EP3237505A1 - Method for impregnating a fibrous substrate with a (meth)acrylic mixture, composition of said (meth)acrylic mixture, and composite material produced after polymerisation of said (meth)acrylic mixture - Google Patents

Method for impregnating a fibrous substrate with a (meth)acrylic mixture, composition of said (meth)acrylic mixture, and composite material produced after polymerisation of said (meth)acrylic mixture

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Publication number
EP3237505A1
EP3237505A1 EP15828360.6A EP15828360A EP3237505A1 EP 3237505 A1 EP3237505 A1 EP 3237505A1 EP 15828360 A EP15828360 A EP 15828360A EP 3237505 A1 EP3237505 A1 EP 3237505A1
Authority
EP
European Patent Office
Prior art keywords
meth
acrylic
μιτι
weight
mixture
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.)
Withdrawn
Application number
EP15828360.6A
Other languages
German (de)
French (fr)
Inventor
Pierre Gerard
Gilles Francois
Sébastien TAILLEMITE
Mélanie LAFARGE
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 EP3237505A1 publication Critical patent/EP3237505A1/en
Withdrawn legal-status Critical Current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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/285—Acrylic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical
    • 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
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • the invention relates to a process for impregnating a fibrous substrate, a liquid polymer-based resin composition for carrying out said impregnation method, and the impregnated substrate obtained by implementing said method. impregnation.
  • the invention relates to an industrial process for impregnating a fibrous substrate with a viscous liquid mixture based on methacrylic or acrylic components.
  • a method makes it possible in particular to obtain three-dimensional parts, for example parts or sets of mechanical parts, used in various fields such as aeronautics, automotive, or rail transport, construction.
  • a composite material is an assembly of at least two immiscible components. A synergistic effect is obtained by such an assembly, so that the composite material obtained has particular mechanical and / or thermal properties that each of the initial components does not have or has but to a lesser degree relative to the composite material.
  • a composite material is constituted by at least one reinforcing material giving said composite material good mechanical properties, including good resistance to efforts. mechanical forces experienced by the composite material, and by a matrix material forming a continuous phase and ensuring the cohesion of said composite material.
  • the matrix material is generally a polymer. This polymer may be either a thermosetting polymer or a thermoplastic polymer.
  • the preparation of the composite material is carried out by a mixture of the matrix material and the reinforcing material, or by wetting or impregnation of the reinforcing material with the matrix material, and then by polymerization of the obtained system.
  • said reinforcement may consist of reinforcing fillers such as gravel, sand, or glass beads.
  • said reinforcement may consist of fibers of variable dimensions.
  • the polymer matrix generally comprises a polymerization initiator in order to polymerize the polymer matrix impregnating the reinforcing material.
  • This polymerization initiator is often in solid form, and therefore has the disadvantage of forming a solid deposit in the polymer matrix by decantation.
  • the matrix is therefore highly heterogeneous and the subsequent polymerization, thus taking place in a heterogeneous medium, does not make it possible to obtain composite materials having good mechanical properties.
  • an initiator in solid form can cause obstruction of the supply lines of an injection machine used to synthesize the composite material, thus causing its blocking or even breaking.
  • a first solution may consist in solubilizing the initiator in a solvent such as acetone, ethanol, or a phthalate, but this generates high costs and the presence of an organic solvent is not desirable. in the methods of manufacturing such composite materials.
  • the level of solvent required to solubilize the initiator is generally too high and incompatible with the ratio of (meth) acrylic syrup initiator system of machines. This is particularly the case with benzoyl peroxide (BPO) for which the ratio of syrup (meth) acrylic / sum of the syrup (meth) acrylic and initiator system must be less than or equal to 5%. possible
  • liquid initiator An alternative solution is to use a liquid initiator.
  • the kinetics of the reactions implemented in the manufacturing processes of such composite materials is then significantly lower than in the case of the use of a solid initiator, despite the presence of a polymerization accelerator.
  • liquid initiators liquid peroxides are commonly used.
  • Another disadvantage inherent in the use of liquid initiators, such as liquid peroxides, is the fact that they can not be used in a two-component system, the first component being the syrup.
  • (meth) acrylic and the second component is the initiator system, since the accelerator is stable in neither of the two components.
  • US 5,162,280 describes the production of an aqueous dispersion of aromatic diacylperoxide, said aromatic diacylperoxide being a polymerization initiator.
  • This aqueous dispersion comprises, in addition to an aromatic diacylperoxide, a diluent consisting of an alkylene glycol, and two suspending agents consisting respectively of magnesium aluminum silicate and a water-soluble cellulosic ether.
  • this document proposes a dispersion comprising an initiator of aromatic diacylperoxide type in liquid form.
  • this document does not describe the use of such a suspension for the manufacture of polymer-based composite materials.
  • WO2010 / 112534 discloses an aqueous dispersion comprising from 35% to 45% by weight of solid diacyl peroxide whose particles have a median diameter D50 between ⁇ and ⁇ .
  • the aqueous dispersion also comprises from 0.05% to 1% of dispersant, as well as less than 1% of organic solvent.
  • the document WO2014 / 135816 describes a process for impregnating a fibrous substrate with a (meth) acrylic syrup comprising a (meth) acrylic polymer, a (meth) acrylic monomer, and fillers chosen from particles having a swelling rate in the monomer (meth) acrylic less than 200%, and whose average diameter D50 is less than 50 ⁇ .
  • the polymerization of the syrup is carried out by adding an initiator of which only the benzoyl peroxide under a weakly moist powder is described.
  • This initiator is solid and is in the form of BPO powder and not an aqueous dispersion of organic peroxide, in particular BPO.
  • the invention therefore aims to overcome the disadvantages of the prior art by proposing a parts manufacturing process or sets of parts based on polymeric composite material that can be implemented on machines commonly used for molding said parts and / or said sets of parts based on polymeric composite material, without causing blockage or malfunction of such machines.
  • the invention also aims at a process for impregnating a fibrous substrate with a (meth) acrylic mixture comprising a (meth) acrylic syrup and an aqueous dispersion of a radical initiator consisting of an organic peroxide, said mixture being capable of being implemented on machines commonly used for molding said parts and / or sets of parts based on polymeric composite material, without causing blockage or malfunction of such machines.
  • the invention also aims to provide parts obtained by the process also having good mechanical properties.
  • the subject of the invention is a process for impregnating a fibrous substrate, preferably consisting of long fibers, said process being mainly characterized in that it comprises a step of impregnating said fibrous substrate with a liquid (meth) acrylic mixture comprising:
  • a (meth) acrylic syrup comprising at least one (meth) acrylic polymer, and at least one (meth) acrylic monomer, an aqueous dispersion comprising at least one radical initiator consisting of an organic peroxide to start the polymerization of the (meth) monomer acrylic, said at least one radical initiator having a particle size such that the median diameter of the particles by volume (D50) is between 1 ⁇ and 30 ⁇ , preferably between 2 ⁇ and 25 ⁇ , even more preferably between 3.5 ⁇ and 20 ⁇ , advantageously between 3.5 ⁇ and 15 ⁇ , more preferably between 3.5 ⁇ and 13 ⁇ is even more advantageously between 3, 5 ⁇ and 12 ⁇ .
  • D50 median diameter of the particles by volume
  • the impregnation step of the fibrous substrate is carried out in a closed mold
  • the radical initiator is chosen from diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals or azo compounds,
  • the radical initiator consists of benzoyl peroxide (BPO),
  • the radical initiator content relative to the (meth) acrylic monomer or to the mixture of (meth) acrylic monomers is between 100 and 50,000 ppm by weight, preferably between 200 and 40,000 ppm by weight and advantageously between 300 and 30,000. ppm by weight,
  • the weight percentage of radical initiator in the aqueous dispersion is between 30% and 80%, preferably between 35% and 70%, and even more preferably between 35% and 60%,
  • the mass percentage of radical initiator in the (meth) acrylic mixture is less than 5%, preferably less than 3%, and even more preferably less than 2.5%,
  • the mass percentage of radical initiator in the (meth) acrylic mixture is greater than 0.2%, preferably greater than 0.4%, and even more preferably greater than 0.5%,
  • the aqueous dispersion of radical initiator has a viscosity at 20 ° C of between 50 mPa * s and 1000 mPa * s, preferably between 100 mPa * s and 750 mPa * s, and even more preferably between 200 mPa * s and 500 mPa * s,
  • the radical initiator has a particle size such that the diameter D10 of the particles by volume is less than 20 ⁇ , preferably less than 15 ⁇ and even more preferably less than ⁇ ,
  • the aqueous dispersion of radical initiator preferably comprises an emulsifying agent
  • the aqueous dispersion of radical initiator preferably comprises a stabilizer
  • the liquid (meth) acrylic syrup has a dynamic viscosity of between 10 mPa * s and 10 000 mPa * s, preferably between 50 mPa * s and 5000 mPa * s and advantageously between 100 mPa * s and 1000 mPa * s, the dynamic viscosity being measured at 25 ° C,
  • the (meth) acrylic polymer is a homopolymer of methyl methacrylate (MMA) or a copolymer of methyl methacrylate (MMA) or a mixture thereof,
  • the methyl methacrylate (MMA) copolymer comprises at least 70%, preferably at least 80%, advantageously at least 90% and more preferably at least 95% by weight of methyl methacrylate (MMA),
  • the methyl methacrylate (MMA) copolymer comprises from 80% to 99.7%, preferably from 90% to 99.7% and more preferably from 90% to 99.5% by weight of methyl methacrylate and 0.3% by weight of methacrylate. % to 20%, advantageously from 0.3% to 10% and more preferably from 0.5% to 10% by weight of at least one monomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate,
  • the (meth) acrylic polymer in the liquid (meth) acrylic mixture is present at least 10% by weight, preferably at least 15%, advantageously at least 18% and more preferably at least 20% by weight of the total (meth) acrylic liquid mixture,
  • the (meth) acrylic polymer in the liquid (meth) acrylic mixture is present at most 60% by weight, preferably at most 50%, advantageously at most 40% and more preferably at most 35% by weight of the total (meth) acrylic liquid mixture,
  • the (meth) acrylic monomer is selected from acrylic acid, methacrylic acid, acrylic monomers alkyl, methacrylic alkyl monomers and mixtures thereof, the alkyl group may be linear, branched or cyclic and containing 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms,
  • the (meth) acrylic monomer is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid and n-butyl acrylate. , isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and mixtures thereof,
  • the (meth) acrylic monomer is selected from methyl methacrylate, isobornyl acrylate, acrylic acid and mixtures thereof.
  • 50% by weight of the (meth) acrylic monomer or (meth) acrylic monomers is methyl methacrylate
  • the (meth) acrylic syrup further comprises at least one filler and / or at least one additive such as impact modifiers or block copolymers, thermal stabilizers, UV stabilizers, flame retardants, lubricants, mold release agents, colorants, or mixtures thereof,
  • the additives are selected from impact modifiers or block copolymers, thermal stabilizers, UV stabilizers, flame retardants, lubricants, mold release agents, colorants, or mixtures thereof, and are present in the blend.
  • the fillers are selected from calcium carbonate (CaCO 3), titanium dioxide (TiO 2), and silica (SiO 2), and are present in the aqueous dispersion at a concentration of between 0.01 wt% and 40 wt% so that the dynamic viscosity of the liquid (meth) acrylic syrup is between 10 mPa * s and 1000 mPa * s.
  • the (meth) acrylic mixture further comprises an activator in the (meth) acrylic syrup,
  • the activator is chosen from tertiary amines such as N, -dimethyl-p-toluidine (DMPT), N, N-dihydroxyethyl-p-toluidine (DHEPT), transition metal catalysts soluble in organic compounds or their mixtures,
  • the content of the activator relative to the (meth) acrylic monomer of the liquid (meth) acrylic syrup is from 100 ppm to 10,000 ppm by weight, preferably from 200 ppm to 7000 ppm, and preferably from 300 ppm to 4000 ppm by weight,
  • the (meth) acrylic mixture comprises between 95% and 99% by weight, preferably between 96% and 98.5% by weight, and even more preferably between 97% and 98% by weight of (meth) acrylic syrup, and between 1% and 5% by weight, preferably between 1.5% and 4% by weight, and even more preferably between 2% and 3% by weight of aqueous dispersion.
  • the invention also relates to a liquid (meth) acrylic mixture for carrying out the process for impregnating a fibrous substrate, said mixture being characterized in that it comprises:
  • a (meth) acrylic syrup comprising at least one (meth) acrylic polymer, and at least one (meth) acrylic monomer, an aqueous dispersion comprising at least one radical initiator consisting of an organic peroxide to start the polymerization of the (meth) monomer acrylic, said at least one radical initiator having a particle size such that the median diameter of the particles by volume (D50) is between 1 ⁇ and 30 ⁇ , preferably between 2 ⁇ and 25 ⁇ . ⁇ and even more preferably between 3.5 ⁇ and 20 ⁇ and advantageously between 3.5 ⁇ and 15 ⁇ .
  • D50 median diameter of the particles by volume
  • the invention also relates to a method for manufacturing mechanical parts or structured elements or articles, said method being characterized in that it comprises the following steps:
  • the method further comprises, prior to step a), a step of preparing the liquid (meth) acrylic mixture by mixing a (meth) acrylic syrup comprising at least one (meth) acrylic polymer, and at least one monomer (meth) acrylic and an aqueous dispersion comprising at least one radical initiator consisting of an organic peroxide to start the polymerization of the (meth) acrylic monomer, said at least one radical initiator having a particle size such that the median diameter of the particles in volume (D50) is between 1 ⁇ and 30 ⁇ , preferably between 2 ⁇ and 25 ⁇ and even more preferably between 3.5 ⁇ and 20 ⁇ and advantageously between 3.5 ⁇ and 15 ⁇ , more preferably between 3 , 5 ⁇ and 13 ⁇ is even more advantageously between 3.5 ⁇ and 12 ⁇ .
  • a step of preparing the liquid (meth) acrylic mixture by mixing a (meth) acrylic syrup comprising at least one (meth) acrylic polymer, and at least one monomer (meth) acrylic and an a
  • step a) The impregnation of the fibrous substrate in step a) is carried out in a closed mold
  • Step a) and step b) are carried out in the same closed mold
  • the process is selected from resin transfer molding or infusion.
  • the invention further relates to a mechanical part or structural composite material obtained by the manufacturing process.
  • Said part can notably be an automobile part, a boat part, a train piece, a sports article, an airplane or helicopter part, a spaceship or rocket part, a photovoltaic module part. , a piece of wind turbine, a piece of furniture, a building or building room, a piece of telephone or cell phone, a computer or television room, a printer or photocopier
  • the method for impregnating a fibrous substrate comprises a step of impregnating said fibrous substrate with a (meth) acrylic mixture in which the mixture comprises:
  • a liquid (meth) acrylic syrup comprising at least one (meth) acrylic polymer, and at least one (meth) acrylic monomer
  • the radical initiator consists of an organic peroxide whose particle size is such that the median diameter of the particles in volume (D50) is between 1 ⁇ and 30 ⁇ , preferably between 2 ⁇ and 25 ⁇ and still more preferred between 3.5 ⁇ and 20 ⁇ and advantageously between 3.5 ⁇ and 15 ⁇ , more preferably between 3.5 ⁇ and 13 ⁇ is even more advantageously between 3.5 ⁇ and 12 ⁇ .
  • (meth) acrylic mixture corresponds to the polymer matrix as described above.
  • (meth) acrylic this mixture comprises is so named because of its liquid and viscous appearance, and can also be called prepolymer because it comprises at least one monomer (Meth) acrylic polymer capable of undergoing polymerization to form a (meth) acrylic polymer.
  • fibrous substrate refers to fabrics, felts or nonwovens which may be in the form of strips, webs, braids, locks or pieces.
  • (meth) acrylic refers to any type of acrylic and methacrylic monomers.
  • polymerization refers to the process of converting a monomer or mixture of monomers into a polymer.
  • composite material refers to a multicomponent material comprising a plurality of different phase domains, of which at least one type of phase domain is a continuous phase and wherein at least one component is a polymer .
  • initiator refers to a chemical species that reacts with a monomer to form an intermediate compound capable of successfully bonding to a large number of other monomers to form a polymeric compound.
  • D50 or “median diameter” refers to the particle diameter that divides the particle distribution of a substance into two parts of equal areas. In the case of the median diameter D 50 by volume, 50% of the total volume of the particles corresponds to the volume of the particles with a diameter of less than D 50, and 50% of the total volume of the particles corresponds to the volume of the particles with a diameter greater than D 50.
  • D10 is understood to mean the particle diameter that divides the particle distribution of a substance into two parts of 10% / 90% ratio areas. In the case of D10 by volume, 10% of the total volume of the particles corresponds to the volume of the particles with a diameter of less than D10, and 90% of the total volume of the particles corresponds to the volume of the particles of diameter greater than D10.
  • the (meth) acrylic polymer may be chosen from alkyl polymethacrylates or alkyl polyacrylates. According to a preferred embodiment, the (meth) acrylic polymer is polymethyl methacrylate (PMMA). It must therefore be understood that polymethyl methacrylate (PMMA) may designate a homopolymer of methyl methacrylate (MMA) or a copolymer of MMA or mixtures thereof.
  • it may be a mixture of at least two MMA homopolymers having a different molecular weight, or a mixture of at least two MMA copolymers having an identical monomer composition and a different molecular weight, or a mixture of at least two MMA copolymers having a different monomer composition. It can also be a mixture of at least one MMA homopolymer and at least one MMA copolymer.
  • the MMA copolymer comprises at least 70%, preferably at least 80%, advantageously at least 90% and more advantageously at least 95% by weight of methyl methacrylate.
  • the MMA copolymer may also comprise from 0.3 to 30% by weight of at least one monomer containing at least one ethylenic unsaturation and being capable of copolymerizing with methyl methacrylate.
  • monomers there may be mentioned in particular: acrylic and methacrylic acids and alkyl (meth) acrylates in which the alkyl group contains from 1 to 12 carbon atoms.
  • the comonomer is an alkyl acrylate wherein the alkyl group contains from 1 to 4 carbon atoms.
  • the methyl methacrylate (MMA) copolymer comprises from 80% to 99.7%, advantageously from 90% to 99.7% and more advantageously from 90% to 99.5% by weight. weight of methyl methacrylate and from 0.3% to 20%, advantageously from 0.3% to 10% and more preferably from 0.5% to 10% by weight of at least one monomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate.
  • the comonomer is selected from methyl acrylate or ethyl acrylate or mixtures thereof.
  • the (meth) acrylic polymer (s) in the liquid (meth) acrylic syrup are present at a level of at least 10% by weight, preferably at least 15%, advantageously at least 18% or more. advantageously at least 20% by weight of the total liquid (meth) acrylic syrup.
  • the (meth) acrylic polymer (s) in the liquid (meth) acrylic syrup are present up to at most 60% by weight, preferably at most 50%, advantageously at most 40% and more. preferably at most 35% by weight of the total liquid (meth) acrylic syrup.
  • the weight average molecular weight of the (meth) acrylic polymer is generally high, and can therefore be greater than 50,000 g / mol, preferably greater than 100,000 g / mol.
  • the weight average molecular weight can be measured by size exclusion chromatography (SEC).
  • the monomer (s) (meth) acrylic (s) included in the (meth) acrylic syrup in addition to the (meth) acrylic polymer may (be) chosen from acrylic acid, the methacrylic acid, acrylic alkyl monomers, alkyl methacrylic monomers and mixtures thereof.
  • the (meth) acrylic monomer is chosen from acrylic acid, methacrylic acid, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof, the alkyl group being linear and branched. or cyclic and containing from 1 to 22 carbon atoms, preferably from 1 to 12 carbon atoms.
  • the (meth) acrylic monomer is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, and the like.
  • the (meth) acrylic monomer is selected from methyl methacrylate, isobornyl acrylate or acrylic acid and mixtures thereof.
  • At least 50% by weight, preferably at least 60% by weight of the (meth) acrylic monomer or (meth) acrylic monomers is methyl methacrylate.
  • % by weight of the (meth) acrylic monomer is a mixture of methyl methacrylate with isobornyl acrylate and / or acrylic acid.
  • the (meth) acrylic monomer or the (meth) acrylic monomers of the liquid (meth) acrylic syrup are present at a level of at least 40% by weight, preferably 50% by weight, advantageously 60% by weight and more preferably 65% by weight of the total liquid (meth) acrylic syrup.
  • a fibrous substrate comprises fabrics, felts or nonwovens which may be in the form of strips, sheets, braids, locks or pieces.
  • the fibrous material can have different shapes and dimensions, one-dimensional, two-dimensional or three-dimensional.
  • a fibrous substrate comprises an assembly of one or more fibers. When the fibers are continued, their assembly forms tissues.
  • the one-dimensional form corresponds to linear fibers.
  • the fibers may be discontinuous or continuous.
  • the fibers may be arranged randomly or in the form of a continuous filament in parallel with each other.
  • a fiber is defined by its length ratio, which is the ratio between the length and diameter of the fiber.
  • the fibers used in the present invention are long fibers or continuous fibers.
  • the fibers have a length ratio of at least 1000, preferably at least 1500, more preferably at least 2000, preferably at least 3000 and most preferably at least 5000. 000.
  • the two-dimensional form corresponds to fibrous mats or non-woven reinforcements or woven rovings or bundles of fibers, which may also be braided.
  • the three-dimensional shape corresponds, for example, to fibrous mats or non-woven reinforcements or bundles of fibers or their mixtures, stacked or folded, an assembly of the two-dimensional form in the third dimension.
  • the origins of the fibrous material may be natural or synthetic.
  • a natural material mention may be made of vegetable fibers, wood fibers, animal fibers or mineral fibers.
  • Natural fibers are, for example, sisal, jute, hemp, flax, cotton, coconut fibers and banana fibers.
  • Animal fibers are for example wool or hair.
  • polymer fibers chosen from thermosetting polymer fibers, thermoplastic polymers or mixtures thereof.
  • the polymeric fibers may consist of polyamide (aliphatic or aromatic), polyester, polyvinyl alcohol, polyolefins, polyurethanes, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins and esters of vinyl.
  • the mineral fibers may also be chosen from glass fibers, especially of type E, R or S2, carbon fibers, boron fibers or silica fibers.
  • the fibrous substrate of the present invention is chosen from vegetable fibers, wood fibers, animal fibers, mineral fibers, synthetic polymer fibers, glass, carbon fibers or their mixtures.
  • the fibrous substrate is chosen from mineral fibers.
  • the (meth) acrylic mixture comprises an aqueous dispersion comprising at least one initiator to start the polymerization of the (meth) acrylic monomer (s) included in the (meth) acrylic syrup in addition to the polymer (s) (s) (meth) acrylic (s).
  • the aqueous dispersion comprising at least one initiator to start the polymerization is not a filler, since the initiator reacts to start the polymerization.
  • initiators or initiator systems that are activated by heat.
  • the heat-activated initiator is preferably a radical initiator.
  • Said radical initiator may be chosen from diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals or azo compounds.
  • the initiator is chosen from isopropyl carbonate, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, per (2- tert-butyl ethylhexanoate),
  • Azobisisobutyronitrile (AIBN), azobisisobutyramide, 2,2'-azobis (2,4-dimethylvaleronitrile) or 4, 4'-azobis (4-cyanopentanoic acid).
  • AIBN Azobisisobutyronitrile
  • azobisisobutyramide 2,2'-azobis (2,4-dimethylvaleronitrile) or 4, 4'-azobis (4-cyanopentanoic acid
  • the initiator is chosen from peroxides containing 2 to 20 carbon atoms. More preferably, the initiator is benzoyl peroxide (BPO).
  • the aqueous dispersion advantageously comprises between 30% and 80%, preferably between 35% and 70%, and even more preferably between 35% and 60% of radical initiator.
  • Such an aqueous dispersion having a high content of organic peroxide contributes to allow optimal and complete polymerization of the (meth) acrylic mixture.
  • the aqueous dispersion advantageously comprises between 0.01% and 10%, preferably between 0.05% and 7%, and even more preferably between 0.1% and 5% of a surfactant.
  • the aqueous dispersion advantageously comprises between 0.01% and 10%, preferably between 0.05% and 7%, and even more preferably between 0.1% and 5% of a stabilizer.
  • the weight percentage of the radical initiator in the (meth) acrylic mixture comprising the (meth) acrylic syrup and the radical initiator dispersion is less than 5%, preferably less than 3%, and even more preferably less than 2.5%.
  • the viscosity of the aqueous dispersion of radical initiator is between 50 mPa * s and 1000 mPa * s, preferably between 100 mPa * s and 750 mPa * s, and even more preferably between 200 mPa * s and 500 mPa * s, said viscosity being measured at 20 ° C at 50 rpm.
  • the viscosity can be measured with a rheometer or viscometer, for example a Brookfield type viscometer such as Brookfield DVII.
  • the particle size of the initiator of the aqueous dispersion is such that the median diameter of the particles by volume
  • (D50) is between 1 ⁇ and 30 ⁇ , preferably between 2 ⁇ and 25 ⁇ and even more preferably between 3.5 ⁇ and 20 ⁇ and advantageously between 3.5 ⁇ and 15 ⁇ , more advantageously between 3, 5 ⁇ and 13 ⁇ is even more advantageously between 3.5 ⁇ and 12 ⁇ .
  • Such a particle size makes it possible to obtain a homogeneous dispersion of the initiator in the water, thus favoring the impregnation of the fibrous substrate with the mixture comprising said dispersion aqueous and (meth) acrylic syrup.
  • the homogeneity of the dispersion also allows an optimal and complete polymerization of the (meth) acrylic syrup subsequent to the impregnation of the fibrous substrate with said (meth) acrylic syrup.
  • Such a polymerization according to the invention leads to high molecular weights, generally greater than 100,000 g / mol, preferably greater than 500,000 g / mol, and even more preferably greater than 1,000,000 g / mol. Such molecular weight values make it possible to obtain a composite material having very good mechanical properties.
  • Such a particle size also makes it possible to obtain an aqueous dispersion of stable radical initiator, so that the initiator is perfectly soluble in said aqueous dispersion and in the (meth) acrylic mixture obtained after mixing the syrup.
  • (meth) acrylic does not obstruct the supply lines of the injection machine used for the implementation of the method of impregnating the fibrous substrate and / or the method of manufacturing mechanical parts or structured elements or of composite material according to the invention, and is also not able to obstruct said supply lines of the injection machine.
  • said (meth) acrylic mixture does not obstruct the injection lines of the injection machine used for the implementation of the process for impregnating the fibrous substrate and / or the method for manufacturing mechanical parts or structured elements or articles of composite material according to the invention, and is also not able to obstruct said injection lines of the injection machine.
  • An advantage of such an aqueous dispersion of radical initiator according to the invention is its good solubilization in the (meth) acrylic syrup, so as to form a homogeneous (meth) acrylic mixture. It is thus possible to use a static mixer for mixing the aqueous dispersion of radical initiator with the (meth) acrylic syrup. It remains of course possible to use other types of mixers suitable for producing such a mixture, such as a mechanical mixer, or a rotating bowl mixer.
  • Another advantage of such an aqueous dispersion of radical initiator according to the invention is to allow homogeneous polymerization of the (meth) acrylic mixture.
  • the polymerization is homogeneous throughout the volume of the mold used for the process for impregnating the fibrous substrate and / or for the process for manufacturing parts made of composite material, thus resulting in the formation of regular pieces having a number of imperfections reduced compared to composite material parts obtained by a manufacturing process different from that described in this document.
  • the (meth) acrylic monomer or the mixture of (meth) acrylic monomers as defined above may optionally be accompanied by an appropriate inhibitor in order to prevent said (meth) acrylic monomer from spontaneously polymerizing.
  • an inhibitor may be incorporated into the (meth) acrylic syrup.
  • Suitable inhibitors include hydroquinone (HQ), methylhydroquinone (MEHQ), 2,6-di-tert-butyl-4-methoxyphenol (Topanol O) and 2,4-dimethyl-6-tert. - Butylphenol (Topanol A).
  • the (meth) acrylic mixture may further comprise an activator for the polymerization, said activator being capable of being incorporated into the (meth) acrylic syrup.
  • the polymerization activator or accelerator is chosen from tertiary amines such as N, -dimethyl-p-toluidine
  • DMPT dihydroxyethyl-p-toluidine
  • DHEPT transition metal catalysts soluble in organic compounds or mixtures thereof.
  • the liquid (meth) acrylic syrup does not contain metal-based catalysts.
  • the content of the activator relative to the (meth) acrylic monomer of the liquid (meth) acrylic syrup is from 100 ppm to 10,000 ppm by weight, preferably from 200 ppm to 7000 ppm and preferably from 300 ppm to 4000 ppm by weight.
  • the (meth) acrylic mixture may also comprise a chain-limiting agent in order to regulate the molecular weight of the polymer (s) formed. It may be, for example, ⁇ -terpinene or terpinolene.
  • the content of the limiting agent is generally between 0 and 500 ppm and preferably between 0 and 100 ppm, relative to the (meth) acrylic monomer or the mixture of (meth) acrylic monomers of the (meth) acrylic syrup.
  • the (meth) acrylic mixture may also comprise other additives and fillers.
  • a filler is not considered an additive in the context of the present invention.
  • Such fillers and additives may be incorporated into the (meth) acrylic syrup.
  • additives and / or fillers may be added to the (meth) acrylic mixture prior to impregnation.
  • additives mention may be made of organic additives such as impact resistance modifiers or block copolymers, thermal stabilizers, UV stabilizers, lubricants and mixtures thereof.
  • the modifier of the impact resistance is in the form of fine particles comprising an elastomeric core and at least one thermoplastic envelope, the size of the particles being generally less than 1 ⁇ and advantageously between 50 and 300 ⁇ .
  • the impact modifier is prepared by emulsion polymerization.
  • the content of the impact modifier in the liquid (meth) acrylic syrup is 0 to 50% by weight, preferably 0 to 25% by weight and preferably 0 to 20% by weight.
  • the additives are selected from impact modifiers or block copolymers, thermal stabilizers, UV stabilizers, flame retardants, lubricants, release agents, dyes, or mixtures thereof.
  • the additives are present in the (meth) acrylic mixture at a content of between 0.01% by weight and 50% by weight so that the dynamic viscosity of the (meth) acrylic syrup is between 10 mPa * s and 1000 mPa * s at 20 ° C.
  • fillers mention may be made of carbon nanotubes or mineral fillers, including mineral nanofillers (TiO 2 , silica).
  • the fillers are chosen from calcium carbonate (CaCO 3), titanium dioxide (TiO 2) and silica (SiO 2 ).
  • the fillers are present in the aqueous dispersion at a content of between 0.01% by weight and 40% by mass, so that the dynamic viscosity of the liquid (meth) acrylic mixture is between 10 mPa * s and 1000 mPa * s at 20 ° C. ° C.
  • the (meth) acrylic mixture comprises between 95% and 99% by weight, preferably between 96% and 98.5% by weight, and even more preferably between 97% and 98% by weight. by weight of (meth) acrylic syrup, and between 1% and 5% by weight, preferably between 1.5% and 4% by weight, and even more preferably between 2% and 3% by weight of aqueous dispersion.
  • the method comprises the following steps:
  • step b) the polymerization of the liquid (meth) acrylic mixture impregnating said fibrous substrate.
  • the impregnation of the fibrous substrate in step a) is preferably carried out in a closed mold.
  • step a) and step b) are carried out in the same closed mold.
  • Mechanical parts or structured elements or articles based on composite material can be obtained by different methods. Examples include infusion, vacuum bag molding, pressure bag molding, autoclave molding, resin transfer molding (RTM), injection reaction molding (RIM), injection molding Reinforced reaction (R-RIM) and its variants, press molding or compression molding.
  • RTM resin transfer molding
  • IM injection reaction molding
  • R-RIM injection molding Reinforced reaction
  • Preferred manufacturing methods for manufacturing mechanical parts or structured elements or composite material articles are processes in which the liquid (meth) acrylic mixture is transferred to the fibrous substrate by impregnating said fibrous substrate in a mold, more preferably in a closed mold.
  • the manufacturing method is chosen from resin transfer molding or infusion.
  • All methods include the step of impregnating the fibrous substrate with the liquid (meth) acrylic mixture prior to the polymerization step in a mold.
  • the polymerization step of the liquid (meth) acrylic mixture impregnating said fibrous substrate takes place after the impregnation step in the same mold.
  • Resin transfer molding is a process using a two-sided molding assembly that forms the two surfaces of a composite material.
  • the bottom side is a rigid mold.
  • the upper side may be a rigid or flexible mold.
  • Flexible molds can be made from composite materials, silicone or extruded polymeric films such as nylon. Both sides snap together to form a molding cavity.
  • the distinctive feature of resin transfer molding is that the fibrous substrate is placed in this cavity and the molding assembly is closed prior to introduction of the liquid (meth) acrylic syrup.
  • Resin transfer molding includes many variations that differ in the mechanics of introducing liquid (meth) acrylic syrup into the level of the fibrous substrate in the molding cavity. These variations range from vacuum infusion to vacuum resin transfer molding (VARTM). This process can be performed at room temperature or elevated.
  • VARTM vacuum resin transfer molding
  • the liquid (meth) acrylic syrup must have the appropriate viscosity for this method of preparation of the polymeric composite material.
  • the liquid (meth) acrylic syrup is sucked into the fibrous substrate present in a special mold by applying a slight vacuum.
  • the fibrous substrate is infused and completely impregnated with the liquid (meth) acrylic syrup.
  • An advantage of this process is the large amount of fibrous material in the composite.
  • (meth) acrylic substantially homogeneous then injected into a mold in which is previously deposited a fibrous substrate.
  • Said fibrous substrate is impregnated with the (meth) acrylic mixture, and then a polymerization of the obtained system makes it possible to form a composite material part.
  • the output flow rate that is to say the rate of injection of the (meth) acrylic mixture into the mold, is less than 4 kg / minute, preferably less than 3.4 kg / minute.
  • the mechanical parts include automobile parts, boat parts, train parts, sporting goods, aircraft or helicopter parts, spaceship or rocket parts, photovoltaic module parts, wind turbine parts, furniture parts, construction or building parts, parts phone or cell phone, computer or television parts, printer and photocopier parts.
  • a (meth) acrylic syrup is prepared by dissolving
  • component A 25 parts by weight of a BS520-type copolymer (PMMA-polyacrylate) in 75 parts by weight of methyl methacrylate stabilized with MEHQ (hydroquinone monomethyl ether), and 0.5 part by weight of N, Dihydroxyethyl-p-toluidine (DHEPT).
  • PMMA-polyacrylate a BS520-type copolymer
  • MEHQ hydroquinone monomethyl ether
  • DHEPT Dihydroxyethyl-p-toluidine
  • BPO benzoyl peroxide
  • component B Three different formulations of benzoyl peroxide (BPO) are prepared, the BPO being called component B.
  • the various formulations, designated BPO 1, BPO 2, and BPO 3, are indicated in Table I below.
  • the viscosity of these formulations is measured using a Brookfield type viscometer at 50 rpm and at 20 ° C.
  • the particle size and the diameter D50 of the dispersions or suspensions of BPO are measured by laser diffraction using a HELOS SUCELL apparatus of SYMPATEC GmbH.
  • the various BPO formulations are marketed under the trade names Luperox® ANS50G, Luperox® A40FP-EZ9 and Perkadox® L-40RPS, by the company Arkema.
  • the methacrylic syrup (component A) and the various BPO formulations (component B) indicated above, can be used for RTM molding using the PatriotTM Pro Thermoplastic Resin Injection System injection machine, manufactured by Magnum Venus Products, Kent (WA). It is a pneumatic machine with a maximum compressed air pressure of 7 bar, with recirculation loops and cleaning systems for each component.
  • the output flow rate can be up to 3.4 kg per minute, the volume content of component B relative to component A is between 1.0% and 4.5%.
  • the (meth) acrylic liquid mixture comprising the (meth) acrylic syrup and one of the above formulations is injected into a closed mold comprising a glass fabric as a fibrous substrate, and polymerized at 25 ° C. for 40 to 50 minutes. - With the formulation BP01, only two pieces could be realized. Subsequently, the machine was blocked. Main filter and injection lines were clogged.

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Abstract

The invention relates to a method for impregnating a fibrous substrate consisting of long fibres with a liquid (meth)acrylic mixture mainly containing methacrylic and/or acrylic components. The invention also relates to such a (meth)acrylic mixture and the composition thereof, said (meth)acrylic mixture comprising a (meth)acrylic syrup and an aqueous dispersion of a radical initiator. The invention further relates to a method for producing mechanical parts of structured elements or items in a composite material by impregnation of the fibrous substrate with the (meth)acrylic mixture followed by polymerisation of said (meth)acrylic mixture, and to such parts produced according to said production method and used in different fields such as the automobile, aeronautics or construction industries.

Description

PROCÉDÉ D'IMPRÉGNATION D'UN SUBSTRAT FIBREUX AVEC UN MÉLANGE (MÉTH) ACRYLIQUE, COMPOSITION DUDIT MÉLANGE  PROCESS FOR IMPREGNATING A FIBROUS SUBSTRATE WITH A (METH) ACRYLIC MIXTURE, COMPOSITION OF SAID MIXTURE
(MÉTH) ACRYLIQUE, ET MATERIAU COMPOSITE OBTENU APRÈS POLYMÉRISATION DUDIT MÉLANGE (MÉTH) ACRYLIQUE  (METH) ACRYLIC, AND COMPOSITE MATERIAL OBTAINED AFTER POLYMERIZATION OF THE (METH) ACRYLIC MIXTURE
[Domaine d'invention] [Invention field]
[001] L'invention concerne un procédé d'imprégnation d'un substrat fibreux, une composition liquide de résine à base de polymère pour la mise en œuvre dudit procédé d'imprégnation, et le substrat imprégné obtenu par la mise en œuvre dudit procédé d'imprégnation.  The invention relates to a process for impregnating a fibrous substrate, a liquid polymer-based resin composition for carrying out said impregnation method, and the impregnated substrate obtained by implementing said method. impregnation.
[002] Plus particulièrement, l'invention concerne un procédé industriel d'imprégnation d'un substrat fibreux par un mélange liquide visqueux à base de composants méthacryliques ou acryliques. Un tel procédé permet notamment l'obtention de pièces tridimensionnelles, par exemple des pièces ou des ensembles de pièces mécaniques, utilisées dans des domaines variés tels que l'aéronautique, l'automobile, ou encore le transport ferroviaire, la construction.  More particularly, the invention relates to an industrial process for impregnating a fibrous substrate with a viscous liquid mixture based on methacrylic or acrylic components. Such a method makes it possible in particular to obtain three-dimensional parts, for example parts or sets of mechanical parts, used in various fields such as aeronautics, automotive, or rail transport, construction.
[Art antérieur] [Prior art]
[003] Certaines pièces ou certains ensembles de pièces tels que ceux précédemment cités sont parfois amenés à subir des contraintes mécaniques ou efforts mécaniques élevés. De telles pièces sont dès lors très largement fabriquées à partir de matériaux composites.  [003] Certain parts or sets of parts such as those mentioned above are sometimes subject to mechanical stresses or high mechanical forces. Such parts are therefore very largely made from composite materials.
[004] Un matériau composite est un assemblage d'au moins deux composants non miscibles. Un effet de synergie est obtenu par un tel assemblage, de sorte que le matériau composite obtenu possède des propriétés notamment mécaniques et/ou thermiques que chacun des composants initiaux ne possède pas ou possède mais à un degré inférieur par rapport au matériau composite.  [004] A composite material is an assembly of at least two immiscible components. A synergistic effect is obtained by such an assembly, so that the composite material obtained has particular mechanical and / or thermal properties that each of the initial components does not have or has but to a lesser degree relative to the composite material.
[005] De plus, un matériau composite est constitué par au moins un matériau de renfort conférant audit matériau composite de bonnes propriétés mécaniques, notamment une bonne tenue aux efforts mécaniques subis par le matériau composite, et par un matériau de matrice formant une phase continue et assurant la cohésion dudit matériau composite. Parmi les différents types de composites utilisés dans l'industrie, les composites à matrices organiques sont les plus représentés. Dans le cas des composites à matrices organiques, le matériau de matrice est généralement un polymère. Ce polymère peut être soit un polymère thermodurcissable, soit un polymère thermoplastique. In addition, a composite material is constituted by at least one reinforcing material giving said composite material good mechanical properties, including good resistance to efforts. mechanical forces experienced by the composite material, and by a matrix material forming a continuous phase and ensuring the cohesion of said composite material. Among the different types of composites used in the industry, organic matrix composites are the most represented. In the case of organic matrix composites, the matrix material is generally a polymer. This polymer may be either a thermosetting polymer or a thermoplastic polymer.
[006] La préparation du matériau composite s'effectue par un mélange du matériau de matrice et du matériau de renfort, ou par mouillage ou imprégnation du matériau de renfort par le matériau de matrice, puis par polymérisation du système obtenu. Dans le cas du mélange de la matrice et du renfort, ledit renfort peut être constitué de charges renforçantes telles que du gravier, du sable, ou des billes de verre. Dans le cas du mouillage ou de l'imprégnation du renfort par la matrice, ledit renfort peut être constitué de fibres de dimensions variables. The preparation of the composite material is carried out by a mixture of the matrix material and the reinforcing material, or by wetting or impregnation of the reinforcing material with the matrix material, and then by polymerization of the obtained system. In the case of mixing the matrix and the reinforcement, said reinforcement may consist of reinforcing fillers such as gravel, sand, or glass beads. In the case of wetting or impregnation of the reinforcement with the matrix, said reinforcement may consist of fibers of variable dimensions.
[007] La matrice polymère comprend généralement un amorceur de polymérisation afin de polymériser la matrice polymère imprégnant le matériau de renfort. Cet amorceur de polymérisation se présente souvent sous forme solide, et présente donc l'inconvénient de former un dépôt solide dans la matrice polymère par décantation. La matrice est dès lors fortement hétérogène et la polymérisation ultérieure, s' effectuant ainsi en milieu hétérogène, ne permet pas d'obtenir des matériaux composites possédant de bonnes propriétés mécaniques. De plus, un amorceur se présentant sous forme solide peut provoquer une obstruction des lignes d'alimentation d'une machine d'injection utilisée pour synthétiser le matériau composite, entraînant ainsi son blocage, voire sa casse.  The polymer matrix generally comprises a polymerization initiator in order to polymerize the polymer matrix impregnating the reinforcing material. This polymerization initiator is often in solid form, and therefore has the disadvantage of forming a solid deposit in the polymer matrix by decantation. The matrix is therefore highly heterogeneous and the subsequent polymerization, thus taking place in a heterogeneous medium, does not make it possible to obtain composite materials having good mechanical properties. In addition, an initiator in solid form can cause obstruction of the supply lines of an injection machine used to synthesize the composite material, thus causing its blocking or even breaking.
[008] Une première solution peut consister à solubiliser l'amorceur dans un solvant tel que l'acétone, l'éthanol, ou encore un phtalate, mais cela engendre des coûts élevés et la présence d'un solvant organique n'est pas souhaitable dans les procédés de fabrication de tels matériaux composites. De plus, le taux de solvant nécessaire pour solubiliser l'amorceur est en général trop élevé et incompatible avec le ratio sirop (méth) acrylique système amorceur des machines. C'est notamment le cas avec le peroxyde de benzoyle (BPO) pour lequel le ratio sirop (méth) acrylique / somme du sirop (méth) acrylique et du système amorceur doit être inférieur ou égal à 5%. possible A first solution may consist in solubilizing the initiator in a solvent such as acetone, ethanol, or a phthalate, but this generates high costs and the presence of an organic solvent is not desirable. in the methods of manufacturing such composite materials. In addition, the level of solvent required to solubilize the initiator is generally too high and incompatible with the ratio of (meth) acrylic syrup initiator system of machines. This is particularly the case with benzoyl peroxide (BPO) for which the ratio of syrup (meth) acrylic / sum of the syrup (meth) acrylic and initiator system must be less than or equal to 5%. possible
[009] Une solution alternative est d'utiliser un amorceur liquide. Cependant, la cinétique des réactions mises en œuvre dans les procédés de fabrication de tels matériaux composites est alors nettement plus faible que dans le cas de l'utilisation d'un amorceur solide, et ce malgré la présence d'un accélérateur de polymérisation. Parmi les amorceurs liquides, les peroxydes liquides sont couramment utilisés. Un autre inconvénient inhérent à l'utilisation d'amorceurs liquides, tel que les peroxydes liquides, est le fait qu'ils ne peuvent pas être utilisés en système bi-composant, le premier composant étant le sirop [009] An alternative solution is to use a liquid initiator. However, the kinetics of the reactions implemented in the manufacturing processes of such composite materials is then significantly lower than in the case of the use of a solid initiator, despite the presence of a polymerization accelerator. Among liquid initiators, liquid peroxides are commonly used. Another disadvantage inherent in the use of liquid initiators, such as liquid peroxides, is the fact that they can not be used in a two-component system, the first component being the syrup.
(méth) acrylique et le deuxième composant étant le système amorceur, puisque l'accélérateur n'est stable dans aucun des deux composants . (meth) acrylic and the second component is the initiator system, since the accelerator is stable in neither of the two components.
[010] Le document US 5,162,280 décrit la réalisation d'une dispersion aqueuse de diacylperoxyde aromatique, ledit diacylperoxyde aromatique étant un amorceur de polymérisation. Cette dispersion aqueuse comprend, en plus d'un diacylperoxyde aromatique, un diluant constitué d'un alkylène glycol, et de deux agents de suspension constitués respectivement de silicate de magnésium et d'aluminium, et d'un éther cellulosique soluble dans l'eau. Ainsi ce document propose une dispersion comportant un amorceur de type diacylperoxyde aromatique sous forme liquide. Cependant, ce document ne décrit pas l'utilisation d'une telle suspension pour la fabrication de matériaux composites à base de polymères . [010] US 5,162,280 describes the production of an aqueous dispersion of aromatic diacylperoxide, said aromatic diacylperoxide being a polymerization initiator. This aqueous dispersion comprises, in addition to an aromatic diacylperoxide, a diluent consisting of an alkylene glycol, and two suspending agents consisting respectively of magnesium aluminum silicate and a water-soluble cellulosic ether. . Thus, this document proposes a dispersion comprising an initiator of aromatic diacylperoxide type in liquid form. However, this document does not describe the use of such a suspension for the manufacture of polymer-based composite materials.
[011] Le document WO2010/112534 décrit une dispersion aqueuse comprenant de 35% à 45% en poids de peroxide de diacyle solide dont les particules ont un diamètre médian D50 compris entre Ιμιτι et ΙΟμπι. La dispersion aqueuse comprend également de 0.05% à 1% de dispersant, ainsi qu'une quantité inférieure à 1% de solvant organique . [012] Le document WO2014/135816 décrit un procédé d'imprégnation d'un substrat fibreux avec un sirop (méth) acrylique comprenant un polymère (méth) acrylique, un monomère (méth) acrylique, et des charges choisies parmi des particules présentant un taux de gonflement dans le monomère (méth) acrylique inférieur à 200%, et dont le diamètre moyen D50 est inférieur à 50μιτι. La polymérisation du sirop est réalisée par ajout d'un amorceur dont seul le peroxyde de benzoyle sous d'un poudre faiblement humide est décrit. Cet amorceur est solide et se présente sous forme de poudre de BPO et non une dispersion aqueuse de peroxyde organique en particulier de BPO. WO2010 / 112534 discloses an aqueous dispersion comprising from 35% to 45% by weight of solid diacyl peroxide whose particles have a median diameter D50 between Ιμιτι and ΙΟμπι. The aqueous dispersion also comprises from 0.05% to 1% of dispersant, as well as less than 1% of organic solvent. The document WO2014 / 135816 describes a process for impregnating a fibrous substrate with a (meth) acrylic syrup comprising a (meth) acrylic polymer, a (meth) acrylic monomer, and fillers chosen from particles having a swelling rate in the monomer (meth) acrylic less than 200%, and whose average diameter D50 is less than 50μιτι. The polymerization of the syrup is carried out by adding an initiator of which only the benzoyl peroxide under a weakly moist powder is described. This initiator is solid and is in the form of BPO powder and not an aqueous dispersion of organic peroxide, in particular BPO.
[013] Le document US 5,300,600 décrit la réalisation d'une dispersion aqueuse de peroxyde aromatique normalement solide à une température voisine de 20 °C, ledit peroxyde aromatique étant un amorceur de polymérisation. Cette dispersion aqueuse comprend en autre, en plus d'un peroxyde aromatique, un agent dispersant consistant en un alcool polyéthéré et une résine phénolique oxydée. Cependant, ce document ne décrit pas l'utilisation d'une telle suspension pour la fabrication de matériaux composites à base de polymères. D'autre part, l'utilisation d'agent dispersant en présence de l' amorceur normalement solide dans une dispersion aqueuse permet certes d'obtenir une composition liquide, mais la taille des particules d' amorceur au sein de la composition est généralement telle que ces particules peuvent quand même venir obstruer les lignes d'alimentation des machines d'injection souvent nécessaires à la fabrication de matériaux composites. Par ailleurs, ce type de composition liquide est généralement peu stable, pouvant conduire notamment à un manque de reproductibilité des procédés mettant en œuvre ladite composition liquide. On pourra également se reporter au document WO 2014013028 dont le procédé d'imprégnation comporte des inconvénients analogues à ceux précédemment cités.  Document US Pat. No. 5,300,600 describes the production of an aqueous dispersion of normally solid aromatic peroxide at a temperature in the region of 20 ° C., said aromatic peroxide being a polymerization initiator. This aqueous dispersion further comprises, in addition to an aromatic peroxide, a dispersing agent consisting of a polyether alcohol and an oxidized phenolic resin. However, this document does not describe the use of such a suspension for the manufacture of polymer-based composite materials. On the other hand, the use of dispersing agent in the presence of the normally solid initiator in an aqueous dispersion makes it possible to obtain a liquid composition, but the size of the initiator particles in the composition is generally such that these particles can still obstruct the supply lines of injection machines often required for the manufacture of composite materials. Moreover, this type of liquid composition is generally unstable, which can lead in particular to a lack of reproducibility of processes using said liquid composition. Reference may also be made to WO 2014013028, the impregnation process of which has disadvantages similar to those mentioned above.
[Problème technique] [Technical problem]
[014] L'invention a donc pour but de remédier aux inconvénients de l'art antérieur en proposant un procédé de fabrication de pièces ou d'ensembles de pièces à base de matériau composite polymère pouvant être mis en œuvre sur des machines couramment utilisées pour le moulage desdites pièces et/ou desdits ensembles de pièces à base de matériau composite polymère, sans provoquer de blocage ou de dysfonctionnement de telles machines. L'invention a également pour but une procédé d'imprégnation d'un substrat fibreux avec une mélange (méth) acrylique comprenant une sirop (méth) acrylique et une dispersion aqueuse en amorceur radicalaire constitué d'un peroxide organique, ladite mélange pouvant être mis en œuvre sur des machines couramment utilisées pour le moulage desdites pièces et/ou desdits ensembles de pièces à base de matériau composite polymère, sans provoquer de blocage ou de dysfonctionnement de telles machines. L'invention a également pour but de proposer des pièces obtenues par le procédé possédant également de bonnes propriétés mécaniques. [014] The invention therefore aims to overcome the disadvantages of the prior art by proposing a parts manufacturing process or sets of parts based on polymeric composite material that can be implemented on machines commonly used for molding said parts and / or said sets of parts based on polymeric composite material, without causing blockage or malfunction of such machines. The invention also aims at a process for impregnating a fibrous substrate with a (meth) acrylic mixture comprising a (meth) acrylic syrup and an aqueous dispersion of a radical initiator consisting of an organic peroxide, said mixture being capable of being implemented on machines commonly used for molding said parts and / or sets of parts based on polymeric composite material, without causing blockage or malfunction of such machines. The invention also aims to provide parts obtained by the process also having good mechanical properties.
[Brève description de l'invention] [Brief description of the invention]
[015] A cet effet, l'invention a pour objet un procédé d'imprégnation d'un substrat fibreux préférentiellement constitué de fibres longues, ledit procédé étant principalement caractérisé en ce qu'il comprend une étape d'imprégnation dudit substrat fibreux avec un mélange (méth) acrylique liquide comprenant :  [015] For this purpose, the subject of the invention is a process for impregnating a fibrous substrate, preferably consisting of long fibers, said process being mainly characterized in that it comprises a step of impregnating said fibrous substrate with a liquid (meth) acrylic mixture comprising:
un sirop (méth) acrylique comprenant au moins un polymère (méth) acrylique, et au moins un monomère (méth) acrylique, une dispersion aqueuse comprenant au moins un amorceur radicalaire constitué d'un peroxyde organique pour démarrer la polymérisation du monomère (méth) acrylique , ledit au moins un amorceur radicalaire présentant une granulométrie telle que le diamètre médian des particules en volume (D50) est compris entre 1 μιτι et 30 μιτι, de préférence entre 2 μιτι et 25 μιτι, de manière encore plus préférée entre 3,5 μιτι et 20 μιτι, avantageusement entre 3,5 μιτι et 15 μιτι, plus avantageusement entre 3,5 μιτι et 13 μιτι est encore plus avantageusement entre 3 , 5μιτι et 12μιτι. [016] Selon d'autres caractéristiques optionnelles du procédé d' imprégnation : a (meth) acrylic syrup comprising at least one (meth) acrylic polymer, and at least one (meth) acrylic monomer, an aqueous dispersion comprising at least one radical initiator consisting of an organic peroxide to start the polymerization of the (meth) monomer acrylic, said at least one radical initiator having a particle size such that the median diameter of the particles by volume (D50) is between 1 μιτι and 30 μιτι, preferably between 2 μιτι and 25 μιτι, even more preferably between 3.5 μιτι and 20 μιτι, advantageously between 3.5 μιτι and 15 μιτι, more preferably between 3.5 μιτι and 13 μιτι is even more advantageously between 3, 5μιτι and 12μιτι. [016] According to other optional features of the impregnation process:
L'étape d'imprégnation du substrat fibreux est réalisée dans un moule fermé,  The impregnation step of the fibrous substrate is carried out in a closed mold,
L'amorceur radicalaire est choisi parmi les peroxydes de diacyle, les peroxyesters, les peroxydes de dialkyle, les peroxyacétals ou les composés azo,  The radical initiator is chosen from diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals or azo compounds,
L'amorceur radicalaire est constitué de peroxyde de benzoyle (BPO) ,  The radical initiator consists of benzoyl peroxide (BPO),
La teneur en amorceur radicalaire par rapport au monomère (méth) acrylique ou au mélange de monomères (méth) acryliques est comprise entre 100 et 50 000 ppm en poids, de préférence entre 200 et 40 000 ppm en poids et avantageusement entre 300 et 30 000 ppm en poids,  The radical initiator content relative to the (meth) acrylic monomer or to the mixture of (meth) acrylic monomers is between 100 and 50,000 ppm by weight, preferably between 200 and 40,000 ppm by weight and advantageously between 300 and 30,000. ppm by weight,
Le pourcentage massique en amorceur radicalaire dans la dispersion aqueuse est compris entre 30% et 80%, de préférence entre 35% et 70%, et de manière encore plus préférée est entre 35% et 60%,  The weight percentage of radical initiator in the aqueous dispersion is between 30% and 80%, preferably between 35% and 70%, and even more preferably between 35% and 60%,
Le pourcentage massique en amorceur radicalaire dans le mélange (méth) acrylique est inférieur à 5%, de préférence inférieur à 3%, et de manière encore plus préférée inférieur a 2,5%,  The mass percentage of radical initiator in the (meth) acrylic mixture is less than 5%, preferably less than 3%, and even more preferably less than 2.5%,
Le pourcentage massique en amorceur radicalaire dans le mélange (méth) acrylique est supérieur à 0,2%, de préférence supérieur à 0,4%, et de manière encore plus préférée supérieur à 0,5%,  The mass percentage of radical initiator in the (meth) acrylic mixture is greater than 0.2%, preferably greater than 0.4%, and even more preferably greater than 0.5%,
La dispersion aqueuse d' amorceur radicalaire présente une viscosité à 20°C comprise entre 50 mPa*s et 1000 mPa*s, de préférence entre 100 mPa*s et 750 mPa*s, et de manière encore plus préférée entre 200 mPa*s et 500 mPa*s,  The aqueous dispersion of radical initiator has a viscosity at 20 ° C of between 50 mPa * s and 1000 mPa * s, preferably between 100 mPa * s and 750 mPa * s, and even more preferably between 200 mPa * s and 500 mPa * s,
L'amorceur radicalaire présente une granulométrie telle que le diamètre D10 des particules en volume est inférieur à 20μιτι, de préférence inférieur à 15μιτι et de manière encore plus préférée inférieur à ΙΟμιτι, La dispersion aqueuse d' amorceur radicalaire comprend préférablement un agent émulsifiant, The radical initiator has a particle size such that the diameter D10 of the particles by volume is less than 20μιτι, preferably less than 15μιτι and even more preferably less than ΙΟμιτι, The aqueous dispersion of radical initiator preferably comprises an emulsifying agent,
La dispersion aqueuse d' amorceur radicalaire comprend préférablement un stabilisant,  The aqueous dispersion of radical initiator preferably comprises a stabilizer,
Le sirop (méth) acrylique liquide a une viscosité dynamique comprise entre 10 mPa*s et 10 000 mPa*s, de préférence entre 50 mPa*s et 5 000 mPa*s et avantageusement entre 100 mPa*s et 1000 mPa*s, la viscosité dynamique étant mesurée à 25°C, The liquid (meth) acrylic syrup has a dynamic viscosity of between 10 mPa * s and 10 000 mPa * s, preferably between 50 mPa * s and 5000 mPa * s and advantageously between 100 mPa * s and 1000 mPa * s, the dynamic viscosity being measured at 25 ° C,
Le polymère (méth) acrylique est un homopolymère de méthacrylate de méthyle (MMA) ou un copolymère de méthacrylate de méthyle (MMA) ou un de leurs mélanges, The (meth) acrylic polymer is a homopolymer of methyl methacrylate (MMA) or a copolymer of methyl methacrylate (MMA) or a mixture thereof,
Le copolymère de méthacrylate de méthyle (MMA) comprend au moins 70 %, de préférence au moins 80 %, avantageusement au moins 90 % et plus avantageusement au moins 95 % en poids de méthacrylate de méthyle (MMA) ,  The methyl methacrylate (MMA) copolymer comprises at least 70%, preferably at least 80%, advantageously at least 90% and more preferably at least 95% by weight of methyl methacrylate (MMA),
Le copolymère de méthacrylate de méthyle (MMA) comprend de 80 % à 99,7 %, avantageusement de 90 % à 99,7 % et plus avantageusement de 90 % à 99,5 % en poids de méthacrylate de méthyle et de 0,3 % à 20 %, avantageusement de 0,3 % à 10 % et plus avantageusement de 0,5 % à 10 % en poids d'au moins un monomère contenant au moins une insaturation éthylénique qui peut copolymériser avec le méthacrylate de méthyle, The methyl methacrylate (MMA) copolymer comprises from 80% to 99.7%, preferably from 90% to 99.7% and more preferably from 90% to 99.5% by weight of methyl methacrylate and 0.3% by weight of methacrylate. % to 20%, advantageously from 0.3% to 10% and more preferably from 0.5% to 10% by weight of at least one monomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate,
Le polymère (méth) acrylique dans le mélange (méth) acrylique liquide est présent à hauteur d'au moins 10 % en poids, de préférence d'au moins 15 %, avantageusement d'au moins 18 % et plus avantageusement d'au moins 20 % en poids du mélange (méth) acrylique liquide total, The (meth) acrylic polymer in the liquid (meth) acrylic mixture is present at least 10% by weight, preferably at least 15%, advantageously at least 18% and more preferably at least 20% by weight of the total (meth) acrylic liquid mixture,
Le polymère (méth) acrylique dans le mélange (méth) acrylique liquide est présent à hauteur d'au plus 60 % en poids, de préférence d'au plus 50 %, avantageusement d'au plus 40 % et plus avantageusement d' au plus 35 % en poids du mélange (méth) acrylique liquide total,  The (meth) acrylic polymer in the liquid (meth) acrylic mixture is present at most 60% by weight, preferably at most 50%, advantageously at most 40% and more preferably at most 35% by weight of the total (meth) acrylic liquid mixture,
Le monomère (méth) acrylique est choisi parmi l'acide acrylique, l'acide méthacrylique, les monomères acryliques d'alkyle, les monomères méthacryliques d'alkyle et leurs mélanges, le groupe alkyle pouvant être linéaire, ramifié ou cyclique et contenant de 1 à 22 atomes de carbone, de préférence de 1 à 12 atomes de carbone, The (meth) acrylic monomer is selected from acrylic acid, methacrylic acid, acrylic monomers alkyl, methacrylic alkyl monomers and mixtures thereof, the alkyl group may be linear, branched or cyclic and containing 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms,
Le monomère (méth) acrylique est choisi parmi le méthacrylate de méthyle, le méthacrylate d'éthyle, l' acrylate de méthyle, 1' acrylate d'éthyle, l'acide méthacrylique, l'acide acrylique, l' acrylate de n-butyle, l' acrylate d' isobutyle, le méthacrylate de n-butyle, le méthacrylate d' isobutyle, 1' acrylate de cyclohexyle, le méthacrylate de cyclohexyle, 1' acrylate d' isobornyle, le méthacrylate d' isobornyle et leurs mélanges,  The (meth) acrylic monomer is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid and n-butyl acrylate. , isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and mixtures thereof,
Le monomère (méth) acrylique est choisi parmi le méthacrylate de méthyle, l' acrylate d' isobornyle, l'acide acrylique et leurs mélanges,  The (meth) acrylic monomer is selected from methyl methacrylate, isobornyl acrylate, acrylic acid and mixtures thereof.
50 % en poids du monomère (méth) acrylique ou des monomères (méth) acryliques est le méthacrylate de méthyle,  50% by weight of the (meth) acrylic monomer or (meth) acrylic monomers is methyl methacrylate,
Le sirop (méth) acrylique comprend en outre au moins une charge et/ou au moins un additif tels que des modificateurs de la résistance aux impacts ou des copolymères séquencés, des stabilisateurs thermiques, des stabilisateurs UV, des agents ignifuges, des lubrifiants, des agents de démoulage, des colorants, ou leurs mélanges,  The (meth) acrylic syrup further comprises at least one filler and / or at least one additive such as impact modifiers or block copolymers, thermal stabilizers, UV stabilizers, flame retardants, lubricants, mold release agents, colorants, or mixtures thereof,
Les additifs sont choisis parmi les modificateurs de la résistance aux impacts ou des copolymères séquencés, les stabilisateurs thermiques, les stabilisateurs UV, les agents ignifuges, les lubrifiants, les agents de démoulage, les colorants, ou leurs mélanges, et sont présents dans le mélange (méth) acrylique liquide à une teneur comprise entre 0.01% massique et 50% massique de sorte que la viscosité dynamique du sirop (méth) acrylique soit comprise entre 10 mPa*s et 1000 mPa*s.  The additives are selected from impact modifiers or block copolymers, thermal stabilizers, UV stabilizers, flame retardants, lubricants, mold release agents, colorants, or mixtures thereof, and are present in the blend. (Meth) acrylic liquid at a content between 0.01% by mass and 50% by weight so that the dynamic viscosity of the (meth) acrylic syrup is between 10 mPa * s and 1000 mPa * s.
Les charges sont choisies parmi le carbonate de calcium (CaCÛ3) , le dioxyde de titane (T1O2) , et la silice (S1O2) , et sont présentes dans la dispersion aqueuse à une teneur comprise entre 0.01% massique et 40% massique de sorte que la viscosité dynamique du sirop (méth) acrylique liquide soit comprise entre 10 mPa*s et 1000 mPa*s. The fillers are selected from calcium carbonate (CaCO 3), titanium dioxide (TiO 2), and silica (SiO 2), and are present in the aqueous dispersion at a concentration of between 0.01 wt% and 40 wt% so that the dynamic viscosity of the liquid (meth) acrylic syrup is between 10 mPa * s and 1000 mPa * s.
Le mélange (méth) acrylique comprend en outre un activateur dans le sirop (méth) acrylique,  The (meth) acrylic mixture further comprises an activator in the (meth) acrylic syrup,
L' activateur est choisi parmi les aminés tertiaires telles que la N, -diméthyl-p-toluidine (DMPT) , la N,N- dihydroxyéthyl-p-toluidine (DHEPT) , les catalyseurs de métaux de transition solubles dans les composés organiques ou leurs mélanges ,  The activator is chosen from tertiary amines such as N, -dimethyl-p-toluidine (DMPT), N, N-dihydroxyethyl-p-toluidine (DHEPT), transition metal catalysts soluble in organic compounds or their mixtures,
La teneur de l' activateur par rapport au monomère (méth) acrylique du sirop (méth) acrylique liquide est de 100 ppm à 10 000 ppm en poids, de préférence de 200 ppm à 7 000 ppm en et avantageusement de 300 ppm à 4 000 ppm en poids ,  The content of the activator relative to the (meth) acrylic monomer of the liquid (meth) acrylic syrup is from 100 ppm to 10,000 ppm by weight, preferably from 200 ppm to 7000 ppm, and preferably from 300 ppm to 4000 ppm by weight,
Le mélange (méth) acrylique comprend entre 95% et 99% en poids, de préférence entre 96% et 98,5% en poids, et de manière encore plus préférée entre 97% et 98% en poids de sirop (méth) acrylique, et entre 1% et 5% en poids, de préférence entre 1,5% et 4% en poids, et de manière encore plus préférée entre 2% et 3% en poids de dispersion aqueuse.  The (meth) acrylic mixture comprises between 95% and 99% by weight, preferably between 96% and 98.5% by weight, and even more preferably between 97% and 98% by weight of (meth) acrylic syrup, and between 1% and 5% by weight, preferably between 1.5% and 4% by weight, and even more preferably between 2% and 3% by weight of aqueous dispersion.
[017] L'invention se rapporte en outre à un mélange (méth) acrylique liquide pour la mise en œuvre du procédé d'imprégnation d'un substrat fibreux, ledit mélange étant caractérisé en ce qu' il comprend : [017] The invention also relates to a liquid (meth) acrylic mixture for carrying out the process for impregnating a fibrous substrate, said mixture being characterized in that it comprises:
un sirop (méth) acrylique comprenant au moins un polymère (méth) acrylique, et au moins un monomère (méth) acrylique, une dispersion aqueuse comprenant au moins un amorceur radicalaire constitué d'un peroxyde organique pour démarrer la polymérisation du monomère (méth) acrylique , ledit au moins un amorceur radicalaire présentant une granulométrie telle que le diamètre médian des particules en volume (D50) est compris entre 1 μιτι et 30 μιτι, de préférence entre 2 μιτι et 25 μπι et de manière encore plus préférée entre 3,5 μιτι et 20 μιτι et avantageusement entre 3,5 μιτι et 15 μιτι. a (meth) acrylic syrup comprising at least one (meth) acrylic polymer, and at least one (meth) acrylic monomer, an aqueous dispersion comprising at least one radical initiator consisting of an organic peroxide to start the polymerization of the (meth) monomer acrylic, said at least one radical initiator having a particle size such that the median diameter of the particles by volume (D50) is between 1 μιτι and 30 μιτι, preferably between 2 μιτι and 25 μιτι. μπι and even more preferably between 3.5 μιτι and 20 μιτι and advantageously between 3.5 μιτι and 15 μιτι.
[018] L'invention se rapporte en outre à un procédé de fabrication de pièces mécaniques ou d'éléments structurés ou d'articles, ledit procédé étant principalement caractérisé en ce qu'il comprend les étapes suivantes : [018] The invention also relates to a method for manufacturing mechanical parts or structured elements or articles, said method being characterized in that it comprises the following steps:
a) l'imprégnation d'un substrat fibreux avec un mélange (méth) acrylique liquide b) la polymérisation du mélange (méth) acrylique liquide imprégnant ledit substrat fibreux.  a) impregnating a fibrous substrate with a liquid (meth) acrylic mixture; b) polymerizing the liquid (meth) acrylic mixture impregnating said fibrous substrate.
[019] Selon d'autres caractéristiques optionnelles du procédé de fabrication : [019] According to other optional features of the manufacturing process:
Le procédé comprend en outre, préalablement à l'étape a), une étape de préparation du mélange (méth) acrylique liquide par mélange d'un sirop (méth) acrylique comprenant au moins un polymère (méth) acrylique, et au moins un monomère (méth) acrylique et d'une dispersion aqueuse comprenant au moins un amorceur radicalaire constitué d'un peroxyde organique pour démarrer la polymérisation du monomère (méth) acrylique, ledit au moins un amorceur radicalaire présentant une granulométrie telle que le diamètre médian des particules en volume (D50) est compris entre 1 μιτι et 30 μιτι, de préférence entre 2 μιτι et 25 μιτι et de manière encore plus préférée entre 3,5 μιτι et 20 μιτι et avantageusement entre 3,5 μιτι et 15 μιτι , plus avantageusement entre 3,5 μιτι et 13 μιτι est encore plus avantageusement entre 3,5μιτι et 12μπι.  The method further comprises, prior to step a), a step of preparing the liquid (meth) acrylic mixture by mixing a (meth) acrylic syrup comprising at least one (meth) acrylic polymer, and at least one monomer (meth) acrylic and an aqueous dispersion comprising at least one radical initiator consisting of an organic peroxide to start the polymerization of the (meth) acrylic monomer, said at least one radical initiator having a particle size such that the median diameter of the particles in volume (D50) is between 1 μιτι and 30 μιτι, preferably between 2 μιτι and 25 μιτι and even more preferably between 3.5 μιτι and 20 μιτι and advantageously between 3.5 μιτι and 15 μιτι, more preferably between 3 , 5 μιτι and 13 μιτι is even more advantageously between 3.5μιτι and 12μπι.
L'imprégnation du substrat fibreux à l'étape a) est réalisée dans un moule fermé,  The impregnation of the fibrous substrate in step a) is carried out in a closed mold,
L'étape a) et l'étape b) sont réalisées dans le même moule fermé ,  Step a) and step b) are carried out in the same closed mold,
Le procédé est choisi parmi le moulage par transfert de résine ou l'infusion. [020] L'invention se rapporte en outre à une pièce mécanique ou structurelle en matériau composite obtenue par le procédé de fabrication. Ladite pièce peut notamment être une pièce d'automobile, une pièce de bateau, une pièce de train, un article de sport, une pièce d'avion ou d'hélicoptère, une pièce de vaisseau spatial ou de fusée, une pièce de module photovoltaïque, une pièce d'éolienne, une pièce de meuble, une pièce de construction ou de bâtiment, une pièce de téléphone ou de téléphone portable, une pièce d'ordinateur ou de télévision, une pièce d' imprimante ou de photocopieuse The process is selected from resin transfer molding or infusion. [020] The invention further relates to a mechanical part or structural composite material obtained by the manufacturing process. Said part can notably be an automobile part, a boat part, a train piece, a sports article, an airplane or helicopter part, a spaceship or rocket part, a photovoltaic module part. , a piece of wind turbine, a piece of furniture, a building or building room, a piece of telephone or cell phone, a computer or television room, a printer or photocopier
[Description détaillée de l'invention] [Detailed description of the invention]
Le Procédé d'imprégnation d'un substrat fibreux  The process for impregnating a fibrous substrate
[021] Le procédé d'imprégnation d'un substrat fibreux, comprend une étape d'imprégnation dudit substrat fibreux avec un mélange (méth) acrylique dans lequel le mélange comporte :  The method for impregnating a fibrous substrate comprises a step of impregnating said fibrous substrate with a (meth) acrylic mixture in which the mixture comprises:
un sirop (méth) acrylique liquide comprenant au moins un polymère (méth) acrylique, et au moins un monomère (méth) acrylique,  a liquid (meth) acrylic syrup comprising at least one (meth) acrylic polymer, and at least one (meth) acrylic monomer,
une dispersion aqueuse comprenant au moins un amorceur radicalaire. Avantageusement, l' amorceur radicalaire est constitué d'un peroxyde organique dont la granulométrie est telle que le diamètre médian des particules en volume (D50) est compris entre 1 μιτι et 30 μιτι, de préférence entre 2 μιτι et 25 μιτι et de manière encore plus préférée entre 3,5 μιτι et 20 μιτι et avantageusement entre 3,5 μιτι et 15 μιτι, plus avantageusement entre 3,5 μιτι et 13 μιτι est encore plus avantageusement entre 3,5μιτι et 12μιτι.  an aqueous dispersion comprising at least one radical initiator. Advantageously, the radical initiator consists of an organic peroxide whose particle size is such that the median diameter of the particles in volume (D50) is between 1 μιτι and 30 μιτι, preferably between 2 μιτι and 25 μιτι and still more preferred between 3.5 μιτι and 20 μιτι and advantageously between 3.5 μιτι and 15 μιτι, more preferably between 3.5 μιτι and 13 μιτι is even more advantageously between 3.5μιτι and 12μιτι.
[022] Le terme « mélange (méth) acrylique » correspond à la matrice polymère telle que décrite précédemment. Le « sirop [022] The term "(meth) acrylic mixture" corresponds to the polymer matrix as described above. The sirup
(méth) acrylique que ce mélange comprend est nommé ainsi du fait de son aspect liquide et visqueux, et peut également être appelé prépolymère du fait qu' il comporte au moins un monomère (méth) acrylique apte à subir une polymérisation pour former un polymère (méth) acrylique . (meth) acrylic this mixture comprises is so named because of its liquid and viscous appearance, and can also be called prepolymer because it comprises at least one monomer (Meth) acrylic polymer capable of undergoing polymerization to form a (meth) acrylic polymer.
[023] Le terme « substrat fibreux » tel qu'utilisé se rapporte à des tissus, des feutres ou des non-tissés qui peuvent être sous la forme de bandes, de nappes, de tresses, de mèches ou de pièces.  [023] The term "fibrous substrate" as used refers to fabrics, felts or nonwovens which may be in the form of strips, webs, braids, locks or pieces.
[024] Le terme « (méth) acrylique » tel qu'utilisé se rapporte à tout type de monomères acryliques et méthacryliques . [024] The term "(meth) acrylic" as used refers to any type of acrylic and methacrylic monomers.
[025] Le terme « monomère » tel qu'utilisé se rapporte à une molécule qui peut subir une polymérisation. [025] The term "monomer" as used refers to a molecule that can undergo polymerization.
[026] Le terme « polymérisation tel qu'utilisé se rapporte au procédé de transformation d'un monomère ou d'un mélange de monomères en un polymère.  The term "polymerization as used" refers to the process of converting a monomer or mixture of monomers into a polymer.
[027] Le terme « matériau composite » tel qu'utilisé se rapporte à un matériau multicomposant comprenant plusieurs domaines de phase différents, parmi lesquels au moins un type de domaine de phase est une phase continue et dans lequel au moins un composant est un polymère .  [027] The term "composite material" as used refers to a multicomponent material comprising a plurality of different phase domains, of which at least one type of phase domain is a continuous phase and wherein at least one component is a polymer .
[028] Le terme « amorceur » tel qu'utilisé se rapporte à une espèce chimique qui réagit avec un monomère pour former un composé intermédiaire capable de se lier avec succès à un grand nombre d'autres monomères pour former un composé polymère.  The term "initiator" as used refers to a chemical species that reacts with a monomer to form an intermediate compound capable of successfully bonding to a large number of other monomers to form a polymeric compound.
[029] On entend par « D50 » ou « diamètre médian » le diamètre particulaire qui divise la distribution des particules d'une substance en deux parties d'aires égales. Dans le cas du diamètre médian D50 en volume, 50% du volume total des particules correspond au volume des particules de diamètre inférieur à D50, et 50% du volume total des particules correspond au volume des particules de diamètre supérieur à D50.  [029] The term "D50" or "median diameter" refers to the particle diameter that divides the particle distribution of a substance into two parts of equal areas. In the case of the median diameter D 50 by volume, 50% of the total volume of the particles corresponds to the volume of the particles with a diameter of less than D 50, and 50% of the total volume of the particles corresponds to the volume of the particles with a diameter greater than D 50.
[030] On entend par « D10 » le diamètre particulaire qui divise la distribution des particules d'une substance en deux parties d'aires de ratio 10% / 90%. Dans le cas de D10 en volume, 10% du volume total des particules correspond au volume des particules de diamètre inférieur à D10, et 90% du volume total des particules correspond au volume des particules de diamètre supérieur à D10. Le polymère (méth) acrylique [030] "D10" is understood to mean the particle diameter that divides the particle distribution of a substance into two parts of 10% / 90% ratio areas. In the case of D10 by volume, 10% of the total volume of the particles corresponds to the volume of the particles with a diameter of less than D10, and 90% of the total volume of the particles corresponds to the volume of the particles of diameter greater than D10. The (meth) acrylic polymer
[031] Le polymère (méth) acrylique peut être choisi parmi les polyméthacrylates d'alkyle ou les polyacrylates d'alkyle. Selon un mode de réalisation préféré, le polymère (méth) acrylique est le polyméthacrylate de méthyle (PMMA) . Il doit être dès lors entendu que polyméthacrylate de méthyle (PMMA) peut désigner un homopolymère de méthacrylate de méthyle (MMA) ou un copolymère de MMA ou leurs mélanges .  [031] The (meth) acrylic polymer may be chosen from alkyl polymethacrylates or alkyl polyacrylates. According to a preferred embodiment, the (meth) acrylic polymer is polymethyl methacrylate (PMMA). It must therefore be understood that polymethyl methacrylate (PMMA) may designate a homopolymer of methyl methacrylate (MMA) or a copolymer of MMA or mixtures thereof.
[032] En particulier, il peut s'agir d'un mélange d'au moins deux homopolymères de MMA ayant un poids moléculaire différent, ou d'un mélange d'au moins deux copolymères de MMA ayant une composition en monomères identique et un poids moléculaire différent, ou d'un mélange d'au moins deux copolymères de MMA ayant une composition en monomères différente. Il peut également s'agir d'un mélange d'au moins un homopolymère de MMA et d'au moins un copolymère de MMA.  [032] In particular, it may be a mixture of at least two MMA homopolymers having a different molecular weight, or a mixture of at least two MMA copolymers having an identical monomer composition and a different molecular weight, or a mixture of at least two MMA copolymers having a different monomer composition. It can also be a mixture of at least one MMA homopolymer and at least one MMA copolymer.
[033] Selon un mode de réalisation, le copolymère de MMA comprend au moins 70 %, de préférence au moins 80 %, avantageusement au moins 90 % et plus avantageusement au moins 95 % en poids de méthacrylate de méthyle. Le copolymère de MMA peut également comprendre de 0,3 à 30 % en poids d'au moins un monomère contenant au moins une insaturation éthylénique et étant apte à copolymériser avec le méthacrylate de méthyle. Parmi ces monomères on peut notamment citer : les acides acrylique et méthacrylique et les (méth) acrylates d'alkyle dans lesquels le groupe alkyle contient de 1 à 12 atomes de carbone. À titre d'exemple, on peut mentionner l'acrylate de méthyle et le (méth) acrylate d'éthyle, de butyle ou de 2-éthylhexyle . De préférence, le comonomère est un acrylate d'alkyle dans lequel le groupe alkyle contient de 1 à 4 atomes de carbone.  [033] According to one embodiment, the MMA copolymer comprises at least 70%, preferably at least 80%, advantageously at least 90% and more advantageously at least 95% by weight of methyl methacrylate. The MMA copolymer may also comprise from 0.3 to 30% by weight of at least one monomer containing at least one ethylenic unsaturation and being capable of copolymerizing with methyl methacrylate. Among these monomers there may be mentioned in particular: acrylic and methacrylic acids and alkyl (meth) acrylates in which the alkyl group contains from 1 to 12 carbon atoms. By way of example, mention may be made of methyl acrylate and ethyl (butyl) or 2-ethylhexyl (meth) acrylate. Preferably, the comonomer is an alkyl acrylate wherein the alkyl group contains from 1 to 4 carbon atoms.
[034] Selon un mode de réalisation préféré, le copolymère de méthacrylate de méthyle (MMA) comprend de 80 % à 99,7 %, avantageusement de 90 % à 99,7 % et plus avantageusement de 90 % à 99,5 % en poids de méthacrylate de méthyle et de 0,3 % à 20 %, avantageusement de 0,3 % à 10 % et plus avantageusement de 0,5 % à 10 % en poids d'au moins un monomère contenant au moins une insaturation éthylénique qui peut copolymériser avec le méthacrylate de méthyle. De préférence, le comonomère est choisi parmi l'acrylate de méthyle ou l'acrylate d'éthyle ou leurs mélanges . [034] According to a preferred embodiment, the methyl methacrylate (MMA) copolymer comprises from 80% to 99.7%, advantageously from 90% to 99.7% and more advantageously from 90% to 99.5% by weight. weight of methyl methacrylate and from 0.3% to 20%, advantageously from 0.3% to 10% and more preferably from 0.5% to 10% by weight of at least one monomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate. Preferably, the comonomer is selected from methyl acrylate or ethyl acrylate or mixtures thereof.
[ 035 ] Le ou les polymères (méth) acryliques dans le sirop (méth) acrylique liquide sont présents à hauteur d'au moins 10 % en poids, de préférence d'au moins 15 %, avantageusement d'au moins 18 % et plus avantageusement d'au moins 20 % en poids du sirop (méth) acrylique liquide total.  [035] The (meth) acrylic polymer (s) in the liquid (meth) acrylic syrup are present at a level of at least 10% by weight, preferably at least 15%, advantageously at least 18% or more. advantageously at least 20% by weight of the total liquid (meth) acrylic syrup.
[ 036 ] Le ou les polymères (méth) acryliques dans le sirop (méth) acrylique liquide sont présents à hauteur d'au plus 60 % en poids, de préférence d'au plus 50 %, avantageusement d'au plus 40 % et plus avantageusement d'au plus 35 % en poids du sirop (méth) acrylique liquide total.  [036] The (meth) acrylic polymer (s) in the liquid (meth) acrylic syrup are present up to at most 60% by weight, preferably at most 50%, advantageously at most 40% and more. preferably at most 35% by weight of the total liquid (meth) acrylic syrup.
[ 037 ] Le poids moléculaire moyen en poids du polymère (méth) acrylique est généralement élevé, et peut être dès lors supérieur à 50 000 g/mol, de préférence supérieur à 100 000 g/mol. [037] The weight average molecular weight of the (meth) acrylic polymer is generally high, and can therefore be greater than 50,000 g / mol, preferably greater than 100,000 g / mol.
Le poids moléculaire moyen en poids peut être mesuré par chromatographie d'exclusion stérique (SEC) . The weight average molecular weight can be measured by size exclusion chromatography (SEC).
Le monomère (méth) acrylique (Meth) acrylic monomer
[ 038 ] Le ou les monomère (s) (méth) acrylique ( s ) compris dans le sirop (méth) acrylique en plus du polymère (méth) acrylique peut (vent) être choisi (s) parmi l'acide acrylique, l'acide méthacrylique, les monomères acryliques d' alkyle, les monomères méthacryliques d' alkyle et leurs mélanges.  [038] The monomer (s) (meth) acrylic (s) included in the (meth) acrylic syrup in addition to the (meth) acrylic polymer may (be) chosen from acrylic acid, the methacrylic acid, acrylic alkyl monomers, alkyl methacrylic monomers and mixtures thereof.
[ 039 ] De préférence, le monomère (méth) acrylique est choisi parmi l'acide acrylique, l'acide méthacrylique, les monomères acryliques d' alkyle, les monomères méthacryliques d' alkyle et leurs mélanges, le groupe alkyle pouvant être linéaire, ramifié ou cyclique et contenant de 1 à 22 atomes de carbone, de préférence de 1 à 12 atomes de carbone.  [039] Preferably, the (meth) acrylic monomer is chosen from acrylic acid, methacrylic acid, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof, the alkyl group being linear and branched. or cyclic and containing from 1 to 22 carbon atoms, preferably from 1 to 12 carbon atoms.
[ 040 ] Avantageusement, le monomère (méth) acrylique est choisi parmi le méthacrylate de méthyle, le méthacrylate d'éthyle, l'acrylate de méthyle, l'acrylate d'éthyle, l'acide méthacrylique, l'acide acrylique, l'acrylate de n-butyle, l'acrylate d'isobutyle, le méthacrylate de n-butyle, le méthacrylate d'isobutyle, l'acrylate de cyclohexyle, le méthacrylate de cyclohexyle, l'acrylate d' isobornyle, le méthacrylate d' isobornyle et leurs mélanges. [040] Advantageously, the (meth) acrylic monomer is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, and the like. n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and mixtures thereof.
[041] Plus avantageusement, le monomère (méth) acrylique est choisi parmi le méthacrylate de méthyle, l'acrylate d' isobornyle ou l'acide acrylique et leurs mélanges. [041] More preferably, the (meth) acrylic monomer is selected from methyl methacrylate, isobornyl acrylate or acrylic acid and mixtures thereof.
[042] Selon un mode de réalisation préféré, au moins 50 % en poids, de préférence au moins 60 % en poids du monomère (méth) acrylique ou des monomères (méth) acryliques est le méthacrylate de méthyle.  [042] According to a preferred embodiment, at least 50% by weight, preferably at least 60% by weight of the (meth) acrylic monomer or (meth) acrylic monomers is methyl methacrylate.
[043] Selon un mode de réalisation davantage préféré, au moins 50 % en poids, de préférence au moins 60 % en poids, de manière davantage préférée au moins 70 % en poids et avantageusement au moins 80 % en poids et encore plus avantageusement 90 % en poids du monomère (méth) acrylique est un mélange de méthacrylate de méthyle avec de l'acrylate d' isobornyle et/ou de l'acide acrylique . [043] According to a more preferred embodiment, at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight and preferably at least 80% by weight and even more preferably 90% by weight. % by weight of the (meth) acrylic monomer is a mixture of methyl methacrylate with isobornyl acrylate and / or acrylic acid.
[044] Le monomère (méth) acrylique ou les monomères (méth) acryliques du sirop (méth) acrylique liquide sont présents à hauteur d'au moins 40 % en poids, de préférence de 50 % en poids, avantageusement de 60 % en poids et plus avantageusement de 65 % en poids du sirop (méth) acrylique liquide total.  [044] The (meth) acrylic monomer or the (meth) acrylic monomers of the liquid (meth) acrylic syrup are present at a level of at least 40% by weight, preferably 50% by weight, advantageously 60% by weight and more preferably 65% by weight of the total liquid (meth) acrylic syrup.
Le substrat fibreux The fibrous substrate
[045] En ce qui concerne le substrat fibreux, on peut mentionner les tissus, les feutres ou les non-tissés qui peuvent être sous la forme de bandes, de nappes, de tresses, de mèches ou de pièces. Le matériau fibreux peut avoir différentes formes et dimensions, monodimensionnelles , bidimensionnelles ou tridimensionnelles. Un substrat fibreux comprend un assemblage d'une ou de plusieurs fibres. Lorsque les fibres sont continués, leur assemblage forme des tissus.  [045] As regards the fibrous substrate, mention may be made of fabrics, felts or nonwovens which may be in the form of strips, sheets, braids, locks or pieces. The fibrous material can have different shapes and dimensions, one-dimensional, two-dimensional or three-dimensional. A fibrous substrate comprises an assembly of one or more fibers. When the fibers are continued, their assembly forms tissues.
[046] La forme monodimensionnelle correspond à des fibres linéaires. Les fibres peuvent être discontinues ou continues. Les fibres peuvent être agencées de manière aléatoire ou sous la forme d'un filament continu en parallèle les unes aux autres. Une fibre est définie par son rapport de longueur, qui est le rapport entre la longueur et le diamètre de la fibre. Les fibres utilisées dans la présente invention sont des fibres longues ou des fibres continues. Les fibres ont un rapport de longueur d'au moins 1 000, de préférence d'au moins 1 500, de manière davantage préférée d'au moins 2 000, avantageusement d'au moins 3 000 et le plus avantageusement d'au moins 5 000. [046] The one-dimensional form corresponds to linear fibers. The fibers may be discontinuous or continuous. The fibers may be arranged randomly or in the form of a continuous filament in parallel with each other. A fiber is defined by its length ratio, which is the ratio between the length and diameter of the fiber. The fibers used in the present invention are long fibers or continuous fibers. The fibers have a length ratio of at least 1000, preferably at least 1500, more preferably at least 2000, preferably at least 3000 and most preferably at least 5000. 000.
[047] La forme bidimensionnelle correspond à des mats fibreux ou des renforts non tissés ou des stratifils tissés ou des faisceaux de fibres, qui peuvent également être tressés.  The two-dimensional form corresponds to fibrous mats or non-woven reinforcements or woven rovings or bundles of fibers, which may also be braided.
[048] La forme tridimensionnelle correspond par exemple à des mats fibreux ou des renforts non tissés ou des faisceaux de fibres ou leurs mélanges, empilés ou pliés, un assemblage de la forme bidimensionnelle dans la troisième dimension.  [048] The three-dimensional shape corresponds, for example, to fibrous mats or non-woven reinforcements or bundles of fibers or their mixtures, stacked or folded, an assembly of the two-dimensional form in the third dimension.
[049] Les origines du matériau fibreux peuvent être naturelles ou synthétiques. En tant que matériau naturel, on peut mentionner les fibres végétales, les fibres de bois, les fibres animales ou les fibres minérales.  [049] The origins of the fibrous material may be natural or synthetic. As a natural material, mention may be made of vegetable fibers, wood fibers, animal fibers or mineral fibers.
[050] Des fibres naturelles sont par exemple le sisal, le jute, le chanvre, le lin, le coton, les fibres de noix de coco et les fibres de banane. Des fibres animales sont par exemple la laine ou les cheveux.  [050] Natural fibers are, for example, sisal, jute, hemp, flax, cotton, coconut fibers and banana fibers. Animal fibers are for example wool or hair.
[051] En tant que matériau synthétique, on peut mentionner des fibres polymères choisies parmi les fibres de polymères thermodurcissables, de polymères thermoplastiques ou leurs mélanges .  [051] As a synthetic material, mention may be made of polymer fibers chosen from thermosetting polymer fibers, thermoplastic polymers or mixtures thereof.
[052] Les fibres polymères peuvent être constituées de polyamide (aliphatique ou aromatique), de polyester, d'alcool polyvinylique, de polyoléfines , de polyuréthanes , de polychlorure de vinyle, de polyéthylène, de polyesters insaturés, de résines époxy et d'esters de vinyle.  [052] The polymeric fibers may consist of polyamide (aliphatic or aromatic), polyester, polyvinyl alcohol, polyolefins, polyurethanes, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins and esters of vinyl.
[053] Les fibres minérales peuvent également être choisies parmi les fibres de verre, notamment de type E, R ou S2, les fibres de carbone, les fibres de bore ou les fibres de silice.  [053] The mineral fibers may also be chosen from glass fibers, especially of type E, R or S2, carbon fibers, boron fibers or silica fibers.
[054] Le substrat fibreux de la présente invention est choisi parmi les fibres végétales, les fibres de bois, les fibres animales, les fibres minérales, les fibres polymères synthétiques, les fibres de verre, les fibres de carbone ou leurs mélanges. De préférence, substrat fibreux est choisi parmi les fibres minérales. [054] The fibrous substrate of the present invention is chosen from vegetable fibers, wood fibers, animal fibers, mineral fibers, synthetic polymer fibers, glass, carbon fibers or their mixtures. Preferably, the fibrous substrate is chosen from mineral fibers.
La dispersion aqueuse The aqueous dispersion
[ 055 ] Le mélange (méth) acrylique comprend une dispersion aqueuse comprenant au moins un amorceur pour démarrer la polymérisation du ou des monomère (s) (méth) acrylique (s) compris dans le sirop (méth) acrylique en plus du ou des polymère (s) (méth) acrylique ( s ) .  [055] The (meth) acrylic mixture comprises an aqueous dispersion comprising at least one initiator to start the polymerization of the (meth) acrylic monomer (s) included in the (meth) acrylic syrup in addition to the polymer (s) (s) (meth) acrylic (s).
[ 056 ] La dispersion aqueuse comprenant au moins un amorceur pour démarrer la polymérisation n'est pas une charge, car l'amorceur réagit pour démarrer la polymérisation. [056] The aqueous dispersion comprising at least one initiator to start the polymerization is not a filler, since the initiator reacts to start the polymerization.
[ 057 ] On peut par exemple mentionner les amorceurs ou les systèmes amorceurs qui sont activés par la chaleur. L'amorceur activé par la chaleur est de préférence un amorceur radicalaire. Ledit amorceur radicalaire peut être choisi parmi les peroxydes de diacyle, les peroxyesters , les peroxydes de dialkyle, les peroxyacétals ou les composés azo.  [057] For example, there may be mentioned initiators or initiator systems that are activated by heat. The heat-activated initiator is preferably a radical initiator. Said radical initiator may be chosen from diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals or azo compounds.
[ 058 ] De préférence, l'amorceur est choisi parmi le carbonate d' isopropyle, le peroxyde de benzoyle, le peroxyde de lauroyle, le peroxyde de caproyle, le peroxyde de dicumyle, le perbenzoate de tert-butyle, le per (2-éthylhexanoate) de tert-butyle, [058] Preferably, the initiator is chosen from isopropyl carbonate, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, per (2- tert-butyl ethylhexanoate),
1 ' hydroperoxyde de cumyle, le 1, 1-di (tert-butylperoxy) -3, 3, 5- triméthylcyclohexane, le peroxyisobutyrate de tert-butyle, le peracétate de tert-butyle, le perpivalate de tert-butyle, le perpivalate d'amyle, le peroctoate de tert-butyle,Cumyl hydroperoxide, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butyl peroxyisobutyrate, tert-butyl peracetate, tert-butyl perpivalate, perpivalate d amyl, tert-butyl peroctoate,
1 ' azobisisobutyronitrile (AIBN) , 1 ' azobisisobutyramide, le 2,2'- azobis (2, 4-diméthylvaléronitrile) ou l'acide 4 , 4 ' -azobis ( 4- cyanopentanoïque) . L'utilisation d'un mélange d' amorceurs radicalaires choisis dans la liste ci-dessus ne sortirait pas de la portée de l'invention. Azobisisobutyronitrile (AIBN), azobisisobutyramide, 2,2'-azobis (2,4-dimethylvaleronitrile) or 4, 4'-azobis (4-cyanopentanoic acid). The use of a radical initiator mixture selected from the above list would not be outside the scope of the invention.
[ 059 ] De préférence, l'amorceur est choisi parmi les peroxydes contenant 2 à 20 atomes de carbone. De manière davantage préférée, l'amorceur est le peroxyde de benzoyle (BPO) .  [059] Preferably, the initiator is chosen from peroxides containing 2 to 20 carbon atoms. More preferably, the initiator is benzoyl peroxide (BPO).
[ 060 ] La teneur en amorceur radicalaire par rapport au monomère (méth) acrylique ou au mélange de monomères (méth) acryliques du sirop (méth) acrylique liquide est comprise entre 100 et 50 000 ppm en poids (50 000 ppm = 5 % en poids), de préférence entre 200 et 40 000 ppm en poids et avantageusement entre 300 et 30 000 ppm en poids . [060] The radical initiator content relative to the (meth) acrylic monomer or the mixture of (meth) acrylic monomers of the liquid (meth) acrylic syrup is between 100 and 50,000 ppm by weight (50,000 ppm = 5% by weight), preferably between 200 and 40,000 ppm by weight and preferably between 300 and 30,000 ppm by weight.
[061] La dispersion aqueuse comprend avantageusement entre 30% et 80%, de préférence entre 35% et 70%, et de manière encore plus préférée entre 35% et 60% d'amorceur radicalaire. Une telle dispersion aqueuse comportant une teneur élevée en peroxyde organique contribue à permettre une polymérisation optimale et complète du mélange (méth) acrylique .  [061] The aqueous dispersion advantageously comprises between 30% and 80%, preferably between 35% and 70%, and even more preferably between 35% and 60% of radical initiator. Such an aqueous dispersion having a high content of organic peroxide contributes to allow optimal and complete polymerization of the (meth) acrylic mixture.
[062] La dispersion aqueuse comprend avantageusement entre 0.01% et 10%, de préférence entre 0.05% et 7%, et de manière encore plus préférée entre 0.1% et 5% d'un surfactant.  [062] The aqueous dispersion advantageously comprises between 0.01% and 10%, preferably between 0.05% and 7%, and even more preferably between 0.1% and 5% of a surfactant.
[063] La dispersion aqueuse comprend avantageusement entre 0.01% et 10%, de préférence entre 0.05% et 7%, et de manière encore plus préférée entre 0.1% et 5% d'un stabilisant.  [063] The aqueous dispersion advantageously comprises between 0.01% and 10%, preferably between 0.05% and 7%, and even more preferably between 0.1% and 5% of a stabilizer.
[064] Selon un mode de réalisation de l'invention, le pourcentage massique de l'amorceur radicalaire dans le mélange (méth) acrylique comprenant le sirop (méth) acrylique et la dispersion d'amorceur radicalaire est inférieur à 5%, de préférence inférieur à 3%, et de manière encore plus préférée inférieur à 2,5%.  [064] According to one embodiment of the invention, the weight percentage of the radical initiator in the (meth) acrylic mixture comprising the (meth) acrylic syrup and the radical initiator dispersion is less than 5%, preferably less than 3%, and even more preferably less than 2.5%.
[065] La viscosité de la dispersion aqueuse d'amorceur radicalaire est comprise entre 50 mPa*s et 1000 mPa*s, de préférence entre 100 mPa*s et 750 mPa*s, et de manière encore plus préférée entre 200 mPa*s et 500 mPa*s, ladite viscosité étant mesurée à 20°C, à 50 tours par minute. La viscosité peut être mesurée avec un rhéomètre ou un viscosimètre, par exemple un viscosimètre de type Brookfield tel que le Brookfield DVII.  [065] The viscosity of the aqueous dispersion of radical initiator is between 50 mPa * s and 1000 mPa * s, preferably between 100 mPa * s and 750 mPa * s, and even more preferably between 200 mPa * s and 500 mPa * s, said viscosity being measured at 20 ° C at 50 rpm. The viscosity can be measured with a rheometer or viscometer, for example a Brookfield type viscometer such as Brookfield DVII.
[066] Par ailleurs, la granulométrie de l'amorceur de la dispersion aqueuse est telle que le diamètre médian des particules en volume [066] Furthermore, the particle size of the initiator of the aqueous dispersion is such that the median diameter of the particles by volume
(D50) est compris entre 1 μιτι et 30 μιτι, de préférence entre 2 μιτι et 25 μιτι et de manière encore plus préférée entre 3,5 μιτι et 20 μιτι et avantageusement entre 3,5 μιτι et 15 μιτι, plus avantageusement entre 3,5 μιτι et 13 μιτι est encore plus avantageusement entre 3,5μιτι et 12μπι. (D50) is between 1 μιτι and 30 μιτι, preferably between 2 μιτι and 25 μιτι and even more preferably between 3.5 μιτι and 20 μιτι and advantageously between 3.5 μιτι and 15 μιτι, more advantageously between 3, 5 μιτι and 13 μιτι is even more advantageously between 3.5μιτι and 12μπι.
[067] Une telle granulométrie permet d'obtenir une dispersion homogène de l'amorceur dans l'eau, favorisant ainsi l'imprégnation du substrat fibreux par le mélange comprenant ladite dispersion aqueuse et le sirop (méth) acrylique . L'homogénéité de la dispersion permet également une polymérisation optimale et complète du sirop (méth) acrylique postérieurement à l'imprégnation du substrat fibreux par ledit sirop (méth) acrylique . [067] Such a particle size makes it possible to obtain a homogeneous dispersion of the initiator in the water, thus favoring the impregnation of the fibrous substrate with the mixture comprising said dispersion aqueous and (meth) acrylic syrup. The homogeneity of the dispersion also allows an optimal and complete polymerization of the (meth) acrylic syrup subsequent to the impregnation of the fibrous substrate with said (meth) acrylic syrup.
[068] Une telle polymérisation selon l'invention conduit à des poids moléculaires élevés, généralement supérieurs à 100 000 g/mol, préférentiellement supérieurs à 500 000 g/mol, et de manière encore plus préférée supérieurs à 1 000 000 g/mol. De telles valeurs de poids moléculaires permettent d'obtenir un matériau composite possédant de très bonnes propriétés mécaniques . [068] Such a polymerization according to the invention leads to high molecular weights, generally greater than 100,000 g / mol, preferably greater than 500,000 g / mol, and even more preferably greater than 1,000,000 g / mol. Such molecular weight values make it possible to obtain a composite material having very good mechanical properties.
[069] Une telle granulométrie permet également d'obtenir une dispersion aqueuse d' amorceur radicalaire stable, de sorte que l'amorceur est parfaitement soluble dans ladite dispersion aqueuse et dans le mélange (méth) acrylique obtenu après mélange du sirop [069] Such a particle size also makes it possible to obtain an aqueous dispersion of stable radical initiator, so that the initiator is perfectly soluble in said aqueous dispersion and in the (meth) acrylic mixture obtained after mixing the syrup.
(méth) acrylique et de ladite dispersion aqueuse. (meth) acrylic and said aqueous dispersion.
[070] La dispersion aqueuse selon l'invention, avant d'être mélangée avec le sirop (méth) acrylique pour former le mélange [070] The aqueous dispersion according to the invention, before being mixed with the (meth) acrylic syrup to form the mixture
(méth) acrylique, n'obstrue pas les lignes d'alimentation de la machine d'injection utilisée pour la mise en œuvre du procédé d'imprégnation du substrat fibreux et/ou du procédé de fabrication de pièces mécaniques ou d'éléments structurés ou d'articles en matériau composite selon l'invention, et n'est pas non plus apte à obstruer lesdites lignes d'alimentation de la machine d'injection. (meth) acrylic, does not obstruct the supply lines of the injection machine used for the implementation of the method of impregnating the fibrous substrate and / or the method of manufacturing mechanical parts or structured elements or of composite material according to the invention, and is also not able to obstruct said supply lines of the injection machine.
[071] De plus, après mélange de la dispersion aqueuse selon l'invention avec le sirop (méth) acrylique pour former le mélange [071] Moreover, after mixing the aqueous dispersion according to the invention with the (meth) acrylic syrup to form the mixture
(méth) acrylique, ledit mélange (méth) acrylique n'obstrue pas les lignes d'injection de la machine d'injection utilisée pour la mise en œuvre du procédé d'imprégnation du substrat fibreux et/ou du procédé de fabrication de pièces mécaniques ou d'éléments structurés ou d'articles en matériau composite selon l'invention, et n'est pas non plus apte à obstruer lesdites lignes d'injection de la machine d'injection. (meth) acrylic, said (meth) acrylic mixture does not obstruct the injection lines of the injection machine used for the implementation of the process for impregnating the fibrous substrate and / or the method for manufacturing mechanical parts or structured elements or articles of composite material according to the invention, and is also not able to obstruct said injection lines of the injection machine.
[072] Un avantage d'une telle dispersion aqueuse d' amorceur radicalaire selon l'invention est sa bonne solubilisation dans le sirop (méth) acrylique, de manière à former un mélange (méth) acrylique homogène. Il est ainsi possible d'utiliser un mélangeur statique pour mélanger la dispersion aqueuse d' amorceur radicalaire avec le sirop (méth) acrylique . Il reste bien entendu possible d'utiliser d'autres types de mélangeurs adaptés à la réalisation d'un tel mélange, tels qu'un mélangeur mécanique, ou un mélangeur à cuve tournante. An advantage of such an aqueous dispersion of radical initiator according to the invention is its good solubilization in the (meth) acrylic syrup, so as to form a homogeneous (meth) acrylic mixture. It is thus possible to use a static mixer for mixing the aqueous dispersion of radical initiator with the (meth) acrylic syrup. It remains of course possible to use other types of mixers suitable for producing such a mixture, such as a mechanical mixer, or a rotating bowl mixer.
[ 073 ] Un autre avantage d'une telle dispersion aqueuse d' amorceur radicalaire selon l'invention est de permettre une polymérisation homogène du mélange (méth) acrylique . En particulier, la polymérisation est homogène dans tout le volume du moule utilisé pour le procédé d'imprégnation du substrat fibreux et/ou pour le procédé de fabrication de pièces en matériau composite, aboutissant ainsi à la formation de pièces régulières possédant un nombre d' imperfections réduit par rapport aux pièces en matériau composite obtenues selon un procédé de fabrication différent de celui décrit dans le présent document.  [073] Another advantage of such an aqueous dispersion of radical initiator according to the invention is to allow homogeneous polymerization of the (meth) acrylic mixture. In particular, the polymerization is homogeneous throughout the volume of the mold used for the process for impregnating the fibrous substrate and / or for the process for manufacturing parts made of composite material, thus resulting in the formation of regular pieces having a number of imperfections reduced compared to composite material parts obtained by a manufacturing process different from that described in this document.
[ 074 ] Le monomère (méth) acrylique ou le mélange de monomères (méth) acryliques tel que défini précédemment peut éventuellement être accompagné d'un inhibiteur approprié afin d'empêcher ledit monomère (méth) acrylique de polymériser spontanément. Un tel inhibiteur peut être incorporé dans le sirop (méth) acrylique . Parmi les inhibiteurs appropriés on peut citer notamment 1 ' hydroquinone (HQ) , la méthylhydroquinone (MEHQ) , le 2,6-di-tert- butyl-4-méthoxyphénol (Topanol 0) et le 2, 4-diméthyl-6-tert- butylphénol (Topanol A) .  [074] The (meth) acrylic monomer or the mixture of (meth) acrylic monomers as defined above may optionally be accompanied by an appropriate inhibitor in order to prevent said (meth) acrylic monomer from spontaneously polymerizing. Such an inhibitor may be incorporated into the (meth) acrylic syrup. Suitable inhibitors include hydroquinone (HQ), methylhydroquinone (MEHQ), 2,6-di-tert-butyl-4-methoxyphenol (Topanol O) and 2,4-dimethyl-6-tert. - Butylphenol (Topanol A).
[ 075 ] Le mélange (méth) acrylique peut comprendre en outre un activateur pour la polymérisation, ledit activateur pouvant être incorporé dans le sirop (méth) acrylique .  [075] The (meth) acrylic mixture may further comprise an activator for the polymerization, said activator being capable of being incorporated into the (meth) acrylic syrup.
[ 076 ] L' activateur de polymérisation ou accélérateur est choisi parmi les aminés tertiaires telles que la N, -diméthyl-p-toluidine [076] The polymerization activator or accelerator is chosen from tertiary amines such as N, -dimethyl-p-toluidine
(DMPT) , la N, -dihydroxyéthyl-p-toluidine (DHEPT) , les catalyseurs de métaux de transition solubles dans les composés organiques ou leurs mélanges . (DMPT), N, -dihydroxyethyl-p-toluidine (DHEPT), transition metal catalysts soluble in organic compounds or mixtures thereof.
[ 077 ] Avantageusement, le sirop (méth) acrylique liquide ne contient pas de catalyseurs à base de métaux.  [077] Advantageously, the liquid (meth) acrylic syrup does not contain metal-based catalysts.
[ 078 ] La teneur de l' activateur par rapport au monomère (méth) acrylique du sirop (méth) acrylique liquide est de 100 ppm à 10 000 ppm en poids, de préférence de 200 ppm à 7 000 ppm et avantageusement de 300 ppm à 4 000 ppm en poids. [078] The content of the activator relative to the (meth) acrylic monomer of the liquid (meth) acrylic syrup is from 100 ppm to 10,000 ppm by weight, preferably from 200 ppm to 7000 ppm and preferably from 300 ppm to 4000 ppm by weight.
[079] La présence d' activateurs ou d'accélérateurs dépend de l'application finale. Lorsqu'une polymérisation à froid est nécessaire ou souhaitée, un accélérateur est généralement nécessaire. Polymérisation à froid signifie que la polymérisation a lieu à température ambiante, ou de manière générale à une température inférieure à 40 °C. Toutefois, pour les applications industrielles, il est possible de réaliser une polymérisation à chaud, à une température dès lors supérieure à 40 °C.  [079] The presence of activators or accelerators depends on the final application. When cold polymerization is needed or desired, an accelerator is generally required. Cold polymerization means that the polymerization takes place at room temperature, or generally at a temperature below 40 ° C. However, for industrial applications, it is possible to carry out a hot polymerization, at a temperature of greater than 40 ° C.
[080] Le mélange (méth) acrylique peut également comprendre un agent limitateur de chaîne afin de réguler le poids moléculaire du ou des polymère (s) formés. Il peut s'agir par exemple du γ-terpinène ou du terpinolène. La teneur de l'agent limitateur est généralement comprise entre 0 et 500 ppm et de préférence entre 0 et 100 ppm, par rapport au monomère (méth) acrylique ou au mélange de monomères (méth) acryliques du sirop (méth) acrylique . [080] The (meth) acrylic mixture may also comprise a chain-limiting agent in order to regulate the molecular weight of the polymer (s) formed. It may be, for example, γ-terpinene or terpinolene. The content of the limiting agent is generally between 0 and 500 ppm and preferably between 0 and 100 ppm, relative to the (meth) acrylic monomer or the mixture of (meth) acrylic monomers of the (meth) acrylic syrup.
[081] Le mélange (méth) acrylique peut également comprendre d'autres additifs et charges. Une charge n'est pas considérée comme un additif dans le cadre de la présente invention. De tels charges et additifs peuvent être incorporés dans le sirop (méth) acrylique . De plus, les additifs et/ou les charges peuvent être ajoutés au mélange (méth) acrylique avant l'imprégnation. [081] The (meth) acrylic mixture may also comprise other additives and fillers. A filler is not considered an additive in the context of the present invention. Such fillers and additives may be incorporated into the (meth) acrylic syrup. In addition, additives and / or fillers may be added to the (meth) acrylic mixture prior to impregnation.
[082] En tant qu'additifs, on peut mentionner les additifs organiques tels que les modificateurs de la résistance aux impacts ou les copolymères séquencés, les stabilisateurs thermiques, les stabilisateurs UV, les lubrifiants et leurs mélanges.  [082] As additives, mention may be made of organic additives such as impact resistance modifiers or block copolymers, thermal stabilizers, UV stabilizers, lubricants and mixtures thereof.
[083] Le modificateur de la résistance aux impacts est sous la forme de fines particules comprenant un noyau élastomère et au moins une enveloppe thermoplastique, la taille des particules étant généralement inférieure à 1 μιτι et avantageusement comprise entre 50 et 300 μιτι. Le modificateur de la résistance aux impacts est préparé par polymérisation en émulsion. La teneur du modificateur de la résistance aux impacts dans le sirop (méth) acrylique liquide est de 0 à 50 % en poids, de préférence de 0 à 25 % en poids et avantageusement de 0 à 20 % en poids. [ 084 ] De préférence, les additifs sont choisis parmi les modificateurs de la résistance aux impacts ou des copolymères séquencés, les stabilisateurs thermiques, les stabilisateurs UV, les agents ignifuges, les lubrifiants, les agents de démoulage, les colorants, ou leurs mélanges. [083] The modifier of the impact resistance is in the form of fine particles comprising an elastomeric core and at least one thermoplastic envelope, the size of the particles being generally less than 1 μιτι and advantageously between 50 and 300 μιτι. The impact modifier is prepared by emulsion polymerization. The content of the impact modifier in the liquid (meth) acrylic syrup is 0 to 50% by weight, preferably 0 to 25% by weight and preferably 0 to 20% by weight. [084] Preferably, the additives are selected from impact modifiers or block copolymers, thermal stabilizers, UV stabilizers, flame retardants, lubricants, release agents, dyes, or mixtures thereof.
[ 085 ] Les additifs sont présents dans le mélange (méth) acrylique à une teneur comprise entre 0.01% massique et 50% massique de sorte que la viscosité dynamique du sirop (méth) acrylique soit comprise entre 10 mPa*s et 1000 mPa*s à 20°C.  [085] The additives are present in the (meth) acrylic mixture at a content of between 0.01% by weight and 50% by weight so that the dynamic viscosity of the (meth) acrylic syrup is between 10 mPa * s and 1000 mPa * s at 20 ° C.
[ 086 ] En tant que charges, on peut citer les nanotubes de carbone ou les charges minérales, y compris les nanocharges minérales (Ti02, silice) . As fillers, mention may be made of carbon nanotubes or mineral fillers, including mineral nanofillers (TiO 2 , silica).
[ 087 ] De préférence, les charges sont choisies parmi le carbonate de calcium (CaCÛ3) , le dioxyde de titane (T1O2) , et la silice (Si02) . [087] Preferably, the fillers are chosen from calcium carbonate (CaCO 3), titanium dioxide (TiO 2) and silica (SiO 2 ).
[ 088 ] Les charges sont présentes dans la dispersion aqueuse à une teneur comprise entre 0.01% massique et 40% massique de sorte que la viscosité dynamique du mélange (méth) acrylique liquide soit comprise entre 10 mPa*s et 1000 mPa*s à 20°C.  [088] The fillers are present in the aqueous dispersion at a content of between 0.01% by weight and 40% by mass, so that the dynamic viscosity of the liquid (meth) acrylic mixture is between 10 mPa * s and 1000 mPa * s at 20 ° C. ° C.
[ 089 ] Par ailleurs, de manière avantageuse le mélange (méth) acrylique comprend entre 95% et 99% en poids, de préférence entre 96% et 98,5% en poids, et de manière encore plus préférée entre 97% et 98% en poids de sirop (méth) acrylique, et entre 1% et 5% en poids, de préférence entre 1,5% et 4% en poids, et de manière encore plus préférée entre 2% et 3% en poids de dispersion aqueuse .  [089] Furthermore, advantageously, the (meth) acrylic mixture comprises between 95% and 99% by weight, preferably between 96% and 98.5% by weight, and even more preferably between 97% and 98% by weight. by weight of (meth) acrylic syrup, and between 1% and 5% by weight, preferably between 1.5% and 4% by weight, and even more preferably between 2% and 3% by weight of aqueous dispersion.
Le procédé de fabrication pour la fabrication de pièces mécaniques ou d'éléments structurés ou d'articles The manufacturing process for the manufacture of mechanical parts or structured elements or articles
[ 090 ] Le procédé comprend les étapes suivantes : [090] The method comprises the following steps:
a) l'imprégnation d'un substrat fibreux avec un mélange (méth) acrylique liquide,  a) impregnating a fibrous substrate with a liquid (meth) acrylic mixture,
b) la polymérisation du mélange (méth) acrylique liquide imprégnant ledit substrat fibreux. [091] L'imprégnation du substrat fibreux à l'étape a) est de préférence réalisée dans un moule fermé. Avantageusement, l'étape a) et l'étape b) sont réalisées dans le même moule fermé. b) the polymerization of the liquid (meth) acrylic mixture impregnating said fibrous substrate. [091] The impregnation of the fibrous substrate in step a) is preferably carried out in a closed mold. Advantageously, step a) and step b) are carried out in the same closed mold.
[092] Les pièces mécaniques ou les éléments structurés ou les articles à base de matériau composite peuvent être obtenus selon différents procédés. On peut mentionner l'infusion, le moulage en sac sous vide, le moulage en sac sous pression, le moulage en autoclave, le moulage par transfert de résine (RTM) , le moulage par injection-réaction (RIM) , le moulage par injection-réaction renforcé (R-RIM) et ses variantes, le moulage sous presse ou le moulage par compression. [092] Mechanical parts or structured elements or articles based on composite material can be obtained by different methods. Examples include infusion, vacuum bag molding, pressure bag molding, autoclave molding, resin transfer molding (RTM), injection reaction molding (RIM), injection molding Reinforced reaction (R-RIM) and its variants, press molding or compression molding.
[093] Les procédés de fabrication préférés pour la fabrication de pièces mécaniques ou éléments structurés ou articles à base de matériau composite sont des procédés selon lesquels le mélange (méth) acrylique liquide est transféré au substrat fibreux par imprégnation dudit substrat fibreux dans un moule, de manière davantage préférée dans un moule fermé.  [093] Preferred manufacturing methods for manufacturing mechanical parts or structured elements or composite material articles are processes in which the liquid (meth) acrylic mixture is transferred to the fibrous substrate by impregnating said fibrous substrate in a mold, more preferably in a closed mold.
[094] Avantageusement, le procédé de fabrication est choisi parmi le moulage par transfert de résine ou l'infusion.  [094] Advantageously, the manufacturing method is chosen from resin transfer molding or infusion.
[095] Tous les procédés comprennent l'étape d'imprégnation du substrat fibreux avec le mélange (méth) acrylique liquide avant l'étape de polymérisation dans un moule. L'étape de polymérisation du mélange (méth) acrylique liquide imprégnant ledit substrat fibreux a lieu après l'étape d'imprégnation dans le même moule.  [095] All methods include the step of impregnating the fibrous substrate with the liquid (meth) acrylic mixture prior to the polymerization step in a mold. The polymerization step of the liquid (meth) acrylic mixture impregnating said fibrous substrate takes place after the impregnation step in the same mold.
[096] Le moulage par transfert de résine est un procédé utilisant un ensemble de moulage à deux côtés qui forme les deux surfaces d'un matériau composite. Le côté inférieur est un moule rigide. Le côté supérieur peut être un moule rigide ou flexible. Des moules flexibles peuvent être fabriqués à partir de matériaux composites, de silicone ou de films polymères extrudés tels que le nylon. Les deux côtés s'emboîtent pour former une cavité de moulage. La caractéristique distinctive du moulage par transfert de résine est que le substrat fibreux est placé dans cette cavité et que l'ensemble de moulage est fermé avant l'introduction du sirop (méth) acrylique liquide. Le moulage par transfert de résine comprend de nombreuses variations qui diffèrent au niveau de la mécanique d'introduction du sirop (méth) acrylique liquide au niveau du substrat fibreux dans la cavité de moulage. Ces variations vont de l'infusion sous vide au moulage par transfert de résine sous vide (VARTM) . Ce procédé peut être réalisé à température ambiante ou élevée. [096] Resin transfer molding is a process using a two-sided molding assembly that forms the two surfaces of a composite material. The bottom side is a rigid mold. The upper side may be a rigid or flexible mold. Flexible molds can be made from composite materials, silicone or extruded polymeric films such as nylon. Both sides snap together to form a molding cavity. The distinctive feature of resin transfer molding is that the fibrous substrate is placed in this cavity and the molding assembly is closed prior to introduction of the liquid (meth) acrylic syrup. Resin transfer molding includes many variations that differ in the mechanics of introducing liquid (meth) acrylic syrup into the level of the fibrous substrate in the molding cavity. These variations range from vacuum infusion to vacuum resin transfer molding (VARTM). This process can be performed at room temperature or elevated.
[097] Avec le procédé d'infusion, le sirop (méth) acrylique liquide doit avoir la viscosité adaptée pour ce procédé de préparation du matériau composite polymère. Le sirop (méth) acrylique liquide est aspiré dans le substrat fibreux présent dans un moule spécial par application d'un léger vide. Le substrat fibreux est infusé et complètement imprégné par le sirop (méth) acrylique liquide.  [097] With the infusion process, the liquid (meth) acrylic syrup must have the appropriate viscosity for this method of preparation of the polymeric composite material. The liquid (meth) acrylic syrup is sucked into the fibrous substrate present in a special mold by applying a slight vacuum. The fibrous substrate is infused and completely impregnated with the liquid (meth) acrylic syrup.
[098] Un avantage de ce procédé est la grande quantité de matériau fibreux dans le composite. An advantage of this process is the large amount of fibrous material in the composite.
[099] Pour la mise en œuvre du procédé d'imprégnation du substrat fibreux et/ou du procédé de fabrication de pièce en matériau composite, il est possible d'utiliser une machine d'injection dont une première entrée est alimentée par le sirop (méth) acrylique, et une deuxième entrée est alimentée par la dispersion d' amorceur radicalaire. Le sirop et la dispersion sont ensuite acheminés vers un mélangeur où ils sont mélangés de manière à obtenir un mélange [099] For the implementation of the process for impregnating the fibrous substrate and / or the process for manufacturing a composite material part, it is possible to use an injection machine whose first inlet is fed with the syrup ( meth) acrylic, and a second inlet is fed by the radical initiator dispersion. The syrup and the dispersion are then conveyed to a mixer where they are mixed to form a mixture
(méth) acrylique sensiblement homogène, puis injectés dans un moule dans lequel est préalablement déposé un substrat fibreux. Ledit substrat fibreux est imprégné par le mélange (méth) acrylique, puis une polymérisation du système obtenu permet de former une pièce en matériau composite. (meth) acrylic substantially homogeneous, then injected into a mold in which is previously deposited a fibrous substrate. Said fibrous substrate is impregnated with the (meth) acrylic mixture, and then a polymerization of the obtained system makes it possible to form a composite material part.
[0100] De préférence, le débit en sortie, c'est-à-dire le débit d'injection du mélange (méth) acrylique dans le moule, est inférieur à 4 kg/minute, de préférence inférieur à 3.4 kg/minute.  Preferably, the output flow rate, that is to say the rate of injection of the (meth) acrylic mixture into the mold, is less than 4 kg / minute, preferably less than 3.4 kg / minute.
[0101] En ce qui concerne l'utilisation des pièces mécaniques ou d'éléments structurés ou d'articles fabriqués, on peut mentionner les applications automobiles, les applications nautiques, les applications ferroviaires, le sport, les applications aéronautiques et aérospatiales, les applications photovoltaïques , les applications informatiques, les applications pour les télécommunications et les applications pour l'énergie éolienne . As regards the use of mechanical parts or structured elements or manufactured articles, mention may be made of automotive applications, nautical applications, railway applications, sports, aeronautical and aerospace applications, applications photovoltaic, computer applications, telecommunications applications and wind energy applications.
[0102] Les pièces mécaniques sont notamment des pièces d'automobile, des pièces de bateau, des pièces de train, des articles de sport, des pièces d'avion ou d'hélicoptère, des pièces de vaisseau spatial ou de fusée, des pièces de module photovoltaïque, des pièces d'éolienne, des pièces de meuble, des pièces de construction ou de bâtiment, des pièces de téléphone ou de téléphone portable, des pièces d'ordinateur ou de télévision, des pièce d'imprimante et de photocopieuse. [0102] The mechanical parts include automobile parts, boat parts, train parts, sporting goods, aircraft or helicopter parts, spaceship or rocket parts, photovoltaic module parts, wind turbine parts, furniture parts, construction or building parts, parts phone or cell phone, computer or television parts, printer and photocopier parts.
[Exemples] [Examples]
[0103] Un sirop (méth) acrylique est préparé par dissolution de [0103] A (meth) acrylic syrup is prepared by dissolving
25 parties en poids d'un copolymère (PMMA - polyacrylate d'éthyle) de type BS520 dans 75 parties en poids de méthacrylate de méthyle stabilisé avec du MEHQ (éther monométhylique d' hydroquinone ) , et 0,5 partie en poids de N, -dihydroxyéthyl-p-toluidine (DHEPT) . Le sirop (méth) acrylique ainsi obtenu est appelé composant A. 25 parts by weight of a BS520-type copolymer (PMMA-polyacrylate) in 75 parts by weight of methyl methacrylate stabilized with MEHQ (hydroquinone monomethyl ether), and 0.5 part by weight of N, Dihydroxyethyl-p-toluidine (DHEPT). The (meth) acrylic syrup thus obtained is called component A.
[0104] On prépare trois formulations différentes de peroxyde de benzoyle (BPO) , le BPO étant appelé composant B. Les différentes formulations, désignées par BPO 1, BPO 2, et BPO 3, sont indiquées dans le Tableau I ci-dessous. La viscosité de ces formulations est mesurée à l'aide d'un Viscosimètre de type Brookfield à 50 tours par minute et à 20°C. La granulométrie et le diamètre D50 des dispersions ou suspensions de BPO est mesuré par diffraction laser en utilisant un appareil HELOS SUCELL de la société SYMPATEC GmbH. Les différentes formulations de BPO sont commercialisées sous les marques Luperox® ANS50G, Luperox ® A40FP- EZ9, et Perkadox® L-40RPS, par la société ARKEMA. Three different formulations of benzoyl peroxide (BPO) are prepared, the BPO being called component B. The various formulations, designated BPO 1, BPO 2, and BPO 3, are indicated in Table I below. The viscosity of these formulations is measured using a Brookfield type viscometer at 50 rpm and at 20 ° C. The particle size and the diameter D50 of the dispersions or suspensions of BPO are measured by laser diffraction using a HELOS SUCELL apparatus of SYMPATEC GmbH. The various BPO formulations are marketed under the trade names Luperox® ANS50G, Luperox® A40FP-EZ9 and Perkadox® L-40RPS, by the company Arkema.
[0105] Tableau I : formulations de BPO [0105] Table I: BPO formulations
[0106] Le sirop méthacrylique (composant A) et les différentes formulations de BPO (composant B) indiquées ci-dessus, peuvent être utilisés pour le moulage par procédé RTM en utilisant la machine d'injection PatriotTM Pro Thermoplastic Resin Injection System, fabriquée par la société Magnum Venus Products, Kent (WA) . Il s'agit d'une machine pneumatique fonctionnant avec une pression maximale d'air comprimé de 7 bars, avec des boucles de recirculation et des systèmes de nettoyage pour chacun des composants. Le débit en sortie peut aller jusqu'à 3,4 kg par minute, la teneur en volume du composant B par rapport au composant A est comprise entre 1.0% et 4.5%. The methacrylic syrup (component A) and the various BPO formulations (component B) indicated above, can be used for RTM molding using the PatriotTM Pro Thermoplastic Resin Injection System injection machine, manufactured by Magnum Venus Products, Kent (WA). It is a pneumatic machine with a maximum compressed air pressure of 7 bar, with recirculation loops and cleaning systems for each component. The output flow rate can be up to 3.4 kg per minute, the volume content of component B relative to component A is between 1.0% and 4.5%.
[0107] Le mélange (méth) acrylique liquide comprenant le sirop (méth) acrylique et l'une des formulations ci-dessus est injecté dans un moule fermé comprenant un tissu de verre en tant que substrat fibreux, et polymérisé à 25 °C pendant 40 à 50 minutes. - Avec la formulation BP01, seulement deux pièces ont pu être réalisées. Par la suite, la machine s'est bloquée. Le filtre principal et les canalisations d'injection étaient bouchés. The (meth) acrylic liquid mixture comprising the (meth) acrylic syrup and one of the above formulations is injected into a closed mold comprising a glass fabric as a fibrous substrate, and polymerized at 25 ° C. for 40 to 50 minutes. - With the formulation BP01, only two pieces could be realized. Subsequently, the machine was blocked. Main filter and injection lines were clogged.
Avec la formulation BP02, une gamme de 30 pièces a été réalisée sur plusieurs jours, ne nécessitant aucune intervention sur la machine.  With the formulation BP02, a range of 30 pieces was made over several days, requiring no intervention on the machine.
Avec la formulation BP03, le filtre de la machine s'est bouché au bout de quelques minutes de fonctionnement, nécessitant l'arrêt et le nettoyage complet de la machine avant redémarrage .  With the formulation BP03, the filter of the machine clogged after a few minutes of operation, requiring the stop and the complete cleaning of the machine before restarting.

Claims

REVENDICATIONS
Procédé d'imprégnation d'un substrat fibreux, ledit procédé étant caractérisé en ce qu'il comprend une étape d' imprégnation dudit substrat fibreux avec un mélange (méth) acrylique liquide comprenant :  A process for impregnating a fibrous substrate, said method being characterized in that it comprises a step of impregnating said fibrous substrate with a liquid (meth) acrylic mixture comprising:
- un sirop (méth) acrylique comprenant au moins un polymère (méth) acrylique, et au moins un monomère (méth) acrylique,a (meth) acrylic syrup comprising at least one (meth) acrylic polymer and at least one (meth) acrylic monomer,
- une dispersion aqueuse comprenant au moins un amorceur radicalaire constitué d'un peroxyde organique pour démarrer la polymérisation du monomère (méth) acrylique, ledit au moins un amorceur radicalaire présentant une granulométrie telle que le diamètre médian des particules en volume (D50) est compris entre 1 μιτι et 30 μιτι, de préférence entre 2 μιτι et 25 μιτι et de manière encore plus préférée entre 3,5 μιτι et 20 μιτι et avantageusement entre 3,5 μιτι et 15 μιτι, plus avantageusement entre 3,5 μιτι et 13 μιτι est encore plus avantageusement entre 3,5μιτι et 12μιτι. an aqueous dispersion comprising at least one radical initiator consisting of an organic peroxide to start the polymerization of the (meth) acrylic monomer, said at least one radical initiator having a particle size such that the median diameter of the particles by volume (D50) is included between 1 μιτι and 30 μιτι, preferably between 2 μιτι and 25 μιτι and even more preferably between 3.5 μιτι and 20 μιτι and advantageously between 3.5 μιτι and 15 μιτι, more preferably between 3.5 μιτι and 13 μιτι is even more advantageously between 3.5μιτι and 12μιτι.
Procédé d' imprégnation selon la revendication 1, caractérisé en ce que l'étape d' imprégnation du substrat fibreux est réalisée dans un moule fermé . Impregnation process according to claim 1, characterized in that the impregnating step of the fibrous substrate is carried out in a closed mold.
Procédé d'imprégnation selon la revendication 1 ou 2, caractérisé en ce que l' amorceur radicalaire est choisi parmi les peroxydes de diacyle, les peroxyesters , les peroxydes de dialkyle, les peroxyacétals ou les composés azo. Impregnation process according to claim 1 or 2, characterized in that the radical initiator is chosen from diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals or azo compounds.
Procédé d'imprégnation selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l' amorceur radicalaire est constitué de peroxyde benzoyle (BPO) . Impregnation process according to any one of Claims 1 to 3, characterized in that the radical initiator consists of benzoyl peroxide (BPO).
Procédé d'imprégnation selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la teneur en amorceur radicalaire par rapport au monomère (méth) acrylique ou au mélange de monomères (méth) acryliques est comprise entre 100 et 50 000 ppm en poids, de préférence entre 200 et 40 000 ppm en poids et avantageusement entre 300 et 30 000 ppm en poids. Impregnation process according to any one of Claims 1 to 4, characterized in that the content of radical initiator relative to the (meth) acrylic monomer or to the mixture of (meth) acrylic monomers is between 100 and 50 000 ppm. weight, preferably between 200 and 40,000 ppm by weight and preferably between 300 and 30,000 ppm by weight.
Procédé d'imprégnation selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le pourcentage massique en amorceur radicalaire dans la dispersion aqueuse est compris entre 30% et 80%, de préférence entre 35% et 70%, et de manière encore plus préférée est entre 35% et 60%. Impregnation process according to any one of Claims 1 to 5, characterized in that the weight percentage of radical initiator in the aqueous dispersion is between 30% and 80%, preferably between 35% and 70%, and even more preferred is between 35% and 60%.
Procédé d'imprégnation selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le pourcentage massique en amorceur radicalaire dans le mélange (méth) acrylique est inférieur à 5%, de préférence inférieur à 3%, et de manière encore plus préférée inférieur àImpregnation process according to any one of Claims 1 to 6, characterized in that the mass percentage of radical initiator in the (meth) acrylic mixture is less than 5%, preferably less than 3%, and even more favorite lower than
2.5%. 2.5%.
Procédé d'imprégnation selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la dispersion aqueuse d'amorceur radicalaire présente une viscosité à 20°C comprise entre 50 mPa*s et 1000 mPa*s, de préférence entre 100 mPa*s et 750 mPa*s, et de manière encore plus préférée entre 200 mPa*s et 500 mPa*s. Impregnation process according to any one of claims 1 to 7, characterized in that the aqueous dispersion of radical initiator has a viscosity at 20 ° C of between 50 mPa * s and 1000 mPa * s, preferably between 100 mPa * s and 750 mPa * s, and even more preferably between 200 mPa * s and 500 mPa * s.
Procédé d'imprégnation selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le polymère (méth) acrylique est un homopolymère de méthacrylate de méthyle (MMA) ou un copolymère de méthacrylate de méthyle (MMA) ou un de leurs mélanges . Impregnation process according to one of Claims 1 to 8, characterized in that the (meth) acrylic polymer is a homopolymer of methyl methacrylate (MMA) or a copolymer of methyl methacrylate (MMA) or a mixture thereof .
Procédé d'imprégnation selon la revendication 9, caractérisé en ce que le copolymère de méthacrylate de méthyle (MMA) comprend au moins 70 %, de préférence au moins 80 %, avantageusement au moins 90 % et plus avantageusement au moins 95 % en poids de méthacrylate de méthyle (MMA) . Impregnation process according to claim 9, characterized in that the methyl methacrylate (MMA) copolymer comprises at least 70%, preferably at least 80%, advantageously at least 90% and more preferably at least 95% by weight of methyl methacrylate (MMA).
Procédé d'imprégnation selon la revendication 9, caractérisé en ce que le copolymère de méthacrylate de méthyle (MMA) comprend de 80 % à 99,7 %, avantageusement de 90 % à 99,7 % et plus avantageusement de 90 % à 99,5 % en poids de méthacrylate de méthyle et de 0,3 % à 20 %, avantageusement de 0,Impregnation method according to claim 9, characterized in that the methyl methacrylate (MMA) copolymer comprises from 80% to 99.7%, preferably from 90% to 99.7% and more preferably from 90% to 99%, 5% by weight of methacrylate from methyl and from 0.3% to 20%, advantageously from 0,
3 % à 10 % et plus avantageusement de 0,5 % à 10 % en poids d'au moins un monomère contenant au moins une insaturation éthylénique qui peut copolymériser avec le méthacrylate de méthyle. From 3% to 10% and more preferably from 0.5% to 10% by weight of at least one monomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate.
Procédé d'imprégnation selon l'une quelconque des revendications 1 à 11, caractérisé en ce que le polymèreImpregnation process according to one of Claims 1 to 11, characterized in that the polymer
(méth) acrylique dans le mélange (méth) acrylique liquide est présent à hauteur d'au moins 10 % en poids, de préférence d'au moins 15 %, avantageusement d'au moins 18 % et plus avantageusement d'au moins 20 % en poids du mélange(meth) acrylic in the liquid (meth) acrylic mixture is present at least 10% by weight, preferably at least 15%, advantageously at least 18% and more preferably at least 20% by weight of the mixture
(méth) acrylique liquide total. total (meth) acrylic acid.
Procédé d'imprégnation selon l'une quelconque des revendications 1 à 12, caractérisé en ce que le polymèreImpregnation process according to any one of Claims 1 to 12, characterized in that the polymer
(méth) acrylique dans le mélange (méth) acrylique liquide est présent à hauteur d'au plus 60 % en poids, de préférence d'au plus 50 %, avantageusement d'au plus 40 % et plus avantageusement d'au plus 35 % en poids du mélange(meth) acrylic in the liquid (meth) acrylic mixture is present at most 60% by weight, preferably at most 50%, advantageously at most 40% and more preferably at most 35% by weight of the mixture
(méth) acrylique liquide total. total (meth) acrylic acid.
4. Procédé d'imprégnation selon l'une quelconque des revendications 1 à 13, caractérisé en ce que le mélange (méth) acrylique comprend en outre en activateur. 4. Impregnation process according to any one of claims 1 to 13, characterized in that the (meth) acrylic mixture further comprises activator.
Procédé d'imprégnation selon la revendication 14, caractérisé en ce que l' activateur est choisi parmi les aminés tertiaires telles que la N, -diméthyl-p-toluidine (DMPT) , la N,N- dihydroxyéthyl-p-toluidine (DHEPT) , les catalyseurs de métaux de transition solubles dans les composés organiques ou leurs mélanges . Impregnation process according to Claim 14, characterized in that the activator is chosen from tertiary amines such as N, -dimethyl-p-toluidine (DMPT) and N, N-dihydroxyethyl-p-toluidine (DHEPT). transition metal catalysts soluble in organic compounds or mixtures thereof.
6. Procédé d'imprégnation selon la revendication 14 ou 15, caractérisé en ce que la teneur de l' activateur par rapport au monomère (méth) acrylique du sirop (méth) acrylique liquide est de 100 ppm à 10 000 ppm (en poids) , de préférence de 200 ppm à 7 000 ppm en poids et avantageusement de 300 ppm à 4 000 ppm. 6. Impregnation process according to claim 14 or 15, characterized in that the content of the activator relative to the (meth) acrylic monomer of the liquid (meth) acrylic syrup is from 100 ppm to 10 000 ppm (by weight) preferably from 200 ppm to 7000 ppm by weight and preferably from 300 ppm to 4000 ppm.
Procédé d'imprégnation selon l'une quelconque des revendications 1 à 16, caractérisé en ce que le mélange Impregnation process according to one of Claims 1 to 16, characterized in that the mixture
(méth) acrylique comprend entre 95% et 99% en poids, de préférence entre 96% et 98,5% en poids, et de manière encore plus préférée entre 97% et 98% en poids de sirop(meth) acrylic comprises between 95% and 99% by weight, preferably between 96% and 98.5% by weight, and even more preferably between 97% and 98% by weight of syrup.
(méth) acrylique, et entre 1% et 5% en poids, de préférence entre 1,5% et 4% en poids, et de manière encore plus préférée entre 2% et 3% en poids de dispersion aqueuse. (meth) acrylic, and between 1% and 5% by weight, preferably between 1.5% and 4% by weight, and even more preferably between 2% and 3% by weight of aqueous dispersion.
8. Mélange (méth) acrylique liquide pour la mise en œuvre du procédé d'imprégnation d'un substrat fibreux selon l'une quelconque des revendications 1 à 17, ledit mélange (méth) acrylique étant caractérisé en ce qu'il comprend : un sirop (méth) acrylique comprenant au moins un polymè (méth) acrylique, et au moins un monomère (méth) acrylique, 8. A liquid (meth) acrylic mixture for carrying out the process for impregnating a fibrous substrate according to any one of claims 1 to 17, said (meth) acrylic mixture being characterized in that it comprises: a (meth) acrylic syrup comprising at least one (meth) acrylic polymer and at least one (meth) acrylic monomer,
- une dispersion aqueuse comprenant au moins un amorceur radicalaire constitué d'un peroxyde organique pour démarrer la polymérisation du monomère (méth) acrylique, ledit au moins un amorceur radicalaire présentant une granulométrie telle que le diamètre médian des particules en volume (D50) est compris entre 1 μιτι et 30 μιτι, de préférence entre 2 μιτι et 25 μιτι et de manière encore plus préférée entre 3,5 μιτι et 20 μιτι et avantageusement entre 3,5 μιτι et 15 μιτι, plus avantageusement entre 3,5 μιτι et 13 μιτι est encore plus avantageusement entre 3,5μιτι et 12μιτι. an aqueous dispersion comprising at least one radical initiator consisting of an organic peroxide to start the polymerization of the (meth) acrylic monomer, said at least one radical initiator having a particle size such that the median diameter of the particles by volume (D50) is included between 1 μιτι and 30 μιτι, preferably between 2 μιτι and 25 μιτι and even more preferably between 3.5 μιτι and 20 μιτι and advantageously between 3.5 μιτι and 15 μιτι, more preferably between 3.5 μιτι and 13 μιτι is even more advantageously between 3.5μιτι and 12μιτι.
9. Procédé de fabrication de pièces mécaniques ou d'éléments structurés ou d'articles, ledit procédé étant caractérisé en ce qu'il comprend les étapes suivantes : 9. A method of manufacturing mechanical parts or structured elements or articles, said method being characterized in that it comprises the following steps:
- a) l'imprégnation d'un substrat fibreux avec un mélange (méth) acrylique liquide seIon l'une quelconque des revendications 1 à 17 avec un mélange (méth) acrylique liquide selon la revendication 18, - b) la polymérisation du mélange (méth) acrylique liquide imprégnant ledit substrat fibreux. a) impregnating a fibrous substrate with a liquid (meth) acrylic mixture according to any one of claims 1 to 17 with a liquid (meth) acrylic mixture according to claim 18, b) the polymerization of the liquid (meth) acrylic mixture impregnating said fibrous substrate.
Procédé de fabrication selon la revendication 19, caractérisé en ce qu'il comprend en outre, préalablement à l'étape a), une étape de formation du mélange (méth) acrylique liquide par mélange d'un sirop (méth) acrylique comprenant au moins un polymère (méth) acrylique, et au moins un monomère (méth) acrylique, et d'une dispersion aqueuse comprenant au moins un amorceur radicalaire constitué d'un peroxyde organique pour démarrer la polymérisation du monomère (méth) acrylique, ledit au moins un amorceur radicalaire présentant une granulométrie telle que le diamètre médian des particules en volume (D50) est compris entre 1 μιτι et 30 μιτι, de préférence entre 2 μιτι et 25 μιτι et de manière encore plus préférée entre 3,5 μιτι et 20 μιτι et avantageusement entre 3,5 μιτι et 15 μπι. Manufacturing method according to claim 19, characterized in that it further comprises, prior to step a), a step of forming the liquid (meth) acrylic mixture by mixing a (meth) acrylic syrup comprising at least a (meth) acrylic polymer, and at least one (meth) acrylic monomer, and an aqueous dispersion comprising at least one radical initiator consisting of an organic peroxide to start the polymerization of the (meth) acrylic monomer, said at least one radical initiator having a particle size such that the median diameter of the particles by volume (D50) is between 1 μιτι and 30 μιτι, preferably between 2 μιτι and 25 μιτι and even more preferably between 3.5 μιτι and 20 μιτι and advantageously between 3.5 μιτι and 15 μπι.
1. Procédé de fabrication selon la revendication 19 ou 20, caractérisé en ce que l'imprégnation du substrat fibreux à l'étape a) est réalisée dans un moule fermé. 1. The manufacturing method according to claim 19 or 20, characterized in that the impregnation of the fibrous substrate in step a) is carried out in a closed mold.
2. Procédé de fabrication selon l'une quelconque des revendications 19 à 21, caractérisé en ce que l'étape a) et l'étape b) sont réalisées dans le même moule fermé. 2. Manufacturing process according to any one of claims 19 to 21, characterized in that step a) and step b) are performed in the same closed mold.
3. Procédé de fabrication selon l'une quelconque des revendications 19 à 22, caractérisé en ce que le procédé est choisi parmi le moulage par transfert de résine ou l'infusion. 3. Manufacturing process according to any one of claims 19 to 22, characterized in that the method is selected from resin transfer molding or infusion.
4. Pièce mécanique ou structurelle en matériau composite obtenue par le procédé de fabrication selon les revendications 19 à 23. 4. Mechanical or structural part of composite material obtained by the manufacturing method according to claims 19 to 23.
5. Pièce selon la revendication 24, ladite pièce étant une pièce d'automobile, une pièce de bateau, une pièce de train, un article de sport, une pièce d'avion ou d'hélicoptère, une pièce de vaisseau spatial ou de fusée, une pièce de module photovoltaïque , une pièce d'éolienne, une pièce de meuble, une pièce de construction ou de bâtiment, une pièce de téléphone ou de téléphone portable, une pièce d'ordinateur ou de télévision, une pièce d'imprimante ou de photocopieuse. 5. Part according to claim 24, said part being an automobile part, a boat part, a train piece, a sporting article, an airplane or helicopter part, a piece of spaceship or rocket. , a piece of module photovoltaic, a piece of wind, a piece of furniture, a building or building room, a piece of telephone or mobile phone, a computer or television room, a printer or photocopier.
EP15828360.6A 2014-12-22 2015-12-22 Method for impregnating a fibrous substrate with a (meth)acrylic mixture, composition of said (meth)acrylic mixture, and composite material produced after polymerisation of said (meth)acrylic mixture Withdrawn EP3237505A1 (en)

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US5162280A (en) 1988-01-27 1992-11-10 Witco Corporation Aqueous dispersions of aromatic diacyl peroxides
US5300600A (en) 1989-10-12 1994-04-05 Witco Corporation Aqueous dispersions of peroxides
DE69917106T2 (en) * 1998-03-06 2005-05-19 Nippon Shokubai Co. Ltd. (Meth) acrylic acid polymer and process for its preparation
TWI506078B (en) * 2008-08-14 2015-11-01 Lucite Int Uk Ltd A hardenable two part acrylic composition
SA110310245B1 (en) * 2009-04-03 2014-11-12 اكزو نوبل كيميكا Aqueous Solid Diacyl Peroxide Suspension
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* Cited by examiner, † Cited by third party
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