JP6024264B2 - Thiophene derivative, water-soluble conductive polymer and aqueous solution thereof, and production method thereof - Google Patents

Description

  The present invention relates to a novel thiophene derivative, polythiophene, a water-soluble conductive polymer aqueous solution using the same, and a method for producing the same.

  Polymers having π-conjugated double bonds such as polyacetylene, polythiophene, polyaniline, and polypyrrole are known to become conductors (conductive polymers) by doping with acceptors and donors. Applications to solid electrolytes, conductive paints, electrochromic elements, transparent electrodes, transparent conductive films, chemical sensors, actuators, etc. are being studied. Conventionally, conductive polymers are insoluble and infusible and thus have a problem in molding processability, and it has been necessary to use a polar organic solvent (for example, an amide solvent) with a large environmental load in order to dissolve the conductive polymer. Therefore, there has been a demand for a water-soluble conductive polymer that can be easily molded and dissolved in water with a small environmental load. In recent years, polythiophene called PEDOT [= poly (3,4-ethylenedioxythiophene)] has been actively studied as a conductive polymer (see, for example, Patent Document 1), but EDOT (= 3), which is a raw material monomer, has been studied. , 4-ethylenedioxythiophene) is poorly water-soluble (2.1 g / L-water, 0.2% by weight), and it is known that the resulting conductive polymer is also water-insoluble.

  For this reason, as a method for obtaining a water-soluble conductive polymer, a method of polymerizing EDOT in the presence of a water-soluble polymer dopant such as PSS (polystyrene sulfonic acid) has been proposed (for example, see Patent Document 2). Called PEDOT-PSS).

  According to Patent Document 2, it is said that the polyanion becomes water-soluble by being taken in as a dopant and water dispersant, and the molding processability is improved. However, since the conductive polymer described in Patent Document 2 contains a large amount of a low-conductivity polymer part that is not involved in doping, heat conductivity is reduced due to low conductivity and a large excess of sulfo groups. There are problems such as low water resistance and equipment corrosion due to strong acidity.

  By the way, since the conductive polymer described in Patent Document 2 has both good conductivity and molding processability, application to a polymer solid electrolyte of a capacitor and printable electronics is also directed.

  As an example of the former, there is a solid electrolyte of an aluminum solid electrolytic capacitor, but there is a problem in increasing the capacity and reducing the ESR as capacitor performance.

  In the latter case, for example, when a technique such as ink jet is applied, if the particle diameter of the conductive polymer in the aqueous solution is large, there is a concern that the nozzle is clogged.

  On the other hand, as an alternative method for obtaining a water-soluble conductive polymer, a substituent (for example, a sulfo group, a sulfonate group, etc.) having water solubility and a doping action is covalently bonded directly or via a spacer to a polymer molecular chain. It is proposed that a water-soluble self-doped conductive polymer excellent in molding processability is obtained by polymerizing the compound introduced in step 1 (see, for example, Patent Documents 3 to 4 and Non-Patent Documents 1 and 2). .

  As an application example of the water-soluble self-doped conductive polymer described in these documents, there is an application of a resist antistatic film forming material used when forming a semiconductor circuit pattern by electron beam lithography. This is because, since the conductive polymer is water-soluble, there is an advantage that it is difficult to damage the fat-soluble resist and can be washed with water after exposure (for example, see Non-Patent Document 3). However, with the recent high integration of semiconductors, there has been a demand for finer pattern formation, and therefore a polymer having higher conductivity (antistatic ability) has been demanded.

  Therefore, it is a self-doping type water-soluble conductive polymer that can provide processability without adding other components that do not contribute to improvement of conductivity due to water solubilization, in addition to good water solubility and conductivity When an aqueous solution is used, a polymer having a sufficiently small particle size has been demanded.

Japanese Patent No. 2721700 Japanese Patent No. 2636968 Japanese Patent Publication No.8-13873 Japanese Patent No. 3182239

Journal of American Chemical Society, 1987, pp. 1858-1859 Chemistry of Materials, 2009, 1815-1821 Electronic Materials, February 1990, 48-55

The present invention has been made in view of the above-described background art, and its purpose is as follows.
(1) providing a novel water-soluble thiophene derivative used as a conductive material; and (2) providing a novel water-soluble polythiophene used as a conductive material.
It is.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention is a novel thiophene derivative, polythiophene, a water-soluble conductive polymer aqueous solution using the same, and a method for producing the same as shown below.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, this invention is a thiophene derivative as shown below, and its manufacturing method.

  [1] A thiophene derivative represented by the following formula (1) or (2).

[In the above formula (1), R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or — (CH ₂ ) ₁ SO _3. M is represented. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. l, n and m each independently represents an integer of 1 to 6; ]

[In the above formula (2), R ¹ , n and m are as defined in the above formula (1). Z represents chloride, bromide, iodide, acetate, trifluoroacetate or trifluoromethanesulfonate. ]
[2] A thiophene derivative represented by the following formula (3) or (4).

In [the formula (3), ^{R 3} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. ]

[In the above formula (4), R ³ has the same meaning as in the above formula (3). Z represents chloride, bromide, iodide, acetate, trifluoroacetate or trifluoromethanesulfonate. ]
[3] A thiophene derivative represented by the following formula () and a compound represented by the following formula (6) are reacted in a polar solvent in the presence of a base, and represented by the above formula (1) or formula (3). The method for producing a thiophene derivative according to the above [1] or [2], wherein the thiophene compound (wherein M does not represent a hydrogen atom) is obtained.

[In the above formula (5), X represents tosylate, mesylate, triflate, chloride, bromide, or iodide. n represents an integer of 1 to 6. ]

[In the above formula (6), R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or — (CH ₂ ) ₁ SO _3. M is represented. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. l and m each independently represents an integer of 1 to 6; ]
[4] An thiophene derivative represented by the above formula (1) or formula (3) (wherein M does not represent a hydrogen atom) is allowed to react with an excess amount of acid, and the above formula (2) or formula ( The method for producing a thiophene derivative according to the above [1] or [2], wherein the thiophene derivative represented by 4) is obtained.

  [5] The thiophene derivative represented by the above formula (2) or formula (4) is converted into an ammonium salt and then dried under reduced pressure under heating, and the thiophene derivative represented by the above formula (1) or formula (3) ( However, M represents a hydrogen atom.) The manufacturing method of the thiophene derivative as described in said [1] or [2] characterized by obtaining.

  [6] Polythiophenes containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (16) and a structural unit represented by the following formula (17).

[In the above formula (16), R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or — (CH ₂ ) ₁ SO _3. M is represented. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . Z represents chloride, bromide, iodide, acetate, trifluoroacetate or trifluoromethanesulfonate. Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. l, n and m each independently represents an integer of 1 to 6; ]

[In the above formula (17), R ¹ , n and m are as defined in the above formula (16). ]
[7] Polythiophenes containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (18) and a structural unit represented by the following formula (19).

[In the above formula (18), R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ . Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. ]

[In the above formula (19), R ¹ has the same meaning as in the above formula (18). Z represents chloride, bromide, iodide, acetate, trifluoroacetate or trifluoromethanesulfonate. ]
[8] The polythiophene according to [6] or [7] above, wherein the polythiophene has a weight average molecular weight in the range of 1,000 to 1,000,000 in terms of polystyrene sulfonic acid.

  [9] A water-soluble conductive polymer aqueous solution comprising an aqueous solution of the polythiophene according to any one of [6] to [8].

  [10] The thiophene derivative according to the above [1] or [2] is polymerized in water or an alcohol solvent in the presence of an oxidizing agent, according to any one of the above [6] to [8] A method for producing polythiophenes.

  [11] A method for producing a conductive coating, comprising applying the aqueous solution according to [9] above to a substrate and drying the substrate.

  [12] Use of the aqueous solution according to [9] above for a conductive film.

  According to the present invention, a novel thiophene derivative used as a conductive material is provided by a simple production method.

  Further, according to the present invention, novel polythiophenes having both good conductivity and sufficient water solubility for molding are provided.

It is an IR analysis result of the polymer (26) obtained in Example 4. It is IR analysis result of the polymer (29) obtained in Example 5.

  Hereinafter, the present invention will be described in detail.

  First, the thiophene derivative of the present invention will be described.

  The thiophene derivative in the present invention is a compound represented by the above formula (1) or (2).

In the above formula (1), R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or — (CH ₂ ) ₁ SO ₃ M. Represents. As the substituent of R ¹ is an alkyl group or an aryl group having a substituent, for example, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, hydroxy group, An amino group, a carboxyl group, etc. are mentioned.

The substituent R ¹ in the above formula (1) is not particularly limited as long as it falls within the above definition. For example, a hydrogen atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, 3,3- C1-C6 alkyl groups such as dimethylbutyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, n-octyl group, trifluoromethyl group; phenyl group, 2-methoxyphenyl group, 3-methoxyphenyl Group, 2-methylphenyl group, 3-methylphenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-triphenyl An aryl group having 1 to 6 carbon atoms such as a fluoromethylphenyl group and a 3- (trifluoromethoxy) phenyl group; — (CH ₂ ) ₁ SO ₃ M can be mentioned.

Among these, R ₁ is preferably a hydrogen atom, a methyl group, an ethyl group, or a — (CH ₂ ) ₁ SO ₃ M group, and more preferably a hydrogen atom or a methyl group.

  N, m, and l in the above formula (1) represent an integer of 1 to 6.

M in the above formula (1) represents an alkali metal selected from the group consisting of a hydrogen atom, Li, Na and K, NH (R ² ) ₃ or HNC ₅ H ₅ .

At that time, it represents R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms. Examples of the substituent R ₂ include the same as R ^1, and more preferably a hydrogen atom or a methyl group. Further, as the substituent of R ² is an alkyl group or an aryl group having a substituent, for example, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, an aryl group having 1 to 20 carbon atoms, hydroxy group, An amino group, a carboxyl group, etc. are mentioned.

  Specific examples of the compound represented by the above formula (1) include N- [3-thienylmethyl] -2-aminoethanesulfonic acid, N- [3-thienylmethyl] -2-aminoethanesulfonic acid sodium. N- [3-thienylmethyl] -2-aminoethanesulfonic acid lithium, N- [3-thienylmethyl] -2-aminoethanesulfonic acid potassium, N- [3-thienylmethyl] -2-aminoethanesulfonic acid Ammonium, pyridinium N- [3-thienylmethyl] -2-aminoethanesulfonate, N- [3-thienylmethyl] -3-aminopropanesulfonic acid, N- [3-thienylmethyl] -3-aminopropanesulfonic acid Sodium, lithium N- [3-thienylmethyl] -3-aminopropanesulfonate, N- [3-thienylmethyl] -3-amino Potassium lopansulfonate, ammonium N- [3-thienylmethyl] -3-aminopropanesulfonate, pyridinium N- [3-thienylmethyl] -3-aminopropanesulfonate, N- [3-thienylmethyl] -4-amino Butanesulfonic acid, sodium N- [3-thienylmethyl] -4-aminobutanesulfonate, lithium N- [3-thienylmethyl] -4-aminobutanesulfonate, N- [3-thienylmethyl] -4-amino Potassium butanesulfonate, ammonium N- [3-thienylmethyl] -4-aminobutanesulfonate, pyridinium N- [3-thienylmethyl] -4-aminobutanesulfonate, N-methyl-N- [3-thienylmethyl ] -2-Aminoethanesulfonic acid, N-methyl-N- [3-thienylmethyl] -2- Sodium minoethanesulfonate, lithium N-methyl-N- [3-thienylmethyl] -2-aminoethanesulfonate, potassium N-methyl-N- [3-thienylmethyl] -2-aminoethanesulfonate, N- Methyl-N- [3-thienylmethyl] -2-aminoethanesulfonate ammonium, N-methyl-N- [3-thienylmethyl] -2-aminoethanesulfonate pyridinium, N-methyl-N- [3-thienyl Methyl] -3-aminopropanesulfonic acid, sodium N-methyl-N- [3-thienylmethyl] -3-aminopropanesulfonate, N-methyl-N- [3-thienylmethyl] -3-aminopropanesulfonic acid Lithium, potassium N-methyl-N- [3-thienylmethyl] -3-aminopropanesulfonate, N-methyl-N- [3-Thienylmethyl] -3-aminopropanesulfonic acid ammonium, N-methyl-N- [3-thienylmethyl] -3-aminopropanesulfonic acid pyridinium, N-methyl-N- [3-thienylmethyl] -4 Aminobutanesulfonic acid, sodium N-methyl-N- [3-thienylmethyl] -4-aminobutanesulfonate, lithium N-methyl-N- [3-thienylmethyl] -4-aminobutanesulfonate, N- Methyl-N- [3-thienylmethyl] -4-aminobutanesulfonate potassium, N-methyl-N- [3-thienylmethyl] -4-aminobutanesulfonate ammonium, N-methyl-N- [3-thienyl Methyl] -4-aminobutanesulfonic acid pyridinium, N- [2- (3-thienyl) ethyl] -2-aminoethanesulfone N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonic acid sodium, N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonic acid lithium, N- [2- (3 -Thienyl) ethyl] -2-aminoethanesulfonate potassium, N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonate ammonium, N- [2- (3-thienyl) ethyl] -2- Pyridinium aminoethanesulfonate, N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonic acid, sodium N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonate, N- [ Lithium 2- (3-thienyl) ethyl] -3-aminopropanesulfonate, potassium N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonate, N [2- (3-Thienyl) ethyl] -3-aminopropanesulfonic acid ammonium, N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonic acid pyridinium, N- [2- (3-thienyl) Ethyl] -4-aminobutanesulfonic acid, sodium N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonate, N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonic acid Lithium, potassium N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonate, ammonium N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonate, N- [2- ( 3-thienyl) ethyl] -4-aminobutanesulfonic acid pyridinium, N-methyl-N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonic acid, N- Sodium methyl-N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonate, lithium N-methyl-N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonate, N- Methyl-N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonate potassium, N-methyl-N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonate ammonium, N- Methyl-N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonic acid pyridinium, N-methyl-N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonic acid, N-methyl -N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonic acid sodium, N-methyl-N- [2- (3-thienyl) ethyl] -3-aminopropanesulfone Lithium, potassium N-methyl-N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonate, N-methyl-N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonic acid Ammonium, N-methyl-N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonic acid pyridinium, N-methyl-N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonic acid N-methyl-N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonate sodium, N-methyl-N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonate lithium N-methyl-N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonate, N-methyl-N- [2- (3-thienyl) ethyl] -4-amino Ammonium Tan sulfonic acid, N- methyl -N- [2- (3- thienyl) ethyl] -4-amino butanoic acid pyridinium, and the like.

  Among them, for example, N- [3-thienylmethyl] -2-aminoethanesulfonic acid, N- [3-thienylmethyl] -3-aminopropanesulfonic acid, N- [3-thienylmethyl] -4-amino Butanesulfonic acid, N-methyl-N- [3-thienylmethyl] -2-aminoethanesulfonic acid, N-methyl-N- [3-thienylmethyl] -3-aminopropanesulfonic acid, N-methyl-N- [3-Thienylmethyl] -4-aminobutanesulfonic acid, N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonic acid, N- [2- (3-thienyl) ethyl] -4-amino Butanesulfonic acid, N-methyl-N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonic acid, N-methyl-N- [2- (3-thienyl) ethyl] -3-aminopro Nsuruhon acid, N- methyl-N-[2-(3- thienyl) ethyl] -4-compound represented by the above formula and amino butanoic acid (3) is preferable.

In the above formula (2), R ¹ , R ² , l, m, and n have the same meaning as in formula (1), and Z represents chloride, bromide, iodide, acetate, trifluoroacetate, and trifluoromethanesulfonate.

  Specific examples of the compound represented by the formula (2) include N- [3-thienylmethyl] -2-aminoethanesulfonic acid hydrochloride, N- [3-thienylmethyl] -3-aminopropane. Sulfonic acid hydrochloride, N- [3-thienylmethyl] -4-aminobutanesulfonic acid hydrochloride, N-methyl-N- [3-thienylmethyl] -2-aminoethanesulfonic acid hydrochloride, N- Methyl-N- [3-thienylmethyl] -3-aminopropanesulfonic acid hydrochloride, N-methyl-N- [3-thienylmethyl] -4-aminobutanesulfonic acid hydrochloride, N- [2- ( 3-thienyl) ethyl] -2-aminoethanesulfonic acid hydrochloride, N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonic acid hydrochloride, N-methyl-N- [2- ( 3-thienyl) ethyl]- Aminoethanesulfonic acid hydrochloride, N-methyl-N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonic acid hydrochloride, N-methyl-N- [2- (3-thienyl) Ethyl] -4-aminobutanesulfonic acid hydrochloride, N- [3-thienylmethyl] -2-aminoethanesulfonic acid trifluoromethanesulfonate, N- [3-thienylmethyl] -3-aminopropanesulfonic acid Trifluoromethanesulfonate, trifluoromethanesulfonate of N- [3-thienylmethyl] -4-aminobutanesulfonic acid, trifluoromethane of N-methyl-N- [3-thienylmethyl] -2-aminoethanesulfonic acid L-methanesulfonate, trifluoromethanesulfone of N-methyl-N- [3-thienylmethyl] -3-aminopropanesulfonic acid Acid salt, trifluoromethanesulfonate of N-methyl-N- [3-thienylmethyl] -4-aminobutanesulfonic acid, trifluoromethane of N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonic acid L-methanesulfonate, trifluoromethanesulfonate of N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonic acid, N-methyl-N- [2- (3-thienyl) ethyl] -2- Aminoethanesulfonic acid trifluoromethanesulfonate, N-methyl-N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonic acid trifluoromethanesulfonate, N-methyl-N- [2- (3-Thienyl) ethyl] -4-aminobutanesulfonic acid trifluoromethanesulfonate, N- [3-thienylmethyl] -2-aminoethane Sulfonic acid trifluoroacetate, N- [3-thienylmethyl] -3-aminopropanesulfonic acid trifluoroacetate, N- [3-thienylmethyl] -4-aminobutanesulfonic acid trifluoroacetate, N -Methyl-N- [3-thienylmethyl] -2-aminoethanesulfonic acid trifluoroacetate, N-methyl-N- [3-thienylmethyl] -3-aminopropanesulfonic acid trifluoroacetate, N- Methyl-N- [3-thienylmethyl] -4-aminobutanesulfonic acid trifluoroacetate, N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonic acid trifluoroacetate, N- [2- (3-Thienyl) ethyl] -4-aminobutanesulfonic acid trifluoroacetate, N-methyl-N- [2- (3-thienyl) ethyl]- Aminoethanesulfonic acid trifluoroacetate, N-methyl-N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonic acid trifluoroacetate, N-methyl-N- [2- ( 3-thienyl) ethyl] -4-aminobutanesulfonic acid trifluoroacetate and the like.

  Among them, for example, N- [3-thienylmethyl] -2-aminoethanesulfonic acid hydrochloride, N- [3-thienylmethyl] -3-aminopropanesulfonic acid hydrochloride, N- [3-thienyl Methyl] -4-aminobutanesulfonic acid, N-methyl-N- [3-thienylmethyl] -2-aminoethanesulfonic acid hydrochloride, N-methyl-N- [3-thienylmethyl] -3-aminopropane Sulfonic acid hydrochloride, N-methyl-N- [3-thienylmethyl] -4-aminobutanesulfonic acid hydrochloride, N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonic acid hydrochloric acid Salt, hydrochloride of N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonic acid, hydrochloric acid of N-methyl-N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonic acid salt N-methyl-N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonic acid hydrochloride, N-methyl-N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonic acid N- [3-thienylmethyl] -2-aminoethanesulfonic acid trifluoroacetate, N- [3-thienylmethyl] -3-aminopropanesulfonic acid trifluoroacetate, N- [3 -Thienylmethyl] -4-aminobutanesulfonic acid trifluoroacetate, N-methyl-N- [3-thienylmethyl] -2-aminoethanesulfonic acid trifluoroacetate, N-methyl-N- [3-thienyl Trifluoroacetate of methyl] -3-aminopropanesulfonic acid, trifluoroacetate of N-methyl-N- [3-thienylmethyl] -4-aminobutanesulfonic acid, N [2- (3-Thienyl) ethyl] -2-aminoethanesulfonic acid trifluoroacetate, N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonic acid trifluoroacetate, N- Methyl-N- [2- (3-thienyl) ethyl] -2-aminoethanesulfonic acid trifluoroacetate, N-methyl-N- [2- (3-thienyl) ethyl] -3-aminopropanesulfonic acid A compound represented by the above formula (4) such as trifluoroacetate salt of N-methyl-N- [2- (3-thienyl) ethyl] -4-aminobutanesulfonic acid is preferred.

  Among these, the raw material monomer for the water-soluble conductive polymer is preferably a thiophene derivative represented by the above formula (3) or (4).

In the above formula (3), R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ₂ ) ₃ or HNC ₅ H ₅ . Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

In the above formula (4), R ³ has the same meaning as in the above formula (3). Z represents chloride, bromide, iodide, acetate, trifluoroacetate or trifluoromethanesulfonate.

  The thiophene derivative represented by the above formula (1) or (3) of the present invention (wherein M does not represent a hydrogen atom) includes the thiophene derivative represented by the above formula (5) and the above formula (6). ) Can be conveniently obtained by reacting in a polar solvent in the presence of a base.

  In the compound represented by the above formula (5), X is tosylate, mesylate, triflate, chloride, bromide, or iodide. n represents an integer of 1 to 6.

  Specific examples of the compound represented by the above formula (5) include 2- (3-thienyl) -ethyl chloride, 2- (3-thienyl) -ethyl bromide, 2- (3-thienyl) -ethylio Dido, 2- (3-thienyl) -ethyl methanesulfonate, 2- (3-thienyl) -ethyl tosylate, 2- (3-thienyl) -ethyl triflate, 3- (3-thienyl) -propyl chloride, 3- (3-thienyl) -propyl bromide, 3- (3-thienyl) -propyl iodide, 3- (3-thienyl) -propyl methanesulfonate, 3- (3-thienyl) -propyl tosylate, 3- (3- Thienyl) -propyl triflate, 4- (3-thienyl) -butyl chloride, 4- (3-thienyl) -butyl bromide, 4- (3-thienyl) Butyl iodide, 4- (3-thienyl) - butyl methanesulfonate, 4- (3-thienyl) - butyl tosylate, 4- (3-thienyl) - butyl triflate, and the like.

In the compound represented by the above formula (6), R ¹ may be the same as the above formula (1).

  Specific examples of the compound represented by the above formula (6) include 2-aminoethanesulfonic acid, sodium 2-aminoethanesulfonic acid, N-methyl-2-aminoethanesulfonic acid, N-methyl-2- Sodium aminoethanesulfonate, 3-aminopropanesulfonic acid, sodium 3-aminopropanesulfonate, N-methyl-3-aminopropanesulfonic acid, sodium N-methyl-3-aminopropanesulfonate, 4-aminobutanesulfonic acid , Sodium 4-aminobutanesulfonate, sodium N-methyl-4-aminobutanesulfonate, sodium N-methyl-4-aminobutanesulfonate, and the like.

  The polar solvent used in this reaction is not particularly limited as long as the reaction proceeds. For example, N, N-dimethylaminoformamide, N-methylformamide, N-methylpyrrolidone, N, N-dimethylacetamide, methanol , Acetone, water and the like. Of these, N, N-dimethylformamide is more preferable. These may be used alone or in any desired mixture.

  The amount of the polar solvent used is not particularly limited as long as the compound represented by the above formulas (5) and (6) as a raw material is dissolved. For example, the polar solvent is represented by the above formulas (5) and (6). The amount of the compound to be prepared is preferably 0.1 to 200 times by weight, more preferably 1 to 100 times by weight.

  The base used in this reaction is not particularly limited as long as the reaction proceeds. For example, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide Examples include rubidium, calcium hydroxide, sodium hydride, pyridine, trimethylamine, triethylamine, and tributylamine. More preferred are sodium carbonate and potassium carbonate.

  As a usage-amount of a base, 1-100 times mole is preferable with respect to the total mole number of the compound represented by the said Formula (5) and (6), More preferably, it is 1-10 times mole, More preferably Is 2-5 moles.

  The reaction temperature of this reaction is not particularly limited as long as the reaction proceeds, and is preferably -20 to 200 ° C, more preferably 0 to 100 ° C, and further preferably 30 to 80 ° C.

  The reaction atmosphere of this reaction is preferably in the air, or in nitrogen or argon, and more preferably in nitrogen.

  The reaction pressure of this reaction may be an atmospheric pressure system or a pressurized system, and is preferably an atmospheric pressure system.

  After obtaining the thiophene derivative represented by the above formula (1) or the formula (3) of the present invention (wherein M does not represent a hydrogen atom) by the above method, an excess amount of acid (hereinafter referred to as “HZ”). The thiophene derivative represented by the above formula (2) or formula (4) respectively corresponding to the nitrogen moiety in the molecule can be easily obtained. be able to.

The excess amount of acid (HZ) is not particularly limited. For example, hydrochloric acid (HCl), hydrobromic acid (HBr), hydrogen iodide (HI), sulfuric acid (H ₂ SO ₄ ), acetic acid (CH ₃ COOH) ), Trifluoroacetic acid (CF ₃ COOH), trifluoromethanesulfonic acid (CF ₃ SO ₃ H), and the like, more preferably hydrochloric acid.

The amount of the acid is preferably equal to or greater than the equivalent of the total number of moles of —SO ₃ M and nitrogen atoms in the above formula (1) or (3), more preferably 1 to 500 times mol. Preferably it is 1-100 times mole.

  Although it will not specifically limit as temperature which makes it react with an acid, if it advances, it is 0-100 degreeC, Preferably it is 0-60 degreeC, More preferably, it is 10-40 degreeC. The atmosphere of the reaction system when reacting with an acid may be in the air, and more preferably an inert gas atmosphere such as nitrogen or argon. The pressure of the reaction system when reacting with the acid may be a normal pressure or a pressurized system, preferably a normal pressure system.

  A solvent may be used when producing the compound represented by the above formula (2) or formula (4). The solvent is not particularly limited as long as it is a solvent in which the compound represented by the above formula (1) or (3) dissolves and is stable with respect to the acid used, and the reaction proceeds. For example, water, alcohol, Toluene, xylene, acetone, dioxane, tetrahydrofuran and the like can be mentioned. Of these, water, alcohol, toluene, and acetone are preferable, and water is more preferable. The amount of the solvent used is not particularly limited as long as the compound represented by the above formula (1) or (3) is dissolved, and is preferably 1 to 500 times by weight, more preferably 1 to 100 times by weight. The amount is more preferably 2.5 to 50 times by weight.

  Isolation of the compound represented by the above formula (2) or formula (4) can be obtained by a general post-treatment operation such as concentration, washing, neutralization, recrystallization and the like. In the case of hydrochloride, the target product is obtained by concentrating the reaction solution.

  By using the aqueous thiophene derivative represented by the above formula (2) or formula (4), for example, ammonia water to make it strongly alkaline (ammonium salt), the compound represented by the following formula (7) can be obtained. Further, by drying under reduced pressure with heating, the thiophene derivative represented by the above formula (1) or (3) (where M represents a hydrogen atom) [represented by the following formula (8) Can be easily obtained.

  The amount of ammonia water used is not particularly limited as long as the ammonia contained is an equimolar amount or more with respect to Z in the above formula (2) or (4). It is -500 times mole, More preferably, it is 1-100 times mole.

  There is no limitation in particular as temperature which processes with ammonia water, if reaction advances, 0-100 degreeC is preferable, More preferably, it is 0-60 degreeC, More preferably, it is 10-40 degreeC.

  The atmosphere of the reaction system when treating with ammonia water may be air, and more preferably an inert gas atmosphere such as nitrogen or argon. The pressure of the reaction system when treating with aqueous ammonia may be a normal pressure or a pressurized system, preferably a normal pressure system.

  A solvent may be used when treating with ammonia water. The solvent is not particularly limited as long as it is a solvent in which the compound of formula (2) or formula (4) dissolves and is stable to the acid used, and the reaction proceeds. For example, water, alcohol, toluene, xylene , Acetone, dioxane, tetrahydrofuran and the like. Of these, water, alcohol, toluene, and acetone are preferable, and water is more preferable.

  The amount of the solvent used is not particularly limited as long as the compound represented by the above formula (2) or (4) is dissolved, but it is preferably 1 to 500 times by weight, more preferably 1 ˜100 times by weight, more preferably 2.5 to 50 times by weight.

  The deammonia reaction in this reaction is carried out by drying under reduced pressure under heating. The decompression condition is not particularly limited as long as it is a degree of decompression that can distill off ammonia. The heating temperature is not particularly limited as long as ammonia is desorbed from sulfonic acid, and is preferably 40 to 200 ° C, more preferably 80 to 150 ° C.

  The above reaction scheme is summarized below.

  As the thiophene derivative of the present invention, those showing water solubility such that the compound dissolves in water at room temperature or under heating at 0.5% by weight or more are more preferable.

  Next, the polythiophenes of the present invention will be described.

  The polythiophenes in the present invention are polythiophenes containing at least one structural unit selected from the group consisting of the structural unit represented by the above formula (16) and the structural unit represented by the above formula (17).

In the above formula (16), R ¹ , M, n and m are as defined in the above formula (1).

In the above formula (17), R ¹ , n, and m have the same meaning as in the above formula (16). The structural unit represented by the above formula (17) represents the doping state of the structural unit represented by the above formula (16).

  The dopant causing the insulator-metal transition by doping is divided into an acceptor and a donor.

The former enters near the polymer chain of the conductive polymer by doping and takes π electrons from the conjugated system of the main chain. As a result, since positive charges (holes, holes) are injected onto the main chain, it is also called a p-type dopant. Specifically, halogens (Br ₂ , I ₂ , Cl ₂ ), Lewis acid (BF ₃ , PF ₅ , AsF ₅ ), protonic acid (H ₂ SO ₄ , HCl, CF ₃ SO ₃ H), transition metal Examples include halide (FeCl ₃ ), organic substance (TCNQ), and the like.

  The latter is also referred to as an n-type dopant because it gives electrons to the conjugated system of the main chain, which moves in the conjugated system of the main chain. Specific examples include alkali metals (Li, Na, K, Cs), alkylammonium ions, and the like.

  The dopant in the present invention is a sulfo group or a sulfonate group that is covalently bonded in the polymer molecule, and is a p-type dopant. Such a polymer that exhibits conductivity without externally adding a dopant is called a self-doped polymer.

  The polythiophenes in the present invention specifically include at least one structural unit selected from the group consisting of the structural unit represented by the above formula (18) and the structural unit represented by the above formula (19). Is preferred.

In the above formula (18), R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M represents a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH (R ₂ ) ₃ or HNC ₅ H ₅ . Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. ]
In the above formula (19), R ¹ has the same meaning as in the above formula (18). The structural unit represented by the above formula (19) represents the doping state of the structural unit represented by the above formula (18).

  The weight average molecular weight of the polythiophenes of the present invention is not particularly limited, but is usually in the range of 1,000 to 1,000,000 in terms of polystyrene sulfonic acid, and preferably 1,000 to 200,000 for water-soluble conductive polymer applications. It is a range. From the viewpoint of removing unreacted monomers, low-molecular impurities and inorganic salts from the polymer, the range of 3.5 to 100,000 is more preferable.

  By making the polythiophene of the present invention into an aqueous solution, it becomes easy to mold into various applications as a water-soluble conductive polymer aqueous solution. Although the preparation method of water-soluble conductive polymer aqueous solution is not specifically limited, It is achieved by mixing and dissolving with water at room temperature or under heating (preferably 100 ° C. or less). At that time, a general mixing and dissolving operation using a stirrer chip or a stirring blade can be used, and as other methods, ultrasonic irradiation, homogenization treatment (for example, use of a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, etc.) May be performed. In the case of homogenizing treatment, it is preferable to carry out the treatment while cooling in order to prevent thermal degradation of the polymer.

  The concentration of the polythiophene in the water-soluble conductive polymer aqueous solution is not particularly limited, but is usually 50% by weight or less, preferably 20% by weight or less, and more preferably 10% by weight or less from the viewpoint of viscosity.

  In the present invention, “water solubility sufficient for molding for various uses” means that the particle diameter (D50) measured with a particle size distribution analyzer is 10% by weight or less in a polymer aqueous solution prepared at room temperature or under heating. The water solubility is such that it is 20 nm or less and passes through a 0.05 μm filter.

Moreover, in this invention, favorable electroconductivity means the electroconductivity whose electrical conductivity (electrical conductivity) in a film state is 10 ^<-1 > S / cm or more.

  Next, the manufacturing method of polythiophene of this invention is demonstrated.

  The method for producing the polythiophene of the present invention is characterized by polymerizing the above-described thiophene compound of the present invention in the presence of an oxidizing agent in water or an alcohol solvent. As a thiophene compound, it can use 1 type or in combination of 2 or more types.

  The solvent used in the polymerization reaction is water or an alcohol solvent. The water may be pure water, and may be distilled water or ion exchange water. Examples of the alcohol solvent include alcohols such as methanol, ethanol, propanol, and butanol. These alcohol solvents may be used alone or in combination with water. In the present invention, water or methanol is preferable, and water is more preferable. In addition, the solvent may be replaced with an inert gas such as degassed or nitrogen.

  The amount of the solvent used in the polymerization reaction is not particularly limited as long as the thiophene compound of the present invention is dissolved, but is preferably 0.1 to 100 times by weight, more preferably the amount of the thiophene compound of the present invention charged. 1 to 20 times by weight.

  The oxidizing agent used in the main polymerization reaction is not particularly limited as long as it allows oxidative polymerization by oxidative dehydrogenation reaction to proceed. For example, persulfuric acid, iron salt (III), hydrogen peroxide Permanganate, dichromate, cerium (IV) sulfate, oxygen and the like, and may be used alone or in admixture of two or more.

  Specific examples of the persulfuric acid include persulfuric acid, ammonium persulfate, sodium persulfate, and potassium persulfate.

Specific examples of the iron salt (III) include FeCl ₃ , Fe ₂ (SO ₄ ) ₃ , iron perchlorate, iron (III) para-toluenesulfonate, and the like. These may use anhydrides or hydrates.

  Specific examples of permanganate include sodium permanganate, potassium permanganate, and magnesium permanganate.

  Specific examples of the dichromate include ammonium dichromate and potassium dichromate.

Of these oxidizing agents, FeCl ₃ , Fe ₂ (SO ₄ ) ₃ , or a combined system of persulfate and iron salt (III) is preferable.

  The amount of the oxidizing agent used in the polymerization reaction is not particularly limited, but is 0.5 to 50 times the mole of the charged thiophene compound of the present invention. More preferably, it is 1-20 times mole. More preferably, it is 1-10 times mole.

  The pressure of the polymerization reaction may be normal pressure, reduced pressure, or increased pressure.

  The reaction atmosphere of the polymerization reaction may be in the air or in an inert gas such as nitrogen or argon. More preferably, it is in an inert gas.

  Although the reaction temperature of this polymerization reaction will not be specifically limited if it is the temperature which can oxidatively polymerize the thiophene compound of this invention, -10-150 degreeC is preferable, More preferably, it is the range of 20-100 degreeC.

  The reaction time of the main polymerization reaction is not particularly limited as long as the oxidation polymerization of the thiophene compound of the present invention is sufficiently advanced, but is preferably 0.5 hours to 200 hours, more preferably 0.5 to 80 hours. .

  The reaction method of the present polymerization reaction is not particularly limited. For example, the thiophene compound of the present invention may be made into an aqueous solution, and an oxidizing agent may be dropped dropwise at once, or conversely, the oxidizing agent may be solid or an aqueous solution. The aqueous solution of the thiophene compound of the present invention may be added dropwise at once or slowly.

  The purification method of the polythiophene of the present invention obtained by the present polymerization reaction is not particularly limited, and examples thereof include solvent washing, reprecipitation, centrifugal sedimentation, ultrafiltration, dialysis, and ion exchange resin treatment. It is done. Each may be performed alone or in combination.

  For example, a typical isolation and purification method for the polythiophenes of the present invention is as follows.

  First, the polymer aqueous solution after the polymerization reaction is added to a poor solvent such as acetone to precipitate the polymer, and then the polymer obtained by filtration under reduced pressure is washed with the poor solvent until the filtrate becomes colorless and transparent. When this polymer contains an Fe salt that is insoluble in water, it is preferably added once to an aqueous sodium hydroxide solution and converted to a Na salt type polymer that dissolves in water.

  Next, this is added to a poor solvent such as alcohol to precipitate the polymer, the alkali is removed, and the solid obtained by filtration under reduced pressure is washed with a poor solvent such as alcohol. Next, it is washed with a poor solvent such as acetone to obtain a Na salt type polymer.

  When the obtained Na salt type polymer is subsequently converted to an H type polymer, it is treated with a cation exchange resin. Examples of the treatment method include a method in which an aqueous solution of the obtained Na salt type polymer is passed through a column filled with a cation exchange resin, a body feed method in which the cation exchange resin is added to the aqueous solution, and the like. In this case, it is preferable to remove the cation exchange resin with a filter paper after the treatment. The aqueous solution thus obtained is roughly concentrated, added to a poor solvent such as acetone for precipitation, and the solid obtained by filtration under reduced pressure is thoroughly washed with the poor solvent and dried under reduced pressure to obtain an H-type polymer. .

  Further, when salts with various amines are formed, for example, an amine salt type polymer can be easily prepared by adding a stock solution of various amines or an aqueous solution thereof or a solution diluted with an appropriate solvent to an aqueous solution of H salt type polymer. Can be converted to For example, when treated with aqueous ammonia, the reaction solution is roughly concentrated, the aqueous solution is added to a poor solvent such as acetone to cause polymer precipitation, and then the solid obtained by vacuum filtration is washed with the poor solvent, Ammonium salt type polymer is obtained by drying under reduced pressure.

  In each step of the post-polymerization treatment, centrifugal sedimentation and homogenization treatment may be performed as necessary. Thereby, improvement of filtration efficiency can be aimed at. Further, when persulfate is used as the polymerization oxidant, ultrafiltration, dialysis, and cation / anion exchange resin mixing treatment are performed to remove inorganic salts.

A conductive film can be produced using the polythiophenes of the present invention. For example, a conductive film can be easily obtained by applying the above water-soluble conductive polymer aqueous solution to a substrate and drying. Examples of the substrate include glass, plastic, polyester, polyacrylate, polycarbonate, resist substrate, and the like. Examples of the coating method include a casting method, a dipping method, a barcode method, a roll coating method, a gravure coating method, a flexographic printing method, a spray coating method, and an inkjet printing method. It not particularly limited as film ^thickness, but preferably in the range of 10 -2 ~10 ² μm. Although it does not specifically limit as surface resistance value of the coating film obtained, The thing of the range of 1-10 < ⁹ > ohm / square is preferable.

  Examples relating to the thiophene derivatives of the present invention are shown below, but the present invention is not construed as being limited to these examples. The analytical instruments and measurement methods used in this example are listed below.

[GC measurement]
Apparatus: manufactured by Shimadzu, GC-2014.

[NMR measurement]
Apparatus: VARIAN, Gemini-200.

[Infrared spectroscopy]
Apparatus: manufactured by PerkinElmer, System 2000 FT IR,
Measuring method: KBr method.

  In this example, compounds (9) to (14) were synthesized according to the following scheme.

  In addition, you may synthesize | combine a compound (11) from a compound (9). In that case, it is compoundable on the same conditions as synthesize | combining from a compound (10).

Synthesis Example 1 Synthesis of compound (9).
To a 300 mL eggplant-shaped flask was added 7.05 g (55.0 mmol) of 3-thiopheneethanol, 10 ml of pyridine and 100 ml of dichloromethane, and then 15.75 g (82.6 mmol) of p-tosyl chloride was separated as a solid in an ice bath. Added. After completion of the reaction by adding 50 ml of water, 150 ml of diethyl ether was added for extraction. The organic layer was washed twice with 50 ml of 2N hydrochloric acid aqueous solution and twice with 50 ml of 5% sodium hydrogen carbonate. Further, the organic layer was washed with 50 ml of saturated brine, and then dried over magnesium sulfate. After filtration and concentration, the resulting concentrate was purified by silica gel chromatography to obtain 12.8 g of compound (9) (white crystals, yield 83%).

Synthesis Example 2 Synthesis of compound (10) [compound represented by the above formula (5)].
To a 300 mL eggplant-shaped flask, 24.2 g (161.2 mmol) of sodium iodide and 100 mL of acetone were added, and then a solution of 12.8 g (45.3 mmol) of Compound (9) obtained in Synthesis Example 1 in 20 mL of acetone at room temperature. After adding in 5 minutes, it was aged at the same temperature for 18 hours. After the reaction, the filtrate obtained by filtration was concentrated and washed with 50 mL of water. Next, the mixture was extracted with 100 mL of ethyl acetate, further washed with 50 mL of saturated brine, and the organic layer was dried over magnesium sulfate. The crude product obtained by concentration was purified by silica gel chromatography to obtain 8.0 g of compound (10) (pale yellow oil, yield 77%).

Example 1 Synthesis of compound (11) [compound other than hydrogen in the above formula (1)].
In a 500 mL four-necked flask in nitrogen, 5.00 g (21.0 mmol) of the compound (10) obtained in Synthesis Example 2, 2.63 g (21.0 mmol) of 2-aminoethanesulfonic acid (compound of formula (6)). ), 8.71 g (63.0 mmol) of potassium carbonate (base) and 210 mL of N, N-dimethylformamide (polar solvent) were added and reacted at 60 ° C. for 24 hours. The disappearance of compound (10) was confirmed by TLC analysis and GC analysis. After allowing to cool, the precipitate was filtered and washed with ethyl acetate. The obtained filtrate was roughly concentrated, washed with a mixed solvent of methylene chloride / hexane, and filtered under reduced pressure to obtain 5.7 g of the objective compound (11) as a white solid. This compound showed water solubility.

¹ H-NMR (200 MHz, d-DMSO) δ (ppm) 7.43 (1H, s), 7.18 (1H, s), 7.02 (1H, s), 3.10-3.36 ( 2H, m), 2.64-2.89 (7H, m).

¹³ C-NMR (50 MHz, d-DMSO) δ (ppm) 27.46, 48.05, 48.87, 54.00, 120.49, 125.16, 128.36, 140.43
IR (KBr) 3441, 3092, 2936, 2850, 1656, 1462, 1191, 1050, 779, 611, 537.

Example 2 Synthesis of Compound (14) [Compound wherein M is Hydrogen in Formula (1) above].
In a 200 mL four-necked flask, 1.00 g (3.70 mmol) of the compound (11) obtained in Example 1 and 20 mL of pure water were added and dissolved, and then 15.6 g (153.6 mmol) of concentrated hydrochloric acid was added. In addition, the mixture was reacted at room temperature for 19 hours. After the reaction, the orange solid obtained by concentration was washed and extracted with 200 mL of acetone, and the white precipitate was removed by filtration. After concentration, compound (12) [compound represented by the above formula (2)] was obtained as a brown oil. Subsequently, 29.6 g (504.7 mmol) of 29% aqueous ammonia was added to the compound (12) and stirred at room temperature for 3 hours. The reaction solution became colorless and transparent, and the compound (13) was produced. This solution was concentrated to dryness under reduced pressure at 90 ° C. for 3 hours to obtain 690 mg of a white solid. The solid was washed and extracted with acetone, the insoluble matter was removed by filtration under reduced pressure, and the pale yellow solid obtained by concentration was washed with an ether / acetone mixed solvent. After filtration under reduced pressure, the residue was dried to obtain 390 mg of the target compound (14) as a pale yellow solid (yield 45%). This compound showed water solubility. It was free sulfonic acid from NMR and IR analysis.

¹ H-NMR (200 MHz, d-DMSO) δ (ppm) 7.54 (1H, d, J = 4.8 Hz), 7.38 (1H, s), 7.12 (1H, s, J = 4) .8 Hz), 3.49-3.01 (9H, m).

¹ H-NMR (200 MHz, d-DMSO, D ₂ O) δ (ppm) 7.54 (1H, d, J = 4.8 Hz), 7.38 (1H, s), 7.12 (1H, s , J = 4.8 Hz), 3.47-3.06 (8H, m).

¹³ C-NMR (50 MHz, d-DMSO) 24.12, 44.61, 49.55, 52.72, 122.23, 126.19, 128.13, 136.42
IR (KBr) 3443, 2928, 2748, 1465, 1414, 1212, 1045, 785, 610, 527.

  Example 3 Synthesis of compound (15) [a compound in which M is other than hydrogen in the above formula (1)].

  In a 500 mL four-necked separable flask in nitrogen, 3.16 g (12.6 mmol, purity 95.0%) of the compound (10) obtained in Synthesis Example 2 and a 65% aqueous solution of sodium N-methyltauratesulfonate [above Compound of formula (6)] 3.13 g (12.6 mmol), potassium carbonate (base) 5.23 g (37.8 mmol), N, N-dimethylformamide (polar solvent) 130 mL were charged and reacted at 70 ° C. for 21 hours. I let you. The disappearance of compound (10) was confirmed by TLC analysis and GC analysis. After allowing to cool, the precipitate was filtered and washed with dimethylformamide. The obtained filtrate was roughly concentrated, washed with a mixed solvent of methylene chloride / hexane, and filtered under reduced pressure to obtain 3.2 g of the objective compound (15) as a pale yellow solid. This compound showed water solubility.

¹ H-NMR (200 MHz, D ₂ O, 2,2,3,3-d (4) -3- (trimethylsilyl) propionic acid sodium) δ (ppm) 7.45-7.41 (1H, m), 7.19 (1H, s), 7.09 (1H, d, 5.0 Hz), 3.15-2.75 (8H, m), 2.32 (3H, s).

¹³ C-NMR (50 MHz, D ₂ O, 2,2,3,3-d (4) -3- (trimethylsilyl) propionate sodium) δ (ppm) 29.57, 43.51, 49.90, 53 .56, 59.26, 124.01, 128.86, 131.06, 142.80.

  In the examples, “showed water solubility” means that the compound was dissolved in water at 0.5% by weight or more at room temperature or under heating.

  Next, examples relating to the polythiophenes of the present invention are shown below, but the present invention is not construed as being limited to these examples. The analytical instruments and measurement methods used in this example are listed below.

[UV-Vis-NIR analysis]
Apparatus: manufactured by SHIMADZU, UV-3100.
[GPC measurement]
Equipment: manufactured by Tosoh Corporation
Column: α-6000 + α-3000,
Detector: UV-8020.

[IR analysis]
Apparatus: System 2000 FT-IR, manufactured by PerkinElmer.
[Surface resistivity measurement]
Apparatus: Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation.
[Film thickness measurement]
Apparatus: manufactured by BRUKER, DEKTAK XT.
[Particle size measurement]
Apparatus: Nikkiso Co., Ltd. Microtrac Nanotrac UPA-UT151.

[Filter flow test]
Filter: Nippon Integris, Optimizer V-47 Disposable filter (new water), particle removal diameter 0.05μm
Example 4 Synthesis of polymer (26) [polymer containing a structural unit represented by the following formula (24) or the following formula (25)].
In a 500 mL separable flask equipped with a stirring blade, a cooling tube, and a thermometer insertion tube, 10.0 g (36.6 mmol) of the compound represented by the above formula (11) obtained in Example 1 was placed, and 293 g After dissolving in water, 1.19 g (7.3 mmol) of FeCl ₃ and 34.8 g (146.3 mmol) of Na ₂ S ₂ O ₈ were added, followed by polymerization at 70 ° C. for 21 hours. After allowing to cool, the mixture was poured into acetone, and the precipitate was collected by vacuum filtration. The obtained Na salt type polymer was redissolved in pure water and washed by ultrafiltration (fractionated molecular weight 10,000). Then, after adding a cation exchange resin (Lewatit S100, H type) and treating at room temperature for 4 hours, the filtrate obtained by removing the resin by vacuum filtration was concentrated and washed with acetone. After drying under reduced pressure, 2.3 g of a water-soluble polymer was obtained [Mw / Mn = 12731/10002 (polystyrene sulfonic acid standard)]. The IR analysis chart of this polymer is shown in FIG. Furthermore, the electrical conductivity of a film obtained by preparing a 1% aqueous solution of this polymer and casting it on glass was 2.0 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed.

Example 5 Synthesis of polymer (29) [polymer containing a structural unit represented by the following formula (27) or the following formula (28)].
In a 500 mL separable flask equipped with a stirring blade, a cooling tube, and a thermometer insertion tube, 1.00 g (3.69 mmol) of the compound represented by the above formula (15) obtained in Example 3 was placed, and 30 g After dissolving in water, 60 mg (0.37 mmol) of FeCl ₃ and 3.51 g (14.7 mmol) of Na ₂ S ₂ O ₈ were added, followed by polymerization at 70 ° C. for 17 hours. After allowing to cool, the mixture was poured into acetone, and the precipitate was collected by vacuum filtration. The obtained Na salt type polymer was redissolved in pure water and washed by ultrafiltration (fractionated molecular weight 10,000). Then, after adding a cation exchange resin (Lewatit S100, H type) and treating at room temperature for 4 hours, the filtrate obtained by removing the resin by vacuum filtration was concentrated and washed with acetone. After drying under reduced pressure, 1.5 g of a water-soluble polymer was obtained. Subsequently, a 3% polymer aqueous solution obtained by re-dissolving in pure water was treated with a dialysis membrane (Spectra / Por MWCO = 0.1-0.5K). Removal was performed and the purified aqueous solution was concentrated. After washing with acetone and drying under reduced pressure, 80 mg of the target acid type polymer was obtained [Mw / Mn = 6095/5319 (polystyrene sulfonic acid standard)]. The IR analysis chart of this polymer is shown in FIG. Furthermore, the conductivity of a film obtained by preparing a 1% aqueous solution of the obtained acid type polymer and casting it on glass was 1.3 S / cm. The particle size (D50) of the polymer in a 0.5% by weight aqueous solution was below the detection limit (0.8 nm), and a 0.05 μm filter was passed.

Comparative Example 1 Synthesis of polymer (36) [polymer containing a structural unit represented by the following formula (34) or the following formula (35)].
The compound was synthesized according to the following scheme with reference to Macromolecules, 1995, pages 975-984.

(1A) Synthesis of 3-allylthiophene (31).
A 300 mL four-necked flask was charged with 20.1 g (123.4 mmol) of 3-bromothiophene (30) and 80 mL of diethyl ether (dehydrated), and cooled to -78 ° C. Thereafter, 92 mL (147.2 mmol) of 1.6 M normal-butyllithium was slowly added dropwise over 1 hour with a dropping funnel. After aging for 2 hours at the same temperature, 15.0 g (123.6 mmol) of allyl bromide was slowly added with a syringe and aged for 5 hours at the same temperature. After heating up to 0 degreeC, it quenched with 100 mL of saturated ammonium chloride aqueous solution, and the organic layer was extracted. Furthermore, it wash | cleaned with water and a saturated salt solution, and the organic layer obtained by liquid-separating was dried with magnesium sulfate. The organic layer obtained by filtration was concentrated at 50 ° C. and <20 Torr, yielding 3.2 g of a brown oil. This was purified by Kugelrohr distillation (70-125 ° C., 25 Torr) to obtain 2.5 g of the desired compound (31) as a colorless transparent oil (yield 16%).
(1B) Synthesis of sodium 3- (3-thienyl) propane-1-sulfonate (32).
3 g (24.2 mmol) of 3-allylthiophene (31) synthesized in (1A) above was dissolved in 37 mL of methanol in a 100 mL eggplant flask, and 0.05 g (0.30 mmol) of azobisisobutyronitrile was then added. Added. Furthermore, a solution prepared by dissolving 2.9 g (27.9 mmol) of NaHSO ₃ and 0.59 g (4.60 mmol) of Na ₂ S ₂ O _{3 in} 24 mL of water was added at room temperature, followed by stirring at 80 ° C. overnight. Meanwhile, the reaction solution changed from a suspension to a homogeneous solution. After cooling, it was concentrated to obtain 7.30 g of a white solid. Subsequently, the white solid obtained by washing with 35 mL of diethyl ether and filtering was dried to obtain 5.14 g of a crude product. Further, the solid was extracted and washed with 100 mL of ethanol, and the filtrate obtained by filtration under reduced pressure was concentrated and dried to obtain the target compound (32) as 2.21 g of white crystals (yield 52%).

(1C) Synthesis of polymer (33).
The compound obtained in (1B) (32) and 0.85 g (3.72 mmol), an aqueous solution of monomers consisting of water 7.6, FeCl ₃ 2.40 g which had charged into the reaction tube in advance 30 mL (14 .8 mmol) was added slowly. Thereafter, polymerization was carried out at room temperature for 22 hours. Meanwhile, the reaction solution became a black solution with a greenish color. After the polymerization, the polymer was precipitated by slowly pouring into 150 mL of acetone with stirring. After thoroughly washing with acetone, 0.17 g of black polymer was obtained. The polymer was suspended in 2 g of water and 1.5 mL of 1N NaOH aqueous solution was added with vigorous stirring. The suspension changed from a suspension to a reddish brown homogeneous solution by adding NaOH aqueous solution. Subsequently, the polymer was precipitated by pouring into 20 mL of methanol. After filtration and drying, 0.12 g of the target Na salt type polymer (33) was obtained as a black solid (yield 14%).

(1D) Synthesis of polymer (36).
In a 30 mL reaction tube, 122 mg of the polymer (33) obtained in (1C) above was suspended in 15 mL of water and stirred for 2 hours. Thereafter, filtration under reduced pressure gave a dark red solution. 2 g of cation exchange resin (Lewatit S100 H type) was added to the solution and stirred overnight. The filtrate obtained by filtration was concentrated and dried to obtain the desired acid type polymer (36) as a black solid in 76 mg (yield 63%). The conductivity of a film obtained by preparing a 0.5 wt% aqueous solution of this polymer and casting it on an alkali-free glass plate was 0.06 S / cm. The particle size (D50) of the polymer in a 0.5 wt% aqueous solution was 10 nm.

Comparative Example 2 Synthesis of polymer (42) [polymer containing a structural unit represented by the following formula (40) or the following formula (41)].
The compound was synthesized according to the following scheme with reference to Japanese Patent No. 3182239.

(2A) Synthesis of 1,3-dihydroisothianaphthene (38).
In a 2 L separable flask, 10.0 g (38.0 mmol) of the compound (37), 25.7 g (75.8 mmol) of tetra-normal-butylammonium hydrogen sulfide, and 950 mL of chloroform were charged. After nitrogen bubbling, an aqueous solution prepared by dissolving 13.9 g (57.8 mmol) of sodium sulfide nonahydrate and 6.4 g (75.6 mmol) of sodium hydrogen carbonate in 700 mL of water was added dropwise at room temperature over 1.5 hours. And further aged for 1 hour. After the reaction, the organic layer was separated and further washed twice with 250 mL of water. The organic layer dried over magnesium sulfate was concentrated to give a mixture of white solid and oil. Subsequently, silica gel column chromatography purification (eluent: hexane / chloroform = 4/1) gave 2.8 g of the objective compound (38) as a colorless transparent oil (yield 55%).

(2B) Synthesis of polymer (39).
A 30-mL reaction tube was charged with 3.0 g of 30% fuming sulfuric acid and cooled in an ice bath. Furthermore, the compound (38) obtained by said (2A) was dripped in the fuming sulfuric acid with the syringe under nitrogen stream. After stirring at room temperature for 1 hour, the mixture was reacted at 70 ° C. for 1 hour. The reaction solution changed from brown to dark blue immediately after dropping. After the reaction, it was added dropwise to 200 mL of a 0.1N NaOH-methanol solution to precipitate the polymer. The polymer was precipitated by centrifugation (3000 rpm), and after drying, 1.4 g of black powder was obtained. Subsequently, it was dissolved in 100 g of water, and inorganic salts were removed by dialysis (dialysis membrane: Spectra / Por MWCO = 0.1-0.5K). The purified aqueous solution was concentrated and dried to obtain 1.1 g of the intended Na salt polymer (39) as a black solid (yield 64%).

(2C) Synthesis of polymer (42).
A 30 mL reaction tube was charged with 160 mg of the Na salt polymer (39) obtained in (2B) and 23 g of water to prepare an aqueous solution. Thereto was added 2.5 g of a cation exchange resin (Lewatit S100) that had been acidified in advance and stirred overnight. The ion exchange resin was removed by filtration, and the obtained filtrate was concentrated and dried to obtain 140 mg of the desired acid polymer (42) as a black solid (yield 89%). The conductivity of a film obtained by preparing a 0.5 wt% aqueous solution of this polymer and casting it on an alkali-free glass plate was 0.1 S / cm. The particle size (D50) of the polymer in a 0.5 wt% aqueous solution was 6 nm.

Comparative Example 3 Synthesis of polymer (47) [polymer containing a structure represented by the following formula (45) or the following formula (46)].
The compounds were synthesized according to the following scheme with reference to Journal of Electroanalytical Chemistry, 1998, pages 217-226 and Chemistry of Materials, 2009, pages 1815-1821.

(3A) Synthesis of compound (44).
A 100 mL eggplant flask was charged with 1.83 g of a commercially available compound (43), 45 mL of toluene, and 0.32 g (13.2 mmol) of 60% NaH, and reacted for 1 hour under reflux conditions. 1.46 g (10.7 mmol) of 1,4-butane sultone dissolved in 12 mL of toluene was added dropwise under reflux. After further aging for 2 hours, the mixture was cooled to room temperature and added to 200 mL of acetone to precipitate a jelly-like solid. After filtration through filter paper, drying under reduced pressure gave 2.0 g of the target compound (53) as a light brown solid (yield 56%).

(3B) Synthesis of polymer (47).
A 50 mL Schlenk tube was charged with 0.81 g (2.44 mmol) of the compound (44) obtained in (3A) above and 12 mL of water to obtain an aqueous monomer solution. An aqueous oxidizing agent solution prepared by dissolving 1.16 g (4.86 mmol) of Na ₂ S ₂ O ₈ and 0.02 g (0.10 mmol) of FeCl ₃ separately in 12 mL of water was slowly added to the aqueous monomer solution. After polymerization at room temperature for 16 hours, the polymerization solution was poured into 160 mL of acetone to precipitate a polymer. The obtained slurry was completely precipitated by centrifugal sedimentation (3000 rpm), and 1.4 g of a black solid was obtained. Subsequently, an aqueous solution having a total amount of 80 g was prepared with water, and inorganic salts were removed by dialysis (dialysis membrane: Spectra / Por MWCO = 0.1-0.5K). The purified aqueous solution was concentrated and dried to obtain 553 mg of the target Na salt polymer (47) as a black solid (yield 69%). The conductivity of a film obtained by preparing a 0.5 wt% aqueous solution of this polymer and casting it on an alkali-free glass plate was 0.3 S / cm. The particle size (D50) of the polymer in the 0.5 wt% aqueous solution was below the detection limit (0.8 nm).

  According to the method for producing a thiophene derivative of the present invention, the novel thiophene derivative of the present invention can be easily provided.

  The thiophene derivative of the present invention can be used as a monomer for an antistatic agent, a solid electrolyte of a solid electrolytic capacitor, a solar cell, an organic EL, a capacitor, or a conductive polymer polythiophene used for a sensor. In addition, since the thiophene derivative of the present invention has a sulfonic acid group, it exhibits water solubility, and further, since a sulfonic acid group serving as a dopant is present in the molecule, the resulting polymer has a water-soluble self-doping conductivity high conductivity. Expected to be a molecule.

  Further, according to the present invention, novel polythiophenes having both good conductivity and sufficient water solubility for molding are provided. The novel polythiophenes can be applied to antistatic agents, capacitor solid electrolytes, conductive paints, electrochromic elements, transparent electrodes, transparent conductive films, chemical sensors, actuators, and the like. In particular, since it is water-soluble, damage to the fat-soluble resist is small, and peeling cleaning is easy. Therefore, it is expected to be used as an antistatic film forming material for suppressing resist charging during electron beam lithography. . In addition, since the polymer particle diameter is very small when an aqueous solution is used, for example, the permeability to the etched aluminum foil subjected to the chemical conversion treatment of the aluminum solid electrolytic capacitor is improved, and the covering area by the conductive polymer is improved. Improvements in capacitor performance such as increased capacitance and lower ESR are expected.

Claims (12)

A thiophene derivative represented by the following formula (1) or (2).

[In the above formula (1), R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or — (CH ₂ ) ₁ SO _3. M is represented. M represents an alkali metal, or NH ^(R _{2) 3} is selected from the group consisting of a hydrogen atom, Li, Na and K. Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. l, n and m each independently represents an integer of 1 to 6; ]

[In the above formula (2), R ¹ , n and m are as defined in the above formula (1). Z represents chloride, bromide, iodide, acetate, trifluoroacetate or trifluoromethanesulfonate. ] The thiophene derivative according to claim 1, which is represented by the following formula (3) or (4).

In [the formula (3), ^{R 3} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M represents an alkali metal, or NH ^(R _{2) 3} is selected from the group consisting of a hydrogen atom, Li, Na and K. Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. ]

[In the above formula (4), R ³ has the same meaning as in the above formula (3). Z represents chloride, bromide, iodide, acetate, trifluoroacetate or trifluoromethanesulfonate. ] A thiophene derivative represented by the following formula (5) and a compound represented by the following formula (6) are reacted in a polar solvent in the presence of a base, and represented by the above formula (1) or (3). The method for producing a thiophene derivative according to claim 1 or 2, wherein a thiophene compound (wherein M does not represent a hydrogen atom) is obtained.

[In the above formula (5), X represents tosylate, mesylate, triflate, chloride, bromide, or iodide. n represents an integer of 1 to 6. ]

[In the above formula (6), R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or — (CH ₂ ) ₁ SO _3. M is represented. M represents an alkali metal, or NH ^(R _{2) 3} is selected from the group consisting of a hydrogen atom, Li, Na and K. Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. l and m each independently represents an integer of 1 to 6; ] The thiophene derivative represented by formula (1) or formula (3) (wherein M does not represent a hydrogen atom) is reacted with an excess amount of acid, and is represented by formula (2) or formula (4). The method for producing a thiophene derivative according to claim 1, wherein the thiophene derivative is obtained. The thiophene derivative represented by the formula (2) or the formula (4) is converted into an ammonium salt and then dried under reduced pressure under heating, and the thiophene derivative represented by the above formula (1) or the formula (3) (where M is The method for producing a thiophene derivative according to claim 1, wherein the method represents a hydrogen atom. Polythiophenes containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (16) and a structural unit represented by the following formula (17).

[In the above formula (16), R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or — (CH ₂ ) ₁ SO _3. M is represented. M represents an alkali metal, or NH ^(R _{2) 3} is selected from the group consisting of a hydrogen atom, Li, Na and K. Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. l, n and m each independently represents an integer of 1 to 6; ]

[In the above formula (17), R ¹ , n and m are as defined in the above formula (16). ] Polythiophenes containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (18) and a structural unit represented by the following formula (19).

In [the formula (18), ^{R 3} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M represents an alkali metal, or NH ^(R _{2) 3} is selected from the group consisting of a hydrogen atom, Li, Na and K. Each R ² independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. ]

[In the above formula (19), R ³ has the same meaning as in the above formula (18) . ] The polythiophene according to claim 6 or 7, wherein the polythiophene has a weight average molecular weight in the range of 1,000 to 1,000,000 in terms of polystyrene sulfonic acid. A water-soluble conductive polymer aqueous solution comprising an aqueous solution of the polythiophenes according to any one of claims 6 to 8. The method for producing a polythiophene according to any one of claims 6 to 8, wherein the thiophene derivative according to claim 1 or 2 is polymerized in water or an alcohol solvent in the presence of an oxidizing agent. . A method for producing a conductive coating, comprising applying the aqueous water-soluble conductive polymer solution according to claim 9 to a substrate and drying the solution. Use of the aqueous water-soluble conductive polymer aqueous solution according to claim 9 for a conductive coating.

Images