Semicrystalline polyamide composition having a high glass transition temperature and a high melting point for thermoplastic materials, a method for producing the same, and use thereof

Abstract

A resin composition for molded parts is provided that has excellent mechanical properties at high temperatures, such as creep or heat resistance, and a shortened injection molding time. [Solution] A composition for thermoplastic materials comprising 0 to 70% by weight of short reinforcing fibers, 30 to 100% by weight of a thermoplastic matrix based on at least one semi-crystalline polyamide polymer, and 0 to 50% by weight of additives and / or other polymers, wherein the composition is a) a reactive composition comprising or consisting of at least one reactive polyamide prepolymer precursor of the semi-crystalline polyamide polymer, or alternatively b) a non-reactive composition of at least one polyamide polymer that is the composition of the thermoplastic matrix defined above, wherein the reactive polyamide prepolymer of composition a) and the polyamide polymer of composition b) comprise or consist of at least one BACT / XT copolyamide.

Description

Technical Field

[0001] The present invention relates to a novel semi-crystalline (sc) polyamide composition based on bis(aminoethyl)cyclohexane (BAC) with a high glass transition temperature for thermoplastic materials.

[0002] The present invention also relates to a method for manufacturing said thermoplastic material, and to the use of said composition for the manufacture of mechanical or structural parts based on said material for material parts and resulting parts, as well as for applications in the fields of automotive, railway, marine, highway transport, wind, sports, space and aviation, construction, signage and leisure, and electrical and electronics.

Background Art

[0003] The main challenge of materials is to find a polyamide resin that meets the following specifications: - High Tg over a wide range of service temperatures; - High Tm for good temperature resistance, but a Tm low enough to be particularly suitable for processing by injection; - Very good compatibility with crystallization so that it can be quickly removed from the mold and thus can cope with intensive production cycles such as those used in the automotive industry, for example; - High rigidity, including at high temperatures, to produce the highest possible modulus of elasticity from the final material.

[0004] Patent document CN104211953 describes a polyamide composition comprising 30 to 99.9% by weight of a polyamide resin containing 60 to 95 mol% of 10T, 5 to 40 mol% of 5’T (where 5’ corresponds to 2-methyl-1,5-pentamethylenediamine), 0 to 70% by weight of a reinforcing filler, and 0.1 to 50% by weight of an additive.

[0005] The polyamide resin has a melting temperature above 260°C and a high molar ratio of 10T.

[0006] EP550314 describes, in its examples, a (non-reactive) copolyamide composition having a melting point above 250°C and a targeted limited Tg, but most of the given examples have a Tg that is too low (<80°C).

[0007] EP1988113 - 40 to 95 mol% of 10T - 5 to 40% of 6T and describes a molding composition based on a 10T / 6T copolyamide having

[0008] In particular, there is a need for polyamides having a high 10T molar ratio and a high melting point above 270°C.

[0009] WO 2011 / 003973 describes a composition comprising 50 to 95 mol% of a linear aliphatic diamine-based motif containing 9 to 12 carbon atoms and terephthalic acid, in combination with 5 to 50% of a motif of a mixture of terephthalic acid and 2,2,4- and 2,4,4-trimethylhexanediamine.

[0010] WO 2014 / 064375 describes, in particular, MXDT / 10T PA having an excellent compromise between the various properties described above. Unfortunately, the meta-xylenediamine (MXD) monomer used is prone to secondary reactions, in particular causing branching.

[0011] The drawbacks of the current state of the art, which have a short production cycle time and lack a good compromise between mechanical performance and suitability for mounting (ease of deformation), in particular for high mechanical performance (mechanical strength) in the case of easy mounting at high temperature and in particular by injection, are overcome by the solution of the present invention which aims at a semi-crystalline PA composition having an excellent compromise between mechanical performance and suitability for mounting (ease of deformation). It is actually highly rigid, has a glass transition temperature >150°C, a Tm between 290°C and 340°C, and an excellent crystallization ability (Tm - Tc < 40°C), which makes it a preferred matrix, in particular for applications in the wind, automotive or aerospace or electrical and electronic industries, in particular for mounting by injection or molding.

[0012] The selection of a semi-crystalline polyamide polymer as a matrix for the thermoplastic material of the present invention is attractive due to significantly improved mechanical properties at high temperatures, such as creep or fatigue resistance, especially compared to amorphous polyamides. Furthermore, a melting point above 200 °C is advantageous in the automotive field due to compatibility with electrophoretic processes that are not possible with amorphous PA types. A Tg above 150 °C is required, especially to provide good mechanical properties to the thermoplastic material over the entire operating temperature range of injection molding. To optimize the mechanical properties and the highest possible crystallization rate and / or crystallization temperature and thus shorten the molding time until the molded part is ejected by selecting the composition of the semi-crystalline polyamide, the degree of crystallinity of the polymer must be as high as possible.

Summary of the Invention

[0013] The subject of the present invention is the implementation of a specific novel specific composition of a thermoplastic material based in particular on a semi-crystalline polyamide having a good compromise between high mechanical performance (mechanical strength), especially in the case of easy implementation at high temperatures. More specifically, for example, both improved processability due to the low initial viscosity of the composition for using lower injection pressures or for molding parts with a higher level of fineness and improved mechanical properties due to achievable high molecular weights are possible with the solution of the present invention by using a composition based on a semi-crystalline reactive polyamide prepolymer in the case of reactive compositions. More specifically, while having a defined high Tg and Tm, due to the easy implementation of the thermoplastic material, the polyamide polymer matrix must also have a high crystallization rate characterized by a difference Tm - Tc between the melting temperature and the crystallization temperature that does not exceed 40 °C, preferably does not exceed 30 °C. Thus, the subject of the present invention is the necessity already defined above: - High Tg over a wide operating temperature; - Tm between 290 °C and 340 °C to facilitate the processing, especially by injection; - Very good compatibility with crystallization to be able to be quickly removed from the mold and thus to be able to cope with intensive production cycles, such as those used in the automotive industry, for example; - To generate the highest possible modulus of elasticity from the final material, high rigidity including at high temperatures It is to develop a polyamide composition that satisfies

[0014] The present invention is - 0 to 70% by weight, preferably 20 to 60% by weight, of short reinforcing fibers - 30 to 100% by weight, preferably 40 to 80% by weight, of a thermoplastic matrix based on at least one semi-crystalline polyamide polymer - 0 to 50% by weight of additives and / or other polymers A composition for a thermoplastic material comprising wherein the semi-crystalline polyamide polymer is a) a reactive composition comprising or consisting of at least one reactive polyamide prepolymer precursor of the semi-crystalline polyamide polymer, or instead of a), b) a non-reactive composition of at least one polyamide polymer that is a composition of the thermoplastic matrix defined above, The reactive polyamide prepolymer of composition a) and the polyamide polymer of composition b) comprise or consist of at least one BACT / XT copolyamide, - BACT is a unit having an amide motif present in a molar content in the range of 70 to 99.1%, preferably 80 to 99%, more preferably 90 to 99%, BAC is selected from 1,3-bis(aminomethyl)cyclohexyl (1,3-BAC), 1,4-bis(aminomethyl)cyclohexyl (1,4-BAC) and mixtures thereof, T is terephthalic acid, - XT is an amide motif unit present in a molar content in the range of 0.9 to less than 30%, preferably 1 to 20%, more preferably 1 to 10%, X is a C4 to C18 linear aliphatic diamine, particularly C9 to C18, preferably C9, C10, C11 or C12, and T is terephthalic acid, preferably C10, C11 or C12, - In the BACT and / or XT units, independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol% of terephthalic acid, based on the total amount of dicarboxylic acids, can be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids containing from 6 to 36 carbon atoms, in particular from 6 to 14 carbon atoms, - In the BACT and / or XT units, independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol% of BAC and / or, where applicable, X, based on the total amount of diamines, can be replaced by other diamines containing from 4 to 36 carbon atoms, in particular from 6 to 12 carbon atoms, - In the copolyamide, up to 30 mol%, preferably up to 20 mol%, preferably up to 10 mol% of the total amount of monomers can be formed by lactam or aminocarboxylic acid, - The total of the monomers replacing terephthalic acid, BAC and X does not exceed a concentration of 30 mol%, preferably 20 mol%, preferably 10 mol% of the total amount of monomers used in the copolyamide, - The BACT and XT units are still present in the polyamide polymer, Relates to a composition.

[0015] The partial substitution of the monomers defined above means the ranges of BACT and XT defined above, i.e. it is clear that if BACT is present, for example, in a proportion of more than 70 to 99.1%, the possible partial substitution of BAC and / or T results, in all cases, in a final proportion of at least more than 70% of BACT, and the same applies to XT.

[0016] Thus, the semi-crystalline polyamide polymer forms the basis of a thermoplastic matrix, Either a di-NH2- or di-CO2H-terminated polyamide prepolymer which can react with another di-CO2H- or di-NH2-terminated polyamide prepolymer respectively to give the semi-crystalline polyamide polymer, or An NH2 or CO2H end-capped prepolymer capable of reacting with itself to provide said semi-crystalline polyamide polymer, or A prepolymer capable of reacting with a chain extender to provide said semi-crystalline polyamide polymer, or A semi-crystalline polyamide polymer already present in the non-reactive composition b) A semi-crystalline polyamide polymer obtainable from the reactive composition a) corresponding thereto.

[0017] In other words, the present invention relates to - 0 to 70% by weight, preferably 20 to 60% by weight, of short reinforcing fibers, - 30 to 100% by weight, preferably 40 to 80% by weight, of a thermoplastic matrix based on at least one semi-crystalline polyamide polymer, - 0 to 50% by weight of additives and / or other polymers A composition for a thermoplastic material comprising Said composition being a) A reactive composition comprising or consisting of at least one reactive polyamide prepolymer precursor of said semi-crystalline polyamide polymer, or Or instead of a), b) A non-reactive composition of at least one polyamide polymer which is a composition of the thermoplastic matrix defined above And Said reactive polyamide prepolymer of composition a) and said polyamide polymer of composition b) comprise or consist of at least one BACT / XT copolyamide, - BACT is a unit having an amide motif present in a molar content in the range of 70 to 99.1%, preferably 80 to 99%, more preferably 90 to 99%, BAC is selected from 1,3-bis(aminomethyl)cyclohexyl (1,3-BAC), 1,4-bis(aminomethyl)cyclohexyl (1,4-BAC) or mixtures thereof, and T is terephthalic acid, - XT is a unit having an amide motif present in a molar content in the range of 0.9 to less than 30%, preferably 1 to 20%, more preferably 1 to 10%, X is a C9 to C18 linear aliphatic diamine, preferably C9, C10, C11 or C12, and T is terephthalic acid, preferably C10, C11 or C12, - In the BACT and / or XT units, independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol% of terephthalic acid, based on the total amount of dicarboxylic acids, can be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids containing from 6 to 36 carbon atoms, in particular from 6 to 14 carbon atoms, - In the BACT and / or XT units, independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol% of BAC and / or, where appropriate, X, based on the total amount of diamines, can be replaced by other diamines containing from 4 to 36 carbon atoms, in particular from 6 to 12 carbon atoms, - In the copolyamide, up to 30 mol%, preferably up to 20%, preferably up to 10 mol%, based on the total amount of monomers, can be formed by lactam or aminocarboxylic acid, - The total of the monomers replacing terephthalic acid, BAC and X does not exceed a concentration of 30 mol%, preferably 20 mol%, preferably 10 mol%, based on the total amount of monomers used in the copolyamide, - The BACT and XT units are still present in the polyamide polymer, Relates to a composition.

[0018] The expression of said reactive polyamide prepolymer of composition a) and said polyamide polymer of composition b) comprising or consisting of at least one BACT / XT copolyamide means that the reactive polyamide prepolymer of composition a) or said polyamide polymer of composition b) consists exclusively of units having BACT and XT amide motifs in the respective proportions defined above, or that the reactive polyamide prepolymer of composition a) or said polyamide polymer of composition b) contains BACT and XT amide motifs in the respective proportions defined above and also contains other units having amide motifs.

[0019] Advantageously, the proportion of units having BACT and XT amide motifs in the reactive polyamide prepolymer of composition a) or said polyamide polymer of composition b) is more than 50%, particularly more than 60%, specifically more than 70%, preferably more than 80%, particularly more than 90%.

[0020] Accordingly, the present invention provides - 0 to 70% by weight, preferably 20 to 60% by weight, of short reinforcing fibers - 30 to 100% by weight, preferably 40 to 80% by weight, of a thermoplastic matrix based on at least one semi-crystalline polyamide polymer - 0 to 50% by weight of additives and / or other polymers A composition for a thermoplastic material, comprising Said semi-crystalline polyamide comprises or consists of at least one BACT / XT copolyamide - BACT is a unit having an amide motif present in a molar content in the range of 70 to 99.1%, preferably 80 to 99%, more preferably 90 to 99%, BAC is selected from 1,3-bis(aminomethyl)cyclohexyl (1,3-BAC), 1,4-bis(aminomethyl)cyclohexyl (1,4-BAC) or a mixture thereof, and T is terephthalic acid - XT is a unit having an amide motif present in a molar content in the range of from 0.9 to less than 30%, preferably from 1 to 20%, more preferably from 1 to 10%, X is a C9 to C18 linear aliphatic diamine, preferably C9, C10, C11 or C12, and T is terephthalic acid, preferably C10, C11 or C12, - In the BACT and / or XT units, independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol% of terephthalic acid, based on the total amount of dicarboxylic acids, can be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids containing from 6 to 36 carbon atoms, in particular from 6 to 14 carbon atoms, - In the BACT and / or XT units, independently of one another, up to 30 mol%, preferably 20 mol%, in particular up to 10 mol% of BAC and / or, where appropriate, X, based on the total amount of diamines, can be replaced by other diamines containing from 4 to 36 carbon atoms, in particular from 6 to 12 carbon atoms, - In the copolyamide, up to 30 mol%, preferably up to 20 mol%, preferably up to 10 mol%, based on the total amount of monomers, can be formed by lactam or aminocarboxylic acid, - The total of the monomers, BAC and X replacing terephthalic acid does not exceed a concentration of 30 mol%, preferably 20 mol%, preferably 10 mol%, based on the total amount of monomers used in the copolyamide, - The BACT and XT units are still present in the polyamide polymer, Relates to a composition.

[0021] The composition according to the invention may comprise short reinforcing fibres or a short fibre reinforcement.

[0022] Preferably, the fibres described as short fibres have a length comprised between 200 and 400 μm.

[0023] These short reinforcing fibres are - natural fibres - Mineral fibers having a melting temperature Tm' that is higher than the melting temperature Tm of the semi-crystalline polyamide of the present invention and higher than the polymerization and / or mounting temperature - Polymer fibers having a melting temperature Tm' that is higher than the polymerization temperature of the semi-crystalline polyamide constituting the matrix of the thermoplastic material or higher than the melting temperature Tm and higher than the mounting temperature, or a glass transition temperature Tg' when there is no melting temperature Tm' - A mixture of the above fibers may be selected from.

[0024] Examples of mineral fibers suitable for the present invention may include the following: inorganic fibers, particularly fibers of nanotubes or carbon nanotubes (CNT), carbon nanofibers or carbon fibers containing graphene; silica fibers such as, for example, particularly type E, R or S2 glass fibers; boron fibers; ceramic fibers, particularly silicon carbide fibers, boron carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers; fibers or filaments containing metals and / or their alloys; metal oxide fibers, particularly those of alumina (Al2O3); metallized fibers, such as metallized glass fibers and metallized carbon fibers, or mixtures of these fibers.

[0025] More specifically, these fibers can be selected as follows: - The mineral fibers can be selected from carbon fibers, carbon nanotube fibers, glass fibers, particularly type E, R or S2, boron fibers; ceramic fibers, particularly silicon carbide fibers, boron carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers; fibers or filaments containing metals and / or their alloys; metal oxide fibers, such as Al2O3; metallized fibers such as metallized glass fibers and metallized carbon fibers, or mixtures of these fibers, - According to the conditions shown above, the polymer fibers are selected from the following: - Thermosetting polymer fibers, more specifically those particularly selected from unsaturated polyesters, epoxy resins, vinyl esters, phenolic resins, polyurethanes, cyanoacrylates, polyimides, such as bis-maleimide resins, aminoplasts obtained by the reaction of amines such as melamine with aldehydes such as glyoxal or formaldehyde, - Thermoplastic polymer fibers, more specifically selected from the following: - Polyamide fibers, particularly polyphthalamide fibers, - Aramid fibers (e.g., Kevlar®) and aromatic polyamides, such as those having one of the following formulas: PPD.T, MPD.I, PAA, and PPA (PPD and MPD are p- and m-phenylenediamine, respectively, PAA is polyarylamide, and PPA is polyphthalamide), - Polyamide block copolymers, such as polyamide / polyether fibers, polyaryl ether ketone (PAEK), such as polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ketone ether ketone ketone (PEKEKK) fibers.

[0026] Preferred short reinforcing fibers are short fibers selected from carbon fibers (including metallized ones), glass fibers (including metallized ones such as E, R, S2), aramid fibers (such as those like Kevlar®), or aromatic polyamide fibers, polyaryl ether ketone (PAEK) fibers, such as polyether ether ketone (PEEK), polyether ketone ketone (PEKK) fibers, polyether ketone ether ketone ketone (PEKEKK) fibers, or mixtures thereof.

[0027] Natural fibers are selected from flax, lysine, wood, sisal, kenaf, coconut, hemp, and jute fibers.

[0028] Preferably, the reinforcing fibers in the composition according to the present invention are selected from glass fibers, carbon fibers, flax fibers, and mixtures thereof, more preferably from glass fibers and carbon fibers, and even more preferably from glass fibers.

[0029] Regarding additives, without being limited thereto, the composition according to a preferred variant of the present invention more specifically contains certain additives such as heat stabilizers. In particular, these stabilizers are antioxidants against thermal oxidation and / or photooxidation of the polymer of the thermoplastic matrix and are organic or inorganic stabilizers.

[0030] The term "organic stabilizer" or more generally "combination of organic stabilizers" refers to phenolic primary antioxidants, phosphite secondary antioxidants, and optionally other stabilizers such as HALS (hindered amine light stabilizers (e.g., Tinuvin 770 from Ciba), anti-UV (e.g., Tinuvin 312 from Ciba), phenolic stabilizers or stabilizers containing phosphorus). Amine antioxidants such as Naugard 445 from Crompton or polyfunctional stabilizers such as Nylostab S-EED from Clariant can also be used.

[0031] The organic stabilizers present can be selected from the following non-limiting list: - Phenolic antioxidants such as Irganox 245, Irganox 1010, Irganox 1098 from Ciba, Irganox MD1024 from Ciba, Lowinox 44B25 from Great Lakes, ADK Stab AO-80 from Adeka Palmarole, - Phosphorus-containing stabilizers such as phosphites, e.g., Irgafos 168 from Ciba, - UV absorbers such as Tinuvin 312 from Ciba, - HALS as described above, - Amine-type stabilizers such as Naugard 445 from Crompton, or hindered amine-type, e.g., Tinuvin 770 from Ciba, - Polyfunctional stabilizers, such as Clariant's Nylostab S-EED.

[0032] Mixtures of two or more of these organic stabilizers can clearly be envisaged.

[0033] The expression "mineral stabilizer" means copper-based or metal oxide-based stabilizers as described in US Patent Publication No. 2008 / 0146717. The following can be listed as mineral stabilizers: copper halides and copper acetate or iron oxides, such as FeO, Fe2O3, Fe3O4, or mixtures thereof. Optionally, other metals such as silver can also be considered, but they are known to have little effect. These copper-based compounds are typically related to alkali metal halides, especially potassium halides.

[0034] These mineral stabilizers tend to prevent the breakage of polymer chains and are thus particularly used when the structure needs to improve its long-term heat resistance with hot air, especially at temperatures of 100 - 120 °C or higher.

[0035] More specifically, copper-based stabilizers are understood to mean compounds containing at least one copper atom in an ionizable ionic form, such as in the form of a complex.

[0036] Copper-based stabilizers can be selected from copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, copper(I) iodide, copper(II) iodide, copper(I) acetate, and copper(II) acetate. Acetates and halides of other metals such as silver in combination with copper-based stabilizers can be mentioned. These copper-based compounds are typically related to alkali metal halides. A well-known example is the mixture of CuI and KI, and the ratio CuI:KI is typically included between 1:5 and 1:15. An example of such a stabilizer is Ciba's Polyadd P201.

[0037] Further details of copper-based stabilizers can be found in U.S. Patent No. 2,705,227. More recently, copper-based stabilizers such as copper complexes like Bruggemann's Bruggolen H3336, H3337, H3373 have emerged.

[0038] Advantageously, the copper-based stabilizer is selected from copper halides, copper acetate, copper halide or copper acetate in a mixture with at least one alkali metal halide, and mixtures thereof, preferably from a mixture of copper iodide and potassium iodide (CuI / KI).

[0039] The additive can advantageously be an impact modifier consisting of a polymer having a flexural modulus of less than 100 MPa measured according to ISO standard 178 and a Tg of less than 0 °C (measured near the inflection point of the DSC thermogram according to standard 11357-2:2013), in particular a polyolefin which is or is not combined with a PEBA (polyether block amide) having a flexural modulus of <200 MPa.

[0040] The polyolefin of the impact modifier may or may not be functionalized, or may be a mixture of at least one functionalized polyolefin and / or at least one non-functionalized polyolefin.

[0041] The additive may be a filler which can in particular be any filler known to those skilled in the art in the field of thermoplastic materials. This may further comprise thermally conductive and / or electrically conductive fillers such as metal powders, powdered carbon black, carbon fibrils, carbon nanotubes (CNT), silicon carbide, boron carbonitride, boron nitride or silicon. Reference can be made in this regard to International Publication No. WO 2010 / 130930, an application by the applicant.

[0042] Regardless of whether they are long, short or continuous, reinforcing fibers are excluded from the additive, and in particular the term "inorganic filler" excludes long, short or continuous reinforcing fibers.

[0043] The additives can also be halogen-free flame retardants, such as those described in US Patent Publication No. 2008 / 0274355, in particular metal phosphinates, metal diphosphinates, polymers containing at least one metal phosphinate, polymers containing at least one diphosphinic acid or metal salt of red phosphorus, antimony oxide, zinc oxide, iron oxide, magnesium oxide or metal borates such as zinc borate, or melamine pyrophosphate and melamine cyanurate. They can also be halogenated flame retardants such as brominated or polybrominated polystyrene, brominated polycarbonate or brominated phenol.

[0044] Advantageously, the additives are selected from antioxidants, heat stabilizers, UV absorbers, light stabilizers, impact modifiers, lubricants, inorganic fillers, flame retardants, nucleating agents, in particular mineral fillers such as talc, and coolants.

[0045] The expression "other polymers" represents any thermoplastic polymer, in particular polyamide polymers, in particular aliphatic, cycloaliphatic or aromatic polyamides, which can be either microcrystalline or amorphous.

[0046] The expression "non-reactive composition" means that the composition is based on a polyamide polymer with a low likelihood of significant further change in molecular weight, i.e., the number average molecular weight (Mn) changes by less than 50% during its implementation, and thus corresponds to the final polyamide polymer of the thermoplastic matrix.

[0047] Due to the presence of low levels of (residual) reactive functional groups having a level of <120 meq / kg, or due to being non-reactive with each other due to the presence of homologous ends of chain-end functional groups, or by either modification and blocking of said reactive functional groups for amine functional groups by a modification reaction with a monofunctional reactive composition, such as a monoacid or monoisocyanate, and for carboxyl functional groups by a reaction with a monoamine, these polyamides according to composition b) are non-reactive.

[0048] Advantageously, the number average molecular weight (Mn) of the final polyamide polymer of the thermoplastic matrix of the material is determined by calculation from the level of end functional groups determined by potentiometric titration in solution and the functionality of the prepolymer or by NMR, preferably in the range of 6000 to 40,000 g / mol, preferably 10,000 to 30,000 g / mol. These Mn values can correspond to an intrinsic viscosity of 0.7 or more determined according to ISO standard 307:2007, which is determined by changing the solvent (using m-cresol instead of sulfuric acid, temperature 20 °C).

[0049] Conversely, the expression "reactive composition" means that the molecular weight of the reactive composition changes during implementation by reaction of the reactive prepolymers with each other by condensation or by reaction with a chain extender by polyaddition without removal of volatile by-products, resulting in the final polyamide polymer of the thermoplastic matrix.

[0050] 1,3-BAC (or 1,3-bis(aminomethyl)cyclohexane, CAS number 2579-20-6) is an alicyclic diamine monomer obtained in particular by hydrogenating meta-xylenediamine (MXDA). 1,3-BAC exists in two isomeric forms, cis and trans, and the CAS number 2579-20-6 corresponds to a mixture of isomers.

[0051] 1,4-BAC (or 1,4-bis(aminomethyl)cyclohexane, CAS number 2549-07-9) is an alicyclic diamine monomer obtained in particular by hydrogenating para-xylenediamine (PXDA). 1,4-BAC exists in two isomeric forms, cis and trans, and the CAS number 2549-07-9 corresponds to a mixture of isomers.

[0052] Advantageously, the 1,3-BAC or 1,4-BAC used in the BACT unit is a mixture of cis and trans isomers, and the respective ratios are from 0 / 100 to 100 / 0, in particular from 75 / 25 to 25 / 75.

[0053] Advantageously, the proportion of the cis isomer in 1,3-BAC is more than 60%, preferably more than 70%, specifically more than 80%, particularly more than 90%.

[0054] Advantageously, the proportion of the trans isomer in 1,4-BAC is more than 60%, preferably more than 70%, specifically more than 80%, particularly more than 90%.

[0055] BAC and / or X can be independently of each other replaced by up to 30 mol% with the other diamines mentioned above, in particular with linear or branched aliphatic diamines, cycloaliphatic diamines or arylaromatic diamines, such as, for example, meta-xylenediamine (MXDA).

[0056] As examples, linear or branched aliphatic diamines are selected from 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine (MPMD), 1,6-hexanediamine, 1,8-octanediamine (OMDA), 1,9-nonanediamine (NMDA), 2-methyl-1,8-octanediamine (MODA), 2,2,4-trimethylhexamethylenediamine (TMHMD), 2,4,4-trimethylhexamethylenediamine (TMHMD), 5-methyl-1,9-nonanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and 1,18-octadecanediamine.

[0057] Cycloaliphatic diamines can be selected from isophoronediamine, norbornanedimethylamine, 4,4'-diaminodicyclohexylmethane (PACM), 2,2-(4,4'-diamino-dicyclohexyl)propane (PACP) and 3,3'-dimethyl-4,4'-diaminodicyclohexylethane (MACM).

[0058] T can be replaced by up to 30 mol% with the other dicarboxylic acids defined above, in particular with other aromatic, aliphatic or cycloaliphatic dicarboxylic acids.

[0059] The aromatic dicarboxylic acid can be selected from naphthalenedicarboxylic acid (NDA) and isophthalic acid (IPA).

[0060] The aliphatic dicarboxylic acid can be selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassilic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and dimerized fatty acids.

[0061] The alicyclic dicarboxylic acid can be selected from cis- and / or trans-cyclohexane-1,4-dicarboxylic acid and / or cis- and / or trans-cyclohexane-1,3-dicarboxylic acid (CHDA).

[0062] BAC and / or X and / or T can be independently replaced by lactam or aminocarboxylic acid by up to 30 mol%.

[0063] The lactam and aminocarboxylic acid can be selected from caprolactam (CL), α,ω-aminocaproic acid, α,ω-aminononanoic acid, α,ω-aminoundecanoic acid (AUA), lauryllactam (LL), and α,ω-aminododecanoic acid (ADA).

[0064] Substitution by another diamine, another diacid, lactam or aminocarboxylic acid or any mixture thereof is possible up to 30 mol% with respect to the total of the BAC, X and T monomers.

[0065] Advantageously, substitution by another diamine, another diacid, lactam or aminocarboxylic acid or any mixture thereof is possible up to 20 mol% with respect to the total of the BAC, X and T monomers.

[0066] Advantageously, substitution by another diamine, another diacid, lactam or aminocarboxylic acid or any mixture thereof is possible up to 10 mol% with respect to the total of the BAC, X and T monomers.

[0067] In an advantageous embodiment, the present invention relates to one of the compositions for thermoplastic materials 1 to 12 as defined below, said composition comprising a semi-crystalline polyamide polymer, optionally including short reinforcing fibers, and said semi-crystalline polyamide polymer comprising a BACT / XT copolyamide in the proportions defined in Table I below. TIFF0007713134000001.tif76170 Table I

[0068] Advantageously, compositions 1 to 12 comprise from 0 to 50% by weight of additives and / or other polymers.

[0069] Advantageously, said composition comprises a semi-crystalline polyamide polymer, optionally short reinforcing fibers, and from 0 to 50% by weight of additives and / or other polymers, and said semi-crystalline polyamide polymer comprises a BACT / XT copolyamide in the proportions defined in Table 1.

[0070] Advantageously, said composition comprises a semi-crystalline polyamide polymer, optionally short reinforcing fibers, and from 0 to 50% by weight of additives and / or other polymers, and said semi-crystalline polyamide polymer consists of a BACT / XT copolyamide in the proportions defined in Table 1.

[0071] Advantageously, the proportion of additives and / or other polymers in the above composition is greater than 0% by weight and up to 50% by weight.

[0072] Advantageously, in the above composition, X is a C9, C10, C11 or C12 diamine, in particular C10, C11 or C12.

[0073] Accordingly, the inventors have unexpectedly found that the compositions of the present invention have an excellent compatibility with crystallization compared to the compositions of the prior art, have a high Tg and Tm, and in particular have a high enthalpy (and thus a high modulus of elasticity at high temperatures).

[0074] In an advantageous embodiment, the present invention relates to the above composition, wherein the semi-crystalline polyamide polymer has a melting temperature Tm of 290 °C to 340 °C, preferably 300 to 330 °C, more preferably 310 to 330 °C, as determined according to ISO standard 11357-3 (2013).

[0075] In an advantageous embodiment, the present invention relates to the above composition, wherein the semi-crystalline polyamide polymer has a glass transition temperature Tg of > 150 °C, preferably > 160 °C, more preferably > 170 °C, as determined according to ISO standard 11357-2:2013.

[0076] Advantageously, Tg is in the range of 155 to 190 °C.

[0077] In an advantageous embodiment, the present invention relates to the above composition, wherein the semi-crystalline polyamide polymer has a difference Tm-Tc between the melting temperature and the crystallization temperature of < 40 °C, preferably < 30 °C, as determined according to ISO standard 11357-3:2013.

[0078] In an advantageous embodiment, the present invention relates to the above composition, wherein the enthalpy of crystallization of the semi-crystalline polyamide polymer, measured by differential scanning calorimetry (DSC) according to ISO standard 11357-3:2013, is more than 40 J / g, preferably 45 J / g, even more preferably 50 J / g.

[0079] In an advantageous embodiment, the present invention relates to the above composition, wherein the semi-crystalline polyamide polymer has a melting temperature: Tm in the range of 290 °C to 340 °C and a Tg of > 150 °C.

[0080] In an advantageous embodiment, the present invention relates to the above composition, wherein the semi-crystalline polyamide polymer has a melting temperature: Tm in the range of 290 °C to 340 °C and a Tg of > 160 °C.

[0081] In an advantageous embodiment, the present invention relates to the above composition, characterized in that the semi-crystalline polyamide polymer has a melting temperature: Tm included between 290 °C and 340 °C and a Tg > 170 °C.

[0082] In an advantageous embodiment, the present invention relates to the above composition, characterized in that the semi-crystalline polyamide polymer has a melting temperature: Tm included between 300 °C and 330 °C and a Tg > 150 °C.

[0083] In an advantageous embodiment, the present invention relates to the above composition, characterized in that the semi-crystalline polyamide polymer has a melting temperature: Tm included between 300 °C and 330 °C and a Tg > 160 °C.

[0084] In an advantageous embodiment, the present invention relates to the above composition, characterized in that the semi-crystalline polyamide polymer has a melting temperature: Tm included between 300 °C and 330 °C and a Tg > 170 °C.

[0085] In an advantageous embodiment, the present invention relates to the above composition, characterized in that the semi-crystalline polyamide polymer has a melting temperature: Tm included between 310 °C and 330 °C and a Tg > 150 °C.

[0086] In an advantageous embodiment, the present invention relates to the above composition, characterized in that the semi-crystalline polyamide polymer has a melting temperature: Tm included between 310 °C and 330 °C and a Tg > 160 °C.

[0087] In an advantageous embodiment, the present invention relates to the above composition, characterized in that the semi-crystalline polyamide polymer has a melting temperature: Tm included between 310 °C and 330 °C and a Tg > 170 °C.

[0088] In an advantageous embodiment, the present invention relates to the above composition, characterized in that the semi-crystalline polyamide has the following characteristics (Table II). TIFF0007713134000002.tif237170TIFF0007713134000003.tif186170Table II

[0089] In an advantageous embodiment, the invention relates to the above composition, characterized in that the BAC is 1,3 - BAC.

[0090] Advantageously, for 1,3 - BAC, the cis and trans isomers are in a mixture in respective ratios from 0 / 100 to 100 / 0, in particular from 75 / 25 to 25 / 75.

[0091] Advantageously, the proportion of the cis isomer in 1,3 - BAC is more than 60%, preferably more than 70%, specifically more than 80%, in particular more than 90%.

[0092] In an advantageous embodiment, the invention relates to the above composition, characterized in that the BAC is 1,3 - BAC and the XT is selected from 9T, 10T, 11T and 12T, more preferably 10T, 11T and 12T.

[0093] Advantageously, the XT is 11T or 12T.

[0094] Advantageously, the XT is 10T, where 10 corresponds to 1,10 - decanediamine.

[0095] In an advantageous embodiment, the invention relates to the above composition, characterized in that the sum of terephthalic acid, BAC and the monomers replacing X is equal to 0. Thus, in this latter embodiment, there are no further possible substitutions of the monomers in the above compositions 1 to 93.

[0096] In an advantageous embodiment, the invention relates to the above composition, characterized in that the semi - crystalline polyamide is the non - reactive composition according to b).

[0097] This means that, since there is no reaction in this composition, it is identical to the matrix polymer (polyamide) of the thermoplastic material, and this composition remains stable with respect to molecular weight and does not change during heating for the implementation of the thermoplastic material of the present invention. Regarding the Tm, Tg, Tm-Tc and Delta Hc already described above, the characteristics of the polyamide polymer in this composition are the same as those of the final polymer.

[0098] The polyamide according to b) is obtained by a conventional polycondensation reaction from monomer components, in particular those related to the substitution of the monomers, which are diamines, diacids, and optionally amino acids or lactams.

[0099] In an advantageous embodiment, the present invention relates to a composition as described above, characterized in that the polyamide composition is a reactive prepolymer composition according to a) and a precursor of the polyamide polymer of the thermoplastic material matrix.

[0100] Depending on the reactive composition a), three possibilities can be distinguished, which are shown in detail below.

[0101] Advantageously, the composition a) comprises or consists of at least one reactive prepolymer that holds two terminal functional groups X' and Y' on the same chain, which are co-reactive with each other by condensation, and X' and Y' are an amine and a carboxyl, or a carboxyl and an amine, respectively.

[0102] The prepolymer is a reactive polyamide that holds two terminal functional groups X' and Y' on the same chain (i.e., on the same prepolymer), which are reactive with each other by condensation.

[0103] This condensation (or polycondensation) reaction can cause the removal of by-products. These can preferably be discharged by working in a process using an open mold technique. In the case of a closed mold method, there is a step of preferably degassing the by-products removed by the reaction under reduced pressure, which is done to prevent the formation of microbubbles of by-products in the final thermoplastic material, since if the microbubbles are not removed by this method, it can affect the mechanical properties of the said material.

[0104] The term "reactive" means that the Mn of the prepolymer changes by more than 50% after reaction with itself or with another prepolymer, or by chain extension.

[0105] After condensation, the characteristics of the final polyamide polymer obtained in this composition are the same, and Tm, Tg, Tm - Tc and Delta Hc are as defined above.

[0106] Advantageously, the reactive composition a) comprises at least two polyamide prepolymers each retaining two identical terminal functional groups X' or Y' and being co-reactive with each other, and the functional group X' of the prepolymer can react only with the other prepolymer's functional group Y', in particular by condensation. More specifically, X' and Y' are each an amine and a carboxyl, or a carboxyl and an amine.

[0107] In this process, this condensation (or polycondensation) reaction can cause the removal of by-products that can be removed as described above.

[0108] After condensation, the characteristics of the final polyamide polymer obtained in this composition are the same, and Tm, Tg, Tm - Tc and Delta Hc are as defined above.

[0109] Advantageously, the composition a) or the precursor composition is a1) At least one thermoplastic polyamide prepolymer of said polymer having n reactive terminal functional groups X', selected from the following: - n is from 1 to 3, preferably from 1 to 2, more preferably 1 or 2, more specifically 2, NH2, -CO2H and -OH, preferably NH2 and -CO2H a2) At least one chain extender Y - A' - Y, wherein A' is a dicarbon hydrocarbon substituent, has a non - polymer structure, has two identical terminal reactive functional groups Y, and is reactive by polyaddition with at least one functional group X' of the prepolymer a1), and preferably has a molecular weight of less than 500, more preferably less than 400 Comprising or consisting of these.

[0110] Suitable examples of the chain extender a2) according to the functional group X' retained by the semi - crystalline polyamide prepolymer a1) may be listed as follows: - When X is NH2 or OH, preferably NH2: 〇 The chain extender Y - A' - Y corresponds to any of the following: · Y selected from the group of maleimide, blocked isocyanate, oxazinone, oxazolinone and epoxy, And ■ A' is a hydrocarbon spacer optionally containing one or more heteroatoms, bonded to each other at the Y functional groups, and in particular A' is, * When Y is oxazinone and oxazolinone, a covalent bond between the two Y functional groups (groups), or * An aliphatic hydrocarbon chain, or an aromatic and / or alicyclic hydrocarbon chain (the latter two contain at least one optionally substituted 5 - or 6 - membered carbon ring, and optionally, the aliphatic hydrocarbon chain has a molecular weight of from 14 to 400 g.mol -1 of). A reactive functional group or a hydrocarbon spacer or carbon substituent retaining the Y group, selected from ○ Alternatively, the chain extender Y-A'-Y corresponds to Y which is a caprolactam group, A' can be a carbonyl substituent such as carbonyl biscaprolactam, or A' can be terephthaloyl or isophthaloyl, 〇 Or, the chain extender Y-A'-Y holds a cyclic anhydride group Y, preferably, this extender is selected from alicyclic and / or aromatic carboxylic dianhydrides, more preferably ethylene tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, hexafluoroisopropylidene bisphthalic dianhydride, 9,9-bis(trifluoromethyl)xanthene tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride or a mixture thereof, And - When X' is COOH: 〇 The chain extender Y-A'-Y is ■ Y selected from the group of epoxy, oxazoline, oxazine, imidazoline or aziridine, such as 1,1'-iso- or tere-phthaloyl-bis(2-methyl aziridine) ■ A' which is a carbon spacer (substituent) as described above corresponds to.

[0111] More specifically, when the functional group Y in the extender Y-A'-Y is selected from oxazinone, oxazoline, oxazine, oxazoline or imidazoline, in the chain extender represented by Y-A'-Y, A' is alkylene, for example -(CH2) m-(m ranges from 1 to 14, preferably from 2 to 10), or A' can represent a substituted (alkyl) or unsubstituted cycloalkylene and / or arylene, such as benzene arylene, such as o-, m- or p-phenylene, or naphthalene arylene, and preferably, A' is arylene and / or cycloalkylene.

[0112] In the case of carbonyl- or terephthaloyl- or isophthaloyl-biscaprolactam as the Y-A'-Y chain extender, the preferred condition is to avoid the removal of by-products, such as caprolactam, when the polymerization is carried out in the molten state.

[0113] In the above possible case where Y represents a blocked isocyanate functional group, this blocking can be obtained by a blocking agent that blocks the isocyanate functional group, such as epsilon-caprolactam, methyl ethyl ketoxime, dimethylpyrazole or diethyl malonate.

[0114] Similarly, when the extender is a dianhydride that reacts with a P(X')n prepolymer (X' = NH2), the preferred condition is to avoid the formation of imide rings during polymerization and implementation in the molten state.

[0115] Examples of chain extenders having a reactive functional group Y = epoxy suitable for the implementation of the present invention include optionally substituted aliphatic, cycloaliphatic or aromatic diepoxides. Examples of aliphatic diepoxides include diglycidyl ethers of aliphatic diols such as diglycidyl ethers of bisphenol A (BADGE), such as aromatic diepoxides of bisphenol A diglycidyl ether. Examples of cycloaliphatic diepoxides include diglycidyl ethers of cycloaliphatic diols or hydrogenated bisphenol A. More generally, suitable examples of diepoxides according to the present invention include bisphenol A diglycidyl ether (BADGE) and its hydrogenated (cycloaliphatic) derivatives, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether or hydroquinone diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether with Mn < 500, polypropylene glycol diglycidyl ether with Mn < 500, polytetramethylene glycol diglycidyl ether with Mn < 500, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether with Mn < 500, bisphenol A polypropylene glycol diglycidyl ether with Mn < 500, carboxylic acid diglycidyl esters such as glycidyl terephthalate or epoxidized diolefins (dienes) or epoxidized fatty acid esters having two ethylenic unsaturations, diglycidyl 1,2-cyclohexanedicarboxylate and mixtures of the listed diepoxides.

[0116] Examples of chain extenders that retain oxazoline or oxazine Y - reactive functional groups suitable for the implementation of the present invention include those referred to as "A", "B", "C", and "D" on page 7 of EP0581642, and their preparation methods and the modes of reaction described therein. In this document, "A" is bis - oxazoline, "B" is bis - oxazine, "C" is 1,3 - phenylene bis - oxazoline, and "D" is 1,4 - phenylene bis - oxazoline.

[0117] Examples of chain extenders having imidazoline Y - reactive functional groups suitable for the implementation of the present invention include those described in Table 1 on pages 7 to 8 and page 10 of EP0,739,924 ("A" to "F"), and their preparation methods and the modes of reaction described therein.

[0118] Examples of chain extenders having Y = oxazinone or oxazolinone reactive functional groups suitable for the implementation of the present invention include those referred to as "A" to "D" on pages 7 to 8 of EP0581641, and their preparation methods and the modes of reaction described therein.

[0119] The spacer A' can be a single covalent bond with the corresponding extender that is bis - (benzoxazinone), bis - oxazinone, and bis - oxazolinone. The Y groups derived from oxazinone or oxazolinone benzoxazinone are examples of suitable oxazinone (6 - membered ring) and oxazolinone (5 - membered ring) Y groups. A' can also be an alkylene of C1 to C 14 , preferably C2 to C 10 and can be, but A' is preferably an arylene, more specifically phenylene (substituted with Y at the 1,2 or 1,3 or 1,4 position) or a naphthalene substituent (disubstituted with Y) or phthaloyl (iso - or terephthaloyl), or A' can be cycloalkylene.

[0120] Regarding Y functional groups such as oxazine (6-membered ring), oxazoline (5-membered ring), and imidazoline (5-membered ring), the substituent A’ can be as described above, where A’ can be a single covalent bond, and the corresponding chain extenders are bisoxazine, bisoxazoline, and bisimidazoline respectively. A can also be an alkylene from C1 to C 14 , preferably from C2 to C 10 . The substituent A’ is preferably arylene, more specifically, phenylene (substituted with Y at the 1,2 or 1,3 or 1,4 position) or naphthalene substituent (disubstituted with Y) or phthaloyl (iso- or terephthaloyl), or A’ can be cycloalkylene.

[0121] When Y is aziridine (a 3-membered nitrogen heterocycle equivalent to ethylene oxide with -NH- replacing -O-), the substituent A’ can be phthaloyl (1,1’-iso- or terephthaloyl) having 1,1’-isophthaloyl bis(2-methylaziridine) as an example of this type of chain extender.

[0122] By being able to promote the (co)addition reaction, due to the presence of a catalyst for the reaction between the prepolymer P(X’)n and the Y-A’-Y chain extender at a level in the range of 0.001 to 2%, preferably 0.01 to 0.5%, based on the total weight of both given comonomers, the production cycle can be shortened.

[0123] Depending on the specific case of the selection of the chain extender, A’ represents an alkylene such as -(CH2) m -(where m ranges from 1 to 14, preferably from 2 to 10), or represents an alkyl-substituted or unsubstituted arylene such as benzene arylene (o-, m-, -p phenylene, etc.) or naphthalene (having arylene: naphthalenylene). Preferably, A’ represents an arylene that can be a substituted or unsubstituted benzene or naphthalene.

[0124] As already mentioned, the chain extender (a2) has a non-polymeric structure and preferably has a molecular weight of 500 or less, more preferably 400 or less.

[0125] According to the above three options, the reactive prepolymer of the reactive composition a) preferably has a number average molecular weight Mn in the range of 500 to 20,000, particularly 500 to 10,000, specifically 1000 to 6000. All weight Mn are determined by potentiometric measurements or NMR (Postma et al. (Polymer, 47, 1899 - 1911 (2006)).

[0126] In the case of the reactive composition of the invention according to definition a), the reactive prepolymer is prepared by the conventional polycondensation reaction between the corresponding diamine and diacid components and, optionally, (by substitution) amino acids or lactams. Prepolymers retaining X' and Y' amine and carboxyl reactive groups on the same chain can be obtained, for example, by adding combinations of monomers (amino acids, diamines, diacids) that have a total equal amount of amine and carboxyl motifs but do not perform the reaction for complete conversion. Another method for producing these prepolymers retaining X' and Y' functional groups is, for example, to combine a prepolymer retaining two identical X' = amine functional groups with a diacid prepolymer retaining Y': carboxyl at the overall molar level of acid functional groups equal to that of the starting amine functional group X'.

[0127] To obtain a prepolymer functionalized with the same functional group (amine or carboxyl) on the same chain, it is sufficient to have an excess of diamine (or overall amine functional groups) to have amine - terminal functional groups, or an excess of diacid (or overall carboxyl functional groups) to have carboxyl - terminal functional groups.

[0128] In the case of a prepolymer P(X')n having n identical X' functional groups, the functional group 1 can be obtained in the presence of a blocked monofunctional component (a mono - acid or mono - amine depending on the nature of X' = amine or carboxyl).

[0129] The functional group with n = 2 can be obtained from bifunctional components: diamine and diacid, and the excess of one of them binds to X' according to the excess amount.

[0130] For example, regarding n = 3, the prepolymer P(X')n requires the presence of a trifunctional component, for example, the presence of triamine (1 mol per chain of the prepolymer) together with diamine in the reaction with diacid. The preferred functional group of P(X')n is n = 2.

[0131] In an advantageous embodiment, the present invention relates to the above composition, and the composition a) or the precursor composition is a1) at least one thermoplastic polyamide prepolymer of the polymer having n reactive terminal functional groups X', and a2) at least one chain extender Y - A' - Y comprises or consists of, X' is NH2 or OH, in particular, NH2, and Y is selected from anhydrides, in particular tetracarboxylic dianhydrides 3,3',4,4'-benzophenone, oxazinone, oxazolinone and epoxy.

[0132] In an advantageous embodiment, the present invention relates to the above composition, and the composition a) or the precursor composition is a1) at least one thermoplastic polyamide prepolymer of the polymer having n reactive terminal functional groups X', and a2) at least one chain extender Y - A' - Y, comprises or consists of the following, X' is CO2H, and Y is selected from epoxy and oxazoline.

[0133] Advantageously, X' is CO2H, and Y - A' - Y is selected from phenylene bisoxazoline, preferably 1,3-phenylene-bis(2-oxazoline) or 1,4-phenylene-bis(2-oxazoline) (PBO).

[0134] In a preferred embodiment, the present invention is the above composition, wherein the composition is a1) at least one amine prepolymer (-NH2 retained) of the thermoplastic polymer of the matrix, in particular at least 50%, more specifically 100% of the terminal groups of the prepolymer a1) are primary amine functional groups -NH2, at least one amine prepolymer and a2) at least one non-polymer chain extender that retains a cyclic carboxylic anhydride, preferably retained by an aromatic ring, and has, as substituents, an ethylene or acetylene unsaturated group, preferably a group containing acetylene, wherein the carboxyl anhydride group can be in the form of an acid, ester, amide or imide, and the extender a2) is present at a level corresponding to an a2) / (-NH2) molar ratio of less than 0.36, preferably in the range of 0.1 to 0.35, more preferably in the range of 0.15 to 0.35, even more preferably in the range of 0.15 to 0.31, and the thermoplastic polymer of the matrix is a product of a polymerization reaction by extending the prepolymer a1) with the extender a2).

[0135] By the selection of components a1) and a2) and their specific molar ratios, the reaction results in a final thermoplastic polymer that is not crosslinked.

[0136] It should be noted that the prepolymer a1) retains a primary amine group represented by -NH2. More specifically, the average number of primary amine groups per molecule of the prepolymer a1), also called the average functional group of the primary amine group, can vary from 1 to 3, preferably from 1 to 2. In particular, at least 50% of the functional groups of the terminal groups of the prepolymer a1) are primary amine functional groups -NH2, which may be either a carboxyl group having no reactive group or a block chain end, in which case the average functional group of -NH2 can thereby vary from 1 to 3, preferably from 1 to 2.

[0137] In the context of the present invention, the term "thermoplastic" means that the polymer obtained from the reaction of the prepolymer a1) and the extender a2) is essentially thermoplastic, which means that the polymer contains less than 15% by weight, preferably less than 10% by weight, more preferably less than 5% by weight, and even more preferably 0% (within 0.5% or within 1%) by weight of a crosslinked polymer that is infusible or insoluble.

[0138] The extender a2) can be selected from the following: - Anhydrides and anhydride derivatives in the form of acids, esters, amides or imides of ethynyl o-phthalic acid, methylethynyl o-phthalic acid, phenylethynyl o-phthalic acid, naphthylethynyl o-phthalic acid, 4-(o-phthaloylethynyl) o-phthalic acid or 4-(phenylethynylketone) o-phthalic acid (the latter is also called 4-(phenylethynyl) trimellitic). - Acids or esters or amides of the following acids: ethynylisophthalic acid, methylethynylisophthalic acid, phenylethynylisophthalic acid, naphthylethynylisophthalic acid, 4-(o-phthaloylethynyl)isophthalic acid, 4-(phenylethynylketone)isophthalic acid, ethynylterephthalic acid, methylethynylterephthalic acid, phenylethynylterephthalic acid, naphthylethynylterephthalic acid, 4-(o-phthaloylethynyl)terephthalic acid, ethynylbenzoic acid, methylethynylbenzoic acid, phenylethynylbenzoic acid, naphthylethynylbenzoic acid, 4-(o-phthaloylethynyl)benzoic acid.

[0139] Advantageously, the extender a2) is selected from aromatic anhydride compounds, preferably o-phthalic acid substituted by a substituent defined by an R-C≡C-(R')x group at the 4-position of the aromatic ring (R is C1-C2 alkyl or H or aryl, especially phenyl, or R is a residue of an aromatic carboxylic acid anhydride, preferably o-phthalic acid bonded to an acetylene triple bond by carbon at the 4-position of the aromatic ring, x is equal to 0 or 1, and when x is equal to 1, R' is a carbonyl group).

[0140] Advantageously, the extender a2) is selected from aromatic o-phthalic anhydride compounds having a substituent selected from methylethynyl, phenylethynyl, 4-(o-phthaloyl)ethynyl, and phenylethynyl ketone (also called phenylethynyl trimellitic anhydride) retained at the 4-position, preferably a substituent selected from methylethynyl and phenylethynyl ketone retained at the 4-position.

[0141] Advantageously, regardless of the above and its structure, the extender a2) has a molecular weight of 500 or less, preferably 400 or less.

[0142] Advantageously, regardless of the above and its structure, the level of the extender a2) varies from 1 to 20%, preferably 5 to 20% in the polyamide polymer.

[0143] In an advantageous embodiment, the present invention relates to the above composition, characterized in that it relates to a molding composition.

[0144] According to another aspect, the present invention is a method for manufacturing a thermoplastic material, particularly a mechanical part or a structural part based on the above material having the above composition, comprising at least one step of polymerizing at least one reactive composition a) according to the present invention, or a step of molding or mounting at least one non-reactive composition b) according to the above by extrusion, injection, or molding.

[0145] In an advantageous embodiment, the present invention is a manufacturing method for the above thermoplastic material, i) Optionally, without fiber reinforcement, injection into an open or closed mold of the above composition or injection without using a mold, ii) In the case of the above reactive polyamide composition a), by heating the composition from step i) using a chain extender, optionally by polycondensation reaction or polyaddition reaction in bulk in a molten state, and in the case of polycondensation, optionally using a vacuum extraction system under vacuum, removal of the condensation product under vacuum when accompanied by a closed mold, and in other cases and preferably in an open mold or without a mold, a polymerization reaction in polycondensation. iii) In the case of the non-reactive polyamide composition b), the step of implementing or shaping the composition from step i) to form the final part in a mold or using another implementation system, and in the case of the reactive composition a), the step of implementing simultaneously with the polymerization step ii) by molding or using another implementation system It relates to a manufacturing method, characterized by including the above.

[0146] According to another aspect, the present invention relates to a semi-crystalline polyamide polymer, which corresponds to (or is) the polymer of the thermoplastic matrix of the above thermoplastic material, and the polymer is obtained from the above non-reactive polymer by the composition b) or the above reactive composition by the composition a). It relates to a semi-crystalline polyamide polymer, characterized in that it is a polymer that can be obtained.

[0147] By definition, this thermoplastic polymer is one of the essential components of the composition of the thermoplastic material of the present invention, and therefore, it is part of the present invention as a product related to the present invention having the same inventive concept facing the same technical problems to be solved. Therefore, the present invention also targets the use of the above thermoplastic polymer as a thermoplastic matrix for the above fiber-reinforced thermoplastic material.

[0148] According to another aspect, the present invention relates to the use of the above composition or a non-reactive polymer by the composition b) or a polymer that can be obtained from the reactive composition by the composition a) for the manufacture of mechanical parts or structural parts, single-layer or multi-layer tubes or films based on the above thermoplastic material.

[0149] In an advantageous embodiment, the present invention relates to the above use, characterized in that the mechanical parts or structural parts of the thermoplastic material relate to applications in the fields of automobiles, railways, marine (offshore), wind power, photovoltaics, solar power generation (including solar panels and parts for solar power plants), sports, aerospace, road transportation (related to trucks), construction, civil engineering, signage and leisure.

[0150] In another advantageous embodiment, the present invention relates to the above use, characterized in that the mechanical part in the field of motor vehicles is, in particular, under the engine hood for the transport of fluids in devices for the intake, cooling (e.g., by air or cooling liquid, etc.), fuel or fluid, in particular oil, water, etc., or for the transport or transfer of fluids.

[0151] In yet another advantageous embodiment, the present invention relates to the above use, characterized in that the mechanical part or structural part in the field of electricity or electronics is an electrical or electronic device article such as an encapsulated solenoid, pump, telephone, computer, printer, fax, modem, monitor, remote control, camera, circuit breaker, electrical cable conduit, optical fiber, switch and multimedia system.

[0152] Method for determining the described characteristics - The intrinsic viscosity is measured in m-cresol. This method is well known to those skilled in the art. It follows ISO standard 307:2007, but the solvent is changed (using m-cresol instead of sulfuric acid, and the temperature is 20 °C).

[0153] - The glass transition temperature Tg is measured using a differential scanning calorimeter (DSC) after the second heating pass, in accordance with ISO standard 11357-2:2013. The heating and cooling rates are 20 °C / min.

[0154] - The melting temperature Tm and the crystallization temperature Tc are measured by DSC in accordance with ISO standard 11357-3:2013. The heating and cooling rates are 20 °C / min.

[0155] - The crystallization enthalpy of the polymer matrix is measured using differential scanning calorimetry (DSC) in accordance with ISO standard 11357-3:2013.

Examples

[0156] A - Preparation of polyamide polymer by a direct route (without using chain extension) The following procedure is an example of a preparation method and is not limiting. It is a representative example of all the compositions according to the present invention.

[0157] Add 5 kg of the following raw materials to a 14-liter autoclave reactor: - 500 g of water, - diamine, - amino acid (optional), - terephthalic acid, optionally one or other diacids, - monofunctional chain regulator: benzoic acid in an amount suitable for the target Mn and varying from 50 to 100 g, - 35 g of sodium hypophosphite in solution, - 0.1 g of WACKER AK1000 antifoaming agent (from Wacker Silicones).

[0158] The properties and molar ratios of the molecular motifs and structures of the polyamides (referenced for each test) are shown in Table III below.

[0159] Purge the residual oxygen in the sealed reactor, and then heat the added materials to a temperature of 230 °C. After stirring for 30 minutes under these conditions, gradually relieve the vapor formed under the pressure in the reactor over 60 minutes while gradually increasing the temperature of the materials to reach Tm + 10 °C under atmospheric pressure.

[0160] Subsequently, continue the polymerization under a nitrogen blanket of 20 L / h until a viscous polymer is obtained.

[0161] Subsequently, empty the polymer through the bottom valve, then cool it in a water bath, and then form it into granules.

[0162] The results are shown in Tables III and IV below. These were obtained starting from 1,3-BAC with a cis / trans ratio of 75 / 25 mol%. TIFF0007713134000004.tif56170C shows a comparative example. I shows the present invention. *According to Patent Publication No. 2015-017177. Table III

[0163] The results in Table III show that when the mole fraction of BACT is from 70 to 99.1 mol%, the melting temperature is included in the range of 290°C to 340°C.

[0164] At the same time, Tg is very high and can be adjusted from 155°C (not shown in the table) to about 190°C. TIFF0007713134000005.tif138170(*): No crystallization upon cooling. Table IV

[0165] The results in Table IV show that full substitution of BAC or the 10T motif or a part of 10T of 30% or more results in a composition that does not have at least one of the required values of Tm, Tg, Tm-Tc, and ΔHc.

Claims

1. - 0 to 70% by weight of short reinforcing fibers, - a thermoplastic matrix based on 30 to 100% by weight of at least one semi-crystalline polyamide polymer, - 0 to 50% by weight of additives and / or other polymers A composition for a thermoplastic material comprising: wherein the composition a) is a reactive composition comprising or consisting of at least one reactive polyamide prepolymer precursor of the semi-crystalline polyamide polymer, the reactive polyamide prepolymer of composition a) comprises or consists of at least one BACT / XT copolyamide, - BACT is a unit having an amide motif present in a molar content in the range of 70 to 99.1%, BAC is selected from 1,3-bis(aminomethyl)cyclohexyl (1,3-BAC), 1,4-bis(aminomethyl)cyclohexyl (1,4-BAC) or mixtures thereof, T is terephthalic acid, - XT is a unit having an amide motif present in a molar content in the range of 0.9 to 30%, X is a C9 to C18 linear aliphatic diamine, T is terephthalic acid, - In the BACT and / or XT units, independently of one another, up to 30 mol% of terephthalic acid relative to the total amount of dicarboxylic acids can be replaced by other aromatic, aliphatic or alicyclic dicarboxylic acids containing 6 to 36 carbon atoms, - In the BACT and / or XT units, independently of one another, up to 30 mol% of BAC and / or, where applicable, X relative to the total amount of diamines can be replaced by other diamines containing 4 to 36 carbon atoms, - In the copolyamide, up to 30 mol% of the total amount of monomers can be formed by lactam or aminocarboxylic acid, - provided that the total of the monomers replacing terephthalic acid, the monomers replacing BAC, and the monomers replacing X does not exceed a concentration of 30 mol% relative to the total amount of monomers used in the copolyamide, - provided that the BACT and XT units are still present in the polyamide polymer. Composition.

2. The composition according to claim 1, characterized in that BAC is 1,3-BAC.

3. The composition according to claim 1 or 2, characterized in that BAC is 1,3-BAC and XT is selected from 9T, 10T, 11T and 12T.

4. The composition according to any one of claims 1 to 3, characterized in that XT is 10T and 10 corresponds to 1,10-decanediamine.

5. - 0 to 70% by weight of short reinforcing fibers, - 30 to 100% by weight of a thermoplastic matrix based on at least one semi-crystalline polyamide polymer, - 0 to 50% by weight of additives and / or other polymers A composition for a thermoplastic material comprising: wherein the composition a) is a reactive composition comprising or consisting of at least one reactive polyamide prepolymer precursor of the semi-crystalline polyamide polymer, or instead of a) b) a non-reactive composition of at least one polyamide polymer, which is a composition of the thermoplastic matrix defined above and the reactive polyamide prepolymer of composition a) and the polyamide polymer of composition b) comprise or consist of at least one BACT / XT copolyamide, - BACT is a unit having an amide motif present in a molar content in the range of 70 to 99.1%, BAC is selected from 1,3-bis(aminomethyl)cyclohexyl (1,3-BAC), 1,4-bis(aminomethyl)cyclohexyl (1,4-BAC) or mixtures thereof, T is terephthalic acid, - XT is 10T, 10 corresponds to 1,10-decanediamine, - In the BACT and / or XT units, independently of each other, up to 30 mol% of terephthalic acid relative to the total amount of dicarboxylic acids can be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids containing 6 to 36 carbon atoms, - In the BACT and / or XT units, independently of each other, up to 30 mol% of BAC and / or, where applicable, X relative to the total amount of diamines can be replaced by other diamines containing 4 to 36 carbon atoms, - In the copolyamide, up to 30 mol% of the total amount of monomers can be formed by lactam or aminocarboxylic acid, - provided that the total of the monomers replacing terephthalic acid, the monomers replacing BAC, and the monomers replacing X does not exceed a concentration of 30 mol% relative to the total amount of monomers used in the copolyamide, - provided that the BACT and XT units are still present in the polyamide polymer, Composition.

6. The composition according to claim 5, characterized in that the BAC is 1,3 - BAC.

7. The composition according to claim 5 or 6, which is a non - reactive composition according to b).

8. The composition according to claim 5 or 6, which is a reactive composition according to a).

9. The composition according to any one of claims 1 to 8, wherein the semi - crystalline polyamide polymer has a melting temperature Tm ranging from 290 °C to 340 °C, determined in accordance with ISO standard 11357 - 3 (2013).

10. The composition according to any one of claims 1 to 9, wherein the semi - crystalline polyamide polymer has a glass transition temperature Tg > 150 °C, determined in accordance with ISO standard 11357 - 2:2013.

11. The composition according to any one of claims 1 to 10, wherein the semi - crystalline polyamide polymer has a difference Tm - Tc between the melting temperature and the crystallization temperature < 40 °C, determined in accordance with ISO standard 11357 - 3:2013.

12. The composition according to any one of claims 1 to 11, characterized in that the enthalpy of crystallization of the semi - crystalline polyamide polymer measured by differential scanning calorimetry (DSC) in accordance with ISO standard 11357 - 3:2013 is greater than 40 J / g.

13. The composition according to any one of claims 1 to 12, further comprising at least one additive.

14. The composition according to claim 13, characterized in that the additive is selected from antioxidants, heat stabilizers, UV absorbers, light stabilizers, impact resistance improvers, lubricants, inorganic fillers, flame retardants, nucleating agents and coolants.

15. The composition according to any one of claims 1 to 14, characterized in that it is related to a molding composition.

16. A method for manufacturing a thermoplastic material, having the composition according to any one of claims 1 to 14, comprising at least one step of polymerizing at least one reactive composition a), or a step of molding or mounting at least one non - reactive composition b) by extrusion molding or injection molding.

17. i) An injection step without using a mold for injection or casting into an open or closed mold of the composition according to any one of claims 1 to 14, optionally without fiber reinforcement. ii) In the case of the reactive polyamide composition a), by heating the composition from step i) using a chain extender, optionally by polycondensation or polyaddition reaction in bulk in the molten state, and in the case of polycondensation, optionally using an extraction system under vacuum, when accompanied by a closed mold, with removal of the condensation product under vacuum, a polymerization reaction step iii) In the case of the non-reactive polyamide composition b), a step of mounting or molding the composition from step i) to form a final part in a mold or using another mounting system, and in the case of the reactive composition a), a step of mounting simultaneously with the polymerization step ii) by molding or using another mounting system The method according to claim 16, characterized by comprising the above.

18. A semi-crystalline polyamide polymer contained in a composition for a thermoplastic material according to any one of claims 5 to 8, wherein the semi-crystalline polyamide polymer is a polymer obtainable from the above non-reactive polymer according to the composition b) or the above reactive composition according to the composition a).

19. Use of a composition according to any one of claims 5 to 8 or a polymer obtainable from the non-reactive polymer according to the composition b) or the reactive composition according to the above composition a) for the manufacture of mechanical or structural parts, single-layer or multi-layer tubes or films based on the thermoplastic material.

20. The use according to claim 19, characterized in that the mechanical or structural parts of the composite material relate to applications in the fields of automotive, electrical or electronic, railway, marine, wind power, photovoltaic, solar power generation (including solar panels and parts for solar power plants), sports, aerospace, road transport (related to trucks), construction, civil engineering, signage and leisure.

21. The use according to claim 19, characterized in that the mechanical parts for automotive applications are under the engine hood for fluid transport.

22. The use according to claim 19, characterized in that the mechanical or structural parts for applications in the electrical or electronic field are electrical or electronic equipment articles such as encapsulated solenoids, pumps, telephones, computers, printers, fax machines, modems, monitors, remote controls, cameras, circuit breakers, electrical cable conduits, optical fibers, switches and multimedia systems.

23. A thermoplastic material, characterized by being produced by the use of at least one composition for a thermoplastic material according to any one of claims 1 to 14.

24. A mechanical or structural part of a thermoplastic material, characterized by being produced by the use of at least one composition according to any one of claims 1 to 14, by the use of the polyamide polymer according to claim 18, by the use of the thermoplastic material according to claim 23, or by the use of a thermoplastic material obtained by the method according to claim 16 or 17.

25. The part according to claim 24, characterized by being related to a mechanical part for an application in the automotive field, such as a part under the engine hood for the transport of fluids.

26. The part according to claim 24, characterized by being related to a mechanical or structural part for an application in the electrical or electronic field, such as an electrical or electronic equipment article, such as an encapsulated solenoid, pump, telephone, computer, printer, fax, modem, monitor, remote control, camera, circuit breaker, electrical cable conduit, optical fiber, switch and multimedia system.

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