EP3642267A1 - Materiau fibreux impregne de prepolymere thermoplastique reactif - Google Patents

Materiau fibreux impregne de prepolymere thermoplastique reactif

Info

Publication number
EP3642267A1
EP3642267A1 EP18733251.5A EP18733251A EP3642267A1 EP 3642267 A1 EP3642267 A1 EP 3642267A1 EP 18733251 A EP18733251 A EP 18733251A EP 3642267 A1 EP3642267 A1 EP 3642267A1
Authority
EP
European Patent Office
Prior art keywords
prepolymer
fibrous material
polyamide
thermoplastic
fibers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18733251.5A
Other languages
German (de)
English (en)
French (fr)
Inventor
Gilles Hochstetter
Mathieu Capelot
Thibaut SAVART
Arthur Pierre BABEAU
Denis Huze
François TANGUY
Patrice Gaillard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP3642267A1 publication Critical patent/EP3642267A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02—Polyamines

Definitions

  • the present invention relates to a fibrous material impregnated with reactive thermoplastic prepolymer of low average molecular weight Mn number.
  • the invention relates to a fibrous material impregnated with at least one reactive thermoplastic prepolymer and optionally a chain extender, characterized in that said at least one reactive thermoplastic prepolymer is partially polymerized, optionally with said chain extender. and has a number average molecular weight Mn of from 500 to 10,000, preferably from 4000 to 8000, and a fiber content in said impregnated fibrous material of from 45 to 65% by volume, preferably from 50 to 60% by weight. volume, especially 54 to 60%.
  • fibrous material means an assembly of reinforcing fibers. Before it is shaped, it is in the form of wicks. After shaping, it comes in the form of strips (or tape), or tablecloths. When the reinforcing fibers are continuous, their assembly constitutes a unidirectional reinforcement or a fabric or a nonwoven (NCF). When the fibers are short, their assembly constitutes a felt or a mat of fibers.
  • Such impregnated fibrous materials are particularly intended for the production of lightweight composite materials for the manufacture of mechanical parts having a three-dimensional structure and having good mechanical and thermal properties.
  • these fibrous materials are able to evacuate electrostatic charges.
  • the use of flame retardant resins or flame retardant additives in non-flame resins allows impregnated fibrous materials to be fire resistant. They therefore have properties compatible with the manufacture of parts in particular in the fields of mechanics, aeronautics, nautical, automotive, oil and gas, particularly offshore, gas storage, energy, health and medical, sports and recreation, and electronics.
  • Such impregnated fiber materials are also referred to as composite materials. They comprise the fibrous material, constituted by the reinforcing fibers, and a matrix constituted by the polymer impregnating the fibers.
  • the primary role of this matrix is to maintain the reinforcing fibers in a compact form and to give the desired shape to the final product.
  • This matrix also ensures the charge transfer between the fibers and therefore conditions the mechanical strength of the composite.
  • Such a matrix also serves to protect the reinforcing fibers against abrasion and an aggressive environment, to control the surface appearance and to disperse any fillers between the fibers.
  • the role of this matrix is important for the long-term behavior of the composite material, especially with regard to fatigue and creep.
  • a good quality of the three-dimensional composite parts made from impregnated fibrous materials passes in particular through control of the impregnating process of the reinforcing fibers by the thermoplastic polymer and thus the impregnated fibrous material obtained.
  • the term "band” is used to designate strips of fibrous material whose width is greater than or equal to 400 mm.
  • ribbon is used to designate ribbons of calibrated width and less than or equal to 400 mm.
  • wick is also used to refer to the fibrous material.
  • thermoplastic polymer or thermosetting polymer was carried out according to several processes which depend in particular on the nature of the polymer, the type of final desired composite material and its field of application. applications, some of these processes consisting of an impregnation step followed by a heat calendering step of the impregnated fibrous material or a drying step optionally followed by a step of melting the thermoplastic polymer.
  • thermosetting polymers such as epoxy resins for example, such as described in the patent WO2012 / 066241 A2.
  • thermoplastic polymers of low viscosity are suitable for the use of thermoplastic polymers of low viscosity only.
  • Thermoplastic polymers in particular those with a high glass transition temperature, have a melt viscosity that is too high to allow satisfactory impregnation of fibers and semi-finished or finished products of good quality.
  • the international application WO 2014/064375 describes a method of manufacturing a thermoplastic composite material, in particular a mechanical part or a structural part based on said material, comprising a step of implementing or molding a non-reactive polyamide composition after impregnation of a fibrous material to form the final composite part in a mold or with another processing system or a step of melt impregnation of a fibrous material with a composition of reactive prepolymer and implemented by molding or by another implementation system with simultaneously a step of polymerization of the reactive composition.
  • Said implementation can be carried out according to a RTM, S-RIM, injection-compression, pultrusion or infusion process.
  • thermomechanical constitutive polymer when the reactive prepolymer has a Tg or Tf temperature close to the Tf or Tg of the final polymer, the prepolymer begins to polymerize before the injection is completed, causing defects in the part (lack of material, inhomogeneity of properties). thermomechanical constitutive polymer ).
  • the object of the invention is therefore to remedy at least one of the drawbacks of the prior art, and in particular to obtain fibrous material impregnated with a reactive thermoplastic prepolymer which subsequently makes possible the preparation of a composite material impregnated with a polymer.
  • non-reactive thermoplastic in particular a mechanical part or a structural part based on said material, with a short cycle time, in particular of the order of one minute for thermo stamping, an energy cost less than prior art and the use of simpler hardware and therefore a reduced hardware investment.
  • the invention aims in particular to provide a fibrous material impregnated with a reactive thermoplastic prepolymer, having a fiber content in said impregnated fibrous material being comprised of 45 to 65% by volume, preferably 50 to 60% by volume, in particular 54% by weight. at 60% and likely to react later during its implementation to obtain thereafter a fibrous material impregnated with a non-reactive thermoplastic polymer and having mechanical performance necessary for the final composite part.
  • the subject of the invention is an impregnated fibrous material comprising a fibrous material made of continuous fibers and at least one reactive thermoplastic prepolymer, and optionally a chain extender, characterized in that the said at least one reactive thermoplastic prepolymer is partially polymerized.
  • a number average molecular weight (Mn) of from 500 to 10,000, preferably from 4000 to 8000, the fiber content in said impregnated fibrous material being 45 to 65% by weight. volume, preferably 50 to 60% by volume, especially 54 to 60%.
  • the reactive thermoplastic prepolymer is a non-reactive thermoplastic polymer precursor.
  • reactive thermoplastic prepolymer means that the molecular weight of said reactive prepolymer will evolve during its subsequent use by reaction of reactive prepolymers with each other by condensation with evolution of water or by substitution or reaction of reactive prepolymers with a chain extender by polyaddition and without elimination of volatile by-products to drive subsequently after processing to the final thermoplastic non-reactive polymer of the thermoplastic matrix.
  • non-reactive final thermoplastic polymer means that the final thermoplastic polymer has a molecular weight that is no longer likely to change significantly, that is to say that its number-average molecular mass (Mn) changes from less than 50% during its implementation and therefore corresponding to the final polymer of the thermoplastic matrix.
  • partially polymerized means that the prepolymers have an initial molecular weight Mni and an initial melt viscosity ⁇ corresponding to the molecular weight and the viscosity obtained during their preparation.
  • this mass evolves by partial reaction of the thermoplastic prepolymers, with each other or with the chain extender, which means that the number-average molecular weight Mn2 and the melt viscosity n.2 prepolymer after impregnation are greater than or equal to the initial molecular weight Mni and an initial melt viscosity ⁇ - ⁇ .
  • Said partially polymerized reactive prepolymers optionally with the chain extender, have a number average molecular weight (Mn2) ranging from 500 to 10,000, preferably from 4000 to 8000.
  • This number average molecular weight is obviously in the solid state after cooling of the prepolymer.
  • Said final non-reactive thermoplastic polymer is derived from a reactive thermoplastic prepolymer comprising or not a chain extender or a polymerization of a mixture of reactive prepolymers, optionally a prepolymer with the chain extender.
  • the number-average molecular mass Mn of said final non-reactive thermoplastic polymer is greater than 10,000, preferably in a range from 10,000 to 40,000, preferably from 12,000 to 30,000, determined in particular by calculation from the terminal function rate determined by potentiometric titration in solution and the functionality of said prepolymers or by NMR assay (Postma et al (Polymer, 47, 1899-191 1 (2006)).
  • said impregnated fibrous material is non-flexible.
  • said at least one reactive thermoplastic prepolymer that is partially polymerized, optionally with said chain extender has a melt viscosity of from 0.1 to 100 Pa.s.
  • the melt viscosity is measured by oscillatory rheology at a temperature Tf ⁇ T ⁇ Tf + 50 ° C, at 10 rad / sec under a nitrogen sweep with 5% deformation on a Physica MCR301 apparatus between two parallel planes of 25 mm in diameter.
  • the partially polymerized prepolymer optionally with said chain extender, has a low number average molecular weight Mn or a melt viscosity of 0.1 to 100 Pa.s, which means that this prepolymer and optionally The chain extender has a low viscosity and therefore a high fluidity, thus permitting good impregnation of said fibrous material on both sides and in the core of the fibrous material.
  • the impregnation on both sides does not necessarily mean that the impregnation is similar on both sides of said fibrous material.
  • the impregnation can lead to an impregnated material having a zone rich in thermoplastic prepolymer and optionally a chain extender on one side of said material and a fiber-rich zone on the opposite face of said material, which means that the material impregnated with prepolymer is asymmetrical.
  • the volume ratio of the fibers is constant in at least 70% of the volume of the band or ribbon, especially in at least 80% of the volume of the band or ribbon, in particular in at least 90% of the volume of the band or ribbon, more particularly in at least 95% of the volume of the tape or ribbon.
  • the distribution of the fibers is homogeneous in at least 95% of the volume of the band or ribbon.
  • homogeneous means that the impregnation is uniform and that there is no dry fiber, i.e., not impregnated, in at least 95% of the volume of the strip or strip of material fibrous impregnated.
  • the measurement of the volume ratio of fibers is carried out locally on a representative elementary volume (VER).
  • VER representative elementary volume
  • constant means that the volume fiber ratio is constant at the nearest measurement uncertainty of plus or minus 1%.
  • the impregnation with the prepolymer is homogeneous and at heart.
  • Thermoplastic, or thermoplastic prepolymer is understood to mean a material that is generally solid at ambient temperature, that can be semi-crystalline or amorphous, and that softens upon an increase in temperature, in particular after passing its glass transition temperature (Tg). and flows at a higher temperature when it is amorphous, or can present a blunt fusion at the passage of its so-called melting temperature (Tf) when it is semi-crystalline, and which becomes solid again during a decrease in temperature below his crystallization temperature (for a semi-crystalline) and below its glass transition temperature (for an amorphous).
  • Tg glass transition temperature
  • Tf melting temperature
  • Tg and Tf are determined by Differential Scanning Calorimetry (DSC) according to standard 1 1357-2: 2013 and 1 1357-3: 2013 respectively.
  • thermoplastic prepolymer reactive thermoplastic prepolymer
  • partially polymerized reactive thermoplastic prepolymer refer to the same compound.
  • thermoplastic prepolymer constituting the impregnating matrix of the fibrous material
  • thermoplastic prepolymer it is advantageously a thermoplastic prepolymer or a mixture of thermoplastic prepolymers.
  • This prepolymer or mixture of thermoplastic prepolymers can be milled in powder form so that it can be used in a device such as a tank, in particular in a fluidized bed or in an aqueous dispersion.
  • the device in the form of a tank, in particular in a fluidized bed, can be open or closed.
  • Mn are determined in particular by the calculation from the rate of terminal functions determined by potentiometric titration in solution and the functionality of said prepolymers. Mn masses can also be determined by size exclusion chromatography or by NMR.
  • said at least one partially polymerized reactive thermoplastic prepolymer comprises at least one reactive (polyamide) prepolymer carrying on the same chain (ie on the same prepolymer), two terminal functions X 'and Y' functions respectively coreactive between them by condensation, with X 'and Y' being amine and carboxy or carboxy and amine respectively.
  • said at least partially polymerized reactive thermoplastic prepolymer consists of at least one reactive (polyamide) prepolymer carrying on the same chain (ie on the same prepolymer), two terminal functions X 'and Y' functions respectively coreactive between them by condensation, with X 'and Y' being amine and carboxy or carboxy and amine respectively.
  • said at least one partially polymerized reactive thermoplastic prepolymer comprises at least two polyamide prepolymers which are reactive with one another and each carrying two identical terminal functions X 'or Y' (same for the same prepolymer and different between the two prepolymers), said function X 'of a prepolymer that can react only with said function Y' of the other prepolymer, in particular by condensation, more particularly with X 'and Y' being amino and carboxy or carboxy and amine respectively.
  • said at least one partially polymerized reactive thermoplastic prepolymer consists of at least two polyamide prepolymers which are reactive with each other and each carrying two identical terminal functions X 'or Y' (identical for the same prepolymer and different between the two prepolymers), said function X 'of a prepolymer that can react only with said function Y' of the other prepolymer, in particular by condensation, more particularly with X 'and Y' being amino and carboxy or carboxy and amine respectively.
  • the at least two prepolymers may be mixed together or not beforehand.
  • This condensation reaction (or polycondensation) can cause the elimination of by-products.
  • These can be removed by preferably working in a method using open mold technology.
  • a step of degassing, preferably under vacuum, by-products removed by the reaction is present, this to avoid the formation of microbubbles by-products in the final composite material , which (microbubbles) can affect the mechanical performance of said material if they are not removed as well.
  • reaction of the two prepolymers can be total or partial.
  • said at least one reactive thermoplastic prepolymer partially polymerized with the chain extender comprises:
  • a2) at least one Y-A'-Y chain extender, with A being a hydrocarbon biradical carrying 2 identical Y terminal reactive reactive functions by polyaddition (without elimination of reaction by-product), with at least one function X of said prepolymer a1), preferably of molecular weight less than 500 and more preferably less than 400.
  • said at least one reactive thermoplastic prepolymer partially polymerized with the chain extender is composed of a1) and a2) defined above.
  • Y is chosen from: oxazine, oxazoline, oxazolinone, oxazinone, imidazoline, epoxy, isocyanate, maleimide, cyclic anhydride, especially oxazine, oxazoline, oxazolinone, oxazinone, imidazoline, maleimide, cyclic anhydride and preferably X1 is CO2H and Y1 is chosen from an epoxy and an oxazoline.
  • NH2 (amine) means primary and secondary amine.
  • elongators a2) as a function of the X functions carried by said semicrystalline polyamide prepolymer a1), the following may be mentioned:
  • Y chosen from the groups: maleimide, optionally blocked isocyanate, oxazinone and oxazolinone, cyclic anhydride, preferably oxazinone and oxazolinone, in particular maleimide, oxazinone and oxazolinone, cyclic anhydride, preferably oxazinone and oxazolinone;
  • a ' is a spacer or a carbon radical carrying the functions or reactive groups Y, chosen from:
  • either the chain extender Y-A'-Y corresponds to Y being a caprolactam group and to A 'may be a carbonyl radical such as carbonyl biscaprolactam or A' may be a terephthaloyl or isophthaloyl,
  • either said chain extender Y-A'-Y carries a group Y of cyclic anhydride and preferably this extender is chosen from a cycloaliphatic and / or aromatic carboxylic dianhydride and more preferably it is chosen from ethylenetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 1,2-dianhydride, , 3,4-Cyclobutanetetracarboxylic acid, hexafluoroisopropylidene bisphthalic dianhydride, 9,9-bis (trifluoromethyl) xanthenetetracarboxylic dianhydride, 3,3 ', 4,
  • said Y-A'-Y chain extender corresponds to:
  • Y chosen from the groups: oxazoline, oxazine, imidazoline or aziridine, such as 1,1'-iso- or terephthaloylbis (2-methylaziridine) or epoxy, A 'being a spacer or a carbon radical as defined above.
  • said Y function is chosen from oxazinone, oxazolinone, oxazine, oxazoline or imidazoline, in particular oxazoline, in this case, in the chain extender represented by Y-A ' -Y, A 'may represent an alkylene such that - (CH2) m- with m ranging from 1 to 14 and preferably from 2 to 10 or A may represent cycloalkylene and / or substituted arylene (alkyl) or unsubstituted, such as benzene arylenes, such as o-, m-, -p phenylenes or naphthalenic arylenes and preferably A 'is arylene and / or cycloalkylene.
  • the chain extender may be chosen from bisphenol A diglycidyl ether (DGEBA), and its hydrogenated derivative (cycloaliphatic) bisphenol F diglycidyl ether, tetrabromo bisphenol A diglycidyl ether, or hydroquinone diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether Mn ⁇ 500 , polypropylene glycol diglycidyl ether of Mn ⁇ 500, polytetramethylene glycol diglycidyl ether of Mn ⁇
  • this blocking can be obtained by blocking agents of the isocyanate function, such as epsilon-caprolactam, methyl ethyl ketoxime, dimethyl pyrazole, diethyl malonate.
  • blocking agents of the isocyanate function such as epsilon-caprolactam, methyl ethyl ketoxime, dimethyl pyrazole, diethyl malonate.
  • the preferred conditions avoid any formation of imide ring during the polymerization and during the implementation in the state molten.
  • the group Y is preferably chosen from: isocyanate (not blocked), oxazinone and oxazolinone, more preferably oxazinone and oxazolinone, with a spacer or hydrocarbon radical A 'being as defined above.
  • chain extenders carrying oxazoline or oxazine reactive functions Y that are suitable for the implementation of the invention, reference may be made to those described under references “A”, “B", “C” and “D”. on page 7 of application EP 0 581 642, as well as to their preparation processes and the other reaction modes which are exposed to them.
  • "A” in this document is bisoxazoline, "B” bisoxazine, "C” 1, 3 phenylene bisoxazoline and "D” 1,4-phenylene bisoxazoline.
  • reaction product obtained has at least one repeating unit of the following structure:
  • P is an acid-terminated polyamide HO-C (O) -P-C (O) -OH obtained from the amide units (A), (B) or (C),
  • a ' is a phenyl
  • Y-imidazoline reactive chain extenders suitable for the implementation of the invention, reference may be made to those described ("A" to "F") on pages 7 to 8 and Table 1 of the page 10 in the application EP 0 739 924 as well as their processes of preparation and their modes of reaction which are exposed to it.
  • Y oxazinone or oxazolinone reactive functional chain extenders which are suitable for the implementation of the invention, reference may be made to those described under references “A” to "D” on pages 7 to 8 of EP 0 581 641, and to their preparation processes and their reaction modes which are exposed to them.
  • groups Y oxazinones (6-atom ring) and oxazolinones (5-atom ring) are suitable Y groups derived from: benzoxazinone oxazinone or oxazolinone, with spacer A as a simple covalent bond with corresponding respective lengtheners being: bis- (benzoxazinone), bisoxazinone and bisoxazolinone.
  • A may also be a C1 to C14 alkylene, preferably a C2 to C10 alkylene, but preferably A 'is an arylene and more particularly it may be a phenylene (substituted with Y at the 1, 2 or 1, 3 or 1, 4 positions). or a naphthalene radical (disubstituted by Y) or phthaloyl (iso- or terephthaloyl) or A 'may be a cycloalkylene.
  • the radical A can be as described above with A possibly being a single covalent bond and with the respective corresponding extenders being: bisoxazine, bisoxazoline and bisimidazoline.
  • a ' may also be a C1 to C14 alkylene, preferably a C2 to C10 alkylene.
  • the radical A is preferably arylene and more particularly it may be phenylene (substituted with Y at the 1, 2 or 1, 3 or 1, 4 positions) or a naphthalene (disubstituted with Y) or phthaloyl (iso- or terephthaloyl) radical or A 'may be cycloalkylene.
  • the radical A ' may be a phthaloyl (1, 1' iso). or terephthaloyl) with, as an example of such an extender, isophthaloyl-bis (2-methyl aziridine).
  • a catalyst for the reaction between said P (X) n prepolymer and said Y-A'-Y extender at a level ranging from 0.001 to 2%, preferably from 0.01 to 0.5% relative to The total weight of two co-reactants mentioned can accelerate the (poly) addition reaction and thus shorten the production cycle.
  • a catalyst may be chosen from: 4,4'-dimethylaminopyridine, p-toluenesulphonic acid, phosphoric acid, NaOH and optionally those described for polycondensation or transesterification as described in EP 0 425 341, page 9, lines 1 to 7.
  • a ' may represent an alkylene, such that - (CH2) m - with m ranging from 1 to 14 and preferably from 2 to 10 or represents a substituted arylene alkyl or unsubstituted, such as benzene arylenes (such as o-, m-, -p) or naphthalenic phenylenes (with arylenes: naphthalenylenes).
  • A represents an arylene which may be benzene or naphthenic substituted or not.
  • said chain extender (a2) preferably has a molecular weight of less than 500, more preferably less than 400.
  • the denatured elongation rate used varies from 1 to 20%, in particular from 5 to 20%, especially from 10 to 20% by weight.
  • said reactive prepolymers are prepared by conventional polycondensation reaction between the corresponding diamine and diacid components and optionally amino acids or lactams.
  • Prepolymers carrying X 'and Y' amino and carboxy functions on the same chain can be obtained for example by adding a combination of monomers (amino acid, diamine, diacid) having in total an equal amount of amino and carboxy units.
  • prepolymers functionalized with identical functions amines or carboxy
  • n 3 for example, for a prepolymer P (X1) n, the presence of a trifunctional component is required, for example the presence of a triamine (one mole per prepolymer chain) with a diamine in the reaction with a diacid .
  • thermoplastic prepolymer or thermoplastic prepolymer mixture further comprises carbonaceous fillers, in particular carbon black or carbon nanofillers, preferably chosen from carbon nanofillers, in particular graphenes and / or carbon nanotubes, and or carbon nanofibrils or mixtures thereof.
  • carbonaceous fillers in particular carbon black or carbon nanofillers, preferably chosen from carbon nanofillers, in particular graphenes and / or carbon nanotubes, and or carbon nanofibrils or mixtures thereof.
  • said thermoplastic prepolymer comprises at least one additive, especially chosen from a catalyst, an antioxidant, a thermal stabilizer, a UV stabilizer, a light stabilizer, a lubricant, a filler, a plasticizer, a flame retardant, a nucleating agent , a dye, an electrical conductive agent, a thermal conductive agent or a mixture thereof.
  • a catalyst an antioxidant, a thermal stabilizer, a UV stabilizer, a light stabilizer, a lubricant, a filler, a plasticizer, a flame retardant, a nucleating agent , a dye, an electrical conductive agent, a thermal conductive agent or a mixture thereof.
  • said additive is chosen from a flame retardant agent, an electrical conductive agent and a thermal conductive agent.
  • Said flame retardants may be halogen-free flame retardants, as described in US 2008/0274355 and in particular a metal salt selected from a metal salt of phosphinic acid, a metal salt of diphosphinic acid, a polymer containing at least one salt phosphinic acid, a polymer containing at least one metal salt of diphosphinic acid or red phosphorus, an antimony oxide, a zinc oxide, an iron oxide, a magnesium oxide or metal borates such as zinc borate or melamine pyrophosphates and melamine cyanurates.
  • They may also be halogenated flame retardants such as brominated or polybrominated polystyrene, brominated polycarbonate or brominated phenol.
  • thermoplastic prepolymer or thermoplastic prepolymer blend may further comprise liquid crystal polymers or cyclized poly (butylene terephthalate), or mixtures containing said liquid crystal polymers or said cyclized poly (butylene terephthalate) as that additives, like resin CBT100 marketed by CYCLICS CORPORATION.
  • liquid crystal polymers or cyclized poly (butylene terephthalate) or mixtures containing said liquid crystal polymers or said cyclized poly (butylene terephthalate) as that additives, like resin CBT100 marketed by CYCLICS CORPORATION.
  • thermoplastic prepolymers forming part of the impregnation matrix of the fibrous material are precursors of polymers and can be chosen from: the family of aliphatic, cycloaliphatic polyamides (PA) or semi-aromatic PAs (also called polyphthalamides (PPAs)) )
  • polyureas in particular aromatic
  • PAEK polyarylether ketones
  • PEEK polyether ether ketone
  • PAEKK polyaryletherketone ketones
  • PEKK polyetherketone ketone
  • polyarylsulfides in particular polyphenylene sulfides (PPS),
  • polyarylsulphones in particular polyphenylene sulphones (PPSU),
  • polystylenes in particular polypropylene (PP);
  • PLA polylactic acid
  • PVA polyvinyl alcohol
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PCTFE polychlorotrifluoroethylene
  • the prepolymer may be in the form of homopolyamide or copolyamide.
  • the proportion by weight of prepolymer P1 and P2 is from 1 -99% to 99-1%.
  • thermoplastic prepolymer when said thermoplastic prepolymer is mixed and used in a tank, it is added to the tank in powder form previously obtained by “dry blend” or “compound” or directly into the tank in the form of "dry blend".
  • the mixture of two prepolymers P1 and P2 is a mixture of PEKK and PEI.
  • the PEKK PEI mixture is from 90-10% to 60-40% by weight, in particular from 90-10% to 70-30% by weight.
  • the number-average molecular weight Mn of said final non-reactive thermoplastic polymer is greater than 10,000, preferably in a range from 10,000 to 40,000, preferably, in a range from 10,000 to 40,000, preferably from 12,000 to 30,000.
  • Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in m-cresol according to ISO 307: 2007 but changing the solvent (use of m-cresol in place of sulfuric acid and the temperature being 20 ° C).
  • the Mn are determined in particular by the calculation from the terminal function rate determined by potentiometric titration in solution.
  • Mn masses can also be determined by size exclusion chromatography or by NMR.
  • the polyamide may be a homopolyamide or a copolyamide or a mixture thereof.
  • the prepolymers constituting the matrix are chosen from polyamides (PA), in particular chosen from aliphatic polyamides, cycloaliphatic polyamides, and semi-aromatic polyamides (polyphthalamides) optionally modified with urea units, and their copolymers, polymethyl methacrylate (PPMA) and its copolymers, polyetherimides (PEI), polyphenylene sulphide (PPS), polyphenylene sulphone (PPSU), polyetherketoneketone (PEKK), Poly (ether ether ketone) (PEEK), fluorinated polymers such as polyvinylidene fluoride (PVDF).
  • PA polyamides
  • PPMA polymethyl methacrylate
  • PEI polyetherimides
  • PPS polyphenylene sulphide
  • PPSU polyphenylene sulphone
  • PEKK polyetherketoneketone
  • the VDF content must be greater than 80% by weight, or even better 90% by weight, to ensure good mechanical strength to the structural part, especially when subjected to thermal and chemical stresses.
  • the comonomer may be a fluorinated monomer such as, for example, vinyl fluoride.
  • PAEK PolyArylEtherKetone
  • PEK polyether ketones PEEK poly (etheretherketone)
  • PEKK poly etherketoneketone
  • Tg glass transition temperature
  • said at least one thermoplastic prepolymer is selected from polyamides, PEKK, PEI and a mixture of PEKK and PEI.
  • said polyamide is chosen from aliphatic polyamides, cycloaliphatic polyamides and semi-aromatic polyamides (polyphthalamides).
  • said aliphatic polyamide prepolymer is chosen from:
  • polyamide 6 PA-6
  • polyamide 11 PA-11
  • polyamide 12 PA-12
  • polyamide 66 PA-66
  • polyamide 46 PA-46
  • polyamide 610 PA-610
  • polyamide 612 PA-612
  • polyamide 1010 PA-1010
  • PA-1012 polyamide 1 1/1010 and polyamide 12/1010, or a mixture of them or a copolyamide thereof
  • block copolymers in particular polyamide / polyether (PEBA)
  • said semi-aromatic polyamide is a semi-aromatic polyamide, optionally modified with urea units, in particular an MXD6 PA and an MXD10 PA or a semi-aromatic polyamide of formula X / YAr, as described in EP1505099, in particular a semi-aromatic polyamide of formula A / XT in which A is chosen from a unit obtained from an amino acid, a unit obtained from a lactam and a unit corresponding to the formula (diamine Ca).
  • XT denotes a unit obtained from the polycondensation of a diamine in Cx and terephthalic acid, with x representing the number of carbon atoms of the diamine in Cx, x being between 6 and 36, advantageously between 9 and 18, in particular a polyamide of formula A / 6T, A / 9T, A / 10T or A / 1 1T, A being as defined above, in particular a polyamide PA 6 / 6T, a PA 66 / 6T, a PA 6I / 6T, PA MPMDT / 6T, PA PA1 1 / 10T, PA 1 1 / 6T / 10T, PA PA MXDT / 10T, PA MPMDT / 10T, PA PA / 10T, PA PA / 6T , PA BACT / 10T / 6T.
  • T is terephthalic acid
  • MXD is m-xylylene diamine
  • MPMD is methylpentamethylene diamine
  • BAC is bis (aminomethyl) cyclohexane.
  • the partially polymerized reactive prepolymer optionally with a chain extender, has a glass transition temperature Tg greater than or equal to 80 ° C., preferably greater than or equal to 100 ° C., in particular greater than or equal to 120 ° C., in particular greater than or equal to 140 ° C, or is a semi-crystalline prepolymer whose melting temperature Tf is greater than or equal to 150 ° C.
  • Fibrous material As regards the fibers of constitution of said fibrous material, they are in particular fibers of mineral, organic or vegetable origin in the form of locks.
  • fibers of mineral origin mention may be made of carbon fibers, glass fibers, basalt fibers, silica fibers, or silicon carbide fibers, for example.
  • these are carbon fibers whose fiber number per wick is greater than or equal to 30K, in particular is greater than or equal to 50K or glass fibers whose weight is greater than or equal to 1200 Tex, in particular greater or equal to 2400 Tex, in particular greater than or equal to 2400 Tex.
  • thermoplastic or thermosetting polymer-based fibers such as semi-aromatic polyamide fibers, aramid fibers or polyolefin fibers, for example.
  • they are based on amorphous thermoplastic polymer and have a glass transition temperature Tg greater than the Tg of the prepolymer or thermoplastic prepolymer mixture of constitution of the impregnation matrix when the latter is amorphous, or greater than the Tf of the prepolymer or mixture of thermoplastic prepolymer of constitution of the impregnation matrix when the latter is semi-crystalline.
  • thermoplastic polymers are based on semicrystalline thermoplastic polymer and have a melting temperature Tf greater than the Tg of the prepolymer or thermoplastic prepolymer mixture of constitution of the impregnation matrix when the latter is amorphous, or greater than the Tf of the prepolymer or mixture of thermoplastic prepolymer of constitution of the impregnation matrix when the latter is semicrystalline.
  • Tf melting temperature
  • fibers of vegetable origin mention may be made of natural fibers based on flax, hemp, lignin, bamboo, silk, especially spider, sisal, and other cellulosic fibers, in particular viscose fibers. These plant-based fibers can be used pure, treated or coated with a coating layer, in order to facilitate the adhesion and impregnation of the thermoplastic prepolymer matrix.
  • the fibrous material may also be a fabric, braided or woven with fibers.
  • organic fibers may be mixed with the mineral fibers to be impregnated with thermoplastic prepolymer, optionally with a chain extender, and form the impregnated fibrous material.
  • the locks of organic fibers may have several grammages. They can also have several geometries.
  • the fibers may be in the form of short fibers, which then compose the felts or nonwovens which may be in the form of webs, webs, or pieces, or in the form of continuous fibers, which make up 2D fabrics, unidirectional (UD) or non-woven fibers or tows.
  • the fibers constituting the fibrous material may also be in the form of a mixture of these reinforcing fibers of different geometries.
  • the fibers are continuous.
  • the fibrous material is constituted by continuous fibers of carbon, glass or silicon carbide or their mixture, in particular carbon fibers. It is used in the form of a lock or several locks.
  • thermoplastic prepolymer of impregnation must be distributed as homogeneously as possible within the fibers in order to obtain a minimum of porosities, ie a minimum of voids between the fibers.
  • porosities in this type of material can act as points of concentration of stress, when placed under tensile stress, for example, and which then form fracture initiation points of the impregnated fibrous material. and mechanically weaken it.
  • a homogeneous distribution of the prepolymer or mixture of prepolymers thus improves the mechanical strength and the homogeneity of the composite material formed from these impregnated fibrous materials.
  • the level of fibers in said impregnated fibrous material is 45 to 65% by volume, preferably 50 to 60% by volume, especially 54 to 60% by volume.
  • the measurement of the impregnation rate can be carried out by image analysis (use of microscope or camera or digital camera, in particular), a cross section of the ribbon, by dividing the surface of the tape impregnated with the polymer. by the total surface of the product (surface impregnated plus surface of the porosities).
  • image analysis use of microscope or camera or digital camera, in particular
  • a cross section of the ribbon by dividing the surface of the tape impregnated with the polymer. by the total surface of the product (surface impregnated plus surface of the porosities).
  • the porosity of said impregnated fibrous material is less than 10%, especially less than 5%, in particular less than 2%.
  • the porosity rate is greater than 0% but lower than the rates mentioned above.
  • the porosity rate corresponds to the closed porosity rate and can be determined either by electron microscopy or as being the relative difference between the theoretical density and the experimental density of said impregnated fibrous material as described in the examples of the present invention.
  • the fibrous material impregnated with a partially polymerized thermoplastic prepolymer, optionally with a chain extender may be prepared in two steps: A first step of pre-impregnating with a thermoplastic prepolymer and optionally a chain extender and a second heating step by means of at least one docking piece (E) and at least one heating system, said piece of being located at the level of the heating system
  • the first pre-impregnation step for obtaining a material can be carried out according to the techniques well known to those skilled in the art and in particular chosen from those described above.
  • powdered pre-impregnation technology by melting, in particular by pultrusion, by extrusion at the head end of the molten prepolymer, by continuous passage of the fibers in an aqueous dispersion of prepolymer powder or aqueous dispersion of prepolymer particles or an aqueous prepolymer emulsion or suspension, by fluidized bed, equipped or not with at least one jetting ( ⁇ '), by spray nozzle or spray gun in a tank, equipped or not with at least one docking ( ⁇ ').
  • the pre-impregnation step depends on the nature of the reactive prepolymer used.
  • the use of the molten route imposes the use of an extruder and this cause polymerization of the prepolymer in this extruder, to lead to the final non-reactive thermoplastic polymer at the exit of the extruder, which would significantly impair the quality of impregnation of the fibers; this could even in some cases block the screw of the extruder.
  • the squeeze may be a concave, convex or cylindrical compression roll, in particular it is cylindrical.
  • FIG. 1 shows an example of a vessel provided with a jig
  • FIG. 2 shows an example of a vessel comprising a fluidized bed in which the jig is a cylindrical compression roller.
  • the same tank can be used without the presence of a fluidized bed and equipped with a spray gun.
  • the melt impregnation can be carried out only by the separate introduction of the different reactive species together, in a mixer, just before the impregnation of the fibers or directly in the impregnation chamber.
  • the pre-impregnation stage is carried out by means of an aqueous dispersion of prepolymer particles or of an aqueous emulsion or suspension of prepolymer, of a fluidized bed or of a projection by nozzle or spray gun by dry route. in a tank, in particular by means of a fluidized bed.
  • the pre-impregnation is carried out with a system as defined above and one or more jets (E ") is (are) present (s) upstream of said system.
  • (E) and (E ") can be identical or different in terms of material or shape and its characteristics (diameter, length, width, height ... depending on the shape).
  • the pre-impregnation stage can be carried out by melting, in particular by pultrusion.
  • the melt pre-impregnation techniques are well known to those skilled in the art and are described in the references above.
  • the pre-impregnation step is carried out in particular by passing said wick or said locks in a bath comprising the prepolymer matrix and then passing through a heated die, the bath being provided with fixed or rotating locks on which the wick scrolls thus causing a blooming of said wick for pre-impregnation of said wick.
  • the pre-impregnation may especially be carried out as described in US
  • the pre-impregnation step is carried out by a high speed melt, that is to say with a running speed of said wick or said wicks greater than or equal to 5 m / min, in particular greater than 9 m. / min.
  • the pre-impregnation stage may be carried out in a fluidized bed.
  • This system describes the use of a vessel comprising a fluidized bed to perform the pre-impregnation step and can be used in the context of the invention.
  • the vessel comprising the fluidized bed is provided with at least one docking piece ( ⁇ ') (FIG. 1) which may be a compression roller (FIG. 2)).
  • docking part ( ⁇ ') we mean any system on which the wick to the possibility of scrolling in the tank.
  • the docking piece ( ⁇ ') can have any shape from the moment the wick can scroll on contact.
  • FIG. 1 An example of a docking piece ( ⁇ '), without restricting the invention to it, is detailed in FIG.
  • parts (E) and ( ⁇ ') can be identical or different in terms of material or shape and its characteristics (diameter, length, width, height ... depending on the form).
  • the step of pre-impregnating the fibrous material is carried out by passing one or more wicks in a continuous pre-impregnation device, comprising a tank (10) provided with at least one docking piece ( ⁇ ') and comprising a fluidized bed (12) of powder of said at least one prepolymer and optionally a chain extender.
  • the powder of said at least one prepolymer and optionally a chain extender is suspended in a gas G (air for example) introduced into the tank and circulating in the tank (10) through a hopper (1 1).
  • the wick (s) are circulated in this fluidized bed (12).
  • the tank may have any shape, in particular cylindrical or parallelepipedal, in particular a rectangular parallelepiped or a cube, advantageously a rectangular parallelepiped.
  • the tank (10) can be an open or closed tank.
  • the tank is closed, it is then equipped with a sealing system so that the powder of said at least one prepolymer and optionally a chain extender can not leave said tank.
  • This pre-impregnation stage is therefore carried out dry, that is to say that said at least one prepolymer and optionally a chain extender is in powder form, in particular in suspension in a gas, in particular air, but can not be dispersed in a solvent or in water.
  • Each wick prepreg is unwound from a reel device under the traction generated by cylinders (not shown).
  • Each reel is provided with a brake (not shown) so as to apply tension to each fiber strand.
  • an alignment module allows to arrange the fiber locks parallel to each other. In this way the fiber locks can not be in contact with each other, which makes it possible to avoid mechanical degradation of the fibers by friction between them.
  • the fiber wick or the parallel fiber locks then pass into a tank (10), in particular comprising a fluidized bed (12), provided with a docking piece ( ⁇ ') which is a compression roll (24). in the case of Figure 2.
  • the fiber lock or the parallel fiber locks then spring (ent) from the tank after pre-impregnation after possible control of the residence time in the powder.
  • the term "residence time in the powder” means the time during which the wick is in contact with said powder in the fluidized bed.
  • an optional de-sizing step can be performed before the fibrous material passes into the tank.
  • sizing refers to the surface treatments applied to the reinforcing fibers at the end of the die (textile size) and on the fabrics (plastic sizing).
  • the vessel used in the process of the invention comprises a fluidized bed and said pre-impregnation stage is carried out with simultaneous expansion of said wick or said wicks between the inlet and the outlet of the vessel comprising said fluidized bed.
  • inlet of the tank of said fluidized bed corresponds to the vertical tangent of the edge of the vessel which comprises the fluidized bed.
  • outlet of the tank of said fluidized bed corresponds to the vertical tangent of the other edge of the vessel which comprises the fluidized bed.
  • the distance between the inlet and the outlet thereof is therefore the diameter in the case of a cylindrical tank, the side in the case of a cubic tank or the width or the length in the case of a rectangular parallelepipedic tank.
  • the development consists in singling out as much as possible each fiber constituting said wick of the other fibers which surround it in its nearest space. It corresponds to the transverse spreading of the wick.
  • the transverse spreading or the width of the wick increases between the inlet of the fluidized bed (or of the vessel comprising the fluidized bed) and the outlet of the fluidized bed (or of the vessel comprising the fluidized bed) and thus allows improved pre-impregnation of the fibrous material.
  • At least one docking ( ⁇ '), in particular a cylindrical compression roller, in the pre-impregnation stage thus allows an improved pre-impregnation compared with the methods of the prior art.
  • compression roll means that the wicking bit rests partially or completely on the surface of said compression roller, which induces the development of said wick.
  • said at least one compression roller is of cylindrical shape and the percentage of expansion of said wick or said wicks between the inlet and the output of the tank of said fluidized bed is from 1% to 1000%, preferably from 100% to 800%, preferably from 200% to 800%, preferably from 400% to 800%.
  • the percentage of bloom is equal to the ratio of the final width of the lock to the initial width of the lock multiplied by 100.
  • the diameter of said at least one compression roller is from 3 mm to 500 mm, preferably from 10 mm to 100 mm, in particular from 20 mm to 60 mm.
  • the compression roller is cylindrical and not grooved and in particular is metallic.
  • the starting piece ( ⁇ ') is at least one compression roll
  • a single compression roll is present in the fluidized bed and said pre-impregnation is carried out at the angle ⁇ formed by said wick or wicks between the inlet of said compression roller and the vertical tangent to said compression roller.
  • the angle ⁇ formed by said wick or said wicks between the inlet of said compression roller and the vertical tangent to said compression roller allows the formation of an area in which the powder will concentrate thus leading to a "wedge effect" which with the simultaneous development of the wick by said compression roller allows a pre-impregnation over a larger width of the wick and therefore improved pre-impregnation compared to techniques of the improved prior art.
  • the angle ⁇ is from 0 to 89 °, preferably 5 ° to 85 °, preferably from 5 ° to 45 °, preferably from 5 ° to 30 °.
  • an angle ⁇ of 0 to 5 ° is likely to generate risks of mechanical stress, which will lead to breakage of the fibers and an angle ⁇ of 85 ° to 89 ° does not create enough mechanical stress for create the "corner effect".
  • a value of the angle ai equal to 0 ° therefore corresponds to a vertical fiber. It is obvious that the height of the cylindrical compression roller is adjustable thus allowing to position the fiber vertically.
  • the inlet edge of the vessel (23a) is equipped with a roller, in particular a cylindrical and rotating roller, on which said wick or said wicks runs, thus leading to a prior development.
  • the angle ⁇ 1 is as defined above.
  • the inlet edge of the tank (23a) is equipped with a roller, in particular a cylindrical and rotary roller, on which said wick or said wicks runs, thus leading to a development prior to the pre-impregnation.
  • the blooming is initiated at the entrance edge of the tank (23a) and continues at the said one or more of the aforementioned ( ⁇ ') jams.
  • one or more embellishments (E ") are present upstream of the vessel comprising the fluidized bed at which the blooming is initiated.
  • the cracks (E") are as defined for ( ⁇ ). ').
  • the blooming is initiated at the level of the aforementioned jam (E ") above and possibly continues at the level of the inlet edge of the tank of the tank and then at the level of the said ( ⁇ ') ci above defined.
  • the percentage of development of said wick or said wicks between the entry of the jams (E ") and the outlet of the tank of said fluidized bed is comprised from 1% to 1000%, preferably from 100% to 800%, preferably from 200% to 800%, preferably 400% to 800%.
  • two, three or more rollers may be present in the fluidized bed.
  • the volume diameter D90 of the thermoplastic polymer powder particles is 30 to 500 ⁇ , advantageously 80 to 300 ⁇ .
  • the volume diameter D10 of the thermoplastic polymer powder particles is from 5 to 200 ⁇ , advantageously from 15 to 100 ⁇ .
  • the volume diameter of the thermoplastic polymer powder particles is included in the D90 / D10 ratio, ie between 1.5 and 50, advantageously between 2 and 10.
  • the average diameter D50 by volume of the thermoplastic polymer powder particles is between 10 and 300 ⁇ , in particular from 30 to 200 ⁇ , more particularly from 45 to 200 ⁇ " ⁇ .
  • the step of pre-impregnating the fibrous material may also be carried out by passing one or more wicks in a continuous projection pre-impregnation device, comprising a vessel, comprising one or more nozzles or one or more gun (s) projecting the reactive prepolymer powder, optionally with a chain extender, on the fibrous material at the roll inlet.
  • a continuous projection pre-impregnation device comprising a vessel, comprising one or more nozzles or one or more gun (s) projecting the reactive prepolymer powder, optionally with a chain extender, on the fibrous material at the roll inlet.
  • the reactive prepolymer powder is thrown into the tank by means of nozzle (s) or gun (s) at the part of the binder including the compression roller (input) on said fibrous material.
  • the wick or wicks are circulated in this tank.
  • two, three or more rollers may be present each provided with a pistol.
  • the pre-impregnation step can therefore be carried out by any means provided or not with at least one docking ( ⁇ ').
  • the presence of the docking allows the development of the wick and promotes pre-impregnation.
  • the presence of this docking is not essential from the moment when a heating system provided with at least one docking piece (E) is present after the pre-impregnation stage.
  • the term "docking piece (E)" means any system on which the wick has the ability to scroll.
  • the docking piece (E) can have any shape from the moment the wick can scroll on. It can be fixed or rotating.
  • the heating system is any system that emits heat or emits radiation that can heat the mating part (E) and the wick pre-impregnated with resin.
  • It can be an infra-red heating, a UV lamp, a convection heating.
  • the engaging piece (E) is therefore conductive or absorbs radiation emitted by heat.
  • heat-conducting bartack (E) means that the bartack (E) is made of a material capable of absorbing and conducting heat. It can also be a heating system by microwave or laser.
  • the docking piece is non-conductive of heat or does not absorb the radiation emitted by heat.
  • non-heat-conductive (E) -center means that the bartack (E) is made of a material incapable of absorbing and conducting heat.
  • Said at least one docking piece (E) is located or included in the environment of the heating system, that is to say, it is not outside the heating system.
  • said heating system overcomes said at least one mating piece (E).
  • the heating system is at a height sufficient for the deduction of at least one prepolymer and optionally the chain extender present on the wick to melt but without degrading said prepolymer and optionally the chain extender. Nevertheless, said heating system comprises either only said at least one mating piece (E) but may also comprise a portion of the wick, outside said mooring system (E), said wick portion being located before and / or after said docking system (E).
  • FIG. 4 A representation of a heating system and three mishaps (E), corresponding to R'i, R'2 and R'3, is shown in Figure 4, without being limited in any way to it.
  • the height between the heating system and the interferences is from 1 to 100 cm, preferably from 2 to 30 cm, in particular from 2 to 10 cm.
  • the heating system shown in Figure 4 is a horizontal system. However, the heating system (s) can be arranged vertically with also vertical scrolling of the wick through the jams.
  • the speed of travel of the wick at the level of the heating system is sufficient for said prepolymer and optionally the chain extender to melt and optionally to partially polymerize but without causing the complete polymerization of the prepolymers or the prepolymer with extender. chain.
  • this heating step makes it possible to complete the impregnation of the wick carried out beforehand during the pre-impregnation stage and in particular to obtain a homogeneous and thorough impregnation without causing the complete polymerization which would lead to the final thermoplastic polymer . .
  • a first blooming occurs during this step, in particular if the pre-impregnation step is carried out with the use of sparing pieces ( ⁇ '). , such as in a fluidized bed with at least one docking as described above.
  • a first development of the wick occurs at the level of said compression rollers corresponding to the "wedge effect" ( ⁇ ') with the "corner effect” due to the partial or total movement of said wick on said piece (s) of ( ⁇ ') and a second expansion occurs during the heating step, at said compression rollers corresponding to the parts of the boot (E) due to the partial or total movement of said wick on said part ( s) (E).
  • This second expansion is preceded during the passage of the wick in the heating system, before its partial or total scrolling on the said room (s) of docking (E), a retraction of the wick due to the merger polymer on said wick.
  • This second expansion combined with the melting of said polymer matrix by the heating system and the retraction of the wick make it possible to homogenise the pre-impregnation and thus finalize the impregnation and thus to have an impregnation at heart and to have a high level of fibers by volume, especially constant in at least 70% of the volume of the band or ribbon, in particular in at least 80% of the volume of the band or ribbon, in particular in at least 90% of the volume of the band or ribbon, more particularly in at least 95% of the volume of the tape or ribbon, as well as to decrease the porosity.
  • the development is a function of the fibrous material used. For example, the blooming of a carbon fiber material is much greater than that of a flax fiber.
  • the development is also a function of the number of fibers in the wick, their average diameter and their cohesion by the size.
  • the percentage of expansion during the heating step between the inlet of the first compression roller R'i and the outlet of the third compression roller R'3 is approximately 20 to 150%, in particular 50 at 75%.
  • the tape After passing the tape through the first heating system, the tape retracts.
  • the various bloomings during the heating step combined with the melting of the thermoplastic polymer and the shrinkage of the wick during said heating step make it possible to obtain a fiber content impregnated after the heating step of 45% to 45%. 64% by volume, preferably 50 to 60% by volume, in particular 54 to 60% by volume (rate of fibers which can not be attained by standard melting techniques), the fiber content by volume and the distribution of the fibers being substantially identical on average on both sides of the median plane of the fibrous material over the entire length of said fibrous material, thus leading in particular to the production of a fibrous material, in particular a monolayer material.
  • the porosity rate in said impregnated fibrous material is less than 10%, especially less than 5%, in particular less than 2%.
  • Step of formatting a step of shaping the wick or said parallel locks of said impregnated fibrous material is performed.
  • a calendering system as described in WO 2015/121583 may be used.
  • the present invention relates to the use of an impregnated fibrous material, as defined above, for the preparation of an impregnated fibrous material comprising a fibrous material made of continuous fibers and at least one non-reactive thermoplastic polymer of which the number-average molecular mass Mn is greater than 10,000, preferably in a range from 10,000 to 40,000, preferably from 12,000 to 30,000.
  • melt viscosity is greater than 100 Pa.s, especially greater than 200 Pa.s, preferably> 400 Pa.s and more preferably> 600 Pa.s.
  • preparation of said impregnated fibrous material comprising a fibrous material made of continuous fibers and at least one non-reactive thermoplastic polymer is carried out by heating allowing the polymerization of said reactive thermoplastic prepolymer.
  • the present invention relates to the use of an impregnated fibrous material, as defined above, for the preparation of calibrated ribbons suitable for the manufacture of three-dimensional composite parts, by automatic removal of said ribbons by means of of a robot.
  • the present invention relates to a ribbon comprising at least one fibrous material as defined above.
  • said ribbon is a single unidirectional ribbon or a plurality of unidirectional parallel ribbons.
  • said ribbon has a width (I) and a thickness (ep) adapted for robot removal in the manufacture of parts in three dimensions, without the need for slitting, and preferably at a width (I) of at least 5 mm. and up to 400mm, preferably between 5 and 50mm and even more preferably between 5 and 20mm.
  • the thermoplastic prepolymer of said tape is a polyamide chosen from, in particular, an aliphatic polyamide such as PA 6, PA 1 1, PA 12, PA 66, PA 46, PA 610, PA 612, PA 1010, PA 1012, PA 1 1 / 1010 or PA 12/1010 or a semi-aromatic polyamide such as PA MXD6 and PA MXD10 or selected from PA 6 / 6T, PA 6I / 6T, PA 66 / 6T, PA 1 1 / 10T, PA 1 1 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T, PA BACT / 6T, PA BACT / 10T and PA BACT / 10T / 6T, PEEK, PEKK and PEI or a mixture thereof.
  • an aliphatic polyamide such as PA 6, PA 1 1, PA 12, PA 66, PA 46, PA 610, PA 612, PA 1010, PA 1012, PA 1 1 / 1010 or PA 12/10
  • PA 6 is chosen from, in particular, an aliphatic polyamide such as PA 6, PA 11, PA 12, PA 1 1/1010 or PA 12/1010 or a semi-aromatic polyamide such as PA MXD6.
  • PA MXD10 or selected from PA 6 / 6T, PA 6I / 6T, PA 66 / 6T, PA 1 1 / 10T, PA 1 1 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T and PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T.
  • the present invention relates to the use of a ribbon as defined above, in the manufacture of composite parts in three dimensions.
  • Said fibrous material impregnated with a prepolymer as defined above may be used for thermo stamping, for example, by preforming by flat by robotic deposition of tape impregnated with a prepolymer and then preheating said impregnated tape to perform the recovery in viscosity at the molten state and therefore the increase in number average molecular weight and then transfer ribbon impregnated with non-reactive thermoplastic final polymer in a mold allowing a cycle time of about 1 min and a much lower energy cost.
  • said manufacture of said composite parts relates to the fields of transport, in particular automobile, oil and gas, in particular offshore, gas storage, aeronautical, nautical, railway; renewable energy, in particular wind turbine, tidal turbine, energy storage devices, solar panels; thermal protection panels; sports and recreation, health and medical and electronics.
  • the present invention relates to a three-dimensional composite part characterized in that it results from the use of at least one unidirectional tape of fibrous material impregnated as defined above.
  • the fibrous material is chosen from carbon fiber and glass fiber tows.
  • the thermoplastic prepolymer used for impregnating the carbon fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, a PA BACT / 10T / 6T, an MXD6 PA and an MXD10 PA, a PEKK and an PEI or a mixture thereof.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • a semi-aromatic polyamide in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT /
  • the thermoplastic prepolymer used for impregnating the glass fiber is chosen from a polyamide, in particular an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, a PA BACT / 10T / 6T, an MXD6 PA and an MXD10 PA, a PEKK and an PEI or a mixture thereof.
  • a polyamide in particular an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • a semi-aromatic polyamide in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT
  • the fibrous material comprises strands of carbon fiber and the thermoplastic prepolymer used to impregnate the carbon fiber is chosen from a polyamide, in particular an aliphatic polyamide such as PA 1 1, PA 12, PA, PA 1 1/1010 and PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, a PA BACT / 10T / 6T, an PA MXD6 and an PA MXD10, a PEKK and a PEI or a mixture of these.
  • a polyamide in particular an aliphatic polyamide such as PA 1 1, PA 12, PA, PA 1 1/1010 and PA 12/1010
  • a semi-aromatic polyamide in particular a PA 1 1 / 10T, a PA 1 1 / 6T
  • the fibrous material consists of carbon fiber locks and the thermoplastic prepolymer used for impregnating the carbon fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • a semi-aromatic polyamide in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA M
  • the fibrous material comprises glass fiber strands and the thermoplastic prepolymer used for impregnating the glass fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, PA 1 1/1010 and a PA 12/1010
  • a semi-aromatic polyamide in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT /
  • the fibrous material consists of glass fiber strands and the thermoplastic prepolymer used for impregnating the glass fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, PA 1 1/1010 and a PA 12/1010
  • a semi-aromatic polyamide in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT
  • the fibrous material comprises strands of carbon fiber and the thermoplastic prepolymer used for impregnating the carbon fiber is chosen from a polyamide, in particular an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 80 ° C or Tf is ⁇ 150 ° C .
  • a polyamide in particular an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • the fibrous material consists of carbon fiber locks and the thermoplastic prepolymer used to impregnate the carbon fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, or a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, one PA MXDT / 10T, one PA MPMDT / 10T, one PA BACT / 10T, one PA BACT / 6T, one PA BACT / 10T / 6T, one PA MXD6 and one PA MXD10, one PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 80 ° C or Tf is ⁇ 150 ° C.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, or a semi-aromatic poly
  • the fibrous material comprises strands of carbon fiber and the thermoplastic prepolymer used for impregnating the carbon fiber is chosen from a polyamide, in particular an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 100 ° C or Tf is ⁇ 150 ° C .
  • a polyamide in particular an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • the fibrous material consists of carbon fiber locks and the thermoplastic prepolymer used to impregnate the carbon fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 100 ° C or Tf is ⁇ 150 ° C.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • a semi-aromatic polyamide
  • the fibrous material comprises strands of carbon fiber and the thermoplastic prepolymer used for impregnating the carbon fiber is chosen from a polyamide, in particular an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 120 ° C or Tf is ⁇ 150 ° C .
  • a polyamide in particular an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • the fibrous material consists of carbon fiber locks and the thermoplastic prepolymer used to impregnate the carbon fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 120 ° C or Tf is ⁇ 150 ° C .
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, PA 1 1/1010 and a PA 12/1010
  • a semi-aromatic polyamide in particular
  • the fibrous material comprises strands of carbon fiber and the thermoplastic prepolymer used for impregnating the carbon fiber is chosen from a polyamide, in particular an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, a PA BACT / 10T / 6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer ⁇ 140 ° C or Tf is ⁇ 150 ° C.
  • a polyamide in particular an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • the fibrous material consists of carbon fiber locks and the thermoplastic prepolymer used for impregnating the carbon fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof and Tg of said thermoplastic prepolymer ⁇ 140 ° C or Tf is ⁇ 150 ° C .
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • a semi-aromatic polyamide in particular
  • the fibrous material comprises strands of fiberglass fiber and the thermoplastic prepolymer used for impregnating the glass fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12 and a PA 1 1/1010 , a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 80 ° C or Tf is ⁇ 150 ° C.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12 and a PA 1 1/1010 , a PA 12/1010, a semi-ar
  • the fibrous material consists of fiberglass fiber tows and the thermoplastic prepolymer used to impregnate the glass fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1 / 1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a BACT / 6T PA, a BACT / 10T / 6T PA, an MXD6 PA and an MXD10 PA, a PEKK and a PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 80 ° C or the Tf is ⁇ 150 ° C.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1 / 1010 and a
  • the fibrous material comprises strands of fiberglass fiber and the thermoplastic prepolymer used for impregnating the glass fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 100 ° C or Tf is ⁇ 150 ° C.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • a semi-aromatic polyamide in
  • the fibrous material consists of fiberglass fiber tows and the thermoplastic prepolymer used to impregnate the glass fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1 / 1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a BACT / 6T PA, a BACT / 10T / 6T PA, an MXD6 PA and an MXD10 PA, a PEKK and a PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 100 ° C or the Tf is ⁇ 150 ° C.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1 / 1010 and a
  • the fibrous material comprises strands of fiberglass fiber and the thermoplastic prepolymer used for impregnating the glass fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 120 ° C or Tf is ⁇ 150 ° C.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • a semi-aromatic polyamide in
  • the fibrous material consists of fiberglass fiber tows and the thermoplastic prepolymer used to impregnate the glass fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1 / 1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a BACT / 6T PA, a BACT / 10T / 6T PA, an MXD6 PA and an MXD10 PA, a PEKK and a PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 120 ° C where the Tf is ⁇ 150 ° C.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1 / 1010 and a
  • the fibrous material comprises strands of fiberglass fiber and the thermoplastic prepolymer used for impregnating the glass fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, PA PA MXD6 and PA MXD10, PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 140 ° C or Tf is ⁇ 150 ° C.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1/1010 and a PA 12/1010
  • the fibrous material consists of fiberglass fiber tows and the thermoplastic prepolymer used to impregnate the glass fiber is chosen from a polyamide, especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1 / 1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, or PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T, PEKK and PEI or a mixture thereof and the Tg of said thermoplastic prepolymer is ⁇ 140 ° C or Tf is ⁇ 150 ° C.
  • a polyamide especially an aliphatic polyamide such as PA 1 1, PA 12, a PA 1 1 / 1010 and a PA 12/1010
  • a semi-aromatic polyamide in particular a PA 1 1 /
  • the fibrous material comprises strands of glass fibers or of carbon fibers as defined above and the thermoplastic prepolymer used for impregnating the fiber is chosen from an aliphatic polyamide such as PA 1 1, PA 12, PA 1 1/1010 and a PA 12/1010, a semi-aromatic polyamide, in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, or PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T and the Tg and Tf of said thermoplastic prepolymer are as defined above.
  • an aliphatic polyamide such as PA 1 1, PA 12, PA 1 1/1010 and a PA 12/1010
  • a semi-aromatic polyamide in particular a PA 1 1 / 10T, a PA 1 1 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT
  • FIG. 1 details a tank (10) comprising a fluidized bed (12) with a height-adjustable bartack (22).
  • the edge of the tank inlet is equipped with a rotating roller 23a on which the wick 21a runs and the edge of the tank outlet is equipped with a rotary roller 23b on which the wick 21b runs.
  • Fig. 2 shows a single-roll embodiment with a vessel (10) comprising a fluidized bed (12) in which a single cylindrical compression roll (24) is present and showing the angle CM.
  • the arrows at the fiber indicate the direction of travel of the fiber.
  • Fig. 3 shows a single-pressurized embodiment with a tub (30) including a powder spraying gun (31) in which a single cylindrical compression roll (33) is present and showing the angle ⁇ ' ⁇ .
  • the arrows at the fiber indicate the direction of travel of the fiber.
  • Figure 4 shows a diagram of a three-roll heating system.
  • the diameter of a fiber is 7 ⁇ .
  • FIG. 6 shows a scanning electron microscope image of a sectional view of a 1/4 "Toray, 12K T700S 31 E carbon fiber wick impregnated with a two-function MPMDT / 10T reactive prepolymer powder. co-reactants NH2 and CO2H with a Tg 125 ° C of Mn 5100 and then polymerization with a heating system.
  • the diameter of a fiber is 7 ⁇ .
  • Example 1 Procedure comprising a step of pre-impregnating a fibrous material (carbon fiber) with a non-reactive polyamide powder in a fluidized bed with a single roller preceded by jams upstream of the tank and a heating step by Infra Red (Comparative example)
  • the rolls are 54 cm apart (distance between the first and the last roll)
  • the fibrous material (1 ⁇ 4 "carbon fiber wick) was pre-impregnated with a MPMDT / 10T polyamide of particle size defined above according to the following procedure:
  • the heating system used is that described in Figure 1 but with eight cylindrical rollers R'i to R's fixed diameter 8 mm.
  • the speed of advancement of the wick is 10 m / min
  • the infrared used has a power of 25 kW, the height between the infrared and the upper roller is 4 cm and the height between the infrared and the lower rollers is 9 cm.
  • the angles ⁇ to ⁇ are identical and 25 °.
  • the height h is 20 mm
  • the length I is 1000 mm
  • the eight rolls are each 43 mm apart. Calender using two series-mounted calender fitted with IR of 1 kW each after the heating step.
  • Figure 5 shows the impregnated fibrous material obtained with MPMDT / 10T.
  • Example 2 Procedure comprising a step of pre-impregnating a fibrous material (carbon fiber) with a prepolymer powder MPMDT / 10T reactive fluidized bed with a single roller preceded by jams upstream of the tank and a step Infra Red heating system according to the invention
  • Example 2 The same procedure as for Example 1 was carried out using an MPMDT / 10T prepolymer bearing two co-reactive functions NH2 and CO2H with Tg 125 ° C and Mn 5100.
  • the Mn of the MPMDT / 10T after passing under the heating system is 16000.
  • Figure 6 shows the fibrous material impregnated with MPMDT / 10T prepolymer obtained. This demonstrates the effectiveness of the impregnation process with a reactive prepolymer powder carrying two co-reactive functions NH2 and CO2H and then polymerization with an infrared heating system.
  • Example 3 Determination of the porosity ratio the relative difference between theoretical density and experimental density (general method)
  • thermoplastic matrix The density of the thermoplastic matrix
  • the weight of the reinforcement is the weight of the reinforcement:
  • the number of samples must be at least 30 for the result to be representative of the studied material.
  • the measurement of the fiber content is determined according to ISO 1172: 1999 or by thermogravimetric analysis (TGA) as determined for example in B. Benzler, Ap extensionsslabor, Mettler Toledo, Giesen, UserCom 1/2001.
  • TGA thermogravimetric analysis
  • the measurement of the carbon fiber content can be determined according to ISO 14127: 2008.
  • the porosity is then the relative difference between theoretical density and experimental density.

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EP18733251.5A 2017-06-22 2018-06-21 Materiau fibreux impregne de prepolymere thermoplastique reactif Pending EP3642267A1 (fr)

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CN109910329B (zh) * 2019-03-26 2021-01-08 中国人民解放军国防科技大学 一种基于弱浸渍预浸料的碳纳米管层间增强树脂基层合复合材料及其制备方法
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FR3017320B1 (fr) * 2014-02-13 2016-07-22 Arkema France Procede de preparation d'un materiau fibreux pre-impregne par polymere thermoplastique a l'aide d'un gaz supercritique
FR3017329B1 (fr) 2014-02-13 2016-07-29 Arkema France Procede de fabrication d'un materiau fibreux pre-impregne de polymere thermoplastique en lit fluidise
FR3019826B1 (fr) * 2014-04-15 2017-10-20 Arkema France Composition thermoplastique a base de polyamide polymere issu d'un prepolymere et d'un allongeur de chaine et procede de fabrication
FR3019825B1 (fr) * 2014-04-15 2017-10-27 Arkema France Materiau composite thermoplastique a base de polyamide semi-cristallin et procede de fabrication
FR3019822B1 (fr) * 2014-04-15 2017-10-20 Arkema France Procede de fabrication d'un materiau thermoplastique a base de polyamide semi-cristallin
FR3037962B1 (fr) * 2015-06-24 2019-11-29 Arkema France Procede en moule ouvert pour un materiau composite de matrice en polyamide semi-cristallin renforce fibres a partir de composition precurseur reactive de prepolymere
FR3039554B1 (fr) * 2015-07-29 2018-12-07 Arkema France Procede pour materiau fibreux pre-impregne par un polymere thermoplastique a l'aide d'un polymere a cristaux liquides
US10982041B2 (en) * 2016-02-25 2021-04-20 Swancor Advanced Materials Co., Ltd. Epoxy resin oligomer

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KR102330131B1 (ko) 2021-11-22
WO2018234441A1 (fr) 2018-12-27
JP7041694B2 (ja) 2022-03-24
KR20200020847A (ko) 2020-02-26
FR3067969A1 (fr) 2018-12-28
FR3067969B1 (fr) 2022-08-12
CN110785455A (zh) 2020-02-11
JP2020524616A (ja) 2020-08-20

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