TWI675033B - Compound containing a heterocyclic ring, polymer using the same, and use thereof - Google Patents

Abstract

A heterocyclic-containing compound represented by the following chemical formula (1). In the formula (1), one of X ₁ and X ₂ represents an alkoxy group which may have a substituent, an alkyleneoxy group which may have a substituent, a thiocyanate group which may have a substituent, and An amino group or an alkylthio group which may have a substituent, the other represents hydrogen, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group which may have a substituent, and an alkyleneoxy group which may have a substituent , A thiocyanate group which may have a substituent, an amino group which may have a substituent, or an alkylthio group which may have a substituent, or X ₁ and X ₂ represent the number of carbon atoms which may have a substituent, which are connected to each other 1 to Alkylenedioxy group of 12 or an alkylenedithio group having 1 to 12 carbon atoms which may have a substituent, R represents an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms 1, alkyleneoxy group having 1 to 12 carbon atoms having a repeating unit of 1 to 50, phenyl group which may have a substituent, heterocyclic group which may have a substituent or fused ring group which may have a substituent, W represents a hydroxyl group or The following chemical formula (2). X ₁ and X ₂ in Formula (2) are the same as Chemical Formula (1).

Description

Heterocyclic compound, polymer using the same and use thereof

The present invention relates to a heterocyclic-containing compound, a polymer using the same, and uses thereof.

There are many existing technologies that use conductive polymers as conductivity-imparting materials that can be used in antistatic agents, functional capacitors, transparent electrode materials, and the like, or as hole-transporting materials such as OLED, OPV, and organic semiconductor sensors. The conductive polymer is composed of a combination of a main skeleton and a dopant. The main skeleton has a conjugate structure and electrons can be moved. The dopant is used to carry an electron or a hole carrier in the expanded conjugate structure. ) Is given to the main skeleton. The conductive main skeleton is typified by polymers such as 3,4-ethylenedioxythiophene (EDOT), pyrrole, and aniline, and is generally a skeleton having a chemical structure in which a π-electron conjugated system is developed. As the dopant corresponding thereto, there are various dopants such as inorganic Lewis acid and organic proton acid. Among them, as the organic proton acid, a sulfonic acid compound is usually used.

In the related art of the conductive polymer, there is a conductive polymer in which polyaniline, which is a main skeleton, is doped with bis (2-ethylhexyl) sulfosuccinate (for example, Patent Document 1) ); Polyethylene dioxythiophene (PEDOT) as the main skeleton, doped with polystyrene sulfonic acid (PSS) PEDOT / PSS, etc.

In particular, regarding PEDOT / PSS, there are many related technologies (for example, Patent Document 2), and many materials are generally used. PEDOT / PSS is used in industrial production because PEDOT of the main skeleton is highly conductive or can impart excellent processing adaptability. The excellent processing adaptability refers to adjusting the molecular weight and doping amount of PSS used as a dopant. , Undoped sulfonic acid concentration, etc. can stably disperse nanometer-level small liquid particle size in water, and it is easy to produce a uniform film by coating.

In addition, in general, when a conductive polymer is used alone, the physical strength, solvent resistance, and the like of the coating film are often insufficient. Therefore, it is used as an aqueous coating material mixed with an aqueous emulsion binder and various additives.

[Existing technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent 3426637

[Patent Document 2] Japanese Patent 2636968

[Patent Document 3] WO2010 / 095648

However, as a problem of PEDOT / PSS, since the residual sulfo group derived from PSS can stably disperse gel particles in water, in addition to low acidity caused by metal corrosion and sulfo groups over time In addition to poor storage stability due to detachment and poor heat resistance due to de-doping during heating, there are various problems such as the water resistance of the coating film is essentially intersected. Therefore, composite coatings with various materials have been used to improve coatings. Film physical properties. In addition, as a coating material prepared by mixing various materials, when mixing, the binder and various additives are limited to water-based substances, and there are also restrictions on the miscibility with the above materials, and there are various problems. In order to solve these problems, various improvement methods have been proposed: introducing an oil-soluble functional group into the main frame of the conductive polymer; and / or neutralizing the sulfo group of the dopant PSS; changing the composition of the dopant (for example, Patent Document 3).

The introduction of an oil-soluble functional group into the conductive polymer main skeleton is limited to the introduction of a functional group at the 3, 4 position or the introduction of a functional group to an ethylene dioxy group, so the range of chemical modification is very limited. On the other hand, there are examples of sulfo-modification of PEDOT / PSS using an amine compound, which can reduce metal corrosion or improve miscibility with a binder, but there is still a problem that water cannot be avoided. In order to improve the miscibility by changing the composition of the dopant, although it is possible to improve the miscibility in an organic solvent or the like, it is difficult to achieve a balance between conductivity and coating film uniformity.

In addition, an organic thin-film solar cell using a conductive polymer has a structure in which an electron transport layer / power generation layer / hole transport layer is laminated between electrodes, and the electron transport layer and the electricity are selected according to the ionization potential of the power generation layer. The hole transport layer is preferably 0.2 to 0.3 eV in difference with the ionization potential of the power generation layer for efficient electron transfer. As a specific structure, a structure using an organic semiconductor (poly 3-hexylthiophene: P3HT) / PCBM is reported, and PEDOT / PSS is used as a hole transport layer. Relative to the ionization potential of 4.7eV of P3HT, the ionization potential between 5.0 ~ 5.1eV of PEDOT / PSS and the organic semiconductor as a power generation layer is adjusted to a certain range, and it is used for the purpose of improving the extraction efficiency of holes.

However, in order to improve the power generation efficiency (increase the voltage), it is difficult to efficiently perform charge separation in PEDOT / PSS while adjusting the ionization potential while changing the composition of organic semiconductors. Conductive polymer.

Regarding the adjustment of the ionization potential, changes in the dopants and changes in the functional group of the PEDOT main skeleton were studied. However, the changes in the dopants are limited to fine adjustments of about 0.1 to 0.2 eV, and it is difficult to change them significantly. In addition, regarding the functional group change of the conductive polymer main skeleton, the synthesis of the monomer is complicated, and it is difficult to perform simple oxidative polymerization when the polymer is polymerized due to changes in the donor properties of the monomer. Therefore, CC cross-coupling and the like are required. In addition to the complicated synthesis method, the main skeleton needs to be doped after being polymerized. In addition, the obtained conductive polymer has problems such as insufficient conductivity, coating properties, and film-forming properties.

On the other hand, as for an organic pigment, a compound having a conjugated structure based on the condensation of an aldehyde and a heterocyclic ring has been studied as an organic pigment to form a porphyrin by the condensation of pyrrole and an aldehyde. In addition, applications for semiconductors have also been studied by imparting solubility and the like, but the film forming properties are poor due to low solubility and it is difficult to purify them, and they have not been applied to conductive materials.

In addition, when thiophene is used as a heterocyclic ring, there are problems such that the activity with aldehyde is weak, and the synthesis cannot proceed sufficiently.

However, when the present inventors used thiophene having an electron-donating group at the 3,4-position, especially 3,4-ethylenedioxythiophene (EDOT), they found that the thiophene porphyrin can be carried out under ordinary porphyrin synthesis conditions. Synthesis.

In addition, it was found that thiophene having an electron-donating group at the 3,4-position can be used to quantify the molecular weight of a compound obtained by an alternate condensation reaction with an aldehyde; it can be copolymerized with a thiophene-based monomer; The doped conductive polymer can be obtained by oxidative polymerization in the coexistence of an agent; and the donor property of the conjugated methine moiety can be adjusted by adjusting the electron donating property and electron accepting property of the substituent of the introduced aldehyde , Can adjust the ionization potential of the conductive polymer.

The present invention has been made in view of the above circumstances, and provides a heterocyclic-containing compound represented by the following chemical formula (1).

(In formula (1), one of X ₁ and X ₂ represents an alkoxy group which may have a substituent, an alkylene oxide group which may have a substituent, a thiocyanate group which may have a substituent, and a substituent which may have The amino group or an alkylthio group which may have a substituent, and the other represents hydrogen, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group which may have a substituent, and an alkylene oxide which may have a substituent Group, a thiocyanate group which may have a substituent, an amino group which may have a substituent, or an alkylthio group which may have a substituent, or X ₁ and X ₂ represent the number of carbon atoms which may have a substituent, which are connected to each other 1 An alkylene dioxy group of ~ 12 or an alkylene dithio group having 1 to 12 carbon atoms which may have a substituent, R represents an alkyl group of 1 to 12 carbon atoms, and an alkoxy group of 1 to 12 carbon atoms Group, alkyleneoxy group having 1 to 12 carbon atoms having a repeating unit of 1 to 50, phenyl group which may have a substituent, heterocyclic group which may have a substituent, or fused ring group which may have a substituent, W represents The hydroxyl group may be represented by the following chemical formula (2).)

(X ₁ and X ₂ in Formula (2) are the same as Chemical Formula (1).)

According to experiments by the present inventors, it has been found that by selecting a compound having various functional groups as a raw material compound to be used, functional groups can be easily introduced into the production composition, and this method can easily impart functionality to the material.

Hereinafter, various embodiments of the present invention will be exemplified. The embodiments shown below can be combined with each other.

It is preferable that the compound represented by the said chemical formula (1) is obtained by condensing the heterocyclic compound of a chemical formula (3) and the aldehyde derivative of a chemical formula (4).

(X ₁ and X ₂ in formula (3) and R in formula (4) are the same as chemical formula (1).)

Preferably, both X ₁ and X ₂ represent an alkoxy group which may have a substituent, an alkylene oxide group which may have a substituent, a thiocyanate group which may have a substituent, an amino group which may have a substituent, or a substituent which may have Alkylthio, or X ₁ and X ₂ represent an alkylenedioxy group having 1 to 12 carbon atoms which may have a substituent or an alkylene group having 1 to 12 carbon atoms which may have a substituent. Alkyl dithio.

Preferably, X ₁ and X _{2 each} represent an alkoxy group having 1 to 12 carbon atoms which may have a substituent, an alkylene oxide group having 1 to 12 carbon atoms which may have a substituent, or X ₁ and X ₂ The alkylene dioxy group having 1 to 12 carbon atoms, which may have a substituent, connected to each other.

Preferably, R is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a phenyl group which may have a substituent.

A polymer is preferably obtained by polymerizing one or more of the above-mentioned heterocyclic-containing compounds having a repeating unit of the chemical formula (5) or the chemical formula (6).

(In the formulae (5) and (6), X ₁ , X ₂ and R are the same as the chemical formula (1), and n is 2 to 100.)

A polymer is preferably obtained by polymerizing the heterocyclic-containing compound in the presence of one or two or more of the sulfonic acid compound anions or salts thereof.

A polymer composition containing the above polymer and a polymerization solvent is preferred.

A coating film is preferably obtained by coating the polymer composition.

FIG. 1 (a) shows the NMR measurement result of the monomer 1 synthesized in the synthesis method 1 of the present invention. 1 (b) shows an NMR measurement result of the monomer 3 synthesized in the synthesis method 3 of the present invention.

FIG. 2 (c) shows the NMR measurement results of the monomer 4 synthesized in the synthesis method 4 of the present invention, and FIG. 2 (d) shows the NMR measurement results of the polymer 8 synthesized in the synthesis method 11 of the present invention.

FIG. 3 (a) shows an IR measurement result of the monomer 1 synthesized in the synthesis method 1 of the present invention, and FIG. 3 (b) shows an IR measurement result of the polymer 8 synthesized in the synthesis method 11 of the present invention.

FIG. 4 (c) shows the IR measurement results of the monomer 3 synthesized in the synthesis method 3 of the present invention, and FIG. 4 (d) shows the IR measurement results of the monomer 4 synthesized in the synthesis method 4 of the present invention.

FIG. 5 (e) shows the IR measurement results of the polymer 5 synthesized in the synthesis method 9 of the present invention, and FIG. 5 (f) shows the IR measurement results of the polymer 11 synthesized in Comparative Example 1.

FIG. 6 shows the LC-MS measurement results of the polymer 8 synthesized in the synthesis method 11 of the present invention.

FIG. 7 (a) shows UV measurement results of the monomer 1 synthesized in the synthesis method 1 of the present invention, the monomer 3 synthesized in the synthesis method 3, and the monomer 4 synthesized in the synthesis method 4, and FIG. 7 (b) Polymer 1 synthesized in Synthesis Method 6 of the present invention, Polymer 3 synthesized in Synthesis Method 7, polymer 4 synthesized in Synthesis Method 8, polymer 5 synthesized in Synthesis Method 9, and polymerization synthesized in Synthesis Method 11. UV measurement results of the product 8 and the polymer 11 synthesized in Comparative Example 1.

8 (a) shows the measurement results of the decomposition start temperature of the polymer 4 synthesized in the synthesis method 8 of the present invention, and FIG. 8 (b) shows the decomposition start temperature of the polymer 5 synthesized in the synthesis method 9 of the present invention. Determination results.

FIG. 9 (c) shows the measurement results of the decomposition start temperature of the polymer 11 synthesized in Comparative Example 1. FIG.

Hereinafter, one embodiment of the present invention will be described in detail.

The present invention relates to a heterocyclic-containing compound having a novel structure represented by the following chemical formula (1). The use of the heterocyclic-containing compound is not limited, and as an example, it can be used as an organic conductor material (more specifically, a monomer of the main chain of a conductive polymer and a semiconductor polymer).

First, a structure and a synthesis method of a heterocyclic-containing compound will be described, and then a method of synthesizing a polymer that can be used as a conductive polymer by using the compound as a monomer will be described.

<Heterocyclic compound>

The heterocyclic-containing compound of the present invention is represented by the following chemical formula (1).

(In formula (1), one of X ₁ and X ₂ represents an alkoxy group which may have a substituent, an alkylene oxide group which may have a substituent, a thiocyanate group which may have a substituent, and a substituent which may have The amino group or an alkylthio group which may have a substituent, and the other represents hydrogen, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group which may have a substituent, and an alkylene oxide which may have a substituent Group, a thiocyanate group which may have a substituent, an amino group which may have a substituent, or an alkylthio group which may have a substituent, or X ₁ and X ₂ represent the number of carbon atoms which may have a substituent and are connected to each other 1 An alkylene dioxy group of ~ 12 or an alkylene dithio group having 1 to 12 carbon atoms which may have a substituent, R represents an alkyl group of 1 to 12 carbon atoms, and an alkoxy group of 1 to 12 carbon atoms Group, alkyleneoxy group having 1 to 12 carbon atoms having a repeating unit of 1 to 50, phenyl group which may have a substituent, heterocyclic group which may have a substituent, or fused ring group which may have a substituent, W represents a hydroxyl group Or it is represented by the following chemical formula (2).)

(X ₁ and X ₂ in Formula (2) are the same as Chemical Formula (1).)

The electron-donating group of at least one of X ₁ and X ₂ is preferably directly bonded to the heterocyclic ring.

The alkoxy group, alkyleneoxy thiocyanate group, amino group, alkylthio group, and alkylene dioxy group in which X ₁ and X _{2 are} bonded may be substituted in the above X ₁ and X ₂ The substituent of the dithio group and the alkyl group having 1 to 12 carbon atoms is not limited, and a substituent that does not impede electron donation to a heterocyclic ring is preferred. Specifically, it may be a linear, branched or cyclic alkyl group, Sulfo, hydroxy, carboxy, amino, amido, ester, and straight or branched alkyl, alkoxyalkyl, alkyleneoxy substituted with sulfo, hydroxy, carboxy, amino, halo There may be multiple substituents.

The above-described alkyl group X ₁ and X ₂ is an alkoxy group, an alkylene group, an alkylthio group, X ₁ and X ₂ linked together alkylenedioxy group, alkylene group, and said substituent group The number of carbon atoms of the carboxyl group, the amido group, the ester group, the alkoxyalkyl group, and the alkyleneoxy group is not particularly limited, and is, for example, 1 to 20, and preferably 1 to 12. Specifically, the number of carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, and may be exemplified here. The value is within a range between any two values.

One of the above X ₁ or X ₂ is hydrogen or an alkyl group having 1 to 12 carbon atoms, but preferably does not include that both are alkyl groups, both are hydrogen, one is hydrogen and the other is alkane Base combination.

The above X ₁ and X ₂ alkylene dioxy groups having 1 to 12 carbon atoms which may have a substituent, and alkylene dithio groups having 1 to 12 carbon atoms which may have a substituent may have an oxygen analog, The nitrogen analog and sulfur analog structures replace the ethylene structure in the alkylene backbone.

The substituent of the phenyl group which may have a substituent, the heterocyclic group which may have a substituent, and the fused ring group which may have a substituent may have multiple alkyl groups having 1 to 12 carbon atoms and carbon atoms. 1 to 12 alkoxy groups, 1 to 12 carbon atoms, 1 to 12 alkyleneoxy groups, 1 to 12 carbon atoms, fused ring groups, hydroxyl groups, aldehyde groups, carboxyl groups, halogen groups, or these Alkali metal salt, sulfo group or alkali metal salt thereof, phosphate group or alkali metal salt thereof, amino group, cyano group.

The aforementioned phenyl group which may have a substituent, a heterocyclic group which may have a substituent, the aforementioned alkyl group which may have a substituent in a fused ring group which may have a substituent, an alkoxy group, an alkyleneoxy group, a phenyl group, a hetero group The cyclic group, fused ring group, and amino group may have any substituent at any position.

The above-mentioned alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkylene oxide group having 1 to 12 carbon atoms having a repeating unit of 1 to 50 may have any substitution at any position. base.

Examples of the heterocyclic group include a monovalent group derived from a heterocyclic compound such as a azole ring, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, Pyrazine ring, triazine ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline Ring, quinazoline ring, phthalazine ring, thienylthiophene ring, oxazole ring, azaoxazole ring (representing a heterocyclic ring substituted with any one or more of the carbon atoms constituting the oxazole ring), diphenyl A benzothiazole ring, a dibenzofuran ring, a dibenzothiophene ring, a ring in which any one or more of the carbon atoms constituting the benzothiophene ring or the dibenzofuran ring is replaced with a nitrogen atom, and a benzodifuran ring , Benzodithiophene ring, acridine ring, benzoquinoline ring, phenazine ring, phenanthridine ring, phenanthroline ring, cyclamate ring, quinoxaline ring, tepenizine ring, quinindoline ring, tribenzodithiazine ring , Tribenzodioxazine ring, Phannathrazine ring, atrazine ring, naphthalene interazadiazepine ring, naphthofuran ring, naphthothiophene ring, naphthodifuran ring, naphthodithiophene ring, anthracene Benzofuran ring, anthrano difuran ring, anthranothiophene ring, anthrano dithiophene ring, thioanthracene ring, phenothi ring, dibenzoxazole ring, indene Oxazole ring, dithienylbenzene ring, epoxy ring, aziridine ring, thiopropane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxane Heterocyclic pentane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, cyclobutane ring, thiazolidine ring, ε-caprolactone ring, ε-caprolactam ring , Pyrimidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, pyrazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane Alkane ring, tetrahydrothioan ring, thiomorpholine ring, thiomorpholine-1,1-dioxide ring, pyranose ring, diazabicyclo [2,2,2] -octyl ring, phen Oxazine ring, phenothiazine ring, Oxanthrene ring, thioxanthene ring, phenothiazine ring.

Examples of the fused ring include a naphthalene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a pyrene ring, a naphthalene ring, a triphenylene ring, a fluorene ring, a halo ring, a fluorene ring, a fluoranthene ring, Pentacene ring, fluorene ring, pentaphen ring, fluorene ring, dermatanone ring, etc.

Examples of the optional substituent include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 12 carbon atoms having a repeating unit of 1 to 50, Phenyl, naphthyl, hydroxyl, aldehyde, amino, cycloalkyl having 3 to 8 carbon atoms, and the like.

Depending on the reaction conditions, the above W can be synthesized by selecting a hydroxyl group or a heterocyclic residue represented by the chemical formula (2). It is a hydroxyl group under basic conditions and a heterocyclic residue under acidic conditions.

<Synthesis of heterocyclic compound>

The heterocyclic compound containing the chemical formula (1) can be obtained by condensing a heterocyclic compound of the chemical formula (3) and an aldehyde derivative of the chemical formula (4).

(X ₁ and X ₂ in formula (3) and R in formula (4) are the same as chemical formula (1).)

The heterocyclic compound of the above-mentioned chemical formula (3) can be mainly classified into the following two types of chemical formulas (3-A) and (3-B).

(In formula (3-A), one of X ₃ and X ₄ represents an alkoxy group having 1 to 12 carbon atoms which may have a substituent, an alkylene oxide group having 1 to 12 carbon atoms which may have a substituent, A thiocyanate group which may have a substituent, an amino group which may have a substituent, or an alkylthio group which may have a substituent, and the other represents hydrogen, an alkyl group having 1 to 12 carbon atoms which may have a substituent, and may have a substituent. Alkyloxy group having 1 to 12 carbon atoms, alkyleneoxy group having 1 to 12 carbon atoms which may have substituents, thiocyanate group which may have substituents, amino group which may have substituents or substitution Alkylthio.)

The X ₃ and X ₄ alkoxy groups having 1 to 12 carbon atoms which may have a substituent, alkylene oxide groups having 1 to 12 carbon atoms which may have a substituent, a thiocyanate group which may have a substituent, The substituent of the amino group which may have a substituent, the alkylthio group which may have a substituent, and the alkyl group having 1 to 12 carbon atoms which may have a substituent is not limited, and the same substituents as those of the above-mentioned X ₁ and X ₂ may be used. Substituents.

(In the formula (3-B), Y ₁ and Y ₂ represent an oxygen atom, a sulfur atom, and a selenium atom, X ₅ is an alkylene group having 1 to 12 carbon atoms which may have a substituent, and may have any arbitrary position. The substituent may have an oxygen analog, a nitrogen analog, or a sulfur analog structure instead of the ethylene structure in the alkylene main chain.)

The substituent of the alkylene group having 1 to 12 carbon atoms which may have a substituent in X ₅ is not limited, and the same substituents as those in the substituents in X ₁ and X ₂ may be used.

The aldehyde derivative of the above-mentioned chemical formula (4) can be mainly classified into the following two types of chemical formulas (4-A) and (4-B).

(In formula (4-A), R ₂ to R ₆ may have a plurality of alkyl groups having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 1 to 50 carbon atoms having a repeating unit 1 ~ 12 alkyleneoxy, phenyl, heterocyclyl, fused ring, hydroxy, aldehyde, carboxyl, halogen or its alkali metal salt, sulfo or its alkali metal salt, phosphate or its alkali metal salt, Amino, cyano.)

(In formula (4-B), R ₇ may represent an alkylene group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkylene having 1 to 12 repeating units having 1 to 50 carbon atoms. An oxy group, a heterocyclic group which may have a substituent, and a fused ring group which may have a substituent. The above-mentioned alkyl group, alkoxy group, and alkylene oxide group may have any substituent at any position.)

<Alkaline conditions>

Weigh heterocyclic compounds and place them in a reaction vessel. Add alkali and solvent while sealing inert gas. And stir. Add the aldehyde derivative while stirring, and react while stirring.

After the reaction is completed, add ion-exchanged water, and add a small amount of acid to neutralize it to pH = 6 ~ 8 while stirring. Through the purification step, a heterocyclic compound containing a hydroxyl group in a side chain is obtained.

The reaction container is not particularly limited, and a container made of glass or Teflon (registered trademark) can be used.

After the heterocyclic compound is weighed and placed in the reaction vessel, a volatile component removing step may be adopted. The volatile component removing step may use a vacuum pump or the like to remove the volatile components under reduced pressure conditions or heating conditions under heating, or a combination of reduced pressure conditions and heating conditions may be used.

Examples of the volatile component include water, an organic solvent, an unreacted substrate, and the like, which are compounds that cannot be removed when synthesizing a heterocyclic compound.

Examples of the inert gas include nitrogen, argon, and helium.

The above stirring method is not particularly limited, and a stirrer or an oscillator may be used.

The stirring temperature when synthesizing an intermediate reactant of a heterocyclic compound under basic conditions is -40 to 50 ° C, and preferably -10 to 30 ° C. Specifically, the temperature is, for example, -40, -30, -20, -10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 ° C. The temperature may also be a value exemplified here. Within the range between any two values.

In addition, the stirring temperature during the condensation reaction with the aldehyde derivative is 25 ° C to 100 ° C. Choose 40 ℃ ~ 80 ℃. Specifically, the temperature is, for example, 25, 30, 40, 50, 60, 70, 80, 90, or 100 ° C, and may be within a range between any two values among the values exemplified here.

At this time, if the temperature at which the intermediate reactant of the heterocyclic compound is synthesized is too high, the formation of by-products increases, and therefore the reaction is preferably performed at a low temperature.

The stirring time under alkaline conditions is not particularly limited, and is, for example, 1 to 12 hours, and preferably 2 to 6 hours. Specifically, the time is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 hours, and may be within a range between any two of the values exemplified here. .

The base under basic conditions is not particularly limited, and any base that can perform a condensation reaction between a heterocyclic compound and an aldehyde derivative may be used, and examples thereof include TMP base (MAGNESIUM CHLORO TETRAMETHYLPIPERIDID LITHIUMCHLORID COMPLEX) and lithium diisopropylamidamine , N-butyllithium, sec-butyllithium, t-butyllithium, sodium ethoxide and the like.

The solvent under basic conditions is not particularly limited, and a solvent capable of performing a condensation reaction between a heterocyclic compound and an aldehyde derivative may be used, and examples thereof include tetrahydrofuran and tert-butyl methyl ether.

The acid under basic conditions is not particularly limited, and any acid that can be neutralized after the condensation reaction of the heterocyclic compound and the aldehyde derivative is completed may be used. Examples of the acid include hydrochloric acid, nitric acid, and sulfuric acid. Acid, etc.

The aforementioned purification step is a step of performing an extraction step, a fractionation step, and the like. As an extraction step, What is necessary is just to be able to recover the oil layer containing a target object, and liquid separation extraction etc. are mentioned. As the separation step, the target substance may be separated, and examples thereof include column chromatography and distillation.

<Acid conditions>

Heterocyclic compounds and acids are weighed and placed in a reaction vessel, replaced with an inert gas, the aldehyde derivative and the solvent are added dropwise, and the reaction is performed while stirring.

After the reaction is completed, a base and a solvent are added. Through the purification step, a heterocyclic-containing compound having a heterocyclic residue in a side chain is obtained.

The reaction vessel, the inert gas, the stirring method, and the purification step are not particularly limited, and the same conditions as those under alkaline conditions can be used.

The temperature at the time of stirring under acidic conditions is 0 to 100 ° C, and preferably 50 to 90 ° C. Specifically, the temperature is, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 ° C, and may be any of the values exemplified here. Within a range between 2 values.

The stirring time under acidic conditions is not particularly limited, and is, for example, 1 to 12 hours, and preferably 2 to 6 hours. Specifically, the time is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 hours, and may be within a range between any two of the values exemplified here. .

The acid under acidic conditions is not particularly limited, and any acid that allows a condensation reaction of a heterocyclic compound and an aldehyde derivative to be performed may be used. Examples include perchloric acid, sulfuric acid, methanesulfonic acid, trifluoroacetic acid, and Toluenesulfonic acid and so on.

The solvent under acidic conditions is not particularly limited, and a solvent that allows a condensation reaction of a heterocyclic compound and an aldehyde derivative to proceed is exemplified by toluene, benzene, methyl ethyl ketone, and heptane.

The base under acidic conditions is not particularly limited, and any base that can complete the condensation reaction of a heterocyclic compound and an aldehyde derivative may be used, and examples include dimethylaminoethanol, triethylamine, and pyridine.

By synthesizing a heterocyclic-containing compound in this way, when synthesizing a polymer using a plurality of heterocyclic-containing compounds described later, it is possible to synthesize adjacent functional groups in a preferred combination, which can further improve the effect and prevent the use of multiple heterocyclic compounds and The combination of functional groups formed when an aldehyde derivative is directly synthesized into a polymer is irregular and the effect disappears or decreases.

In addition, compared with the case where a polymer is synthesized directly from a heterocyclic compound and an aldehyde derivative, when a polymer is synthesized from a heterocyclic compound, the reaction time can be shortened, the probability of side reactions can be reduced, and the generation of impurities can be suppressed. Since purification can be performed at a stage containing a heterocyclic compound, the purity of the polymer can be improved.

In addition, a cyclic compound such as thienylporphyrin can be obtained by using the synthetic mechanism of the present invention. A synthesis reference example will be described later.

<Synthesis of Polymer>

A polymer containing a heterocyclic compound is added to the reaction vessel and heated to stir to obtain a polymer. A preferred method of synthesis is to weigh the dopant (sulfonic acid compound anion or its salt) and a polymerization solvent, and after stirring, add an oxidant and stir.

After the reaction was completed, ions were removed to obtain a polymer composition.

The polymer composition is a mixture of a polymer and a polymerization solvent, and may be dispersed or completely dissolved in the polymerization solvent. The polymerization solvent is removed from the polymer composition by a known method such as drying under reduced pressure to obtain a polymer.

The polymer has a repeating unit of the following chemical formula (5) or chemical formula (6).

(In the formulae (5) and (6), X ₁ , X ₂ and R are the same as the chemical formula (1), and n is 2 to 100.)

When a heterocyclic compound containing a hydroxyl group in a side chain synthesized under basic conditions is used, a polycondensation reaction occurs to obtain a polymer represented by the chemical formula (5) in which water molecules are separated. In the case of a heterocyclic-containing compound having a heterocyclic residue in a side chain synthesized under an acidic condition, an oxidative polymerization reaction occurs to obtain a polymer represented by Chemical Formula (6).

The reaction container and the stirring method are not particularly limited, and the same conditions as those under alkaline conditions can be used.

The temperature at the time of polymer synthesis is 0 to 100 ° C, and preferably 15 to 35 ° C. Specifically, the temperature is, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 ° C, and may be any of the values exemplified here. Within a range between 2 values.

The stirring time at the time of polymer synthesis is not particularly limited, but it is 1 to 12 hours, and preferably 2 to 6 hours. Specifically, the time is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 hours, and may be within a range between any two of the values exemplified here. .

The dopant is not particularly limited, and examples thereof include an aqueous solution of polystyrene sulfonic acid, 2-sulfoethyl (meth) acrylate, 3-propylsulfonium poly (meth) acrylate, and a copolymer thereof. Polyanion, or its alkali metal salt, p-toluenesulfonic acid, dodecylsulfonic acid, dodecylbenzenesulfonic acid, bis (2-ethylhexyl) sulfosuccinic acid, polyoxyethylene polycyclic benzene Monoanions such as ether sulfonates and polyoxyethylene aryl ether sulfates, or alkali metal salts thereof.

The polymerization solvent is not particularly limited, and examples thereof include alcohol solvents such as water, methanol, ethanol, isopropanol, and butanol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and methyl Dissolve Fibre agents, ethyl cellosolvents, propylene glycol solvents such as propylene glycol methyl ether, propylene glycol ethyl ether, lactic acid solvents such as methyl lactate and ethyl lactate, toluene, ethyl acetate, and the like.

The oxidizing agent is not particularly limited, and an oxidizing agent may be used for the polymerization reaction, and examples thereof include ammonium persulfate, potassium persulfate, sodium peroxodisulfate, iron (III) chloride, iron (III) sulfate, and hydroxide Iron (III), iron (III) tetrafluoroborate, iron (III) hexafluorophosphate, copper (II) sulfate, copper (II) chloride, copper (II) tetrafluoroborate, copper (II) hexafluorophosphate, and Ammonium oxodisulfate, hydrogen peroxide, etc.

These dopants and oxidants may be used singly or in combination.

The oxidizing agent may be added at one time, or may be added in multiple times according to the progress of the reaction.

The above-mentioned ion removal method is not particularly limited, and a method capable of removing ions may be used, and examples thereof include a method using an excessive amount of ion exchange resin, ultrafiltration, and solvent washing by polymer precipitation.

A resin having an ionization potential of 5.2 (preferably 5.4, more preferably 5.6) eV higher than the obtained polymer composition. With the increase of the ionization potential (5.0 to 5.1 eV) of PEDOT / PSS, when the polymerizable composition of the present invention is used in a semiconductor, an effect that the open-circuit voltage is also increased accordingly is obtained.

The polymer composition can be applied to obtain a uniform film. Kinds can provide physical strength, solvent resistance, etc. required for different applications.

The coating method is not particularly limited, and a known coating method can be used.

In the synthesis of the polymer, the above-mentioned heterocyclic ring-containing compound may be used alone, or a plurality thereof may be used to form a copolymer.

In addition, even if the above heterocyclic-containing compound is combined with a known monomer or polymer to synthesize a copolymer, it is possible to impart a unique effect to the functional group.

The repeating unit of the polymer is not particularly limited, but it is 2 to 100, and preferably 2 to 20. Specifically, it is, for example, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100, and may be within a range between any two of the values exemplified here.

A plurality of functional groups may be introduced, and multiple effects may be imparted simultaneously.

By introducing an alkyl group as a functional group, an effect of being more soluble in an organic solvent and the like can be imparted. By being more soluble in a solvent, application to equipment applications where mixing of water becomes a problem becomes easy, and when a coating film is formed, a uniform film can be expected to be formed at a low temperature.

By introducing a phenol or a carboxyl group as a functional group, a crosslinking reaction can be caused by adding a cross-linking agent such as an epoxy group or a carbodiimide to give a film stability effect. By improving the stability of the film, The solvent resistance is improved, and peeling due to an electrolyte solution or the like is less likely to occur.

By introducing a sulfonic acid as a functional group, a self-doping effect can be imparted. Since no dopant needs to be added, the operation becomes simple and the cost is advantageous. In addition, since the dopant exists in the molecule, the dopant exists uniformly, and stable thermal characteristics and electrical conductivity can be expected.

In this way, by using the heterocyclic-containing compound of the present invention as a conductive polymer material, various functional groups can be easily introduced into the side chain, and thus a polymer having the functions described above can be synthesized.

In addition, by changing the composition and mixing ratio of the heterocyclic-containing compound, the ionization potential can be easily adjusted.

The uses of the polymer, polymer composition, and coating film of the present invention are not limited, but antistatic agents for various applications and antistatic films using the antistatic agent, p-type organic semiconductors, n-type organic semiconductors, Solid electrolyte of solid electrolytic capacitor and its additive, electrochromic element, transparent electrode of organic thin film solar cell, counter electrode of dye-sensitized solar cell and its auxiliary agent, organic electroluminescence, chemical sensor, fuel cell, contact Additives in electronic devices such as control panels or liquid crystal displays, adhesives, carbon, etc.

[Example]

<Synthesis of Monomer (Heterocyclic Compound)>

Synthesis method 1: Synthesis of monomer 1 (basic conditions)

14.2 g of 3,4-ethylenedioxythiophene (EDOT) was weighed and placed in a 300 ml reaction container, and the volatile components were removed by vacuuming at 40 ° C for 1 hour using a vacuum pump. At the same time, 100 ml of a TMP alkali / THF solution (1 mol / L) was added while passing dry nitrogen gas, and the mixture was reacted at room temperature for 2 hours under stirring. While stirring, 10 g of benzaldehyde was added, and the temperature was raised to 50 ° C. After 6 hours of reaction, it was cooled to room temperature.

After the above reaction was completed, 50 g of ion-exchanged water was added, and 0.1 N hydrochloric acid was added in small amounts one by one while stirring to neutralize to pH = 7. Liquid separation extraction was performed, and the oil layer was recovered. This liquid separation extraction was repeated twice. An excessive amount of magnesium sulfate was added to the oil layer for dehydration, the magnesium sulfate was filtered off, and the filtrate was concentrated with an evaporator. The target substance was separated and extracted by column chromatography using a hexane / ethyl acetate solvent to obtain monomer 1 as a brown liquid.

The identification of monomer 1 was confirmed using LC-MS, NMR, and IR. The results of NMR are shown in Fig. 1a, and the results of IR are shown in Fig. 3a.

Synthesis method 2: Synthesis of monomer 2 (basic conditions)

Except having changed benzaldehyde to 2-ethylhexylaldehyde, it synthesize | combined by the same method as the synthesis method 1, and obtained the monomer 2 of pale yellow liquid.

Synthesis method 3: Synthesis of monomer 3 (acidic conditions)

270 g of EDOT and 1 g of tetrafluoroacetic acid were weighed and placed in a 500 ml reaction container, and nitrogen substitution was performed for 1 hour, and the mixture was heated to 60 ° C., and 6 g of benzaldehyde and 100 g of toluene were added dropwise over 7 hours. After heating for 3 hours and cooling to room temperature, 50 g of toluene and 1.2 g of triethylamine were added and stirred. 50 g of ion-exchanged water was added for liquid separation extraction, and the oil layer was recovered. This liquid separation extraction was repeated three times using 50 g of ion-exchanged water. Excess magnesium sulfate was added to the oil layer for dehydration, magnesium sulfate was filtered off, and the filtrate was concentrated with an evaporator, and then evaporated under reduced pressure. The EDOT was fractionally distilled and concentrated by a distillation apparatus, and the target substance was separated and extracted from the remaining components by column chromatography using a hexane / ethyl acetate solvent to obtain a pale yellow crystalline monomer 3.

The identification of monomer 3 was confirmed by LC-MS, NMR, and IR. The results of NMR are shown in Fig. 1b, and the results of IR are shown in Fig. 4c.

Synthesis method 4: Synthesis of monomer 4 (acidic conditions)

6 g of benzaldehyde was changed to 11 g of syringaldehyde, and toluene was changed to methyl ethyl ketone, except that synthesis was carried out in the same manner as in Synthesis Method 3 to obtain pale red crystalline monomer 4. The results of NMR are shown in Fig. 2c, and the results of IR are shown in Fig. 4d.

Synthesis method 5: Synthesis of monomer 5 (acidic conditions)

Except having changed 6g of benzaldehyde to 7.3g of 2-ethylhexylaldehyde, it synthesize | combined by the same method as the synthesis method 3, and the pale yellow liquid monomer 5 was obtained.

Synthesis of monomer 6 (acidic conditions)

6 g of benzaldehyde was changed to 7.5 g of 2-deoxy-D-ribose, and 100 g of toluene was changed to 50 g of methyl ethyl ketone and 50 g of ethanol. Yellow solid monomer 6.

<Synthesis of Polymer>

Synthesis method 6: Synthesis of polymer 1

Weigh 0.65g of monomer 1 and polystyrenesulfonic acid aqueous solution (Mw = 75000, solid content 19%) 7.8 g and 30 g of ion-exchanged water were placed in a 300 ml reaction container. After stirring for about 30 minutes, 0.04 g of iron (III) chloride and 0.4 g of ammonium peroxodisulfate were added. After stirring at room temperature for 4 hours, sodium peroxodisulfate was added. 0.9 g, and stirred for 4 hours. After the reaction, the ions were removed with an excess of ion exchange resin to obtain polymer 1 in a tan polymer dispersion.

Synthesis of polymer 2

Except that monomer 1 was changed to monomer 2, synthesis was performed in the same manner as in Synthesis Method 6 to obtain polymer 2 in a polymer dispersion.

Synthesis method 7: Synthesis of polymer 3

To a 200 ml reaction vessel, 3.1 g of an aqueous polystyrene sulfonic acid solution (Mw = 75000, 19% solids content), 10 g of ion-exchanged water, and 0.057 g of iron (III) sulfate were added, and the mixture was heated and stirred at 50 ° C. to add to a brown uniform solution. A solution obtained by dissolving 0.37 g of monomer 3 in 5 g of ethyl acetate was added with 0.3 g of ammonium persulfate, and stirred for 5 hours to cool. After the reaction, the ions were removed by an excess of ion exchange resin to obtain a polymer 3 in a dark green polymer dispersion.

Synthesis method 8: Synthesis of polymer 4

0.37 g of monomer 3 of Synthesis Method 7 was changed to 0.2 g of Monomer 3 and 0.1 g of EDOT (monomer molar ratio was 50:50), and polymerization was performed in the same manner as in Synthesis Method 7 to obtain a dark blue Polymer dispersion of polymer 4. The measurement results of the decomposition initiation temperature are shown in Fig. 8a.

Synthesis method 9: Synthesis of polymer 5

Polymerization was performed in the same manner as in Synthesis Method 7 except that 0.37 g of Monomer 3 in Synthesis Method 7 was changed to 0.45 g in Monomer 4, to obtain Polymer 5 in a dark blue-violet polymer dispersion. The result of IR is shown in FIG. 5e, and the measurement result of the decomposition start temperature is shown in FIG. 8b.

Synthesis method 10: Synthesis of polymer 6

To a 200 ml reaction vessel were added 3.1 g of an aqueous polystyrene sulfonic acid solution (Mw = 75000, 19% solids content), 10 g of ion-exchanged water, 0.057 g of iron (III) chloride, and 0.017 g of p-toluenesulfonic acid, and heated at 50 ° C After stirring, a solution obtained by dissolving 0.34 g of monomer 4 and 0.035 g of EDOT (monomer molar ratio 75:25) in 5 g of ethyl acetate was added to the brown homogeneous solution, and 0.4 g of sodium peroxodisulfate was added and stirred for 5 hours. And cool. After the reaction was completed, the ions were removed with an excess of ion exchange resin to obtain a polymer 6 in a dark blue polymer dispersion.

Synthesis of polymer 7

Except that monomer 3 was changed to monomer 5, synthesis was performed in the same manner as in Synthesis Method 7 to obtain polymer 7 in a polymer dispersion.

Synthesis method 11: Synthesis of polymer 8

Weigh out 1g of monomer, 50g of toluene, and 0.2g of tetrafluoroacetic acid in a 300ml reaction vessel, and perform nitrogen substitution while heating to 50 ° C while stirring. After 7 hours of reaction, the reaction mixture was cooled, and the precipitate was filtered off, washed with isopropyl alcohol, and dried to obtain an orange crystalline polymer 8.

Identification of polymer 8 was confirmed by LC-MS, NMR, and IR. The results of NMR are shown in Fig. 2d, and the results of IR are shown in Fig. 3b.

The LC-MS measurement result of the polymer 8 is shown in FIG. 6. From the measurement results of LC-MS, it was found that the repeating unit was about 2 to 20.

Synthesis method 12: Synthesis of polymer 9

Weigh 80g of EDOT, 48g of sodium 2-thiobenzaldehyde, 60g of ethyl acetate, and 1.5g of tetrafluoroacetic acid into a 300ml reaction vessel, and perform nitrogen substitution while heating to 50 ° C while stirring. After 7 hours of reaction, 10 g of methanol was added and cooled. The reaction solution was transferred into a 500 ml container, and then 200 g of ethyl acetate was added and stirred. Thereafter, the precipitate was filtered off and the crystals were recovered, and then dissolved in methanol / water = 90/10 to remove insoluble matters, and the solution was recrystallized to obtain a green crystalline polymer 9.

From the measurement results of LC-MS, it was found that the repeating unit was about 3 to 20.

Synthesis of polymer 10

Polymerization was carried out in the same manner as in Synthesis Method 7 except that 0.37 g of Monomer 3 in Synthesis Method 7 was changed to 0.44 g in Monomer 6 and ethyl acetate was changed to isopropanol.

[Comparative example]

Comparative Example 1: Synthesis of Polymer 11

Except that monomer 3 was changed to 0.15 g of EDOT, synthesis was performed in the same manner as in Synthesis Method 7 to obtain polymer 11 in a dark blue polymer dispersion. The result of IR is shown in FIG. 5f, and the result of measurement of the decomposition start temperature is shown in FIG. 9c. Comparative Example 2: Synthesis of Polymer 12

1g of monomer, 1.14g of 3-hexylthiophene, 50g of toluene, and 0.2g of tetrafluoroacetic acid were weighed and heated to 50 ° C. while stirring with nitrogen substitution. After 7 hours of reaction, the reaction status was confirmed by thin-layer chromatography. Only the color development of the raw materials did not occur.

The molar ratios of the polymers 1 to 9 and 11 are collectively shown in Table 1.

<Conductivity measurement sample preparation method>

16 g of polymer was weighed and placed in a sample bottle, and pulverized by a probe type ultrasonic pulverizer. The pulverized polymer 1 was directly used as a measurement sample 1.

In addition, 1 g of the polymer 1 after pulverization was weighed in the same manner, and 0.08 g of dimethyl fluorene was added and stirred sufficiently to obtain a measurement sample 2.

For polymers 2 to 8, 10, and 11, measurement samples 1 and 2 were prepared in the same manner.

<Production Method of Conductivity Measurement Film>

An area of 2 cm × 2 cm was made on a glass plate on which the surface was cleaned with isopropyl alcohol (IPA), and a measurement sample 1 of 0.2 g of polymer 1 was dropped into the glass plate to develop uniformly, and dried at 120 ° C. for 30 minutes to prepare a measurement. Film 1.

For measurement samples 1 and 2 of polymer 1, and measurement samples 1 and 2 of polymers 2 to 8, 10, and 11, measurement films 1 and 2 were produced in the same manner.

<Preparation method for measuring decomposition starting temperature>

The polymer 1 was placed in a sample bottle under reduced pressure, and the pressure was reduced to 30 Pa or lower at 10 ° C to dry the water to obtain polymer 1 powder.

For the measurement of electrical conductivity, Loresta GP manufactured by Mitsubishi Analytech was used.

The particle size distribution was measured using Nanotrac UPA manufactured by Nikkiso Co., Ltd.

For the measurement of the decomposition initiation temperature, TG-DTA (STA7220) manufactured by Hitachi High-Tech Science was used.

The ionization potential was measured using PYS-202 manufactured by Sumitomo Heavy Industries, Ltd.

<Coating film state evaluation method>

After coating the film, the state of the coating film was visually observed, and the uniformity of the coating film and the presence or absence of gloss on the surface were evaluated according to the following criteria.

◎: The coating film is uniform and the surface is shiny

○: The coating film is slightly uneven or the surface gloss is slightly foggy.

The evaluation results of the polymers 1 to 8, 10, and 11 are shown in Table 2.

<Evaluation of Solvent Resistance of Film>

The solvent resistance of the film was evaluated under the following conditions, and the results are shown in Table 3.

Curing agent mixing ratio: polymer / epoxy curing agent (ethylene glycol diglycidyl ether) = 1g / 0.1g (5% methanol)

Drying conditions: 120 ℃ × 1 hour

Evaluation method: One drop of methanol was added dropwise to the dry coating film, and the change in appearance was visually confirmed.

The solvent resistance of the film was evaluated under the following conditions, and the results are shown in Table 4.

Curing agent mixing ratio: polymer / isocyanate curing agent (DURANATE WB40-80D: manufactured by Asahi Kasei Chemical Co., Ltd.) = 1 g / 0.1 g (5% dilution with acetone)

Drying conditions: 120 ℃ × 1 hour

Evaluation method: One drop of methanol was added dropwise to the dry coating film, and the change in appearance was visually confirmed.

From the results of Tables 3 and 4, it was found that the solvent resistance of the dried film can be controlled by crosslinking with the curing agent by introducing a hydroxyl group into the side chain.

<Evaluation of self-doping>

The self-doping was evaluated under the following conditions, and the results are shown in Table 5.

The polymer 9 was dissolved in ion-exchange water to 1.5%, and the solution was used as it was, and a solution in which Na was removed with a cation exchange resin was prepared.

The appearance and conductivity of the coating film after drying at 105 ° C for 30 minutes were measured.

From the results in Table 5, it can be seen that by performing Na removal treatment, conductivity can be obtained without a dopant, and self-doping can be performed.

Reference Example 1: Synthesis of thienylporphyrin

Weigh 355 mg of 3,4-ethylenedioxythiophene, 255 mg of benzaldehyde, and 250 mL of dichloromethane in a 500 mL reaction container, and stir in a dry nitrogen environment. Furthermore, 60 mg of Lewis acid (BF ₃ ‧ O (Et) ₂ ) was added and reacted at room temperature for 3 hours. Then, 603 mg of dichlorodicyanobenzoquinone was added, and it stirred for 1 hour. The solvent was removed, and the residue was dissolved in 80 mL of toluene, and 655 mg of dichlorodicyanobenzoquinone was added thereto, and reacted for 1 hour under reflux in a nitrogen atmosphere. After removing the solvent, the crystals were re-dissolved in 120 mL of dichloromethane, and water and brine were separated and washed three times. Sodium sulfate was added to the organic solvent layer to dehydrate.

Thereafter, the target substance was separated and extracted using a methanol / dichloromethane solution by column chromatography.

Claims (6)

A polymer having a repeating unit of formula (5) or formula (6), In the formulae (5) and (6), X ₁ and X ₂ represent an alkylenedioxy group having 1 to 12 carbon atoms, which may have a substituent, and R represents 1 to 12 carbon atoms. Alkyl, phenyl which may have a substituent, and n is 2 to 100. A polymer obtained by polymerizing a heterocyclic-containing compound in the presence of one or more of a sulfonic acid compound anion or a salt thereof, wherein the heterocyclic-containing compound is represented by the following chemical formula ( 1) means, In formula (1), X ₁ and X ₂ represent an alkylene dioxy group having 1 to 12 carbon atoms, which may have a substituent, and R represents an alkyl group having 1 to 12 carbon atoms. , A phenyl group which may have a substituent, W represents a hydroxyl group or is represented by the following chemical formula (2), X ₁ and X ₂ in the formula (2) are the same as the chemical formula (1). The polymer according to claim 2, wherein the compound represented by the chemical formula (1) of the heterocyclic-containing compound is obtained by condensing a heterocyclic compound of the chemical formula (3) and an aldehyde derivative of the chemical formula (4) of, X ₁ and X ₂ in Formula (3) and R in Formula (4) are the same as in Chemical Formula (1). A polymer composition containing the polymer according to any one of claims 1 to 3 and a polymerization solvent. A coating film obtained by coating the polymer composition of claim 4. A method for producing a polymer, comprising: polymerizing a polymer; and polymerizing a heterocyclic-containing compound represented by the following chemical formula (1) in the presence of a sulfonic acid compound anion or a salt thereof, In the formula (1), X ₁ and X ₂ represent an alkylene dioxy group having 1 to 12 carbon atoms, which may have a substituent, and R represents an alkyl group having 1 to 12 carbon atoms, Phenyl which may have a substituent, W represents a hydroxyl group or is represented by the following chemical formula (2), X ₁ and X ₂ in the formula (2) are the same as the aforementioned chemical formula (1).