# US 9,040,700 B2 · Method of producing polymeric phenazonium compounds

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,040,700 B2
- Document ID: US9040700B2
- Status: Granted
- Kind: B2
- Application number: 14/181,866
- Filed: 2014-02-17
- Published: 2014-06-12
- Granted: 2015-05-26
- Earliest claimed: 2010-09-24
- Applicants: MacDermid Acumen, Inc.
- Inventors: Andrew M. Krol; Ernest Long; Lev Taytsas
- Web page: https://patentgrep.com/patent/US9040700B2

## CPC

- C08G 73/0633: {with only two nitrogen atoms in the ring}
- C07D 241/46: Phenazines
- C08G 73/0694: {with only two nitrogen atoms in the ring, e.g. polyquinoxalines}
- C25D 3/38: of copper
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR

## Abstract

A process of making a polymeric phenazonium compound having the general formula: wherein R1, R2, R4, R5, R6, R8, and R9 are the same or different, and represent hydrogen, a low alkyl or a substituted aryl, R3 starts with NH2 and is diazotized followed by a polymerization, R5 and R8 may alternatively represent monomeric or polymeric phenazonium radicals, R7 is a carbon in the aromatic ring, Rx and Ry represent any combination of CH3, C2H5, and hydrogen, except that Rx and Ry cannot both be hydrogen, A is an acid radical, and n is an integer from 2 to 100, preferably from 2 to 20 is described. The polymeric phenazonium compound is usable as an additive in a metal plating bath comprising copper. The method includes the steps of a) dissolving an effective amount of an amino compound in a formic acid solution; b) adding a nitrite salt to diazotize the amino compound; and c) adding sulfamic acid to neutralize any excess nitrous acid that may be formed in step b), whereby a polymeric phenazonium compound is produced with a smaller quantity of unreacted monomer remaining in the end product than those produced using methods of the prior art.

## Claims

### Claim 1

A process of making a polymeric phenazonium compound to be used in a metal plating bath comprising copper, commencing with the general formula:
Wherein R1, R2, R4, R5, R6, R8, and R9 are the same or different, and represent hydrogen, a low alkyl or a substituted aryl, R3 starts with NH2 and is diazotized followed by polymerization, R5 and R8 may alternatively represent monomeric or polymeric phenazonium radicals, R7 is a carbon in the aromatic ring, Rx and Ry represent any combination of CH3, C2H5,
and hydrogen, except that Rx and Ry cannot both be hydrogen, A is an acid radical, and n is an integer from 2 to 100, the method comprising the steps of:
a) dissolving an effective amount of an amino compound in a formic acid solution;
b) adding a nitrite salt to diazotize the amino compound; and
c) adding sulfamic acid to neutralize any excess nitrous acid that may be formed in step b),
whereby a polymeric phenazonium compound of the general formula specified above is produced.

### Claim 2 (depends on 1)

The method according to claim 1, wherein n is an integer from 2 to 20.

### Claim 3 (depends on 1)

The method according to claim 1, wherein said amino compound is selected from the group consisting of 2-methyl-3-amino-7-dimethylamino-5-phenyl-phenazonium hydrogen sulfate, 2-methyl-3-amino-7-dimethylamino-5-phenyl-phenazonium chloride, 3-amino-7-dimethylamino-5-methyl-phenazonium acetate, 2-methyl-3-amino-7-phenylamino-5-phenyl-phenazonium hydrogen sulfate, 2-methyl-3-amino-7-dimethylamino-phenazonium hydrogen sulfate, 3-amino-7-methylamino-5-phenyl-phenazonium acetate, 2-phenyl-3-amino-7-ethylamino-5-phenyl-phenazonium chloride, 1,2,6,9-tetramethyl-3-amino-7-dimethylamino-5-phenyl-phenazonium hydrogen sulfate, 2,8-dimethyl-3-amino-7-diethylamino-5-tolyl-phenazonium chloride, and 2,9-diphenyl-3-amino-6-methyl-7-dimethylamino-5-phenyl-phenazonium hydrogen sulfate.

### Claim 4 (depends on 1)

The method of claim 1, wherein the nitrite salt is sodium nitrite.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the amino compound is dissolved in the formic acid at a temperature of between about −10 to about 0 C.

### Claim 6 (depends on 1)

The process according to claim 1, wherein after step b) the reaction is warmed to at least 20 C.

### Claim 7 (depends on 1)

The process according to claim 1, wherein the concentration of the amino compound in the formic acid solution is between about 100 g/L and about 200 g/L.

### Claim 8 (depends on 7)

The process according to claim 7, wherein the concentration of the amino compound in the formic acid solution is between about 120 g/L and about 185 g/L.

### Claim 9 (depends on 1)

The process according to claim 1, wherein the process of producing the polymeric phenazonium compound does not include a step of neutralizing the polymeric phenazonium compound with a base.

### Claim 10 (depends on 1)

The process according to claim 1, wherein the concentration of polymerized phenazonium compound is between about 30 g/L and about 34 g/L.