• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to the field of thermoplastic composite materials. More particularly, the invention relates to the use of a thermoplastic prepreg for the manufacture of fire-resistant composite materials. Said prepreg comprises a thermoplastic polymer and a fiber reinforcement consisting of at least one continuous unidirectional fiber.
    公开号:FR3033574A1
    申请号:FR1556359
    申请日:2015-07-06
    公开日:2016-09-16
    发明作者:Gilles Hochstetter；Marc Audenaert；Sebastien Taillemite
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to the field of thermoplastic composite materials. More particularly, the invention relates to a fluorinated flame retardant thermoplastic composition, to the prepreg prepared from this composition and to the composite material containing said prepreg and to processes for the manufacture and uses of said material. In addition, the invention relates to the use of a thermoplastic prepreg for the manufacture of fire-resistant composite materials. TECHNICAL BACKGROUND The composite material parts used for the interior layout of airplanes, trains, boats and buses, as well as for buildings receiving the public, must respect, inter alia, standards related to the fire behavior of the building. material. These standards take into account, in particular the reaction to fire, the emission of smoke, the toxicity of the fumes and the release of heat from the materials during a fire. These standards are intended to ensure an optimal level of safety for the users of the means of transport or the building, allowing them to evacuate the place where a fire is declared, which requires that the materials constituting it do not contribute to the development of the fire, does not generate smoke or that the products of combustion are not toxic. These standards include, for example, EN 45545, which applies to the railway industry, FAR 25.853 and corresponding AITMs for the aviation industry, IMO MSC 653 and 61 for the marine industry. and ASTM E84 for the building. In the case of the most stringent standards, in particular for the interior design of aircraft, boats or trains in certain countries, only composite materials based on phenolic resins may be used. However, these phenolic resins have many disadvantages, namely: the toxicity of the components for molding the parts, due to the presence of phenol and formaldehyde in the resin and the presence of highly corrosive acid in the hardener; the low level of mechanical performance of the parts, in particular the low flexural and shear stresses; the low resistance to UV, the absence of recycling channels for parts in 3033574 2 end of life or for waste production; the difficulty of assembling inserts on the phenolic resin composite material; the low adhesion of paints or adhesives requiring the use of an adhesion primer, and the relatively short stability of phenolic prepregs, of a few months, with the need for temperature controlled storage. Polyphenylene sulphide resins can also be used, but their very high price limits their use in the aeronautical sector. In addition, the use of these resins is problematic because of their availability only in the form of reinforced plates with fibrous reinforcement, which allows only the molding of parts of little complex shape, the very high molding temperature necessary for softening of the resin, typically greater than 300 ° C, the low adhesion of paints, their low resistance to UV, and their low toughness. There is therefore still a need to develop new composite materials that overcome the aforementioned drawbacks.
    [0002] The applicant has already described, for example in documents EP 2 160 275 and EP 2 586 585, the preparation of various thermoplastic composite materials having high mechanical performances, in particular in terms of modulus, resistance to hot creep and tensile stress, which evolve little to a temperature of at least 90 ° C. These materials are intended for the manufacture of mechanical or structural parts such as the nose, wing or cabin of rockets or airplanes; off-shore flexible armor; automotive bodywork, engine chassis or automobile support parts; or the structural elements in the field of the building or the bridges and roadways. It has now been found that by making a selection among several parameters characterizing known thermoplastic composite materials, it is possible to provide novel compositions and composites having, in addition to good mechanical properties, outstanding fire resistance properties. and good smoke and toxicity properties, particularly recommending them for the manufacture of parts for semi-structural applications for the interior design of airplanes, trains, boats and buses, as well as for buildings receiving the public.
    [0003] SUMMARY OF THE INVENTION The invention relates first of all to a flame-retardant composition comprising a thermoplastic fluoropolymer grafted with a polar carboxylic function and a fibrous reinforcement consisting of at least one continuous mineral or organic fiber.
    [0004] According to one embodiment, this grafted fluoropolymer may be obtained by grafting at least one polar carboxylic monomer, for example carrying at least one carboxylic acid or anhydride function on a fluorinated polymer. According to one embodiment, said continuous mineral or organic fiber is unidirectional and has a form factor greater than 1000.
    [0005] According to a second aspect, the subject of the invention is a thermoplastic prepreg consisting of said flame retardant composition. According to one embodiment, the mass content of said mineral or organic fibers in the prepreg is between 30 and 90%, preferably between 40 and 80%, advantageously between 45 and 65% and even more preferably between 50 and 60%. .
    [0006] In another aspect, the invention relates to a composite material comprising said prepreg. According to one embodiment, this composite material is of the monolithic type, namely that it consists only of the prepreg. According to another embodiment, this composite material is of the sandwich type comprising a core material between two skins made of prepreg. Another aspect of the invention relates to the various processes for manufacturing the composite material of the invention, namely continuous lamination in the case of two-dimensional parts, vacuum molding and thermo-compression in the case of parts. in three dimensions.
    [0007] The invention also relates to the use of said composite materials for the manufacture of molded or rolled parts in the aeronautical field, naval, rail or road transport, or building, particularly said parts being mechanical parts or structure. In yet another aspect, the invention relates to the use of a prepreg comprising a thermoplastic polymer and a fiber reinforcement consisting of at least one unidirectional continuous fiber for the manufacture of fire-resistant composite materials. According to one embodiment, said thermoplastic polymer is a fluoropolymer, a polyamide, a polyolefin, especially polypropylene, a polyester or a copolymer or a mixture of at least two of these polymers. According to one embodiment, said thermoplastic polymer is a fluorinated polymer, in particular a vinylidene fluoride (VDF) -based polymer. According to one embodiment, said continuous fiber is selected from glass, carbon, aramid fibers and natural fibers such as flax, hemp or sisal. DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows.
    [0008] The invention provides a flame retardant composition comprising a thermoplastic fluoropolymer grafted with a carboxylic polar function and a fibrous reinforcement consisting of at least one continuous mineral or organic fiber. According to one embodiment, this grafted fluoropolymer is prepared according to a process comprising: (a) mixing, preferably in the molten state, a fluoropolymer with a polar monomer bearing an acid or carboxylic anhydride function, ( b) the possible transformation of this mixture into granules, powder, film or plate, (c) the irradiation of this mixture, optionally in the absence of oxygen under a dose ranging from 1 to 15 Mrad of photonic or electronic irradiation for grafting the polar monomer onto the fluoropolymer, and (d) optionally removing residual polar monomer unreacted with the fluoropolymer. A preparation process of this type is described in particular in application EP 1 484 346. According to one embodiment, said fluoropolymer is a "PVDF" resin, this term covering here a homopolymer of poly (vinylidene fluoride) or a copolymer of vinylidene fluoride (VDF) and at least one other comonomer selected from vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro (methylvinyl) ether perfluoro (ethylvinyl) ether and perfluoro (propylvinyl) ether, wherein the VDF is at least 50% by weight. The carboxylic polar function grafted on the fluoropolymer is carried by at least one polar monomer chosen from unsaturated mono- and di-carboxylic acids having from 2 to 20 carbon atoms, and in particular from 4 to 10 carbon atoms, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, cyclohex-4-ene-1,2-dicarboxylic acid, 4-methyl-cyclohex-4-ene-1,2-dicarboxylic acid, bicyclo (2, 2.1) hept-5-ene-2,3-dicarboxylic, and undecylenic, as well as their anhydrides. The mineral or organic fiber present in the composition is chosen from: carbon fibers; silica fibers such as glass fibers, especially of type E, R or S2; boron fibers; ceramic fibers, especially silicon carbide, boron carbide, boron carbonitride, silicon nitride, boron nitride; basalt fibers; fibers or filaments based on metals and their alloys; fibers based on metal oxides; natural fibers such as flax, hemp, sisal fibers; metallized carbon fibers and metallized glass fibers or mixtures of the fibers mentioned.
    [0009] According to one embodiment, said mineral or organic fiber is chosen from glass and carbon fibers. According to one embodiment, said continuous mineral or organic fiber is unidirectional and has a form factor (length to diameter ratio of the fiber) greater than 1000. The fibers can be used as such, in the form of unidirectional son, or after a weaving step, in the form of a fabric consisting of a multidirectional network of fibers (2D, 3D or other). The composition according to the invention may also contain one or more additives, chosen from plasticizers, dyes, anti-static agents, flame retardants and lubricating agents.
    [0010] According to a second aspect, the subject of the invention is a thermoplastic prepreg consisting of said flame retardant composition. This thermoplastic prepreg consists of one or more thermoplastic webs. A thermoplastic web comprises a fibrous reinforcement which is a unidirectional web of continuous fibers without any overlap between the fibers and a thermoplastic polymer as the bulk matrix impregnating said fibrous reinforcement. This thermoplastic web is in roll form, with a width of between 5 and 1500 mm, preferably between 25 and 1000 mm and more advantageously between 100 and 800 mm. This thermoplastic sheet has a thickness of between 0.1 mm and 0.7 mm, preferably between 0.15 and 0.5 mm and more advantageously between 0.2 and 0.4 mm. This thermoplastic prepreg is manufactured by lamination or thermocompression of said thermoplastic webs. When the thermoplastic prepreg comprises several thermoplastic plies, the continuous fibers of the various plies may either all be oriented in the same direction (0 °), be oriented perpendicularly (0 ° 90 °), or be oriented with particular angles , chosen for the mechanical characteristics they bring to the final piece, such as 0 ° -45 ° for example. This prepreg enjoys high mechanical performance due to the absence of overlap of said fibers between the different plies. This thermoplastic prepreg is in roll form, with a width of between 5 and 3000 mm, preferably between 20 and 1500 mm and more advantageously between 100 and 1300 mm, and a length greater than 100 meters, preferably greater than 500. meters, and more preferably greater than 1000 meters. These dimensions ensure optimum productivity conditions for the composite material manufacturer. In the prepreg according to the invention, the mass content of said mineral or organic fibers is between 30 and 90%, preferably between 40 and 80%, advantageously between 45 and 65% and even more preferably between 50 and 60%. . The interest of PVDF resin-based prepreg resides first and foremost in their good fire properties, and also, quite unexpectedly, in their good smoke and toxicity properties. Indeed, the rate of emission of HF (hydrofluoric acid) during the combustion of a composite material comprising said prepreg is well below the maximum level authorized by the standards FAR 25.853 and AITM 3.0005. Another advantage of the PVDF resin prepregs is the possibility of molding sandwich materials with a PVDF foam or a PVDF honeycomb, by thermo-welding the PVDF resin prepreg with said foam or said honeycomb, thus ensuring perfect compatibility between the skins and the core material. Said foam or said PVDF honeycomb is thermoplastic, which allows the thermoforming of the core material for parts having a complex shape. Another advantage of PVDF resin-based prepregs is the low melting point (170 ° C.) of the latter, which makes it possible to perform a low-temperature molding, unlike polyphenylenesulphide resin, and with a very short time. short, due to the absence of a chemical reaction during consolidation, unlike phenolic resins. Another advantage of the PVDF resin-based prepregs is the possibility of assembling inserts on the composite material made from said prepreg, by welding injected parts made of short fiber compounds based on PVDF resin, place and place of gluing, which is complex, or screwing, these inserts. Another advantage of PVDF resin prepregs, whether or not in combination with a PVDF core material, is the possibility of recycling, due to the thermoplastic nature of the resin. It is in particular possible to recycle the production waste composite materials made with said prepreg, as well as parts at the end of life. A recycling path consists in grinding this waste or parts at the end of its life and compounding this pulp with PVDF granules, in order to obtain a compound based on PVDF resin and short fiber. This compound is therefore a way of recycling the fiber and the PVDF matrix. Another advantage of prepregs based on PVDF resin is their very long stability, of several years, even of several decades, and this without temperature-controlled storage.
    [0011] Another advantage of PVDF resin prepregs is the possibility of painting or gluing using acrylic paints or adhesives. Another advantage of PVDF resin-based prepregs is their very high chemical resistance and their exceptional resistance to UV, and therefore the exceptional lifetime that it gives to the composite material.
    [0012] Another advantage of PVDF resin prepregs is the ability to mold a composite material by covering it with a decorative film to improve the final appearance of the part as well as its strength. Films based on PVDF resin or Tedlar® are particularly suitable for this application. Another aspect of the invention therefore consists of a composite material comprising the prepreg described above. Monolithic or sandwich composite materials can be made from these prepregs. A monolithic composite material consists only of prepreg, while a sandwich composite material comprises a core material between two skins made of prepreg. As the core material, foams and honeycombs can be mentioned which make it possible to lighten the work while maintaining a high level of rigidity. Another aspect of the invention relates to the various processes for manufacturing the composite material of the invention, namely continuous lamination in the case of two-dimensional parts, vacuum molding and thermo-compression in the case of parts. in three dimensions.
    [0013] The continuous lamination allows the manufacture of monolithic panels or sandwich continuously in a mill exerting a low pressure, between 0.1 and 3 bar, preferably between 0.5 and 2 bar, and at a temperature between 180 ° C. and 240 ° C, preferably between 190 and 220 ° C.
    [0014] 3033574 8 Vacuum molding allows the manufacture of simple or complex form parts, monolithic or sandwich. The part is molded between a rigid mold and a flexible sheet, between which a vacuum is created (between 0.1 mbar and 900 mbar, preferably between 1 mbar and 200 mbar), and at a temperature between 180 ° C and 240 Preferably between 190 ° and 220 ° C. The rigid mold may be of composite material or metal. The flexible tarpaulin may be a silicone tarpaulin or a thermoplastic film (polyamide, polyimide, etc.). Thermocompression allows the manufacture of simple or complex form parts, monolithic or sandwich. The part is molded between a rigid mold and a rigid counter mold, between which a pressure is applied (between 0.1 bar and 50 bar, preferably between 1 bar and 15 bar), and at a temperature between 180 ° C. and 240 ° C, preferably between 190 and 220 ° C. The mold is usually made of metal. These composite materials are used for the manufacture of molded or rolled parts in the aeronautical, naval, rail or road transport, or building, said parts being structural mechanical parts (requiring a module greater than 15 GPa 15) or semi-structural (whose module is between 8 and 15 GPa). According to another aspect, the invention relates to the use of a prepreg comprising a thermoplastic polymer and a fiber reinforcement consisting of at least one continuous unidirectional fiber for the manufacture of fire-resistant composite materials.
    [0015] Said thermoplastic polymer is chosen from fluorinated polymers, polyamides, polyolefins, especially polypropylene, polyesters or copolymers or mixtures between at least two of these polymers. According to one embodiment, said thermoplastic polymer is a "PVDF" resin, this term covering here as well a homopolymer of polyvinylidene fluoride or a copolymer of vinylidene fluoride (VDF) and at least one other comonomer selected from vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro (methylvinyl) ether, perfluoro (ethylvinyl) ether and perfluoro (propylvinyl) ether, wherein VDF is at least 50% by weight.
    [0016] According to one embodiment, the PVDF is grafted with a polar carboxylic function carried by at least one polar monomer chosen from unsaturated mono- and di-carboxylic acids having from 2 to 20 carbon atoms, and in particular from 4 to 10 carbon atoms. carbon, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, cyclohex-4-ene-1,2-dicarboxylic acid, 4-methyl-cyclohex-4-ene-1,2-dicarboxylic acid , bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic, and undecylenic, as well as their anhydrides. According to another embodiment, the PVDF is ungrafted. The continuous fiber used in the composition of said prepreg is selected from glass, carbon, aramid fibers and natural fibers such as flax, hemp or sisal. The mass content of said fibers is between 30 and 90%, preferably between 40 and 80%, advantageously between 45 and 65% and even more preferably between 50 and 60%, relative to the total weight of the prepreg. It has been found that the hydrofluoric acid emissions during the combustion of said prepreg are less than 200 ppm, preferably less than 100 ppm and more preferably less than 50 ppm, according to the FAR 25.853 and AITM 3.0005 standards. This is particularly recommended for the manufacture of parts for: - interior fittings for aircraft, train, boat, bus: seats, partitions, interior siding, floors, cockpit furniture, passenger zone furniture 15, trolleys, equipment in technical areas, ballistic protections, including exterior, bathroom, toilets; - building parts: ventilation equipment, ballistic protection, facings and interior or exterior equipment, elements involved in the building structure.
    [0017] EXAMPLES The following examples illustrate the invention without limiting it. Prepregs were made from a homopolymer of PVDF grafted with about 0.6% maleic anhydride and a continuous fiber, by dusting and then heat-compression under 10 bar for 15 minutes. The quantities of HF emitted during this operation were measured according to the AITM 3.0005 standard. The values obtained are shown in Table 1.
    [0018] Temperature Type of Thickness of HF Emissions fiber thermocompression continuous preimpregnated fiber Lin 230 ° C 45% 1.8 mm <30 ppm Carbon 200 ° C 50% 1.2 mm <20 ppm Table 1 5
    权利要求:
    Claims (9)
    [0001]
    REVENDICATIONS1. Use of a prepreg comprising a thermoplastic polymer and a fiber reinforcement consisting of at least one continuous unidirectional fiber for the manufacture of fire-resistant composite materials.
    [0002]
    2. Use according to claim 1 wherein said thermoplastic polymer is a fluoropolymer, a polyamide, a polyolefin, especially polypropylene, a polyester or a copolymer or a mixture between at least two of these polymers.
    [0003]
    3. Use according to one of claims 1 or 2 wherein said continuous fiber is selected from glass fibers, carbon, aramid and natural fibers such as flax, hemp or sisal.
    [0004]
    4. Use according to one of claims 1 to 3 wherein the mass content of said fibers is between 30 and 90%, preferably between 40 and 80%, preferably between 45 and 65% and even more preferably between 50 and 60% .
    [0005]
    5. Use according to one of claims 1 to 4 wherein the hydrofluoric acid emissions during combustion of said prepreg are less than 200 ppm, preferably less than 100 ppm and more preferably less than 50 ppm, according to the standards. FAR 25.853 and AITM 3.0005.
    [0006]
    6. Use according to one of claims 1 to 5 wherein said fluoropolymer is a polyvinylidene fluoride (PVDF) or a copolymer of vinylidene fluoride and at least one other comonomer selected from vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro (methylvinyl) ether, perfluoro (ethylvinyl) ether and perfluoro (propylvinyl) ether, in which vinylidene fluoride represents at least 50 % in weight.
    [0007]
    7. Use according to claim 6, wherein said PVDF is grafted with a polar carboxylic function carried by at least one polar monomer chosen from unsaturated mono- and di-carboxylic acids having from 2 to 20 carbon atoms, and in particular from 4 to 10 carbon atoms, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, cyclohex-4-ene-1,2-dicarboxylic acid, 4-methyl-cyclohex-4-ene-1,2- Dicarboxylic, bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic, and undecylenic, as well as their anhydrides.
    [0008]
    The use of claim 6, wherein said PVDF is ungrafted.
    [0009]
    9. Use according to one of claims 1 to 8 wherein said composite materials are intended for interior fittings of aircraft, boats, buses, trains such as: seats, partitions, interior siding, floors, cockpit furniture , passenger zone furniture, trolleys, equipment in technical areas, ballistic protections, bathrooms, toilets, or for the building, such as: ventilation equipment, ballistic protections, facings and equipment, interior or exterior, elements participating in the building structure .
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    引用文献:
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    法律状态:
    2016-02-08| PLFP| Fee payment|Year of fee payment: 2 |
    2016-09-16| PLSC| Publication of the preliminary search report|Effective date: 20160916 |
    2017-02-13| PLFP| Fee payment|Year of fee payment: 3 |
    2018-02-23| PLFP| Fee payment|Year of fee payment: 4 |
    2020-02-14| PLFP| Fee payment|Year of fee payment: 6 |
    2021-02-10| PLFP| Fee payment|Year of fee payment: 7 |
    2022-02-09| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1551977A|FR3033573B1|2015-03-10|2015-03-10|THERMOPLASTIC COMPOSITION AND PRE-IMPREGNE, COMPOSITE MATERIAL BASED ON SAID PRE-IMPREGN AND USES OF SAID COMPOSITE MATERIAL|
    FR1551977|2015-03-10|
    FR1556359A|FR3033574B1|2015-03-10|2015-07-06|THERMOPLASTIC COMPOSITION AND PRE-IMPREGNE, COMPOSITE MATERIAL BASED ON SAID PRE-IMPREGN AND USES OF SAID COMPOSITE MATERIAL|FR1556359A| FR3033574B1|2015-03-10|2015-07-06|THERMOPLASTIC COMPOSITION AND PRE-IMPREGNE, COMPOSITE MATERIAL BASED ON SAID PRE-IMPREGN AND USES OF SAID COMPOSITE MATERIAL|
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