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    • 专利摘要:
    The invention relates to a reactive molding composition, in particular for thermoplastic composite material, comprising a precursor reactive composition of a semi-crystalline thermoplastic polymer which is a semi-crystalline polyamide and optionally at least one fibrous reinforcement and with adite precursor composition comprising a) at least one polyamide prepolymer having n identical functions X among carboxy or amine and b) at least one non-polymeric extender carrying two epoxy Y functions reactive with said X functions with n ranging from 1 to 3, polymer and prepolymer a) being of specific composition comprising at least two amide A units of 55-95 mol% and B of 5-45 mol% with A corresponding to xT where x is a C9-C18 linear aliphatic diamine and B is x'.T or x 'can be B1): specific branched aliphatic diamine depending on x, B2): MXD or B3): linear aliphatic diamine which depends on x, said polyamide having a Tg d at least 80 ° C and a Tf of less than or equal to 280 ° C. The invention also covers a method of manufacturing said composite material, a precursor composition and its use for parts of composite material as well as said parts.
    公开号:FR3019828A1
    申请号:FR1453353
    申请日:2014-04-15
    公开日:2015-10-16
    发明作者:Gilles Hochstetter；Thierry Briffaud；Mathieu Capelot
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The invention relates to a reactive molding composition, in particular for a thermoplastic composite material with a semi-crystalline polyamide (PA) thermoplastic matrix having a glass transition temperature Tg of at least 80.degree. C., preferably at least 80.degree. at least 90 ° C and melting temperature Tf less than or equal to 280 ° C and also covers 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 composite material parts as well as the resulting composite part and for applications in the fields of: automotive, railway, marine, road transport, wind, sports, aeronautics and space, building, signage and recreation. EP 0261 020 describes the use of semi-crystalline reactive prepolymers based on PAs 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.
    [0002] EP 550 314 describes copolyamide (non-reactive) compositions in its Examples by seeking high melting temperatures and limited Tg with most of the examples cited having too low Tg (<80 ° C) or Tf too high (> 300 ° C). EP 1 988 113 discloses a molding composition based on a 10T / 6T copolyamide with: 40 to 95 mol% of 10T-5 to 40% of 6T. In particular, 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 280 ° C. WO 2011/003973 discloses 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 unit-associating unit. terephthalic acid to a mixture of 2,2,4 and 2,4,4 trimethylhexanediamine.
    [0003] US 2011306718 discloses a process for pultrusion of low Tg reactive aliphatic polyamides associated with chain extenders of polymeric structure bearing several (and far greater than 2) functions of anhydrides or epoxides. This document does not describe any non-polymeric extender. The 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 surmounted by the solution of the present invention which is directed to reactive molding compositions for a semi-crystalline PA allowing easier operation at lower temperatures with economy on the overall energy balance of the process of implementation a shorter production cycle time and improved productivity by rapid crystallizability of said polyamide polymer and while maintaining a high level of mechanical performance of said final materials. More particularly, in the case of these 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.
    [0004] The choice of 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. In addition, 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. As for the amorphines, a Tg of greater than or equal to 80 ° C. and preferably greater than or equal to 90 ° C., more preferably greater than 100 ° C., is sought to ensure good mechanical properties to the composite over the entire temperature range. use for example up to 80 ° C and preferably up to 90 ° C for wind, up to 100 ° C for the automobile and up to 120 ° C for aeronautics. On the other hand, a melting point that is too high, in particular greater than 280.degree. C., is, however, detrimental since it requires the use of the composite at higher temperatures with constraints on the molding material to be used and on the 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, that is to say the final matrix polymer, must be as high as possible but with a melting temperature Tf which is not too high, that is to say mp 280 ° C. and more particularly Tf. 270 ° C allowing optimum mechanical performance and a crystallization rate and / or the highest possible crystallization temperature with reduction of the molding time before ejection of the molded composite part and with a selective choice of the composition of said semi-crystalline polyamide . Therefore, the object of the present invention is the implementation of new specific compositions of thermoplastic composite, in particular based on semi-crystalline polyamide, having a good compromise between high mechanical performance or mechanical strength, in particular when hot and an easy implementation - 3 -. The objective is 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. More particularly, the solution of the invention, in the case of these reactive compositions, allows using semi-crystalline reactive polyamide prepolymer compositions, both a reaction kinetics and a fast crystallization kinetics with a reaction time. shorter cycle. In particular, the polyamide polymer matrix while having a high Tg and a limited Tf as defined above, with an easy implementation of said composite, must also have a high crystallization rate, characterized firstly by a temperature difference. melting point and Tf-Tc crystallization not exceeding 50 ° C, preferably not exceeding 40 ° C and more particularly not exceeding 30 ° C. More preferably, this difference Tf-Tc does not exceed 30 ° C, unless Tf-Tg is <150 ° C, in which case, if 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 ambient temperature, that is to say 23 ° C and 100 ° C with a maintenance of at least 75% performance mechanical, in terms of modulus, compared to those at ambient (23 ° C). Therefore, the object of the invention is to develop a reactive molding composition based on polyamide meeting these needs. Thus, the first object of the invention relates to a specific reactive molding composition, in particular for thermoplastic composite material, which composition comprises a specific precursor reactive composition of a semi-crystalline thermoplastic polymer which is a semi-crystalline polyamide (PA). and optionally said molding composition comprises at least one fibrous reinforcement and in this case preferably based on long fibers, said precursor reactive composition comprising at least one reactive polyamide prepolymer between and at least one polyaddition chain extender which carries functions epoxy reactive with the functions of said polyamide prepolymer. 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. The invention also relates to the specific precursor reactive composition of the semicrystalline PA of the invention and its use for the manufacture of a thermoplastic composite material and more particularly of mechanical parts or structure based on this material.
    [0005] The invention also relates to the parts or articles and the thermoplastic composite material that results from said molding composition or the precursor composition. The first subject of the invention therefore relates to a reactive molding composition, in particular for thermoplastic composite material, which composition comprises a precursor reactive composition of a semicrystalline thermoplastic polymer which is a semi-crystalline polyamide and optionally at least one fiber reinforcement and in this case (presence of fibrous reinforcement) preferably based on long fibers and with: - said reactive precursor composition of said thermoplastic polyamide polymer comprising: a) at least one thermoplastic polyamide prepolymer bearing n identical terminal reactive functions X , chosen from: -NH 2 or -CO 2 H, preferably -CO 2 H, with n being 1 to 3, preferably 1 to 2, more preferably 1 or 2, more particularly 2 and b) at least one Y-chain extender, A'-Y, with A 'being a single bond linking the two functions Y or a hydrocarbon biradical of non-polymeric structure and bearing 2 functions Y epoxy terminal reactive reagents by polyaddition with at least one X function of said prepolymer a), preferably said elongator b) having a molecular weight of less than 500, more preferably less than 400, and with said semi-crystalline polyamide polymer derived from the polyaddition reaction between said components a) and b) of said precursor composition having a glass transition temperature Tg of at least 80 ° C and preferably at least 90 ° C and a melting temperature Tf less than or equal to 280 ° C, and with - said polyamide polymer and its prepolymer a) comprising in their structure amide units A and B different 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%, chosen from the xT units, where x is a linear aliphatic diamine; ## STR1 ## 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 branch) 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 'being 2-methyl pentamethylene diamine (MPMD) or o B2) m-xylylenediamine (MXD) or o B3) a linear aliphatic diamine of C4 to 018 when in unit A, said diamine x is a diamine linear aliphatic C11 to 018 and x 'is a C18 diamine at 018 when in the pattern To said diamine x is a diamine of Cg or O10, and preferably 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); C: optional amide unit different from 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 the unit B, - D: optional amide unit different from A, B and C when C is present and selected from aliphatic amide units derived from: amino acids or lactams C6 to O12, preferably C6, C1 and O12 or mixtures thereof - reaction of a C6 to 018 linear aliphatic diacid, preferably C6 to 012 and a linear aliphatic diamine C6 to 018, preferably C6 to 012 or a mixture thereof s and under the condition that the sum of the molar levels of A + B + C + D is equal to 100%. The sum of the molar rates in the absence of C and D is reduced to A + B = 100%, with A and B being 100% complementary. If C is present without D, then this sum is reduced to A + B + C = 100%. If only D is present without C, said sum of 100% corresponds to A + B + D. Said composition is more particularly a composition for thermoplastic composite material and in this case it comprises said fibrous reinforcement, preferably based on long fibers. Composition "for thermoplastic composite material" means that said composition makes it possible to obtain a thermoplastic composite material. According to a first possibility in said molding composition of the invention, said polyamide prepolymer a) but also the polyamide polymer obtained by polyaddition of said prepolymer a) with said extender b) comprises said amide unit according to C, different from A and B where the unit C as defined above is present and as a partial replacement of B and at a molar level of up to 25%, preferably up to 20%, more preferably up to 15% with respect to said unit B. When the pattern C is present and that it corresponds to x'T with x 'as defined above for the pattern B, in this case C being different from B by definition, said pattern C can 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 can be based on x' being defined according to B1) or B2). More particularly, in this unit C of said composition, 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 may be chosen from a cyclohexane ring-based structure or a decahydronaphthalenic ring-based structure (hydrogenated naphthalenic structure). Preferably, 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. above. More particularly, said unit C is chosen from units derived from: - a cycloaliphatic diamine and terephthalic acid or - diacid chosen from isophthalic, naphthenic or cyclohexane and diamine x or x 'as defined above for patterns A and B respectively. According to another variant of the composition of the invention, 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. Thus, according to this variant, said composition comprises said unit D as defined above, in particular chosen from: amino acids or lactams C6 to C12, preferably C6, C11 and C12 or mixtures thereof or the units resulting from the reaction of a linear aliphatic diacid C6 to C18, preferably C6 to 012 and a linear aliphatic diamine C6 to C18, preferably C6 to C12 and preferably with the units A and B respectively being based on diamines x and x 'as defined above. Preferably, 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. Thus, 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.
    [0006] More particularly, the difference Tf-Tc, between the melting temperature Tf and the crystallization temperature Tc 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. In particular, 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.
    [0007] According to a particular option, the crystallization enthalpy of said matrix polymer, measured in Differential Scanning Calorimetry (DSC) according to the ISO 11357-3 Standard, is greater than 40 J / g, preferably greater than 45 J / g. Preferably, said amide unit A, as defined according to the invention above and hereinafter, is present at a molar level ranging from 55 to 80%, preferably from 55 to 75%, more preferably from 55 to 70%. with respect to all the units of said matrix polymer (polyamide) as defined above according to the invention. According to a first preferred option of the composition according to the invention described above, said composition has a pattern B which corresponds to x'T with x 'defined according to option B1) described above, in particular with as diamine plus preferred for said pattern B, being MPMD. The unit A remains as defined above, that is to say x.T, with x a linear aliphatic diamine C9 to C18, preferably C9, C10, C11 or C12. According to a second preferred option of said composition, it has a pattern B which corresponds to x'T where x 'is MXD (m-xylylenediamine) according to option B2) defined above. Pattern A remains as defined for the first option cited. This second option constitutes together with the first mentioned above the most preferred of the invention and in particular this second option is the most preferred of the invention. A third preferred option is that where B is defined according to option B1) or B2) or B3) as defined above and with the presence of a pattern C as defined above, replacing 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. More preferably still, said polyamide composition is based on the A and B patterns selected as follows: for the A motif being 9T, said pattern B is 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 ratio of B ranging from 30 to 45%, - for the pattern A being 10T, 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% for the pattern A being 11T, 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%, - for the pattern A being 12T, 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%. According to this selection, a first 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 ratio 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 11T 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%. Finally, another particular composition corresponds to a pattern A being a pattern 12T 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%. 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 inherent viscosities. greater than or equal to 0.8. As regards the number-average molecular weight M n of said polyamide prepolymer a), it is at least two-fold lower than that of the final polymer resulting from said prepolymer a), said polymer constituting the thermoplastic matrix of a thermoplastic composite material in the case of presence of a fibrous reinforcement. More particularly, the Mn of said prepolymer a) can vary from 500 to 10,000, preferably from 1,000 to 6,000. The semi-crystalline structure of said semi-crystalline polyamide polymer is essentially provided by the structure of said prepolymer a) which is also semicrystalline. Said extender b) may be selected from optionally substituted aliphatic, cycloaliphatic or aromatic diepoxides. Examples of aliphatic diepoxides are diglycidyl ethers of aliphatic diols, aromatic diepoxides of diglycidyl ethers of bisphenol A such as diglycidyl ether of bisphenol A (DGEBA) and cycloaliphatic diepoxides, diglycidyl ethers of cycloaliphatic diols or bisphenol. Has hydrogenated. More generally, as suitable examples of diepoxides according to the invention, mention may be made of bisphenol A diglycidyl ether (DGEBA) and its hydrogenated derivative (cycloaliphatic), bisphenol F diglycidyl ether, tetrabromo bisphenol 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 Mn <500, polypropylene glycol diglycidyl ether of Mn <500, polytetramethylene glycol diglycidyl ether of Mn <500, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether of Mn <500, bisphenol A polypropylene glycol diglycidyl ether of Mn <500, diglycidyl esters of dicarboxylic acid such as the glycidyl ester of terephthalic acid or epoxidized diolefins (dienes) or epoxidized ethylenically unsaturated double fatty acids, diglycidyl 1,2 cyclohexane dicarboxylate and the mixtures of diepoxides mentioned. Advantageously, when the identical terminal reactive functions X of said prepolymer are -CO2H, a catalyst specific to the esterification reaction may be used. Such catalysts are generally acidic or basic catalysts. Such catalysts are known to those skilled in the art and may, for example, be found in "Epoxy Resins, Chemistry and Technology", Second Ed., Edited by C.A. May, Marcel Dekker, New York, 1988.
    [0008] By way of example, mention may be made, as suitable catalysts, of the following: imidazoles, such as 2-methylimidazole or 1,2-dimethylimidazole; quaternary ammonium salts, such as those of tetramethylammonium, in particular tetramethylammonium acetate, tetramethylammonium chloride, tetramethylammonium bromide or those of tetrabutylammonium such as tetrabutylammonium acetate, tetrabutylammonium chloride, tetrabutylammonium bromide or those of benzyltriethylammonium such as benzyltriethylammonium acetate, benzyltriethylammonium chloride, benzyltriethylammonium bromide, phosphines, such as triphenylphosphine, tertiary amines, such as benzyldimethylamine or 2,4,6-tri (dimethylaminomethyl) phenol (under the name Ancamine® K54) - strong acids such as para-toluene sulfonic acid - metal salts, such as zinc acetate, zinc acetylacetonate or zirconium acetylacetonate m.
    [0009] The amount of catalyst used in the compositions of the invention may vary from 0.01 to 10 mol% total of epoxy contained in the Y-A'-Y chain extender. Preferably, the ratio of acidic groups to epoxy Y groups is from 0.9 to 1.0 and preferably 1.0. More particularly, said reactive molding composition comprises in addition to said precursor reactive composition at least one fibrous reinforcement, preferably based on long fibers, in particular with circular section with LtD> 1000, preferably> 2000 and more particularly selected from glass, carbon, ceramic, aramid fibers or mixtures thereof. 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 at least one composition as defined according to the invention which comprises a step of melt impregnation of at least one fibrous reinforcement with a precursor reactive composition as defined above according to the invention, in an open mold or closed or out of mold.
    [0010] More particularly, said process comprises the following steps: i) melt impregnation of a fibrous reinforcement with a precursor reactive composition as defined above according to the invention, in an open mold or closed or out of mold, so to obtain a molding composition with fiber reinforcement as defined above according to the invention, ii) heating the composition of step i) with melt mass polyaddition polymerization reaction, between components a ) and b) of said precursor reactive composition, with chain extension, iii) implemented by molding or by another implementation system and simultaneously with the polymerization step ii).
    [0011] According to one option, the method of the invention comprises simultaneously or deferred an implementation step comprising molding and shaping said fibrous reinforcement impregnated with step i) to form the final composite part in a mold. Even more particularly in said process, said implementation is carried out according to a RTM technique, injection-compression, pultrusion or infusion.
    [0012] More particularly during the melt impregnation, the viscosity of said precursor reactive composition remains at the impregnation temperature of less than 100 Pa.s and preferably <50 Pa.s. The melt viscosity of said precursor reactive composition or prepolymer a) or polymer is measured according to the manufacturer's reference manual of the measuring apparatus used, which is a Physica MCR301 rheometer, under a nitrogen sweep. the temperature given under shear of 100s-1, between two parallel planes with a diameter of 50 mm. The Mn of the prepolymer a) or the 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 relative to the OH terminal functions and direct assay for NH 2 or carboxy) and from the theoretical functionality n calc (vs X) calculated from the material balance and the functionality of the reactants (see in description the general calculation method). Measurement of intrinsic or inherent viscosity is performed in m-cresol.
    [0013] 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 heat-up, according to the ISO 11357-2 standard. The heating and cooling rate is 20 ° C / min. The melting temperature Tf and the crystallization temperature Tc are measured by DSC, after a first heating, according to ISO 11357-3. The heating and cooling rate is 20 ° C / min. The invention also covers said precursor reactive composition as defined above, which comprises said reactive components prepolymer a) and lengthening agent b) as defined above. Next, the invention covers the use of said precursor composition as defined above (in the absence of fiber reinforcement) for the melt impregnation of a fibrous reinforcement, as precursor of the thermoplastic polymer matrix, for the manufacture of mechanical parts or structure based on composite material. More particularly, said mechanical or structural parts of said composite material relate to applications in the field of automotive, rail, marine or maritime, wind, photovoltaic, solar including solar panels and solar power plant components, sports, aeronautics and space, road transport for trucks, building, civil engineering, signage and recreation, electrical or electronics. Depending on the end use of said parts, the Tg of the thermoplastic polymer matrix, semi-crystalline polyamide according to the invention, can be adapted to the needs. In particular, when the use relates to applications in the field of wind power, the Tg of said polyamide is at least 80 ° C and preferably at least 90 ° C.
    [0014] When it relates to automotive applications, the Tg of said polyamide polymer is at least 100 ° C. and when it relates to applications in the field of aeronautics, the T g of said polyamide polymer is at least 120 ° C. Finally, the invention also relates to a molded part which results from the use of at least one molding composition without fibrous reinforcement or a precursor reactive composition as defined above according to the invention. More particularly, it is a composite material part obtained from a composition comprising, in addition to said precursor reactive composition, at least one fibrous reinforcement based on long fibers, in particular of circular section with L / D (length L on diameter D)> 1000, preferably> 2000 and more particularly selected from glass, carbon, ceramic, aramid or mixtures thereof.
    权利要求:
    Claims (30)
    [0001]
    REVENDICATIONS1. A reactive molding composition, in particular for thermoplastic composite material, characterized in that it comprises a precursor reactive composition of a semicrystalline thermoplastic polymer which is a semicrystalline polyamide and optionally at least one fibrous reinforcement and in this case of preferably based on long fibers and in that: - said reactive precursor composition of said thermoplastic polyamide polymer comprises: a) at least one thermoplastic polyamide prepolymer, bearing n identical terminal reactive functions X, chosen from: -NH 2 or -CO 2 H, preferably -CO2H, with n being 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 bond simple binding the two functions Y or a hydrocarbon biradical of nonpolymeric structure and bearing 2 terminal reactive functions Y epoxy, reactive by polyaddition with minus a function X of said prepolymer a), preferably said elongator b) having a molecular weight less than 500, more preferably less than 400, and in that - said semi-crystalline polyamide polymer resulting from the polyaddition reaction between said components ) and b) of said precursor composition has a glass transition temperature Tg of at least 80 ° C, preferably at least 90 ° C and a melting temperature Tf less than or equal to 280 ° C, and in that said polyamide polymer and its prepolymer a) comprise in their structure 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 rate ranging from at 95%, preferably from 55 to 85%, more preferably from 55 to 80%, selected from the units xT, where x is a linear aliphatic diamine of C 9 to C 18, preferably C 9, C 10, C 11 and C 12 and T is the aci terephthalic acid, B: 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%, depending on the Tf of the pattern A-based polyamide and said amide unit B is selected from the units x'.T where x 'is selected from: B1) a branched aliphatic diamine carrying a single branching (or branching) methyl or ethyl and having a main chain length different from at least two carbon atoms from the main chain length of the diamine x of said associated A-unit, preferably x 'being the
    [0002]
    2-methyl pentamethylene diamine (MPMD) or o B2) m-xylylene diamine (MXD) or o B3) a linear aliphatic diamine in C4 to 018 when in the unit A, said diamine x is a linear aliphatic diamine in C18 to C18 and x 'is a C8 to C18 diamine when in unit A, said diamine x is a C8 or C10 diamine, and preferably B is 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), - C: optional amide unit different from A and B, selected 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 the unit B; D: optional amide unit other than A, B and C when C is present and selected from aliphatic amide units from: inoacids or lactams C6 to O12, preferably C6, C11 and O12 or mixtures thereof, the reaction of a linear aliphatic diacid C6 to 018, preferably C6 to 012 and a linear aliphatic diamine C6 to 018 preferably C6 to O12 or mixtures thereof and provided that the sum of the molar levels of A + B + C + D is 100%. 2. Composition according to claim 1, characterized in that said amide unit C is present and partially replaces B at a molar level of up to 25% relative to said pattern B.
    [0003]
    3. Composition according to one of claims 1 to 2, characterized in that said pattern D is present and partially replacing B at a molar rate of up to 70% relative to said pattern B.
    [0004]
    4. Composition according to one of claims 1 to 3, characterized in that the difference Tf-Tc, between the melting temperature Tf and the crystallization temperature Tc of said matrix polymer, does not exceed 50 ° C, preferably does not exceed not 40 ° C and more particularly does not exceed 30 ° C.-15-
    [0005]
    5. Composition according to one of claims 1 to 4, characterized in that the crystallization enthalpy of said matrix polymer, measured in Differential Scanning Calorimetry (DSC) according to ISO 11357-3, is greater than 40 J / g, preferably greater than 45 J / g.
    [0006]
    6. Composition according to one of claims 1 to 5, characterized in that 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% by relative to all the units of said polymer.
    [0007]
    7. Composition according to one of claims 1 to 6, characterized in that said pattern B corresponds to x'T with x 'chosen according to option B1), in particular with the diamine x' being M PM D.
    [0008]
    8. Composition according to one of claims 1 to 6, characterized in that said pattern B corresponds to x'T with x 'selected according to option B2), x' being the MXD.
    [0009]
    9. Composition according to one of claims 1 to 6, characterized in that said pattern B corresponds to x'T with x 'being a linear aliphatic diamine as defined according to option B3).
    [0010]
    10. Composition according to one of claims 1 to 6, characterized in that 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 11T, 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 30 to 45% - for the pattern A being 10T, said pattern B is selected from: 9T, 11T, 12T, 13T, 14T, 15T, 16T, 17T and 18T, MPMD 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 at 45% - for the pattern A being 11T, 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 45% - for the pattern A being 12T, 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%.
    [0011]
    11. Composition according to claim 10, characterized in that the pattern A is a 9T pattern and the pattern B is selected from: 10T, 11T, 12T, 13T, 14T, 15T, 16T, 17T and -16- 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 ratio of B ranging from 30 to 45%.
    [0012]
    12. Composition according to claim 10, characterized in that the pattern A is a pattern 10T and the 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, more preferably MPMD.T or MXD.T and MXD.T with a molar ratio of B ranging from 25 to 45%.
    [0013]
    13. Composition according to claim 10, characterized in that the pattern A is a pattern 11T and the 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%.
    [0014]
    14. Composition according to claim 10, characterized in that the pattern A is a pattern 12T and the pattern B is selected from:, 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%.
    [0015]
    15. Composition according to one of claims 7 to 14, characterized in that the pattern C and / or D as defined in one of claims 1 to 3 partially replaces the pattern B with a molar rate up to 70%. preferably less than 40% relative to the molar level of said pattern B.
    [0016]
    16. Composition according to one of claims 1 to 15, characterized in that said reactive prepolymers a) have a number average molecular weight Mn ranging from 500 to 10,000, preferably from 1000 to 6000.
    [0017]
    17. Composition according to one of claims 1 to 16, characterized in that said elongator is an optionally substituted aliphatic, cycloaliphatic or aromatic diepoxide.
    [0018]
    18. Composition according to one of claims 1 to 17, characterized in that it comprises at least one fibrous reinforcement preferably with long fibers, in particular circular section with L / D> 1000, preferably> 2000 and more particularly selected from glass, carbon, ceramic, aramid fibers or mixtures thereof.
    [0019]
    19. A process for producing a thermoplastic composite material, in particular a mechanical part or a structural part based on at least one composition as defined according to one of claims 1 to 18, characterized in that it comprises a step of melt impregnation of at least one fibrous reinforcement with a precursor reactive composition as defined according to one of claims 1 to 17, in an open or closed mold or out of mold.
    [0020]
    20. The method of claim 19, characterized in that it comprises the following steps: i) impregnation in the molten state of a fibrous reinforcement with a precursor reactive composition as defined in one of claims 1 to 17, in an open or closed mold or out of mold, in order to obtain a molding composition with fiber reinforcement as defined according to one of claims 1 to 18, ii) heating the composition of step i) with polymerization reaction by melt mass polyaddition, between components a) and b) of said precursor reactive composition, with chain extension, iii) carried out by molding or by another implementation system and simultaneously with the step ii) polymerization.
    [0021]
    21. The method of claim 20, characterized in that it comprises simultaneously or deferred an implementation step comprising molding and shaping said fibrous reinforcement impregnated with step i) to form the final composite part in a mold.
    [0022]
    22. The method of claim 21, characterized in that said implementation is performed according to a RTM technique, injection-compression, pultrusion or infusion.
    [0023]
    23. Precursor reactive composition as defined in one of claims 1 to 17, characterized in that it comprises said prepolymer components a) and lengtheners b).
    [0024]
    24. Use of a precursor composition as defined in one of claims 1 to 17 (in the absence of fiber reinforcement) or according to claim 23, for the melt impregnation of a fibrous reinforcement, as a precursor. of the thermoplastic polymer matrix, for the manufacture of mechanical parts or structure based on composite material.
    [0025]
    25. Use according to claim 24, characterized in that said mechanical or structural parts of said composite material relate to applications in the field of automotive, rail, marine or maritime, wind, photovoltaic, solar including solar panels and components of solar power plants, sports, aeronautics and space, road transport relating to trucks, building, civil engineering, protective panels and recreation, electrical or electronics.
    [0026]
    26. Use according to claim 25, characterized in that it relates to applications in the field of wind energy and in that the Tg of said polyamide is at least 80 ° C and preferably at least 90 ° C .-18-
    [0027]
    27. Use according to claim 25, characterized in that it relates to applications in the automotive field and in that the Tg of said polyamide polymer is at least 100 ° C.
    [0028]
    28. Use according to claim 25, characterized in that it relates to applications in the field of aeronautics and in that the Tg of said polyamide polymer is at least 120 ° C.
    [0029]
    29. Molded part, characterized in that it results from the use of at least one molding composition as defined in one of claims 1 to 18 or a precursor composition according to claim 23.
    [0030]
    30. Part according to claim 29, characterized in that it is piece of composite material based on a composition as defined in claim 18.
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    同族专利:
    公开号 | 公开日
    EP3131956B1|2019-05-22|
    US20170037186A1|2017-02-09|
    JP2017518396A|2017-07-06|
    KR20160147266A|2016-12-22|
    EP3131956A1|2017-02-22|
    FR3019828B1|2020-09-18|
    WO2015159022A1|2015-10-22|
    CN106232726A|2016-12-14|
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    法律状态:
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    2017-03-13| PLFP| Fee payment|Year of fee payment: 4 |
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    2020-03-12| PLFP| Fee payment|Year of fee payment: 7 |
    2022-01-07| ST| Notification of lapse|Effective date: 20211205 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1453353A|FR3019828B1|2014-04-15|2014-04-15|COMPOSITION AND PROCESS FOR COMPOSITE MATERIAL WITH IMPREGNATION BY REACTIVE COMPOSITION OF A POLYAMIDE PREPOLYMER AND A DIEPOXIDE CHAIN EXTENSION|FR1453353A| FR3019828B1|2014-04-15|2014-04-15|COMPOSITION AND PROCESS FOR COMPOSITE MATERIAL WITH IMPREGNATION BY REACTIVE COMPOSITION OF A POLYAMIDE PREPOLYMER AND A DIEPOXIDE CHAIN EXTENSION|
    KR1020167031770A| KR20160147266A|2014-04-15|2015-04-15|Composition and method for composite material impregnated with reactive composition of a polyamide polymer and a diepoxide chain extender|
    US15/304,620| US20170037186A1|2014-04-15|2015-04-15|Composition and method for a composite material impregnated with reactive composition of a polyamide prepolymer and a diepoxide chain extender|
    PCT/FR2015/051021| WO2015159022A1|2014-04-15|2015-04-15|Composition and method for composite material impregnated with reactive composition of a polyamide polymer and a diepoxide chain extender|
    CN201580020220.3A| CN106232726A|2014-04-15|2015-04-15|By compositions and the method for the composite of the reactive composition dipping of Polvamide prepolymer and diepoxides chain spreading agent|
    EP15725738.7A| EP3131956B1|2014-04-15|2015-04-15|Composition and method for composite material impregnated with reactive composition of a polyamide polymer and a diepoxide chain extender|
    JP2016562787A| JP2017518396A|2014-04-15|2015-04-15|Compositions and methods for composites impregnated with reactive compositions of polyamide prepolymers and diepoxide chain extenders|
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