Classifications

• • 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
• • 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
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/40—Shaping or impregnating by compression not applied
  • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
  • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
  • B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
• • 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
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/40—Shaping or impregnating by compression not applied
  • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
  • B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
• • 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
  • 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
  • C08G69/28—Preparatory processes
• • 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
  • C08G69/44—Polyester-amides
• • 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
  • C08G69/48—Polymers modified by chemical after-treatment
• • 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
• • 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
  • C08L77/12—Polyester-amides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
• • 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
  • C08G2120/00—Compositions for reaction injection moulding processes
• • 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
  • 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
  • C08J2377/12—Polyester-amides

Definitions

• the invention relates to a specific non-reactive molding composition, in particular for a thermoplastic composite material with a semi-crystalline polyamide (PA) matrix having a glass transition temperature Tg of at least 80 ° C. and preferably at least 80 ° C. 90 ° C and melting temperature Tf less than or equal to 280 ° C, this polymer having a specific structure and also a method of manufacturing said composite material in particular mechanical parts or structure based on said material, the use of the composition of the invention for parts of composite material and the resulting composite part and for applications in the fields of: automotive, rail, marine, road transport, wind, sports, aeronautics and space , building, signs 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 2,586,585 discloses a method of manufacturing a composite material with fiber reinforcement comprising impregnating said fibrous reinforcement with a reactive precursor composition of a thermoplastic polymer, said precursor composition comprising a reactive prepolymer P (X) n and an extender of chain carrying two Y functions reactive with the X functions of said prepolymer.
• a reactive precursor composition of a thermoplastic polymer said precursor composition comprising a reactive prepolymer P (X) n and an extender of chain carrying two Y functions reactive with the X functions of said prepolymer.
• 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.
• a semi-crystalline polyamide polymer as a matrix of the composite material of the invention, has the advantage, compared to amorphous polyamides, of significantly improved mechanical performance, especially at high temperature, such as resistance to creep or cracking. tired.
• 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 80.degree. C., preferably at least 90.degree. C. is required to ensure good mechanical properties for the composite over the entire operating temperature range, for example up to 80.degree.
• 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 must be as high as possible but with a not too high melting point Tf (Tf ⁇ 280 ° C.
• the object of the present invention is the implementation of new specific compositions of thermoplastic composite, in particular based on semicrystalline polyamide, having a good compromise between high mechanical performances (mechanical strength), especially when 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 polyamide polymer matrix while having a high Tg and a limited Tf as defined, with an easy implementation of said composite, must also have a high crystallization rate, characterized firstly by a difference between the melting temperature. and crystallization Tf-Tc not exceeding 50 ° C, preferably not exceeding 40 ° C and more preferably not exceeding 30 ° C. More preferably, 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.
• 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 specific polymer of the invention having the characteristics indicated above, is derived from the polyaddition reaction of a polyamide prepolymer a) with a non-polymeric extender b).
• this specific semicrystalline polyamide polymer used according to the present invention for impregnation in the molten state of a fiber reinforcement for the preparation of a thermoplastic composite material, has the additional advantage of having an easy implementation with improved fluidity, that is to say a melt viscosity at the same temperature for the impregnation of said fibrous reinforcement lower than that of the same polyamide but without incorporation of said elongator b) ( only difference) and also with the advantage of initially having a high molecular mass Mn and precontrol prior to the step of impregnating said fibrous reinforcement without high viscosity.
• the first subject of the invention relates to a specific semi-crystalline polyamide (PA) non-reactive molding composition for a thermoplastic composite material, said polyamide having a Tg of at least 80 ° C., preferably at least 90 ° C. C and a Tf of less than or equal to 280 ° C, preferably less than 280 ° C with said polymer semi-crystalline polyamide of said composition being a non-reactive polymer and resulting from a polyaddition reaction between a) at least one reactive polyamide prepolymer of said semi-crystalline polyamide, bearing n identical reactive functions X among amine, carboxy or hydroxyl, preferably carboxy or amine, with n ranging from 1 to 3, preferably from 1 to 2 and more particularly from 2 and b) at least one non-polymeric Y-A'-Y chain extender with Y identical functions and reactive with said functions X said prepolymer a), with Y preferably being selected from: oxazine, oxazoline, o
• the invention also relates to a method of manufacturing a thermoplastic composite material by using said specific polymer of the invention to impregnate a fibrous reinforcement.
• the first object of the invention relates to a non-reactive molding composition, in particular for a thermoplastic composite material, comprising at least one thermoplastic polymer and optionally reinforcing fibers, also hereinafter referred to as fibrous reinforcement and in this case, said at least one polymer capable of impregnating said fibers or said fibrous reinforcement and forming the thermoplastic matrix of said composite material, said composition being characterized by the fact that:
• said at least one thermoplastic polymer is a semi-crystalline polyamide polymer with a glass transition temperature Tg of at least 80 ° C, preferably at least 90 ° C and a melting temperature Tf of not more than 280 ° C .; and a polyaddition polymer between a) at least one thermoplastic polyamide prepolymer, bearing n identical terminal reactive functions X, chosen from: -MIH2, -CO2H and -OH, preferably NH2 and -CO2H with n being from 1 to 3, preferably 1 to 2, more preferably 1 or 2, more particularly 2 and b) at least one Y-A'-Y chain extender, with A 'being a single bond linking the two Y functions or a hydrocarbon biradical, non-polymeric structure and carrying 2 identical Y terminal reactive functional groups, with said Y functions being reactive by polyaddition with at least one X function of said prepolymer a) and preferably with Y being chosen from oxazine, oxazo
• thermoplastic polyamide polymer and its prepolymer a comprising in their respective structures different amide units A and B and optionally amide units C and D, 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%, selected from the units xT, where x is a linear aliphatic diamine in Cg to C 1, preferably C 8, C 10, C n and C 12 and where T is terephthalic acid, B: is an amide unit other than A, which unit B is present at a molar ratio ranging from 5 to 45%, preferably from 15 to 45%, more preferably from 20 to 45%, as a function of the Tf of the polyamide based on unit A and said amide unit B is chosen from among the units x'.T where x 'is chosen from: o B1) a branched aliphatic diamine bearing a single branch (or branching) methyl or ethyl and having a main chain length different from at least two carbon atoms with respect to the main chain length of the diamine x of said associated A unit, preferably x
• B being selected from x'.T, where x 'is MPMD according to B1) or MXD according to B2) or a linear aliphatic diamine as defined above according to B3) and more preferably x' is MPMD according to B1 ) or MXD according to B2) and even more preferably MXD according to B2),
• amide unit other than A and B chosen from amide units based on a cycloaliphatic and / or aromatic structure or based on x'T as defined above for B but with x 'different from x 'for pattern B,
• D optional amide unit other than A, B and C when C is present and selected from aliphatic amide units from:
• Amino acids or lactams C6 to C12 preferably C6, C11 and C12 or mixtures thereof ⁇ reacting a linear aliphatic diacid C6-Cis, preferably C6 to C12 and a linear aliphatic diamine C6-Cis, preferably C6 to C12, or mixtures thereof
• non-reactive molding composition means that 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 term of molecular weight during its heating for the impregnation of a fibrous reinforcement and the implementation of the composite material of the invention.
• the characteristics of the polyamide polymer in this composition are the same, with Tg and Tf of the polyamide polymer of the thermoplastic matrix of said composite.
• the number-average molecular weight Mn of said polymer (polyamide) of the thermoplastic matrix of said composite and therefore of the polymer of said molding composition is preferably in a range from 12000 to 40000, preferably from 12000 to 30000.
• the polyamides according to the invention are non-reactive, either by the low rate of reactive residual functions present, in particular with a rate of said functions ⁇ 120 meq / kg, or by the presence of the same type of terminal functions at the end of the chain and therefore non-reactive with each other, either by modifying and blocking said reactive functions by a monofunctional reactive component, for example for the amine functions by modification reaction with a monoacid or a monoisocyanate and for carboxy functions by reaction with a monoamine.
• Said non-reactive molding composition comprises, in particular in addition to said at least one semicrystalline polyamide polymer as defined above, at least one fibrous reinforcement, this molding composition being more particularly a composition for a thermoplastic composite material.
• Said molding composition may also comprise, in addition to said polymer, conventional fillers and additives which are not reinforcing fibers.
• Such fillers may be chosen from mineral fillers such as carbonates, pigments and carbonaceous fillers. More particularly, said molding composition comprises carbonaceous fillers, in particular carbon black or carbon nanofillers, these nanofillers being preferably chosen from graphenes and / or carbon nanotubes and / or carbon nanofibrils or mixtures thereof.
• said composition may comprise said at least one polymer, said fibrous reinforcement and said fillers, in particular said carbonaceous nanofillers.
• said amide unit C is present and partially replaces B at a molar level of up to 25% relative to said unit B.
• Said unit D may also be present and as a partial replacement of B to a molar level of up to 70% relative to said pattern B.
• the difference Tf-Tc between the melting temperature Tf and the crystallization temperature Te of said impregnating polymer which serves as a matrix, does not exceed 50 ° C., preferably does not exceed 40 ° C., more preferably does not exceed 30 ° C.
• the crystallinity of said polyamide polymer is characterized by the enthalpy of crystallization, measured in Differential Scanning Calorimetry (DSC) according to the ISO Standard 1357-3, which is preferably greater than 40 J / g and more preferably greater than 45 J / boy Wut. More particularly, said amide unit A is present with a molar level ranging from 55 to 80%, preferably from 55 to 75%, more preferably from 55 to 70% relative to all the units of said polymer.
• a first preferred option for said pattern B corresponds to x'T with x 'chosen according to option B1), in particular with x' being MPMD.
• said pattern B corresponds to x'T with x 'chosen according to option B2), x' being the MXD.
• said unit B corresponds to a linear aliphatic diamine according to option B3).
• the patterns A and B are selected as follows: for the pattern A being 9T, said pattern B is selected from: 10T, 11T, 12T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD.T and MXD.T, preferably 1T, 12T, 13T, 14T,
• said 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, 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%
• 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, 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%.
• part of the pattern B which can be up to 70%, preferably less than 40 mol% relative to B, is replaced by a pattern C and / or D as already defined. above.
• said polymer of said molding composition used as impregnating polymer of the fiber reinforcement for the manufacture of a thermoplastic composite material is a polyaddition polymer between at least one prepolymer a) reactive by functions X and at least one elongator b) reactive by Y functions, as already defined above.
• Said reactive prepolymers a) preferably have a number-average molecular weight Mn ranging from 500 to 10,000 and preferably from 1,000 to 6,000.
• Y-imidazoline reactive chain extenders examples include those described ("A" to "F") on pages 7 to 8 and Table 1 on page 10 in EP 0 739 924 of the Applicant and their preparation processes and their reaction modes which are exposed.
• Y oxazinone or oxazolinone reactive chain extender
• groups Y oxazinones (ring with 6 atoms) and oxazolinones (ring with 5 atoms) are suitable Y groups derived from: benzoxazinone oxazinone or oxazolinone, with A 'being a simple covalent bond with for respective corresponding extenders being: bis (benzoxazinone), bisoxazinone and bisoxazolinone.
• a ' may also be a C1 to C12, preferably a C2 to C10, alkylene, but preferably A' is an arylene and more particularly it may be a phenylene (1, 2 or 1, 3 or 1, 4 substituted with Y ) or a naphthalene radical (disubstituted by Y) or phthaloyl (iso- or terephthaloyl) or A 'may be a cycloalkylene.
• Y functions such as oxazine (6-ring), oxazoline (5-ring) and imidazoline
• the radical A ' may be as described above with A' being a single covalent bond and with the respective corresponding extenders being: bisoxazine, bisoxazoline and bisimidazoline.
• A may also be a C1 to C14 alkylene, preferably a C2 to C10 alkylene.
• the radical A ' is preferably an arylene and more particularly it may be a phenylene (1, 2 or 1, 3 or 1, 4 substituted with Y) or a naphthalene radical (disubstituted by Y) or a phthaloyl (iso- or terephthaloyl) or A 'may be cycloalkylene.
• a catalyst for the reaction between the prepolymer a) (P (X) n) and the 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 said two co-reactants can accelerate the (poly) addition reaction and thus shorten the duration of the polyaddition reaction to obtain said polymer.
• 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.
• said elongator corresponds to Y selected from oxazinone, oxazolinone, oxazine, oxazoline or imidazoline, preferably oxazoline and A represents a single covalent bond between the two functions Y or alkylene - (Chbjm- with m ranging from 1 to 14 and preferably from 2 to 10 or A representing a cycloalkylene or substituted arylene alkyl or unsubstituted, in particular benzene arylenes, among phenylenes o-, m-, p- or naphthalenic arylenes, preferably A 'being a cycloalkylene or an arylene or A 'being a simple covalent bond between the two functions Y.
• Said reactive prepolymers a) of the precursor composition for preparing said semi-crystalline polyamide polymer have a number average molecular weight Mn which can range from 500 to 10,000, preferably from 1,000 to 6,000.
• the weight ratio of said elongator b) in said semicrystalline polyamide thermoplastic polymer may vary, in particular according to the molecular weight M n of said prepolymer a), from 1 to 20%, preferably from 5 to 20% by weight.
• a chain of said polymer may comprise at least 2 chains of said prepolymer a) linked together by an elongator molecule b) and preferably the number of prepolymer chains a) per chain of said polymer may vary from 2 to 80 and more preferably from 2 to 50.
• the Mn of said polymer can vary from 12,000 to 40,000, preferably from 12,000 to 30,000.
• thermoplastic polyamide polymer has a repetitive unitary structure according to the following formula (I):
• R being identical to A 'as defined above according to the invention for said Y-A'-Y extender and chosen from a single bond or hydrocarbon chain which may be aliphatic or cycloaliphatic or optionally substituted aromatic,
• R ' being an optionally substituted aliphatic or cycloaliphatic or aromatic hydrocarbon chain and whose shortest chain connecting the neighboring -O- and -NH- units has 2 or 3 carbon atoms
• said preferred extender b) is chosen from: phenylene bis oxazolines, preferably 1,3-phenylene bis (2-oxazoline) and 1,4-phenylene bis (2- oxazoline).
• the melt viscosity of said polymer at the impregnation temperature is preferably ⁇ 200 Pa.s and more preferably less than 150 Pa.s.
• the impregnation temperature is in a range from Tf + 10 to Tf + 80 ° C, more preferably Tf +10 to Tf + 50 ° C, with Tf being the melting temperature of said polyamide polymer. .
• said molding composition comprises a fibrous reinforcement with long fibers, in particular of circular section with L / D> 1000, preferably> 2000 and more particularly selected from glass, carbon and ceramic fibers. aramid or mixtures thereof.
• the second subject of the invention relates to a method for manufacturing a thermoplastic composite material, in particular a mechanical part or a structural part based on at least one composition as defined above, said method comprising a step i) of melt impregnation of a fibrous reinforcement by a molding composition, as defined above but without said fibrous reinforcement or by at least one polymer as defined according to the invention, in an open mold or in a closed mold or outside mold and optionally followed by a step ii) of final implementation consecutive or separate from said step i).
• said method may comprise simultaneously or deferred an implementation step ii) comprising molding and final shaping said preimpregnated fibrous reinforcement of step i) to form the final composite part in a mold or out of mold.
• step ii) can be carried out according to a RTM technique, injection-compression, in particular under reduced pressure, pultrusion or by infusion or by thermocompression of prepreg under reduced pressure also commonly called “tarpaulin technique under vacuum ".
• RTM stands for Resin Transfer Molding (Resin Transfer Molding).
• the last subject of the invention concerns the use of a composition as defined above according to the invention but without said fibrous reinforcement or the use of a polymer as contained in said composition defined according to the invention for the melt impregnation of a fibrous reinforcement as a thermoplastic matrix of a composite material, for the manufacture of mechanical parts or structural parts of said composite material.
• said mechanical parts or structural parts of said composite material relate to applications in the automotive, railway, marine or maritime, wind, photovoltaic, solar, including solar panels and solar power plant components, sports, aerospace, transportation truck, building, civil engineering, protection and recreation panels, electrical or electronics.
• thermoplastic matrix polyamide of at least
• the melt viscosity of the polymer 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 of 100s -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 X according to a potentiometric method (back-titration of a reagent in excess with respect to the OH terminal functions and direct assay for Nhb or carboxy) and from the theoretical functionality ncale (vs X) calculated from the material balance and the functionality of the reactants. It can also be measured by size exclusion chromatography in PMMA equivalents according to indication.
• 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 2nd pass in heaters, according to ISO 1 1357-2.
• the heating and cooling rate is 20 ° C / min.
• the melting point Tf and the crystallization temperature Tc is measured by DSC, after a 1st heater, according to 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 nature and molar ratios of the molecular patterns and structures of the reactive prepolymer polyamides are given below.
• 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 gradually increasing the material temperature so that it is established at a minimum of Tf + 10 ° C at atmospheric pressure.
• the oligomer (prepolymer) is then drained through the bottom valve, then cooled in a bucket of water, and then ground.
• the mixture is introduced under nitrogen flushing in a DSM brand micro-extruder (volume 15 mL) co-rotating conical screw preheated to 280 ° C, under rotation of the screws at 100 r / min.
• the mixture is left under recirculation in the micro-extruder and the increase in viscosity is monitored by measuring the normal force. After about 2 minutes, a plateau is reached and the contents of the micro-extruder are drained in the form of a rod.
• the air-cooled product is granulated.
• Comparative polyamides lacking PA chain extenders are synthesized according to a protocol similar to the reactive prepolymers P (X) n.
• the Mn is adjusted according to a controlled excess of diacid, according to the method well known to those skilled in the art.
• the Amino and diacid components are the same with the same proportions of the components except adjusting the ratio of acid / amine functions to have the desired Mn comparable to that of the polymer obtained with the extender described above.
• This greater fluidity of the polyamide according to the invention is an advantage of the invention compared to the state of the art in the context of a more effective impregnation of a fiber reinforcement for the preparation of thermoplastic composite materials with fibrous reinforcement. having said polymer as a thermoplastic matrix, with increased mechanical performance of said materials.

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• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
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