• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The present invention relates to a method of manufacturing a thermoplastic composite material with fibrous reinforcement and a matrix which is a semi-crystalline polyamide of Tg of at least 80 ° C and Tf less than or equal to 280 ° C and greater than 200. C., prepared in situ by melt polymerization by polycondensation, of a reactive precursor composition comprising, according to A, at least one first polyamide prepolymer A1 carrying two identical functions X or Y and at least one second polyamide prepolymer; A2 carrying two identical functions X or Y, different from those of A1 and coreactive compared to those of A1 or a precursor composition comprising according to B at least one carrier prepolymer (on the same chain) of two different functions X and Y coreactive with one another or a precursor composition according to a mixture of (A + B) with X and Y being respectively carboxy or amine and conversely with said process comprising the successive steps of i) preparation of the reaction mixture A: (A1 + A2) or of the reaction mixture (A + B): (A1 + A2 + B) or of the melting of said prepolymer according to B, ii) impregnation of said fibers, by injection in the molten state of said reactive precursor composition, iii) in-situ polymerization by mass melt polycondensation, iv) cooling and demolding of said material and with said final polyamide of said matrix and said prepolymers A1, A2 or B having the same specific composition in amide units. The invention also covers the reactive precursor composition, the resulting composite part and its use.
    公开号:FR3044956A1
    申请号:FR1562134
    申请日:2015-12-10
    公开日:2017-06-16
    发明作者:Mathieu Capelot；Gilles Hochstetter
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    The present invention relates to a method of manufacturing a fiber reinforced composite material part (also called "fibrous reinforcement" later) in a closed mold, preferably by the resin transfer molding technique (RTM), in particular c-RTM (RTM with compression) or by the RIM technique (injection molding reaction) in particular S-RIM (structural RIM), more preferably by c-RTM, using a specific reactive composition based on prepolymer, said reactive composition being precursor of the final polymer of the thermoplastic matrix which is a semi-crystalline polyamide having a high glass transition temperature (Tg) and greater than 80 ° C and a high melting point and lower than 280 ° C, with ease of impregnation fibrous substrate and ease of implementation of said composite material at controlled temperatures, without risk of thermal degradation of said matrix polymer thermoplastic ice. The composite material products resulting from this process are used in mechanical applications such as structural parts in the automotive, road, rail, maritime, aeronautical or aerospace sectors or in mechanical engineering or in building construction or in parks and recreation or for reinforcements of shields or projectile impact protection panels. 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. EP 550 314 describes, among its examples, (non-reactive) copolyamide compositions, looking for melting temperatures (Tf) above 250 ° C and limited Tg's with most of the examples cited having too low Tg (<80 ° C). C) or too high Tf (> 300 ° C).
    EP 1 988 113 discloses a molding composition based on a 10T / 6T copolyamide with:
    40 to 95 mol% from 10T 5 to 40 mol%. from 6T.
    In particular, polyamides having a high melting point and greater than 270 ° C. are used. The examples mentioned and Figure 1 in this document teach us that the melting temperature of these compositions is at least about 280 ° C. WO 2011/003973 discloses compositions comprising from 50 to 95 mol%. a linear aliphatic diamine unit containing from 9 to 12 carbon atoms and terephthalic acid and from 5 to 50% of a unit combining terephthalic acid with a mixture of 2,2,4 and 2, 4,4-trimethylhexanediamine. 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. WO 2013/060976 discloses a composite material process based on a precursor reactive composition comprising a reactive prepolymer with identical reactive functions and a non-polymeric chain extender carrying functions reactive with the functions of said polyaddition prepolymer. WO 2014/064375 discloses a reactive composition of semi-crystalline polyamide prepolymer, but in all examples with a reactive precursor composition, the elongation is achieved by a different type of extender with respect to a polyamide prepolymer.
    The first disadvantage overcome by the present invention with respect to the state of the art concerns an improved and more homogeneous impregnation of the fibers of the fibrous reinforcement by the use of a specific precursor composition for the semicrystalline polymer matrix of the composite material in question. and with characteristics of reactive polyamide prepolymers used allowing a sufficiently low viscosity for good impregnation and adhesion to the fibers with mechanical performances which result more homogeneous and at the same time a good reactivity and kinetics of reaction and crystallization adapted to the process used . On the other hand, the present invention provides a good compromise between mechanical performance and processability (ease of processing) at lower temperatures. Indeed, the solution of the present invention aims polyamide (PA) semi-crystalline compositions for easier implementation at lower temperatures with a saving on the energy balance of the implementation method. In particular, this is enabled by the fast crystallization ability of said semi-crystalline polyamide polymer by the specific choice of its composition and this while maintaining at a high level the mechanical performance of said final materials. More particularly, the precursor reactive compositions used by the process, according to the present invention, allow a better control of the reaction kinetics, while having a crystallization rate of the fast formed polymer and a speed and / or a crystallization temperature adapted to the reaction. process used.
    The choice of a semi-crystalline polyamide polymer as the matrix of the composite material of the invention has, compared with the amorphous polyamides, significantly improved mechanical performance, especially at high temperatures, 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 amorphous materials, a Tg greater than or equal to 80 ° C. is required to ensure good mechanical properties for the composite over the entire operating temperature range, for example up to 90 ° C. for the wind turbine, up to 100 ° C for the automobile and up to 120 ° C for the aeronautics. By cons, a melting point too high, especially greater than 280 ° C, is harmful because it requires the implementation of the composite at higher temperatures with constraints of molding material to use (and associated heating system) and an overconsumption of energy with in addition to the risks of thermal degradation by heating at temperatures higher than the melting temperature of said polyamide. Such thermal degradation results in degradation of the properties of the final thermoplastic matrix and thus of the composite material and final composite part. 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 performances and the crystallization rate and / or the temperature of highest crystallization possible. Thus, a selective choice of the composition of said semi-crystalline polyamide makes it easier to implement for a method of implementation, preferably under the conditions of implementation by RTM (resin transfer molding), in particular RTM (RTM with compression) or by the RIM technique, in particular S-RIM, more preferably by c-RTM. Therefore, the object of the present invention is the implementation of new specific compositions of thermoplastic composite material, in particular based on semicrystalline polyamide, having a good compromise between high mechanical performances (mechanical strength), in particular with hot and easy implementation. This means that the present invention aims at compositions that are easy to implement with lower processing and processing temperatures than those for other compositions of the state of the art, with a global implementation energy balance. more favorable and higher productivity. More particularly, the solution of the invention with its specific reactive compositions based on semi-crystalline reactive polyamide prepolymers allows both controlled kinetics of reaction during impregnation and rapid crystallization kinetics. More particularly, in specific cases depending on the composition and / or the specific conditions of RTM molding as c-RTM or RIM as S-RIM, in particular RTM, it allows a production of composite parts molded with a slower polymerization kinetics than monomeric reactive extenders by polyaddition. This facilitates the impregnation of the fibrous reinforcements, while allowing a shorter molding cycle that is to say less than 10 min and preferably less than 5 min, thanks to fast kinetics of crystallization. A particular characteristic of the invention is that the reactive system is chemically homogeneous, since it does not comprise a reactive extender of a chemical nature different from that of the prepolymer, said elongator being capable of disrupting the final polymer and thus hindering its crystallization. More particularly, the polyamide polymer matrix, while having a high Tg and a limited Tf as already defined, must also have a high crystallization rate. This performance can be characterized by the difference between the melting temperature Tf and crystallization Te, Tf-Tc which does not exceed 60 ° C, preferably does not exceed 50 ° C and more particularly does not exceed 40 ° C. The mechanical performance or mechanical strength of the composite can be evaluated by the variation of the mechanical modulus between the ambient temperature (23 ° C) and 100 ° C with a maintenance of at least 75% of the mechanical performances, in terms of stress at break, compared to those at room temperature (23 ° C).
    In particular, the precursor reactive compositions based on a reactive prepolymer having identical reactive functional groups and a non-polymeric chain extender carrying coreactive functions with those of said polyaddition-polymerizing prepolymer, according to the state of the art, exhibit disadvantage of leading to compositions with a very fast reaction kinetics problem during the impregnation stage because, if the polymerization is too fast, the impregnation is more difficult. The solution of the present invention based on the use of reactive precursor compositions based on reactive prepolymers (i.e. without a non-polymeric extender) as described below, polymerizing by polycondensation, allows for slower and controlled kinetics. during the impregnation step, thus permitting easier impregnation, in particular under the conditions of use of said composite material by RTM, in particular c-RTM (RTM with compression) or by the RIM technique, in particular S- RIM, more preferably by c-RTM.
    In addition, the use of prepolymer makes it possible to carry out the polymerization step after an effective impregnation because of the low viscosity of said prepolymer-based reactive precursor composition prior to the significant polymerization prior to this separate polymerization step.
    Therefore, the object of the invention is to develop a composite material process with a precursor composition based on specific polyamide prepolymer meeting all these needs.
    The first subject of the invention relates to a method of manufacturing by closed-mold molding of a composite material comprising a fibrous reinforcement and a semi-crystalline polyamide thermoplastic matrix, said process comprising the preparation in the molten state of said precursor reactive composition. based on a polyamide prepolymer of specific composition, the impregnation of said fibrous reinforcement by injection into a closed mold containing said fibrous reinforcement of said melt reactive composition and the bulk and melt polymerization of said composition, with possibility of postpolymerization if the polymerization is not complete and finally a cooling and demolding of said composite material part thus manufactured, preferably said process being a process with a molding according to the RTM technique (resin transfer molding). The term "resin" in RTM is here identified with said precursor reactive composition.
    The second subject of the invention relates to said precursor reactive composition as used in said process. The invention also covers the piece of composite material obtained by said method.
    The first object of the invention therefore relates to a method of manufacturing a piece of thermoplastic composite material by closed mold molding, said material comprising reinforcing fibers and a polyamide thermoplastic matrix impregnating said fibers, said matrix being a semi-rigid polyamide. crystalline with a glass transition temperature Tg of at least 80 ° C, preferably at least 90 ° C and more preferably at least 100 ° C and with a melting temperature Tf being less than or equal to 280 ° C and greater than 200 ° C., preferably greater than 220 ° C., prepared in situ by melt mass polymerization by polycondensation, of a reactive precursor composition comprising, according to A, at least one first polyamide prepolymer A1 carrying two identical functions X (X and X) or Y (Y and Y) and at least one second polyamide prepolymer A2 carrying two identical functions X (X and X) or Y (Y and Y), different of those of A1 and coreactive with respect to those of A1 or of a precursor composition comprising, according to B, at least one carrier prepolymer (on the same chain) of two different functions X and Y that are coreactive with one another or a precursor composition according to mixture of (A + B), with said X and Y functions respectively being carboxy (X) and amine (Y) and conversely (Y and X) and with said process comprising the following successive steps: i) preparation of the reactive mixture A: (A1 + A2) or reactive mixture (A + B): (A1 + A2 + B) by mixing the components in the molten state or by melting said prepolymer B if only one component of said precursor reactive composition, at a higher temperature at that of the melting temperature Tf of the mixture A or of the mixture (A + B) or of the Tf of said prepolymer B if only one component of said precursor composition, ii) injection into a closed mold comprising said fibers of said composite melt reactive precursor ion as obtained in step i) and impregnation of said fibers with said melt reactive precursor composition, which is, as the case may be, the mixture A or (A + B) or said prepolymer B, preferably with a viscosity <100 Pa.s, more preferably <50 Pa.s, more preferably <10 Pa.s, iii) in-situ polymerization by mass melt polycondensation in said closed mold and with a polymerization time and temperature controlled so that the polymerization temperature is greater than the crystallization temperature Te of said thermoplastic matrix polyamide, iv) optionally, cooling said composite material part, v) demolding said part, and with said final polyamide of said matrix and said prepolymers A1, A2 or B having the same composition in amide units and said amide units being derived from: a) a diacid component which is from 95 to 100%, preferably to 100 mol% of terephthalic structure with 0 to 5 mol% of isophthalic diacid, preferably a) being 100% terephthalic diacid, b) a diamine component composed of: b1) from 55 to 85%, preferably from 55 to 80% by moles of a linear aliphatic diamine of C8, C10, C11 or C12 and b2) of from 15 to 45%, preferably from 20 to 45% by mole, a diamine other than b1), selected from: b21) a mono- aminated aliphatic diamine with a methyl or ethyl substituent and having a chain length difference relative to the associated diamine b1), of at least two carbons, preferably said diamine b2) being 2-methyl pentamethylenediamine b22) m-xylylene diamine (mXD) or b23) a C4 to C18 linear aliphatic diamine when b1) is a C10-C12 linear aliphatic diamine and with b23) being a diamine C10-C18 when said diamine b1 is a diamine in Cg, and c) optionally, an amino acid or, as the case may be, the corresponding lactam C6 to C12, preferably C6, C12 or C12 and more preferably Cn, with c) representing not more than 30% by mole with respect to a) or with respect to b), preferably, said process being a RTM (resin transfer molding) process, in particular c-RTM or a RIM process, in particular s-RIM, more preferably being a RTM process, in particular c-RTM.
    According to a more particularly preferred option of said process, it is a process with a molding technique by RTM (resin transfer molding) and more preferably by c-RTM.
    The method may include an additional post-polymerization step. This is done in the mold or out of the mold, if there is need to perfect the polymerization in the case where the polymerization of step iii) is not complete, which remains a possible option. Preferably, this post-polymerization is carried out outside the mold. According to a preferred option, there is no post-polymerization.
    The polymerization temperature is above the crystallization temperature Te of the prepolymer polyamide having the highest Tc and preferably above at least Te + 5 ° C.
    According to one particular option, the diamine b1) is 1,10-decamethylene diamine and the diamine b2) selected from MPMD or mXD with a) being terephthalic acid.
    Preferably, said polyamide comprises b1), b2) and c) and, in this case, the molar ratio in% of c / (b1 + b2) which means that c / b varies from 5 to 30% and preferably from 10 to 30%.
    More preferably, said polyamide comprises (in its unitary structure) component c) which is selected from 11-amino acid undecanoic or 12-amino acid lauric or lauryl lactam.
    Even more preferentially, said polyamide of said thermoplastic matrix has as components (as said prepolymers A1, A2 and B have): a) terephthalic acid, b1) 1,10-decamethylene diamine, b2) 1,6-hexamethylene diamine or MPMD or mXD; and c) 11-amino-undecanoic acid or 12-amino-lauric acid or lauryl lactam.
    More particularly, said polyamide (matrix as prepolymers A1, A2 and B) has as components: a) terephthalic acid, b1) 1,10-decamethylene diamine, b2) 1,6-hexamethylene diamine or MPMD or mXD and c) 11-amino undecanoic acid.
    Even more particularly, said polyamide (matrix as prepolymers A1, A2 and B) has as components: a) terephthalic acid, b1) 1,10-decamethylene diamine, b2) 1,6-hexamethylene diamine and c) l 11-amino undecanoic acid.
    According to another particularly preferred option, said polyamide has as components: a) terephthalic acid, b1) 1,10-decamethylene diamine, b2) 1,6-hexamethylene diamine and c) 12-amino undecanoic acid.
    In the preferred case where said component c) is present, said reactive prepolymer compositions (A1 + A2), B or (A1 + A2 + B) according to the invention allow a lower melt viscosity compared with the same compositions without c), comparable molecular weight. This allows a significant improvement in the impregnation of said fibrous reinforcement. Alternatively, for a constant melt viscosity, the presence of c) allows for higher molecular prepolymer weights.
    More particularly, the molar rate of b1 / (b1 + b2) varies from 55 to 75% and the molar rate of b2 / (b1 + b2) varies from 25 to 45%.
    According to one particular variant, said reactive precursor composition comprises at least one nanocharge of carbonic origin chosen from: carbon black, graphenes, carbon nanofibrils and carbon nanotubes, said nanofiller being added in previously dispersed form in the most fluid constituent.
    The method of the invention relates in particular and preferably to a process with a molding technique by RTM and more particularly it is a method with a molding technique c-RTM (RTM compression).
    According to a particular and preferred option, said precursor composition, as defined above, can comprise in addition to said prepolymers, an additive which absorbs the radiation of a UV laser at a specific wavelength or an IR heating or a microwave heating or induction heating for the purposes of reheating said composite material (composite part), before a complementary processing operation, in particular by heat-stamping, or by overmolding.
    As regards said fibers of said fibrous reinforcement, they are long fibers of L / D> 1000, preferably> 2000 (L being the length and D the diameter of said fibers). Preferably, said fibers are selected from mineral fibers, preferably glass, carbon or basalt, in particular glass and carbon or from synthetic, preferably aramid or polyaryl ether ketone fibers. Said fibers may represent levels of 45 to 75% by volume of said composite material, preferably 50 to 70%.
    More particularly, the method of the invention relates to the manufacture of a structural part based on said composite material. More particularly, said piece is a piece in the field of road transport, rail, maritime, aeronautical or aerospace or in the mechanical engineering or in the building or in parks and recreation or to make a reinforcement of shields or protective panels against impact projectiles. In particular, said structural part may be an automobile part, possibly inserted into a metal structure such as the white box of a vehicle, possibly subjected (with said inserted composite part) to a thermochemical treatment cycle by cataphoresis. This means that said composite parts for this use must withstand cataphoresis treatment conditions. In particular, a high Tf of said part allows such a treatment.
    More particularly, the difference Tf-Tc between the melting temperature Tf and the crystallization temperature Te of said polymer (polyamide) matrix does not exceed 60 ° C, preferably does not exceed 50 ° C and more particularly does not exceed 40 ° C .
    According to a particular option, the enthalpy of crystallization of said matrix polymer, measured in Differential Scanning Calorimetry (DSC) according to the ISO 11357-3: 2013 Standard, is greater than 40 J / g, preferably greater than 45 J / g.
    Said prepolymers A1, A2 and B, as defined above, have a number-average molecular mass Mn ranging from 500 to 10,000, preferably from 750 to 6000, more preferably from 750 to 3000. All the masses Mn are determined by the calculation from the rate of terminal functions determined by solution potentiometric titration and the functionality of said prepolymers. The said polyamide prepolymers may be prepared according to the methods as described in the examples of reactive prepolymers in WO 2014/064375.
    Regarding the different parameters defined according to the invention, their determination is carried out as explained below.
    The melt viscosity of the prepolymer or precursor composition is measured according to the manufacturer's reference manual of the measuring apparatus used which is a Physica MCR301 rheometer, under a nitrogen sweep at the given temperature under shear of 1 s-1, between two parallel planes with a diameter of 50 mm.
    The Mn of the prepolymer or the thermoplastic polymer is determined from the titration (assay) of the terminal functions according to a potentiometric method (direct assay for NH2 or COOH) 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. ISO 307: 2007 is followed but changing the solvent (use of m-cresol in place of sulfuric acid, temperature (20 ° C), and concentration (0.5% by mass).
    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: 2013 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 ISO 11357-3: 2013 standard. 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 ISO 11357-3: 2013 standard.
    The second subject of the invention covers said reactive precursor composition based on polyamide prepolymer, for carrying out the process as described above according to the present invention, composition as already defined above. It corresponds to the mixture A: (A1 + A2), the mixture (A + B) or the prepolymer B as already defined above. Preferably, said reactive precursor composition comprises at least one nanocharge of carbonic origin chosen from: carbon black, graphenes, carbon nanofibrils and carbon nanotubes, said nanofiller being added in previously dispersed form in the most fluid component.
    Another subject of the invention relates to a piece of composite material obtained by a process as defined above according to the invention or by using a precursor composition as defined above according to the invention.
    More particularly, the invention covers a composite material part obtained according to the method as defined above according to the invention, with said part being a structural part in the field of automobile, road, rail, maritime transport. , aeronautical or aerospace or in mechanical engineering or construction or in parks and recreation or for reinforcement of shields or projectile impact protection panels.
    权利要求:
    Claims (21)
    [1" id="c-fr-0001]
    1. A method of manufacturing a piece of thermoplastic composite material by closed mold molding, said material comprising reinforcing fibers and a polyamide thermoplastic matrix impregnating said fibers, characterized in that said matrix is a semi-crystalline polyamide with a temperature glass transition Tg of at least 80 ° C, preferably at least 90 ° C and more preferably at least 100 ° C and with a melting temperature Tf less than or equal to 280 ° C and greater than 200 ° C, preferably greater than 220 ° C., prepared in situ by melt mass polymerization by polycondensation, of a reactive precursor composition comprising, according to A, at least one first polyamide prepolymer A1 bearing two identical functions X (X and X) or Y (Y and Y) and at least one second polyamide prepolymer A2 carrying two identical functions X (X and X) or Y (Y and Y), different from those of A1 and coreacti with respect to those of A1 or of a precursor composition comprising, according to B, at least one carrier prepolymer (on the same chain) of two different functions X and Y coreactive with each other or of a precursor composition according to a mixture of (A + B) ), with said X and Y functions being respectively carboxy (X) and amine (Y) and conversely (Y and X) and in that said process comprises the following successive steps: i) preparation of the reactive mixture A: (A1 + A2) ) or the reactive mixture (A + B): (A1 + A2 + B) by mixing the components in the molten state or melting of said prepolymer B if only component of said precursor reactive composition, at a temperature greater than that of the temperature melting point Tf of the mixture A or of the mixture (A + B) or of the Tf of said prepolymer B if only one component of said precursor composition, ii) injection into a closed mold comprising said fibers of said reactive precursor composition, melted state as obtained in step i) and impregnation of said fibers with said melt reactive precursor composition, which is, as the case may be, A or (A + B) or said prepolymer B, preferably with a viscosity <100 Pa.s, more preferably <50 Pa.s, more preferably <10 Pa.s, iii) in-situ bulk melt polycondensation polymerization in said closed mold and with a polymerization time and temperature controlled so that the polymerization temperature is greater than the crystallization temperature Te of said thermoplastic matrix polyamide, iv) optionally, cooling said composite material part, v) demolding said part, and with said final polyamide of said matrix and said prepolymers A1, A2 or B having the same composition in amide units and said amide units being derived from: a) a diacid component which is from 95 to 100%, preferably from 100 to 100%; n moles of terephthalic structure with presence of 0 to 5 mol% of isophthalic diacid, preferably a) being 100% terephthalic diacid, b) a diamine component composed of: b1) from 55 to 85%, preferably from 55 to 85%, preferably at 80 mol% of a linear aliphatic diamine of Cg, Cio, Cn or C12 and b2) of 15 to 45%, preferably 20 to 45 mol% of a diamine different from b1), selected from: b21 ) a mono- methylated aliphatic diamine with a methyl or ethyl substituent and having a chain length difference with respect to the associated diamine b1), of at least two carbons, preferably said diamine b2) being 2-methyl pentamethylene diamine b22) the m-xylylene diamine (mXD) or b23) a C4-C18 linear aliphatic diamine when b1) is a C10-C12 linear aliphatic diamine and with b23) being a C10-C18 diamine when said diamine b1 is a C8 diamine , and c) optionally, an amino acid or following the corresponding lactam C6 to C12, preferably Ce, Cn or C12 and more preferably Cn, with c) representing not more than 30 mol% relative to a) or with respect to b), preferably, said method being an RTM (resin transfer molding) method, in particular c-RTM or a RIM process, in particular s-RIM, more preferably being an RTM process, in particular c-RTM.
    [2" id="c-fr-0002]
    2. Method according to claim 1, characterized in that it is a RTM process (resin transfer molding).
    [3" id="c-fr-0003]
    3. Method according to claim 1 or 2, characterized in that it comprises an additional step of post-polymerization.
    [4" id="c-fr-0004]
    4. Method according to one of claims 1 to 3, characterized in that said polyamide comprises b1), b2) and c) and that the molar ratio in% of c / (b1 + b2) varies from 5 to 30% and preferably from 10 to 30%.
    [5" id="c-fr-0005]
    5. Method according to one of claims 1 to 4, characterized in that said polyamide comprises c) selected from amino-11 undecanoic acid or amino-12 lauric acid or lauryl lactam.
    [6" id="c-fr-0006]
    6. Method according to one of claims 1 to 5, characterized in that said polyamide has as components a) terephthalic acid, b1) 1,10-decamethylene diamine, b2) 1,6-hexamethylene diamine or the 2-methyl pentamethylenediamine (MPMD) or mXD and c) 11-amino undecanoic acid or 12-amino lauric acid or lauryl lactam.
    [7" id="c-fr-0007]
    7. Method according to one of claims 1 to 6, characterized in that said polyamide has as components a) terephthalic acid, b1) 1,10-decamethylene diamine, b2) 1,6-hexamethylene diamine and c) l 11-amino undecanoic acid.
    [8" id="c-fr-0008]
    8. Method according to one of claims 1 to 6, characterized in that said polyamide has as components a) terephthalic acid, b1) 1,10-decamethylene diamine, b2) 1,6-hexamethylene diamine and c) l 12-amino-undecanoic acid.
    [9" id="c-fr-0009]
    9. Method according to one of claims 1 to 5, characterized in that b1) is 1,10-decamethylene diamine and b2) is selected from 2-methyl pentamethylene diamine (MPMD) or mXD and a) is terephthalic acid.
    [10" id="c-fr-0010]
    10. Method according to one of claims 1 to 9, characterized in that the molar rate of b1 / (b1 + b2) varies from 55 to 75% and that the molar rate of b2 / (b1 + b2) varies from 25 to at 45%.
    [11" id="c-fr-0011]
    11. Method according to one of claims 1 to 10, characterized in that said reactive precursor composition comprises at least one nanocharge of carbon origin selected from: carbon black, graphenes, carbon nanofibrils and carbon nanotubes, said nanoburden being added in previously dispersed form in the most fluid component.
    [12" id="c-fr-0012]
    12. Method according to one of claims 1 to 11, characterized in that it is a method c-RTM (RTM with compression).
    [13" id="c-fr-0013]
    13. Method according to one of claims 1 to 12, characterized in that said precursor composition further comprises said prepolymers an additive which absorbs the radiation of a UV laser at a specific wavelength or IR heating or a microwave heating or induction heating for the purposes of heating said composite, before a complementary processing operation, in particular by hot stamping or overmolding.
    [14" id="c-fr-0014]
    14. Method according to one of claims 1 to 13, characterized in that said fibers are long fibers L / D> 1000, preferably> 2000.
    [15" id="c-fr-0015]
    15. Method according to one of claims 1 to 14, characterized in that said fibers are selected from mineral fibers, preferably glass, carbon or basalt, in particular glass or carbon or from synthetics, preferably the aramid fibers or polyaryl ether ketones.
    [16" id="c-fr-0016]
    16. Method according to one of claims 1 to 15, characterized in that it relates to the manufacture of a structural part based on said composite material.
    [17" id="c-fr-0017]
    17. The method of claim 16, characterized in that said room is a room in the field of road transport, rail, maritime, aeronautical or aerospace or in the mechanical engineering or in the building or in parks and recreation or to make a reinforcement of shields or protective panels against impact projectiles.
    [18" id="c-fr-0018]
    18. A method according to one of claims 16 or 17, characterized in that said structural part is an automobile part, optionally inserted into a metal structure as the blank body of a vehicle, optionally subjected to a thermochemical treatment cycle by cataphoresis.
    [19" id="c-fr-0019]
    19. Prepolymer reactive precursor composition for carrying out the method according to one of claims 1 to 18, characterized in that it comprises according to A at least one first polyamide prepolymer A1 carrying two identical functions X (X and X or Y (Y and Y) and at least one second polyamide prepolymer A2 carrying two identical functions X (X and X) or Y (Y and Y), different from those of A1 and coreactive with respect to those of A1 or it comprises according to B at least one carrier prepolymer (on the same chain) of two different functions X and Y coreactive to each other or a precursor composition according to a mixture of (A + B), with said X and Y functions being respectively carboxy (X) and amine (Y) and conversely (Y and X) and with said prepolymers A1, A2 or B having an amide unit composition derived from: a) a diacid component which is 95 to 100%, preferably 100 % by mole of terephthalic structure with pr 0 to 5 mol% of isophthalic diacid, preferably a) being 100% terephthalic diacid, b) a diamine component composed of: b1) from 55 to 85%, preferably from 55 to 80 mol%, a linear aliphatic diamine C9, C10, C11 or C12 and b2) of 15 to 45%, preferably 20 to 45 mol% of a diamine different from b1), selected from: b21) a aliphatic diamine monoramified with methyl or ethyl substituent and having a chain length difference with respect to the associated diamine b1), of at least two carbons, preferably said diamine b2) being 2-methyl pentamethylene diamine b22) m-xylylene diamine (mXD ) or b23) a C4 to C18 linear aliphatic diamine when b1) is a C10 to C12 linear aliphatic diamine and b23) is a C10 to C18 diamine when said diamine b1 is an optional C9 diamine, and c) , an amino acid or, as the case may be, the corresponding lactam in Ce to C 12, preferably Ce, Cn or C12 and more preferably Cn, with c) representing not more than 30 mol% with respect to a) or with respect to b).
    [20" id="c-fr-0020]
    20. Molded part made of composite material, characterized in that it is obtained by a process as defined according to one of claims 1 to 18 or by using a precursor composition as defined according to claim 19.
    [21" id="c-fr-0021]
    21. Part according to claim 20, characterized in that it is a structural part in the field of the automobile, road transport, rail, maritime, aeronautical or aerospace or in the mechanical engineering or in the building or in parks and recreation or for reinforcement of shields or protection panels against impact projectiles.
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    同族专利:
    公开号 | 公开日
    JP2018538174A|2018-12-27|
    WO2017098178A1|2017-06-15|
    KR20180092967A|2018-08-20|
    FR3044956B1|2018-06-15|
    US20180346666A1|2018-12-06|
    US10961362B2|2021-03-30|
    CN108291022B|2021-04-13|
    JP6803912B2|2020-12-23|
    EP3387042A1|2018-10-17|
    CN108291022A|2018-07-17|
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    法律状态:
    2016-11-11| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-16| PLSC| Publication of the preliminary search report|Effective date: 20170616 |
    2017-11-13| PLFP| Fee payment|Year of fee payment: 3 |
    2019-11-14| PLFP| Fee payment|Year of fee payment: 5 |
    2020-11-12| PLFP| Fee payment|Year of fee payment: 6 |
    2021-11-09| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1562134|2015-12-10|
    FR1562134A|FR3044956B1|2015-12-10|2015-12-10|PROCESS FOR A FIBER-REINFORCED POLYAMIDE MATRIX COMPOSITE MATERIAL FROM REACTIVE PRE-CEMENTITIOUS PRECURSOR COMPOSITION|FR1562134A| FR3044956B1|2015-12-10|2015-12-10|PROCESS FOR A FIBER-REINFORCED POLYAMIDE MATRIX COMPOSITE MATERIAL FROM REACTIVE PRE-CEMENTITIOUS PRECURSOR COMPOSITION|
    KR1020187015959A| KR20180092967A|2015-12-10|2016-12-09|Method for preparing fiber-reinforced polyamide matrix composite material from reactive prepolymer precursor composition|
    EP16825808.5A| EP3387042A1|2015-12-10|2016-12-09|Method for producing a fibre-reinforced polyamide matrix composite material, from a reactive prepolymer precursor composition|
    CN201680071215.XA| CN108291022B|2015-12-10|2016-12-09|Method for producing fiber-reinforced polyamide matrix composites from reactive prepolymer precursor components|
    PCT/FR2016/053294| WO2017098178A1|2015-12-10|2016-12-09|Method for producing a fibre-reinforced polyamide matrix composite material, from a reactive prepolymer precursor composition|
    JP2018530125A| JP6803912B2|2015-12-10|2016-12-09|Method for Producing Fiber Reinforced Polyamide Matrix Composite from Reactive Prepolymer Precursor Composition|
    US15/778,080| US10961362B2|2015-12-10|2016-12-09|Method for producing a fibre-reinforced polyamide matrix composite material from a reactive prepolymer precursor composition|
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