# US 10,767,012 B2 · Functionalized polyamides and methods of preparing the same

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- Number: US 10,767,012 B2
- Document ID: US10767012B2
- Status: Granted
- Kind: B2
- Application number: 15/949,784
- Filed: 2018-04-10
- Published: 2018-10-11
- Granted: 2020-09-08
- Earliest claimed: 2017-04-10
- Assignees: Firestone Fibers & Textiles Company, LLC
- Applicants: Firestone Fibers & Textiles Company, LLC
- Inventors: Laura S. Kocsis; William L. Hergenrother; Terrence E. Hogan; Kevin J. Bishop; Waruna C. B. Kiridena
- Web page: https://patentgrep.com/patent/US10767012B2

## CPC

- C08G 69/48: Polymers modified by chemical after-treatment
- C08G 69/16: Preparatory processes
- C08G 69/42: Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen (C08G69/12, C08G69/32 take precedence)
- B60C 9/0042: {Reinforcements made of synthetic materials}
- C08G 69/26: derived from polyamines and polycarboxylic acids
- C08G 2380/00: Tyres
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES

## Abstract

A functionalized polyamide is prepared by reacting a thio acid with an amide monomer or a mixture of a diamine and a dicarboxylic acid. In the reaction, the amide monomer is preferably a lactam compound, the thio acid has a formula of HOOC-A-SH wherein A represents an alkylene group containing from 1 to 10 carbon atoms, the diamine is an aliphatic diamine and the dicarboxylic acid is a aliphatic dicarboxylic acid. The functionalized polyamide can be vulcanized directly with rubber, which results in the use of less dip for adhering the tire cord to the rubber.

## Claims

### Claim 1

A process of preparing a functionalized polyamide comprising reacting a thio acid with (i) an amide monomer or (ii) a mixture of a diamine and a dicarboxylic acid, wherein the thio acid has the general formula HOOC-A-SH wherein A represents an alkylene group containing from 2 to 10 carbon atoms, further wherein 0.01 to 2 weight percent of the thio acid, based upon the weight of the (i) the amide monomer or (ii) the mixture of the diamine and the dicarboxylic acid, is used to prepare the functionalized polyamide.

### Claim 2 (depends on 1)

The process of claim 1, wherein the thio acid is 3-mercaptopropionic acid.

### Claim 3 (depends on 1)

The process of claim 1, wherein the amide monomer is ε-caprolactam.

### Claim 4 (depends on 1)

The process of claim 1, wherein the diamine is hexamethylene diamine and the dicarboxylic acid is adipic acid.

### Claim 5 (depends on 1)

The process of claim 1, wherein the thio acid is reacted with the amide monomer or the mixture of the diamine and the dicarboxylic acid at a temperature of 150° C. to 300° C.

### Claim 6 (depends on 1)

The process of claim 1, wherein the thio acid is 3-mercaptopropionic acid, the amide monomer is ε-caprolactam, the diamine is hexamethylene diamine, and the dicarboxylic acid is adipic acid.

### Claim 7 (depends on 1)

The process of claim 1, wherein 0.1 to 0.5 weight percent of the thio acid, based upon the weight of the (i) the amide monomer or (ii) the mixture of the diamine and the dicarboxylic acid, is used to prepare the functionalized polyamide.

### Claim 8

A functionalized polyamide comprising a terminal free thiol prepared by a process comprising reacting a thio acid with (i) an amide monomer or (ii) a mixture of a diamine and a dicarboxylic acid, wherein the thio acid has the general formula HOOC-A-SH wherein A represents an alkylene group containing from 2 to 10 carbon atoms, further wherein 0.01 to 2 weight percent of the thio acid, based upon the weight of the (i) the amide monomer or (ii) the mixture of the diamine and the dicarboxylic acid, is used to prepare the functionalized polyamide.

### Claim 9 (depends on 8)

The functionalized polyamide of claim 8, wherein the thio acid is 3-mercaptopropionic acid.

### Claim 10 (depends on 8)

The functionalized polyamide of claim 8, wherein the amide monomer is ε-caprolactam.

### Claim 11 (depends on 8)

The functionalized polyamide of claim 8, wherein the diamine is hexamethylene diamine and the dicarboxylic acid is adipic acid.

### Claim 12 (depends on 8)

The functionalized polyamide of claim 8, wherein the thio acid is reacted with the amide monomer or the mixture of the diamine and the dicarboxylic acid at a temperature of 150° C. to 300° C.

### Claim 13 (depends on 8)

The functionalized polyamide of claim 8, wherein the thio acid is 3-mercaptopropionic acid, the amide monomer is ε-caprolactam, the diamine is hexamethylene diamine, and the dicarboxylic acid is adipic acid.

### Claim 14 (depends on 8)

The functionalized polyamide of claim 8, wherein the functionalized polyamide is a sulfur-functionalized nylon-6.

### Claim 15 (depends on 8)

The functionalized polyamide of claim 8, wherein the functionalized polyamide is a sulfur-functionalized nylon-6,6.

### Claim 16 (depends on 8)

The functionalized polyamide of claim 8, wherein the functionalized polyamide has a total sulfur content of at least 300 ppm.

### Claim 17 (depends on 8)

The functionalized polyamide of claim 8, wherein 0.1 to 0.5 weight percent of the thio acid, based upon the weight of the (i) the amide monomer or (ii) the mixture of the diamine and the dicarboxylic acid, is used to prepare the functionalized polyamide.

### Claim 18 (depends on 8)

A tire cord comprising a cord comprising the functionalized polyamide of claim 8.

### Claim 19 (depends on 1)

The process of claim 1, wherein 0.1 to 0.5 or less weight percent of the thio acid, based upon the weight of the (i) the amide monomer or (ii) the mixture of the diamine and the dicarboxylic acid, is used to prepare the functionalized polyamide, and wherein the functionalized polyamide is a functionalized nylon having a total sulfur content of at least 300 ppm.

### Claim 20 (depends on 8)

The functionalized polyamide of claim 8, wherein 0.1 to 0.5 or less weight percent of the thio acid, based upon the weight of the (i) the amide monomer or (ii) the mixture of the diamine and the dicarboxylic acid, is used to prepare the functionalized polyamide, and wherein the functionalized polyamide is a functionalized nylon having a total sulfur content of at least 300 ppm.