• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    The present invention relates to a method of manufacturing in an open mold a thermoplastic composite material with fiber reinforcement and a matrix which is a semi-crystalline polyamide with a Tg of at least 80 ° C. and a Tf of less than or equal to 280 ° C. greater than 200 ° 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 or Y and at least one second polyamide prepolymer A2 carrying two identical functions X or Y, different from 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 coreactive between them or a precursor composition according to the mixture of (A + B) with X and Y being respectively carboxy or amine and conversely with said process comprising the successive steps of i) preparing reactive mixture A: (A1 + A2) or reactive mixture (A + B): (A1 + A2 + B) or melting said prepolymer according to B, ii) coating continuously by deposition-impregnation of said fibers, by said reactive precursor composition, iii) in-situ polymerization by mass melt polycondensation in an open heating die, iv) cooling 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 material, their use and end-articles.
    公开号:FR3037962A1
    申请号:FR1555819
    申请日:2015-06-24
    公开日:2016-12-30
    发明作者:Mathieu Capelot；Gilles Hochstetter
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a process for the preparation of a fiber-reinforced composite material (also called "fibrous reinforcement" thereafter) in an open mold and, in particular, in pultrusion using a specific reactive composition based on a prepolymer, said composition reactive being precursor of the final polymer of the thermoplastic matrix which is of 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 of the fibrous substrate and ease of use of said composite material at controlled temperatures, without risk of thermal degradation of said thermoplastic matrix polymer. 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.
    [0002] 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 teach us that the melting temperature of these compositions is at least about 280 ° C.
    [0003] 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.
    [0004] US Pat. No. 3,131,667,18 describes a method of pultrusion of low Tg reactive aliphatic polyamides associated with chain extenders of polymeric structure carrying 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 semicrystalline polyamide prepolymer reactive composition but in all the examples with a reactive precursor composition, the elongation is made by an extender of a different nature 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 the characteristics of reactive polyamide prepolymers used allowing a sufficiently low viscosity for good impregnation and adhesion to the fibers with mechanical performance which results in a 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 compositions (PA) semi-crystalline allowing easier implementation at lower temperatures with a saving on the energy balance of the implementation method. In particular, this is enabled by the rapid crystallizability of said semi-crystalline polyamide polymer by the specific choice of its composition and this while maintaining a high level of mechanical performance of said final materials. More particularly, the precursor reactive compositions used in the process according to the present invention allow better control of the reaction kinetics while having a fast formed polymer crystallization rate and a suitable rate and / or crystallization temperature. to the process used. The choice of a semi-crystalline polyamide polymer as the matrix of the composite material of the invention has, as an advantage over amorphous polyamides, significantly improved mechanical performance, especially at high temperature, such as creep or fatigue resistance. In addition, having a melting point above 200 ° C has the advantage in the automobile of being compatible with cataphoresis treatments, which does not allow an amorphous PA type structure. As for amorphous materials, a Tg greater than or equal to 90 ° 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. On the other hand, an excessively high melting point, in particular greater than 280 ° C., is detrimental because it requires the use of the composite at higher temperatures with constraints of molding material to be used (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.
    [0005] Such thermal degradation results in the assignment of the properties of the final thermoplastic matrix and thus 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 point Tf (Tm <280 ° C. and more particularly 270 ° C.) to optimize the mechanical performance and the crystallization rate and / or the temperature of the polymer. crystallization as high as possible. Thus, a selective choice of the composition of said semi-crystalline polyamide allows easier implementation for an open mold implementation process, in particular under the conditions of implementation by pultrusion. 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 is directed to 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 energy balance of 25%. overall 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 specific conditions of pultrusion, it allows a production of pultruded profiles with a rate higher than that of pultrusion processes of a thermosetting composition or a precursor composition monomeric. 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 Tc, Tf-Tc which does not exceed 60 ° C, preferably does not exceed 50 ° C and more particularly does not exceed 40 ° C. 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 performance, in terms of breaking stress, compared to those at ambient (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 problematic 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 kinetics and controlled during the impregnation step, thus allowing easier impregnation in open mold and in particular in the conditions of implementation of said composite material by pultrusion. More particularly, the solution of the present invention based on the use of reactive prepolymers (without a non-polymeric extender) also makes it possible to limit the amount of water released during the polymerization (in polycondensation), which facilitates its extraction from the open mold. and allows to obtain a composite without defects (microbubbles). In addition, the use of prepolymer makes it possible to carry out the polymerization step separately from the impregnation step (without significant polymerization prior to this separate polymerization step) because the viscosity of the prepolymer reactive composition is sufficient to maintain the preforming the composite material at the outlet of a die (after passing through a die) and before said separate polymerization. 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.
    [0006] The first object of the invention relates to a method of manufacturing an open mold 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 continuous impregnation of said fibrous reinforcement with said reactive composition, the bulk and melt polymerization of said composition, with passage through a die preforming said composite material and with possibility of post-polymerization if the polymerization is not complete and finally a cooling of said composite material thus manufactured. The second subject of the invention concerns said precursor reactive composition as used in said process. The invention also covers the composite material obtained by said method and an article obtained from said composite material. The first object of the invention therefore relates to a method of manufacturing an open mold thermoplastic composite material, said material comprising reinforcing fibers (fibrous reinforcement) and a polyamide thermoplastic matrix impregnating said fibers, with said matrix being a polyamide semi-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 of less than or equal to 280 ° C 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 carrier polyamide Al prepolymer of 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 Al and coreactive with respect to those of Al 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 which are coreactive with each other or of a precursor composition according to a mixture of (A + B): (Al + A2 + 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: (Al + A2) or of the reactive mixture (A + B): (Al + A2 + B) by mixing the components in the molten state or melting of said prepolymer B if only one component of said reactive composition precursor, at a temperature higher than 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) continuous impregnation of said fibers, by said Precursor composition ctive, which is the mixture A or (A + B) or said prepolymer B as the case may be, in the molten state, preferably with a viscosity <100 Pa.s, more preferably <50 Pa.s, more preferably <10 Pa.s under the impregnation conditions, in an open heated impregnation chamber (2), said impregnation being followed by preforming at the outlet of the impregnation chamber (2) by means of a die ( 3), iii) in situ melt polycondensation polymerization in mass in said impregnation chamber (2) and / or outside said impregnation chamber, in a dedicated zone (4) separated from said impregnation chamber (2) and / or outside said impregnation chamber, in a dedicated zone (4) separated from said impregnation chamber; impregnation chamber (2) and a die (3) for preforming said material and with said zone (4) located after the impregnation chamber and said die (3) and with a duration and a temperature controlled, so that the polymerization temperature is higher than the temperature of the polymerization melting Tf of said thermoplastic matrix polyamide, iv) cooling of said material which can take place in the ambient air, and with said final polyamide of said matrix and said prepolymers A1, A2 or B having the same composition in amide units, 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% by weight; terephthalic diacid (also known as terephthalic acid), b) a diamine component composed of: b1) from 55 to 85 (:) / 0, preferably from 55 to 80 mol% of a C6, C10, C11 aliphatic linear diamine or 012 and 20b2) from 15 to 45 (:) / 0, preferably from 20 to 45 mol% of a diamine different from b1), selected from: b21) a mono-substituted aliphatic diamine with methyl or ethyl substituent and having a difference in chain length with respect to the associated diamine b1), of at least two carbons, preferably said diamine b2) being 2-methyl pentamethylene diamine (MPMD) b22) m-xylylene diamine (mXD) or b23) a linear aliphatic diamine of C4 to 018 when b1) is a linear C10 aliphatic diamine at 012 and with b23) is a C10 diamine at 018 when said diamine b1) is a C6 diamine, and c) optionally an amino acid or, as the case may be, the corresponding lactam C6 to C12, preferably C6, C11 or C12 and more preferably C11, with c) representing not more than 30% by mole with respect to a) or with respect to b). Said die (3) in addition to its function of preformatting said composite material also has the function of compacting the composite material passing through said die (3) by eliminating the porosities resulting from the formation of microbubbles of steam. water formed by said polycondensation reaction. More particularly, said impregnation step is followed by preforming said material at the outlet of the impregnation chamber (2) by means of a die (3).
    [0007] More particularly, said polymerization is carried out in said impregnation chamber (2) with optional additional polymerization, called post-polymerization, in said zone (4) separated from said impregnation chamber (2) and said die ( 3). According to a particular option of said process before step i) and step ii), there is a preheating step in a dedicated zone (1) of said fibers before entering said impregnation chamber (2). The polymerization temperature is above the melting temperature T f of the thermoplastic matrix polyamide and preferably at least 10 ° C higher. The degree of polymerization at the outlet of the die (3) may be identical to that of the final polyamide targeted for said thermoplastic matrix. In this case, there is no need for additional polymerization called "post-polymerization". According to another possibility, the degree of polymerization at the outlet of said die (3) may be less than that of the final polyamide targeted for said thermoplastic matrix and in this case, said method comprises an additional step of post-polymerization in a zone dedicated (4) separated from said die (3). It is also possible that the polymerization takes place only in said separate zone (4) separated. Said dedicated zone (4) separated from said die (3) may be an oven, optionally a vacuum oven and optionally there may be an additional step of shaping said composite material at the outlet of said oven (4).
    [0008] According to another preferred option, said heating impregnating chamber (2) has a temperature gradient (increasing) between the inlet and the outlet of said impregnation chamber (2). This gradient can be adapted according to the degree of polymerization aimed at leaving the die (3) and the kinetics of the reaction. 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%.
    [0009] More preferably, said polyamide comprises (in its unitary structure) the component c) which is chosen 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 (such as said prepolymers Al, A2 and B a): a) terephthalic acid, 131) 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, 131) 1,10-decamethylene diamine, b2) 1,6-hexamethylenediamine or MPMD or mXD and c) 11-amino undecanoic acid. Even more particularly, said polyamide (matrix as prepolymers Al, A2 and B) has as components: a) terephthalic acid, 131) 1,10-decamethylene diamine, b2) 1,6-hexamethylene diamine and c) l 11-amino undecanoic acid.
    [0010] According to another particularly preferred option, said polyamide has as components: a) terephthalic acid, 131) 1,10-decamethylene diamine, b2) 1,6-hexamethylenediamine and c) 12-amino-undecanoic acid . In the preferred case where said component c) is present, said reactive prepolymer compositions (Al + A2, B or Al + A2 + B) according to the invention allow a lower melt viscosity compared to the same compositions. without c), comparable molecular weight. This allows a significant improvement in the impregnation of said fibrous reinforcement. Alternatively, at constant melt viscosity the presence of c) makes it possible to have higher prepolymer molecular weights, which amounts to a lower concentration of reactive functions X, Y by polycondensation and thus a lower concentration. of condensation water to be eliminated, with facilitation of its elimination (condensation water) and finally better advancement of the polycondensation (final molecular weight of the higher matrix polyamide) and with fewer defects (microbubbles) in the composite material final related to this condensation water.
    [0011] More particularly, the molar ratio of 131 / (b1 + b2) varies from 55 to 75% and the molar ratio of b2 / (b1 + b2) varies from 25 to 45%. According to a 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 form previously dispersed in at least one constituent a ), b) or c) the most fluid.
    [0012] The method of the invention relates in particular and preferably to pultrusion and more particularly it is a pultrusion with said fibers being pultruded continuously. More particularly, said fibers pultruded by appropriate traction means first pass into a preheating zone (1) before the impregnation chamber (2) where the precursor reactive composition is continuously deposited in the molten state with polymerization. partial or complete in-situ and at the preforming exit of the impregnated fibrous material thus polymerized by the die (3) with possible post-polymerization in a separate zone (4) to perfect said polymerization and before cooling said material which can be done at the ambient air or by controlled cooling means (controlled cooling rate). The material thus obtained can then be converted by thermo stamping or overmoulding of another compatible thermoplastic polymer. 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 microwave heating or induction heating for the purposes of reheating said composite, in particular pultruded, before a complementary processing operation, in particular pultrusion, either by thermal 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 60 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 panels of protection against projectiles impact. 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 3037962 for this use must withstand the 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 Tc of said polymer (polyamide) matrix does not exceed 60 ° C., preferably does not exceed 50 ° C. and more particularly does not exceed 40 ° C. 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 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 weight 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 terminal function rate determined by potentiometric titration in solution and the functionality of said prepolymers. 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 meter used, which is a Physica MCR301 rheometer, under a nitrogen sweep at the given temperature under shear. 100 s-1, between two parallel planes with a diameter of 50 mm. The Mn of the prepolymer or the thermoplastic polymer is determined from the titration (assay) of the terminal functions according to a potentiometric method (direct assay for NH 2 or carboxy) and from the theoretical functionality which is 2 (in terminal functions). for prepolymers and linear polymers prepared from bifunctional monomers alone. Measurement of intrinsic or inherent viscosity is performed in m-cresol. The method is well known to those skilled in the art. The ISO 937 standard is followed, but changing the solvent (use of m-cresol in place of sulfuric acid and the temperature being 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.
    [0013] The melting temperature Tf and the crystallization temperature Tc are measured by DSC, after a first heating, according to the ISO 11357-3 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 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: (Al + A2), to the mixture (A + B) or to 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 at least one constituent a), b ) or c) the most fluid. Another subject of the invention relates to a 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. Finally, it covers a composite article obtained from a composite material manufactured according to the method as defined above according to the invention. More particularly, said article is a structural part in the field of the automobile, road transport, railway, maritime, aeronautical or aerospace or mechanical engineering or in the building or in parks and recreation or for reinforcements of shields or protective panels against impact projectiles.
    权利要求:
    Claims (26)
    [0001]
    REVENDICATIONS1. A process for producing an open mold thermoplastic composite material, said material comprising reinforcing fibers and a polyamide thermoplastic matrix impregnating said fibers, characterized in that said matrix is a semicrystalline polyamide 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 less than or equal to 280 ° C and greater than 200 ° C, preferably greater than 220 ° C 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 from those of Al and coreactive with respect to those of Al or a a precursor composition comprising, according to B, at least one carrier prepolymer (on the same chain) of two different functions X and Y coreactive to one another or of a precursor composition according to a mixture of (A + B), with said functions X and Y being respectively carboxy (X) and amine (Y) and vice versa (Y and X) and in that said process comprises the following successive steps: i) preparation of the reaction mixture A: (Al + A2) or of the reaction mixture (A + B) (Al + A2 + B) by mixing the components in the molten state or melting of said prepolymer B if only one component of said precursor reactive composition, at a temperature higher than 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) continuous impregnation of said fibers with said reactive precursor composition, which is the mixture A or (A + B) or said prepolymer B as the case may be,in the molten state, preferably with a viscosity <100 Pa.s, more preferably <50 Pa.s, more preferably <10 Pa.s under the impregnation conditions, in an open heating impregnation chamber (2) , said impregnation being followed by preforming at the outlet of the impregnation chamber (2) by means of a die (3), iii) in-situ polymerization by mass melt polycondensation in said chamber; impregnation (2) and / or outside said impregnation chamber, in a dedicated zone (4) separated from said impregnation chamber (2) and a die (3) for preforming said material and with said zone ( 4) located after the impregnation chamber and said die (3) and with a controlled polymerization time and temperature so that the polymerization temperature is higher than the melting temperature Tf of said thermoplastic matrix polyamide , iv) cooling said maté 5, and with said final polyamide of said matrix and said prepolymers A1, A2 or B having the same amide unit composition and said amide units being derived from: a) a diacid component which is from 95 to 100%, preferably from 100 mol% of terephthalic structure with 0 to 5 mol% of isophthalic diacid, preferably a) being 100% terephthalic diacid, b) a diamine component consisting of: b1) from 55 to 85 (:) Preferably from 55 to 80 mol% of a linear aliphatic diamine of C 8, C 10, C 11 or O 12 and b 2) of from 15 to 45 (%), preferably from 20 to 45 mol% of a diamine other than b1), selected from: b21) a monoamined 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 the
    [0002]
    2-methyl pentamethylenediamine 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 a C6 diamine, and c) optionally, an amino acid or, as the case may be, the corresponding lactam C6 to C12, preferably C6, Ci or C12 and more preferably C11, with c) not representing more than 30 mol% with respect to a) or with respect to b). 2. Method according to claim 1, characterized in that said polymerization is carried out in said impregnation chamber (2) with optional additional polymerization, called post-polymerization, in said zone (4) separated from said chamber 30. impregnation (2) and said die (3).
    [0003]
    3. Method according to claim 1 or 2, characterized in that before step i) and step ii) there is a preheating step in a dedicated zone (1) of said fibers before entering said chamber impregnation (2). 3037962 14
    [0004]
    4. Method according to one of claims 1 to 3, characterized in that the degree of polymerization output of the die (3) is identical to that of the final polyamide referred to said thermoplastic matrix.
    [0005]
    5. Method according to one of claims 1 to 3, characterized in that the degree of polymerization at the outlet of said die (3) remains lower than that of the final polyamide referred to for said thermoplastic matrix and that in this case, said method comprises an additional step of post-polymerization in a dedicated zone (4) separated from said die (3).
    [0006]
    6. Method according to claim 5, characterized in that said dedicated zone (4) 10 separated from said die (3) is an oven, optionally a vacuum oven and optionally there is an additional step of forming said composite material at the outlet of said furnace.
    [0007]
    7. Method according to one of claims 1 to 6, characterized in that said impregnating chamber (2) heating has a temperature gradient (increasing) between the inlet and the outlet of said impregnation chamber (2) . 15
    [0008]
    8. Method according to one of claims 1 to 7, 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%.
    [0009]
    9. Method according to one of claims 1 to 8, characterized in that said polyamide comprises c) selected from amino-11 undecanoic acid or lauric amino-12 acid or lauryl lactam.
    [0010]
    10. Method according to one of claims 1 to 9, 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. 25
    [0011]
    11. Method according to one of claims 1 to 10, characterized in that said polyamide has as components a) terephthalic acid, b1) 1,10-decamethylene diamine, b2) 1,6-hexamethylene diamine and c ) 11-amino undecanoic acid.
    [0012]
    12. Method according to one of claims 1 to 10, characterized in that said polyamide has as components a) terephthalic acid, b1) 1,10-decamethylene diamine, b2) 1,6-hexamethylenediamine and c) 12-amino undecanoic acid.
    [0013]
    13. Method according to one of claims 1 to 9, characterized in that b1) is 1,10-decamethylene diamine and b2) is selected from MPMD or mXD and a) is terephthalic acid. 3037962 15
    [0014]
    14. Method according to one of claims 1 to 13, 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%.
    [0015]
    15. Method according to one of claims 1 to 14, characterized in that 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 at least one constituent a), b) or c) the most fluid.
    [0016]
    16. Method according to one of claims 1 to 15, characterized in that it is a pultrusion with said fibers being pultruded continuously.
    [0017]
    17. Method according to one of claims 1 to 16, characterized in that said precursor composition further comprises said prepolymers an additive that 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 reheating said composite, in particular pultruded, before a complementary processing operation, in particular pultrusion, either by thermal stamping or overmolding.
    [0018]
    18. Method according to one of claims 1 to 17, characterized in that said fibers are long fibers of LJD> 1000, preferably> 2000. 20
    [0019]
    19. Method according to one of claims 1 to 18, characterized in that said fibers are selected from mineral fibers, preferably glass, carbon or basalt, in particular glass or carbon or from synthetic, preferably aramid fibers or polyaryl ether ketones.
    [0020]
    20. Method according to one of claims 1 to 19, characterized in that it relates to the manufacture of a structural part based on said composite material.
    [0021]
    21. The method of claim 20, 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. 30
    [0022]
    22. Method according to one of claims 20 or 21, characterized in that said structural part is an automotive part, possibly inserted into a metal structure as the blank body of a vehicle, optionally subjected to a thermochemical treatment cycle by cataphoresis. 3037962 16
    [0023]
    23. Prepolymer reactive precursor composition for carrying out the method according to one of claims 1 to 22, characterized in that it is as defined according to one of claims 1 to 17.
    [0024]
    24. Composite material, characterized in that it is obtained by a process as defined in one of claims 1 to 22 or by using a precursor composition as defined according to claim 23.
    [0025]
    25. Composite article, characterized in that it is obtained from a composite material manufactured by the process as defined according to one of claims 1 to 22.
    [0026]
    26. Article according to claim 25, 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 building or in parks and recreation or for reinforcements of shields or projectile impact protection panels.
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    同族专利:
    公开号 | 公开日
    EP3313917B1|2020-01-01|
    US20180223057A1|2018-08-09|
    FR3037962B1|2019-11-29|
    WO2016207553A1|2016-12-29|
    EP3313917A1|2018-05-02|
    JP2018525455A|2018-09-06|
    US10738170B2|2020-08-11|
    KR20180022655A|2018-03-06|
    ES2770873T3|2020-07-03|
    CN107735434A|2018-02-23|
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    法律状态:
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    2016-12-30| PLSC| Search report ready|Effective date: 20161230 |
    2017-05-11| PLFP| Fee payment|Year of fee payment: 3 |
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    2019-05-10| PLFP| Fee payment|Year of fee payment: 5 |
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    2021-05-13| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1555819A|FR3037962B1|2015-06-24|2015-06-24|OPEN MOLD PROCESS FOR A FIBER-REINFORCED SEMI-CRYSTALLINE POLYAMIDE MATRIX COMPOSITE MATERIAL FROM PREPOLYMER REACTIVE PRECURSOR COMPOSITION|
    FR1555819|2015-06-24|FR1555819A| FR3037962B1|2015-06-24|2015-06-24|OPEN MOLD PROCESS FOR A FIBER-REINFORCED SEMI-CRYSTALLINE POLYAMIDE MATRIX COMPOSITE MATERIAL FROM PREPOLYMER REACTIVE PRECURSOR COMPOSITION|
    US15/579,968| US10738170B2|2015-06-24|2016-06-23|Method for the open-mold production of a fiber-reinforced semi-crystalline polyamide matrix composite material from a prepolymer reactive precursor composition|
    CN201680032764.6A| CN107735434A|2015-06-24|2016-06-23|The method that fibre-reinforced semicrystalline polyamides groundmass composite material is manufactured by the die sinking of prepolymer reactive precursor composition|
    PCT/FR2016/051536| WO2016207553A1|2015-06-24|2016-06-23|Method for the open-mould production of a fibre-reinforced semi-crystalline polyamide matrix composite material from a prepolymer reactive precursor composition|
    EP16747811.4A| EP3313917B1|2015-06-24|2016-06-23|Method for the open-mould production of a fibre-reinforced semi-crystalline polyamide matrix composite material from a prepolymer reactive precursor composition|
    JP2017563188A| JP2018525455A|2015-06-24|2016-06-23|Open mold manufacturing method of fiber reinforced semi-crystalline polyamide matrix composite from prepolymer reactive precursor composition|
    KR1020177034682A| KR20180022655A|2015-06-24|2016-06-23|Method for the open-mould production of a fibre-reinforced semi-crystalline polyamide matrix composite material from a prepolymer reactive precursor composition|
    ES16747811T| ES2770873T3|2015-06-24|2016-06-23|Open-mold process for a fiber-reinforced semi-crystalline polyamide matrix composite material from a reactive prepolymer precursor composition|
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