# US 12,600,832 B2 · Fibrous material impregnated with reactive thermoplastic prepolymer

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- Number: US 12,600,832 B2
- Document ID: US12600832B2
- Status: Granted
- Kind: B2
- Application number: 16/624,441
- Filed: 2018-06-21
- Published: 2020-07-09
- Granted: 2026-04-14
- Earliest claimed: 2017-06-22
- Assignees: Arkema France
- Applicants: Arkema France
- Inventors: Gilles Hochstetter; Mathieu Capelot; Thibaut Savart; Arthur Pierre Babeau; Denis Huze; François Tanguy; Patrice Gaillard
- Web page: https://patentgrep.com/patent/US12600832B2

## CPC

- C08J 5/243: {using carbon fibres}
- C08L 77/00: Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain (of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08); Compositions of derivatives of such polymers
- C08J 2367/00: Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J 2377/06: Polyamides derived from polyamines and polycarboxylic acids (C08J2377/10 takes precedence)
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The present invention relates to an impregnated fibrous material comprising a fibrous material made of continuous fibers and at least one reactive thermoplastic prepolymer, and optionally a chain extender, characterized in that the at least one reactive thermoplastic prepolymer is partially polymerized, optionally with the chain extender, and has a number-average molecular weight (Mn) ranging from 500 to 10,000, preferably from 4,000 to 8000, the proportion of fibers in the impregnated fibrous material being 45 to 65% by volume, preferably 50 to 60% by volume, and in particular 54 to 60%.

## Claims

### Claim 1

An impregnated fibrous material comprising a fibrous material made of continuous fibers and at least one reactive thermoplastic prepolymer in a solid state,
wherein said at least one reactive thermoplastic prepolymer is partially polymerized without a chain extender and has a number-average molecular weight Mn from 500 to 10,000, the proportion of fibers in said impregnated fibrous material being 45 to 65% by volume,
wherein said at least one partially polymerized reactive thermoplastic prepolymer has a molten viscosity of 0.1 to 100 Pa.s,
wherein a preimpregnation step is done using an aqueous dispersion of prepolymer particle or an emulsion or aqueous suspension of prepolymer, a fluidized bed or spraying of a nozzle or spray gun by dry route in a tank, excluding a molten route, the fluidized bed having at least one supporting part which includes a compression roller,
wherein the at least one reactive thermoplastic prepolymer is selected from: polyaryl ether ketones (PAEK); polyaryl ether ketone ketone (PAEKK); aromatic polyether imides (PEI); polyaryl sulfones; polyarylsulfides; polyamides (PA); PEBAs; polyolefins; and mixtures thereof,
wherein said at least one partially polymerized reactive thermoplastic prepolymer comprises at least two polyamide prepolymers that react together and each carry respectively two identical terminal functions X′ or Y′, where said function X′ of a prepolymer can react only with said function Y′ of the other prepolymer.

### Claim 2 (depends on 1)

The impregnated fibrous material according to claim 1, wherein said at least one thermoplastic prepolymer is selected from polyamides, PEKK, PEI and a mixture of PEKK and PEI.

### Claim 3 (depends on 2)

The impregnated fibrous material according to claim 2, wherein said polyamide is selected from aliphatic polyamides, cycloaliphatic polyamides and semi-aromatic polyamides.

### Claim 4 (depends on 3)

The impregnated fibrous material according to claim 3, wherein said aliphatic polyamide is selected from polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 66 (PA-66), polyamide 46 (PA-46), polyamide 610 (PA-610), polyamide 612 (PA-612), polyamide 1010 (PA-1010), polyamide 1012 (PA-1012), polyamide 11/1010, polyamide 12/1010, or a mixture thereof or a copolyamide thereof, and block copolymers.

### Claim 5 (depends on 1)

The impregnated fibrous material according to claim 1, wherein said at least one reactive thermoplastic prepolymer has a glass transition temperature Tg≥80° C., or a melting temperature Tf≥150° C.

### Claim 6 (depends on 1)

The impregnated fibrous material according to claim 1, wherein said fibrous material comprises continuous fibers selected from carbon, glass, silicon carbide, basalt, silica, flax or hemp, lignin, bamboo, sisal, silk, or cellulose, or amorphous thermoplastic fibers with a glass transition temperature Tg higher than the Tg of said prepolymer or said prepolymer mixture when the latter is amorphous or higher than the Tf of said prepolymer or said prepolymer mixture when the latter is semi-crystalline, or the semicrystalline thermoplastic fibers with a melting temperature Tf higher than the Tg of said prepolymer or said prepolymer mixture when the latter is amorphous or higher than the Tf of said prepolymer or said prepolymer mixture when the latter is semi-crystalline, or a mixture of two or more of said fibers.

### Claim 7 (depends on 1)

The impregnated fibrous material according to claim 1, wherein said thermoplastic prepolymer further comprises carbonaceous fillers.

### Claim 8 (depends on 1)

The impregnated fibrous material according to claim 1, wherein said thermoplastic prepolymer further comprises liquid crystal polymers or cyclic poly(butylene terephthalate), or mixtures containing said liquid crystal polymers or said cyclic poly(butylene terephthalate) as additives.

### Claim 9 (depends on 1)

A method for preparing an impregnated fibrous material comprising a fibrous material with continuous fibers and at least one nonreactive thermoplastic polymer, the number-average molecular weight Mn of which is greater than 10,000, the method comprising using the impregnated fibrous material of claim 1.

### Claim 10 (depends on 1)

A method of preparing calibrated ribbons suitable for the manufacture of three-dimensional composite parts by automatic application of said ribbons by means of a robot, the method comprising using the fibrous material of claim 1 to prepare the calibrated ribbons.

### Claim 11 (depends on 1)

A ribbon comprising at least one fibrous material as defined in claim 1.

### Claim 12 (depends on 11)

The ribbon according to claim 11, wherein the ribbon is made of a single unidirectional ribbon or a plurality of parallel unidirectional ribbons.

### Claim 13 (depends on 11)

The ribbon according to claim 11, wherein the ribbon has a width (I) and thickness (ep) suitable for robot application in the manufacture of three- dimensional parts, without the need for slitting.

### Claim 14 (depends on 11)

The ribbon according to claim 11, wherein the thermoplastic prepolymer is a polyamide prepolymer chosen from an aliphatic polyamide selected from PA 6, PA 11, PA 12, PA 66, PA 46, PA 610, PA 612, PA 1010, PA-1012, PA 11/1010 and PA12/1010, a semi-aromatic polyamide chosen from PA 11/10T, PA 11/6T/10T, PA MXDT/10T, PA MPMDT/10T and PA BACT/10T, PA BACT/6T, PA BACT/10T/6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture of PEKK and PEI.

### Claim 15 (depends on 11)

A method of manufacturing three-dimensional composite parts, the method comprising using the ribbon according to claim 11 to manufacture three-dimensional composite parts.

### Claim 16 (depends on 15)

The method according to claim 15, wherein said composite parts relates to the fields of transportation, petroleum and gas, gas storage, aeronautics, nautical and rail; renewable energies, energy storage devices, solar panels; thermal protection panels; sports and recreation, health and medical, and electronics.

### Claim 17 (depends on 1)

The impregnated fibrous material according to claim 1, wherein said function X′ of the prepolymer can react only with said function Y′ of the other prepolymer by condensation.

### Claim 18 (depends on 17)

The impregnated fibrous material according to claim 17, wherein said function X′ of the prepolymer can react only with said function Y′ of the other prepolymer with X′ and Y′ being amine and carboxyl or carboxyl and amine respectively.