JP2018204029A - Heterocycle-containing compound, polymer comprising the compound, and use therefor - Google Patents

Abstract

To provide a polymer obtained by oxidation polymerization in coexistence with a dopant; further provide a polymer that can control donor properties of a conjugated methine part by control of electron-donating and electron-accepting properties of a substituent of aldehyde, and can control the ionization potential.SOLUTION: The present invention provides a compound represented by formula (1) (where, Xand Xare an alkoxy group, an alkylene oxide group, mutually coupled alkylenedioxy groups, or the like, W is a hydroxyl group or formula (2)). (In formula (2) Xand Xare the same as in formula (1)).SELECTED DRAWING: Figure 1

Description

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

  There are many conventional techniques using conductive polymers as conductivity imparting materials that can be used for antistatic agents, functional capacitors, transparent electrode materials, etc., or as hole transport materials for OLEDs, OPVs, organic semiconductor sensors, etc. . The conductive polymer has a conjugated structure and a combination of a main skeleton capable of electron transfer and a dopant for imparting electron or hole carriers in the expanded conjugate to the main skeleton. As the conductive main skeleton, a skeleton having a chemical structure in which a π-electron conjugated system is developed, such as a polymer such as 3,4-ethylenedioxythiophene (EDOT), pyrrole, and aniline, is generally used. There are various dopants such as inorganic Lewis acids and organic proton acids. Of these, sulfonic acid compounds are generally used as organic protonic acids.

Among the prior arts related to conductive polymers, the main skeleton is a conductive polymer (for example, Patent Document 1) in which bis-2-ethylhexylsulfosuccinic acid is doped to polyaniline on the main skeleton, and polyethylenedioxythiophene (PEDOT). PEDOT / PSS doped with polystyrene sulfonic acid (PSS).
In particular, there are many related techniques for PEDOT / PSS (for example, Patent Document 2), which is a material that is often used. PEDOT / PSS has a very small particle size in the order of nanometers by adjusting the main conductive PEDOT, the molecular weight of the PSS used as a dopant, the amount of doping, the concentration of undoped sulfonic acid, etc. Has been imparted with excellent processability such that a uniform film can be easily dispersed in water and a uniform film can be easily produced by coating.
In general, the conductive polymer alone is often insufficient in physical strength, solvent resistance and the like of the coating film, and is used as a water-based paint in which a water-based emulsion binder and various additives are mixed.

Patent 3426637 Patent 2636968 WO2010 / 095648

However, PEDOT / PSS is characterized by the fact that gel particles are dispersed and stabilized in water by the residual sulfo group derived from PSS. Therefore, due to the metal corrosivity due to low acidity and the occurrence of sulfo group elimination over time, etc. In addition to storage stability and poor heat resistance due to de-dopants during heating, there are various problems such as inherently poor water resistance of the coating film, and physical properties of the coating film have been improved as a composite paint with various materials. I came. In addition, when blended as a paint in which various materials are mixed, there are various problems such as binders and various additives being limited to water-based systems and limitations on miscibility with the materials. In order to solve this problem, various improvement methods have been proposed, introducing an oil-soluble functional group into the conductive polymer main skeleton, and / or neutralizing treatment of the sulfo group of PSS as a dopant, A technique such as a change is proposed (for example, Patent Document 3).
Introduction of oil-soluble functional groups into the conductive polymer main skeleton is limited to introduction at the 3rd and 4th positions or introduction of functional groups into ethylenedioxy groups, so the range of chemical modification is very limited. It is mentioned that. On the other hand, although there is an example in which the sulfo group of PEDOT / PSS is modified with an amine compound, it is said that the use of water is unavoidable although it is possible to reduce metal corrosivity and improve the miscibility with the binder. There was a problem. As for the miscibility improvement by changing the dopant composition, although it is possible to improve the miscibility with an organic solvent or the like, it is difficult to balance the electrical conductivity and the uniformity of the coating film.

  An organic thin film solar cell using a conductive polymer has a structure in which an electron transport layer / a power generation layer / a hole transport layer are stacked between electrodes, and an electron transport layer and a hole transport according to the ionization potential of the power generation layer. The layer is selected, and it is said that the difference in ionization potential with the power generation layer is preferably 0.2 to 0.3 eV for efficient electron transfer. As a specifically reported configuration, a configuration using an organic semiconductor (poly-3-hexylthiophene: P3HT) / PCBM has been reported, and PEDOT / PSS is used as a hole transport layer. Purpose of improving hole extraction efficiency by matching the ionization potential of PEDOT / PSS 5.0 to 5.1 eV and the ionization potential of the organic semiconductor as the power generation layer with a certain width to the ionization potential 4.7 eV of P3HT Used in.

However, at present, the ionization potential is adjusted with the composition change of the organic semiconductor for the purpose of improving the power generation efficiency (voltage improvement), and efficient charge separation is difficult with PEDOT / PSS. There is a need for a conductive polymer having an ionization potential.
Regarding the adjustment of the ionization potential, changes in the dopant and changes in the functional groups of the PEDOT main skeleton have been studied. However, the change in the dopant is limited to a fine adjustment of about 0.1 to 0.2 eV, and a large change is difficult. Met. In addition, regarding the functional group change of the conductive polymer main skeleton, monomer synthesis is complicated, and it is difficult to synthesize by simple oxidative polymerization when polymerizing due to the change in the donor property of the monomer itself. Therefore, a complicated synthesis method such as CC cross-coupling is necessary, and further, it is necessary to perform doping treatment on the main skeleton after polymerizing, and the obtained conductive polymer is sufficient. There were problems such as inability to obtain conductivity, coating properties, and film formability.

  On the other hand, with regard to compounds having a conjugated structure resulting from condensation of an aldehyde and a heterocycle, studies on porphyrins by condensation of pyrrole and aldehyde have long been made as organic pigments. Further, application as a semiconductor has been studied by imparting solubility and the like, but it has not been used as a conductive material due to poor film formation due to low solubility and difficulty in purification.

Further, when thiophene is used as a heterocycle, there is a problem that the activity with aldehyde is weak and the synthesis does not proceed sufficiently.
However, the inventors have synthesized thienoporphyrin under normal porphyrin synthesis conditions when thiophene having an electron donating group at the 3,4-position, particularly 3,4-ethylenedioxythiophene (EDOT) is used. I found out that it is possible.

  In addition, using thiophene having an electron donating group at the 3,4-position, it is possible to increase the molecular weight of the compound obtained by the alternating condensation reaction with aldehyde, and it is possible to copolymerize with thiophene monomers. In addition, by conducting oxidative polymerization in the presence of a dopant, a doped conductive polymer can be obtained. Furthermore, by adjusting the electron donating and electron accepting properties of the introduced aldehyde substituent, conjugation can be achieved. It was clarified that the donor property of the methine moiety can be adjusted and the ionization potential of the conductive polymer can be adjusted.

  This invention is made | formed in view of such a situation, and the heterocyclic containing compound represented by following Chemical formula (1) is provided.

(In formula (1), one of X1 and X2 is an alkoxy group that may have a substituent, an alkylene oxide group that may have a substituent, a thiocyano group that may have a substituent, or a substituent. An amino group that may have a substituent, or a thioalkyl group that may have a substituent, the other having hydrogen, an alkyl group having 1 to 12 carbon atoms that may have a substituent, and a substituent. 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 a thioalkyl group which may have a substituent Or an alkylenedioxy group having 1 to 12 carbon atoms which may have a substituent in which X1 and X2 are linked, or an alkylenedithio group having 1 to 12 carbon atoms which may have a substituent. R represents alkyl having 1 to 12 carbons , An alkoxy group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 50 carbon atoms having 1 to 50 repeating units, an optionally substituted phenyl group, an optionally substituted heterocyclic group, Alternatively, it represents a condensed ring group which may have a substituent, and W is represented by a hydroxyl group or the following chemical formula (2).
(X1 and X2 in Formula (2) are the same as in Chemical Formula (1).)

  According to the experiments by the present inventors, it is possible to easily introduce a functional group into a product composition by selecting a raw material compound having various functional groups. It was found that sex can be imparted.

Hereinafter, various embodiments of the present invention will be exemplified. The following embodiments can be combined with each other.
Preferably, the compound represented by the chemical formula (1) is obtained by condensing a heterocyclic compound of the chemical formula (3) and an aldehyde derivative of the chemical formula (4).
(X1 and X2 in formula (3) and R in formula (4) are the same as in chemical formula (1).)
Preferably, X1 and X2 each have 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, or a substituent. An optionally substituted amino group, or a thioalkyl group that may have a substituent, or an alkylenedioxy group having 1 to 12 carbon atoms that may have a substituent in which X1 and X2 are linked, or a substituent It is a C1-C12 alkylene dithio group which may have a group.
Preferably, X1 and X2 each 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, or X1 And an alkylenedioxy group having 1 to 12 carbon atoms which may have a substituent linked to X2.
Preferably, R is 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.
Preferably, the polymer obtained by superposing | polymerizing 1 type (s) or 2 or more types of the said heterocyclic containing compound which has a repeating unit of Chemical formula (5) or Chemical formula (6).
(In the formulas (5) and (6), X1, X2 and R are the same as those in the chemical formula (1), and n is 2 to 100.)
Preferably, a polymer obtained by polymerizing the heterocycle-containing compound and the sulfonic acid compound anion or a salt thereof in the presence of one or more kinds.
Preferably, a polymer composition comprising the polymer and a polymerization solvent.
Preferably, the coating film obtained by apply | coating the said polymer composition.

FIG. 1 (a) shows the result of NMR measurement of monomer 1 synthesized by synthesis method 1 of the present invention, and FIG. 1 (b) shows the result of NMR measurement of monomer 3 synthesized by synthesis method 3 of the present invention. Show. FIG. 2 (c) shows the result of measuring NMR of the monomer 4 synthesized by the synthesis method 4 of the present invention, and FIG. 2 (d) shows the result of measuring NMR of the polymer 8 synthesized by the synthesis method 11 of the present invention. Indicates. FIG. 3 (a) shows the result of measuring the IR of monomer 1 synthesized by synthesis method 1 of the present invention, and FIG. 3 (b) shows the result of measuring the IR of polymer 8 synthesized by synthesis method 11 of the present invention. Indicates. FIG. 4 (c) shows the result of measuring the IR of monomer 3 synthesized by the synthesis method 3 of the present invention, and FIG. 4 (d) shows the result of measuring the IR of monomer 4 synthesized by the synthesis method 4 of the present invention. Show. FIG. 5 (e) shows the result of measuring IR of the polymer 5 synthesized by the synthesis method 9 of the present invention, and FIG. 5 (f) shows the result of measuring IR of the polymer 11 synthesized in Comparative Example 1. . FIG. 6 shows the results of LC-MS measurement of the polymer 8 synthesized by the synthesis method 11 of the present invention. FIG. 7 (a) shows the results of measuring the UV of the monomer 1 synthesized by the synthesis method 1, the monomer 3 synthesized by the synthesis method 3, and the monomer 4 synthesized by the synthesis method 4, and FIG. The polymer 1 synthesized by the synthesis method 6 of the present invention, the polymer 3 synthesized by the synthesis method 7, the polymer 4 synthesized by the synthesis method 8, the polymer 5 synthesized by the synthesis method 9, and the synthesis The result of having measured UV of the polymer 8 synthesize | combined by the method 11 and the polymer 11 synthesize | combined by the comparative example 1 is shown. FIG. 8A shows the result of measuring the decomposition start temperature of the polymer 4 synthesized by the synthesis method 8 of the present invention, and FIG. 8B shows the start of decomposition of the polymer 5 synthesized by the synthesis method 9 of the present invention. The result of measuring the temperature is shown. FIG. 9C shows the result of measuring the decomposition start 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 heterocycle-containing compound having a novel structure represented by the following chemical formula (1). Although the use of this heterocyclic compound is not limited, as an example, it can be used as an organic conductor material (more specifically, a conductive polymer and a monomer of a main chain of a semiconductor polymer).
First, the constitution and synthesis method of the heterocycle-containing compound will be described, and then, a method for synthesizing a polymer that can be used as a conductive polymer using this compound as a monomer will be described.

<Heterocycle-containing compound>
The heterocycle-containing compound of the present invention is represented by the following chemical formula (1).

(In formula (1), one of X1 and X2 is an alkoxy group that may have a substituent, an alkylene oxide group that may have a substituent, a thiocyano group that may have a substituent, or a substituent. An amino group that may have a substituent, or a thioalkyl group that may have a substituent, the other having hydrogen, an alkyl group having 1 to 12 carbon atoms that may have a substituent, and a substituent. 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 a thioalkyl group which may have a substituent Or an alkylenedioxy group having 1 to 12 carbon atoms which may have a substituent in which X1 and X2 are linked, or an alkylenedithio group having 1 to 12 carbon atoms which may have a substituent. R represents alkyl having 1 to 12 carbons , An alkoxy group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 50 carbon atoms having 1 to 50 repeating units, an optionally substituted phenyl group, an optionally substituted heterocyclic group, Alternatively, it represents a condensed ring group which may have a substituent, and W is represented by a hydroxyl group or the following chemical formula (2).
(X1 and X2 in Formula (2) are the same as in Chemical Formula (1).)

  It is preferable that at least one of X1 and X2 has an electron donating group directly bonded to the heterocycle.

  An alkoxy group which may have a substituent of X1 and X2, an alkylene oxide group, a thiocyano group, an amino group, a thioalkyl group, an alkylenedioxy group in which X1 and X2 are linked, an alkylenedithio group, or an alkyl group having 1 to 12 carbon atoms; The substituent of the alkyl group is not limited, but a substituent that does not inhibit the electron donating property relative to the heterocycle is preferable, and specifically, a linear, branched, or cyclic alkyl group, sulfo group , Hydroxyl group, carboxyl group, amino group, amide group, ester group, and straight or branched alkyl group, alkoxyalkyl group, alkylene substituted with sulfo group, hydroxyl group, carboxyl group, amino group, halogen group It may be an oxide group and may have a plurality of substituents.

  X1 and X2 alkoxy groups, alkylene oxide groups, thioalkyl groups, alkylenedioxy groups in which X1 and X2 are linked, alkylenedithio groups, and alkyl groups, carboxyl groups, amide groups, ester groups, alkoxy groups of the substituents Although carbon number of an alkyl group and an alkylene oxide group does not specifically limit, For example, it is 1-20, Preferably it is 1-12. Specifically, this carbon number is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20. It may be within a range between any two of the numerical values exemplified in.

  One of X1 and X2 may be hydrogen or an alkyl group having 1 to 12 carbon atoms, but it is better to exclude a combination in which both are alkyl groups, both are hydrogen, one is hydrogen and the other is an alkyl group.

  The alkylene dioxy group having 1 to 12 carbon atoms which may have a substituent of X1 and X2 and the alkylenedithio group having 1 to 12 carbon atoms which may have a substituent are an ethylene structure in the alkylene main chain. Instead of, it may have an oxygen analog, nitrogen analog, or sulfur analog structure.

  Examples of the substituent in the phenyl group which may have a substituent of R, the heterocyclic group which may have a substituent, and the condensed ring group which may have a substituent include alkyl having 1 to 12 carbon atoms. Group, an alkoxy group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 50 carbon atoms and 1 to 50 carbon atoms, a phenyl group, a heterocyclic group, a condensed ring group, a hydroxy group, an aldehyde group, a carboxy group, and a halogen group. Alternatively, it may have a plurality of alkali metal salts thereof, sulfo groups or alkali metal salts thereof, phosphoric acid groups or alkali metal salts thereof, amino groups, and cyano groups.

  The alkyl group, alkoxy group, alkylene oxide of the substituent in the phenyl group which may have a substituent of R, the heterocyclic group which may have a substituent, the condensed ring group which may have a substituent The group, phenyl group, heterocyclic group, condensed ring group and amino group may have an arbitrary substituent at an arbitrary position.

  The alkyl group having 1 to 12 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, and the alkylene oxide group having 1 to 50 carbon atoms and having 1 to 50 carbon atoms have an arbitrary substituent at an arbitrary position. May be.

  Examples of the heterocyclic group include silole ring, furan ring, thiophene ring, oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole. Ring, thiazole ring, indole ring, benzimidazole ring, benzthiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, thienothiophene ring, carbazole ring, azacarbazole ring (any of the carbon atoms constituting the carbazole ring) A ring in which any one or more of the carbon atoms constituting the dibenzosilole ring, dibenzofuran ring, dibenzothiophene ring, benzothiophene ring or dibenzofuran ring are replaced by a nitrogen atom, Benzo Furan ring, benzodithiophene ring, acridine ring, benzoquinoline ring, phenazine ring, phenanthridine ring, phenanthroline ring, cyclazine ring, kindlin ring, tepenidine ring, quinindrine ring, triphenodithiazine ring, triphenodioxazine ring, Nantrazine ring, anthrazine ring, perimidine ring, naphthofuran ring, naphthothiophene ring, naphthodifuran ring, naphthodithiophene ring, anthrafuran ring, anthradifuran ring, anthrathiophene ring, anthradithiophene ring, thianthrene ring, phenoxathiin ring , Dibenzocarbazole ring, indolocarbazole ring, dithienobenzene ring, epoxy ring, aziridine ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrole Ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ε-caprolactone ring, ε-caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine Ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thiomorpholine ring, thiomorpholine-1,1-dioxide ring, pyranose ring, diazabicyclo [2,2 , 2] -octane ring, phenoxazine ring, phenothiazine ring, oxanthrene ring, thioxanthene ring, monovalent group derived from phenoxathiin ring, and the like.

  Examples of the condensed ring include naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, pentacene ring, perylene ring. , Pentaphen ring, picene ring, pyranthrene 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, an alkylene oxide group having 1 to 50 carbon atoms and 1 to 50 carbon atoms, a phenyl group, a naphthyl group, and a hydroxy group. Group, aldehyde group, amino group, cycloalkyl group having 3 to 8 carbon atoms, and the like.

  The W can be synthesized by selecting a hydroxy group or a heterocyclic residue represented by the chemical formula (2) according to reaction conditions. Under basic conditions it becomes a hydroxy group, and under acidic conditions it becomes a heterocyclic residue.

<Synthesis of heterocycle-containing compound>
The heterocyclic compound represented by the chemical formula (1) is obtained by condensing a heterocyclic compound of the chemical formula (3) and an aldehyde derivative of the chemical formula (4).

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

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

(In formula (3-A), X3 and X4 are each an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and an alkylene oxide group having 1 to 12 carbon atoms which may have a substituent. Represents a thiocyano group which may have a substituent, an amino group which may have a substituent, or a thioalkyl group which may have a substituent, the other being hydrogen, a carbon which may have a substituent It may have an alkyl group having 1 to 12 carbon atoms, 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 a substituent. Represents a good thiocyano group, an amino group which may have a substituent, or a thioalkyl group which may have a substituent.)

  C1-C12 alkoxy group which may have a substituent of said X3 and X4, C1-C12 alkylene oxide group which may have a substituent, Thiocyano group which may have a substituent , The amino group which may have a substituent, the thioalkyl group which may have a substituent, the substituent of the alkyl group having 1 to 12 carbon atoms which may have a substituent is not limited, Substituents similar to the substituents for X1 and X2 can be used.

(In Formula (3-B), Y1 and Y2 represent an oxygen atom, a sulfur atom, and a selenium atom, and X5 is an alkylene group having 1 to 12 carbon atoms that may have a substituent. And may have an oxygen analog, nitrogen analog, or sulfur analog structure in place of the ethylene structure in the alkylene main chain.)

  Although the substituent of the C1-C12 alkylene group which may have the said X5 substituent is not limited, The substituent similar to the said X1 and X2 substituent can be used.

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

(In the formula (4-A), R2 to R6 are 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 50 carbon atoms and a phenyl group. , Heterocyclic group, condensed ring group, hydroxy group, aldehyde group, carboxy group, halogen group or alkali metal salt thereof, sulfo group or alkali metal salt thereof, phosphoric acid group or alkali metal salt thereof, amino group, cyano You may have two or more groups.)

(In formula (4-B), R7 represents 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 50 carbon atoms and 1 to 50 carbon atoms, and a substituent. The heterocyclic group which may have and the condensed ring group which may have a substituent are represented, The said alkyl group, alkoxy group, and alkylene oxide group may have arbitrary substituents in arbitrary positions. )

<Basic conditions>
A heterocyclic compound is weighed in a reaction vessel, and a base and a solvent are added and stirred while an inert gas is sealed. Add the aldehyde derivative with stirring and react with stirring.
After completion of the reaction, ion-exchanged water is added, and acid is added little by little while stirring to neutralize to pH = about 6-8. Through the purification step, a heterocyclic-containing compound having a hydroxyl group in the side chain is obtained.

  Although the said reaction container is not specifically limited, The product made from glass, the product made from Teflon (trademark), etc. can be utilized.

After measuring the heterocyclic compound in the reaction vessel, a volatile component removal step of removing volatile components may be used. In the volatile component removal step, the volatile component may be removed using a vacuum pump or the like under reduced pressure conditions or heating conditions by heating, or the reduced pressure conditions and heating conditions may be combined.
Examples of the volatile component include water, organic solvents, unreacted substrates, and the like, which are compounds that could not be removed when the heterocyclic compound was synthesized.

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

  The stirring method is not particularly limited, but a stirrer or a shaker may be used.

The stirring temperature at the time of synthesizing the intermediate reactant of the heterocyclic compound under basic conditions is −40 to 50 ° C., preferably −10 to 30 ° C. Specifically, this temperature is, for example, −40, −30, −20, −10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 ° C., and is exemplified here. It may be within a range between any two of the numerical values.
Furthermore, as stirring temperature at the time of condensation reaction with an aldehyde derivative, it is 25 to 100 degreeC, Preferably it is 40 to 80 degreeC. Specifically, this 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 here. .
At this time, when the temperature at the time of synthesizing the intermediate reactant of the heterocyclic compound is too high, the production of by-products is increased, so that the reaction at a low temperature is preferable.

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

  The base under basic conditions is not particularly limited as long as the condensation reaction of the heterocyclic compound and the aldehyde derivative proceeds, and TMP base (MAGNESIUMCHLOROTRATRAMETHYLPIPERIDID LITHIUMCHLORID COMPLEX), lithium diisopropylamide, n-butyllithium, Examples include sec-butyl lithium, tert-butyl lithium, sodium ethoxide, and the like.

  The solvent under basic conditions is not particularly limited as long as the condensation reaction of the heterocyclic compound and the aldehyde derivative proceeds, and examples thereof include tetrahydrofuran and tert-butyl methyl ether.

  The acid under basic conditions is not particularly limited as long as the acid can be neutralized after completion of the condensation reaction of the heterocyclic compound and the aldehyde derivative, such as hydrochloric acid, nitric acid, sulfuric acid, or 0.1N. Examples thereof include an aqueous solution.

  The said refinement | purification process is a process of performing an extraction process, a fractionation process, etc. The extraction step is not limited as long as the oil layer containing the target product can be recovered, and examples include separation extraction. As the fractionation step, it is sufficient if the target product can be isolated, and examples thereof include column chromatography and distillation.

<Acid condition>
A heterocyclic compound and an acid are weighed in a reaction vessel, substituted with an inert gas, an aldehyde derivative and a solvent are dropped, and the reaction is conducted with stirring.
After the reaction is complete, base and solvent are added. By the purification step, a heterocyclic-containing compound having a heterocyclic residue in the side chain is obtained.

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

  As temperature at the time of stirring on acidic conditions, it is 0-100 degreeC, Preferably it is 50-90 degreeC. Specifically, this temperature is, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 ° C., and the numerical value exemplified here It may be within the range between any two.

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

  The acid under acidic conditions is not particularly limited as long as the condensation reaction of the heterocyclic compound and the aldehyde derivative proceeds. Perchloric acid, sulfuric acid, methanesulfonic acid, trifluoroacetic acid, p-toluenesulfone Examples include acids.

  The solvent under acidic conditions is not particularly limited as long as the condensation reaction of the heterocyclic compound and the aldehyde derivative proceeds, and examples thereof include toluene, benzene, methyl ethyl ketone, heptane and the like.

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

  Thus, by synthesizing the heterocyclic ring-containing compound, when synthesizing a polymer using a plurality of types of heterocyclic ring-containing compounds described later, a preferred combination of functional groups can be synthesized side by side, and more effective. It is possible to increase the number of heterocyclic compounds and aldehyde derivatives to directly synthesize the polymer, and the functional group combination that occurs when the polymer is directly randomized is prevented from being lost or reduced. Can do.

  Compared to the case where a polymer is directly synthesized from a heterocyclic compound and an aldehyde derivative, the reaction time can be shortened when the polymer is synthesized from a heterocyclic compound, and the occurrence of side reactions is reduced, thereby generating impurities. It is possible to suppress the above, and the purity of the polymer can be increased because it can be purified at the stage of the heterocycle-containing compound.

  In addition, if the synthesis mechanism of the present invention is used, a cyclic compound such as thienoporphyrin can be obtained. A synthesized reference example will be described later.

<Synthesis of polymer>
A polymer can be obtained by adding a heterocycle-containing compound to a reaction vessel and stirring with heating. As a preferred synthesis method, a dopant (sulfonic acid compound anion or a salt thereof) and a polymerization solvent are weighed, stirred, and then oxidized. Add and stir.
After completion of the reaction, the ion content is removed to obtain a polymer composition.

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

  The 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 those in the chemical formula (1), and n is 2 to 100.)

  When a heterocycle-containing compound having a hydroxy group in the side chain synthesized under basic conditions is used, a polymer represented by the chemical formula (5) in which a condensation polymerization reaction proceeds and water molecules are eliminated is obtained. When a heterocyclic compound having a heterocyclic residue in the side chain synthesized under acidic conditions is used, an oxidative polymerization reaction proceeds to obtain a polymer represented by chemical formula (6).

  The reaction vessel and the stirring method are not particularly limited, and the same conditions as basic conditions can be used.

  As temperature at the time of the synthesis | combination of a polymer, it is 0-100 degreeC, Preferably it is 15-35 degreeC. Specifically, this temperature is, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 ° C., and the numerical value exemplified here It may be within the range between any two.

  Although the stirring time at the time of the synthesis | combination of a polymer is not specifically limited, It is 1 to 12 hours, Preferably it is 2 to 6 hours. This time is specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 hours, and is a range between any two of the numerical values exemplified here. It may be within.

  Although it does not specifically limit as said dopant, Polysulfonic acid aqueous solution, poly 2-sulfoethyl (meth) acrylate, polyanions, such as poly 3-propyl sulfo (meth) acrylate and its copolymer, or its alkali metal salt, p- Monoanions such as toluenesulfonic acid, dodecylsulfonic acid, dodecylbenzenesulfonic acid, di (2-ethylhexyl) sulfosuccinic acid, polyoxyethylene polycyclic phenyl ether sulfonic acid ester, polyoxyethylene aryl ether sulfuric acid ester, or alkali metal salts thereof Etc.

  The polymerization solvent is not particularly limited, but alcohol solvents such as water, methanol, ethanol, isopropyl alcohol and butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether And glycol solvents such as propylene glycol ethyl ether, lactic acid solvents such as methyl lactate and ethyl lactate, toluene, and ethyl acetate.

  The oxidizing agent is not particularly limited, and may be any oxidizing agent that allows a polymerization reaction to proceed. For example, ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxodisulfate, iron (III) chloride, iron (III) sulfate, water Iron (III) oxide, iron (III) tetrafluoroborate, iron (III) hexafluorophosphate, copper (II) sulfate, copper (II) chloride, copper (II) tetrafluoroborate, copper hexafluorophosphate (II And ammonium oxodisulfate, hydrogen peroxide and the like.

  As the dopant and the oxidizing agent, only one kind may be used, or a plurality of kinds may be used.

  The oxidizing agent may be added at once, or may be added in a plurality of times while observing the progress of the reaction.

  The ion content removal method is not particularly limited, and any method that can remove the ion content may be used. Examples include a method of passing an excess ion exchange resin, ultrafiltration, and solvent washing by polymer precipitation.

  The resulting polymer composition has a high ionization potential of 5.2 (preferably 5.4, more preferably 5.6) eV or higher. When the polymerizable composition of the present invention is used for a semiconductor by an amount higher than the ionization potential (5.0 to 5.1 eV) of PEDOT / PSS, there is an effect of increasing the open-circuit voltage.

  The said polymer composition can produce | generate a uniform film | membrane by application | coating, and can give the physical intensity | strength, solvent tolerance, etc. which are required according to a use with the kind of functional group to introduce | transduce.

  Although it does not specifically limit as said coating method, A well-known coating method can be utilized.

  In the synthesis of the polymer, only one kind of the heterocycle-containing compound may be used, or a plurality of kinds may be used as a copolymer.

  Moreover, even if a copolymer is synthesized by combining the heterocyclic ring-containing compound with a known monomer or polymer, an effect specific to a functional group can be imparted.

  Although it does not specifically limit as a repeating unit of a polymer, It is 2-100, Preferably it is 2-20. Specifically, for example, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100, even if it is within the range between any two of the numerical values exemplified here Good.

  There may be a plurality of functional groups to be introduced, and a plurality of effects can be imparted simultaneously.

  By introducing an alkyl group as a functional group, an effect of being easily dissolved in an organic solvent or the like can be imparted. By being easily dissolved in a solvent, it can be easily applied to a device application in which mixing of water becomes a problem, and a uniform film can be formed at a low temperature when a coating film is formed.

  By introducing a phenol or carboxy group as a functional group, a crosslinking reaction occurs due to the addition of a crosslinking agent such as epoxy or carbodiimide, and a film stability effect can be imparted. By improving the film stability, it can be expected that the solvent resistance of the coating film is increased and peeling due to the electrolyte solution is less likely to occur.

  By introducing sulfonic acid as a functional group, an effect capable of self-doping can be imparted. Since the addition of a dopant is unnecessary, the operation is simple and advantageous in terms of cost, and since the dopant is present in the molecule, the dopant is present uniformly, and stable thermal characteristics and conductivity can be expected.

As described above, since the heterocycle-containing compound of the present invention is used as a conductive polymer material, various functional groups can be easily introduced into the side chain, so that a polymer having the function introduced above is synthesized. be able to.
Furthermore, the ionization potential can be easily adjusted by changing the composition and blending ratio of the heterocycle-containing compound.

  The use of the polymer, polymer composition and coating film of the present invention is not limited, but antistatic agents for various uses, antistatic films using the same, p-type organic semiconductors, n-type organic semiconductors, solid electrolytic capacitors Solid electrolytes and additives thereof, electrochromic elements, transparent electrodes of organic thin film solar cells, counter electrodes of dye-sensitized solar cells and auxiliary agents thereof, organic electroluminescence, chemical sensors, fuel cells, electronic devices such as touch panels and liquid crystal displays It can be suitably used as an additive for adhesives, carbon and the like.

<Synthesis of monomer (heterocycle-containing compound)>
Synthesis method 1: Synthesis of monomer 1 (basic conditions)
In a 300 ml reaction vessel, 14.2 g of 3,4-ethylenedioxythiophene (EDOT) was weighed and evacuated using a vacuum pump at 40 ° C. for 1 hour to remove volatile components. While adding dry nitrogen, 100 ml of a TMP base / THF solution (1 mol / L) was added, and the mixture was reacted at room temperature for 2 hours while stirring. 10 g of benzaldehyde was added with stirring, the temperature was raised to 50 ° C., the reaction was performed for 6 hours, and then cooled to room temperature.
After completion of the reaction, 50 g of ion-exchanged water was added, and 0.1N hydrochloric acid was added little by little while stirring to neutralize to pH = 7. Liquid separation extraction was performed, the oil layer was collected, and this liquid separation extraction was repeated twice. Add excess magnesium sulfate to the oil layer to dehydrate, filter the magnesium sulfate, concentrate the filtrate with an evaporator, fractionate the target product with column chromatography using hexane / ethyl acetate solvent, and prepare a brown liquid monomer 1 was obtained.
The identification of the monomer 1 was confirmed by LC-MS, NMR and IR. Fig. 1a shows the NMR results and Fig. 3a shows the IR results.

Synthesis method 2: Synthesis of monomer 2 (basic conditions)
Synthesis was performed in the same manner as in Synthesis Method 1 except that benzaldehyde was changed to 2-ethylhexyl aldehyde to obtain a light yellow liquid monomer 2.

Synthesis method 3: Synthesis of monomer 3 (acidic conditions)
EDOT (270 g) and tetrafluoroacetic acid (1 g) were weighed in a 500 ml reaction vessel, purged with nitrogen for 1 hour, heated to 60 ° C., and dropped with 6 g of benzaldehyde and 100 g of toluene over 7 hours. After heating for 3 hours, the mixture was cooled to room temperature, and 50 g of toluene and 1.2 g of triethylamine were added and stirred. Separation extraction was performed by adding 50 g of ion-exchanged water, the oil layer was recovered, and this separation-extraction was repeated three times using 50 g of ion-exchanged water. Excess magnesium sulfate is added to the oil layer for dehydration, the magnesium sulfate is filtered off, the filtrate is concentrated with an evaporator, EDOT is distilled off with a vacuum distillation apparatus and concentrated, and the residue is hexane / ethyl acetate. The target product was separated by column chromatography using a solvent to obtain light yellow crystalline monomer 3.
The identification of the monomer 3 was confirmed by LC-MS, NMR and IR. Fig. 1b shows the NMR results and Fig. 4c shows the IR results.

Synthesis method 4: Synthesis of monomer 4 (acidic conditions)
Synthesis was performed in the same manner as in Synthesis Method 3 except that 6 g of benzaldehyde was changed to 11 g of syringaldehyde and toluene was changed to methyl ethyl ketone, to obtain monomer 4 of pale red crystals. Fig. 2c shows the NMR results, and Fig. 4d shows the IR results.

Synthesis method 5: Synthesis of monomer 5 (acidic conditions)
Synthesis was carried out in the same manner as in Synthesis Method 3 except that 6 g of benzaldehyde was changed to 7.3 g of 2-ethylhexyl aldehyde to obtain a light yellow liquid monomer 5.

Synthesis of monomer 6 (acidic conditions)
Synthesis was performed in the same manner as in 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 to obtain monomer 6 of a pale yellow solid. It was.

<Synthesis of polymer>
Synthesis Method 6: Synthesis of Polymer 1 0.65 g of Monomer 1, 7.8 g of polystyrene sulfonic acid aqueous solution (Mw = 75,000, solid content 19%), 30 g of ion-exchanged water and 30 g of ion-exchanged water were weighed in a 300 ml reaction vessel. After about 30 minutes, 0.04 g of iron (III) chloride and 0.4 g of ammonium peroxodisulfate were added, and after stirring for 4 hours at room temperature, 0.9 g of sodium peroxodisulfate was added and stirred for 4 hours. After the reaction was completed, the ion content was removed by passing an excess ion exchange resin to obtain polymer 1 of a brown polymer dispersion.

The polymer 2 was synthesized by the same method as the synthesis method 6 except that the synthetic monomer 1 of the polymer 2 was changed to the monomer 2 to obtain a polymer 2 of a polymer dispersion.

Synthesis Method 7: Synthesis of Polymer 3 3.1 g of an aqueous polystyrene sulfonic acid solution (Mw = 75,000, solid content 19%), 10 g of ion-exchanged water, and 0.057 g of iron (III) sulfate were added to a 200 ml reaction vessel and added to 50 ml. The mixture was heated and stirred at 0 ° C., a solution in which 0.37 g of monomer 3 was dissolved in 5 g of ethyl acetate in a brown uniform liquid was added, 0.3 g of ammonium peroxodisulfate was added, and the mixture was stirred for 5 hours and cooled. After completion of the reaction, the ion content was removed by passing through an excess ion exchange resin to obtain a polymer 3 of a dark green polymer dispersion.

Synthesis Method 8: Synthesis of Polymer 4 Polymerization was conducted in the same manner as in Synthesis Method 7 except that 0.37 g of monomer 3 in Synthesis method 7 was changed to 0.2 g of monomer 3 and 0.1 g of EDOT (monomer molar ratio 50:50). A polymer 4 of a deep blue polymer dispersion was obtained. FIG. 8a shows the result of the decomposition start temperature measurement.

Synthesis Method 9: Synthesis of Polymer 5 Polymerization 5 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 of monomer 4, and polymer 5 in a deep blue-violet polymer dispersion. Got. FIG. 5e shows the IR, and FIG. 8b shows the result of the decomposition start temperature measurement.

Synthesis Method 10: Synthesis of Polymer 6 Polystyrenesulfonic acid aqueous solution (Mw = 75,000, solid content 19%) 3.1 g, ion-exchanged water 10 g, iron (III) chloride 0.057 g, p-toluene in a 200 ml reaction vessel Add 0.017 g of sulfonic acid and heat and stir at 50 ° C. Add a solution of 0.34 g of monomer 4 and 0.035 g of EDOT (75:25 in terms of monomer molar ratio) dissolved in 5 g of ethyl acetate in the brown homogeneous liquid. Then, 0.4 g of sodium peroxodisulfate was added, and the mixture was stirred for 5 hours and cooled. After completion of the reaction, the ion content was removed by passing through an excess ion exchange resin to obtain a polymer 6 of a deep blue polymer dispersion.

The polymer 7 was synthesized by the same method as the synthesis method 7 except that the synthetic monomer 3 of the polymer 7 was changed to the monomer 5 to obtain a polymer 7 of a polymer dispersion.

Synthesis Method 11: Synthesis of Polymer 8 1 g of monomer 1, 50 g of toluene, and 0.2 g of tetrafluoroacetic acid were weighed into a 300 ml reaction vessel, and heated and stirred at 50 ° C. while purging with nitrogen. After reacting for 7 hours, the mixture was cooled, and the precipitate was collected by filtration, washed with isopropyl alcohol, and dried to obtain orange crystalline polymer 8.
The identification of the polymer 8 was confirmed by LC-MS, NMR and IR. Fig. 2d shows NMR results, and Fig. 3b shows IR results.

  The result of having measured LC-MS of the polymer 8 in FIG. 6 is shown. From the measurement result by LC-MS, it was found that the number of repeating units was about 2 to 20.

Synthesis Method 12: Synthesis of Polymer 9 80 g of EDOT, 48 g of 2-sulfobenzaldehyde sodium, 60 g of ethyl acetate and 1.5 g of tetrafluoroacetic acid were weighed into a 300 ml reaction vessel, and the mixture was heated to 50 ° C. with nitrogen substitution. did. After reacting for 7 hours, 10 g of methanol was added and cooled, the reaction solution was transferred to a 500 ml container, and then 200 g of ethyl acetate was added and stirred. Thereafter, the precipitate was separated by filtration and the crystals were collected, and then dissolved in methanol / water = 90/10 to remove insolubles. The solution was recrystallized to obtain a green crystalline polymer 9.
From the measurement result of LC-MS, it turned out that it is about 3-20 as a repeating unit.

Monomer 3 0.37 g of Synthesis Process 7 of Polymer 10 was changed to a monomer 6 0.44 g, except for changing the ethyl acetate to isopropyl alcohol is similarly polymerized with synthesis 7, a polymer was obtained 10 .

Comparative example

Comparative Example 1: Polymer 11 was synthesized in the same manner as in Synthesis Method 7 except that the synthetic monomer 3 was changed to 0.15 g of EDOT to obtain a polymer 11 of a deep blue polymer dispersion. FIG. 5f shows the IR, and FIG. 9c shows the result of the decomposition start temperature measurement.

Comparative Example 2: Synthetic monomer 1 of polymer 12 1 g, 1.14 g of 3-hexylthiophene, 50 g of toluene and 0.2 g of tetrafluoroacetic acid were weighed and stirred at 50 ° C. with nitrogen substitution. After the reaction for 7 hours, the reaction state was confirmed by thin layer chromatography, but it was not reacted only by light emission derived from the raw material.

  Table 1 shows a summary of the molar ratios of polymers 1-9 and 11.

<Conductivity measurement sample adjustment method>
6 g of the polymer 1 was weighed into a sample bottle and crushed by a probe type ultrasonic crusher. The polymer 1 after pulverization was used as the measurement sample 1 as it was.
Similarly, 1 g of the polymer 1 after pulverization was weighed, 0.08 g of dimethyl sulfoxide was added, and the mixture was well stirred to obtain a measurement sample 2.
Measurement samples 1 and 2 were similarly prepared for the polymers 2 to 8, 10 and 11.

<Conductivity measurement film preparation method>
An area of 2 cm x 2 cm is prepared using a tape on a glass plate whose surface is cleaned with isopropyl alcohol (IPA), 0.2 g of measurement sample 1 of polymer 1 is hung, uniformly spread, and dried at 120 ° C for 30 minutes. Thus, the measurement film 1 was produced.
Measurement films 1 and 2 were similarly prepared for measurement sample 2 of polymer 1 and measurement samples 1 and 2 of polymers 2 to 8, 10, and 11.

<Decomposition start temperature measurement sample adjustment method>
The polymer 1 was put in a vacuum dryer in a sample bottle, and the water was dried by reducing the pressure to 10 Pa or less at 30 ° C. to obtain a polymer 1 powder.

Loresta GP made by Mitsubishi Analitech was used for the measurement of conductivity.
For measurement of the particle size distribution, Nanotrac UPA manufactured by Nikkiso was used.
For the measurement of the decomposition start temperature, TG-DTA (STA7220) manufactured by Hitachi High-Tech Science was used.
For measurement of the ionization potential, PYS-202 manufactured by Sumitomo Heavy Industries, Ltd. was used.

<Coating state evaluation method>
After coating, the coating state was visually evaluated for the uniformity of the coating and the presence or absence of surface gloss on the following criteria.
◎: Uniform coating and surface gloss ○: Coating is slightly non-uniform or surface gloss slightly cloudy

  Table 2 shows the results of evaluating the polymers 1-8, 10, and 11.

<Membrane solvent resistance evaluation>
Table 3 shows the results of evaluating the film solvent resistance under the following conditions.
Curing agent blending ratio: polymer / epoxy curing agent (ethylene glycol diglycidyl ether) = 1 g / 0.1 g (5% methanol)
Drying conditions: 120 ° C. × 1 hour Evaluation method: One drop of methanol was dropped on the dried coating film, and changes in appearance were visually confirmed.

Table 4 shows the results of evaluating the film solvent resistance under the following conditions.
Curing agent blending ratio: polymer / isocyanate curing agent (Duranate WB40-80D: manufactured by Asahi Kasei Chemicals Corporation) = 1 g / 0.1 g (5% acetone diluted)
Drying conditions: 120 ° C. × 1 hour Evaluation method: One drop of methanol was dropped on the dried coating film, and changes in appearance were visually confirmed.

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

<Evaluation of self-doping>
Table 5 shows the results of evaluation of self-doping under the following conditions.
The polymer 9 was dissolved in ion exchange water so as to be 1.5%, and a solution as it was and a solution from which Na was removed with a cation exchange resin were 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 was found that by performing the Na removal treatment, conductivity was obtained without a dopant and self-doping was possible.

Reference example 1: Thienoporphyrin synthesis
355 mg of 3,4-ethylenedioxythiophene, 255 mg of benzaldehyde, and 250 mL of dichloromethane were weighed in a 500 mL reaction vessel and stirred in a dry nitrogen atmosphere. Further, 60 mg of Lewis acid (BF ₃ .O (Et) ₂ ) was added and reacted at room temperature for 3 hours. Thereafter, 603 mg of dichlorodicyanobenzoquinone was added and stirred for 1 hour. The solvent was removed, the residue was redissolved in 80 mL of toluene, 655 mg of dichlorodicyanobenzoquinone was added, and the mixture was reacted for 1 hour while refluxing in a nitrogen atmosphere. After removing the solvent, the crystals were redissolved in 120 mL of dichloromethane, washed with water and brine three times, and dehydrated by adding sodium sulfate to the organic solvent layer.
Then, the target substance was fractionated by column chromatography using a methanol / dichloromethane solution.

Claims (10)

The polymer which has a repeating unit of Chemical formula (5) or Chemical formula (6).
(In the formulas (5) and (6), one of X1 and X2 is an alkoxy group which may have a substituent, an alkylene oxide group which may have a substituent, or a thiocyano which may have a substituent. A group, an amino group which may have a substituent, or a thioalkyl group which may have a substituent, the other being hydrogen, an alkyl group having 1 to 12 carbon atoms which may have a substituent, a substituent 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 a substituent Represents a thioalkyl group, or an alkylenedioxy group having 1 to 12 carbon atoms which may have a substituent in which X1 and X2 are linked, or 1 to 12 carbon atoms which may have a substituent. Represents an alkylenedithio group, and R represents a carbon number of 1 to 12. An alkyl group, an alkoxy group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 50 carbon atoms and a repeating unit of 1 to 50 carbon atoms, an optionally substituted phenyl group, and an optionally substituted heterocyclic ring Represents a condensed ring group which may have a group or a substituent, and n is 2 to 100.)   X1 and X2 may have 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, or a substituent. Represents an amino group or a thioalkyl group which may have a substituent, or an alkylenedioxy group having 1 to 12 carbon atoms which may have a substituent in which X1 and X2 are linked, or a substituent. The polymer according to claim 1, which represents an alkylenedithio group having 1 to 12 carbon atoms.   X1 and X2 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 X1 and X2 may be The polymer of Claim 1 or Claim 2 showing the C1-C12 alkylene dioxy group which may have the connected substituent.   The said R is a C1-C12 alkyl group, a C1-C12 alkoxy group, the phenyl group which may have a substituent, The heavy as described in any one of Claims 1-3. Coalescence.   A polymer composition comprising the polymer according to any one of claims 1 to 4 and a polymerization solvent. The coating film obtained by apply | coating the polymer composition of Claim 5. The manufacturing method of a polymer provided with the superposition | polymerization process of superposing | polymerizing the heterocyclic containing compound represented by following Chemical formula (1) in presence of a sulfonic acid compound anion or its salt.
(In formula (1), one of X1 and X2 is an alkoxy group that may have a substituent, an alkylene oxide group that may have a substituent, a thiocyano group that may have a substituent, or a substituent. An amino group that may have a substituent, or a thioalkyl group that may have a substituent, the other having hydrogen, an alkyl group having 1 to 12 carbon atoms that may have a substituent, and a substituent. 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 a thioalkyl group which may have a substituent Or an alkylenedioxy group having 1 to 12 carbon atoms which may have a substituent in which X1 and X2 are linked, or an alkylenedithio group having 1 to 12 carbon atoms which may have a substituent. R represents alkyl having 1 to 12 carbons , An alkoxy group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 50 carbon atoms having 1 to 50 repeating units, an optionally substituted phenyl group, an optionally substituted heterocyclic group, Alternatively, it represents a condensed ring group which may have a substituent, and W is represented by a hydroxyl group or the following chemical formula (2).
(X1 and X2 in Formula (2) are the same as in Chemical Formula (1).)   X1 and X2 may have 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, or a substituent. Represents an amino group or a thioalkyl group which may have a substituent, or an alkylenedioxy group having 1 to 12 carbon atoms which may have a substituent in which X1 and X2 are linked, or a substituent. The method for producing a polymer according to claim 7, which represents an alkylenedithio group having 1 to 12 carbon atoms.   X1 and X2 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 X1 and X2 may be The manufacturing method of the polymer of Claim 7 or Claim 8 showing the C1-C12 alkylenedioxy group which may have the connected substituent.   The R according to any one of claims 7 to 9, wherein R is 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. Manufacturing method of coalescence.