that has excellent conductivity and sufficiently retains the conductivity even under severe conditions.
JP 2000-204074 A JP 2003-40856 A JP 2003-64165 A JP 2003-160647 A

  The problem to be solved by the present invention is to obtain a conductive polymer material that has excellent conductivity and retains the conductivity sufficiently even under severe conditions, for example, even when exposed to high temperature and high humidity. It is in providing a dopant agent that can be used.

  Therefore, as a result of researches to solve the above problems, the present inventors have found that a specific perfluoroalkylnaphthalene sulfonate is correctly suitable as a dopant agent used for preparing a conductive polymer material. .

  That is, the present invention is characterized by comprising one or two or more selected from perfluoroalkylnaphthalene sulfonates formed from perfluoroalkylnaphthalene sulfonate ions represented by the following chemical formula 1 and the following counter cations. The present invention relates to a dopant agent for preparing a conductive polymer material.

In chemical formula 1,
a: integer of 1 to 7 p, q: integer of 1 to 3 X: residue obtained by removing p + q hydrogen atoms from naphthalene

  Counter cation: lithium ion, sodium ion, potassium ion or trivalent iron ion

  In the perfluoroalkylnaphthalene sulfonate formed from the perfluoroalkylnaphthalene sulfonate ion represented by Chemical Formula 1 and the counter cation, 1) p in Chemical Formula 1 is 1 as the perfluoroalkylnaphthalene sulfonate ion and Monoperfluoroalkylnaphthalene monosulfonate using the case where q is 1 2) As perfluoroalkylnaphthalene sulfonate ion, p in Chemical Formula 1 is 2 and q is 1 Diperfluoroalkylnaphthalene monosulfonate, 3) a triperfluoroalkylnaphthalene monosulfonate using a perfluoroalkylnaphthalenesulfonate ion in which p in Chemical Formula 1 is 3 and q is 1. 4 ) Perfluoroalkyl naphthalene sulphur Monoperfluoroalkyl naphthalene disulfonate using p1 in Chemical Formula 1 as 1 and q being 2 as the acid ion, 5) p in Chemical Formula 1 as 2 as the perfluoroalkylnaphthalene sulfonate ion And diperfluoroalkylnaphthalene disulfonate using the case where q is 2, and 6) as the perfluoroalkylnaphthalene sulfonate ion, when p in Chemical Formula 1 is 3 and q is 2. Triperfluoroalkylnaphthalene disulfonate, 7) monoperfluoroalkylnaphthalene trisulfonate using p = 1 in the chemical formula 1 and q being 3 as the perfluoroalkylnaphthalene sulfonate ion, 8) As perfluoroalkylnaphthalene sulfonate ion in Diperfluoroalkylnaphthalene trisulfonate using a compound in which q is 2 and q is 3, 9) when p in Chemical Formula 1 is 3 and q is 3 as a perfluoroalkylnaphthalene sulfonate ion And triperfluoroalkylnaphthalene trisulfonates are used. Among these, a part of the monoperfluoroalkylnaphthalene monosulfonate using a perfluoroalkylnaphthalenesulfonate ion in which p in Chemical Formula 1 is 1 and q is 1 is a dispersant. And known as an antistatic agent (JP 2003-267946 A, JP 2003-277347 A).

  Monoperfluoroalkylnaphthalene monosulfonate using perfluoroalkylnaphthalene sulfonate ion in which p in Chemical Formula 1 is 1 and q is 1 is mono (2,2,3,3-tetra Fluoropropyl) naphthalene monosulfonate, mono (2,2,3,3,4,4-hexafluorobutyl) naphthalene monosulfonate, mono (2,2,3,3,4,4,5,5) -Octafluoropentyl) naphthalene monosulfonate, mono (2,2,3,3,4,4,5,5,6,6-decafluorohexyl) naphthalene monosulfonate, mono (2,2,3 , 3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) naphthalene monosulfonate, mono (2,2,3,3,4,4,5,5,6,6) , 7,7, , 8-Tetradecafluorooctyl) naphthalene monosulfonate, mono (2,2,3,3,4,5,5,6,6,7,7,8,8,9,9-hexadeca) Fluorononyl) naphthalene monosulfonate and the like.

  Diperfluoroalkylnaphthalene monosulfonate using a perfluoroalkylnaphthalene sulfonate ion in which p in Chemical Formula 1 is 2 and q is 1 is di (2,2,3,3-tetra Fluoropropyl) naphthalene monosulfonate, di (2,2,3,3,4,4-hexafluorobutyl) naphthalene monosulfonate, di (2,2,3,3,4,4,5,5 -Octafluoropentyl) naphthalene monosulfonate, di (2,2,3,3,4,4,5,5,6,6-decafluorohexyl) naphthalene monosulfonate, di (2,2,3 , 3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) naphthalene monosulfonate, di (2,2,3,3,4,4,5,5,6,6) , 7,7,8,8-tetra Cafluorooctyl) naphthalene monosulfonate, di (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl) naphthalene A monosulfonic acid salt etc. are mentioned.

  Triperfluoroalkylnaphthalene monosulfonate using a perfluoroalkylnaphthalenesulfonate ion in which p in Chemical Formula 1 is 3 and q is 1 is tri (2,2,3,3-tetra Fluoropropyl) naphthalene monosulfonate, tri (2,2,3,3,4,4-hexafluorobutyl) naphthalene monosulfonate, tri (2,2,3,3,4,4,5,5 -Octafluoropentyl) naphthalene monosulfonate, tri (2,2,3,3,4,4,5,5,6,6-decafluorohexyl) naphthalene monosulfonate, tri (2,2,3 , 3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) naphthalene monosulfonate, tri (2,2,3,3,4,4,5,5,6,6) , 7,7, , 8-Tetradecafluorooctyl) naphthalene monosulfonate, tri (2,2,3,3,4,5,5,6,6,7,7,8,8,9,9-hexadeca) Fluorononyl) naphthalene monosulfonate and the like.

  Monoperfluoroalkylnaphthalenedisulfonates using perfluoroalkylnaphthalenesulfonate ions in which p in Chemical Formula 1 is 1 and q is 2 are mono (2,2,3,3-tetrafluoro). Propyl) naphthalene disulfonate, mono (2,2,3,3,4,4-hexafluorobutyl) naphthalene disulfonate, mono (2,2,3,3,4,4,5,5-octafluoro Pentyl) naphthalene disulfonate, mono (2,2,3,3,4,4,5,5,6,6-decafluorohexyl) naphthalene disulfonate, mono (2,2,3,3,4) 4,5,5,6,6,7,7-dodecafluoroheptyl) naphthalene disulfonate, mono (2,2,3,3,4,4,5,5,6,6,7,7,8) , 8-teto Decafluorooctyl) naphthalene disulfonate, mono (2,2,3,3,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl) naphthalene disulfone Examples include acid salts.

  Diperfluoroalkylnaphthalene disulfonate using a perfluoroalkylnaphthalenesulfonate ion in which p in Chemical Formula 1 is 2 and q is 2 is di (2,2,3,3-tetrafluoro Propyl) naphthalene disulfonate, di (2,2,3,3,4,4-hexafluorobutyl) naphthalene disulfonate, di (2,2,3,3,4,4,5,5-octafluoro Pentyl) naphthalene disulfonate, di (2,2,3,3,4,4,5,5,6,6-decafluorohexyl) naphthalene disulfonate, di (2,2,3,3,4,4) 4,5,5,6,6,7,7-dodecafluoroheptyl) naphthalene disulfonate, di (2,2,3,3,4,4,5,5,6,6,7,7,8) , 8-Tetradecafluoro Octyl) naphthalene disulfonate, di (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl) naphthalene disulfonate Etc.

  A triperfluoroalkylnaphthalene disulfonate using a perfluoroalkylnaphthalenesulfonate ion in which p in Chemical Formula 1 is 3 and q is 2 is tri (2,2,3,3-tetrafluoro). Propyl) naphthalene disulfonate, tri (2,2,3,3,4,4-hexafluorobutyl) naphthalene disulfonate, tri (2,2,3,3,4,4,5,5-octafluoro Pentyl) naphthalene disulfonate, tri (2,2,3,3,4,4,5,5,6,6-decafluorohexyl) naphthalene disulfonate, tri (2,2,3,3,4) 4,5,5,6,6,7,7-dodecafluoroheptyl) naphthalene disulfonate, tri (2,2,3,3,4,4,5,5,6,6,7,7,8 , 8-teto Decafluorooctyl) naphthalene disulfonate, tri (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl) naphthalene disulfone Examples include acid salts.

  Monoperfluoroalkylnaphthalene trisulfonic acid using perfluoroalkylnaphthalenesulfonic acid ion in which p in Chemical Formula 1 is 1 and q is 3 is mono (2,2,3,3-tetrafluoro). Propyl) naphthalene trisulfonate, mono (2,2,3,3,4,4-hexafluorobutyl) naphthalene trisulfonate, mono (2,2,3,3,4,4,5,5- Octafluoropentyl) naphthalene trisulfonate, mono (2,2,3,3,4,4,5,5,6,6-decafluorohexyl) naphthalene trisulfonate, mono (2,2,3 3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) naphthalene trisulfonate, mono (2,2,3,3,4,4,5,5,6,6) 7, 7, 8 8-tetradecafluorooctyl) naphthalene trisulfonate, mono (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro Nonyl) naphthalene trisulfonate and the like.

  Diperfluoroalkylnaphthalene trisulfonate using a perfluoroalkylnaphthalenesulfonate ion in which p in Chemical Formula 1 is 2 and q is 3 is di (2,2,3,3-tetra Fluoropropyl) naphthalene trisulfonate, di (2,2,3,3,4,4-hexafluorobutyl) naphthalene trisulfonate, di (2,2,3,3,4,4,5,5 -Octafluoropentyl) naphthalene trisulfonate, di (2,2,3,3,4,4,5,5,6,6-decafluorohexyl) naphthalene trisulfonate, di (2,2,3 , 3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) naphthalene trisulfonate, di (2,2,3,3,4,4,5,5,6,6) , 7,7,8,8-tetra Cafluorooctyl) naphthalene trisulfonate, di (2,2,3,3,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl) naphthalene Examples include trisulfonate.

  A triperfluoroalkylnaphthalene trisulfonate using a perfluoroalkylnaphthalenesulfonate ion in which p in Chemical Formula 1 is 3 and q is 3 is tri (2,2,3,3-tetra Fluoropropyl) naphthalene trisulfonate, tri (2,2,3,3,4,4-hexafluorobutyl) naphthalene trisulfonate, tri (2,2,3,3,4,4,5,5 -Octafluoropentyl) naphthalene trisulfonate, tri (2,2,3,3,4,4,5,5,6,6-decafluorohexyl) naphthalene trisulfonate, tri (2,2,3 , 3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) naphthalene trisulfonate, tri (2,2,3,3,4,4,5,5,6,6) , 7,7, , 8-tetradecafluorooctyl) naphthalene trisulfonate, tri (2,2,3,3,4,5,5,6,6,7,7,8,8,9,9-hexadeca) Fluorononyl) naphthalene trisulfonate and the like.

  In the perfluoroalkylnaphthalene sulfonate exemplified above, the cation forming a pair of perfluoroalkylnaphthalene sulfonate ions represented by Chemical Formula 1 is a lithium ion, a sodium ion, a potassium ion, or a trivalent iron ion.

  The dopant agent for preparing a conductive polymer material according to the present invention (hereinafter simply referred to as the dopant agent of the present invention) comprises one or more selected from perfluoroalkylnaphthalene sulfonates as described above. is there. In the case of one, the dopant agent of the present invention consists of a single substance, and in the case of two or more, the dopant agent of the present invention consists of a mixture. Those consisting of a mixture are preferred. Among them, as the perfluoroalkylnaphthalene sulfonate ion, a perfluoroalkyl naphthalene monosulfonate using a compound in which q in Chemical Formula 1 is 1 and a compound in which q in Chemical Formula 1 is 2 were used. More preferred are perfluoroalkylnaphthalene polysulfonates and / or mixtures with perfluoroalkylnaphthalene polysulfonates using those where q in Chemical Formula 1 is 3, in such mixtures, perfluoroalkylnaphthalene monosulfonate and perfluoro Alkylnaphthalene polysulfonic acid salt using perfluoroalkylnaphthalene sulfonate ion when p in chemical formula 1 is 1 and / or using p 2 in chemical formula 1 being 2 Is particularly preferred.

  In the above mixture, the perfluoroalkylnaphthalene monosulfonate and the perfluoroalkylnaphthalene polysulfonate may have any content, but perfluoroalkylnaphthalene monosulfonate / perfluoroalkylnaphthalene polysulfonate = 0.5. What is contained in the ratio of /99.5-70/30 (mol%) is preferable, and what is contained in the ratio of 1 / 99-45 / 55 (mol%) is more preferable.

The mixture of perfluoroalkylnaphthalene sulfonates described above can be produced by various methods, but those obtained through the following first step, second step and third step are preferred.
1st process: The process of carrying out the sulfonation reaction of the naphthalene and 90-100% concentration sulfuric acid under the temperature of 70-250 degreeC, and producing | generating the mixture of a naphthalenesulfonic acid.
Second Step: A mixture of naphthalenesulfonic acid produced in the first step and a perfluoroalkyl alcohol represented by the following chemical formula 2 are subjected to a perfluoroalkylation reaction at a temperature of 0 to 150 ° C. using an acid catalyst, Forming a mixture of perfluoroalkylnaphthalene sulfonic acids;
Third step: A step of neutralizing the mixture of perfluoroalkylnaphthalenesulfonic acid generated in the second step and an alkali in an aqueous alcohol solution to generate a mixture of perfluoroalkylnaphthalenesulfonate.

In chemical formula 2,
b: an integer from 1 to 7

  In the first step, naphthalene and sulfuric acid are sulfonated to form a mixture of naphthalenesulfonic acid. Here, sulfuric acid having a concentration of 90 to 100% is used. The charging ratio of naphthalene and sulfuric acid is usually naphthalene / sulfuric acid = 15/85 to 60/40 (mol%), but is preferably 25/75 to 50/50 (mol%). The sulfonation reaction is performed at a temperature of 70 to 250 ° C., but is preferably performed at a temperature of 160 to 210 ° C. Formation of a mixture of naphthalene sulfonic acids can be confirmed by analysis by high performance liquid chromatography. In the first step, a reaction liquid containing a mixture of the produced naphthalenesulfonic acid is obtained, but this can be used as it is for the second step.

  In the second step, the mixture of naphthalenesulfonic acid generated in the first step and the perfluoroalkyl alcohol represented by Chemical Formula 2 are perfluoroalkylated to form a mixture of perfluoroalkylnaphthalenesulfonic acid. The charging ratio of the mixture of naphthalene sulfonic acid and perfluoroalkyl alcohol is usually a mixture of naphthalene sulfonic acid / perfluoroalkyl alcohol = 15 / 85-60 / 40 (mol%), but 25 / 75-50 / 50 ( Mol%). An acid catalyst is used for the perfluoroalkylation reaction. Examples of the acid catalyst include anhydrous aluminum chloride, anhydrous zinc chloride, boron trifluoride, hydrofluoric acid, sulfuric acid and the like, and among them, anhydrous aluminum chloride is preferable. The amount of the acid catalyst used is usually 0.0001 to 2 moles per mole of perfluoroalkyl alcohol. The perfluoroalkylation reaction is carried out at a temperature of 0 to 150 ° C., preferably 25 to 80 ° C. Formation of a mixture of perfluoroalkylnaphthalenesulfonic acid can be confirmed by analysis by high performance liquid chromatography. In the second step, a reaction solution containing a mixture of the perfluoroalkylnaphthalenesulfonic acid thus produced is obtained, but this can be used as it is for the third step.

  In the third step, the mixture of perfluoroalkylnaphthalenesulfonic acid generated in the second step and the alkali are neutralized in an aqueous alcohol solution to form a mixture of perfluoroalkylnaphthalenesulfonate. The amount of alkali used in the neutralization reaction is usually an amount corresponding to 1.0 to 1.1 equivalents of the acid value of the reaction solution containing the mixture of perfluoroalkylnaphthalenesulfonic acid produced in the second step. Examples of the alkali include hydroxides, carbonates, alcoholates and the like of atoms corresponding to the counter cation described above. Examples thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium ethylate, sodium ethylate, potassium ethylate, iron hydroxide and the like. The neutralization reaction is usually carried out at a temperature of 0 to 90 ° C. by adding the reaction liquid containing the perfluoroalkylnaphthalenesulfonic acid mixture produced in the second step to an alcohol aqueous solution in which an alkali is dissolved with stirring. Thus a mixture of perfluoroalkylnaphthalene sulfonates is formed. The mixture of perfluoroalkylnaphthalene sulfonates is obtained by separating and purifying from the reaction solution obtained in the third step described above. For example, sodium sulfate by-produced from the reaction solution is first filtered off to obtain a filtrate containing a mixture of perfluoroalkylnaphthalene sulfonates. Next, the solvent is distilled off from the filtrate under reduced pressure to obtain a solid content. Finally, the solid content is purified by recrystallization or column chromatography to obtain a mixture of perfluoroalkylnaphthalene sulfonates.

Moreover, what is obtained through the following A process, B process, and C process for the mixture of perfluoroalkyl naphthalene sulfonate is preferable.
Step A: A step of producing a mixture of perfluoroalkylnaphthalene by subjecting naphthalene and the perfluoroalkyl alcohol represented by Chemical Formula 2 to a perfluoroalkylation reaction at a temperature of 0 to 150 ° C. using an acid catalyst.
Step B: A step of allowing the mixture of perfluoroalkylnaphthalene produced in Step A and fuming sulfuric acid to undergo a sulfonation reaction at a temperature of 40 to 250 ° C. to produce a mixture of perfluoroalkylnaphthalenesulfonic acid.
Step C: A step of neutralizing the mixture of perfluoroalkylnaphthalenesulfonic acid generated in Step B and an alkali in an aqueous alcohol solution to form a mixture of perfluoroalkylnaphthalenesulfonate.

  In Step A, naphthalene and perfluoroalkyl alcohol represented by Chemical Formula 2 are perfluoroalkylated to form a mixture of perfluoroalkylnaphthalene. The charging ratio of naphthalene and perfluoroalkyl alcohol is usually naphthalene / perfluoroalkyl alcohol = 15/85 to 70/30 (mol%), preferably 25/75 to 50/50 (mol%). . In step A, an acid catalyst is used in the perfluoroalkylation reaction. Examples of the acid catalyst include anhydrous aluminum chloride, anhydrous zinc chloride, boron trifluoride, hydrofluoric acid, sulfuric acid and the like, and among them, anhydrous aluminum chloride is preferable. The amount of the acid catalyst used is usually 0.0001 to 2 moles per mole of perfluoroalkyl alcohol. The perfluoroalkylation reaction is carried out at a temperature of 0 to 150 ° C., but is preferably carried out at a temperature of 25 to 80 ° C. The formation of a mixture of perfluoroalkylnaphthalene can be confirmed by analysis by high performance liquid chromatography. In step A, a reaction liquid containing a mixture of the generated perfluoroalkylnaphthalene is obtained. Therefore, a mixture of perfluoroalkylnaphthalene as a product is separated from the reaction liquid, and this is supplied to step B. For example, water is added to the reaction solution while cooling it to 10 ° C. or lower to deactivate the acid catalyst and stratify and separate into an aqueous layer and an oil layer, then remove the aqueous layer and wash the oil layer with water. Is subjected to dehydration treatment and supplied to step B.

  In step B, the mixture of perfluoroalkylnaphthalene produced in step A is sulfonated with fuming sulfuric acid to produce a mixture of perfluoroalkylnaphthalenesulfonic acid. The charging ratio of the mixture of perfluoroalkylnaphthalene and fuming sulfuric acid is usually perfluoroalkylnaphthalene mixture / fuming sulfuric acid = 15 / 85-60 / 40 (mol%), but 25 / 75-50 / 50 (mol%). It is preferable that The sulfonation reaction is carried out at a temperature of 40 to 250 ° C., preferably 60 to 160 ° C. Formation of a mixture of perfluoroalkylnaphthalenesulfonic acid can be confirmed by analysis by high performance liquid chromatography. In Step B, a reaction solution containing a mixture of the perfluoroalkylnaphthalenesulfonic acid thus produced is obtained, but this can be used as it is in Step C.

  In step C, the mixture of perfluoroalkylnaphthalene sulfonic acid generated in step B and an alkali are neutralized in an aqueous alcohol solution to form a mixture of perfluoroalkyl naphthalene sulfonate. The amount of alkali used in the neutralization reaction is usually an amount corresponding to 1.0 to 1.1 equivalents of the acid value of the reaction solution containing the mixture of perfluoroalkylnaphthalenesulfonic acid produced in Step B. The type of alkali and the neutralization reaction are the same as described above for the third step. Thus a mixture of perfluoroalkylnaphthalene sulfonates is formed. A mixture of perfluoroalkylnaphthalene sulfonates can be obtained by separating and purifying from the reaction solution obtained in step C described above. Such separation and purification operations are the same as described above.

  The electron conjugated polymer to which the dopant agent of the present invention is applied may be a polymer having an electron conjugated molecular structure, specifically, a structural unit formed from a pyrrole monomer, a thiophene monomer Examples include a polymer having a repeating unit of at least one selected from a structural unit formed from a body and a structural unit formed from an aniline monomer, among which a structural unit formed from a pyrrole monomer A polymer having a repeating unit as is preferred.

  As a method for doping the electron-conjugated polymer with the dopant agent of the present invention, known methods such as an immersion method, an electrolytic oxidation polymerization method, and a chemical oxidation polymerization method can be applied. In the doping by the dipping method, a solvent that dissolves the dopant agent of the present invention is used. Examples of such a solvent include water, acetonitrile, propylene carbonate, nitrobenzene, and benzonitrile. In doping by electrolytic oxidation polymerization, a predetermined current is applied to a solution containing the dopant agent of the present invention and a monomer that will form a conjugated polymer. Further, in doping by chemical oxidative polymerization, a transition metal complex having a conjugate base of the dopant agent of the present invention as a ligand is contacted with a monomer that will form an electron conjugated system in a solvent.

  The conductive polymer material thus obtained has excellent conductivity and sufficiently retains the conductivity even under severe conditions, for example, when exposed to high temperature and high humidity. Therefore, such a conductive polymer material can be applied to capacitor electrode materials, battery electrode materials, electromagnetic wave shielding materials, conductive adhesives, conductive paints, wiring materials, display materials, overcurrent protection elements, semiconductor elements, and the like.

  According to the dopant agent of the present invention, it is possible to obtain a conductive polymer material having excellent conductivity and sufficiently maintaining the conductivity even under severe conditions, for example, even when exposed to high temperature and high humidity. Can do.

Examples of the dopant agent of the present invention include the following 1) to 13).
1) A dopant agent comprising a perfluoroalkylnaphthalene sulfonate formed from (2,2,3,3-tetrafluoropropyl) naphthalene sulfonate ion and lithium ion.

  2) A dopant agent comprising a perfluoroalkylnaphthalene sulfonate formed from (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene sulfonate ion and sodium ion.

  3) (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononyl) formed from naphthalene sulfonate ion and potassium ion A dopant agent comprising a perfluoroalkylnaphthalene sulfonate.

  4) A dopant agent comprising a perfluoroalkylnaphthalene sulfonate formed from tri (2,2,3,3-tetrafluoropropyl) naphthalene sulfonate ion and sodium ion.

  5) A dopant agent comprising a perfluoroalkylnaphthalene sulfonate formed from di (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalenedisulfonate ion and sodium ion.

  6) From (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononyl) naphthalene trisulfonate ion and sodium ion A dopant agent comprising a formed perfluoroalkylnaphthalene sulfonate.

  7) (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononyl) naphthalene trisulfonate ion and trivalent iron A dopant agent comprising a perfluoroalkylnaphthalene sulfonate formed from ions.

8) A dopant agent comprising a mixture of perfluoroalkylnaphthalene sulfonates obtained through the following first step, second step and third step.
First step: A step of allowing 12.8 g of naphthalene and 20.4 g of 96% sulfuric acid to undergo a sulfonation reaction at a temperature of 190 ° C. to form a mixture of naphthalenesulfonic acid.
Second step: A mixture of naphthalenesulfonic acid produced in the first step and 23.2 g of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were mixed with 96% sulfuric acid 20 And a perfluoroalkylation reaction at a temperature of 100 ° C. using 4 g to produce a mixture of (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalenesulfonic acid.
Third step: A mixture of (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalenesulfonic acid produced in the second step and 25.3 g of potassium hydroxide in an aqueous alcohol solution To produce a mixture of perfluoroalkylnaphthalene sulfonates formed from (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene sulfonate ions and potassium ions Process.

9) A dopant agent comprising a mixture of perfluoroalkylnaphthalene sulfonates obtained through the following first step, second step and third step.
First step: a step of producing a mixture of naphthalene sulfonic acids by subjecting 12.8 g of naphthalene and 20.4 g of 96% sulfuric acid to a sulfonation reaction at a temperature of 180 ° C.
Second Step: A mixture of naphthalene sulfonic acid produced in the first step and 23.2 g of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol were mixed with 96% sulfuric acid 25 .2g, and a perfluoroalkylation reaction at a temperature of 100 ° C. to produce a mixture of (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalenesulfonic acid.
Third step: A mixture of (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalenesulfonic acid produced in the second step and 25.0 g of sodium hydroxide in an aqueous alcohol solution To produce a mixture of perfluoroalkylnaphthalene sulfonates formed from (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene sulfonate ions and sodium ions Process.

10) A dopant agent comprising a mixture of perfluoroalkylnaphthalene sulfonates obtained through the following first step, second step and third step.
First step: a step of producing a mixture of naphthalene sulfonic acids by subjecting 12.8 g of naphthalene and 20.4 g of 96% sulfuric acid to a sulfonation reaction at a temperature of 180 ° C.
Second step: A mixture of naphthalene sulfonic acid produced in the first step and 13.2, g of 2,2,3,3-tetrafluoropropanol, 15.2 g of 96% sulfuric acid and perfluorocarbon at a temperature of 100 ° C. Alkylating reaction to produce a mixture of (2,2,3,3-tetrafluoropropyl) naphthalenesulfonic acid.
Third step: A mixture of (2,2,3,3-tetrafluoropropyl) naphthalenesulfonic acid produced in the second step and 24.6 g of potassium hydroxide are neutralized in an aqueous alcohol solution, Generating a mixture of perfluoroalkylnaphthalenesulfonates formed from (2,2,3,3-tetrafluoropropyl) naphthalenesulfonate ions and potassium ions.

11) A dopant agent comprising a mixture of perfluoroalkylnaphthalene sulfonates obtained through the following first step, second step and third step.
First step: a step of producing a mixture of naphthalene sulfonic acids by subjecting 12.8 g of naphthalene and 20.4 g of 96% sulfuric acid to a sulfonation reaction at a temperature of 180 ° C.
Second step: A mixture of naphthalene sulfonic acid produced in the first step and 13.2, g of 2,2,3,3-tetrafluoropropanol, 15.2 g of 96% sulfuric acid and perfluorocarbon at a temperature of 100 ° C. Alkylating reaction to produce a mixture of (2,2,3,3-tetrafluoropropyl) naphthalenesulfonic acid.
Third step: A mixture of (2,2,3,3-tetrafluoropropyl) naphthalenesulfonic acid produced in the second step and 18.0 g of ferric hydroxide were neutralized in an aqueous alcohol solution. Forming a mixture of perfluoroalkylnaphthalene sulfonates formed from (2,2,3,3-tetrafluoropropyl) naphthalene sulfonate ions and trivalent iron ions.

12) A dopant agent comprising a mixture of perfluoroalkylnaphthalene sulfonates obtained through the following Step A, Step B and Step C.
Step A: 12.8 g of naphthalene, 23.2 g of 2,2,3,3,4,4,5,5-octafluoro-1-propanol and 17.6 g of anhydrous aluminum chloride at a temperature of 90 ° C. To produce a mixture of (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene.
Step B: 33.2 g of a mixture of (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene produced in Step A and 30.6 g of 25% fuming sulfuric acid were mixed at 80 ° C. A step of sulfonating at a temperature to form a mixture of (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalenesulfonic acid.
Step C: A mixture of (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalenesulfonic acid produced in Step B and 25.0 g of sodium hydroxide in an aqueous alcohol solution A step of forming a mixture of perfluoroalkylnaphthalenesulfonate formed from (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalenesulfonate ion and sodium ion .

13) A dopant agent comprising a mixture of perfluoroalkylnaphthalene sulfonates obtained through the following Step A, Step B and Step C.
Step A: 12.8 g of naphthalene and 43.2 g of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononyl alcohol 12.4 g of anhydrous aluminum chloride and a perfluoroalkylation reaction at a temperature of 90 ° C. to give 2,2,3,3,4,4,5,5,6,6,7,7,8,8 , 9,9-hexadecylfluorononylnaphthalene mixture.
Step B: Mixture of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononylnaphthalene formed in Step A45. 9 g and 16.2 g of 25% fuming sulfuric acid were subjected to a sulfonation reaction at a temperature of 120 ° C. to obtain 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, Forming a mixture of 8,9,9-hexadecylfluorononylnaphthalenesulfonic acid;
Step C: A mixture of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononylnaphthalenesulfonic acid produced in Step B And 7.8 g of lithium hydroxide are neutralized in an aqueous alcohol solution to give 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9, Producing a mixture of 9-hexadecylfluorononylnaphthalene sulfonate ions and perfluoroalkyl naphthalene sulfonates formed from lithium ions.

  Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following examples and comparative examples, “part” means “part by weight” and “%” means “% by weight” unless otherwise specified.

Test Category 1 (Synthesis of perfluoroalkylnaphthalene sulfonate as a dopant agent)
Example 1 {Synthesis of perfluoroalkylnaphthalene sulfonate (P-1)}
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel, 12.8 g (0.1 mol) of naphthalene and 13.2 g (0.2.3) of 2,2,3,3-tetrafluoro-1-propanol were added. 1 mol) and 17.6 g of anhydrous aluminum chloride were charged, and a perfluoroalkylation reaction was carried out for 5 hours while stirring at a temperature of 90 ° C. The reaction solution was cooled to 10 ° C. and washed twice with water, and then the layer was separated and the aqueous layer was removed. Anhydrous sodium sulfate was added to the resulting oil layer and filtered to obtain a brown liquid product 20 0.6 g was obtained. 20.6 g of this product was charged into a four-necked flask similar to the above, and the inner solution was kept at 40 ° C. or lower and 14.2 g of 25% fuming sulfuric acid was added, followed by sulfonation at a temperature of 80 ° C. for 2 hours. Reaction was performed. The sulfonation reaction solution was added dropwise to a separately prepared mixed solution consisting of 7.1 g of lithium hydroxide, 49 g of water, and 73 g of methanol at a temperature of 10 ° C. or less to carry out a neutralization reaction. The neutralization reaction solution was filtered, and the solvent was distilled off from the filtrate under reduced pressure, followed by vacuum drying. The vacuum-dried product was subjected to preparative high performance liquid chromatography described below, and an eluate having a retention time of 5.5 to 6.5 minutes was fractionated. The fraction solution was concentrated under reduced pressure at 40 ° C. or lower and further dried under vacuum to obtain a white solid perfluoroalkylnaphthalene sulfonate (P-1). This white solid was lithium mono (2,2,3,3-tetrafluoropropyl) naphthalene monosulfonate by the analysis described below.

・ Preparative high performance liquid chromatography Column packing: Hitachi gel 3053 (trade name, manufactured by Hitachi, Ltd.)
Column diameter: 50mm
Column length: 150mm
Eluent: acetonitrile / 0.05M sodium perchlorate aqueous solution = 10/90 (volume ratio)
Flow rate: 156 ml / min Column temperature: 40 ° C
Measurement wavelength: 254 nm

・ Analysis method and analysis value Fluorine content by flask combustion method: 23.15%
Sulfur content by ICP emission spectroscopy: 9.77%
Lithium content by atomic absorption method: 2.11%
Main peaks of FT-IR (unit: cm ⁻¹ ) (transmittance): 3428 (86%), 3054 (89%), 3012 (85%), 2959 (83%), 2923 (80%), 2852 (80%), 1957 (94%), 1844 (94%), 1624 (92%), 1597 (92%), 1506 (87%), 1435 (94%), 1348 (89%), 1211 (65 %), 1144 (69%), 1115 (72%), 1081 (72%), 978 (91%), 908 (92%), 866 (94%), 827 (90%), 798 (84%) 769 (82%), 746 (92%), 690 (81%), 619 (80%), 582 (91%), 526 (90%), 476 (86%), 444 (84%)
UV λmax: 316 nm, 283 nm, 232 nm
Chemical shift δ by ¹ H-NMR (unit: ppm): 8.8, 7.9, 7.9, 7.5, 7.5, 7.4, 6.5, 4.2
Chemical shift by ¹³ C-NMR (unit: ppm): 143.6, 133.3, 129.2, 128.8, 127.5, 127.4, 125.4, 125.3, 124.2, 124 1, 120.0, 119.6, 119.3, 116.6, 116.5, 116.3, 115.9, 113.4, 112.9, 112.5, 110.1, 109.7 , 106.8, 106.4, 105.9, 62.3, 61.9, 61.6.

Example 2 {Synthesis of perfluoroalkylnaphthalene sulfonate (P-2)}
A four-necked flask equipped with a thermometer, stirrer, reflux condenser and dropping funnel was charged with 12.8 g (0.1 mol) of naphthalene and 10.2 g of 96% sulfuric acid, and stirred for 1 hour at a temperature of 80 ° C. Sulfonation reaction was performed. The sulfonation reaction liquid is cooled to 30 ° C., 23.2 g (0.1 mol) of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol is added, and the inner solution is subsequently added. After adding 5.9 g of 96% sulfuric acid while stirring at 40 ° C. or lower, a perfluoroalkylation reaction was performed at a temperature of 100 ° C. for 12 hours. The reaction solution was dropped into a separately prepared mixed solution composed of 6.4 g of sodium hydroxide, 20 g of water and 30 g of methanol at a temperature of 10 ° C. or less to carry out a neutralization reaction. The neutralization reaction solution was filtered, and the solvent was distilled off from the filtrate under reduced pressure, followed by vacuum drying. The vacuum dried product was subjected to preparative high performance liquid chromatography as described above, and an eluate having a retention time of 5.5 to 6.5 minutes was fractionated. The fraction solution was concentrated under reduced pressure at 40 ° C. or lower and further dried under vacuum to obtain a white solid perfluoroalkylnaphthalene sulfonate (P-2). This white solid was sodium mono (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene monosulfonate by the analysis described below.

・ Analysis method and analysis value Fluorine content by flask combustion method: 34.21%
Sulfur content by ICP emission spectroscopy: 7.22%
Sodium content by atomic absorption method: 5.17%
Main peaks of FT-IR (unit: cm ⁻¹ ) (transmittance): 3435 (71%), 3050 (72%), 3010 (77%), 2955 (82%), 2927 (78%), 2854 (79%), 1950 (83%), 1844 (84%), 1664 (75%), 1631 (74%), 1597 (81%), 1506 (73%), 1458 (79%), 1398 (77 %), 1298 (56%), 1215 (44%), 1072 (51%), 964 (80%), 908 (83%), 868 (86%), 841 (74%), 802 (58%) 769 (62%), 742 (83%), 692 (59%), 619 (58%), 570 (73%), 526 (70%), 476 (84%), 438 (88%)
UV λmax: 317 nm, 284 nm, 227 nm
Chemical shift δ by ¹ H-NMR (unit: ppm): 8.8, 8.0, 7.9, 7.5, 7.5, 7.4, 7.0, 4.3
Chemical shift by ¹³ C-NMR (unit: ppm): 143.5, 133.7, 129.8, 129.1, 128.0, 127.6, 125.8, 125.8, 124.6, 124 6,119.1,118.7,118.2,116.9,115.3,114.9,114.6,114.2,113.8,113.7,113.4,112.3 , 111.9, 111.4, 111.1, 110.6, 110.0, 109.9, 109.8, 109.5, 108.5, 108.1, 107.7, 107.6, 107 1,106.8,106.7,106.4,106.3,105.2,104.8,104.4,62.4,62.1,61.8

Example 3 {Synthesis of perfluoroalkylnaphthalene sulfonate (P-3)}
In a four-necked flask equipped with a thermometer, stirrer, reflux condenser and dropping funnel, 12.8 g (0.1 mol) of naphthalene and 2,2,3,3,4,4,5,5,6,6 7,7,8,8,9,9-Hexadecylfluoro-1-nonyl alcohol 43.2 g (0.1 mol) and 96% sulfuric acid 12.3 g were charged at 70 ° C. or less, and at a temperature of 70 ° C. The sulfonation reaction and perfluoroalkylation reaction were carried out for 2 hours with stirring. The reaction solution was cooled to 40 ° C. or lower, fuming sulfuric acid (15.2 g) was added, and the reaction was performed at a temperature heated to 80 ° C. for 2 hours, and then cooled to room temperature. The reaction solution was added dropwise to a separately prepared mixed solution composed of 27 g of potassium hydroxide, 103 g of water and 155 g of methanol at a temperature of 10 ° C. or less to carry out a neutralization reaction. The neutralization reaction solution was filtered, and the solvent was distilled off from the filtrate under reduced pressure, followed by vacuum drying. The vacuum dried product was subjected to preparative high performance liquid chromatography as described above, and an eluate having a retention time of 5.5 to 6.5 minutes was fractionated. The fraction solution was concentrated under reduced pressure at 40 ° C. or lower, and further vacuum-dried to obtain a white solid perfluoroalkylnaphthalenesulfonate (P-3). This white solid was analyzed by the analysis described below as mono (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononyl). It was potassium naphthalene monosulfonate.

・ Analysis method and analysis value Fluorine content by flask combustion method: 46.03%
Sulfur content by ICP emission spectroscopy: 4.85%
Potassium content by atomic absorption method: 5.92%
Main peaks of FT-IR (unit: cm ⁻¹ ) (transmittance): 3427 (74%), 3054 (81%), 3012 (84%), 2958 (83%), 2923 (82%), 2852 (84%), 1948 (87%), 1836 (88%), 1660 (83%), 1597 (84%), 1506 (82%), 1458 (84%), 1348 (79%), 1209 (42 %), 1146 (56%), 1111 (65%), 1064 (61%), 1005 (74%), 914 (88%), 858 (86%), 825 (78%), 798 (73%) 769 (71%), 740 (76%), 688 (69%), 617 (71%), 573 (76%), 519 (79%), 478 (85%), 430 (85%)
UV λmax: 318 nm, 283 nm, 227 nm
Chemical shift δ by ¹ H-NMR (unit: ppm): 8.8, 8.0, 7.9, 7.5, 7.5, 7.4, 7.2, 4.3
Chemical shift by ¹³ C-NMR (unit: ppm): 143.5, 133.4, 129.5, 128.9, 127.7, 127.4, 125.6, 125.5, 125.4, 124 3, 120.0, 119.6, 119.2, 117.2, 116.6, 116.2, 115.8, 115.0, 114.6, 114.4, 114.2, 114.0 , 113.6, 113.2, 112.8, 112.5, 111.7, 111.3, 110.9, 110.6, 110.1, 109.7, 109.3, 108.4, 108 0.0, 107.6, 107.0, 106.6, 105.1, 104.7, 104.2, 62.4, 62.1, 61.7

Example 4 {Synthesis of perfluoroalkylnaphthalene sulfonate (P-4)}
A perfluoroalkylnaphthalene sulfonate (P-4) was synthesized in the same manner as the perfluoroalkylnaphthalene sulfonate (P-1) of Example 1.

Example 5 {Synthesis of perfluoroalkylnaphthalene sulfonate (P-5)}
A perfluoroalkylnaphthalene sulfonate (P-5) was synthesized in the same manner as the perfluoroalkylnaphthalene sulfonate (P-2) of Example 2.

Example 6 {Synthesis of perfluoroalkylnaphthalene sulfonate (P-6)}
A perfluoroalkylnaphthalene sulfonate (P-6) was synthesized in the same manner as the perfluoroalkylnaphthalene sulfonate (P-3) of Example 3.

Example 7 {Synthesis of perfluoroalkylnaphthalene sulfonate (P-7)}
A perfluoroalkylnaphthalene sulfonate (P-7) was synthesized in the same manner as the perfluoroalkylnaphthalene sulfonate (P-2) of Example 2.

Example 8 {Synthesis of mixture of perfluoroalkylnaphthalene sulfonate (P-8)}
12.8 g (0.1 mol) of naphthalene and 2,2,3,3,4,4,5,5-octafluoropentanol in a four-necked flask equipped with a thermometer, stirrer, reflux condenser and dropping funnel 23.2 g (0.1 mol) and 17.6 g of anhydrous aluminum chloride were charged, and a perfluoroalkylation reaction was performed for 5 hours while stirring at a temperature of 90 ° C. The reaction solution was cooled to 10 ° C. and washed twice with water, and then the layer was separated and the aqueous layer was removed. Anhydrous sodium sulfate was added to the resulting oil layer and filtered to obtain a brown liquid product 33. 0.2 g was obtained. 33.2 g of this product was charged into a four-necked flask similar to the above, and the inner solution was kept at 40 ° C. or lower, 30.6 g of 25% fuming sulfuric acid was added, and then sulfonated at a temperature of 80 ° C. for 2 hours. Reaction was performed. The sulfonation reaction solution was added dropwise to a separately prepared mixed solution consisting of 25 g of sodium hydroxide, 68 g of water and 120 g of methanol at a temperature of 10 ° C. or less to carry out a neutralization reaction. The neutralization reaction solution was filtered, and the solvent was distilled off from the filtrate under reduced pressure, followed by vacuum drying. The vacuum-dried product was subjected to fractionation type high performance liquid chromatography as described above for fractionation. The fraction solution was concentrated under reduced pressure at 40 ° C. or lower and further dried under vacuum to obtain a white solid perfluoroalkylnaphthalenesulfonate mixture (P-8). This white solid was subjected to analytical high performance liquid chromatography, and when the analysis was performed in which the retention time of each peak shown in the chart was compared and identified with the retention time of a separately synthesized standard, this white solid was found to be mono ( 2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene monosulfonate sodium and di (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene mono It consists of sodium sulfonate and sodium tri (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene monosulfonate (2,2,3,3,4,4,5,5 -50 mol% of a mixture of sodium octafluoropentyl) naphthalene monosulfonate, mono (2,2,3,3,4,4,5,5-octafluoropenthi ) Consisting of sodium naphthalene disulfonate and sodium mono (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene trisulfonate (2,2,3,3,4,4,5) , 5-octafluoropentyl) sodium naphthalene polysulfonate was a mixture of 50 mol%.

Example 9 {Synthesis of mixture of perfluoroalkylnaphthalene sulfonate (P-9)}
A mixture of perfluoroalkylnaphthalene sulfonate (P-9) was synthesized in the same manner as the mixture of perfluoroalkylnaphthalene sulfonate (P-8) in Example 8.

Example 10 {Synthesis of mixture of perfluoroalkylnaphthalene sulfonate (P-10)}
A four-necked flask equipped with a thermometer, stirrer, reflux condenser and dropping funnel was charged with 12.8 g (0.1 mol) of naphthalene and 20.4 g of 96% sulfuric acid, and stirred for 1 hour at a temperature of 190 ° C. Sulfonation reaction was performed. The reaction solution was cooled to 30 ° C., 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (23.2 g, 0.1 mol) was added, 20.4 g of 96% sulfuric acid was added while stirring at a temperature not higher than 0 ° C., and then a perfluoroalkylation reaction was performed at a temperature of 100 ° C. for 12 hours. The reaction solution was dropped into a separately prepared mixed solution composed of 25.3 g of potassium hydroxide, 30 g of water, and 100 g of methanol at a temperature of 10 ° C. or less to carry out a neutralization reaction. The neutralization reaction solution was filtered, and the solvent was distilled off from the filtrate under reduced pressure, followed by vacuum drying. The vacuum dried product was subjected to preparative high performance liquid chromatography as described above to fractionate the eluate. The fraction solution was concentrated under reduced pressure at 40 ° C. or lower and further dried under vacuum to obtain a white solid perfluoroalkylnaphthalene sulfonate mixture (P-10). When this white solid was subjected to analytical high performance liquid chromatography and analyzed in the same manner as described above, this white solid was mono (2,2,3,3,4,4,5,5-octafluoropentyl). Potassium naphthalene monosulfonate and di (2,2,3,3,4,4,5,5-octafluoropentyl) potassium naphthalene monosulfonate and tri (2,2,3,3,4,4,5 19 mol% of a mixture of potassium (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene monosulfonate consisting of potassium 5-octafluoropentyl) naphthalene monosulfonate, mono (2 , 2,3,3,4,4,5,5-octafluoropentyl) potassium naphthalene disulfonate and mono (2,2,3,3,4,4,5,5-octafluoropentyl) Consisting of a full talent potassium Li sulfonic acid mixture of (2,2,3,3,4,4,5,5-octafluoropentyl) potassium naphthalene polysulfonic acid is a mixture consisting of the ratio of 81 mol%.

Examples 11 to 13 {Synthesis of mixtures of perfluoroalkylnaphthalene sulfonates (P-11) to (P-13)}
In the same manner as the mixture of perfluoroalkylnaphthalene sulfonate (P-10) of Example 10, mixtures of perfluoroalkyl naphthalene sulfonate (P-11) to (P-13) were synthesized. The contents of each perfluoroalkylnaphthalene sulfonate synthesized as described above and the mixture thereof are summarized in Table 1.

In Table 1,
* 1: Sodium mono (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene monosulfonate (corresponding to p = 1 and q = 1 in chemical formula 1) and di (2, 2,3,3,4,4,5,5-octafluoropentyl) sodium naphthalene monosulfonate (corresponding to p = 2 and q = 1 in chemical formula 1) and tri (2,2,3,3,4) , 4,5,5-octafluoropentyl) sodium naphthalene monosulfonate (corresponding to p = 3 and q = 1 in chemical formula 1) (2,2,3,3,4,4,5,5) A mixture of sodium octafluoropentyl) naphthalene monosulfonate / sodium mono (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalenedisulfonate (p = 1 in chemical formula 1, q = 2) and mono (2, 2, 3, 3, 4, 4, 5, (Octafluoropentyl) naphthalene sodium trisulfonate (corresponding to p = 1 and q = 3 in Chemical Formula 1) (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene Mixture of sodium polysulfonate = mixture of 50/50 (mol%) * 2: Mono (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9, 9-hexadecylfluorononyl) naphthalene monosulfonic acid (corresponding to p = 1 and q = 1 in Chemical Formula 1) / mono (2,2,3,3,4,4,5,5,6,6,7) , 7,8,8,9,9-hexadecylfluorononyl) lithium naphthalenedisulfonate (corresponding to p = 1 and q = 2 in chemical formula 1) and mono (2,2,3,3,4,4,4) 5,5,6,6,7,7,8,8,9,9-hexadecylfluorononyl) naphthalene Lithium sulfonate (corresponding to p = 1 and q = 3 in chemical formula 1) (2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, Mixture of 9,9-hexadecylfluorononyl) naphthalene polysulfonate = 50/50 (mol%) * 3: Mono (2,2,3,3,4,4,5,5-octafluoropentyl) Potassium naphthalene monosulfonate (corresponding to p = 1 and q = 1 in chemical formula 1) and di (2,2,3,3,4,4,5,5-octafluoropentyl) potassium naphthalene monosulfonate (chemical formula P = 2 in 1 and corresponding to q = 1) and potassium tri (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene monosulfonate (p = 3 in Chemical Formula 1, (corresponding to q = 1) (2,2,3,3,4,4,5,5-octaf) Olopentyl) potassium naphthalene monosulfonate mixture / mono (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene disulfonate (corresponding to p = 1 and q = 2 in Chemical Formula 1) ) And mono (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene trisulfonate (corresponding to p = 1 and q = 3 in Chemical Formula 1) (2, Mixture of potassium 2,3,3,4,4,5,5-octafluoropentyl) naphthalene polysulfonate = mixture of 19/81 (mol%) * 4: Mono (2,2,3,3,4,4) , 5,5-octafluoropentyl) naphthalene monosulfonate (corresponding to p = 1 and q = 1 in Chemical Formula 1) and di (2,2,3,3,4,4,5,5-octafluoro Pentyl) naphthalene monosulfone A mixture of sodium (2,2,3,3,4,4,5,5-octafluoropentyl) naphthalene monosulfonate / mono (corresponding to p = 2 in formula 1 and q = 1) 2,2,3,3,4,4,5,5-octafluoropentyl) sodium naphthalenedisulfonate (corresponding to p = 1 and q = 2 in chemical formula 1) and mono (2,2,3,3 4,4,5,5-octafluoropentyl) sodium naphthalene trisulfonate (corresponding to p = 1 and q = 3 in Chemical Formula 1) (2,2,3,3,4,4,5, 5-octafluoropentyl) sodium naphthalene polysulfonate mixture = 10/90 (mol%) mixture * 5: potassium mono (2,2,3,3-tetrafluoropentyl) naphthalene monosulfonate (p in Chemical Formula 1) = 1, equivalent to q = 1 / Potassium mono (2,2,3,3-tetrafluoropentyl) naphthalenedisulfonate (corresponding to p = 1 and q = 2 in Chemical Formula 1) and mono (2,2,3,3-tetrafluoropentyl) naphthalene Potassium trisulfonate (corresponding to p = 1, q = 3 in chemical formula 1) and potassium di (2,2,3,3-tetrafluoropentyl) naphthalene disulfonate (p = 2 in chemical formula 1, q = 2 And di (2,2,3,3-tetrafluoropentyl) naphthalene trisulfonate (corresponding to p = 2 and q = 3 in Chemical Formula 1) (2,2,3,3- Mixture of tetrafluoropentyl) naphthalene polysulfonate potassium = 50/50 (mol%) * 6: iron mono (2,2,3,3-tetrafluoropropyl) naphthalene monosulfonate (p = 1 in Chemical Formula 1) , Q = 1 Equivalent) / mono (2,2,3,3-tetrafluoropropyl) iron naphthalene disulfonate (equivalent to p = 1 and q = 2 in Chemical Formula 1) and mono (2,2,3,3-tetrafluoropropyl) ) A mixture of iron mono (2,2,3,3-tetrafluoropropyl) naphthalene polysulfonate consisting of iron naphthalene trisulfonate (corresponding to p = 1 and q = 3 in chemical formula 1) = 45/55 (moles) %) Mixture

Test Category 2 (Preparation of conductive polymer material and its evaluation)
-Preparation of conductive polymer material 0.01 mol of perfluoroalkylnaphthalene sulfonate as a dopant agent synthesized in Test Category 1 and 0.6729 g (0.01 mol) of pyrrole are dissolved in 100 ml of pure water and electrolyzed. An oxidation polymerization reaction solution was prepared. Nitrogen gas was bubbled into the reaction solution for about 30 minutes to replace the nitrogen, and two 2 cm square plates of stainless steel 304 were immersed at 1 cm intervals, one serving as the working electrode and the other as the counter electrode. A constant current (2.5 mA / cm) was passed between the two immersed electrodes for 20 minutes to conduct electropolymerization, and a polypyrrole film was formed on the electrodes. The polypyrrole film produced on the electrode was washed with pure water and acetone, then peeled off from the electrode, and dried in vacuum for 12 hours to obtain a pre-heat treatment conductive polymer material (Sample A). Separately, the pre-heat treatment conductive polymer material obtained in the same manner was further heat-treated in air at 125 ° C. for 300 hours to obtain a heat-treated conductive polymer material (Sample B). Separately, the conductive polymer material before heat treatment obtained in the same manner was further heat-treated at 85 ° C. for 300 hours in an atmosphere having a relative humidity of 85% to obtain a conductive polymer material (sample C) that had been heat-treated at high humidity. .

-Electrical conductivity evaluation About the sample A, the sample B, and the sample C obtained above, those electrical conductivities were measured by the four-probe method. Sample A was evaluated according to the following Evaluation Criteria 1. For Sample B and Sample C, the conductivity retention was determined by the following Equation 1 and evaluated according to the following Evaluation Criteria 2. The results are summarized in Table 2.

In Equation 1,
D ¹ : Electric conductivity of sample B or sample C D ² : Electric conductivity of sample A

Evaluation criteria 1
A: Electrical conductivity is 100 S / cm or more, and conductivity is excellent.
○: The electric conductivity is 30 S / cm or more and less than 100 S / cm, and the conductivity is good.
(Triangle | delta): Electric conductivity is less than 30 S / cm, and electroconductivity is a little inferior.

Evaluation criteria 2
A: The conductivity retention is 90% or more, which is excellent.
○: The conductivity retention is 70 to 90%, which is good.
Δ: Conductivity retention is less than 70%, which is slightly inferior.

In Table 2,
R-1: 4-fluoro-2-sulfobenzamide R-2: 3-sulfobenzamide R-3: 4-benzoylaminobenzenesulfonic acid

Claims (10)

A conductive polymer comprising one or more selected from perfluoroalkylnaphthalenesulfonates formed from perfluoroalkylnaphthalenesulfonate ions represented by the following chemical formula 1 and the following counter cations: Dopant agent for material preparation.

(In chemical formula 1,
a: integer of 1 to 7 p, q: integer of 1 to 3 X: residue obtained by removing p + q hydrogen atoms from naphthalene)
Counter cation: lithium ion, sodium ion, potassium ion or trivalent iron ion   The dopant agent for preparing a conductive polymer material according to claim 1, comprising a mixture of two or more selected from perfluoroalkylnaphthalene sulfonates.   The mixture was a perfluoroalkylnaphthalene monosulfonate using a perfluoroalkylnaphthalene sulfonate ion when q in Chemical Formula 1 is 1, and a case where q in Chemical Formula 1 is 2 The dopant for preparing a conductive polymer material according to claim 2, which is a mixture with a perfluoroalkylnaphthalene polysulfonate and / or a perfluoroalkylnaphthalene polysulfonate using one in which q in Chemical Formula 1 is 3.   Perfluoroalkylnaphthalene monosulfonate and perfluoroalkylnaphthalene polysulfonate are further used as perfluoroalkylnaphthalenesulfonate ions when p in Chemical Formula 1 is 1 and / or p in Chemical Formula 1 is 2 The dopant agent for preparing a conductive polymer material according to claim 3, which is used in the case of   The conductive material according to claim 3 or 4, wherein the mixture contains perfluoroalkylnaphthalene monosulfonate / perfluoroalkylnaphthalene polysulfonate = 0.5 / 99.5 to 70/30 (mol%). Dopant agent for polymer material preparation.   The conductive polymer material preparation according to claim 3 or 4, wherein the mixture contains perfluoroalkylnaphthalene monosulfonate / perfluoroalkylnaphthalene polysulfonate = 1/99 to 45/55 (mol%). Dopant agent. The conductive polymer material preparation dopant agent according to any one of claims 2 to 6, wherein the mixture is obtained through the following first step, second step and third step.
1st process: The process of carrying out the sulfonation reaction of the naphthalene and 90-100% concentration sulfuric acid under the temperature of 70-250 degreeC, and producing | generating the mixture of a naphthalenesulfonic acid.
Second Step: A mixture of naphthalenesulfonic acid produced in the first step and a perfluoroalkyl alcohol represented by the following chemical formula 2 are subjected to a perfluoroalkylation reaction at a temperature of 0 to 150 ° C. using an acid catalyst, Forming a mixture of perfluoroalkylnaphthalene sulfonic acids;
Third step: A step of neutralizing the mixture of perfluoroalkylnaphthalenesulfonic acid generated in the second step and an alkali in an aqueous alcohol solution to generate a mixture of perfluoroalkylnaphthalenesulfonate.

(In chemical formula 2,
b: an integer from 1 to 7)   In the first step, naphthalene / sulfuric acid is used at a ratio of 15/85 to 60/40 (mol%), and in the second step, a mixture of naphthalene sulfonic acid / perfluoroalkyl alcohol = 15/85 to 60/40 (mol) The dopant agent for preparing a conductive polymer material according to claim 7, which is used at a ratio of%). The conductive polymer material preparation dopant agent according to any one of claims 2 to 6, wherein the mixture is obtained through the following step A, step B and step C.
Step A: A step of producing a mixture of perfluoroalkylnaphthalene by subjecting naphthalene and the perfluoroalkyl alcohol represented by Chemical Formula 2 to a perfluoroalkylation reaction at a temperature of 0 to 150 ° C. using an acid catalyst.
Step B: A step of allowing the mixture of perfluoroalkylnaphthalene produced in Step A and fuming sulfuric acid to undergo a sulfonation reaction at a temperature of 40 to 250 ° C. to produce a mixture of perfluoroalkylnaphthalenesulfonic acid.
Step C: A step of neutralizing the mixture of perfluoroalkylnaphthalenesulfonic acid generated in Step B and an alkali in an aqueous alcohol solution to form a mixture of perfluoroalkylnaphthalenesulfonate. In step A, naphthalene / perfluoroalkyl alcohol = 15/85 to 70/30 (mol%), and in step B, mixture of perfluoroalkylnaphthalene / fuming sulfuric acid = 15/85 to 60/40 (mol%) The dopant agent for preparing a conductive polymer material according to claim 9, which is used at a ratio of