Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • 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
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
  • B29C70/021—Combinations of fibrous reinforcement and non-fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the invention relates to a composition of or for a thermoplastic composite material with a semi-crystalline polyamide (PA) matrix with a glass transition temperature Tg of at least 90 ° C. and a melting temperature Tf of less than or equal to 280 ° C. and also covers a method of manufacturing said composite material, in particular mechanical or structural parts based on said material, the use of the composition of the invention for pieces of composite material as well as the composite part resulting therefrom and for Applications in the fields of: automotive, rail, marine, road transport, wind, sports, aeronautics and space, building, signage and recreation.
• PA semi-crystalline polyamide
• EP 0261 020 describes the use of semi-crystalline reactive prepolymers based on PA 6, 11 and 12 for the manufacture of a thermoplastic composite by a pultrusion process.
• Prepolymers of aliphatic structure as described have low Tg and insufficient mechanical performance when hot.
• EP 550 314 describes, among its examples, (non-reactive) copolyamide compositions in search of melting temperatures above 250 ° C and limited Tg's with most of the examples cited having a Tg too low ( ⁇ 80 ° C) or too high Tf (> 300 ° C).
• EP 1 988 13 discloses a molding composition based on a 10T / 6T copolyamide with:
• polyamides having a high melting point and greater than 270 ° C. are used.
• the examples mentioned and Figure 1 teach us that the melting temperature of these compositions is at least about 280 ° C.
• WO 201 1/003973 describes compositions comprising from 50 to 95 mol% of a linear aliphatic diamine-based unit containing from 9 to 12 carbon atoms and terephthalic acid and from 5 to 50% of a unit-forming unit. terephthalic acid to a mixture of 2,2,4 and 2,4,4 trimethylhexanediamine.
• US 201 1306718 discloses a method of pultrusion of low Tg reactive aliphatic polyamides associated with chain extenders of polymeric structure bearing several (and much greater than 2) functions of anhydrides or epoxides. This document does not describe any non-polymeric extender. Disadvantages of the state of the art, with the absence of a good compromise between mechanical performance and processability (ease of processing) at lower temperatures with a shorter production cycle time are overcome by the solution of the present invention which aims at semi-crystalline PA compositions, allowing easier implementation at lower temperatures with a saving on the overall energy balance of the implementation method, a cycle time shorter production time and improved productivity, by rapid crystallization ability of said polyamide polymer and while maintaining a high level of mechanical performance of said final materials. More particularly, in the case of reactive compositions, it is desired to have a faster reaction kinetics while having a higher crystallization rate and / or crystallization temperature of the polymer also formed.
• a semi-crystalline polyamide polymer as the matrix of the composite material of the invention, has as interest compared with amorphous polyamides, significantly improved mechanical performance especially at hot, such as resistance to creep or fatigue.
• having a melting point above 200 ° C has the advantage in the automobile to be compatible with cataphoresis treatments, which does not allow an amorphous PA type structure.
• a Tg of greater than or equal to 90 ° C is sought to ensure good mechanical properties to the composite over the entire operating temperature range, for example up to 90 ° C. for the wind turbine, up to 100 ° C. ° C for the automobile and up to 120 ° C for the aeronautics.
• a melting point that is too high, in particular greater than 280 ° C., is, however, detrimental since it requires the use of the composite at higher temperatures with constraints of molding material to be used (and heating system associated) and energy overconsumption with in addition to the risk of thermal degradation by heating at temperatures higher than the melting temperature of said polyamide, resulting in the assignment of the properties of the final thermoplastic matrix and the composite resulting therefrom.
• the crystallinity of said polymer should be as high as possible but with a not too high melting temperature Tf (Tf ⁇ 280 ° C. and more particularly ⁇ 270 ° C.) to optimize the mechanical performance and the crystallization rate and / or the temperature of the polymer.
• the object of the present invention is the implementation of new specific compositions of thermoplastic composite, in particular based on of semi-crystalline polyamide, having a good compromise between high mechanical performance (mechanical strength) especially hot and easy implementation. This means that there is a goal of compositions that are easy to implement with lower processing and processing temperatures than those for other compositions of the state of the art, with an overall energy balance of more favorable implementation, shorter cycle time and higher productivity.
• the solution of the invention in the case of reactive compositions, allows using compositions based on semi-crystalline reactive polyamide prepolymers, both a reaction kinetics and a fast crystallization kinetics with a cycle time. shorter.
• the polyamide polymer matrix while having a high Tg and a limited Tf as defined, with easy implementation of said composite, must also have a high crystallization rate, characterized firstly by a difference between melting temperature and of crystallization Tf-Tc not exceeding 50 ° C, preferably not exceeding 40 ° C and more particularly not exceeding 30 ° C.
• this difference Tf-Tc does not exceed 30 ° C., unless Tf-Tg is ⁇ 150 ° C., in which case (Tf-Tg ⁇ 150 ° C.) the difference Tf-Tc can vary up to 50 ° C. vs.
• the mechanical performance or mechanical strength of the composite can be evaluated by the variation of the mechanical module between the ambient temperature (23 ° C) and 100 ° C with a maintenance of at least 75% of the mechanical performances, in terms of module , compared to those at room temperature (23 ° C). Therefore, the object of the invention is to develop a polyamide composition meeting these needs.
• the first object of the invention relates to a specific semi-crystalline polyamide (PA) composition for a thermoplastic composite material or a thermoplastic composite material composition, with a thermoplastic matrix having a Tg of at least 90 ° C and a Tf less than or equal to 280 ° C, preferably less than 280 ° C.
• This composition may be reactive via prepolymers reactive with each other by condensation or with a chain extender by polyaddition and without elimination of volatile by-products. It may alternatively be a non-reactive composition based on polymeric polyamides corresponding to the final polymer of the thermoplastic matrix.
• Said specific composition is based on the selective choice of at least two different amide units A and B and specific molar proportions with optional presence of at least a third (C) and optionally a fourth (D) unit amide, these patterns being different from each other.
• a second object of the invention relates to a specific method of manufacturing said thermoplastic composite material and more particularly to manufacturing mechanical parts or structural parts based on said composite material.
• thermoplastic polymer of the thermoplastic matrix of said composite material is also concerned by the present invention.
• Another object of the invention relates to the use of the PA specific composition of the invention for the manufacture of a thermoplastic composite material of the same composition and more particularly of mechanical parts or structure based on this material.
• Another object of the invention relates to the thermoplastic composite material which results from said composition for composite material.
• the invention covers a mechanical part or structural part based on composite material obtained by the specific process of the invention or which results from the use of the PA specific composition of the invention.
• the first object relates to a composition for thermoplastic composite material or a composition of thermoplastic composite material, said composite material comprising reinforcing fibers or in other words a fibrous reinforcement and a thermoplastic matrix impregnating said fibers (or said fibrous reinforcement), said matrix being based on at least one thermoplastic polymer, with regard to said composition:
• thermoplastic matrix polymer being a semicrystalline polyamide polymer with a glass transition temperature Tg of at least 90 ° C, preferably at least 100 ° C, more preferably at least 110 ° C, more preferably preferably at 120 ° C., a melting temperature Tf of less than or equal to 280 ° C., in particular less than 280 ° C., preferably less than or equal to
• composition further comprising said reinforcing fibers:
• a reactive composition comprising or consisting of at least one prepolymer (or oligomer, with oligomer and prepolymer meaning the same thing for the rest) reactive polyamide, said composition being a precursor composition of said polyamide polymer of said matrix, or alternatively to at)
• thermoplastic matrix with Tg and Tf as defined above, and with :
• composition a) or b) comprising or consisting of one or more polyamides, including random or block copolyamides which are prepolymers (or oligomers) according to a) or which are polymers according to b) and which comprise amide units A and B different and optional amides C and D different, selected as follows:
• A is a majority amide unit present at a molar level ranging from 55 to 95%, preferably from 55 to 85%, more preferably from 55 to 80%, still more preferably from 55 to 75%, in particular from 55 to 70%; %, selected from xT units, where x is a linear aliphatic diamine C 9 to C 8, preferably C 9, C 1 0, C 11, C 12 and where T is terephthalic acid,
• A is an amide unit other than A, which unit B is present at a molar level ranging from 5 to 45%, preferably from 15 to 45%, more preferably from 20 to 45%, still more preferably from 25 to 45% , in particular from 30 to 45%, as a function of the Tf of the polyamide based on unit A and with said amide unit B being chosen from among the units x'.T, where x 'is chosen from:
• B1 a branched aliphatic diamine carrying a single branch (branch meaning the same) methyl or ethyl, preferably methyl, in particular 2-methyl pentamethylene diamine (MPMD) or 2-methyl octamethylenediamine (MOMD) and having a a main chain length different from at least two carbon atoms from the main chain length of the diamine x of said associated A motif, preferably x '(according to B1)) being MPMD or
• said unit B is chosen from the units x'.T, where x 'is the MPMD according to option B1) or the MXD according to option B2) or a linear aliphatic diamine as defined above according to option B3) or more preferentially x 'is MPMD according to B1) or MXD according to B2) and even more preferably x' is MXD according to B2)
• - D optional amide unit other than A, B and C, when C is present and selected from aliphatic amide units from:
• Said composition is more particularly a composition for thermoplastic composite material. This means that it makes it possible to obtain a thermoplastic composite material.
• said polyamide whether polymer or prepolymer, comprises said amide unit according to C, different from A and B or the pattern C as defined above is present and in place and at a molar level of up to 25%, preferably up to 20%, more preferably up to 15%, with respect to said B-unit.
• said pattern C When the pattern C is present and it corresponds to x'T with x 'as defined above for the pattern B, in which case C is different from B by definition, said pattern C may be based on x' being defined according to B1 and in this case said pattern B may have x 'defined according to either B2 or B3. If C is based on x 'according to B2, in this case the pattern B can be based on x' being according to B1 or B3. If C is based on x 'according to B3, in this case the pattern B may be based on x' being defined according to B1 or B2.
• said aromatic structure may be chosen for example from the isophthalic and / or naphthalene structure.
• a terephthalic structure is possible in particular for the diacid component when the diamine is cycloaliphatic.
• Said cycloaliphatic structure can be selected from a cyclohexane ring-based structure or a decahydronaphthalenic ring-based structure (hydrogenated naphthalenic structure).
• the structure of C is derived from an aliphatic diamine and a cycloaliphatic and / or aromatic diacid, for example as defined above, or a cycloaliphatic diacid and diamine, for example as defined above.
• said pattern C is chosen from the motifs derived from:
• diacid chosen from isophthalic, naphthenic or cyclohexane and diamine x or x 'as defined above for the units A and B respectively.
• said unit D is present and partially replaces B with a molar level of up to 70%, preferably up to 15% relative to said unit B.
• said composition comprises said unit D as defined above, in particular chosen from: amino acids or lactams C 6 to C 12, preferably C 6 , C n and C 12 or mixtures thereof or the units resulting from the reaction a linear aliphatic diacid in C 6 to C 8, preferably C 6 to C 12 and a linear aliphatic diamine C 6 to C 8, preferably C 6 to C 12 and preferably with the units a and B being respectively based on diamines x and x 'as defined above.
• the C and / or D unit when present, partially replaces the B unit with a molar ratio (C + D) of up to 70% and preferably less than 40% with respect to the molar ratio of said B unit. as defined according to the invention.
• a part of the unit B as defined according to the invention which represents less than 50%, preferably less than 40% by mol relative to B, can be replaced by a C and / or D unit as defined above. according to the invention.
• the difference Tf-Tc, between the melting temperature Tf and the crystallization temperature Te of said polymer (polyamide) matrix does not exceed 50 ° C., preferably does not exceed 40 ° C. and more particularly does not exceed 30 ° C. ° C.
• Tf-Tc does not exceed 30 ° C unless Tf-Tg is less than 150 ° C, in which case Tf-Tc can be up to 50 ° C.
• the enthalpy of crystallization of said matrix polymer measured in Differential Scanning Calorimetry (DSC) according to the ISO Standard 1 1357-3, is greater than 40 J / g, preferably greater than 45 J / g.
• said amide unit A is present at a molar level ranging from 55 to 80%, more preferably from 55 to 75%, even more preferably 55 to 70%, relative to all the units of said matrix polymer (polyamide) as defined above according to the invention.
• said composition has a pattern B with x 'defined according to option B1 described above, in particular with the diamine most preferred for said pattern B, being MPMD.
• the unit A remains as defined above, that is to say xT, with x a linear aliphatic diamine C 9 to C 18, preferably C 9 , Ci 0 , Cn or Ci 2 .
• a second preferred option of said composition has a pattern B where x 'is the MXDA according to option B2 defined above. Pattern A remains as defined for the first option cited.
• a third preferred option is that where B is defined according to the option B1 or B2 or B3 as defined above and with the presence of a pattern C as defined above in replacement of B and up to 25%, preferably up to 20%, more preferably up to 15% by mole and in particular with B being defined according to the first or second option as defined above.
• said polyamide composition is based on the A and B units selected as follows:
• said pattern B is selected from: 10T, 11T, 12T, 13T,
• pattern B is selected from: 9T, 11T, 12T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, preferably 12T, 13T, 14T, 15T ,
• said pattern B is selected from: 9T, 10T, 12T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, preferably 9T, 13T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, more preferably MPMD.T or MXD.T, with a molar ratio of B ranging from 20 to 45%,
• said pattern B is selected from: 9T, 10T, 1T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, preferably 9T, 10T, 14T, 15T , 16T, 17T and 18T, MPMD.T and MXD.T, more preferably MPMD.T or MXD.T, with a molar ratio of B ranging from 20 to 45%.
• a first and more particular composition of the invention may be defined, with the pattern A being a 9T pattern and the pattern B being selected from: 10T, 11T, 12T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, preferably 11T, 12T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, more preferably MPMD.T or MXD.T, with a molar rate of B ranging from 30 to 45%.
• a second particular composition corresponds to a pattern A being a 10T pattern and the pattern B being selected from: 9T, 11T, 12T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, preferably 12T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, more preferably MPMD.T or MXD.T, with a molar ratio of B ranging from 25 to 45%.
• a third particular composition corresponds to a pattern A being a pattern 11 T and the pattern B being selected from: 9T, 10T, 12T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, Preferably, 9T, 13T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, more preferably MPMD.T or MXD.T, with a molar ratio of B ranging from 20 to 45%.
• compositions corresponds to a pattern A being a 12T pattern and the pattern B being selected from: 9T, 10T, 11T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T preferably, 9T, 10T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, more preferably MPMD.T or MXD.T, with a molar ratio of B ranging from 20 to 45%.
• said polyamide composition may be a non-reactive composition according to b).
• said composition is the same as that of the matrix polymer (polyamide) of said composite because there is no reaction in this composition, which remains stable and non-evolutive in terms of molecular weight during its heating for the implementation composite material of the invention.
• the characteristics of the polyamide polymer in this composition are the same, with Tg and Tf as defined above, than those of the final polymer which is the semicrystalline polyamide obtained by a reactive composition a) (see below), said polymer constituting by definition said thermoplastic matrix of said composite.
• the polyamides according to b) are obtained by conventional polycondensation reaction from the monomeric components which are diamines, diacids and optionally amino acids or lactams, with the proportion and nature of the monomers being chosen according to the selected units of the invention, and B and possibly C and D.
• the number-average molecular weight Mn of said final polymer (polyamide) of the thermoplastic matrix of said composite is preferably in a range from 10,000 to 40,000, preferably from 12,000 to 30,000. These Mn values may correspond to at inherent viscosities greater than or equal to 0.8.
• These polyamides according to composition b) are non-reactive, either by the low level of reactive (residual) functions present, in particular with a level of said functions ⁇ 120 meq / kg, or by the presence of the same type of terminal functions at the end of the reaction.
• this reactive prepolymer has an Mn of at least two times lower than that of said final matrix polymer.
• said polyamide composition may be a reactive prepolymer composition according to a) and precursor or precursor composition of said polyamide polymer of said matrix of the composite.
• said composition a) may comprise or consist of at least one reactive (polyamide) prepolymer carrying on the same chain (ie on the same prepolymer), two terminal functions X 'and Y 'functions respectively coreactive between them by condensation, with X' and Y 'being amine and carboxy or carboxy and amine respectively.
• said reactive composition a) may comprise or consist of at least two polyamide prepolymers which are reactive with one another and each carrying two identical terminal functions X 'or Y' (same for the same prepolymer and different between the two).
• said function X 'of a prepolymer being able to react only with said function Y' of the other prepolymer, in particular by condensation, more particularly with X 'and Y' being amine and carboxy or carboxy and amine respectively.
• This condensation reaction (or polycondensation) can cause the elimination of by-products.
• These can be removed by preferably working in a method using open mold technology. In the case of a closed mold process, a step of degassing, preferably under vacuum, by-products removed by the reaction is present, this to avoid the formation of microbubbles by-products in the final composite material , which (microbubbles) can affect the mechanical performance of said material if they are not removed as well.
• said composition a) or precursor composition a) may comprise or consist of: a1) at least one prepolymer of said thermoplastic polyamide polymer (of the matrix) as already defined above with this prepolymer bearing n terminal functional functions X, identical chosen from: -NH 2 (amine), -C0 2 H (carboxy) and -OH (hydroxyl), preferably -NH 2 (amine) and -C0 2 H (carboxy), with n being 1 to 3, preferably 1 to 2, more preferably 1 or 2, more particularly 2
• a2) at least one Y-A'-Y chain extender, with A 'being a hydrocarbon biradical of non-polymeric structure (neither polymer nor oligomer nor prepolymer), carrying 2 identical terminal reactive functions Y, reactive by polyaddition (without elimination reaction by-product), with at least one function X of said prepolymer a1), preferably of molecular weight less than 500 and more preferably less than 400.
• NH 2 (amine) means primary and secondary amines.
• the semi-crystalline structure of said polyamide polymer of the matrix of said composite is essentially provided by the structure of said prepolymer a1) which is also semi-crystalline.
• extenders a2) as a function of the X functions carried by said semi-crystalline polyamide prepolymer a1), the following may be mentioned: when X is NH 2 or OH, preferably NH 2 :
• ⁇ Y chosen from the groups: maleimide, optionally blocked isocyanate, oxazinone and oxazolinone, preferably oxazinone and oxazolinone and
• ⁇ A ' is a carbon-carbon or spacer radical bearing functions or reactive groups Y, selected from:
• chain extender Y-A'-Y corresponds to Y being a caprolactam group and A 'may be a carbonyl radical such as carbonyl biscaprolactam or A may be a terephthaloyl or isophthaloyl, o or said chain extender Y-A'-Y carries a group Y of cyclic anhydride and preferably this extender is chosen from a cycloaliphatic and / or aromatic carboxylic dianhydride and more preferably it is chosen from: ethylenetetracarboxylic dianhydride, dianhydride pyromellitic, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,1,5,8-naphthalenetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, dianhydride 1 ,
• said chain extender Y-A'-Y corresponds to:
• ⁇ Y chosen from the groups: oxazoline, oxazine, imidazoline or aziridine such as 1, 1 '-iso- or terephthalic phthaloyl-bis (2-methyl aziridine)
• ⁇ A ' is a spacer (group) carbon as defined above.
• said Y function is selected from oxazinone, oxazolinone, oxazine, oxazoline or imidazoline
• A can represent an alkylene such that - (CH 2 ) m - with m ranging from 1 to 14 and preferably from 2 to 10 or
• this blocking can be obtained by blocking agents of the isocyanate function, such as epsilon-caprolactam, methyl ethyl ketoxime, dimethyl pyrazole, diethyl malonate.
• the preferred conditions avoid any formation of imide ring during the polymerization and during the implementation at the same time. melted state.
• the group Y is preferably chosen from: isocyanate (not blocked), oxazinone and oxazolinone, more preferably oxazinone and oxazolinone, with the spacer (radical) A 'being as defined above.
• chain extenders carrying oxazoline or oxazine reactive functions Y that are suitable for the implementation of the invention, reference may be made to those described under references “A”, “B”, “C” and “D”. on page 7 of application EP 0 581 642, as well as to their preparation processes and the other reaction modes which are exposed to them.
• "A” in this document is bisoxazoline, "B” bisoxazine, "C” 1, 3 phenylene bisoxazoline and "D" 1,4-phenylene bisoxazoline.
• Y-imidazoline reactive chain extenders suitable for the implementation of the invention, reference may be made to those described ("A" to "F") on pages 7 to 8 and Table 1 of the page 10 in the application EP 0 739 924 as well as their processes of preparation and their modes of reaction which are exposed to it.
• Y oxazinone or oxazolinone reactive functional chain extenders which are suitable for the implementation of the invention, reference may be made to those described under references “A” to "D” on pages 7 to 8 of EP 0 581 641, and to their preparation processes and their reaction modes which are exposed to them.
• groups Y oxazinones (6-atom ring) and oxazolinones (5-atom ring) are suitable Y groups derived from: benzoxazinone oxazinone or oxazolinone, with as spacer A 'can be a single bond covalently with respective corresponding lengtheners being: bis- (benzoxazinone), bisoxazinone and bisoxazolinone.
• a ' may also be alkylene Ci to C 4, preferably C 2 to C 1 0 but preferably A' is an arylene and more particularly it may be a phenylene (Y-substituted in positions 1 and 2 or 1, 3 or 1, 4) or naphthalene (disubstituted with Y) or phthaloyl (iso- or terephthaloyl) or A may be cycloalkylene.
• the radical A ' can be as described above with A' being a simple covalent bond and with the extenders respective corresponding ones being: bisoxazine, bisoxazoline and bisimidazoline.
• a ' may also be alkylene Ci to C 4, preferably C 2 to Ci 0.
• the radical A ' is preferably arylene and, more particularly, it may be phenylene (substituted with Y at the 1, 2 or 1, 3 or 1, 4 positions). or a naphthalene radical (disubstituted by Y) or phthaloyl (iso- or terephthaloyl) or A 'may be a cycloalkylene.
• the radical A ' may be a phthaloyl (1, 1' iso). or terephthaloyl) with, as an example of such an extender, isophthaloyl-bis (2-methyl aziridine).
• a catalyst for the reaction between said P (X) n prepolymer and said Y-A'-Y extender at a level ranging from 0.001 to 2%, preferably from 0.01 to 0.5% relative to The total weight of two co-reactants mentioned can accelerate the (poly) addition reaction and thus shorten the production cycle.
• a catalyst may be chosen from: 4,4'-dimethylaminopyridine, p-toluenesulphonic acid, phosphoric acid, NaOH and optionally those described for polycondensation or transesterification as described in EP 0 425 341, page 9, lines 1 to 7.
• a ' may represent an alkylene, such that - (CH 2 ) m - with m ranging from 1 to 14 and preferably from 2 to 10 or represents a substituted arylene alkyl or unsubstituted, such as benzene arylenes (such as o-, m-, -p) or naphthalenic phenylenes (with arylenes: naphthalenylenes).
• a ' represents an arylene which can be benzene or naphthenic substituted or not.
• said chain extender (a2) has a non-polymeric structure and preferably a molecular weight of less than 500, more preferably less than 400.
• Said reactive prepolymers of said reactive composition a), according to the three options mentioned above, have a number average molecular weight Mn ranging from 500 to 10,000, preferably from 1000 to 6000. All masses Mn are determined by calculation from the rate of terminal functions determined by potentiometric titration in solution and the functionality of said prepolymers.
• said reactive prepolymers are prepared by conventional polycondensation reaction between the corresponding diamine and diacid components and optionally (depending on the D-unit) amino acids or lactams respecting the nature and proportions patterns A and B and optionally C and D according to the invention.
• Prepolymers carrying X 'and Y' amino and carboxy functions on the same chain can be obtained for example by adding a combination of monomers (amino acid, diamine, diacid) having in total an equal amount of amino and carboxy units.
• n 3
• a trifunctional component for example the presence of a triamine (one mole per prepolymer chain) with a diamine in the reaction with a diacid .
• the reinforcing fibers or fibrous reinforcement may be an assembly of fibers, preferably of long fibers, that is to say having a shape factor defined by the length to diameter ratio of the fiber, which means that these fibers have a circular section, greater than 1000, preferably greater than 2000.
• the fibers can be continuous, in the form of unidirectional reinforcement (UD) or multidirectional (2D, 3D).
• UD unidirectional reinforcement
• 2D, 3D multidirectional reinforcement
• they may be in the form of fabrics, webs, strips or braids and may also be cut, for example in the form of nonwovens (mats) or in the form of felts.
• These reinforcing fibers may be chosen from:
• the mineral fibers which have melting temperatures Tf which are higher than and higher than the melting temperature Tf of said semi-crystalline polyamide of the invention and which are higher than the polymerization and / or processing temperature.
• the polymer or polymer fibers having a melting temperature Tf or, in the absence of Tf, a glass transition temperature Tg 'greater than the polymerization temperature or higher than the melting temperature Tf of said semi-crystalline polyamide constituting said matrix of the composite and greater than the temperature of implementation
• Suitable mineral fibers for the invention include carbon fibers, which include carbon nanotube or carbon nanotube (CNT) fibers, carbon nanofibers, or graphenes; silica fibers such as glass fibers, especially of type E, R or S2; boron fibers; ceramic fibers, in particular silicon carbide fibers, boron carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers; fibers or filaments based on metals and / or their alloys; fibers of metal oxides, especially alumina (Al 2 O 3 ); metallized fibers such as metallized glass fibers and metallized carbon fibers or mixtures of the aforementioned fibers.
• CNT carbon nanotube or carbon nanotube
• Silica fibers such as glass fibers, especially of type E, R or S2
• boron fibers ceramic fibers, in particular silicon carbide fibers, boron carbide fibers, boron carbon
• these fibers can be chosen as follows:
• the mineral fibers may be chosen from: carbon fibers, fibers of carbon nanotubes, glass fibers, in particular of type E, R or S2, boron fibers, ceramic fibers, in particular silicon carbide fibers, carbide fibers of boron, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers, metal-based fibers or filaments and / or their alloys, metal oxide-based fibers such as Al 2 0 3 metallized fibers such as metallized glass fibers and metallized carbon fibers or mixtures of the aforementioned fibers, and
• polymer or polymer fibers under the abovementioned condition, are chosen from:
• thermoset polymer fibers and more particularly chosen from: unsaturated polyesters, epoxy resins, vinyl esters, phenolic resins, polyurethanes, cyanoacrylates and polyimides, such as resins bismaleimide, aminoplasts resulting from the reaction of an amine such as melamine with an aldehyde such as glyoxal or formaldehyde
• Thermoplastic polymer fibers and more particularly chosen from: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), high density polyolefins such as polyethylene (PET), polypropylene (PP) and PET / PP copolymers, PVOH (polyvinyl alcohol)
• polyamide fibers having one of the formulas: 6, 1 1, 12, 6.10, 6.12, 6.6, 4.6, ⁇ aramid fibers (such as Kevlar ® ) and aromatic polyamides such as those corresponding to one of the formulas: PPD.T, MPD.I, PAA and PPA, with PPD and MPD respectively being the p- and m- phenylene diamine, PAA being polyarylamides and PPA being polyphthalamides
• Polyamide block copolymer fibers such as polyamide / polyether, polyaryletherketone (PAEK) fibers such as polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherketoneetherketoneketone (PEKEKK).
• PAEK polyaryletherketone
• PEEK polyetheretherketone
• PEKK polyetherketoneketone
• PEKEKK polyetherketoneetherketoneketone
• the preferred reinforcing fibers are long fibers (circular section) chosen from: carbon fibers, including metallized fibers, glass fibers, including metallized type E, R, S2, aramid fibers (such as Kevlar ® ) or aromatic polyamides, polyarylethersketone (PAEK) fibers, such as polyetheretherketone (PEEK), polyetherketoneketone (PEKK) fibers, polyetherketoneetherketoneketone (PEKEKK) fibers or mixtures thereof.
• carbon fibers including metallized fibers, glass fibers, including metallized type E, R, S2, aramid fibers (such as Kevlar ® ) or aromatic polyamides, polyarylethersketone (PAEK) fibers, such as polyetheretherketone (PEEK), polyetherketoneketone (PEKK) fibers, polyetherketoneetherketoneketone (PEKEKK) fibers or mixtures thereof.
• PEEK polyetheretherketone
• PEKK polyetherket
• the more preferred fibers are selected from: glass fibers, carbon fibers, ceramic and aramid fibers (such as Kevlar ®) or mixtures thereof. These fibers have a circular section.
• Said fibers may represent levels of 40 to 70% by volume and preferably 50 to 65% by volume of said composite material.
• the assembly of fibers can be random (matte), unidirectional (UD) or multidirectional (2D, 3D or other). Its basis weight, that is to say its weight per square meter, can range from 100 to 1000 g / m 2 , preferably from 200 to 700 g / m 2 .
• the fibers may be in woven or non-woven form, particularly in the form of fabrics and reinforcing fabrics. They can in particular be assembled and linked in the form of a preform already having the shape of the final piece.
• a suitable binder it is possible to use a composition according to a) or b) and, failing that, a binder compatible therewith (composition a) or b)).
• composition according to the invention comprises a fibrous reinforcement based on fibers, preferably long fibers, in particular with L / D greater than 1000, preferably greater than 2000 and more particularly selected from glass, carbon and ceramic fibers. aramid or mixtures thereof.
• the composition according to the invention is a molding composition.
• it may comprise, in addition to reinforcing fibers preferably long, other fillers and additives.
• Suitable fillers include, for example: inorganic or organic fillers: carbon black, carbon nanotubes (CNTs), carbon nanofibrils, glass beads, recycled polymers milled in powder form.
• additives absorbing in the UV or IR so as to allow the welding of the composite obtained, by laser (UV or IR) technology and thermal stabilizers chosen from sterically hindered phenol type antioxidants or sterically hindered amines (HALS).
• UV or IR laser
• thermal stabilizers chosen from sterically hindered phenol type antioxidants or sterically hindered amines (HALS).
• HALS sterically hindered phenol type antioxidants
• HALS sterically hindered amines
• the second subject of the invention relates to a process for manufacturing a thermoplastic composite material, in particular a mechanical part or a structural part based on said material, of composition as defined according to the invention as described herein.
• -High which process comprises at least one polymerization step of at least one reactive composition a) as defined above according to the invention or a molding step or implementation of at least one non-reactive composition b) as defined above according to the invention.
• said method may comprise the following steps:
• step ii) polymerization reaction by heating said composition of step i), in the case of a reactive composition a) of polyamide as defined according to the invention, with chain extension (increase in molecular weight), as the case may be by polycondensation reaction (including self-condensation of the same prepolymer), or by melt mass polyaddition reaction, with polycondensation, vacuum evacuation of condensation products in the case of polycondensation of a closed mold, using a vacuum extraction system, otherwise and preferably with the polycondensation being carried out in open mold or out of mold
• step iii) implementing or molding said composition of step i), in the case of a non-reactive polyamide composition b) as defined according to the invention, to form the final composite part in a mold or with a other implementation system and in the case of a reactive composition a) a step of implementation by molding or by another implementation system and simultaneously with the polymerization step ii).
• said implementation can be carried out preferably according to a RTM, S-RIM, injection-compression, pultrusion or infusion process, in particular in the case of a reactive composition a).
• thermoplastic polymer in particular the polymer which corresponds to (or is) the polymer of the thermoplastic matrix of said thermoplastic composite material of the present invention, said polymer being a non-reactive polymer as defined according to composition b) defined above or a polymer obtainable from said reactive composition a) as defined above according to the present invention.
• This thermoplastic polymer is by definition one of the essential components of the composition of the thermoplastic composite material of the present invention and is therefore part of the invention as a product related to the present invention with the same common inventive concept facing the same technical problem to solve.
• thermoplastic polymer according to the invention as a thermoplastic matrix of a thermoplastic composite based on a fibrous reinforcement as described above. More particularly preferred are the polymers corresponding to the polyamide compositions as defined according to the first preferred composition option, with B being defined according to option B1) or the second option with B defined according to option B2) or according to the third preferred option of composition, where B is defined according to options B1) or B2) and C is present as defined above.
• Another subject of the invention relates to the use of a composition as defined above according to the invention or the use of a semi-crystalline polyamide polymer according to the invention for the manufacture of a thermoplastic composite material , more particularly a mechanical part or a structural part (including structural and semi-structural part) based on said composition or said composite material.
• said mechanical parts or structural parts of said composite material relate to applications in the field of automotive, railway, marine, wind, photovoltaic, solar, including solar panels and solar power plant components, sports, aeronautics and space, road transport (for trucks), building, civil engineering, signage or recreation.
• three more preferred applications can be distinguished as a function of the operating temperature of said composite material parts according to the invention: in wind power, with a Tg of said thermoplastic matrix polyamide of at least 90 ° C
• Tg for a Tg of at least 100 ° C, it can have two possible applications: automobile and wind and if the Tg is at least 120 ° C in addition to aeronautics as an application, it can also be used wind and the automobile.
• the present invention also covers a thermoplastic composite material resulting from the use of at least one composition for thermoplastic composite material as defined above according to the present invention.
• the invention relates to a mechanical part or piece of thermoplastic composite material structure, which results from the use of at least one composition of the invention as defined above or the use of a polymer semi-crystalline polyamide as defined according to the invention or a thermoplastic composite material as defined above or which part is obtained by a process as defined above according to the invention.
• said structural part is an automotive part after cataphoresis treatment, in particular with a Tg of at least 90 ° C.
• it is a piece for a wind turbine, in particular with a Tg of at least 100 ° C.
• the melt viscosity of the prepolymer or precursor composition is measured according to the reference manual of the manufacturer of the measuring apparatus used, which is a Physica MCR301 rheometer, under a nitrogen sweep at the given temperature under shear. 100 s "1 , between two parallel planes with a diameter of 50 mm.
• the Mn of the prepolymer or thermoplastic polymer is determined from the titration (assay) of the terminal functions according to a potentiometric method (direct assay for NH 2 or carboxy) and from the theoretical functionality which is 2 (in terminal functions ) for prepolymers and linear polymers prepared from bifunctional monomers alone. Measurement of intrinsic or inherent viscosity is performed in m-cresol. The method is well known to those skilled in the art. The ISO 937 standard is followed but the solvent is changed (use of m-cresol instead of sulfuric acid and the temperature is 20 ° C).
• the glass transition temperature Tg of the thermoplastic polymers used is measured using a differential scanning calorimeter (DSC), after a second heating passage, according to the ISO 1 1357-2 standard.
• the heating and cooling rate is 20 ° C / min.
• the melting temperature Tf and the crystallization temperature Te are measured by DSC, after a first heating, according to the standard ISO 1,1357-3.
• the heating and cooling rate is 20 ° C / min.
• the enthalpy of crystallization of said matrix polymer is measured in Differential Scanning Calorimetry (DSC) according to the standard ISO 1,1357-3.
• the monofunctional chain regulator benzoic acid in an amount adapted to the target Mn and variant (benzoic acid) of 50 to 100 g,
• the closed reactor is purged of its residual oxygen and then heated to a temperature of 230 ° C. with respect to the material introduced. After stirring for 30 minutes under these conditions, the pressurized steam which has formed in the reactor is progressively relaxed in 60 minutes, while progressively increasing the material temperature so that it is set at Tf + 10 ° C at atmospheric pressure.
• the polymerization is then continued under a nitrogen sweep of 20 l / h until the target mass Mn indicated in the table of characteristics is obtained.
• the polymer is then drained by the bottom valve and then cooled in a water tank and then granulated.
• the representative tests of the invention show superior performance compared to the comparative tests outside the invention, some of which are representative of the state of the prior art cited, in particular in terms of small Tf-Tc difference ( ⁇ 30 ° C). and for Tf-Tc ranging from 30 to 50 ° C with Tf-Tg difference ⁇ 150 ° C.
• the closed reactor is purged of its residual oxygen and then heated to a temperature of 230 ° C of the material. After stirring for 30 minutes under these conditions, the pressurized steam which has formed in the reactor is gradually relieved in 60 minutes, while progressively increasing the material temperature so that it is established at Tf + 10. ° C at atmospheric pressure.
• the oligomer (prepolymer) is then drained by the bottom valve and then cooled in a water tank and ground.
• the granules from step A are compounded on an Evolum 32 twin-screw extruder according to a flat temperature profile of 280 ° C.
• the flow rate is 40 kg / h and the speed is 300 rpm.
• the polymer (49.65% by weight) and the additives (0.3% Calcium Sterarate and 0.4% Irganox 1010) are introduced into the main hopper.
• the fiberglass ASAHI CS 692 FT (49.65% by weight) is introduced via a lateral gaveur second part of extruder. The rushes are cooled in water and granulated.
• the 10.T / MXDT composition still exhibits a higher crystallization ability associated with a very high Tg and particularly low Tf-Tg.

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