# US 9,752,029 B2 · Thermoplastic composite material made of a semi-crystalline polyamide and method for manufacturing same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,752,029 B2 - Document ID: US9752029B2 - Status: Granted - Kind: B2 - Application number: 14/438,062 - Filed: 2013-10-21 - Published: 2015-09-24 - Granted: 2017-09-05 - Earliest claimed: 2012-10-23 - Assignees: Arkema France - Applicants: Arkema France - Inventors: Thierry Briffaud; Gilles Hochstetter - Web page: https://patentgrep.com/patent/US9752029B2 ## CPC - C08L 77/06: Polyamides derived from polyamines and polycarboxylic acids (C08L77/10 takes precedence) - B29C 70/021: {Combinations of fibrous reinforcement and non-fibrous material} - C08G 69/265: {from at least two different diamines or at least two different dicarboxylic acids} - C08J 5/04: Reinforcing macromolecular compounds with loose or coherent fibrous material - C08K 7/04: inorganic - C08J 2377/06: Polyamides derived from polyamines and polycarboxylic acids (C08J2377/10 takes precedence) - C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - 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) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) ## Abstract A composition for a thermoplastic composite material having a thermoplastic matrix made of a semi-crystalline polyamide having a specific composition that includes at least two amide units, A, 55-95 mol %, and B, 5-45 mol %. A corresponds to x.T, wherein x is a C9-C18 linear aliphatic diamine and B corresponds to x′.T, wherein x′ can be B1): a specific branched x-dependent aliphatic diamine, B2): MXD or B3): a linear x-dependent aliphatic diamine, said polyamide having a glass transition temperature Tg of at least 90° C. and a melting point no higher than 280° C. Also, a method for manufacturing said composite material, the semi-crystalline polyamide polymer, the use of the composition and of the polymer for parts made of composite material, as well as the material and the resulting composite part. ## Claims ### Claim 1 A thermoplastic composite material, said thermoplastic composite material comprising reinforcing fibers or a fibrous reinforcement, and a thermoplastic matrix which impregnates said reinforcing fibers or said fibrous reinforcement, wherein said thermoplastic matrix comprises one or more polyamides which comprise different amide units A and B and, optionally, amide units C and D, selected as follows: A: is a major amide unit present at a molar content ranging from 55% to 95%, chosen from x.T units, where x is a C9 to C18, linear aliphatic diamine, and where T is terephthalic acid, B: is an amide unit different than A, said unit B being present at a molar content ranging from 5% to 45%, according to the Tm of the polyamide based on unit A and said amide unit B being chosen from x′.T units, where x′ is chosen from: B1) a branched aliphatic diamine bearing a single methyl or ethyl branching and having a main chain length which is different by at least two carbon atoms compared with the main chain length of the diamine x of said associated unit A, or B2) m-xylylenediamine (MXD) or B3) a C4 to C18 linear aliphatic diamine when, in the unit A, said diamine x is a C11 to C18 linear aliphatic diamine and x′ is a C9 to C18 diamine when, in the unit A, said diamine x is a C9 or C10 diamine, C: optional amide unit different than A and than B, chosen from amide units based on a cycloaliphatic and/or aromatic structure or based on x′T as defined above for B but with x′ being different than x′ for the unit B, D: optional amide unit different than A, than B and than C when C is present, and chosen from the aliphatic amide units derived from: amino acids or lactams which are C6 to C12, or mixtures thereof, the reaction of a C6 to C18, linear aliphatic diacid and of a C6 to C18, linear aliphatic diamine, or mixtures thereof, and under the condition that the sum of the molar contents of A+B+C+D is equal to 100%; wherein at least one polyamide of the one or more polyamides is a semi-crystalline polyamide polymer with a glass transition temperature Tg of at least 90° C. and with a melting temperature Tm below or equal to 280° C., wherein a difference between the melting temperature Tm and crystallization temperature Tc, (Tm−Tc), of said semi-crystalline polyamide, does not exceed 50° C.; and wherein enthalpy of crystallization of said semi-crystalline polyamide, measured by differential scanning calorimetry (DSC) according to standard ISO 11357-3, is greater than 40 J/g. ### Claim 2 (depends on 1) The thermoplastic composite material as claimed in claim 1, wherein said amide unit C is present and partially replaces B at a molar content ranging up to 25% relative to said unit B. ### Claim 3 (depends on 1) The thermoplastic composite material as claimed in claim 1, wherein said unit D is present and partially replaces B at a molar content ranging up to 70%, relative to said unit B. ### Claim 4 (depends on 1) The thermoplastic composite material as claimed in claim 1, wherein said amide unit A is present with a molar content ranging from 55% to 80%, relative to all the units of said polymer. ### Claim 5 (depends on 1) The thermoplastic composite material as claimed in claim 1, wherein said unit B corresponds to x′T with x′ being 2-methylpentamethylenediamine (MPMD). ### Claim 6 (depends on 1) The thermoplastic composite material as claimed in claim 1, wherein said unit B corresponds to x′T with x′ chosen according to option B2), x′ being MXD. ### Claim 7 (depends on 1) The thermoplastic composite material as claimed in claim 1, wherein said unit B corresponds to a linear aliphatic diamine according to option B3). ### Claim 8 (depends on 1) The thermoplastic composite material as claimed in claim 1, wherein the units A and B are selected as follows: for the unit A being 9T, said unit B is selected from: 10T, 11T, 12T, 13T, 14T, 15T, 16T, 17T and 18T, 2-methylpentamethylenediamine (MPMD).T and MXD.T, with a molar content of B ranging from 30% to 45%, for the unit A being 10T, said unit B is selected from: 9T, 11T, 12T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, with a molar content of B ranging from 25% to 45%, for the unit A being 11T, said unit B is selected from: 9T, 10T, 12T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, with a molar content of B ranging from 20% to 45%, for the unit A being 12T, said unit B is selected from: 9T, 10T, 11T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, with a molar content of B ranging from 20% to 45%. ### Claim 9 (depends on 5) The thermoplastic composite material as claimed in claim 5, wherein a part of the unit B which is up to 70 mol %, relative to B, is replaced with a unit C and/or D. ### Claim 10 (depends on 1) The thermoplastic composite material as claimed in claim 1, wherein the thermoplastic composite material comprises a fibrous reinforcement with long fibers with L/D>1000. ### Claim 11 (depends on 1) A process for manufacturing a final composite part comprising the thermoplastic composite material as defined in claim 1, wherein the process comprises at least one step of molding or processing said thermoplastic composite material. ### Claim 12 (depends on 11) The process as claimed in claim 11, wherein the process comprises the following steps: i) impregnation in the molten state of a fibrous reinforcement with the thermoplastic matrix, in an open or closed mold or outside the mold, in order to obtain the thermoplastic composite material, ii) processing or molding of said thermoplastic composite material of step i) so as to form the final composite part in a mold or with another processing system. ### Claim 13 A polyamide polymer which comprises different amide units A and B and, optionally, amide units C and D, selected as follows: A: is a major amide unit present at a molar content ranging from 55% to 95%, chosen from x.T units, where x is a C9 to C18, linear aliphatic diamine, and where T is terephthalic acid, B: is an amide unit different than A, said unit B being present at a molar content ranging from 5% to 45%, according to the Tm of the polyamide based on unit A and said amide unit B being chosen from x′.T units, where x′ is chosen from: B1) a branched aliphatic diamine bearing a single methyl or ethyl branching and having a main chain length which is different by at least two carbon atoms compared with the main chain length of the diamine x of said associated unit A, or B2) m-xylylenediamine (MXD) or B3) a C4 to C18 linear aliphatic diamine when, in the unit A, said diamine x is a C11 to C18 linear aliphatic diamine and x′ is a C9 to C18 diamine when, in the unit A said diamine x is a C9 or C10 diamine, C: optional amide unit different than A and than B, chosen from amide units based on a cycloaliphatic and/or aromatic structure or based on x′T as defined above for B but with x′ being different than x′ for the unit B, D: optional amide unit different than A, than B and than C when C is present, and chosen from the aliphatic amide units derived from: amino acids or lactams which are C6 to C12, or mixtures thereof, the reaction of a C6 to C18, linear aliphatic diacid and of a C6 to C18, linear aliphatic diamine, or mixtures thereof, and under the condition that the sum of the molar contents of A+B+C+D is equal to 100%; wherein the polymer is a semi-crystalline polyamide polymer with a glass transition temperature Tg of at least 90° C. and with a melting temperature Tm below or equal to 280° C., wherein a difference between the melting temperature Tm and crystallization temperature Tc, (Tm−Tc), of said semi-crystalline polyamide, does not exceed 50° C.; and wherein enthalpy of crystallization of said semi-crystalline polyamide, measured by differential scanning calorimetry (DSC) according to standard ISO 11357-3, is greater than 40 J/g. ### Claim 14 (depends on 1) A method for manufacturing mechanical or structural parts based on a composite material, comprising using the thermoplastic composite material as claimed in claim 1. ### Claim 15 (depends on 14) The method as claimed in claim 14, wherein said mechanical or structural parts made of said composite material concern applications in the following fields: the motor vehicle industry, the railroad industry, the marine or maritime industry, wind power, photovoltaics, solar panels and components for solar power stations, sports, aeronautics and space, road transport, the construction industry, civil engineering, panels, and leisure. ### Claim 16 (depends on 1) A mechanical or structural part made of thermoplastic composite material, wherein it results from the thermoplastic composite material as defined in claim 1. ### Claim 17 (depends on 16) The structural part as claimed in claim 16, where in it is a motor vehicle part post-treated by cataphoresis. ### Claim 18 (depends on 16) The part as claimed in claim 16, wherein it is a part for wind power. ### Claim 19 (depends on 16) The part as claimed in claim 16, wherein it is a part for aeronautics. ### Claim 20 (depends on 1) The thermoplastic composite material as claimed in claim 1, wherein said semi-crystalline polyamide polymer has a glass transition temperature Tg of at least 100° C. ### Claim 21 (depends on 1) The thermoplastic composite material as claimed in claim 1, wherein said semi-crystalline polyamide polymer has a melting temperature Tm below or equal to 270° C. ### Claim 22 (depends on 1) The thermoplastic composite material as claimed in claim 1, wherein the reinforcing fibers or fibrous reinforcement is/are circular in cross-section.