Conductive aniline polymer, method for producing same, and method for producing conductive film

Patent metadata

Field	Value
Publication number	US-9799420-B2
Application number	US-201514637831-A
Country	US
Kind code	B2
Filing date	Mar 4, 2015
Priority date	Oct 26, 2010
Publication date	Oct 24, 2017
Grant date	Oct 24, 2017

Abstract

When measuring the molecular mass distribution of conductive aniline polymer of formula (1) by GPC and converting its retention time into molecular mass (M) in terms of sodium polystyrene sulfonate, for the molecular mass (M), the area ratio (X/Y) of the area (X) of a region of 15,000 Da or more to the area (Y) of a region of less than 15,000 Da is 1.20 or more. A method for producing such a polymer includes: polymerization step (Z1) where specific aniline derivative (A) is polymerized in a solution containing basic compound (B), solvent (C), and oxidizing agent (D) at a liquid temperature lower than 25° C.; or polymerization step (Z2) where specific aniline derivative (A) and oxidizing agent (D) are added to and polymerized in a solution of a conductive aniline polymer (P-1) with a unit of formula (1) dissolved or dispersed in a solvent (C).

First claim

The invention claimed is:

1. A method for producing a conductive aniline polymer, wherein the conductive aniline polymer comprises a repeating unit represented by formula (1) and has an area ratio X/Y of 1.20 or more, which area ratio X/Y is calculated by:
(I) preparing a test solution by dissolving a conductive aniline polymer in an eluent adjusted to pH 10 or more so that a solid content concentration of the conductive aniline polymer in the test solution is 0.1% by mass;
(II) subjecting the test solution to a polymer materials evaluation system equipped with a gel permeation chromatograph to determine a molecular mass distribution of the test solution to obtain a chromatogram thereof;
(III) converting the retention time in the chromatogram obtained in (II) to a molecular mass M in terms of sodium polystyrene sulfonate;
(IV) determining an area X of a region having a molecular mass of 15,000 Da or more in the converted molecular mass M in terms of sodium polystyrene sulfonate;
(V) determining an area Y of a region having a molecular mass of less than 15,000 Da in the converted molecular mass M in terms of sodium polystyrene sulfonate; and
(VI) determining the area ratio X/Y of the area X to the area Y,

wherein R 1 to R 4 are each independently —H, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, an acidic group or a salt thereof, a hydroxy group, a nitro group, —F, —Cl, —Br, or —I; and at least one of R 1 to R 4 is an acidic group or a salt thereof, provided that the acidic group is a sulfonic acid group or a carboxyl group,
the method comprising:
a polymerizing Z1 where an aniline derivative A represented by formula (2) is polymerized in a solution containing a basic compound B, a solvent C, and an oxidizing agent D at a temperature lower than 25° C.,

wherein R 5 to R 9 are each independently —H, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, an acidic group or a salt thereof, a hydroxy group, a nitro group, —F, —Cl, —Br, or —I; and at least one of R 5 to R 9 is an acidic group or a salt thereof, provided that the acidic group is a sulfonic acid group or a carboxyl group.

2. The method of claim 1 , wherein the solvent C comprises 35% by volume or more of water relative to an entire volume of the solvent C.

3. The method of claim 2 , further comprising purifying a solution comprising a product obtained in the polymerizing Z1 by membrane filtration.

4. The method of claim 2 , further comprising purifying a solution comprising a product obtained in the polymerizing Z1 by precipitation.

5. The method of claim 4 , further comprising purifying by membrane filtration a solution comprising a purified substance obtained in the precipitation.

6. A method for producing the conductive aniline polymer of claim 1 , comprising a polymerizing Z2 where an aniline derivative A represented by formula (2) and an oxidizing agent D are added to and polymerized in a solution in which the conductive aniline polymer is dissolved in a solvent C, or added to and polymerized in a dispersion in which the conductive aniline polymer is dispersed in the solvent C,

wherein R 5 to R 9 are each independently —H, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, an acidic group or a salt thereof, a hydroxy group, a nitro group, —F, —Cl, —Br, or —I; and at least one of R 5 to R 9 is an acidic group or a salt thereof, provided that the acidic group is a sulfonic acid group or a carboxyl group.

7. The method of claim 6 , wherein the solvent C comprises 35% by volume or more of water relative to an entire volume of the solvent C.

8. The method of claim 7 , further comprising purifying a solution comprising a product obtained in the polymerizing Z2 by membrane filtration.

9. The method of claim 7 , further comprising purifying a solution comprising a product obtained in the polymerizing Z2 by precipitation.

10. The method of claim 9 , further comprising purifying by membrane filtration a solution comprising a purified substance obtained in the precipitation.

11. The method of claim 6 , further comprising purifying a solution comprising a product obtained in the polymerizing Z2 by membrane filtration.

12. The method of claim 6 , further comprising purifying a solution comprising a product obtained in the polymerizing Z2 by precipitation.

13. The method of claim 12 , further comprising purifying by membrane filtration a solution comprising a purified substance obtained in the precipitation.

14. The method of claim 1 , further comprising purifying a solution comprising a product obtained in the polymerizing Z1 by membrane filtration.

15. The method of claim 1 , further comprising purifying a solution comprising a product obtained in the polymerizing Z1 by precipitation.

16. The method of claim 15 , further comprising purifying by membrane filtration a solution comprising a purified substance obtained in the precipitation.

17. The method of claim 1 , wherein a starting polymerization reaction temperature of the solution is less than 5° C., and a maximum polymerization temperature is less than 25° C.

18. The method of claim 17 , wherein the solvent C comprises 35% by volume or more of water relative to an entire volume of the solvent C.

19. The method of claim 1 , wherein the conductive aniline polymer has an area ratio X/Y of 1.20-2.51.

20. A method for producing a conductive film comprising applying a solution comprising the conductive aniline polymer of claim 1 to a base material and drying the solution applied to the base material.

Assignees

• Mitsubishi Chem Corp

Inventors

• Yamada Kohei
• Horiuchi Yasushi
• Hachiya Yukiko
• Uzawa Masashi
• Sakai Takahiro
• Takagi Tamae

Classifications

• C09D5/24

  Electrically-conducting paints {(conductive materials H01B1/00)} · CPC title

• C08L79/02

  Polyamines · CPC title

• C08G73/0266

  Polyanilines or derivatives thereof · CPC title

• H01B13/30

  Drying; Impregnating (H01B13/32 takes precedence) · CPC title

• C09D179/02

  Polyamines · CPC title