Polythiophene, water-soluble electrically conductive polymer using it, and method for producing it

Patent metadata

Field	Value
Publication number	US-9718905-B2
Application number	US-201314412006-A
Country	US
Kind code	B2
Filing date	Jul 3, 2013
Priority date	Jul 3, 2012
Publication date	Aug 1, 2017
Grant date	Aug 1, 2017

Abstract

To provide a water-soluble polythiophene used as an electrically conductive material, and its production method.
A polythiophene comprising at least one type of structural units selected from the group consisting of structural units represented by the formula (1), structural units represented by the formula (2), structural units represented by the formula (3), structural units represented by the formula (4), structural units represented by the formula (5) and structural units represented by the formula (6). The polythiophene is obtained by polymerizing at least one thiophene compound selected from the group consisting of a thiophene compound represented by the formula (15), a thiophene compound represented by the formula (16) and a thiophene compound represented by the formula (17) in water or an alcohol solvent in the presence of an oxidizing agent.

First claim

The invention claimed is:

1. A polythiophene comprising at least one type of structural units selected from the group consisting of structural units represented by the following formula (3), structural units represented by the following formula (4), structural units represented by the following formula (5) and structural units represented by the following formula (6):

wherein Ar is a C 6-20 arylene group which may have a substituent, X is a C 1-6 alkylene group which may have a substituent, M is a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH(R 1 ) 3 or HNC 5 H 5 , R 1 is each independently a hydrogen atom or a C 1-6 alkyl group which may have a substituent, n is an integer of from 0 to 6, m in an integer of 0 or 1, and l is an integer of from 1 to 4;

wherein Ar, X, n, m and l are as defined in the above formula (3);

wherein R is a C 1-6 linear or branched alkyl group, or a fluorine atom, M is a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH(R 1 ) 3 or HNC 5 H 5 , and R 1 is each independently a hydrogen atom, or a C 1-6 alkyl group which may have a substituent; and

wherein R is as defined in the above formula (5).

2. The polythiophene according to claim 1 , which contains at least one type of structural units selected from the group consisting of structural units represented by the following formula (13):

wherein M is a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH(R 1 ) 3 or HNC 5 H 5 , R 1 is each independently a hydrogen atom or a C 1-6 alkyl group which may have a substituent, X is a C 1-6 alkylene group which may have a substituent, R 2 is a hydrogen atom, or a C 1-6 alkyl group or alkoxy group which may have a substituent, n is an integer of from 0 to 6, m is an integer of 0 or 1, and l is an integer of from 1 to 4; and
structural units represented by the following formula (14):

wherein R 2 , X, n, m, and l are as defined in the above formula (13).

3. The polythiophene according to claim 2 , wherein in the structural units represented by the formula (13) or (14), R 2 is a hydrogen atom and l=1.

4. The polythiophene according to claim 1 , which has a weight average molecular weight within a range of from 1,000 to 1,000,000 as calculated as polystyrene sulfonic acid.

5. A water-soluble electrically conductive polymer aqueous solution comprising an aqueous solution of the polythiophene as defined in claim 1 .

6. A method for producing an electrically conductive coating film, which comprises applying the aqueous solution as defined in claim 5 to a substrate, followed by drying.

7. Use of the aqueous solution as defined in claim 5 for an electrically conductive coating film.

8. A method for producing the polythiophene as defined in claim 1 , which comprises polymerizing at least one thiophene compound selected from the group consisting of a thiophene compound represented by the following formula (16) and a thiophene compound represented by the following formula (17) in water or an alcohol solvent in the presence of an oxidizing agent:

wherein Ar is a C 6-20 arylene group which may have a substituent, X is a C 1-6 alkylene group which may have a substituent, M is a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH(R 1 ) 3 or HNC 5 H 5 , R 1 is each independently a hydrogen atom or a C 1-6 alkyl group which may have a substituent, n is an integer of from 0 to 6, m is an integer of 0 or 1, and l is an integer of from 1 to 4; and

wherein R is a C 1-6 linear or branched alkyl group or a fluorine atom, M is a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH(R 1 ) 3 or HNC 5 H 5 , and R 1 is each independently a hydrogen atom or a C 1-6 alkyl group which may have a substituent.

9. The production method according to claim 8 , wherein the thiophene compound is at least one member selected from the group consisting of a compound represented by the following formula (21):

wherein M is a hydrogen atom, an alkali metal selected from the group consisting of Li, Na and K, NH(R 1 ) 3 or HNC 5 H 5 , R 1 is each independently a hydrogen atom or a C 1-6 alkyl group which may have a substituent, R 2 is a hydrogen atom, or a C 1-6 alkyl group or alkoxy group which may have a substituent, X is a C 1-6 alkylene group which may have a substituent, n is an integer of from 0 to 6, m is an integer of 0 or 1, and l is an integer of from 1 to 4.

10. The method for producing a polythiophene according to claim 8 , wherein the oxidizing agent is an iron (III) salt or a combination of a persulfate and an iron (III) salt.

Assignees

• Tosoh Corp

Inventors

• Yano Hirokazu
• Nishiyama Masakazu
• Awano Hiroshi

Classifications

• C07D495/04 Primary

  Ortho-condensed systems · CPC title

• C08G2261/1452

  containing sulfonyl or sulfonate-groups · CPC title

• C09D145/00

  Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers (based on polymers of cyclic esters of polyfunctional acids C09D131/00; based on polymers of cyclic anhydrides or imides C09D135/00) · CPC title

• C08G2261/64

  Solubility · CPC title

• C08G2261/54

  electrochromatic · CPC title