Sulfonated aniline-type copolymer and process for production thereof

• US 5,354,816 A
• Filed: 12/24/1992
• Issued: 10/11/1994
• Est. Priority Date: 12/27/1991
• Status: Expired due to Term

• Current Assignee: Mitsubishi Rayon Company Limited (Mitsubishi Chemical Holdings Corporation)
• Original Assignee: Nitto Chemical Industry Co., Ltd. (Mitsubishi Chemical Group Corp.)
• Inventors: Saitoh, Takashi, Shimizu, Shigeru, Nakamura, Tomio
• Primary Examiner(s): Kight, III, John
• Assistant Examiner(s): DODSON, SHELLEY A
• Application Number:
  US07/996,786
• Time in Patent Office: 656 Days
• Field of Search: 525/535, 525/540, 528/391
• US Class Current: 525/535
• CPC Class Codes: C08G 73/0266 Polyanilines or derivatives thereof
• CPC Class Codes: C09K 3/16 Anti-static materials
• CPC Class Codes: H01B 1/128 comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes

Abstract

Sulfonated aniline-type copolymer and a process for their preparation are disclosed.

These products comprise a water soluble and alcohol soluble copolymer of a compound (A) selected from the group of aniline, N-alkylaniline and phenylenediamine, and aminobenzene sulfonic acid (B); said sulfonated product being a following compound of a general formulae I to V stated in the specification, or a mixture thereof.

Also, process for the sulfonated aniline-type copolymer comprises the steps:

copolymerizing a compound (A) selected from the group of aniline, N-alkyl aniline and phenylene diamine, and aminobenzene sulfonic acid (B) to obtain a copolymer; and

sulfonating the thus obtained copolymer with a sulfonating agent.

Claims

1. A process for preparing a sulfonated copolymer which comprises copolymerizing (A) a compound selected from the group consisting of an aniline compound, an N-alkyl aniline compound a phenylenediamine compound and mixtures thereof with (B) an aminobenzenesulfonic acid compound to obtain a first sulfonated copolymer;

and further sulfonating the thus obtained first sulfonated copolymer with a sulfonating agent.

2. A process for preparing a sulfonated copolymer as in claim 1 wherein the first sulfonated copolymer is a compound selected from the group consisting of:

##STR2## and mixtures thereof;

wherein R₁, R₂, R₃ and R₄ are independently selected from the group consisting of hydrogen, methoxy, C₁ -C₂ alkyl hydroxyl and sulfonic acid, wherein at least one of the R₁, R₂, R₃ and R₄ is sulfonic acid;

R'"'"' is hydrogen or C₁ -C₄ alkyl;

x is a number from 0-1.

3. A process for preparing a sulfonated copolymer as in claim 2 wherein R'"'"' is methyl.

4. A process for preparing a sulfonated copolymer as in claim 2 wherein a sulfonic acid is incorporated into an aromatic ring of the first sulfonated copolymer in a ratio of from 40 to 80 percent.

5. A process for preparing a sulfonated copolymer as in claim 2 wherein the molecular weight of the first sulfonated copolymer ranges from 300 to 500,000 daltons.

6. A process for preparing a sulfonated copolymer as in claim 1 wherein the phenylenediamine compound is a compound selected from the group consisting of phenylenediamine, N-phenylphenylenediamine, N,N'"'"'-diphenylphenylenediamine, N-aminophenyl-N'"'"'-phenylphenylenediamine and hydroxydiphenylamine.

7. A process for preparing a sulfonated copolymer as in claim 1 wherein the aniline compound is a compound selected from the group consisting of aniline and phenylenediamine.

8. A process for preparing a sulfonated copolymer as in claim 1 wherein the N-alkylaniline compound is a compound selected from the group consisting a N-methylaniline, N-ethylaniline, N-n-propylaniline, N-iso-propylaniline and N-butylaniline.

9. A process for preparing a sulfonated copolymer as in claim 1 wherein the aminobenzenesulfonic acid compound is a compound selected from the group consisting of o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid and anilinedisulfonic acid.

10. A process for preparing a sulfonated copolymer as in claim 1 wherein the mixture of the N-alkyl aniline compound and the aniline compound have a ratio of 0 to 30:

100.

11. A process for preparing a sulfonated copolymer as in claim 1 wherein the aniline, N-alkylaniline, or phenylenediamine compound is in a ratio to the aminobenzenesulfonic acid compound of 100:

10-500 parts by weight.

12. A process for preparing a sulfonated copolymer as in claim 1 wherein copolymerizing occurs by oxidation polymerization with an oxidizing agent in an acid solvent.

13. A process for preparing a sulfonated copolymer as in claim 1 wherein the sulfonating agent is a compound selected from the group consisting of a concentrated sulfuric acid, a fuming sulfuric acid, a fuming sulfuric acid complex and a sulfur trioxide.