TW201630917A - Heterocycle-containing compound, polymer using said compound, and use thereof - Google Patents

Abstract

Provided is a heterocycle-containing compound capable of, when a raw material compound having various functional groups is selected as one that is to be used, easily introducing a functional group into a produced composition. The present invention provides a heterocycle-containing compound represented by chemical formula (1). (In formula (1), one of X1 and X2 represents an optionally substituted alkoxy group, an optionally substituted alkylene oxide group, an optionally substituted thiocyano group, an optionally substituted amino group, or an optionally substituted thioalkyl group, and the other represents hydrogen, an optionally substituted alkyl group having 1-12 carbon atoms, an optionally substituted alkoxy group, an optionally substituted alkylene oxide group, an optionally substituted thiocyano group, an optionally substituted amino group, or an optionally substituted thioalkyl group, or X1 and X2 are linked together and represent an optionally substituted alkylene dioxy group having 1-12 carbon atoms, or an optionally substituted alkylene dithio group having 1-12 carbon atoms, R represents an alkyl group having 1-12 carbon atoms, an alkoxy group having 1-12 carbon atoms, 1-50 repeating units of an alkylene oxide group having 1-12 carbon atoms, an optionally substituted phenyl group, an optionally substituted heterocyclic group, or an optionally substituted condensed ring group, and W represents a hydroxyl group or chemical formula (2).) (In formula (2), X1 and X2 are identical to those in chemical formula (1).).

Description

Compound containing a heterocyclic ring, polymer using the same, and use thereof

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

Many prior art techniques use a conductive polymer as a conductivity imparting material which can be used for an antistatic agent, a functional capacitor, a transparent electrode material, or the like, or a hole transporting material such as an OLED, an OPV, an organic semiconductor sensor or the like. The conductive polymer is composed of a combination of a main skeleton having a conjugated structure and electrons movable, and a dopant for using an electron or hole carrier in the conjugated structure that has been expanded. ) is given to the main skeleton. The conductive main skeleton is represented by a polymer such as 3,4-ethylenedioxythiophene (EDOT), pyrrole or aniline, and is usually a skeleton having a chemical structure in which a π-electron conjugated system is developed. Examples of the dopant corresponding thereto include various dopants such as inorganic Lewis acid and organic protic acid. Among them, as the organic protic acid, a sulfonic acid compound is usually used.

In the prior art related to the conductive polymer, there is a conductive polymer in which poly(phenylene) sulfosuccinate is doped with polyphenylamine as a main skeleton (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), which are materials which are generally used. PEDOT/PSS is applied to industrial production because PEDOT of the main skeleton is highly conductive or can impart excellent processing adaptability, and the excellent processing adaptability refers to adjusting the molecular weight and doping amount of PSS used as a dopant. The concentration of the undoped sulfonic acid or the like can stably disperse the particle size of the nano-sized liquid in the water stably, and a uniform film can be easily produced by coating.

In addition, when the conductive polymer is used alone, the physical strength and solvent resistance of the coating film are often insufficient, and thus it is used as an aqueous coating material in which a water-based emulsion binder and various additives are mixed.

[Prior Art Literature]

[Patent Literature]

Patent Document 1 Japanese Patent 3426637

[Patent Document 2] Japanese Patent 2,636,968

Patent Document 3] WO2010/095648

However, as a problem of PEDOT/PSS, since it is characterized by residual sulfo groups derived from PSS, gel particles can be stably dispersed in water, so in addition to low acidity, metal corrosion, sulfo group warp time The detachment or the like causes poor storage stability, and the de-doping at the time of heating causes deterioration of heat resistance, and various problems such as the water resistance of the coating film are substantially inconsistent, and thus the coating is conventionally improved by a composite coating with various materials. Membrane properties. Further, as a coating material obtained by mixing various materials, the binder and various additives are limited to the water-based material when mixed, and there are also limitations in the compatibility with the above materials, and various problems exist. In order to solve these problems, various improvement methods have been proposed: introducing an oil-soluble functional group into a main skeleton of a conductive polymer; and/or neutralizing a sulfo group of a dopant PSS; changing a dopant composition, etc. (for example, Patent Document 3).

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

Further, 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 an electron transport layer and electricity are selected in accordance with an ionization potential of a power generation layer. In the hole transport layer, the difference between the ionization potential of the power generation layer and the power generation layer is preferably 0.2 to 0.3 eV for high-efficiency electron transfer. As a specific configuration, a configuration using an organic semiconductor (poly-3-hexylthiophene: P3HT)/PCBM has been reported, and PEDOT/PSS has been used as a hole transport layer. With respect to the ionization potential of P3HT of 4.7 eV, the ionization potential between the ionization potential of PEDOT/PSS of 5.0 to 5.1 eV and the organic semiconductor as the power generation layer is adjusted to a certain extent to improve the extraction efficiency of the hole.

However, in order to improve the power generation efficiency (increasing the voltage), it is difficult to efficiently perform charge separation in PEDOT/PSS while changing the composition of the organic semiconductor, and thus it is necessary to have an ionization potential suitable for the semiconductor of the power generation layer. Conductive polymer.

Regarding the adjustment of the ionization potential, changes in the dopant and changes in the PEDOT main skeleton functional group have been studied. However, the change of the dopant is limited to a fine adjustment of about 0.1 to 0.2 eV, and it is difficult to change it greatly. In addition, the change of the functional group of the main skeleton of the conductive polymer is complicated by the synthesis of the monomer, and it is difficult to carry out simple oxidative polymerization synthesis when the monomer itself is polymerized. Therefore, CC cross-coupling is required. In addition to the complicated synthesis method, it is necessary to dope the main skeleton after the macromolecule, and the obtained conductive polymer may not have sufficient conductivity, coatability, film formability, and the like.

On the other hand, as a compound having a conjugated structure based on condensation of an aldehyde and a heterocyclic ring, as an organic pigment, research has been conducted to form a porphyrin by condensing a ring of pyrrole and an aldehyde. In addition, application as a semiconductor has been studied by imparting solubility, etc., but the solubility is poor, the film formation property is poor, and it is difficult to purify, and it is not applied to a conductive material.

Further, when thiophene is used as the hetero ring, there is a problem that the activity with the aldehyde is weak and the synthesis cannot be sufficiently carried out.

However, when the present inventors used thiophene having an electron-donating group at the 3,4-position, particularly 3,4-ethylenedioxythiophene (EDOT), it was found that the thiophene porphyrin can be subjected to usual porphyrin synthesis conditions. Synthesis.

Further, it has been found that a thiophene having an electron-donating group at the 3,4-position can be polymerized by an alternating condensation reaction with an aldehyde; it can be copolymerized with a thiophene monomer; The doped conductive polymer can be obtained by oxidative polymerization in the coexistence of the agent; and the donor property of the conjugated methine moiety can be adjusted by adjusting the electron donating property and electron acceptability of the substituent of the introduced aldehyde. The ionization potential of the conductive polymer can be adjusted.

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

(In the formula (1), one of X1 and X2 represents an alkoxy group which may have a substituent, an alkylene oxide group which may have a substituent, a thiocyano group which may have a substituent, an amino group which may have a substituent, or The 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, an alkylene oxide group which may have a substituent, and the like a thiocyano group having a substituent, an amino group which may have a substituent or an alkylthio group which may have a substituent, or X1 and X2 represent an alkylene group having 1 to 12 carbon atoms which may have a substituent a dioxy group or an alkylene disulfide group having 1 to 12 carbon atoms which may have a substituent, R represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a repeating unit of 1 ~50 olefination with 1 to 12 carbon atoms An oxy group, a phenyl group which may have a substituent, a heterocyclic group which may have a substituent, or a fused ring group which may have a substituent, and W represents a hydroxyl group or is represented by the following chemical formula (2). )

(X1 and X2 in the formula (2) are the same as the 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, a functional group can be easily introduced into a production composition, and by this method, functionality can be easily imparted to a material.

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

The compound represented by the above formula (1) is preferably obtained by condensing a heterocyclic compound of the formula (3) with an aldehyde derivative of the formula (4).

(X1 and X2 in the formula (3) and R in the formula (4) are the same as the chemical formula (1).)

It is preferable that both of X1 and X2 represent an alkoxy group which may have a substituent, an alkylene oxide group which may have a substituent, a thiocyano group which may have a substituent, an amino group which may have a substituent, or an alkyl sulfide which may have a substituent a group, or X1 and X2, which represent the number of carbon atoms which may have a substituent An alkylene dioxy group of ~12 or an alkylene disulfide group having 1 to 12 carbon atoms which may have a substituent.

It is preferable that both of X1 and X2 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 X1 and X2 represent a bond between the two. An alkylenedioxy group having 1 to 12 carbon atoms which may have a substituent.

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

A polymer is preferably obtained by polymerizing the above-described heterocyclic-containing compound having one or two or more repeating units of the chemical formula (5) or the chemical formula (6).

(In the formulas (5) and (6), X1, X2 and R are the same as the chemical formula (1), and n is 2 to 100.)

A polymer which is obtained by polymerizing the above-mentioned compound containing a hetero ring in the presence of one or more kinds of the sulfonic acid compound anion or a salt thereof is preferred.

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

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

Fig. 1(a) shows the results of NMR measurement of the monomer 1 synthesized in the synthesis method 1 of the present invention, 1(b) shows the results of NMR measurement of the monomer 3 synthesized in the synthesis method 3 of the present invention.

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

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

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

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

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

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

Fig. 8(a) shows the measurement results of the decomposition initiation temperature of the polymer 4 synthesized in the synthesis method 8 of the present invention, and Fig. 8(b) shows the decomposition initiation temperature of the polymer 5 synthesized in the synthesis method 9 of the present invention. The result of the measurement.

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

Hereinafter, an 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 a main chain of a conductive polymer and a semiconductor polymer).

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

<compound containing a heterocyclic ring>

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

(In the formula (1), one of X1 and X2 represents an alkoxy group which may have a substituent, an alkylene oxide group which may have a substituent, a thiocyano group which may have a substituent, an amino group which may have a substituent, or The 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, an alkylene oxide group which may have a substituent, and the like a thiocyano group having a substituent, an amino group which may have a substituent or an alkylthio group which may have a substituent, or X1 and X2 represent an alkylene group having 1 to 12 carbon atoms which may have a substituent a dioxy group or an alkylene disulfide group having 1 to 12 carbon atoms which may have a substituent, R represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a repeating unit of 1 ~50 an alkyleneoxy group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, a heterocyclic group which may have a substituent or a fused ring group which may have a substituent, W It represents a hydroxyl group or is represented by the following chemical formula (2). )

(X1 and X2 in the formula (2) are the same as the chemical formula (1).)

It is preferred that the electron-donating group of at least one of X1 and X2 is directly bonded to the hetero ring.

The above-mentioned X1 and X2 may have a substituent alkoxy group, an alkylene oxide thiocyano group, an amino group, an alkylthio group, an alkylenedioxy group in which X1 and X2 are bonded, an alkylene disulfide group, and a carbon. The substituent of the alkyl group having 1 to 12 atoms is not limited, and a substituent which does not hinder electron donating to the hetero ring is preferable, and specifically, a linear, branched or cyclic alkyl group, a sulfo group, a hydroxyl group, or the like may be used. a carboxyl group, an amino group, a decylamino group, an ester group, and a linear or branched alkyl group substituted by a sulfo group, a hydroxyl group, a carboxyl group, an amino group or a halogen group, an alkoxyalkyl group, an alkylene oxide group, and a substituent may have Multiple.

An alkoxy group, an alkylene oxide group, an alkylthio group, and an alkylene dioxy group, an alkylene disulfide group, and an alkyl group, a carboxyl group or a hydrazine of the above substituent, which are bonded to the above X1 and X2; The number of carbon atoms of the amine group, the ester group, the alkoxyalkyl group or the alkylene oxide group is not particularly limited, and is, for example, 1 to 20, preferably 1 to 12. Specifically, the number of carbon atoms is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, and may be exemplified herein. The value is in the range between any two values.

One of the above X1 or X2 is hydrogen or an alkyl group having 1 to 12 carbon atoms, but preferably does not include A combination in which both are alkyl groups, both of which are hydrogen, one of which is hydrogen and the other of which is an alkyl group.

The alkylene dioxy group having 1 to 12 carbon atoms which may have a substituent of the above X1 and X2, and the alkylene disulfide having 1 to 12 carbon atoms which may have a substituent may have an oxygen analog or a nitrogen similarity The structure of the sulfur analog replaces the ethylene structure in the alkylene backbone.

The phenyl group which may have a substituent of R, the heterocyclic group which may have a substituent, the substituent in the fused ring group which may have a substituent, may have a plurality of alkyl groups having 1 to 12 carbon atoms, carbon atoms Alkoxy groups of 1 to 12, repeating units of 1 to 50, alkyleneoxy groups having 1 to 12 carbon atoms, phenyl groups, heterocyclic groups, fused ring groups, hydroxyl groups, aldehyde groups, carboxyl groups, halogen groups or An alkali metal salt, a sulfo group or an alkali metal salt thereof, a phosphate group or an alkali metal salt thereof, an amino group, or a cyano group.

The above-mentioned alkyl group, alkoxy group, alkylene oxide group, phenyl group, heterocyclic group of the above-mentioned R, a phenyl group which may have a substituent, a heterocyclic group which may have a substituent, a substituent in the fused ring group which may have a substituent The cyclic group, the fused ring group, and the amino group may have any substituent at any position.

The alkyl group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms in the above R, and the alkyleneoxy group having 1 to 50 carbon atoms and 1 to 12 repeating units may have an arbitrary substitution at any position. base.

Examples of the heterocyclic group include a monovalent group derived from a heterocyclic compound: a thioring ring, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and the like. Pyrazine ring, triazine ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, anthracene ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline a ring, a quinazoline ring, a pyridazine ring, a thienylthiophene ring, an indazole ring, an azaindazole ring (a heterocyclic ring indicating that any one or more of the carbon atoms constituting the indazole ring is substituted by a nitrogen atom), diphenyl a thiazole ring, a dibenzofuran ring, a dibenzothiophene ring, a ring or a benzodifuran ring in which any one or more of the carbon atoms constituting the benzothiophene ring or the dibenzofuran ring is substituted by a nitrogen atom , benzodithiophene ring, acridine ring, benzoquinoline ring, phenazine ring, phenanthridine ring, phenanthroline ring, cyclamate ring, quinoxaline ring, tepenizine ring, quinindoline ring, tribenzodithiazine ring , tribenzodioxazine ring, Phenanthrazine ring, atrazine ring, naphthalene diazabenzene ring, naphthopyrene ring, naphthothiophene ring, naphthodifuran ring, naphthobithiophene ring, anthracene And furan ring, indenodifuran ring, indenothiophene ring, indenodithiophene ring, thioindole ring, phenothiazine ring, dibenzoxazole ring, anthracene Indazole ring, dithienylbenzene ring, epoxy ring, aziridine ring, thiirane 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 , acridine ring, hexahydropyridazine ring, hexahydropyrimidine ring, pyridazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane Alkane ring, tetrahydrothiopyran ring, thiomorpholine ring, thiomorpholine-1,1-dioxide ring, pyranose ring, diazabicyclo[2,2,2]-octane ring, phenanthrene Oxazine ring, phenothiazine ring, Oxanthrene ring, thioxanthene ring, phenothiazine ring.

Examples of the fused ring include a naphthalene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a ring, a naphthylene ring, a triphenyl ring, an anthracene ring, a halo ring, an anthracene ring, and a fluoranthene ring. And pentacene ring, anthracene ring, penfenone ring, anthraquinone ring, dermatanone ring and the like.

Examples of the optional substituent include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkyleneoxy group having 1 to 50 carbon atoms and 1 to 12 repeating units. A phenyl group, a naphthyl group, a hydroxyl group, an aldehyde group, an amino group, a cycloalkyl group having 3 to 8 carbon atoms, or 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 formula (2). It is a hydroxyl group under basic conditions and a heterocyclic residue under acidic conditions.

<Synthesis of a compound containing a hetero ring>

The heterocyclic ring-containing compound represented by the above chemical formula (1) can be obtained by condensing a heterocyclic compound of the chemical formula (3) with an aldehyde derivative of the chemical formula (4).

(X1 and X2 in the formula (3) and R in the formula (4) are the same as the chemical formula (1).)

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

(In the formula (3-A), one of X3 and X4 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, and may have a thiocyano group of 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 a carbon which may have a substituent An alkoxy group having 1 to 12 atoms, an alkyleneoxy group having 1 to 12 carbon atoms which may have a substituent, a thiocyano group which may have a substituent, an amino group which may have a substituent or an alkyl sulfide which may have a substituent base.)

The alkoxy group having 1 to 12 carbon atoms which may have a substituent in the above X3 and X4, the alkylene oxide group having 1 to 12 carbon atoms which may have a substituent, the thiocyano group which may have a substituent, may have a substitution The substituent of the amino group of the group, 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 the substituents of the above X1 and X2 can be used.

(In the formula (3-B), Y1 and Y2 represent an oxygen atom, a sulfur atom or a selenium atom, and X5 is an alkylene group having 1 to 12 carbon atoms which may have a substituent, and may have an arbitrary substituent at any position. It may have an oxygen analog, a nitrogen analog, a sulfur analog structure in place of the ethylene structure in the alkylene backbone.)

The substituent of the alkylene group having 1 to 12 carbon atoms which may have a substituent in the above X5 is not limited, and the same substituents as the substituents of the above X1 and X2 may be used.

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

(In the formula (4-A), R2 to R6 may have a plurality of alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, and 1 to 50 carbon atoms having repeating units of 1 to 12; Alkenyloxy group, phenyl group, heterocyclic group, fused ring group, hydroxyl group, aldehyde group, carboxyl group, halogen group or alkali metal salt thereof, sulfo group or alkali metal salt thereof, phosphate group or alkali metal salt thereof, amino group, Cyano.)

(In the formula (4-B), R7 may represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkylene oxide having 1 to 50 carbon atoms and having 1 to 50 repeating units. a heterocyclic group which may have a substituent, a fused ring group which may have a substituent, and the above alkyl group, alkoxy group or alkylene oxide group may have an arbitrary substituent at any position.

<alkaline condition>

The heterocyclic compound was weighed and placed in a reaction vessel, and a base, a solvent, and stirring were added while enclosing the inert gas. The aldehyde derivative was added with stirring and reacted while stirring.

After the completion of the reaction, ion-exchanged water was added, and a small amount of acid was gradually added to the pH to a pH of about 6 to 8 while stirring. By the purification step, a heterocyclic-containing compound having a hydroxyl group in its side chain is obtained.

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

After the weighed heterocyclic compound is placed in the reaction vessel, the volatile component removal step of removing the volatile component may be employed. In the volatile component removal step, the volatile component may be removed by a vacuum pump or the like under reduced pressure or under heating, or may be combined with a reduced pressure condition and a heating condition.

Examples of the volatile component include water, an organic solvent, and an unreacted matrix, and are compounds which are not removed when the heterocyclic compound is synthesized.

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

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

The stirring temperature in the case of synthesizing the intermediate reactant of the heterocyclic compound under alkaline conditions is -40 to 50 ° C, preferably -10 to 30 ° C. The temperature is specifically, for example, -40, -30, -20, -10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50 ° C, and may also be in the numerical values exemplified herein. Any range between 2 values.

Further, the stirring temperature in the condensation reaction with the aldehyde derivative is from 25 ° C to 100 ° C, preferably from 40 ° C to 80 ° C. 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 of the numerical values exemplified herein.

At this time, when the temperature at the time of synthesis of the intermediate reactant of the heterocyclic compound is too high, the formation of by-products increases, and therefore it is preferred to carry out the reaction at a low temperature.

The stirring time under alkaline conditions is not particularly limited, and is, for example, 1 to 12 hours, 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 numerical values exemplified herein. .

The base under alkaline conditions is not particularly limited, and may be a base which can be subjected to a condensation reaction between a heterocyclic compound and an aldehyde derivative, and examples thereof include TMP base (MAGNESIUM CHLORO TETRAMETHYLPIPERIDID LITHIUM CHLORID COMPLEX) and lithium diisopropylamide , n-butyl lithium, sec-butyl lithium, t-butyl lithium, sodium ethoxide, and the like.

The solvent in the alkaline condition is not particularly limited, and a solvent capable of undergoing a condensation reaction between a heterocyclic compound and an aldehyde derivative may be used, and examples thereof include tetrahydrofuran and t-butyl methyl ether.

The acid in the alkaline condition is not particularly limited, and may be an acid which can be neutralized after the condensation reaction of the heterocyclic compound and the aldehyde derivative is completed, and examples thereof include hydrochloric acid, nitric acid, sulfuric acid, or 0.1N thereof. An acid or the like obtained by an aqueous solution.

The above purification step is a step of performing an extraction step, a fractionation step, and the like. As the extraction step, the oil layer containing the target substance can be recovered, and a liquid separation extraction or the like can be given. As the fractionation step, the target can be separated, and column chromatography, distillation, or the like can be given.

<acidic condition>

The heterocyclic compound and the acid were weighed and placed in a reaction vessel, replaced with an inert gas, and an aldehyde derivative and a solvent were added dropwise thereto, and the reaction was carried out while stirring.

After the reaction is completed, a base and a solvent are added. By the purification step, a heterocyclic-containing compound having a heterocyclic residue in its 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 in the alkaline condition can be used.

The temperature at the time of stirring under acidic conditions is 0 to 100 ° C, 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 numerical values exemplified herein. Within the range between 2 values.

The stirring time under acidic conditions is not particularly limited, and is, for example, 1 to 12 hours, 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 numerical values exemplified herein. .

The acid under acidic conditions is not particularly limited, and a heterocyclic compound and an aldehyde derivative can be used. The acid to be subjected to the condensation reaction may be, for example, perchloric acid, sulfuric acid, methanesulfonic acid, trifluoroacetic acid or p-toluenesulfonic acid.

The solvent under acidic conditions is not particularly limited, and a solvent which can be subjected to a condensation reaction between a heterocyclic compound and an aldehyde derivative may be used, and examples thereof include toluene, benzene, methyl ethyl ketone, and heptane.

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

When the heterocyclic-containing compound is synthesized in this manner, when a plurality of heterocyclic-containing compounds described later are used to synthesize a polymer, a preferred combination of functional groups can be synthesized adjacently, and the effect can be further improved, and a plurality of heterocyclic compounds can be prevented from being used. When the aldehyde derivative directly synthesizes the polymer, the combination of the functional groups formed is irregular and the effect disappears or decreases.

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

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

<Synthesis of Polymer>

A compound containing a hetero ring is added to the reaction vessel and heated to obtain a polymer. A preferred synthesis method is to weigh a dopant (sulfonic acid compound anion or a salt thereof) and a polymerization solvent, and after stirring, add an oxidizing agent and stir.

After the reaction is completed, the ions are removed to obtain a polymer composition.

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

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

(In the formulas (5) and (6), X1, X2 and R are the same as the chemical formula (1), and n is 2 to 100.)

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

The reaction vessel and the stirring method are not particularly limited, and the same conditions as in the alkaline condition can be employed.

The temperature at the time of synthesis of the polymer is 0 to 100 ° C, 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 numerical values exemplified herein. Within the range between 2 values.

The stirring time at the time of the synthesis of the polymer is not particularly limited, and is 1 to 12 hours, 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 numerical values exemplified herein. .

The dopant is not particularly limited, and examples thereof include an aqueous solution of polystyrenesulfonic acid, 2-sulfoethyl poly(meth)acrylate, 3-propylsulfonate of poly(meth)acrylate, and copolymers thereof. Or a polyanion, or an alkali metal salt thereof, p-toluenesulfonic acid, dodecylsulfonic acid, dodecylbenzenesulfonic acid, di(2-ethylhexyl)sulfosuccinic acid, polyoxyethylene polycyclic benzene A monoanion such as an ether sulfonate or a polyoxyethylene aryl ether sulfate, or an alkali metal salt thereof.

The polymerization solvent is not particularly limited, and examples thereof include an alcohol solvent such as water, methanol, ethanol, isopropanol or butanol, and a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone. Dissolve A diol solvent such as a fiber, ethyl cellosolve, propylene glycol methyl ether or propylene glycol ethyl ether; a lactic acid solvent such as methyl lactate or ethyl lactate; toluene or ethyl acetate.

The oxidizing agent is not particularly limited, and an oxidizing agent which can be subjected to a polymerization reaction may be mentioned, and examples thereof include ammonium peroxodisulfate, potassium peroxydisulfate, 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 oxosulfate, hydrogen peroxide, and the like.

The above dopant and oxidizing agent may be used alone or in combination of two or more.

The above oxidizing agent may be added in one portion or in multiple portions depending on the progress of the reaction.

The ion removal method is not particularly limited, and a method capable of removing ions may be used, and examples thereof include a method of excessive ion exchange resin, ultrafiltration, solvent cleaning by polymer precipitation, and the like.

The resulting polymer composition has a higher ionization potential of 5.2 (preferably 5.4, further preferably 5.6) eV or higher. When the ionization potential (5.0 to 5.1 eV) of PEDOT/PSS is increased, when the polymerizable composition of the present invention is used for a semiconductor, the effect of increasing the voltage at the open end is accordingly achieved.

The above polymer composition can be obtained by coating to obtain a uniform film, according to the introduced functional group The type can impart physical strength, solvent resistance, and the like required for different uses.

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

In the synthesis of the polymer, the above heterocyclic ring-containing compound may be used alone or in combination of two or more.

Further, 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 peculiar effect to the functional group.

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

The number of functional groups introduced may be plural, and it is also possible to impart various effects at the same time.

By introducing an alkyl group as a functional group, it is possible to impart an effect of being more soluble in an organic solvent or the like. By being more soluble in a solvent, application to equipment having problems in which water is mixed 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 crosslinking agent such as an epoxy group or a carbodiimide to impart a film stability effect. By increasing the stability of the film, it is expected that the film is coated. 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, it is possible to impart a self-doping effect. Since it is not necessary to add a dopant, the operation becomes simple, and it is advantageous in terms of cost. Further, since the dopant exists in the molecule, the dopant is uniformly present, and stable thermal characteristics and electrical conductivity can be expected.

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

Further, the ionization potential can be easily adjusted by changing the composition and mixing ratio of the compound containing a hetero ring.

The use of the polymer, the polymer composition and the coating film of the present invention is not limited, but an antistatic agent for various uses, an antistatic film using the antistatic agent, a p-type organic semiconductor, an n-type organic semiconductor, and the like are preferable. 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, touch Electronic devices such as control panels or liquid crystal displays, additives in adhesives, carbon, etc.

[Examples]

<Synthesis of a monomer (a compound containing a hetero ring)>

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 vessel, and the volatile component was removed by vacuum using a vacuum pump at 40 ° C for 1 hour. At the same time, 100 ml of a TMP base/THF solution (1 mol/L) was added while passing dry nitrogen gas, and the mixture was reacted at room temperature for 2 hours with stirring. 10 g of benzaldehyde was added thereto while stirring, and the temperature was raised to 50 ° C. After reacting for 6 hours, the mixture was cooled to room temperature.

After completion of the above reaction, 50 g of ion-exchanged water was added, and a small amount of 0.1 N hydrochloric acid was added thereto in a small amount to neutralize to pH = 7 with stirring. The liquid separation was carried out, the oil layer was recovered, and the liquid separation was repeated twice. An excess of 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 the object was extracted by column chromatography using hexane/ethyl acetate solvent to give the monomer 1 as a brown liquid.

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)

In the same manner as in the synthesis method 1, except that the benzaldehyde was changed to 2-ethylhexyl aldehyde, the monomer 2 was obtained as a pale yellow liquid.

Synthesis Method 3: Synthesis of Monomer 3 (Acid Conditions)

270 g of EDOT and 1 g of tetrafluoroacetic acid were weighed and placed in a 500 ml reaction vessel, 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, it was cooled to room temperature, and 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, and the liquid separation extraction was repeated three times using 50 g of ion-exchanged water. An excess of 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. In the distillation apparatus, the EDOT fraction was removed and concentrated, and the target product was separated and separated from the residual component by column chromatography using a hexane/ethyl acetate solvent to obtain a pale yellow crystal 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 (Acid Conditions)

The pale red crystal monomer 4 was obtained by the same method as the synthesis method 3 except that 6 g of benzaldehyde was changed to 11 g of syringaldehyde, and toluene was changed to methyl ethyl ketone. 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 (Acid Conditions)

The synthesis was carried out in the same manner as in the synthesis method 3 except that 6 g of benzaldehyde was changed to 7.3 g of 2-ethylhexyl aldehyde to obtain a pale yellow liquid monomer 5.

Synthesis of monomer 6 (acidic conditions)

The synthesis was carried out in the same manner as in the synthesis method 3 except that 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

Weighing monomer 0.655g, 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 vessel, and after stirring for about 30 minutes, 0.04 g of iron (III) chloride and 0.4 g of ammonium peroxydisulfate were added, and the mixture was stirred at room temperature for 4 hours, and then added sodium persulfate. 0.9 g, stirred for 4 hours. After the completion of the reaction, the ions were removed by an excess of ion exchange resin to obtain a polymer 1 of a yellow-brown polymer dispersion.

Synthesis of polymer 2

The monomer 1 was changed to the monomer 2, and the synthesis was carried out in the same manner as in the synthesis method 6, to obtain a polymer 2 of a polymer dispersion.

Synthesis Method 7: Synthesis of Polymer 3

To a 200 ml reaction vessel, 3.1 g of a polystyrenesulfonic acid aqueous solution (Mw = 75,000, solid content: 19%), 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 be added to a brown homogeneous solution. A solution obtained by dissolving 0.37 g of the monomer 3 in 5 g of ethyl acetate was added to 0.3 g of ammonium persulfate, and the mixture was stirred for 5 hours to be cooled. After the completion of the reaction, the ions were removed by an excess of ion exchange resin to obtain a polymer 3 of a dark green polymer dispersion.

Synthesis Method 8: Synthesis of Polymer 4

In the same manner as in the synthesis method 7, except that 0.37 g of the monomer 3 of the synthesis method 7 was changed to 0.2 g of the monomer 3 and 0.1 g of the EDOT (the monomer molar ratio was 50:50), a dark blue color was obtained. Polymer 4 of the polymer dispersion. The measurement result of the decomposition initiation temperature is shown in Fig. 8a.

Synthesis Method 9: Synthesis of Polymer 5

Polymerization 5 was carried out in the same manner as in Synthesis 7 except that 0.37 g of the monomer 3 of the synthesis method 7 was changed to 0.45 g of the monomer 4 to obtain a polymer 5 of a deep blue-violet polymer dispersion. The result of IR is shown in Fig. 5e, and the measurement result of the decomposition starting temperature is shown in Fig. 8b.

Synthesis Method 10: Synthesis of Polymer 6

To a 200 ml reaction vessel, 3.1 g of an aqueous solution of polystyrenesulfonic acid (Mw = 75,000, solid content: 19%), 10 g of ion-exchanged water, 0.057 g of iron (III) chloride, and 0.017 g of p-toluenesulfonic acid were added, and heated at 50 ° C. After stirring, a solution obtained by dissolving 0.34 g of monomer 4 and 0.035 g of EDOT (molar ratio of monomer: 75:25) in 5 g of ethyl acetate was added to the brown homogeneous liquid, and 0.4 g of sodium persulfate was added thereto, followed by stirring for 5 hours. And cool down. After the completion of the reaction, the ions were removed by an excess of ion exchange resin to obtain a polymer 6 of a dark blue polymer dispersion.

Synthesis of Polymer 7

The monomer 7 was changed to the monomer 5, and the synthesis was carried out in the same manner as in the synthesis method 7, to obtain a polymer 7 of a polymer dispersion.

Synthesis 11: Synthesis of Polymer 8

1 g of the monomer, 50 g of toluene, and 0.2 g of tetrafluoroacetic acid were weighed and placed in a 300 ml reaction vessel, and the mixture was heated to 50 ° C while stirring. After reacting for 7 hours, it was cooled, and the precipitate was filtered off with isopropyl alcohol and dried to give an orange crystalline polymer.

The identification of the 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 results of LC-MS measurement of the polymer 8 are shown in Fig. 6. As a result of measurement by LC-MS, it is known that the repeating unit is about 2 to 20.

Synthesis 12: Synthesis of Polymer 9

80 g of EDOT, 48 g of sodium 2-thiobenzaldehyde, 60 g of ethyl acetate, and 1.5 g of tetrafluoroacetic acid were weighed and placed in a 300 ml reaction vessel, and the mixture was heated to 50 ° C while stirring. When the reaction was carried out for 7 hours, 10 g of methanol was added and cooled, and the reaction liquid was transferred to a 500 ml container, and then 200 g of ethyl acetate was added thereto and stirred. Thereafter, the precipitate was filtered off and the crystals were collected, and then dissolved in methanol/water = 90/10 to remove insolubles, and the solution was recrystallized to obtain a green crystalline polymer 9.

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

Synthesis of polymer 10

Polymer 10 was obtained in the same manner as in Synthesis 7 except that 0.37 g of the monomer 3 of the synthesis method 7 was changed to 0.44 g of the monomer 6 and the ethyl acetate was changed to isopropyl alcohol.

[Comparative example]

Comparative Example 1: Synthesis of Polymer 11

In the same manner as in the synthesis method 7, except that the monomer 3 was changed to EDOT 0.15 g, the polymer 11 of the dark blue polymer dispersion was obtained. The result of IR is shown in Fig. 5f, and the result of measurement of decomposition initiation temperature is shown in Fig. 9c. Comparative Example 2: Synthesis of Polymer 12

1 g of the monomer, 1.14 g of 3-hexylthiophene, 50 g of toluene, and 0.2 g of tetrafluoroacetic acid were weighed, and the mixture was heated to 50 ° C while stirring. After 7 hours of reaction, the reaction condition was confirmed by thin layer chromatography, and only the color of the starting material was observed, and no reaction occurred.

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

<Electrical conductivity measurement sample preparation method>

16 g of the 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 the measurement sample 1.

Further, 1 g of the polymer 1 after the pulverization was weighed, and 0.08 g of dimethyl hydrazine was added and stirred well to obtain a measurement sample 2.

Measurement samples 1 and 2 were produced in the same manner for the polymers 2 to 8, 10, and 11.

<Electrical conductivity measuring film production method>

A glass plate having a surface cleaned with isopropyl alcohol (IPA) was used to make an area of 2 cm × 2 cm, and 0.2 g of the measurement sample 1 of the polymer 1 was dropped to spread uniformly, and dried at 120 ° C for 30 minutes to prepare a measurement. Membrane 1.

The measurement films 1 and 2 were prepared in the same manner for the measurement sample 2 of the polymer 1, the measurement samples 1 and 2 of the polymers 2 to 8, 10, and 11.

<Decomposition initiation temperature measurement sample preparation method>

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

The conductivity was measured using a Loresta GP manufactured by Mitsubishi Analytech.

In addition, the measurement of the particle size distribution was performed using a machine mechanically mounted Nanotrac UPA.

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.

<Method of evaluating film state>

After the film coating, the state of the coating film was visually observed, and the uniformity of the coating film and the matteness of 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.

<membrane solvent resistance evaluation>

The film solvent resistance 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 ° C × 1 hour

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

The film solvent resistance 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 Chemicals Co., Ltd.) = 1 g / 0.1 g (5% acetone diluted)

Drying conditions: 120 ° C × 1 hour

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

According to the results of Tables 3 and 4, it is understood that the solvent resistance of the dried film can be controlled by introducing a hydroxyl group into the side chain to carry out crosslinking with the curing agent.

<Evaluation of self-doping>

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

The polymer 9 was dissolved in ion-exchanged water to 1.5%, and the solution was directly used, and a solution of Na was removed with a cation exchange resin.

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

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

Reference Example 1: Synthesis of thienylporphyrin

3,4-ethylenedioxythiophene 355 mg, benzaldehyde 255 mg, and dichloromethane 250 mL were weighed and placed in a 500 mL reaction vessel, and stirred under a dry nitrogen atmosphere. Further, 60 mg of Lewis acid (BF ₃ ‧ O(Et) ₂ ) was added, and the mixture was reacted at room temperature for 3 hours. Thereafter, 603 mg of dichlorodicyanobenzoquinone was added, and the mixture was stirred for 1 hour. The solvent was removed, dissolved in 80 mL of toluene, and 655 mg of dichlorodicyanobenzoquinone was added thereto, and the mixture was reacted for 1 hour while refluxing under a nitrogen atmosphere. After removing the solvent, the crystals were redissolved in 120 mL of dichloromethane, and the mixture was washed three times with water and brine, and sodium sulfate was added to the organic solvent layer for dehydration.

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

Claims (9)

A compound containing a heterocyclic ring represented by the following chemical formula (1), In the formula (1), one of X1 and X2 represents an alkoxy group which may have a substituent, an alkylene oxide group which may have a substituent, a thiocyano group which may have a substituent, an amino group which may have a substituent, or The alkylthio group having 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, an alkylene oxide group which may have a substituent, and may have a thiocyano group of a substituent, an amino group which may have a substituent or an alkylthio group which may have a substituent, or the X1 and X2 represent an alkylene group having 1 to 12 carbon atoms which may have a substituent a bis-oxy group or an alkylene disulfide group having 1 to 12 carbon atoms which may have a substituent; R represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a repeating unit; 1 to 50, an alkylene oxide having 1 to 12 carbon atoms, a phenyl group which may have a substituent, a heterocyclic group which may have a substituent or a fused ring group which may have a substituent, and W represents a hydroxyl group or a chemical formula (2) indicates that X1 and X2 in the formula (2) are the same as the chemical formula (1). The heterocyclic-containing compound according to claim 1, wherein the compound represented by the formula (1) is obtained by condensing a heterocyclic compound of the formula (3) and an aldehyde derivative of the formula (4). X1 and X2 in the formula (3) and R in the formula (4) are the same as the chemical formula (1). The heterocyclic-containing compound according to claim 1 or 2, wherein both of X1 and X2 represent an alkoxy group which may have a substituent, an alkylene oxide which may have a substituent, and a sulfur which may have a substituent a cyano group, an amino group which may have a substituent or an alkylthio group which may have a substituent, or the X1 and X2 represent an alkylene dioxy group having 1 to 12 carbon atoms which may have a substituent Or an alkylene disulfide having 1 to 12 carbon atoms which may have a substituent. The heterocyclic-containing compound according to any one of claims 1 to 3, wherein both of X1 and X2 represent an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and may have a substituent The alkyleneoxy group having 1 to 12 carbon atoms or X1 and X2 represents an alkylene dioxy group having 1 to 12 carbon atoms which may have a substituent. The heterocyclic-containing compound according to any one of claims 1 to 4, wherein R is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and may have a substituent. Phenyl. A polymer obtained by polymerizing a heterocyclic compound according to any one of claims 1 to 5, wherein the polymer has a repeating unit of the formula (5) or the formula (6) , In the formulas (5) and (6), X1, X2 and R are the same as the chemical formula (1), and n is 2 to 100. The polymer obtained by polymerizing the heterocyclic ring-containing compound according to any one of claims 1 to 5 in the presence of one or more of a sulfonic acid compound anion or a salt thereof. A polymer composition comprising the polymer of claim 6 or 7 and a polymerization solvent. A coating film obtained by coating the polymer composition of claim 8.