Method for producing polyaniline having self-doping function and antistatic agent containing polyaniline produced thereby

Patent metadata

Field	Value
Publication number	US-9550861-B2
Application number	US-201414782892-A
Country	US
Kind code	B2
Filing date	Apr 4, 2014
Priority date	Apr 12, 2013
Publication date	Jan 24, 2017
Grant date	Jan 24, 2017

Abstract

An aniline monomer having a phosphonic acid of general formula (4) is polymerized to produce a polyaniline. In the formula, R 1 is NH 2 or NH 3 X, and X is a halogen. R 2 are each independently a phosphonic acid or a salt thereof. R 3 are each independently selected from the group consisting of a halogen atom, alkyl group having 1-15 carbon atoms, aralkyl group having 7-34 carbon atoms, alkoxy group having 1-15 carbon atoms, alkylthio group having 1-15 carbon atoms, alkylamino group having 1-15 carbon atoms, carboxyl group, carboxylic acid alkyl ester group wherein the alkyl group has 1-15 carbon atoms, nitro group, and cyano group. m is an integer of 1-4, n is an integer of 0-3, and the sum of m and n is 1-4. However, none of R 2 and R 3 is present at the para position relative to R 1 .

First claim

The invention claimed is:

1. A method for producing a polyaniline, comprising a step of polymerizing an aniline monomer compound represented by the following general formula (4):

(wherein R 1 is NH 2 or NH 3 X, and X is a halogen atom;
R 2 is each independently a substituent represented by the following general formula (5):

M 1 and M 2 are each independently selected from the group consisting of a hydrogen atom, alkali metal, alkaline earth metal, ammonium group, and pyridinium group, with the proviso that when M 1 or M 2 is an alkaline earth metal, the structure is such that the alkaline earth metal atom is bound to two O − in one phosphonic acid group and M 2 is not present, or such that the alkaline earth metal atom crosslinks O − of two phosphonic acid groups;
R 3 is each independently selected from the group consisting of a halogen atom, alkyl group in which the number of carbon atoms is 1 to 15, aralkyl group in which the number of carbon atoms is 7 to 34, alkoxy group in which the number of carbon atoms is 1 to 15, alkylthio group in which the number of carbon atoms is 1 to 15, alkylamino group in which the number of carbon atoms is 1 to 15, carboxyl group, carboxylic acid alkyl ester group in which the number of carbon atoms of the alkyl group is 1 to 15, nitro group and cyano group;
m is an integer of 1 to 4;
n is an integer of 0 to 3; and
the sum of m and n is 1 to 4;
with the proviso that neither R 2 nor R 3 is present at the para position relative to R 1 ); or
an aniline monomer mixture comprising the aniline monomer compound.

2. The method according to claim 1 , wherein at least one of M 1 and M 2 is a hydrogen atom.

3. The method according to claim 1 , wherein the polymerizing step is performed in the presence of 0.5 to 10 equivalents of an oxidizing agent with respect to the aniline monomer compound or the aniline monomer mixture.

4. The method according to claim 1 , wherein the polymerizing step is performed in the presence of a solvent.

5. The method according to claim 4 , wherein the solvent is at least one selected from ammonia water, pyridine water, pyridine, triethylamine water, triethylamine, water, hydrochloric acid, methanol, ethanol, isopropanol, acetonitrile, dimethylformamide, acetone, 2-butanone and dimethylacetamide.

6. The method according to claim 1 , further comprising a step of synthesizing an aniline monomer compound represented by general formula (4), wherein the synthesizing step comprises: binding a dialkyl phosphite represented by general formula (7):

(wherein M 1A and M 2A are each independently an alkyl group in which the number of carbon atoms is 1 to 15)
to a compound represented by the following general formula (6):

(wherein R 1A is a nitro group or an amino group, and X 1 is each independently a halogen atom;
definitions of R 3 , m and n are the same as the definitions of R 3 , m and n in claim 1 ;
with the proviso that neither X 1 nor R 3 is present in the para position relative to R 1A ).

7. The method according to claim 1 , further comprising a step of synthesizing an aniline monomer compound represented by general formula (4), wherein the synthesizing step comprises nitrating a compound represented by the following general formula (8):

(wherein definitions of R 3 , m and n are the same as the definitions of R 3 , m and n in claim 1 , with the proviso that no substituent is present on the carbon at the para position relative to the carbon to be nitrated in the benzene ring).

8. The method according to claim 6 , wherein R 1A is an amino group, and wherein the method further comprises hydrolyzing alkyl ester of M 1A and M 2A moieties of the compound obtained by binding the dialkyl phosphite to obtain an aniline monomer compound.

9. The method according to claim 6 , wherein R 1A is a nitro group, and wherein the method further comprises reducing a nitro group of the compound, which is obtained by binding the dialkyl phosphite, to an amino group to obtain an amino compound, and hydrolyzing alkyl ester of M 1A and M 2A moieties of the obtained amino compound to obtain an aniline monomer compound.

10. The method according to claim 7 , further comprising a step of reducing the nitro group of the compound obtained by the nitration to obtain an aniline monomer compound.

11. The method according to claim 1 , wherein a reaction temperature of the polymerizing step is in the range from −15° C. to 70° C.

12. The method according to claim 1 , wherein m is 1, and n is 0 or 1.

13. The method according to claim 1 , further comprising a step of performing an ion exchange treatment on the polymerization reaction product to replace a metal atom, an ammonium group or a pyridinium group of the phosphonic acid metal salt, phosphonic acid ammonium salt or phosphonic acid pyridinium salt in the polymerization reaction product with a hydrogen atom.

14. The method according to claim 13 , wherein: the ion exchange treatment step is a step of adding an acidic aqueous solution to the polymerization reaction product to replace a salt moiety of the phosphonic acid salt compound with hydrogen; after the ion exchange treatment step, a step of separating a polyaniline compound from the aqueous solution is performed; and further, thereafter, a step of adding an acidic aqueous solution to replace a salt moiety of the phosphonic acid salt compound with hydrogen and a step of separating a polyaniline compound from the aqueous solution are repeatedly performed.

15. A polyaniline produced by using the method according to claim 1 .

16. An antistatic agent containing the polyaniline according to claim 15 .

Assignees

• Univ Osaka
• Daihachi Chem Ind

Inventors

• Hirao Toshikazu
• Amaya Toru
• Abe Yasushi

Classifications

• C09K3/16

  Anti-static materials · CPC title

• C08L79/02

  Polyamines · CPC title

• C09D5/24

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

• C08G73/0266 Primary

  Polyanilines or derivatives thereof · CPC title