# US 11,993,714 B2 · Block copolymer exhibiting improved abrasion resistance and improved tear resistance

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- Number: US 11,993,714 B2
- Document ID: US11993714B2
- Status: Granted
- Kind: B2
- Application number: 16/763,567
- Filed: 2018-11-16
- Published: 2020-12-10
- Granted: 2024-05-28
- Earliest claimed: 2017-11-17
- Assignees: Arkema France
- Applicants: Arkema France
- Inventors: Quentin P. Pineau; Philippe Denis H. Blondel; Jean-Jacques Flat
- Web page: https://patentgrep.com/patent/US11993714B2

## CPC

- C08L 77/12: Polyester-amides
- C08F 293/00: Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule (on to polymers modified by introduction of unsaturated end groups C08F290/02)
- C08G 69/48: Polymers modified by chemical after-treatment
- C08L 77/02: Polyamides derived from omega-amino carboxylic acids or from lactams thereof (C08L77/10 takes precedence)
- A43B 13/04: Plastics, rubber or vulcanised fibre
- C08G 69/40: Polyamides containing oxygen in the form of ether groups (C08G69/12, C08G69/32 take precedence)
- C08G 69/44: Polyester-amides
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- A43B: CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR

## Abstract

The invention relates to a copolymer containing rigid polyamide PA blocks and flexible blocks, characterized in that it includes at least one carboxylic acid chain end blocked with a polycarbodiimide, said copolymer according to the invention being in noncrosslinked linear form. The invention also relates to the use of a polycarbodiimide in a process for manufacturing a copolymer containing rigid polyamide PA blocks and flexible blocks, including at least one carboxylic acid chain end, for improving the extrudability of the copolymer, the drawability of the copolymer, the abrasion resistance, the tear strength and the durability of the copolymer, without increasing its dispersity.

## Claims

### Claim 1

A block copolymer comprising at least one rigid polyamide PA block and at least one flexible block,
wherein the flexible block comprises at least one block resulting from polyetherdiols,
wherein said block copolymer includes at least one carboxylic acid chain end blocked with a polycarbodiimide, and
wherein said copolymer is in noncrosslinked linear form, its dispersity Mw/Mn being less than 3,
wherein the weight content of the polycarbodiimide represents from 0.5% to 10% by weight, relative to the total weight of the copolymer.

### Claim 2 (depends on 1)

The copolymer as claimed in claim 1, wherein the weight-average molecular mass of the polycarbodiimide is greater than 10,000 g/mol.

### Claim 3 (depends on 1)

The copolymer as claimed in claim 1, wherein said carboxylic acid forms a urea bond by reaction with the carbodiimide of the polycarbodiimide.

### Claim 4 (depends on 1)

The copolymer as claimed in claim 1, wherein said flexible block comprises an additional block, the additional block being at least one block selected from the group consisting of polyether, polyester, polydimethylsiloxane, polyolefin, polycarbonate, and copolymers thereof.

### Claim 5 (depends on 1)

The copolymer as claimed in claim 1, wherein said block resulting from polyetherdiols comprises at least one polyether (PE), selected from the group consisting of poly(tetramethylene glycol) (PTMG), poly(1,2-propylene glycol) (PPG), poly(1,3,propylene glycol) (P03G), poly(ethylene glycol) (PEG) and copolymers thereof.

### Claim 6 (depends on 1)

The copolymer as claimed in claim 1, wherein said flexible block comprises an additional block comprising at least one polyester (PES) selected from the group consisting of polyester diols, poly(caprolactone) and polyesters based on fatty acid dimers.

### Claim 7 (depends on 1)

The copolymer as claimed in claim 1, wherein said polyamide PA block comprises at least one of the following polyamide units: 11, 12, 6, 610, 612, 1010, 1012, and copolyamides thereof.

### Claim 8 (depends on 1)

The copolymer as claimed in claim 1, wherein the weight ratio of the PA blocks to the flexible blocks is within the range from 0.3 to 10.

### Claim 9 (depends on 1)

A process for manufacturing the copolymer as claimed in claim 1, comprising a step of mixing of the block copolymer and of the polycarbodiimide so that at least one carboxylic acid chain end of the block copolymer reacts with a carbodiimide function of the polycarbodiimide.

### Claim 10 (depends on 9)

The process as claimed in claim 9, wherein the mixing is performed using a single-screw or twin-screw extruder or by adding the polycarbodiimide during the synthesis of the block copolymer.