JP7142466B2 - Copolymer having 3,4-ethylenedioxythiophene structure - Google Patents

Description

The present invention relates to a self-doping polythiophene copolymer soluble in an organic solvent and a method for producing the same.

Conductive polymers with a poly(3,4-ethylenedioxythiophene) structure are used in flexible substrate circuits, transparent electrodes, capacitors, static removers, and hole injection/transport materials in organic EL devices and organic solar cells. . Since poly(3,4-ethylenedioxythiophene) is insoluble and infusible by itself, it is provided as an aqueous dispersion by combining PEDOT:PSS with polystyrene sulfonic acid (PSS). PSS functions as a dopant and water dispersant for poly(3,4-ethylenedioxythiophene). Also known is a self-doping poly(3,4-ethylenedioxythiophene) derivative in which a side chain having a sulfonic acid group is introduced into poly(3,4-ethylenedioxythiophene). For example, Patent Documents 1 to 3 disclose that a self-doping poly(3,4-ethylenedioxythiophene) derivative can be obtained by oxidative polymerization of a 3,4-ethylenedioxythiophene derivative having a sulfonic acid group in an aqueous solution. is disclosed. Self-doping poly(3,4-ethylenedioxythiophene) derivatives have sulfonic acid (salt) groups on the side chains of the polymer chain, so they are more dispersible in water than PEDOT:PSS, which is a composite of polymers. Excellent in nature.

U.S. Pat. No. 5,111,327 (1992). International Publication No. 2014/007299 (2014). International Publication No. 2015/194657 (2015).

Conductive polymers having a poly(3,4-ethylenedioxythiophene) structure are provided as aqueous dispersions. Manufacture by coating film formation of a polymer solution is desired. That is, there is a demand for a conductive polymer having a poly(3,4-ethylenedioxythiophene) structure that is soluble in organic solvents.

The inventors of the present invention made intensive studies to solve the above problems, and found that a 3,4-ethylenedioxythiophene derivative having a sulfonic acid alkyl ester group and 3,4-ethylene having an affinity substituent for an organic solvent A copolymer of a 3,4-ethylenedioxythiophene derivative soluble in organic solvents such as N,N-dimethylformamide and N,N-dimethylacetamide is produced by copolymerizing a dioxythiophene derivative with a sulfone derivative. The inventors have found that copolymers of self-doping 3,4-ethylenedioxythiophene derivatives that are soluble or dispersible in these organic solvents can be produced by hydrolyzing the acid ester groups, and have completed the present invention.

That is, the present invention provides the following general formula (1)

(Wherein, m ¹ represents an integer of 2 or 3. M ⁺ represents a hydrogen ion or a cation. R ¹ represents a hydrogen atom or a methyl group.) and a repeating unit represented by the following general formula (2)

{Wherein, Q ¹ is an aliphatic hydrocarbon group having 6 to 22 carbon atoms, the following general formula (3)

(Wherein, a is an integer of 2 to 4, b is an integer of 1 to 5, c is an integer of 1 to 4) and a polyoxymethylene group represented by the following general formula (4)

(In the formula, m ² represents an integer of 2 or 3, R ² represents a hydrogen atom or a methyl group, Z ² represents a 2,2-dimethylpropoxy group, 1-ethylpropoxy group, 3-methyl-2- butoxy group, 2-ethyl-1-butoxy group, 2-methyl-1-pentyloxy group, 3-methyl-2-pentyloxy group, 3,3-dimethyl-2-butoxy group, 2-methyl-3-hexyl oxy group, 2,4-dimethyl-3-pentyloxy group, 2-ethyl-1-hexyloxy group, 2-methyl-3-octyloxy group, 3-hydroxy-2,2-dimethylpropoxy group, 3-hydroxy -2,2-bis(hydroxymethyl)propoxy group, 3-hydroxy-2-hydroxymethyl-2-methylpropoxy group, 2,2-bis(hydroxymethyl)butoxy group, 2-hydroxymethyl-2-methylpentyloxy alkoxy group selected from 3-hydroxy-2,2,4-trimethylpentyloxy group and 2-ethyl-2-hydroxymethylhexyloxy group, alkylamino group having 12 or less carbon atoms, or 12 or less carbon atoms represents the dialkylamino group of.)
represents an organic group selected from the groups represented by }
The present invention relates to a thiophene copolymer containing a repeating unit represented by (hereinafter referred to as the thiophene copolymer of the present invention).

In addition, a composition comprising the thiophene copolymer of the present invention and an organic solvent, wherein the concentration of the thiophene copolymer is 0.2% by weight or more, and production using the composition. It relates to an electrode or electronic device characterized.

Furthermore, the following general formula (5)

(In the formula, m ¹ represents an integer of 2 or 3, R ¹ represents a hydrogen atom or a methyl group, and Z ¹ represents a hydrocarbon group having 3 or 4 carbon atoms, excluding a tert-butyl group.) and a repeating unit represented by the following general formula (2)

{Wherein, Q ¹ is an aliphatic hydrocarbon group having 6 to 22 carbon atoms, the following general formula (3)

(Wherein, a is an integer of 2 to 4, b is an integer of 1 to 5, c is an integer of 1 to 4) and a polyoxymethylene group represented by the following general formula (4)

(In the formula, m ² represents an integer of 2 or 3, R ² represents a hydrogen atom or a methyl group, Z ² represents a 2,2-dimethylpropoxy group, 1-ethylpropoxy group, 3-methyl-2- butoxy group, 2-ethyl-1-butoxy group, 2-methyl-1-pentyloxy group, 3-methyl-2-pentyloxy group, 3,3-dimethyl-2-butoxy group, 2-methyl-3-hexyl oxy group, 2,4-dimethyl-3-pentyloxy group, 2-ethyl-1-hexyloxy group, 2-methyl-3-octyloxy group, 3-hydroxy-2,2-dimethylpropoxy group, 3-hydroxy -2,2-bis(hydroxymethyl)propoxy group, 3-hydroxy-2-hydroxymethyl-2-methylpropoxy group, 2,2-bis(hydroxymethyl)butoxy group, 2-hydroxymethyl-2-methylpentyloxy alkoxy group selected from 3-hydroxy-2,2,4-trimethylpentyloxy group and 2-ethyl-2-hydroxymethylhexyloxy group, alkylamino group having 12 or less carbon atoms, or 12 or less carbon atoms represents the dialkylamino group of.)
Represents a group selected from the groups represented by }
A method for producing a thiophene copolymer, comprising contacting a sulfonate thiophene copolymer containing a repeating unit represented by (hereinafter referred to as the sulfonate thiophene copolymer of the present invention) with a base. (hereinafter referred to as the manufacturing method of the present invention).

Since the thiophene copolymer of the present invention is soluble in an organic solvent, it becomes possible to form a film by coating a conductive polymer without using water in the process of manufacturing electronic devices, etc., which should not tolerate water.

The present invention will be described in more detail below.

In the repeating unit represented by the general formula (1) (hereinafter referred to as the repeating unit (1) of the present invention), M ⁺ represents a hydrogen ion or a cation, but the cation is not particularly limited. represents, for example, an alkali metal ion or an unsubstituted or substituted ammonium ion. Examples of the alkali metal ion include, but are not limited to, lithium ion, sodium ion, potassium ion, and cesium ion. Examples of the unsubstituted or substituted ammonium ion include, but are not limited to, ammonium ion (NH ₄ ⁺ ), trimethylammonium ion, tetramethylammonium ion, diethylammonium ion, triethylammonium ion, tetraethylammonium ion, propyl ammonium ion, dipropylammonium ion, tripropylammonium ion, tetrapropylammonium ion, butylammonium ion, dibutylammonium ion, tributylammonium ion, tetrabutylammonium ion, bis(2-methylpropyl)ammonium ion, tris(2-methyl) propyl)ammonium ion, pentylammonium ion, dipentylammonium ion, hexylammonium ion, dihexylammonium ion, octylammonium ion, dioctylammonium ion, trioctylammonium ion, dioctylmethylammonium ion, 2-ethylhexylammonium ion, bis(2-ethylhexyl) ) ammonium ion, decyl ammonium ion, didecylmethyl ammonium ion, dodecyl ammonium ion, dodecyl dimethyl ammonium ion, didodecyl ammonium ion, didodecyl methyl ammonium ion, tetradecyl ammonium ion, hexadecyl ammonium ion, hexadecyl dimethylammonium ion, Octadecyl ammonium ion, dimethyloctadecyl ammonium ion and the like can be exemplified. Among these, ammonium ion (NH ₄ ⁺ ), trimethylammonium ion, tetramethylammonium ion, diethylammonium ion, triethylammonium ion, tetraethylammonium ion, propylammonium ion, dipropylammonium ion, tripropylammonium ion, tetrapropylammonium ion, butylammonium ion, dibutylammonium ion, tributylammonium ion, tetrabutylammonium ion, hexylammonium ion, dihexylammonium ion, octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, bis (2-Ethylhexyl) ammonium ion, decyl ammonium ion, dodecylammonium ion, dodecyldimethylammonium ion, tetradecylammonium ion, hexadecyl ammonium ion, hexadecyldimethylammonium ion, octadecylammonium ion or dimethyloctadecylammonium ion are preferred.

In general formula (1), m ¹ is preferably 2 because the thiophene copolymer of the present invention exhibits good electrical conductivity.

Among general formula (1), R ¹ is preferably a methyl group in that the thiophene copolymer of the present invention exhibits good conductivity.

In the repeating unit represented by the general formula (2) (hereinafter referred to as the repeating unit (2) of the present invention), the aliphatic hydrocarbon group having 6 to 22 carbon atoms represented by Q ¹ may be a linear may have one or more carbon-carbon unsaturated bonds, such as, but not limited to, hexyl group, 2-methylpentyl group, 3- methylpentyl group, 4-methylpentyl group, 2-ethylbutyl group, 3,3-dimethylbut-2-yl group, 1,2-dimethylbutyl group, cyclohexyl group, hex-5-en-1-yl group, hexa -1-yn-3-yl group, hex-5-yn-1-yl group, heptyl group, hept-2-yl group, 2-methylhex-3-yl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhex-2-yl group, 2,4-dimethylpent-3-yl group, cycloheptyl group, 2-methylcyclohexyl group, cyclohexylmethyl group, 2-cyclopentylethyl group, hept-6-ene-1 -yl group, 3-cyclohexenylmethyl group, hept-1-yn-3-yl group, hept-6-yn-1-yl group, octyl group, octa-2-yl group, octa-3-yl group, octa-4-yl group, 5-methylheptyl group, 5-methylhept-2-yl group, 5-methylhept-3-yl group, 6-methylhept-2-yl group, 2,3-dimethylhept-2-yl group, 2,5-dimethylhex-2-yl group, 2-ethylhexyl group, cyclooctyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 2-ethyl cyclohexyl group, 2-cyclohexylethyl group, 4-methylcyclohexylmethyl group, octa-1-en-3-yl group, octa-3-en-1-yl group, octa-5-en-1-yl group, octa -7-en-1-yl group, octa-1-yn-3-yl group, octa-7-yn-1-yl group, 3,5-dimethylhex-1-yn-3-yl group, nonyl group , non-2-yl group, non-3-yl group, non-4-yl group, non-5-yl group, 2-methyloct-3-yl group, 6-methyloctyl group, 3,5,5- trimethylhexyl group, 2-propylcyclohexyl group, 4-propylcyclohexyl group, 3-cyclohexylpropyl group, non-1-en-3-yl group, non-3-en-1-yl group, non-6-en- 1-yl group, nona-8- en-1-yl group, decyl group, deca-2-yl group, deca-4-yl group, deca-5-yl group, 3,7-dimethyloctyl group, 3,7-dimethyloct-3-yl group , 4-butylcyclohexyl group, menthyl group, 1-cyclohexylbutyl group, dec-1-en-3-yl group, dec-5-en-1-yl group, dec-9-en-1-yl group, 3 , 7-dimethyloct-6-en-1-yl group, deca-7-yn-1-yl group, deca-9-yn-1-yl group, 4-ethyloct-1-yn-3-yl group, undecyl group, undec-2-yl group, undec-3-yl group, undec-4-yl group, undec-5-yl group, undec-6-yl group, 4-pentylcyclohexyl group, 1-cyclohexylpentyl group, undec-10-en-1-yl group, undec-10-yn-1-yl group, dodecyl group, dodec-2-yl group, 2-butyloctyl group, cyclododecyl group, 4-cyclohexylcyclohexyl group, tridecyl group , tridec-2-yl group, tetradecyl group, tetradeca-2-yl group, tetradeca-7-yl group, 7-ethyl-2-methylundec-4-yl group, 2-hexyloctyl group, pentadecyl group, hexadecyl group, 2-hexyldecyl group, heptadecyl group, heptadecan-9-yl group, 2-methylhexadecyl group, octadecyl group, octadec-9-en-1-yl group, octadec-17-en-1-yl group, octa- Examples include 9,12-dien-1-yl group, nonadecyl group, icosanyl group, 2-octyldodecyl group, henicosanyl group and docosanyl group.

As the polyoxymethylene group represented by the general formula (3), the combination of a, b and c is (a, b, c) = (2, 1, 0), (2, 1, 1), ( 2,1,2), (2,1,3), (2,1,4), (2,2,0), (2,2,1), (2,2,2), (2, 2,3), (2,2,4), (2,3,0), (2,3,1), (2,3,2), (2,3,3), (2,3, 4), (2,4,0), (2,4,1), (2,4,2), (2,4,3), (2,4,4), (2,5,0) , (2,5,1), (2,5,2), (2,5,3), (2,5,4), (3,1,0), (3,1,1), ( 3,1,2), (3,1,3), (3,1,4), (3,2,0), (3,2,1), (3,2,2), (3, 2,3), (3,2,4), (3,3,0), (3,3,1), (3,3,2), (3,3,3), (3,3, 4), (3,4,0), (3,4,1), (3,4,2), (3,4,3), (3,4,4), (3,5,0) , (3,5,1), (3,5,2), (3,5,3), (3,5,4), (4,1,0), (4,1,1), ( 4,1,2), (4,1,3), (4,1,4), (4,2,0), (4,2,1), (4,2,2), (4, 2,3), (4,2,4), (4,3,0), (4,3,1), (4,3,2), (4,3,3), (4,3, 4), (4,4,0), (4,4,1), (4,4,2), (4,4,3), (4,4,4), (4,5,0) , (4,5,1), (4,5,2), (4,5,3), (4,5,4) (propane-1,3- An isomer mixture of a diyl structure and a propane-1,2-diyl structure may also be used). Among these combinations, (a, b, c) = (2, 1, 0), (2, 1, 1), (2, 1, 2), (2, 1, 3), (2,1,4), (2,2,0), (2,2,1), (2,2,2), (2,2,3), (2,2,4) , (2,3,0), (2,3,1), (2,3,2), (2,3,3), (2,3,4), (2,4,0), ( 2,4,1), (2,4,2), (2,4,3), (2,4,4), (2,5,0), (2,5,1), (2, 5,2), (2,5,3), (2,5,4), (3,1,0), (3,1,1), (3,1,2), (3,1, 3), (3, 1, 4), (3, 2, 0), (3, 2, 1), (3, 2, 2), (3, 2, 3), (3, 2, 4) , (3,3,0), (3,3,1), (3,3,2), (3,3,3), (3,3,4), (4,1,0), ( 4,1,1), (4,1,2), (4,1,3), (4,1,4) are preferred.

In the substituent represented by the general formula (4), the alkylamino group having 12 or less carbon atoms represented by Z ² is not particularly limited, but examples include methylamino group, ethylamino group, propylamino group, isopropylamino group, cyclopropylamino group, butylamino group, but-2-ylamino group, (2-methylpropyl)amino group, (2-methylprop-2-yl)amino group, cyclobutylamino group, pentylamino group, pent-2-ylamino group, (2-methylbutyl)amino group, (3-methylbutyl)amino group, (2-methylbut-2-yl)amino group, (2,2-dimethylpropyl)amino group, (3-methylbuta -2-yl)amino group, pent-3-ylamino group, (cyclobutylmethyl)amino group, cyclopentylamino group, hexylamino group, hex-2-ylamino group, hex-3-ylamino group, (2-methylpentyl) ) amino group, (3-methylpentyl) amino group, (4-methylpentyl) amino group, (2-ethylbutyl) amino group, (3,3-dimethylbut-2-yl) amino group, (3-methylpenta- 2-yl)amino group, cyclohexylamino group, heptylamino group, hept-2-ylamino group, (2-methylhex-3-yl)amino group, (3-methylhexyl)amino group, (4-methylhexyl)amino group, (5-methylhex-2-yl)amino group, (2,4-dimethylpent-3-yl)amino group, cycloheptylamino group, 2-methylcyclohexyl group, cyclohexylmethyl group, 2-cyclopentylethyl group, Octyl group, octa-2-ylamino group, octa-3-ylamino group, octa-4-ylamino group, (5-methylheptyl)amino group, (5-methylhept-2-yl)amino group, (5-methylhepta- 3-yl) amino group, (6-methylhept-2-yl) amino group, (2,3-dimethylhex-2-yl) amino group, (2,5-dimethylhex-2-yl) amino group, ( 2-ethylhexyl)amino group, cyclooctylamino group, (2,3-dimethylcyclohexyl)amino group, (2,5-dimethylcyclohexyl)amino group, (2,6-dimethylcyclohexyl)amino group, (2-ethylcyclohexyl) ) amino group, (2-cyclohexylethyl)amino group, (4-methylcyclohexylmethyl)amino group, nonylamino group, non-2-ylamino group, non-3-ylamino group , non-4-ylamino group, non-5-ylamino group, (2-methyloct-3-yl) amino group, (6-methyloctyl) amino group, (3,5,5-trimethylhexyl) amino group, ( 2-propylcyclohexyl)amino group, (4-propylcyclohexyl)amino group, (3-cyclohexylpropyl)amino group, decylamino group, dec-2-ylamino group, dec-4-ylamino group, dec-5-ylamino group, (3,7-dimethyloctyl)amino group, (3,7-dimethyloct-3-yl)amino group, (4-butylcyclohexyl)amino group, menthylamino group, (1-cyclohexylbutyl)amino group, undecyl amino group, undec-2-ylamino group, undec-3-ylamino group, undec-4-ylamino group, undec-5-ylamino group, undec-6-ylamino group, (4-pentylcyclohexyl)amino group, (1- cyclohexylpentyl)amino group, dodecylamino group, dodec-2-ylamino group, (2-butyloctyl)amino group, cyclododecylamino group and the like.

In the substituent represented by the general formula (4), the dialkylamino group having 12 or less carbon atoms represented by Z ² is not particularly limited, but examples include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, di(2-methylpropyl)amino group, dipentylamino group, di(2-methylbutyl)amino group, di(3-methylbutyl)amino group, di(2,2-dimethylpropyl)amino group, dihexylamino group, di(2-methylpentyl)amino group, di(3-methylpentyl)amino group, di(4-methylpentyl)amino group, di(2-ethylbutyl)amino group, N-ethylpropylamino group, N- methylbutylamino group, N-methylpentylamino group, N-ethylbutylamino group, N-propyl(but-2-yl)amino group, N-ethylcyclohexylamino group, N-methyloctylamino group, N-ethylheptyl An amino group and the like can be exemplified.

Among general formula (4), R ² is preferably a methyl group because the thiophene copolymer of the present invention exhibits good conductivity.

In general formula (4), m ² is preferably 2 in that the thiophene copolymer of the present invention exhibits good electrical conductivity.

Among general formula (4), Z ² is particularly preferably a 2,2-dimethylpropoxy group because the thiophene copolymer of the present invention exhibits good conductivity.

Q ¹ in the repeating unit (2) of the present invention is an aliphatic hydrocarbon group having 6 to 22 carbon atoms, a substituent represented by general formula (3), or represented by general formula (4). Among the substituents, the substituent represented by the general formula (4) is preferable because the thiophene copolymer of the present invention exhibits good electrical conductivity and is easy to control the solubility.

In the repeating unit represented by the general formula (5), Z ¹ represents a hydrocarbon group having 3 or 4 carbon atoms, excluding a tert-butyl group, and is not particularly limited, but specifically includes a propyl group and isopropyl group, prop-2-en-1-yl group, prop-2-yn-1-yl group, butyl group, isobutyl group, sec-butyl group, but-3-en-1-yl group, but-2- en-1-yl group, but-3-en-2-yl group, 2-methylprop-2-en-1-yl group, but-3-yn-1-yl group, but-2-yn-1- Examples include an yl group and a but-1-yn-3-yl group. A propyl group, an isopropyl group, a prop-2-en-1-yl group, a prop-2-yn-1-yl group, a butyl group, an isobutyl group, and a sec-butyl group are preferable in that raw materials are inexpensive.

By contacting the sulfonic acid ester thiophene copolymer of the present invention with a base, the sulfonic acid ester can be converted to a sulfonate, and the method for producing the thiophene copolymer of the present invention (hereinafter referred to as the production of the present invention). method) will be explained.

As a base that can be used, side reactions other than conversion of a sulfonate ester to a sulfonate are not remarkable, and the solubility of the thiophene copolymer of the present invention can be controlled and the physical properties of the conductive polymer of the present invention can be improved. There is no particular limitation as long as it does not cause significant damage. The optimum base differs depending on the combination of the substituent Z ¹ and Q ¹ of the repeating unit (2) of the present invention, and usable bases include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. Inorganic bases such as alkali metal hydroxides, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, or alkali metal halide salts, and organic compounds such as amines corresponding to said unsubstituted or substituted ammonium ions. A base can be used individually or in combination of 2 or more types. In terms of suppressing side reactions and improving the efficiency of hydrolysis, a method of using an alkali halide salt (publicly known literature: for example, Florian M. Koch et al., Chemistry-A European Journal, Vol. 17, pp. 3679-3692 (2011) ), Mori Hideharu et al., Macromolecules, 43:7021-7032 (2010), Christopher C. Kotoris et al., The Journal of Organic Chemistry, 63:8052-8057 (1998)), and tertiary amines (publicly known literature: for example, JF King et al., Journal of the American Chemical Society, Vol. 104, pp. 7108-7122 (1982), Maria Mahrova et al., Journal of Chemical & Engineering Data, Vol. 57, 241-248 (2012)) is preferred. Examples of alkali metal halide salts include LiI, LiBr, LiCl, NaI, NaBr, NaCl, KI, KBr and KCl. Tertiary amines include trimethylamine, triethylamine, tripropylamine, butyldimethylamine, tributylamine, hexyldimethylamine, dodecyldimethylamine, hexadecyldimethylamine, dimethyloctadecylamine N,N'-dimethylpiperazine, 1,8- Diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane and the like can be mentioned.

When hydrolyzing using an alkali metal halide salt or a tertiary amine, the amount of the alkali metal halide salt or tertiary amine to be used is not particularly limited, and it is appropriate considering the chemical structure and the rate of hydrolysis. The amount to be added may be determined, but it is sufficient to use 0.1 to 100 equivalents with respect to the molar amount of the sulfonate group of the sulfonate thiophene copolymer of the present invention. It is preferred to use 0.5 to 50 equivalents. The production method of the present invention may be carried out in a solvent. Examples of the solvent include hydrocarbons such as hexane, cyclohexane and toluene, ethers such as diethyl ether, tetrahydrofuran (THF), 1,4-dioxane and cyclopentyl methyl ether (CPME), N,N-dimethylformamide (DMF), N, Amides such as N-dimethylacetamide (DMAc), halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, acetone, ketones such as 2-butanone (MEK), methanol, ethanol, propanol, isopropyl alcohol, butanol, Alcohols such as ethylene glycol, 2-methoxyethanol, and water can be mentioned, and these can be used alone or in combination of two or more. There is no limit to the amount of reaction solvent.

The reaction temperature at which the production method of the present invention is carried out can usually be appropriately selected from the range of 0 to 150°C, preferably room temperature to 120°C from the viewpoint of reaction efficiency.

In the thiophene copolymer produced by the production method of the present invention, M ⁺ in the general formula (1) is naturally determined by the selection of the base during hydrolysis, but by further performing an ion exchange treatment, hydrogen ion , alkali metal ions, or unsubstituted or substituted ammonium ions, and may be one type of cation or multiple types of cations.

The method for purifying the thiophene copolymer of the present invention is not particularly limited. be able to.

The thiophene copolymer of the present invention is characterized by having a solubility of 0.2% by weight or more in an organic solvent. The thiophene copolymer of the present invention contains the repeating unit (1) of the present invention and the repeating unit (2) of the present invention. different ratios. As the proportion of the repeating unit (1) increases, the conductivity and hygroscopicity tend to increase and the solubility in organic solvents tends to decrease. As the proportion of the repeating unit (2) increases, the conductivity and hygroscopicity tend to decrease and the solubility in organic solvents tends to increase. The composition ratio (x/y): number of repeating units (1) (x)/repeating The number (y) of the units (2) is not particularly limited, but is generally 0.1/99.9 to 80/20, preferably 5/95 to 50/50 from the viewpoint of the balance between conductivity and solubility. good.

The conductive polymer of the present invention may contain additives in order to exhibit conductivity, solubility, dispersibility, hygroscopicity, acidity, film-forming properties, coating properties, etc. suitable for use. Additives include polyacrylic acid, polymethacrylic acid, polyvinylphosphonic acid, polyvinylsulfonic acid, polystyrenesulfonic acid, Nafion (TM), polyvinyl alcohol and its derivatives, poly(1-vinylpyrrolidin-2-one), poly( 3-vinyl-1,3-oxazolidin-2-one), poly(1-vinyl-1,3-imidazolidin-2-one), polyacrylic acid, polymethacrylic acid, polyvinylphosphonic acid, polyvinylsulfonic acid, poly Acrylamide, poly(alkylacrylamide)s, celluloses, fullerenes, carbon nanotubes, dimethyl sulfoxide, DMF, ethylene glycol, oligo(poly)ethylene glycol, butanediol, oligo(poly)tetramethylene glycol, 2-methoxyethanol, Examples include 2-butoxyethanol, which may be used singly or in combination. The (total) amount of the additive may be 50% or less based on the weight of the thiophene copolymer of the present invention, and is preferably 10% or less in order to easily exhibit the characteristics of the thiophene copolymer.

A conductive polymer solution can be prepared by dissolving or dispersing the conductive polymer of the present invention in a solvent. Solvents that can be used include hydrocarbons such as hexane, cyclohexane, and toluene, ethers such as diethyl ether, THF, 1,4-dioxane, and CPME, amides such as DMF and DMAc, dichloromethane, chloroform, 1,2-dichloroethane, and the like. acetone, ketones such as MEK, alcohols such as methanol, ethanol, propanol, isopropyl alcohol and butanol, and these can be used alone or in combination of two or more. A solvent containing 50% by volume or more of DMF or DMAc is preferably used because of its excellent solubility, dispersibility, and film-forming properties.

Although the concentration of the conductive polymer solution is not particularly limited, it is usually 50% by weight or less, preferably 20% by weight or less from the viewpoint of ease of handling.

When preparing the conductive polymer solution by dissolving or dispersing the conductive polymer of the present invention in a solvent, mixing can be performed using a magnetic stirrer tip or a stirring blade of a mechanical stirrer. , a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, or the like can be appropriately combined for mixing. It is preferable that the temperature during preparation is adjusted to approximately 100° C. or lower.

The shape of the conductive polymer of the present invention when used in an electrode or an electronic device is not particularly limited, and can be selected as necessary from a film-like form, a film-like form, a particle-like form, a fiber-like form, etc. that adhere to a substrate. When it is formed into a film, it can be obtained by coating the conductive polymer solution on a substrate and drying it. The material and shape of the substrate are not particularly limited as long as a film can be formed thereon. Examples of substrate materials include glass, ceramics, silica, inorganic substrates such as alumina, polystyrene, polyester, polyacrylate, polycarbonate, polyurethane, and the like. Examples include polymer base materials such as polyamide, polyimide and cellulose, and resin base materials such as epoxy resin, phenol resin and urea resin. The shape of the base material can be freely selected from dense membranes, compression-molded membranes, porous membranes, particles, woven fabrics, non-woven fabrics, and the like. The coating method is not particularly limited, and examples thereof include casting, dipping, bar coating, roll coating, gravure coating, flexographic printing, spray coating, and inkjet printing. The film thickness is not particularly limited, but is usually about 0.01 to 200 μm. Drying of the film can be performed in the atmosphere or in an inert gas atmosphere such as nitrogen gas under normal pressure or reduced pressure, and the temperature during drying is generally in the range of room temperature to 100 ° C. It should be carried out over several hours to several days. can be done. The conductivity of the formed film is not particularly limited and can be widely controlled depending on the application, but the electrical conductivity is generally about 0.001 to 500 S·cm ⁻¹ .

The conductive polymer of the present invention and the electrodes and electronic devices produced therefrom are, for example, antistatic materials, flexible substrate circuits, transparent electrodes for displays, electrodes for photoelectric conversion elements, solid electrolytes for solid electrolytic capacitors, and solid electrolytes for aluminum solid electrolytic capacitors. It can be applied to separators, organic semiconductors, static removers, hole injection/transport materials in organic EL elements and organic solar cells, and the like.

Next, the method for producing the thiophene copolymer of the present invention will be described.

The raw material monomers used for the production of the thiophene copolymer of the present invention can be synthesized according to the following synthetic route 1 and, if necessary, synthetic route 2. Alcohol (6) having a 3,4-ethylenedioxythiophene structure, which is a common starting material in Synthetic Route 1 and Synthetic Route 2, is available from Sigma-Aldrich, Alfa Chemistry, and the like. For example, L. Zhang et al., Journal of Heterocyclic Chemistry, Vol. 51, pp. 1277-1281 (2014), GG Rodriguez-Calero et al., Electrochimica Acta, Vol. 167, pp. 55-60 (2015), Awano et al., Patent No. 6201595 (2017), M. Sassi et al., Advanced Functional Materials, Vol. 26, pp. 5240-5246 (2016), etc.).

Synthetic route 1 will be described.
(Synthetic route 1)

(Wherein, m represents an integer of 2 or 3. (M ¹ ) ⁺ represents an acceptable counter cation of the sulfonate. R represents a hydrogen atom or a methyl group. Z represents a propoxy group. , isopropoxy group, butoxy group, 1-methylpropoxy group, 2-methylpropoxy group, 2,2-dimethylpropoxy group, 1-ethylpropoxy group, 3-methyl-2-butoxy group, 2-ethyl-1-butoxy group, 2-methyl-1-pentyloxy group, 3-methyl-2-pentyloxy group, 3,3-dimethyl-2-butoxy group, 2-methyl-3-hexyloxy group, 2,4-dimethyl-3 -pentyloxy group, 2-ethyl-1-hexyloxy group, 2-methyl-3-octyloxy group, 3-hydroxy-2,2-dimethylproxy group, 3-hydroxy-2,2-bis(hydroxymethyl) propoxy group, 3-hydroxy-2-hydroxymethyl-2-methylpropoxy group, 2,2-bis(hydroxymethyl)butoxy group, 2-hydroxymethyl-2-methylpentyloxy group, 3-hydroxy-2,2, an alkoxy group selected from a 4-trimethylpentyloxy group and a 2-ethyl-2-hydroxymethylhexyloxy group, an alkylamino group having 12 or less carbon atoms, or a dialkylamino group having 12 or less carbon atoms, X is chlorine; atom, bromine atom, or iodine atom.)
In Synthetic Route 1, a sulfonate having a 3,4-ethylenedioxythiophene structure is obtained by adding a cyclic sultone (7) to the alcoholate anion produced by reacting the alcohol (6) with an anionizing agent. (8) can be synthesized. The anionizing agent that can be used is not particularly limited as long as it can anionize the alcohol and suppress side reactions, but specific examples include sodium hydride, phenyllithium, lithium diisopropylamide, and the like. The reaction for synthesizing the sulfonate (8) from the alcohol (6) proceeds smoothly in an organic solvent. Examples of the organic solvent include hexane, cyclohexane, toluene, diethyl ether, THF and 1,4-dioxane , CPME, DMF, or DMAc can be used singly or in combination of two or more. The reaction temperature can be appropriately selected from the range of -80 to 150°C, or may be changed stepwise within the range of -80 to 150°C.

In synthetic route 1, a commercially available cyclic sultone can be used, and specific examples include 1,3-propanesultone, 1,4-butanesultone, 1-methyl-1,3-propanesultone, and the like. . The counter cation (M ¹ ) ⁺ is naturally determined by the anionizing agent used, e.g. lithium ion, sodium ion, etc., but other acceptable counter cations as sulfonates for solubility control or purification. It can be converted to a counter cation, such as by an ion exchange treatment.

In Synthetic Route 1, sulfonate (8) having a 3,4-ethylenedioxythiophene structure is reacted with a chlorinating agent to produce the corresponding sulfonyl chloride (9), followed by general formula HZ Sulfonic acid ester (11) can be synthesized by reacting the compound represented by (10). When the sulfonyl chloride (9) is produced from the sulfonate (8), the chlorinating agent is not particularly limited as long as the sulfonyl chloride (9) can be produced. Thionyl chloride, oxalyl dichloride, or phosphorus pentachloride is preferred, and oxalyl dichloride is particularly preferred, from the viewpoint of excellent economy. When the chlorinating agent is used, the reaction can proceed smoothly by using an organic solvent. Examples of the organic solvent include hydrocarbons such as hexane, cyclohexane, and toluene, diethyl ether, THF, 1,4-dioxane, and CPME. ethers such as DMF, amides such as DMAc, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc., and these can be used alone or in combination of two or more. The reaction temperature can be appropriately selected from the range of -20 to 150°C. Without purifying the sulfonyl chloride (9) produced in the reaction solution, the sulfonate ester (11) can be produced by adding HZ (10) thereto. If an organic base such as triethylamine or pyridine is added at this time, the reaction proceeds smoothly. The resulting sulfonic acid ester (11) can be purified using column chromatography or the like.

In Synthetic Route 1, a dihalosulfonate ester (12) can be produced by adding a halogenating agent to the sulfonate ester (11) to replace the hydrogen atom on the thiophene ring with a chlorine atom, a bromine atom, or an iodine atom. As the halogenating agent, a known halogenating agent can be used, such as Cl ₂ , Br ₂ , I ₂ , sulfuryl dichloride, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, or phosphorus pentachloride. I can give an example. The reaction between the sulfonate ester (11) and the halogenating agent may be carried out in a solvent, specifically hydrocarbons such as hexane, cyclohexane and toluene, diethyl ether, THF, 1,4-dioxane, CPME and the like. and halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, and these can be used alone or in combination of two or more. A catalytic amount of DMF may be added as necessary. The reaction temperature can usually be selected appropriately from the range of -20 to 100°C. The resulting dihalosulfonic acid ester (12) can be purified using column chromatography or the like.

Next, the synthetic route 2 will be explained.
(Synthetic route 2)

{In the formula, L represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a tosyl group, or a triflate group. Q is an aliphatic hydrocarbon group having 6 to 22 carbon atoms, and general formula (3)

(In the formula, a is an integer of 2 to 4, b is an integer of 1 to 5, and c is an integer of 1 to 4.)
represents a group selected from X has the same meaning as above. }
In Synthetic Route 2, alcohol (6) is reacted with an anionizing agent to form an alcoholate anion, and LQ (13) is added to obtain ether (14) having a 3,4-ethylenedioxythiophene structure. ) can be synthesized. The anionizing agent can be selected from the anionizing agents described in Synthesis Route 1 and used. The reaction for synthesizing the ether (14) from the alcohol (6) proceeds smoothly in an organic solvent, and examples of the organic solvent include hexane, cyclohexane, toluene, diethyl ether, THF, 1,4-dioxane, CPME, DMF, DMAc, or the like can be used alone or in combination of two or more. The reaction temperature can be appropriately selected from the range of -80 to 150°C, or may be changed stepwise within the range of -80 to 150°C.

In Synthetic Route 2, dihaloether (15) can be produced by adding a halogenating agent to ether (14) to replace the hydrogen atom on the thiophene ring with a chlorine atom, a bromine atom, or an iodine atom. As the halogenating agent and reaction conditions, the same halogenating agent and reaction conditions as in the production of the dihalosulfonate ester (12) from the sulfonate ester (11) in Synthesis Route 1 can be applied.

Next, the method for producing the thiophene copolymer of the present invention will be described. The thiophene copolymer of the present invention can be produced by appropriately combining and polymerizing the sulfonate (11), the dihalosulfonate (12), the ether (14) and the dihaloether (15). The polymerization method is not particularly limited as long as side reactions other than polymerization can be suppressed. Various coupling reactions known in the synthesis of polythiophenes can be used, and the polymerization method should be selected with reference to known literature. Known literature includes, for example, "Handbook of Thiophene-based Materials: Volume 1" (Chapter 2, John Wiley & Sons Ltd. 2009), Shota Tanaka et al. A review article such as TCI Mail Contributed Paper No. 153 (2012) can be mentioned. Migita-Kosugi-Stille coupling using organotin compounds, including oxidative polymerization that has been carried out for a long time (publicly known literature: JK Stille, Angewandte Chemie, International Edition in English, Vol. 25, pp. 508-524 (1986) )), Suzuki-Miyaura coupling, Grignard Metathesis (GRIM) polymerization using exchange reaction between a Grignard reagent and a halogen atom, and the like can be applied. Other combinations of sulfonate (11) and dihaloether (15), sulfonate (11) and dihalosulfonate (12), or dihalosulfonate (12) and ether (14) using palladium catalyzed C —H direct arylation polymerization (published literature: A. Kumar et al., Polymer Chemistry, Polymer Chemistry, vol. 1, pp. 286-288 (2010), Q. Wang et al., Journal of The American Chemical Society, vol. 132, pp. 11420-11421 (2010), Y. Fujinami et al., ACS Macro Letters, 1:67-70 (2012), H. Zhao et al., Macromolecules, 45:7783-7790 (2012), J. Kuwabara et al., Polymer Chemistry , 6:891-895 (2015), M. Wakioka et al., Macromolecules, 48:8382-8388 (2015), K. Fujita et al., Macromolecules, 49:1259-1269 (2016)), etc. Applicable.

For the thiophene copolymer of the present invention, production route 1 using oxidative polymerization and production route 2 using GRIM polymerization are preferably used because they are simple and can suppress side reactions.

First, manufacturing route 1 will be described.
(Manufacturing route 1)

(Wherein, m ¹ , M ⁺ , and R ¹ have the same meanings as in the general formula (1) above. m ² , R ² and Z ² have the same meanings as in the general formula (4) above. Q has the same meaning as in general formula (14) above, Q ¹ has the same meaning as in general formula (2) above, Z ¹ has the same meaning as in general formula (2) above It has the same meaning as in general formula (5), x and y represent the number of repetitions in [ ], and x/y (composition ratio) ranges from 0.1/99.9 to 80/20.)
In production route 1, sulfonate ester (11a) and sulfonate ester (11b) or ether (14) are oxidatively polymerized to form sulfonate thiophene copolymer (16), and then hydrolyzed to thiophene copolymerization. Produce coalescence (17).

As a method of oxidative polymerization in production route 1, a known electrolytic oxidative polymerization method or chemical oxidative polymerization method can be appropriately used. A specific method of electrolytic oxidation polymerization is, for example, "New Polymer Experimental Science 3: Synthesis and Reaction of Polymers (2)-Synthesis of Condensed Polymers" (Edited by the Society of Polymer Science, Kyoritsu Shuppan 1996, 331-339 page), etc. Specific methods of chemical oxidation polymerization are described, for example, in Satoru Amou et al., Journal of Polymer Science Part A: Polymer Chemistry, Vol. 37, pp. 1943-1948 (1999); It is advisable to refer to known documents such as page 286 (2013).

Next, manufacturing route 2 will be described.
(Manufacturing route 2)

(Wherein, m ¹ , M ⁺ , and R ¹ have the same meanings as in the general formula (1) above. m ² , R ² and Z ² have the same meanings as in the general formula (4) above. Q has the same meaning as in general formula (15), Q ¹ has the same meaning as in general formula (2), Z ¹ has the same meaning as has the same meaning as the general formula (5), and general formulas (16) and (17) have the same meaning as the general formulas (16) and (17).)
In production route 2, a dihalosulfonate ester (12a) and a dihalosulfonate ester (12b) or a dihaloether (15) are GRIM-polymerized to form a sulfonate thiophene copolymer (16), followed by hydrolysis to thiophene copolymerization. Produce coalescence (17).

As the method of GRIM polymerization in production route 2, methods disclosed in known documents and the like can be applied. A specific method of GRIM polymerization is described, for example, in R.M. S. Loewe et al., Advanced Materials, 11:250-253 (1999); S. Loewe et al., Macromolecules, 34:4324-4333 (2001), M.; C. Iovu et al., Macromolecules, 38:8649-8656 (2005); Miyakoshi et al., Journal of the American Chemical Society, Vol.

The sulfonate ester thiophene copolymer (16) obtained by production route 1 or production route 2 can be purified by combining operations such as precipitation purification, dialysis, ultrafiltration purification, ion exchange treatment and extraction. Subsequently, the thiophene copolymer (17) is obtained by using the production method of the present invention, and the obtained thiophene copolymer (17) is subjected to precipitation purification, dialysis, ultrafiltration purification, ion exchange treatment, extraction, and the like. Can be refined by combining operations. Further, when dissolving or dispersing the sulfonate thiophene copolymer (16) or thiophene copolymer (17) in a solvent, mixing can be performed using a magnetic stirrer tip or a stirring blade of a mechanical stirrer. In addition to ultrasonic irradiation, it is preferable to appropriately combine and mix treatments using a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, or the like. It is preferable that the temperature during preparation is adjusted to approximately 100° C. or lower.

The sulfonic acid ester thiophene copolymer (16) and/or the thiophene copolymer (17) obtained by the oxidation polymerization method tend to aggregate due to progress of doping during the polymerization process, and are not necessarily soluble in organic solvents. Also, in the sulfonic acid ester thiophene copolymer (16) and/or the thiophene copolymer (17) obtained by polymerization by various coupling reactions, doping proceeds due to the influence of oxygen in the air, etc., so that they easily aggregate. . In such a case, for example, by performing a dedoping treatment such as adding a reducing agent such as hydrazine to the dispersed solution of the highly doped sulfonate thiophene copolymer (16) or thiophene copolymer (17), The sulfonate ester thiophene copolymer of the present invention and/or the thiophene copolymer of the present invention that are soluble in organic solvents can be obtained.

The molecular weights of the sulfonate thiophene copolymer of the present invention and the thiophene copolymer of the present invention can be indicated according to the measurement method such as weight average molecular weight, number average molecular weight, viscosity average molecular weight, and the like. The weight-average molecular weight (Mw) is preferably from 1,000 to 1,000,000, and more preferably from 2,000 to 500,000 from the viewpoint of polymer property control and processability. Although the molecular weight distribution (Mw·Mn ⁻¹ ) is not particularly limited, it is preferably in the range of approximately 1 to 50, more preferably in the range of 1 to 10 from the viewpoint of uniformity of the polymer. As a method for calculating the molecular weight, known methods such as a gel permeation chromatography (GPC) method in which standard samples such as polystyrene and polyethylene glycol are used for conversion, a viscosity method, and a light scattering method can be used.

EXAMPLES The present invention will be described in more detail below with reference examples and examples, but the present invention is not limited to these.

The molecular weight of the obtained polymer was determined from the results of gel permeation chromatography (GPC). The GPC system is GL Science GL-7400 (detector: GL-7456, columns (4): TSKgel Super H5000, H4000×2, H2000, column temperature: 40° C., developing solvent: 0.01 M LiCl DMF solution , standard polystyrene conversion) was used.

Reference example-1
Synthesis of isopropyl 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxy-2-yl)methoxy]-1-methylpropanesulfonate (11a-1)

Sodium 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (30 mmol) in THF/chloroform (=1/1 ( v/v)) was dissolved in 90 mL of mixed solvent, 5 drops of DMF were added, 3.00 mL (36.7 mmol) of oxalyl dichloride was slowly added in an ice bath, and the mixture was stirred for 2 hours. After the reaction, the reaction solution was concentrated to obtain 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonyl chloride.

Subsequently, 2.80 mL (36.5 mmol) of isopropanol and 6.50 mL (46.6 mmol) of triethylamine were dissolved in 60 mL of chloroform. , and stirred for 2 hours. After the reaction, the reaction solution was washed with water, and the organic layer was dehydrated with magnesium sulfate and concentrated. By purifying this by silica gel column chromatography (hexane/ethyl acetate = 3/1 (1% triethylamine added)), 7.33 g of colorless liquid (11a-1) was obtained (yield: 69.7% ).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 1.41 (6H, d, J = 6.3 Hz), 1.42 (3H, d, J = 6.9 Hz), 1.78-1 .83 (1H, m), 2.31-2.40 (1H, m), 3.24-3.34 (1H, m), 3.58-3.74 (4H, m), 4.05 (1H, ddd, J = 11.6Hz, 7.3Hz, 5.0Hz), 4.22 (1H, dd, J = 11.6Hz, 2.2Hz), 4.27-4.32 (1H, m ), 4.92-5.01 (1H, m), 6.33 (2H, s).

Reference example-2
Synthesis of isopropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12a-1)

3.76 g (10.7 mmol) of (11a-1) synthesized by the method of Reference Example-1 was dissolved in 50 mL of THF, and 4.01 g (22.5 mmol) of N-bromosuccinimide was added thereto under an ice bath. Stir at room temperature for 2 hours. After the reaction, the mixture was diluted with chloroform and washed with water and saturated aqueous sodium hydrogencarbonate solution, and the organic layer was dehydrated with magnesium sulfate and concentrated. This was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 (1% triethylamine added) to obtain 5.02 g of colorless liquid (12a-1) (yield: 92.0%). .

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 1.42 (6H, d, J = 6.2 Hz), 1.43 (3H, d, J = 5.5 Hz), 1.74-1 .82 (1H, m), 2.30-2.39 (1H, m), 3.23-3.34 (1H, m), 3.59-3.78 (4H, m), 4.08 ~4.15 (1 H, m), 4.29-4, 37 (2 H, m), 4.92-5.02 (1 H, m).

Reference example - 3
Synthesis of 2-methylpropyl 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxy-2-yl)methoxy]-1-methylpropanesulfonate (11a-2)

Sodium 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (30 mmol) was dissolved in 45 mL of THF, and DMF was added to 5 mL. 3.00 mL (36.7 mmol) of oxalyl dichloride was slowly added in an ice bath and stirred for 2 hours. After the reaction, the reaction solution was concentrated to obtain 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonyl chloride.

Subsequently, 3.40 mL (36.8 mmol) of 2-methyl-1-propanol and 6.50 mL (46.6 mmol) of triethylamine were dissolved in 60 mL of THF, and 60 mL of the THF solution of the sulfonic acid chloride synthesized above was slowly added thereto. It was added dropwise and stirred for 2 hours under an ice bath. After the reaction, the reaction solution was washed with water, and the organic layer was dehydrated with magnesium sulfate and concentrated. By purifying this by silica gel column chromatography (hexane/ethyl acetate = 3/1 (1% triethylamine added)), 8.85 g of colorless liquid (11a-2) was obtained (yield: 81.0% ).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.98 (6H, d, J = 6.7 Hz), 1.44 (3H, d, J = 6.9 Hz), 1.76-1 .85 (1H, m), 1.98-2.08 (1H, m), 2.32-2.40 (1H, m), 3.59-3.74 (4H, m), 3.99 (2H, d, J = 6.6Hz), 4.05 (1H, ddd, J = 11.6Hz, 7.4Hz, 4.2Hz), 4.22 (1H, dd, J = 11.6Hz, 2 .2 Hz), 4.27-4.32 (1 H, m), 6.33 (2 H, s).

Reference example - 4
Synthesis of 2-methylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12a -2)

8.85 g (24.3 mmol) of (11a-2) synthesized by the method of Reference Example-3 was dissolved in 120 mL of THF, and 9.09 g (51.1 mmol) of N-bromosuccinimide was added under an ice bath. Stir at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate = 3/1 (1% triethylamine added) to obtain 11.9 g of colorless liquid (12a-2) (yield: 93.0%). 8%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.99 (6H, d, J = 6.8 Hz), 1.45 (3H, d, J = 6.9 Hz), 1.77-1 .86 (1H, m), 1.99-2.09 (1H, m), 2.31-2.40 (1H, m), 3.31-3.41 (1H, m), 3.60 ~3.78 (4H, m), 3.99 (2H, d, J = 6.5Hz), 4.08-4.15 (1H, m), 4.29-4.37 (2H, m) .

Reference example-5
Synthesis of 1-methylpropyl 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (11a-3)

Sodium 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (10 mmol) was dissolved in 30 mL of THF, and DMF was added to 5 mL. 1.00 mL (12.2 mmol) of oxalyl dichloride was slowly added in an ice bath and stirred for 2 hours. After the reaction, the reaction solution was concentrated to obtain 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonyl chloride.

Subsequently, 1.40 mL (15.3 mmol) of 2-butanol and 2.10 mL (15.1 mmol) of triethylamine were dissolved in 20 mL of THF. The mixture was stirred for 2 hours under a bath. After the reaction, the reaction solution was washed with water, and the organic layer was dehydrated with magnesium sulfate and concentrated. By purifying this by silica gel column chromatography (hexane/ethyl acetate = 3/1 (1% triethylamine added)), 2.51 g of colorless liquid (11a-3) was obtained (yield: 68.8% ).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.97 (3H, t, 7.5 Hz), 1.40 (3H, d, J = 6.3 Hz), 1.43 (3H, d , J = 6.9 Hz), 1.62 to 1.87 (1H, m), 2.32 to 2.41 (1H, m), 3.25 to 3.34 (1H, m), 3.58 ~3.77 (4H, m), 4.04 (1H, ddd, J = 11.6Hz, 7.4Hz, 5.3Hz), 4.22 (1H, dd, J = 11.6Hz, 2.2Hz) ), 4.27-4.32 (1 H, m), 4.75-4.82 (1 H, m), 6.33 (2 H, s).

Reference example-6
Synthesis of 1-methylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12a -3)

1.14 g (3.19 mmol) of (11a-3) synthesized by the method of Reference Example-5 was dissolved in 120 mL of THF, and 1.19 g (6.71 mmol) of N-bromosuccinimide was added under an ice bath. Stir at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 (1% triethylamine added) to obtain 1.57 g of colorless liquid (12a-3) (yield: 94.0%). 0%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.98 (3H, t, 7.4 Hz), 1.40 (3H, d, J = 6.3 Hz), 1.44 (3H, d , J = 6.9 Hz), 1.63 to 1.84 (3H, m), 2.32 to 2.40 (1H, m), 3.24 to 3.34 (1H, m), 3.60 ~3.78 (4H,m), 4.08-4.15 (1H,m), 4.29-4.36 (2H,m), 4.75-4.83 (1H,m).

Reference example - 7
Synthesis of 2,2-dimethylpropyl 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (11b-1)

793 mg (18.0 mmol) of sodium hydride (55%) was washed with hexane, dried in vacuo, added with 15 mL of DMF, and treated with 2-hydroxymethyl-2,3-dihydrothieno[3,4-b][1, 4] 15 mL of a DMF solution of 2.58 g (15.0 mmol) of dioxin (hereinafter referred to as alcohol (6)) was slowly added, and the mixture was stirred at room temperature for 15 minutes. After raising the temperature to 60° C. and stirring for 1 hour, 15 mL of a DMF solution of 1.60 mL (15.0 mmol) of 1-methyl-1,3-propanesultone was slowly added, followed by stirring at 60° C. for 2 hours. After the reaction, DMF was distilled off under reduced pressure to obtain 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfone as a brown solid. Sodium acid was obtained. It was used for the next reaction without purification.

¹ H-NMR (400 MHz, D ₂ O, ppm), δ: 1.20 (3H, d, J=6.9 Hz), 1.55-1.64 (1H, m), 2.10-2. 18 (1H, m), 2.84-2.94 (1H, m), 3.56-3.73 (4H, m), 4.02 (1H, dd, J = 12.0, 6.8Hz ), 4.21 (1H, dd, J=12.0, 2.3 Hz), 4.33-4.38 (1H, m), 6.43 (2H, s).

Next, the sodium sulfonate synthesized above was dissolved in 45 mL of a mixed solvent of THF/chloroform (=1/1 volume ratio). Two drops of DMF were added thereto, and 1.47 mL (18.0 mmol) of oxalyl dichloride was slowly added in an ice bath, followed by stirring for 2 hours. The reaction solution was concentrated to obtain 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonic acid chloride.

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 1.63 (3H, d, J = 6.8 Hz), 1.88-1.96 (1H, m), 2.50-2.59 (1H, m), 3.63-3.78 (4H, m), 3.79-3.89 (1H, m), 4.05 (1H, ddd, J = 11.7, 7.2, 5.8 Hz), 4.22 (1H, dd, J=11.7, 2.2 Hz), 4.28-4.33 (1H, m), 6.34 (2H, s).

Subsequently, 1.59 g (18.0 mmol) of 2,2-dimethylpropanol and 3.14 mL (22.5 mmol) of triethylamine were dissolved in 30 mL of chloroform, and 30 mL of the chloroform solution of the sulfonyl chloride synthesized above was slowly added thereto. It was added dropwise and stirred for 2 hours under an ice bath. The organic layer was washed with water, dried over magnesium sulfate, and concentrated. This was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 volume ratio, triethylamine added at 1%) to obtain 4.73 g (12.5 mmol) of colorless liquid (11b-1). rate: 83.4%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.99 (9 H, s), 1.45 (3 H, d, J = 6.9 Hz), 1.77 to 1.85 (1 H, m ), 2.33-2.41 (1H, m), 3.32-3.42 (4H, m), 3.58-3.74 (1H, m), 3.87 (2H, s), 4.05 (1H, ddd, J = 11.7, 7.4, 4.3 Hz), 4.22 (1H, dd, J = 11.7, 2.2 Hz), 4.27 to 4.32 ( 1H, m), 6.33 (2H, s).

EI-MS, m/z: 378 (M) ⁺ , 363 (M-CH ₃ ) ⁺ , 322, 307 (M-CH ₂ C(CH ₃ ) ₃ ) ⁺ , 269, 227, 199, 185, 172, 154, 141, 137, 125, 109, 100.

Reference example - 8
Synthesis of 2,2-dimethylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12b-1)

4.73 g (12.5 mmol) of (11b-1) synthesized by the method of Reference Example-7 was dissolved in 60 mL of THF, 4.68 g (26.3 mmol) of N-bromosuccinimide was added, and the mixture was stirred under an ice bath for 2 hours. Stirred. After adding 100 mL of ethyl acetate, the mixture was washed with saturated brine, and the organic layer was dried over magnesium sulfate and concentrated. This was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 volume ratio, triethylamine added at 1%) to obtain 6.39 g (11.9 mmol) of colorless liquid (12b-1). rate: 95.3%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.99 (9 H, s), 1.45 (3 H, d, J = 6.9 Hz), 1.77 to 1.86 (1 H, m ), 2.32-2.41 (1H, m), 3.32-3.42 (1H, m), 3.60-3.79 (4H, m), 3.88 (2H, s), 4.08-4.15 (1 H, m), 4.29-4.37 (2 H, m).

EI-MS, m/z: 536 (M) ⁺ , 466, 385, 343, 330, 305, 274, 233, 207, 193, 151, 137, 125, 109.

Reference example - 9
Synthesis of 2,2-dimethylpropyl 3-[(5,7-dichloro-2,3-dihydrothieno[3,4-b][1,4]dioxy-2-yl)methoxy]-1-methylpropanesulfonate (12b-2)

1.87 g (4.94 mmol) of (11b-1) synthesized by the method of Reference Example-7 was dissolved in 50 mL of THF, and 25 mL of acetic acid and 1.45 g (10.9 mmol) of N-chlorosuccinimide were dissolved in an ice bath. was added and stirred at room temperature for 24 hours. After the reaction, the mixture was diluted with chloroform and washed with water and saturated aqueous sodium hydrogencarbonate solution, and the organic layer was dehydrated with magnesium sulfate and concentrated. By purifying this by silica gel column chromatography (hexane/ethyl acetate=3/1 volume ratio, 1% triethylamine added), 1.63 g of colorless liquid (12b-2) was obtained (yield: 73.9 %).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.99 (9 H, s), 1.45 (3 H, d, J = 7.0 Hz), 1.77 to 1.86 (1 H, m ), 2.32-2.41 (1H, m), 3.31-3.41 (1H, m), 3.60-3.79 (4H, m), 3.88 (2H, s), 4.08-4.15 (1 H, m), 4.28-4.37 (2 H, m).

Reference example-10
Synthesis of 2,2-dimethylpropyl 3-[(5,7-diiodo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12b-3)

1.96 g (5.18 mmol) of (11b-1) synthesized by the method of Reference Example-7 was dissolved in 50 mL of THF, and 10 mL of acetic acid and 2.57 g (11.4 mmol) of N-iodosuccinimide were added thereto. Stir under bath for 5 hours. After the reaction, the mixture was diluted with ethyl acetate and washed with water and saturated aqueous sodium hydrogencarbonate solution, and the organic layer was dried over magnesium sulfate and concentrated. By purifying this by silica gel column chromatography (hexane/ethyl acetate=3/1 volume ratio, 1% triethylamine added), 2.75 g of colorless liquid (12b-3) was obtained (yield: 84.2 %).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.99 (9 H, s), 1.46 (3 H, d, J = 7.0 Hz), 1.77 to 1.86 (1 H, m ), 2.32 to 2.42 (1H, m), 3.32 to 3.43 (1H, m), 3.60 to 3.78 (4H, m), 3.88 (2H, s), 4.07-4.14 (1 H, m), 4.28-4.36 (2 H, m).

Reference example-11
Synthesis of 2,2-dimethyl-3-hydroxypropyl 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (11b -4)

3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate sodium (15 mmol) in 45 mL of THF, 5 drops of DMF Then, 1.50 mL (18.4 mmol) of oxalyl dichloride was slowly added in an ice bath and stirred for 2 hours. After the reaction, the reaction solution was concentrated to obtain 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonyl chloride.

Subsequently, under an argon atmosphere, 4.70 g (45.1 mmol) of 2,2-dimethyl-1,3-propanediol and 3.20 mL (22.9 mmol) of triethylamine were dissolved in 30 mL of chloroform. 30 mL of a chloroform solution of chloride was slowly added dropwise, and the mixture was stirred for 2 hours under an ice bath. After the reaction, the reaction solution was washed with water, and the organic layer was dehydrated with magnesium sulfate and concentrated. By purifying this by silica gel column chromatography (hexane/ethyl acetate = 1/2 (1% triethylamine added)), 3.66 g of colorless liquid (11b-4) was obtained (yield: 61.9% ).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.96 (6H, d, J = 6.9 Hz), 1.45 (3H, d, J = 6.9 Hz), 1.77-1 .85 (1H, m), 2.08 (1H, brs), 2.32-2.40 (1H, m), 3.36-3.46 (1H+2H, m), 3.59-3.75 (4H, m), 4.01-4.08 (1H+2H, m), 4.22 (1H, dd, J=11.7Hz, 2.2Hz), 4.28-4.33 (1H, m) , 6.34(2H,s).

Reference example - 12
Synthesis of N,N-diethyl-3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonamide (11b-5)

Under an argon atmosphere, sodium 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (15 mmol) in 45 mL of THF solution, Five drops of DMF were added, 1.50 mL (18.4 mmol) of oxalyl dichloride was slowly added in an ice bath, and the mixture was stirred for 2 hours. After the reaction, the reaction solution was concentrated to obtain 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonyl chloride.

Subsequently, under an argon atmosphere, 1.90 mL (18.3 mmol) of diethylamine and 3.14 mL (22.5 mmol) of triethylamine were dissolved in 30 mL of chloroform, and 30 mL of the chloroform solution of the sulfonic acid chloride synthesized above was slowly added dropwise thereto. The mixture was stirred for 2 hours in an ice bath. After the reaction, the reaction solution was washed with water, and the organic layer was dehydrated with magnesium sulfate and concentrated. By purifying this by silica gel column chromatography (hexane/ethyl acetate = 2/1 (1% triethylamine added)), 2.22 g of colorless liquid (11b-5) was obtained (yield: 40.7% ).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 1.20 (6H, t, J = 7.1 Hz), 1.32 (3H, d, J = 6.9 Hz), 1.68-1 .77 (1H, m), 2.24-2.32 (1H, m), 3.13-3.22 (1H, m), 3.25-3.39 (4H, m), 3.56 ~3.74 (4H, m), 4.05 (1H, ddd, J = 11.6Hz, 7.5Hz, 3.3Hz), 4.22 (1H, dd, J = 11.6Hz, 2.2Hz) ), 4.27-4.32 (1H, m), 6.33 (2H, s).

Reference example - 13
Synthesis of N,N-diethyl-3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonamide (12b-5)

2.22 g (6.10 mmol) of (11b-5) synthesized by the method of Reference Example-12 was dissolved in 40 mL of THF, and 2.28 g (12.8 mmol) of N-bromosuccinimide was added under an ice bath. Stir at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate=2/1 (1% triethylamine added) to obtain 2.46 g of colorless liquid (12b-5) (yield: 77.0%). 3%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 1.20 (6H, t, J = 7.1 Hz), 1.33 (3H, d, J = 6.9 Hz), 1.68-1 .77 (1H, m), 2.23-2.31 (1H, m), 3.12-3.22 (1H, m), 3.25-3.39 (4H, m), 3.57 ~3.78 (4H,m), 4.07-4.15 (1H,m), 4.29-4.36 (2H,m).

Reference example - 14
Synthesis of N-isopropyl-3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonamide (11b-6)

3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate sodium (15 mmol) in 45 mL of THF, 5 drops of DMF Then, 1.50 mL (18.4 mmol) of oxalyl dichloride was slowly added in an ice bath and stirred for 2 hours. After the reaction, the reaction solution was concentrated to obtain 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonyl chloride.

Subsequently, 1.60 mL (18.6 mmol) of isopropylamine and 3.20 mL (22.9 mmol) of triethylamine were dissolved in 30 mL of THF. Stirred for 2 hours. After the reaction, the reaction solution was washed with water, and the organic layer was dehydrated with magnesium sulfate and concentrated. By purifying this by silica gel column chromatography (hexane/ethyl acetate = 2/1 (1% triethylamine added)), 3.85 g of colorless liquid (11b-6) was obtained (yield: 73.4% ).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 1.24 (6H, d, J = 6.5 Hz), 1.38 (3H, d, J = 6.9 Hz), 1.69-1 .78 (1H, m), 2.28-2.36 (1H, m), 3.12-3.21 (1H, m), 3.58-3.74 (1H+4H, m), 3.94 (1H, brs), 4.05 (1H, ddd, J=11.6Hz, 7.4Hz, 4.3Hz), 4.22 (1H, dd, J=11.6Hz, 2.2Hz), 4. 27-4.32 (1H, m), 6.33 (2H, s).

Reference example - 15
Synthesis of N-isopropyl-3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonamide (12b -6)

1.93 g (5.51 mmol) of (11b-6) synthesized by the method of Reference Example-14 was dissolved in 30 mL of THF, and 2.08 g (11.7 mmol) of N-bromosuccinimide was added thereto under an ice bath. Stir at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate=2/1 (1% triethylamine added) to obtain 2.70 g of colorless liquid (12b-6) (yield: 96.0 g). 3%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 1.24 (6H, d, J = 6.5 Hz), 1.39 (3H, d, J = 6.8 Hz), 1.69-1 .78 (1H, m), 2.28-2.36 (1H, m), 3.11-3.21 (1H, m), 3.59-3.79 (1H+4H, m), 3.92 (1H, brs), 4.08-4.14 (1H, m), 4.29-4.37 (2H, m).

Reference example - 16
Synthesis of 2-(octyloxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (14-1)

1.06 g (582 mg, 24.0 mmol) of sodium hydride (55%) was washed with hexane, dried in vacuo and then dissolved in 10 mL of THF. 10 mL of the solution was slowly added dropwise and stirred at room temperature for 15 minutes. After that, the temperature was raised to 60° C., and after stirring for 2 hours, 3.50 mL (20.2 mmol) of 1-bromooctane was slowly added, and the mixture was stirred at 60° C. for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 (1% triethylamine added) to obtain 4.10 g of colorless liquid (14-1) (yield: 72.0 g). 0%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.88 (3H, t, J = 6.9 Hz), 1.24-1.34 (10H, m), 1.54-1.61 (2H, m), 3.49 (2H, t, J = 6.7Hz), 3.59 (1H, dd, J = 10.4Hz, 6.0Hz), 3.68 (1H, dd, J = 10.4Hz, 5.0Hz), 4.05 (1H, dd, J = 11.6Hz, 7.5Hz), 4.24 (1H, dd, J = 11.6Hz, 2.2Hz), 4.27 ~4.32 (1H, m), 6.32 (2H, s).

Reference example - 17
Synthesis of 5,7-dibromo-2-(octyloxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (15-1)

4.10 g (14.4 mmol) of (14-1) synthesized by the method of Reference Example-16 was dissolved in 70 mL of THF, and 5.39 g (30.3 mmol) of N-bromosuccinimide was added thereto under an ice bath. Stir at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 (with 1% triethylamine added) to obtain 5.58 g of colorless liquid (15-1) (yield: 87.0 g). 5%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.88 (3H, t, J = 6.8 Hz), 1.24-1.34 (10H, m), 1.53-1.60 (2H, m), 3.50 (2H, t, J = 6.0Hz), 3.62 (1H, dd, J = 10.5Hz, 6.5Hz), 3.73 (1H, dd, J = 10.4 Hz, 4.5 Hz), 4.12 (1H, dd, J=12.2 Hz, 7.7 Hz), 4.30-4.35 (2H, m).

Reference example - 18
Synthesis of 2-(dodecyloxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (14-2)

1.06 g (582 mg, 24.0 mmol) of sodium hydride (55%) was washed with hexane, dried in vacuo and then dissolved in 10 mL of THF. 10 mL of the solution was slowly added dropwise and stirred at room temperature for 15 minutes. Then, the temperature was raised to 60° C., and after stirring for 2 hours, a THF solution of 3.50 mL (20.2 mmol) of 1-bromododecane was slowly added dropwise, followed by stirring at 60° C. for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate=10/1 (with 1% triethylamine added) to obtain 3.26 g of colorless liquid (14-2) (yield: 47.0%). 8%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.88 (3H, t, J = 6.8 Hz), 1.26-1.32 (18H, m), 1.54-1.61 (2H, m), 3.49 (2H, t, J = 6.7Hz), 3.59 (1H, dd, J = 10.4Hz, 6.0Hz), 3.68 (1H, dd, J = 10.4Hz, 5.0Hz), 4.05 (1H, dd, J = 11.6Hz, 7.5Hz), 4.24 (1H, dd, J = 11.6Hz, 2.2Hz), 4.27 ~4.32 (1H, m), 6.32 (2H, s).

Reference example - 19
Synthesis of 5,7-dibromo-2-(dodecyloxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (15-2)

2.16 g (6.33 mmol) of (14-2) synthesized by the method of Reference Example-18 was dissolved in 30 mL of THF, and 2.37 g (13.3 mmol) of N-bromosuccinimide was added thereto under an ice bath. Stir at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate = 10/1 (1% triethylamine added) to obtain 1.87 g of colorless liquid (15-2) (yield: 59. 2%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.88 (3H, t, J = 6.8 Hz), 1.26 (18H, m), 1.53-1.60 (2H, m ), 3.49 (2H, t, J = 6.6Hz), 3.62 (1H, dd, J = 10.5Hz, 6.5Hz), 3.73 (1H, dd, J = 10.5Hz, 4.5 Hz), 4.12 (1H, dd, J=12.2 Hz, 7.7 Hz), 4.30-4.35 (2H, m).

Reference example-20
Synthesis of 2-(hexadecyloxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (14-3)

529 mg (291 mg, 12.0 mmol) of sodium hydride (55%) was washed with hexane, dried in vacuum, dissolved in 5 mL of DMF, and 1.73 g (10.0 mmol) of alcohol (6) in 5 mL of DMF solution. was slowly added dropwise and stirred at room temperature for 15 minutes. After that, the temperature was raised to 60° C., and after stirring for 2 hours, 5 mL of a DMF solution of 3.40 mL (11.1 mmol) of 1-bromohexadecane was slowly added dropwise, and the mixture was stirred at 60° C. for 2 hours. After concentrating the reaction solution, it was diluted with ethyl acetate and washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate = 3/1 (1% triethylamine added) to obtain 2.25 g of colorless liquid (14-3) (yield: 47.0%). 1%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.88 (3H, t, J = 6.8 Hz), 1.26-1.33 (26H, m), 1.54-1.61 (2H, m), 3.49 (2H, t, J = 6.7Hz), 3.59 (1H, dd, J = 10.4Hz, 6.0Hz), 3.68 (1H, dd, J = 10.4Hz, 5.0Hz), 4.05 (1H, dd, J = 11.6Hz, 7.5Hz), 4.24 (1H, dd, J = 11.6Hz, 2.2Hz), 4.27 ~4.32 (1H, m), 6.32 (2H, s).

Reference example-21
Synthesis of 5,7-dibromo-2-(hexadecyloxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (15-3)

1.44 g (3.62 mmol) of (14-3) synthesized by the method of Reference Example-20 was dissolved in 15 mL of THF, and 1.31 g (7.34 mmol) of N-bromosuccinimide was added thereto under an ice bath. Stir at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate=10/1 (with 1% triethylamine added) to obtain 1.87 g of colorless liquid (15-3) (yield: 93.0%). 2%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.88 (3H, t, J = 6.8 Hz), 1.26-1.36 (26H, m), 1.54-1.60 (2H, m), 3.49 (2H, t, J = 6.6Hz), 3.62 (1H, dd, J = 10.5Hz, 6.5Hz), 3.73 (1H, dd, J = 10.5 Hz, 4.5 Hz), 4.12 (1H, dd, J=12.2 Hz, 7.7 Hz), 4.30-4.35 (2H, m).

Reference example-22
Synthesis of 2-(butoxyethoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (14-4))

1.59 g (876 mg, 36.1 mmol) of sodium hydride (55%) was washed with hexane, dried in vacuo, dissolved in 15 mL of DMF, and to this was added 5.17 g (30.0 mmol) of alcohol (6) in DMF. 15 mL of the solution was slowly added dropwise and stirred at room temperature for 15 minutes. After that, the temperature was raised to 60° C., and after stirring for 2 hours, 15 mL of a DMF solution containing 4.30 mL (30.0 mmol) of butyl 2-chloroethyl ether was slowly added dropwise, and the mixture was stirred at 60° C. for 2 hours. After concentrating the reaction solution, it was diluted with ethyl acetate and washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate = 6/1 (1% triethylamine added) to obtain 3.83 g of colorless liquid (14-4) (yield: 46.0%). 8%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.92 (3H, t, J = 7.4 Hz), 1.32-1.41 (2H, m), 1.53-1.60 (2H, m), 3.46 (2H, t, J = 6.7 Hz), 3.57-3.59 (2H, m), 3.65-3.70 (3H, m), 3.77 (1H, dd, J = 10.6Hz, 5.0Hz), 4.06 (1H, dd, J = 11.6Hz, 7.5Hz), 4.25 (1H, dd, J = 11.6Hz, 2 .3 Hz), 4.30-4.35 (1 H, m), 6.32 (2 H, s).

Reference example-23
Synthesis of 5,7-dibromo-2-(butoxyethoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (15-4)

1.92 g (7.06 mmol) of (14-4) synthesized by the method of Reference Example-22 was dissolved in 35 mL of THF, and 2.66 g (14.9 mmol) of N-bromosuccinimide was added thereto under an ice bath. Stir at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 (1% triethylamine added) to obtain 3.01 g of colorless liquid (15-4) (yield: 99.9%). 2%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 0.92 (3H, t, J = 7.4 Hz), 1.32-1.41 (2H, m), 1.53-1.60 (2H, m), 3.46 (2H, t, J = 6.7 Hz), 3.56-3.59 (2H, m), 3.68-3.73 (3H, m), 3.82 (1H, dd, J=10.7 Hz, 4.7 Hz), 4.14 (1 H, dd, J=12.0 Hz, 7.3 Hz), 4.32-4.38 (2H, m).

Reference example-24
2-(2,5,8,11-tetraoxadodecan-1-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (14-5)

1.09 g (597 mg, 24.6 mmol) of sodium hydride (55%) was washed with hexane, dried in vacuo, dissolved in 10 mL of DMF, and to this was added 3.44 g (20.0 mmol) of alcohol (6) in DMF. 10 mL of the solution was slowly added dropwise and stirred at room temperature for 15 minutes. After that, the temperature was raised to 60° C., and after stirring for 2 hours, 10 mL of a DMF solution containing 4.00 mL (23.0 mmol) of diethylene glycol 2-bromoethyl methyl ether was slowly added dropwise, followed by stirring at 60° C. for 2 hours. After concentrating the reaction solution, it was diluted with ethyl acetate and washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate = 2/1 (1% triethylamine added) to obtain 2.33 g of colorless liquid (14-5) (yield: 36.0%). 6%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 3.38 (3H, m), 3.53-3.56 (2H, m), 3.63-3.71 (12H, m), 3.77 (1H, dd, J=10.6Hz, 5.0Hz), 4.06 (1H, dd, J=11.6Hz, 7.5Hz), 4.25 (1H, dd, J=11. 6 Hz, 2.2 Hz), 4.29-4.35 (1 H, m), 6.32 (2 H, s).

Reference example-25
Synthesis of 5,7-dibromo-2-(2,5,8,11-tetraoxadodecan-1-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (15-5 )

2.33 g (7.32 mmol) of (14-5) synthesized by the method of Reference Example-24 was dissolved in 35 mL of THF, and 2.74 g (15.4 mmol) of N-bromosuccinimide was added thereto under an ice bath. Stir at room temperature for 2 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the organic layer was dried over magnesium sulfate. After concentration, this was purified by silica gel column chromatography (hexane/ethyl acetate=2/1 (1% triethylamine added) to obtain 2.70 g of colorless liquid (15-5) (yield: 77.0 g). 5%).

¹ H-NMR (400 MHz, CDCl ₃ , ppm), δ: 3.38 (3H, m), 3.54-3.56 (2H, m), 3.63-3.73 (12H, m), 3.82 (1H, dd, J = 10.7Hz, 4.6Hz), 4.14 (1H, dd, J = 12.1Hz, 7.7Hz), 4.33-4.38 (2H, m) .

Reference example-26
2-methylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12a-2 ) and 2,2-dimethylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate GRIM copolymerization with (12b-1) (feed ratio 3/7) (16-1)

2.86 g (5.49 mmol) of (12a-2) synthesized by the method of Reference Example-4 and 6.86 g (12.8 mmol) of (12b-1) synthesized by the method of Reference Example-8 were placed in an argon atmosphere. 9.5 mL (19.0 mmol) of 2M isopropylmagnesium chloride-THF solution was added thereto, and the mixture was stirred for 1 hour in an ice bath. Then, after stirring at room temperature for 1 hour, 199 mg (0.365 mmol) of 1,3-bis(diphenylphosphino)propane-nickel(II) dichloride complex (Ni(dppp)Cl ₂ ) was added and stirred at room temperature for 2 days. did. The reaction solution was added to methanol, and the formed precipitate was filtered to obtain 6.43 g of black solid sulfonate thiophene copolymer (16-1) (yield: 94.4%). As a result of GPC measurement, the molecular weight was Mn=11,300, Mw=18,700, and Mw/Mn=1.67.

Example-1
Synthesis of thiophene copolymerization (17)-1

6.20 g of the sulfonate thiophene copolymer (16-1) obtained in Reference Example-26 and 2.00 g (20.4 mmol) of potassium acetate were dissolved in 120 mL of DMF under an argon atmosphere, and the mixture was heated at 100°C for 5 hours. Stirred for an hour. The reaction solution was added to acetone, and the formed precipitate was filtered to obtain 6.13 g of thiophene copolymer (17-1K) as a black solid.

Reference example-27
2-methylpropyl 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (11a-2) and 3-[ Oxidative copolymerization with (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate 2,2-dimethylpropyl (11b-1) ( Charge ratio 3/7) (16-2)

Under an argon atmosphere, 9.16 g (57.2 mmol) of iron (III) chloride was suspended in 40 mL of acetonitrile, and 1.56 g (4.29 mmol) of (11a-2) synthesized by the method of Reference Example-3 was added thereto. A solution of 3.79 g (10.0 mmol) of (11b-1) synthesized by the method of Reference Example-7 dissolved in 30 mL of acetonitrile was slowly added dropwise at 0° C. and stirred at room temperature for 20 hours. After the reaction, methanol was added and the generated precipitate was filtered to obtain 3.53 g of a black solid product (yield: 65.9%). 3.53 g of this black solid was suspended in a mixed solution of 50 mL of ethanol and 50 mL of hydrazine monohydrate under an argon atmosphere and stirred at room temperature for 24 hours. Water was added to the reaction solution, and the product was collected by filtration to obtain 3.07 g of black solid sulfonate thiophene copolymer (16-2) (yield: 65.9%). As a result of GPC measurement, the molecular weight was Mn=18,500, Mw=38,700, and Mw/Mn=2.09.

Example-2
Synthesis of thiophene copolymer (17)-2

2.80 g of the sulfonate thiophene copolymer (16-2) obtained in Reference Example-27 and 886 g (9.02 mmol) of potassium acetate were dissolved in 50 mL of DMF under an argon atmosphere and stirred at 100° C. for 5 hours. did. The reaction solution was added to acetone, and the precipitate formed was filtered to obtain 2.86 g of a black solid thiophene copolymer (17-2K).

Reference example-28
2-methylpropyl 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (11a-2) and 3-[ Oxidation with (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate 2,2-dimethylpropyl (11b-1) Copolymerization (feed ratio 5/5) (16-3)

In an argon atmosphere, 9.26 g (57.8 mmol) of iron (III) chloride was suspended in 40 mL of acetonitrile, and 2.63 g (7.22 mmol) of (11a-2) synthesized by the method of Reference Example-3 was added thereto. A solution of 2.74 g (7.23 mmol) of (11b-1) synthesized by the method of Reference Example-7 dissolved in 30 mL of acetonitrile was slowly added dropwise at 0° C. and stirred at room temperature for 20 hours. After the reaction, methanol was added and the generated precipitate was filtered to obtain 4.00 g of a black solid (yield: 74.5%). 4.00 g of this black solid was suspended in a mixed solution of 40 mL of ethanol and 40 mL of hydrazine monohydrate under an argon atmosphere, and stirred at room temperature for 24 hours. Water was added to the reaction solution, and the product was collected by filtration to obtain 2.79 g of black solid sulfonate thiophene copolymer (16-3) (yield: 69.8%). As a result of GPC measurement, the molecular weight was Mn=15,900, Mw=34,300, and Mw/Mn=2.16.

Example-3
Synthesis of thiophene copolymer (17)-3

2.61 g of the sulfonate thiophene copolymer (16-3) obtained in Reference Example-28 and 1.41 g (14.4 mmol) of potassium acetate were dissolved in 50 mL of DMF under an argon atmosphere, and the mixture was heated at 100°C for 5 hours. Stirred for an hour. The reaction solution was added to acetone and the precipitate formed was filtered to obtain 2.82 g of a black solid thiophene copolymer (17-3K).

Reference example-29
2-methylpropyl 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (11a-2) and 3-[ (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate 2,2-dimethyl-3-hydroxypropyl (11b-4) Oxidative copolymerization (feed ratio 3/7) (16-4)

Under an argon atmosphere, 9.18 g (57.3 mmol) of iron (III) chloride was suspended in 40 mL of acetonitrile, and 1.56 g (4.29 mmol) of (11a-2) synthesized by the method of Reference Example-3, A solution of 3.95 g (10.0 mmol) of (11b-4) synthesized by the method of Reference Example-11 dissolved in 30 mL of acetonitrile was slowly added dropwise at 0° C. and stirred at room temperature for 20 hours. Methanol was added to the reaction solution, and after concentration, methanol was added again, and the generated precipitate was filtered to obtain 4.61 g of a black solid (yield: 83.6%). 4.61 g of this black solid was suspended in 50 mL of ethanol and 50 mL of hydrazine monohydrate under an argon atmosphere and stirred at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, water was added, and the product was collected by filtration to obtain 3.97 g of black solid sulfonate thiophene copolymer (16-4) (yield: 86.3%). . As a result of GPC measurement, the molecular weight was Mn=27,100, Mw=84,300, and Mw/Mn=3.12.

Example-4
Synthesis of thiophene copolymer (17)-4

3.70 g of the sulfonate ester thiophene copolymer (16-4) obtained in Reference Example-29 and 1.18 g (12.0 mmol) of potassium acetate were dissolved in 70 mL of DMF under an argon atmosphere, and the mixture was heated at 100°C for 5 hours. Stirred for an hour. The reaction solution was added to acetone and the precipitate formed was filtered to obtain 3.07 g of a black solid thiophene copolymer (17-4K).

Reference example-30
2-methylpropyl 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (11a-2) and N,N - oxidative copolymerization with diethyl-3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonamide (11b-5) ( Charge ratio 3/7) (16-5)

Under an argon atmosphere, 9.17 g (57.2 mmol) of iron (III) chloride was suspended in 40 mL of acetonitrile, and 1.59 g (4.35 mmol) of (11a-2) synthesized by the method of Reference Example-3 was added thereto. A solution of 3.68 g (10.1 mmol) of (11b-5) synthesized by the method of Example-12 dissolved in 30 mL of acetonitrile was slowly added dropwise at 0° C. and stirred at room temperature for 20 hours. Methanol was added to the reaction solution, and after concentration, the generated precipitate was filtered to obtain 4.80 g of a black solid (yield: 92.3%). 4.80 g of this black solid was suspended in 50 mL of ethanol and 50 mL of hydrazine monohydrate under an argon atmosphere and stirred at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, water was added, and the product was collected by filtration to obtain 4.00 g of sulfonate thiophene copolymer (16-5) (yield: 83.3%). As a result of GPC measurement, the molecular weight was Mn=18,300, Mw=55,600, and Mw/Mn=3.03.

Example-5
Synthesis of thiophene copolymer (17)-5

3.70 g of the sulfonate thiophene copolymer (16-5) obtained in Reference Example-30 and 1.23 g (12.8 mmol) of potassium acetate were dissolved in 70 mL of DMF under an argon atmosphere, and the mixture was heated at 100°C for 5 hours. Stirred for an hour. The reaction solution was added to acetone, and the precipitate formed was filtered to obtain 3.01 g of a black solid thiophene copolymer (17-5K).

Reference example - 31
2-methylpropyl 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (11a-2) and N-isopropyl- Oxidative copolymerization with 3-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonamide (11b-6) (feed ratio 3 /7) (16-6)

Under an argon atmosphere, 8.58 g (53.6 mmol) of iron (III) chloride was suspended in 40 mL of acetonitrile, and 1.48 g (4.05 mmol) of (11a-2) synthesized by the method of Reference Example-3, A solution of 3.28 g (9.37 mmol) of (11b-6) synthesized by the method of Reference Example-14 dissolved in 30 mL of acetonitrile was slowly added dropwise at 0° C. and stirred at room temperature for 20 hours. Methanol was added to the reaction solution, and after concentration, the generated precipitate was filtered to obtain 4.17 g of a black solid (yield: 87.8%). 4.03 g of this black solid was suspended in 50 mL of ethanol and 50 mL of hydrazine monohydrate under an argon atmosphere and stirred at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, water was added, and the product was collected by filtration to give 3.36 g of sulfonate thiophene copolymer (16-6) as a black solid (yield: 83.4%). As a result of GPC measurement, the molecular weight was Mn=22,400, Mw=63,600, and Mw/Mn=2.84.

Example-6
Synthesis of thiophene copolymer (17)-6

3.11 g of the sulfonate thiophene copolymer (16-6) obtained in Reference Example-31 and 1.09 g (11.1 mmol) of potassium acetate were dissolved in 60 mL of DMF under an argon atmosphere, and the mixture was heated at 100°C for 5 hours. Stirred for an hour. The reaction solution was added to acetone, and the precipitate formed was filtered to obtain 3.03 g of a black solid thiophene copolymer (17-6K).

Reference example - 32
2-methylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12a-2 ) and N,N-diethyl-3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfone GRIM copolymerization with amide (12b-5) (feed ratio 3/7) (16-7)

159 mg (0.300 mmol) of (12a-2) synthesized by the method of Reference Example-4 and 365 mg (0.700 mmol) of (12b-5) synthesized by the method of Reference Example-13 were added to 2 mL of THF under an argon atmosphere. 500 μL (1.00 mmol) of 2M isopropylmagnesium chloride-THF solution was added thereto and stirred for 1 hour under an ice bath. Then, after stirring at room temperature for 1 hour, 10.5 mg (0.0193 mmol) of Ni(dppp)Cl ₂ was added and stirred at room temperature for 3 hours. The reaction solution was added to methanol, and the precipitate formed was filtered to obtain 232 mg of black solid sulfonate thiophene copolymer (16-7) (yield: 64.1%). As a result of GPC measurement, the molecular weight was Mn=12,700, Mw=21,900, and Mw/Mn=1.92.

Example-7

100 mg of the sulfonate thiophene copolymer (16-7) obtained in Reference Example-32 and 25.1 mg (0.255 mmol) of potassium acetate were dissolved in 2.0 mL of DMF under an argon atmosphere, and the mixture was heated at 100°C for 5 hours. Stirred for an hour. The reaction solution was added to acetone and the precipitate formed was filtered to obtain 105 mg of a black solid thiophene copolymer (17-7K).

Reference example - 33
2-methylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12a-2 ) and GRIM copolymerization of 5,7-dibromo-2-(octyloxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (15-1) (feed ratio 5/ 5) (16-8)

548 mg (1.05 mmol) of (12a-2) synthesized by the method of Reference Example-4 and 464 mg (1.05 mmol) of (15-1) synthesized by the method of Reference Example-17 were added to 4 mL of THF under an argon atmosphere. 1.10 mL (2.20 mmol) of 2M isopropylmagnesium chloride-THF solution was added thereto and stirred for 1 hour under an ice bath. Then, after stirring at room temperature for 1 hour, Ni(dppp)Cl ₂ 22.1 mg (0.0405 mmol) was added and stirred at room temperature for 3 hours. The reaction solution was added to methanol, and the formed precipitate was filtered to obtain 613 mg of black solid sulfonate thiophene copolymer (16-8) (yield: 90.7%). As a result of GPC measurement, the molecular weight was Mn=3,790, Mw=5,710, Mw/Mn=1.51.

Example-8

100 mg of the sulfonate thiophene copolymer (16-8) obtained in Reference Example-33 and 25.6 mg (0.260 mmol) of potassium acetate were dissolved in 1 mL of DMF under an argon atmosphere, and stirred at 100° C. for 5 hours. did. The reaction solution was added to acetone, and the formed precipitate was filtered to obtain 84 mg of a black solid thiophene copolymer (17-8K) (yield: 86.6%).

Reference example - 34
2-methylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12a-2 ) and GRIM copolymerization of 5,7-dibromo-2-(octyloxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (15-1) (feed ratio 3/ 7) (16-9)

156 mg (0.299 mmol) of (12a-2) synthesized by the method of Reference Example-4 and 312 mg (0.706 mmol) of (15-1) synthesized by the method of Reference Example-17 were added to 2 mL of THF under an argon atmosphere. 500 μL (1.00 mmol) of 2M isopropylmagnesium chloride-THF solution was added thereto and stirred for 1 hour under an ice bath. Then, after stirring at room temperature for 1 hour, Ni(dppp)Cl ₂ 11.2 mg (0.0205 mmol) was added and stirred at room temperature for 3 hours. The reaction solution was added to methanol, and the formed precipitate was filtered to obtain 247 mg of black solid sulfonate thiophene copolymer (16-9) (yield: 80.7%). As a result of GPC measurement, the molecular weight was Mn=3,040, Mw=4,340, and Mw/Mn=1.43.

Example-9

107 mg of the sulfonate thiophene copolymer (16-9) obtained in Reference Example-34 and 27.0 mg (0.275 mmol) of potassium acetate were dissolved in 1 mL of DMF under an argon atmosphere and stirred at 100° C. for 5 hours. did. The reaction solution was added to acetone, and the formed precipitate was filtered to obtain 76 mg of a black solid thiophene copolymer (17-9K) (yield: 72.4%).

Reference example-35
2-methylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12a-2 ) and GRIM copolymerization of 5,7-dibromo-2-(dodecyloxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (15-2) (feed ratio 3/7 ) (16-10)

159 mg (0.304 mmol) of (12a-2) synthesized by the method of Reference Example-4 and 357 mg (0.716 mmol) of (15-2) synthesized by the method of Reference Example-19 were added to 2 mL of THF under an argon atmosphere. 500 μL (1.00 mmol) of 2M isopropylmagnesium chloride-THF solution was added thereto and stirred for 1 hour under an ice bath. Then, after stirring at room temperature for 1 hour, Ni(dppp)Cl ₂ 11.1 mg (0.0204 mmol) was added and stirred at room temperature for 3 hours. The reaction solution was added to methanol, and the formed precipitate was filtered to obtain 260 mg of black solid sulfonate thiophene copolymer (16-10) (yield: 75.2%). As a result of GPC measurement, the molecular weight was Mn=2,610, Mw=3,730, and Mw/Mn=1.43.

Example-10

107 mg of the sulfonate thiophene copolymer (16-10) obtained in Reference Example-35 and 26.0 mg (0.265 mmol) of potassium acetate were dissolved in 1 mL of DMF under an argon atmosphere and stirred at 100° C. for 5 hours. did. The reaction solution was added to acetone, and the formed precipitate was filtered to obtain 99 mg of a black solid thiophene copolymer (17-10K) (yield: 93.8%).

Reference example-36
2-methylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12a-2 ) and GRIM copolymerization of 5,7-dibromo-2-(hexadecyloxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (15-3) (feed ratio 3 /7) (16-11)

156 mg (0.300 mmol) of (12a-2) synthesized by the method of Reference Example-4 and 388 mg (0.700 mmol) of (15-3) synthesized by the method of Reference Example-21 were added to 2 mL of THF under an argon atmosphere. 500 μL (1.00 mmol) of 2M isopropylmagnesium chloride-THF solution was added thereto and stirred for 1 hour under an ice bath. Then, after stirring at room temperature for 1 hour, Ni(dppp)Cl ₂ 10.5 mg (0.0192 mmol) was added and stirred at room temperature for 3 hours. The reaction solution was added to methanol, and the formed precipitate was filtered to obtain 352 mg of black solid sulfonate thiophene copolymer (16-11) (yield: 79.9%). As a result of GPC measurement, the molecular weight was Mn=1,320, Mw=1,960, and Mw/Mn=1.49.

Example-11

101 mg of the sulfonic acid ester thiophene copolymer (16-11) synthesized in Reference Example-36 and 25.5 mg (0.260 mmol) of potassium acetate were dissolved in 1 mL of DMF under an argon atmosphere and stirred at 100° C. for 5 hours. . The reaction solution was added to acetone, and the formed precipitate was filtered to obtain 82 mg of a black solid thiophene copolymer (17-11K) (yield: 82.2%).

Reference example - 37
2-methylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12a-2 ) and GRIM copolymerization of 5,7-dibromo-2-(butoxyethoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (15-4) (feed ratio 3/ 7) (16-12)

157 mg (0.301 mmol) of (12a-2) synthesized by the method of Reference Example-4 and 301 mg (0.700 mmol) of (15-4) synthesized by the method of Reference Example-23 were dissolved in 2 mL of THF, 500 μL (1.00 mmol) of 2M isopropylmagnesium chloride-THF solution was added, and the mixture was stirred in an ice bath for 1 hour. Then, after stirring at room temperature for 1 hour, Ni(dppp)Cl ₂ 10.9 mg (0.0200 mmol) was added and stirred at room temperature for 3 hours. The reaction solution was added to methanol, and the formed precipitate was filtered to obtain 242 mg of black solid sulfonate thiophene copolymer (16-12) (yield: 81.2%). As a result of GPC measurement, the molecular weight was Mn=3,380, Mw=4,930, Mw/Mn=1.46.

Example-12

107 mg of the sulfonate ester thiophene copolymer (16-12) obtained in Reference Example-37 and 25.3 mg (0.258 mmol) of potassium acetate were dissolved in 1 mL of DMF under an argon atmosphere and stirred at 100° C. for 5 hours. did. The reaction solution was added to acetone, and the formed precipitate was filtered to obtain 98 mg of a black solid thiophene copolymer (17-12K) (yield: 93.3%).

Reference example-38
2-methylpropyl 3-[(5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]-1-methylpropanesulfonate (12a-2 ) and 5,7-dibromo-2-(2,5,8,11-tetraoxadodecan-1-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxin (15- 5) GRIM copolymerization with (feed ratio 3/7) (16-13)

158 mg (0.301 mmol) of (12a-2) synthesized by the method of Reference Example-4 and 333 mg (0.699 mmol) of (15-5) synthesized by the method of Reference Example-25 were added to 2 mL of THF under an argon atmosphere. 500 μL (1.00 mmol) of 2M isopropylmagnesium chloride-THF solution was added thereto and stirred for 1 hour under an ice bath. Then, after stirring at room temperature for 1 hour, 10.5 mg (0.0193 mmol) of Ni(dppp)Cl ₂ was added and stirred at room temperature for 3 hours. The reaction solution was added to a methanol/water (=1/1) mixed solvent, and the precipitate formed was filtered to obtain 296 mg of a black solid sulfonate thiophene copolymer (16-13) (yield: 89.6). %). As a result of GPC measurement, the molecular weight was Mn=3,540, Mw=4,720, Mw/Mn=2.03.

Example-13

103 mg of the sulfonate thiophene copolymer (16-13) obtained in Reference Example-38 and 25.1 mg (0.251 mmol) of potassium acetate were dissolved in 1 mL of DMF under an argon atmosphere and stirred at 100° C. for 5 hours. did. The reaction solution was added to acetone, and the formed precipitate was filtered to obtain 84 mg of a black solid thiophene copolymer (17-13K) (yield: 83.0%).

Comparative example-1

525 mg (1.01 mmol) of (12a-2) synthesized by the method of Reference Example-4 was dissolved in 2 mL of THF under an argon atmosphere, and 500 μL (1.00 mmol) of 2M isopropylmagnesium chloride-THF solution was added thereto. Stir under bath for 1 hour. Then, after stirring at room temperature for 1 hour, Ni(dppp)Cl ₂ 10.5 mg (0.0192 mmol) was added and stirred at room temperature for 3 hours. The reaction solution was added to methanol, and the formed precipitate was filtered to obtain 282 mg of black solid polythiophene sulfonate (18-1) (yield: 77.4%). As a result of GPC measurement, the molecular weight was Mn=20,000, Mw=37,900, and Mw/Mn=1.90.

50 mg (14 μmol-unit) of the obtained sulfonate ester polythiophene (18-1) and 27 mg (0.28 mmol) of potassium acetate were dissolved in 1 mL of DMF under an argon atmosphere and stirred at 100° C. for 5 hours. The reaction solution was added to acetone, and the formed precipitate was filtered to obtain 43 mg of black solid polythiophene (19-1K) (yield: 91%).

To 10 mg of the obtained polythiophene (19-1K) powder, 5 mL of DMAc or 5 mL of DMF was added, ultrasonically treated for 1 hour, and then stirred overnight. Further, it was treated with an ultrasonic homogenizer (Nippon Seiki U-150T, 20 kHz) for 20 minutes. Polythiophene (19-1K) powder precipitated without dispersing in the solvent in either case where DMAc or DMF was added.

Test example Test example-1
99 g of DMAc was added to 1 g of the thiophene copolymer (17-1K) obtained in Example-1, and the mixture was subjected to ultrasonic treatment for 1 hour and then stirred overnight. Further, it was treated with an ultrasonic homogenizer (Nippon Seiki U-300T, 20 kHz) for 20 minutes. To this 1% DMAc solution of (17-1K), 3.5 g of an ion exchange resin (Amberlyst 15JS-HG) was added and stirred overnight, followed by filtration through a filter with a pore size of 3 to 7 μm to give an acid form of thiophene. A DMAc solution of copolymer (17-1H) was prepared. This was coated on a glass plate and heat-treated at 100° C. for 30 minutes in a nitrogen atmosphere and further at 200° C. for 20 minutes. The film thickness was measured with a stylus type film thickness meter (Brucker DEKTAK), the surface resistance of the cast film of (17-1H) was measured with Mitsubishi Chemical Lorestar TG (4-probe method), and the electrical conductivity was calculated. The conductivity was 195 S/cm.

Test example-2
For the thiophene copolymer (17-2K) obtained in Example-2, the same operation as in Test Example-1 was performed to prepare a DMAc solution of acid form thiophene copolymer (17-2H), The conductivity of the cast film of (17-2H) was calculated. The conductivity was 12 S/cm.

Claims (8)

General formula (1) below

(In the formula, m1 represents an integer of ² or 3. M ⁺ represents a hydrogen ion or a cation. ^R1 represents a hydrogen atom or a methyl group.)
and a repeating unit represented by the following general formula (2)

( In the formula, Q ¹ is the following general formula (4)

(In the formula, ^m2 represents an integer of ² or 3. ^R2 represents a hydrogen atom or a methyl group. Z2 represents an alkylamino group having 12 or less carbon atoms or a dialkylamino group having 12 or less carbon atoms . represents.)
Represents a group represented by )
Thiophene copolymer containing a repeating unit represented by. Thiophene copolymers according to claim 1, characterized in that M ⁺ is a hydrogen ion. A thiophene copolymer according to claim 1 , characterized in that m ¹ is 2 and R ¹ is a methyl group. A thiophene copolymer according to claim 1 , characterized in that m2 is ² and ^R2 is a methyl group. A composition comprising the thiophene copolymer according to any one of claims 1 to 4 and an organic solvent, wherein the concentration of the thiophene copolymer is 0.2% by weight or more. The composition according to claim 5 , wherein the organic solvent is a solvent containing 50% by volume or more of N,N-dimethylformamide or N,N-dimethylacetamide. An electrode or an electronic device produced using the composition according to claim 5 or 6 . General formula (5) below

(In the formula, m ¹ represents an integer of 2 or 3, R ¹ represents a hydrogen atom or a methyl group, and Z ¹ represents a hydrocarbon group having 3 or 4 carbon atoms, excluding a tert-butyl group.)
and a repeating unit represented by the following general formula (2)

( In the formula, Q ¹ is the following general formula (4)

(In the formula, ^m2 represents an integer of ² or 3. ^R2 represents a hydrogen atom or a methyl group. Z2 represents an alkylamino group having 12 or less carbon atoms or a dialkylamino group having 12 or less carbon atoms . represents.)
Represents a group represented by )
2. The method for producing a thiophene copolymer according to claim 1, wherein the sulfonate ester thiophene copolymer containing a repeating unit represented by is brought into contact with a base.