KR20170024548A - Polymer compound for a conductive polymer and method for producing same - Google Patents

Abstract

The present invention relates to a polymer compound for a conductive polymer, which is soluble in an organic solvent, is useful for a dopant for fuel cells of conductive materials, and having a specific super-acidic sulfo group. The polymer compound for a conductive polymer comprises at least one repeating unit a represented by chemical formula (1) and has a weight average molecular weight of 1,000-500,000. In chemical formula (1), R^1 represents H or a methyl group; R^2 represents any one selected from a single bond, an ester group, and a C1-C12 linear, branched or cyclic hydrocarbon group that may have either or both of an ether group and an ester group; Z represents any one selected from a single bond, a phenylene group, a naphthylene group, an ether group and an ester group; and a is more than 0 and is less than or equal to 1.0.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer compound for a conductive polymer and a method for producing the polymer compound.

TECHNICAL FIELD The present invention relates to a polymeric compound for a conductive polymer and a process for producing the same.

A sulfo group-containing polymer is used as a dopant polymer of a fuel cell or a conductive polymer. For the fuel cell, vinyl perfluoroalkyl ether sulfonic acid typified by the registered trademark Nafion and polymers of vinyl sulfonic acid and styrenesulfonic acid are widely used as dopant polymers for conductive polymers (Patent Document 1).

Vinyl perfluoroalkyl ether sulfonic acid is chemically stable and has excellent durability, but has a low glass transition point, and when the fuel cell using the perfluoroalkyl ether sulfonic acid is exposed to high temperature, the polymer causes heat flow and ion conductivity is lowered. In order to enhance the ionic conductivity, a super strong acid polymer having a sulfo group fluorinated at the? Position is effective, but a material having a high glass transition point and a chemically stable property has not been found.

The conductive polymer having a conjugated double bond such as polythiophene, polyaniline, and polypyrrole does not exhibit conductivity itself, but conductivity is exhibited by doping with a strong acid such as sulfonic acid. As the dopant, polystyrenesulfonic acid (PSS) is best used. This is because the conductivity is highest by the doping of PSS.

PSS is a water-soluble resin and hardly soluble in organic solvents. Therefore, polythiophene with PSS as a dopant is also water-soluble.

The polythiophene with PSS as a dopant is expected to be a conductive film for organic EL lighting to replace ITO (indium-tin oxide) because it is highly conductive and highly transparent. However, the light emitting body of the organic EL is chemically changed by moisture, so that it does not emit light. That is, when the conductive film of the water-soluble resin is used for the organic EL, there is a problem that the life of the organic EL is shortened because the resin contains water.

Japanese Patent Application Laid-Open No. 2008-146913

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polymer compound for a conductive polymer having a sulfo group of a specific strong acid, which is soluble in an organic solvent and is suitably used as a dopant for a fuel cell or a conductive material . Another object of the present invention is to provide a method for producing such a polymeric compound for a conductive polymer.

In order to achieve the above object, the present invention provides a conductive polymer-containing polymeric compound comprising at least one repeating unit a represented by the following general formula (1) and having a weight average molecular weight of 1,000 to 500,000, Polymer compound for use in the present invention.

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched, cyclic, or branched alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group, Z is a single bond, a phenylene group, a naphthylene group, an ether group or an ester group, and a is 0 <a? 1.0)

Such a polymer compound for a conductive polymer is a polymer compound for a conductive polymer having a sulfo group of a specific super strong acid which is soluble in an organic solvent and suitably used as a dopant for a fuel cell or a conductive material.

At this time, it is preferable that the polymeric compound for a conductive polymer further has a repeating unit b represented by the following general formula (2).

(Wherein b is 0 < b < 1.0)

If the repeating unit a is copolymerized with the repeating unit b of polystyrene sulfonic acid, it can be used as a high-conductivity dopant polymer.

It is preferable that the repeating unit a represented by the general formula (1) includes at least one repeating unit selected from the repeating units a1 to a4 represented by the following general formulas (3-1) to (3-4) Do.

(R ¹ in the formula are the same as above. A1, a2, a3 and a4 are 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, also 0 <a1 + a2 + a3 + a4? 1.0)

Such a repeating unit is more suitable as a dopant for a fuel cell or a conductive material.

The present invention also provides a method for producing a polymeric compound for a conductive polymer comprising a repeating unit (a) represented by the following general formula (1), wherein a monomer having a salt structure including a sulfonic acid residue and lithium, sodium, potassium, And then converting the structure of the salt containing the sulfonic acid residue and lithium, sodium, potassium, or a nitrogen compound into a sulfo group by ion exchange after polymerization, to provide a process for producing a polymer for a conductive polymer .

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched, cyclic, or branched alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group, Z is a single bond, a phenylene group, a naphthylene group, an ether group or an ester group, and a is 0 <a? 1.0)

With such a production method, a polymeric compound for a conductive polymer containing the repeating unit a represented by the general formula (1) can be easily produced.

Also, at this time, it is preferable that the polymer obtained by carrying out the polymerization reaction using the above sulfonic acid residue and a monomer having a salt structure including lithium, sodium, potassium or nitrogen compound contains a repeating unit represented by the following general formula (4) desirable.

(Wherein R ¹ , R ² , Z and a are as defined above, and X is lithium, sodium, potassium, or a nitrogen compound represented by the following formula (5)

(Wherein R ^101d , R ^101e , R ^101f and R ^101g each represents a hydrogen atom or a straight, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, Or an aralkyl group or an aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, R ^101d and R ^101e , R ^101d and R ^101e , R ^101f may form a ring, in the case of forming a ring, the R ^101d and R ^101e, and R ^101d and R ^101e and R ^101f are heterocyclic aromatic group having the ring nitrogen atom in the alkylene group, or a group represented by the formula having 3-10 carbon atoms Lt; / RTI &gt;

Such a repeating unit is easily converted to the repeating unit a represented by the general formula (1) by ion exchange.

As described above, the polymer compound for a conductive polymer of the present invention is a polymer compound for a conductive polymer having a sulfo group of a specific strong acid, which is soluble in an organic solvent and suitably used as a dopant for a fuel cell or a conductive material.

By using the polymeric compound for a conductive polymer in a fuel cell, it is possible to form a fuel cell material having a high dielectric constant. Further, when used as a dopant for a conjugated double bond polymer, it becomes possible to form a conductive film having high transparency, high conductivity, and high durability. The polymeric compound for a conductive polymer of the present invention has a sulfonic acid structure of a super strong acid having a trifluoromethyl group at the? -Position, so that the ionic bond has a high ability as a dopant and a high stability as an ion. Therefore, it exhibits high conductivity and stability when it is used as a conductive material. Further, since the organic EL device has excellent solubility in an organic solvent, deterioration of the organic EL device can be prevented by using it for a conductive film for organic EL lighting.

In addition, the production method of the present invention makes it possible to easily produce the polymeric compound for a conductive polymer of the present invention.

As described above, there has been a demand for the development of a polymer compound for a conductive polymer having a sulfo group of a specific strong acid, which is soluble in an organic solvent and is suitably used as a dopant for a fuel cell or a conductive material.

DISCLOSURE OF THE INVENTION The present inventors have found that a water-soluble conductive polymer containing water which causes deterioration of an element of an organic EL is used as an organic solvent-soluble type having a very low water content and a water-soluble, The present inventors have attempted to develop a polymer for a dopant that is highly soluble in an organic solvent. In order to increase the solubility in an organic solvent, introduction of fluorine is considered from the point of view of effective long-chain alkyl group and fluorine introduction, and in particular, a polymer compound containing a repeating unit containing a sulfo group having a trifluoromethyl group at the? Can be achieved, and the present invention has been accomplished.

That is, the present invention is a conductive polymer polymer compound containing at least one repeating unit a represented by the following general formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000.

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched, cyclic, or branched alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group, Z is a single bond, a phenylene group, a naphthylene group, an ether group or an ester group, and a is 0 <a? 1.0)

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

The polymer compound for a conductive polymer of the present invention is a polymer containing at least one kind of a repeating unit a represented by the following general formula (1). The polymeric compound for a conductive polymer of the present invention has a high transparency particularly by containing the repeating unit a represented by the general formula (1).

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched, cyclic, or branched alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group, Z is a single bond, a phenylene group, a naphthylene group, an ether group or an ester group, and a is 0 <a? 1.0)

In the general formula (1), R ¹ is a hydrogen atom or a methyl group.

R ² is any of a straight-chain, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have a single bond, an ester group, or an ether group or an ester group or both, and as the hydrocarbon group, For example, an alkylene group, an arylene group (e.g., a phenylene group or a naphthylene group), or an alkenylene group.

Z is a single bond, a phenylene group, a naphthylene group, an ether group or an ester group.

a is 0 < a? 1.0.

The repeating unit a represented by the general formula (1) preferably includes at least one repeating unit selected from the repeating units a1 to a4 represented by the following general formulas (3-1) to (3-4) .

(R ¹ in the formula are the same as above. A1, a2, a3 and a4 are 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, also 0 <a1 + a2 + a3 + a4? 1.0)

Such a repeating unit is more suitable as a dopant for a fuel cell or a conductive material.

The polymer compound for a conductive polymer of the present invention preferably further has a repeating unit b represented by the following general formula (2). If the repeating unit a is copolymerized with the repeating unit b of polystyrene sulfonic acid, it can be used as a high-conductivity dopant polymer.

(Wherein b is 0 < b < 1.0)

As described later, the polymeric compound for a conductive polymer of the present invention may have a repeating unit c other than the repeating unit a and the repeating unit b.

The polymeric compound for a conductive polymer of the present invention has a weight average molecular weight of 1,000 to 500,000, preferably 2,000 to 200,000. When the weight average molecular weight is less than 1,000, the heat resistance becomes poor. On the other hand, if the weight average molecular weight exceeds 500,000, the viscosity increases, the workability deteriorates, and the solubility in organic solvents and water deteriorates.

The weight average molecular weight (Mw) is a polystyrene reduced value measured by gel permeation chromatography (GPC) using water, dimethylformamide (DMF) and tetrahydrofuran (THF) as a solvent.

As described above, the polymer compound for a conductive polymer of the present invention is a polymer compound for a conductive polymer having a sulfo group of a specific strong acid, which is soluble in an organic solvent and is suitably used as a dopant for a fuel cell or a conductive material.

The present invention also provides a method for producing the polymeric compound for a conductive polymer according to the present invention.

That is, the production process of the present invention is a process for producing a polymeric compound for a conductive polymer, which comprises a repeating unit a represented by the following general formula (1), wherein a salt containing a sulfonic acid residue and lithium, sodium, potassium, And after polymerization, the polymer compound for a conductive polymer which converts the structure of the salt containing the sulfonic acid residue and the lithium, sodium, potassium, or nitrogen compound into a sulfo group by ion exchange Method.

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched, cyclic, or branched alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group, Z is a single bond, a phenylene group, a naphthylene group, an ether group or an ester group, and a is 0 <a? 1.0)

Here, the polymer obtained by carrying out the polymerization reaction with a sulfonic acid residue and a monomer having a salt structure including lithium, sodium, potassium or a nitrogen compound preferably contains a repeating unit represented by the following general formula (4).

(Wherein R ¹ , R ² , Z and a are as defined above, and X is lithium, sodium, potassium, or a nitrogen compound represented by the following formula (5)

(Wherein R ^101d , R ^101e , R ^101f and R ^101g each represents a hydrogen atom or a straight, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, Or an aralkyl group or an aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, R ^101d and R ^101e , R ^101d and R ^101e , R ^101f may form a ring, in the case of forming a ring, the R ^101d and R ^101e, and R ^101d and R ^101e and R ^101f are heterocyclic aromatic group having the ring nitrogen atom in the alkylene group, or a group represented by the formula having 3-10 carbon atoms Lt; / RTI &gt;

Such a repeating unit is preferably converted into the repeating unit a represented by the general formula (1) by ion exchange.

Specific examples of the monomer for obtaining a repeating unit a having a structure of a sulfonic acid residue and a salt containing lithium, sodium, potassium, or a nitrogen compound used in the production method of the present invention include the following.

(Wherein R ¹ is as defined above, and X is lithium, sodium, potassium, or a nitrogen compound)

As described above, the repeating unit a represented by the general formula (1) includes at least one kind selected from the repeating units a1 to a4 represented by the general formulas (3-1) to (3-4) . That is, monomers for obtaining the repeating units a1 to a4 among the above-exemplified monomers are particularly preferable.

As described above, the polymeric compound for a conductive polymer of the present invention preferably has a repeating unit b represented by the general formula (2), and specific examples of the monomer for obtaining such a repeating unit b include the following Can be exemplified.

(Wherein X ₂ is a hydrogen atom, a lithium, a sodium, a potassium, a nitrogen compound, or a sulfonium compound)

Examples of the case where X ₂ is a nitrogen compound include compounds represented by the following general formula (5).

(Wherein R ^101d , R ^101e , R ^101f and R ^101g each represents a hydrogen atom or a straight, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, Or an aralkyl group or an aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, R ^101d and R ^101e , R ^101d and R ^101e , R ^101f may form a ring, in the case of forming a ring, the R ^101d and R ^101e, and R ^101d and R ^101e and R ^101f are heterocyclic aromatic group having the ring nitrogen atom in the alkylene group, or a group represented by the formula having 3-10 carbon atoms Lt; / RTI &gt;

As described above, the polymeric compound for a conductive polymer of the present invention may have a repeating unit c other than the repeating unit a and the repeating unit b, and examples of the repeating unit c include styrene type, vinyl naphthalene type, vinyl silane (Meth) acrylate, vinylcarbazole, and the like can be given.

Specific examples of the monomer for obtaining the repeating unit c include the following.

As a method for synthesizing the polymeric compound for a conductive polymer of the present invention, for example, a method of obtaining a polymeric compound of a copolymer by adding a desired monomer in the above-mentioned monomer, a radical polymerization initiator in a solvent, have.

Examples of the solvent used in the polymerization include water, alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, methoxyethanol, ethoxyethanol, n-butanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, dimethylsulfoamide, Examples of the solvent include acetamide, acetone, dimethylsulfoxide, N-methylpyrrolidone, toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone and γ-butyrolactone .

Examples of the radical polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, Azobisisobutyrate, potassium persulfate, ammonium persulfate, aqueous hydrogen peroxide, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2 , 2-azobis (2-methylpropionate), lauroyl peroxide, 2,2'-azobis (2-amidinopropane) dihydrochloride, or 4,4'-azobis Valeric acid), and the like can be mentioned.

The reaction temperature is preferably 50 to 80 占 폚, and the reaction time is preferably 2 to 100 hours, more preferably 5 to 20 hours.

In the polymer for a conductive polymer of the present invention, the monomer as the repeating unit a represented by the general formula (1) may be one kind or a combination of two or more kinds. In order to improve the polymerizability, a methacryl type and a styrene type It is preferable to combine the monomers.

In addition, two or more kinds of monomers forming the repeating unit a may be randomly copolymerized, or each may be copolymerized with a block. In the case where the block copolymerization polymer (block copolymer) is used as the conductive film, it is expected that the conductivity improves by forming the structure even when the repeating unit parts including two or more kinds of the repeating units a are aggregated.

In addition, the monomers for obtaining the repeating units a to c may be randomly copolymerized, or may be copolymerized with each other. In this case also, as in the case of the repeating unit a described above, it is expected that the conductivity is improved by using a block copolymer.

When the random copolymerization is carried out by radical polymerization, a method of mixing the monomers to be copolymerized and the radical polymerization initiator and conducting polymerization by heating is generally used. When the polymerization is initiated in the presence of the first monomer and the radical polymerization initiator and the second monomer is added later, the structure in which the first monomer is polymerized on one side of the polymer molecule and the second monomer is polymerized on the other side . However, in this case, the repeating units of the first and second monomers are mixed in the middle portion, and they are different in shape from the block copolymer. In order to form a block copolymer by radical polymerization, living radical polymerization is preferably used.

A living radical polymerization method referred to as RAFT polymerization (Reversible Addition Fragmentation chain transfer polymerization) is a method in which the radicals at the end of the polymer are always alive and the polymerization is initiated with the first monomer, and the second monomer is added at the step And the second repeating unit can be formed. The triblock copolymer may also be formed when the polymerization is initiated with the first monomer, the second monomer is added at the time of consumption of the first monomer, and subsequently the third monomer is added.

When the RAFT polymerization is carried out, a narrow-dispersion polymer having a narrow molecular weight distribution (dispersion degree) is formed. In particular, when RAFT polymerization is carried out by adding monomers at one time, a polymer having a narrower molecular weight distribution can be formed.

In the polymer compound for a conductive polymer of the present invention, the molecular weight distribution (Mw / Mn) is preferably 1.0 to 2.0, and more preferably 1.0 to 1.5. In the case of narrow dispersion, it is possible to prevent the conductivity of the conductive polymer synthesized by using the polymer compound from becoming uneven.

In order to carry out the RAFT polymerization, a chain transfer agent is required. Specific examples thereof include 2-cyano-2-propylbenzothioate, 4-cyano-4-phenylcarbonothioylthiopentanoic acid, 2- (Dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, 2- (dodecylthiocarbonothioylthio) -2-methylpropanoic acid, cyano Bis (dodecylphenylthiocarbonyl) disulfide, bis (thiobenzoyl) disulfide, bis (dodecylsulfanylthiocarbonyl) disulfide, and the like. Of these, 2-cyano-2-propylbenzothioate is particularly preferable.

Here, the ratio of the repeating units a to c is 0 <a? 1.0, 0? B <1.0, 0? C <1.0, preferably 0.1? A? 0.9, 0.1? B? 0.9, More preferably 0.2? A? 0.8, 0.2? B? 0.8, and 0? C? 0.5.

It is also preferable that a + b + c = 1.

When the repeating unit a includes at least one kind selected from the repeating units a1 to a4 as described above, it is preferable that 0? A1? 1.0, 0? A2? 1.0, 0? A3? 1.0, 1.0, and 0 < a1 + a2 + a3 + a4? 1.0, more preferably 0? A1? 0.9, 0? A2? 0.9, 0? A3? 0.9, 0? A4? 0.9, a1 + a2 + a3 + a4? 0.9, more preferably 0? a1? 0.8, 0? a2? 0.8, 0? a3? 0.8, 0? a4? 0.8 and 0.2? a1 + a2 + a3 + a4? 0.8.

In the method for producing a polymeric compound for a conductive polymer of the present invention, after the monomers are polymerized as described above, the structure of the salt including a sulfonic acid residue and lithium, sodium, potassium, or a nitrogen compound is converted into a sulfo group do.

At this time, the ion exchange may be performed using, for example, an ion exchange resin.

As described above, the polymeric compound for a conductive polymer containing the repeating unit a represented by the general formula (1) can be easily produced.

As described above, the polymer compound for a conductive polymer of the present invention is a polymer compound for a conductive polymer having a sulfo group of a specific strong acid, which is soluble in an organic solvent and suitably used as a dopant for a fuel cell or a conductive material.

By using the polymeric compound for a conductive polymer in a fuel cell, it is possible to form a fuel cell material having a high dielectric constant. Further, when used as a dopant for a conjugated double bond polymer, it becomes possible to form a conductive film having high transparency, high conductivity, and high durability. The polymeric compound for a conductive polymer of the present invention has a sulfonic acid structure of a super strong acid having a trifluoromethyl group at the? -Position, so that the ionic bond has a high ability as a dopant and a high stability as an ion. Therefore, it exhibits high conductivity and stability when it is used as a conductive material. Further, since the organic EL device has excellent solubility in an organic solvent, deterioration of the organic EL device can be prevented by using it for a conductive film for organic EL lighting.

In addition, the production method of the present invention makes it possible to easily produce the polymeric compound for a conductive polymer of the present invention.

<Examples>

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

The monomers used in the synthesis of the examples are shown below.

Monomer 1:

Benzyltrimethylammonium = 3,3,3-trifluoro-2-methacryloyloxy-2-trifluoromethylpropane-1-sulfonate

Monomer 2:

Benzyltrimethylammonium = 3,3,3-trifluoro-2- (3-methacryloyloxy-1-adamantanecarbonyloxy) -2-trifluoromethylpropane-1-sulfonate

Monomer 3:

Benzyltrimethylammonium = 3,3,3-trifluoro-2-trifluoromethyl-2- (4-vinylbenzoyloxy) propane-1-sulfonate

Monomer 4:

Tetrabutylammonium = 3,3,3-trifluoro-2- (4-methacryloyloxy-1-benzoyloxy) -2-trifluoromethylpropane-

[Example 1]

A solution obtained by dissolving 48.1 g of Monomer 1 and 5.13 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added dropwise to 37.5 g of methanol stirred at 64 占 폚 in a nitrogen atmosphere over 4 hours. The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was collected by filtration and vacuum-dried at 50 DEG C for 15 hours to obtain 26.2 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and an ammonium salt was converted into a sulfo group using an ion exchange resin. The resulting polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR and GPC measurements, and the following analysis results were obtained.

Weight average molecular weight (Mw) = 42,000

Molecular weight distribution (Mw / Mn) = 1.61

This polymer compound is referred to as (Polymer 1).

[Example 2]

A solution prepared by dissolving 24.0 g of Monomer 1, 9.5 g of lithium styrene sulfonate, and 5.13 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added to 37.5 g of methanol stirred at 64 ° C for 4 hours . The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 &lt; 0 &gt; C for 15 hours to give 41.5 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and an ammonium salt and a lithium salt were converted into a sulfo group using an ion exchange resin. The resulting polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR and GPC measurements, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 1: styrene sulfonic acid = 1: 1

Weight average molecular weight (Mw) = 46,000

Molecular weight distribution (Mw / Mn) = 1.76

This polymer compound is referred to as (Polymer 2).

[Example 3]

A solution obtained by dissolving 32.8 g of monomer 2, 9.5 g of lithium styrene sulfonate, and 5.13 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added to 37.5 g of methanol stirred at 64 ° C for 4 hours . The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 &lt; 0 &gt; C for 15 hours to give 46.2 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and an ammonium salt and a lithium salt were converted into a sulfo group using an ion exchange resin. The resulting polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR and GPC measurements, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 2: styrene sulfonic acid = 1: 1

Weight average molecular weight (Mw) = 46,000

Molecular weight distribution (Mw / Mn) = 1.52

This polymer compound is referred to as (Polymer 3).

[Example 4]

A solution obtained by dissolving 27.0 g of monomer 3, 9.5 g of lithium styrene sulfonate, and 2.82 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added to 37.5 g of methanol stirred at 64 ° C for 4 hours . The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was filtered off and dried in vacuo at 50 &lt; 0 &gt; C for 15 hours to give 47.3 g of a white polymer.

The obtained white polymer was dissolved in 421 g of methanol, and an ammonium salt and a lithium salt were converted into a sulfo group using an ion exchange resin. The resulting polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR and GPC measurements, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 3: styrene sulfonic acid = 1: 1

Weight average molecular weight (Mw) = 55,000

Molecular weight distribution (Mw / Mn) = 1.81

This polymer compound is referred to as (Polymer 4).

[Example 5]

A solution obtained by dissolving 34.6 g of monomer 4, 9.5 g of lithium styrene sulfonate, and 2.82 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added to 37.5 g of methanol stirred at 64 ° C for 4 hours . The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was filtered off and dried in vacuo at 50 &lt; 0 &gt; C for 15 hours to give 50.2 g of a white polymer.

The obtained white polymer was dissolved in 421 g of methanol, and an ammonium salt and a lithium salt were converted into a sulfo group using an ion exchange resin. The resulting polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR and GPC measurements, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 4: styrene sulfonic acid = 1: 1

Weight average molecular weight (Mw) = 56,000

Molecular weight distribution (Mw / Mn) = 1.68

This polymer compound is referred to as (Polymer 5).

[Example 6]

To 37.5 g of methanol stirred at 64 占 폚 in a nitrogen atmosphere, 52.5 g of the monomer 2, 7.0 g of 4- (1,1,1,3,3,3-hexafluoro-2-propanol) styrene and 2,2 '-Azobis (isobutyric acid) dimethyl dissolved in 112.5 g of methanol was added dropwise over 4 hours. The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was filtered off and vacuum dried at 50 &lt; 0 &gt; C for 15 hours to give 43.2 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and an ammonium salt was converted into a sulfo group using an ion exchange resin. The resulting polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR and GPC measurements, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 2: 4- (1,1,1,3,3,3-hexafluoro-2-propanol) styrene = 4: 1

Weight average molecular weight (Mw) = 41,000

Molecular weight distribution (Mw / Mn) = 1.64

This polymer compound is referred to as (Polymer 6).

[Example 7]

To 37.5 g of methanol stirred at 64 占 폚 in a nitrogen atmosphere were added 52.5 g of Monomer 2 and 52.5 g of methacrylic acid-bis 3,5- (2-hydroxy-1,1,1,3,3,3-hexafluoro -2-propyl) cyclohexyl and 5.13 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added dropwise over 4 hours. The mixture was further stirred at 64 DEG C for 4 hours. After cooling to room temperature, 1,000 g of ethyl acetate was added dropwise with vigorous stirring. The resulting solid was filtered off and dried in vacuo at 50 &lt; 0 &gt; C for 15 hours to give 61.2 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and an ammonium salt was converted into a sulfo group using an ion exchange resin. The resulting polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR and GPC measurements, and the following analysis results were obtained.

Copolymer composition ratio (molar ratio) Monomer 2: Methacrylic acid-bis 3,5- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl)

Weight average molecular weight (Mw) = 23,000

Molecular weight distribution (Mw / Mn) = 1.61

This polymer compound is referred to as (Polymer 7).

Polymers 1 to 7 synthesized as described above were soluble in water, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether, tetrahydrofuran, and dimethylformamide.

As described above, according to the production method of the present invention, the polymeric compound for a conductive polymer of the present invention, which is soluble in an organic solvent and has a specific super strong acid group, can be easily produced.

The present invention is not limited to the above-described embodiments. The above embodiment is an example, and any structure that has substantially the same structure as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Claims (5)

A polymer for a conductive polymer comprising at least one kind of a repeating unit (a) represented by the following general formula (1) and having a weight average molecular weight of 1,000 to 500,000.

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched, cyclic, or branched alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group, Z is a single bond, a phenylene group, a naphthylene group, an ether group or an ester group, and a is 0 <a? 1.0) The conductive polymer polymer compound according to claim 1, wherein the polymer compound for a conductive polymer further has a repeating unit b represented by the following general formula (2).

(Wherein b is 0 < b < 1.0) The positive resist composition according to claim 1 or 2, wherein the repeating unit a represented by the general formula (1) is a repeating unit selected from the repeating units a1 to a4 represented by the following general formulas (3-1) to (3-4) Polymeric compound for a conductive polymer.

(R ¹ in the formula are the same as above. A1, a2, a3 and a4 are 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, also 0 <a1 + a2 + a3 + a4? 1.0) A process for producing a polymeric compound for a conductive polymer comprising a repeating unit (a) represented by the following general formula (1)
A polymerization reaction is carried out using a monomer having a sulfonic acid residue and a salt structure including lithium, sodium, potassium, or a nitrogen compound, and after the polymerization, the sulfonic acid residue and the lithium, sodium, potassium or nitrogen compound And converting the structure of the salt to a sulfo group.

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a linear, branched, cyclic, or branched alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group, Z is a single bond, a phenylene group, a naphthylene group, an ether group or an ester group, and a is 0 <a? 1.0) The positive resist composition according to claim 4, wherein the polymer obtained by carrying out the polymerization reaction by using the monomer having a sulfonic acid residue and a salt structure containing lithium, sodium, potassium, or a nitrogen compound is a polymer comprising a repeating unit represented by the following formula (4) Wherein the polymer is at least one selected from the group consisting of a polyvinyl alcohol and a polyvinyl alcohol.

(Wherein R ¹ , R ² , Z and a are as defined above, and X is lithium, sodium, potassium, or a nitrogen compound represented by the following formula (5)

(Wherein R ^101d , R ^101e , R ^101f and R ^101g each represents a hydrogen atom or a straight, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, Or an aralkyl group or an aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by an alkoxy group, R ^101d and R ^101e , R ^101d and R ^101e , R ^101f may form a ring, in the case of forming a ring, the R ^101d and R ^101e, and R ^101d and R ^101e and R ^101f are heterocyclic aromatic group having the ring nitrogen atom in the alkylene group, or a group represented by the formula having 3-10 carbon atoms Lt; / RTI &gt;