Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • 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
• • 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
  • 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
• • 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
  • B29K2033/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
• • 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
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
  • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
  • B29K2105/0809—Fabrics
• • 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
  • B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
  • B29K2309/08—Glass
• • 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
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
  • B29K2995/0026—Transparent
• • 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
• • 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
• • 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
  • C08J2425/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
  • C08J2425/02—Homopolymers or copolymers of hydrocarbons
  • C08J2425/04—Homopolymers or copolymers of styrene
  • C08J2425/08—Copolymers of styrene
• • 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
  • C08J2435/00—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 at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
  • C08J2435/06—Copolymers with vinyl aromatic monomers

Definitions

• the present invention relates to a liquid (meth) acrylic syrup for impregnating a fibrous substrate.
• the invention relates to a viscous (meth) acrylic liquid syrup containing mainly methacrylic or acrylic components and a component intended to render transparent / translucent a composite material comprising a fibrous substrate based on glass fibers, and a thermoplastic matrix obtained after polymerization of the syrup.
• the invention further relates to a process for impregnating a fibrous substrate comprising long glass fibers with said viscous liquid syrup.
• the invention also relates to a fibrous substrate pre-impregnated with said syrup which is useful for the manufacture of composite parts.
• the present invention also relates to a method of manufacturing composite parts and composite parts obtained by this method.
• a composite material is a macroscopic combination of two or more immiscible materials.
• the composite material is constituted by at least one material that forms the matrix, that is to say a continuous phase ensuring the cohesion of the structure, and a reinforcing material.
• the objective when using a composite material, is to obtain performance that is not available with each of its components when used separately.
• composite materials are widely used in many industrial sectors such as construction, automotive, aerospace, transportation, recreation, electronics and sports, particularly because of their best mechanical performance (superior tensile strength, superior tensile modulus, superior fracture toughness) and low density compared to homogeneous materials.
• the most important class in terms of volume on the commercial industrial scale, is that of organic matrix composites, in which the matrix material is generally a polymer.
• the matrix of a polymeric composite material is either a thermoplastic polymer or a thermosetting polymer.
• Thermosetting polymers consist of three-dimensional crosslinked structures.
• a prepolymer is mixed with the other component, such as beads or glass fibers, or the other component is wetted or impregnated and subsequently baked.
• prepolymers or matrix material for thermosetting polymers are unsaturated polyesters, vinyl esters, epoxy or phenolic materials. The heating of the polymer chains makes it possible to crosslink and harden the material permanently.
• thermosetting polymer matrix A major drawback of a thermosetting polymer matrix is its crosslinking.
• the matrix can not easily be shaped into other forms. Once the polymer is crosslinked, the shape is fixed. This also makes it difficult to recycle the thermosetting composite material and mechanical or structured parts or articles manufactured comprising said thermosetting composite material, which are burned in a cement plant or disposed of in a landfill.
• thermoplastic polymers To allow thermoforming and recycling, it is preferred to use thermoplastic polymers.
• thermoplastic polymers consist of linear or branched polymers which are not crosslinked.
• the thermoplastic polymers are heated to mix the constituents necessary for the manufacture of the composite material and are cooled to freeze the final shape.
• the problem is the very high viscosity of its molten thermoplastic polymers.
• thermoplastic polymer-based polymer composite material In order to prepare a thermoplastic polymer-based polymer composite material, a melt thermoplastic polymer resin, commonly referred to as “syrup”, is used to impregnating the reinforcing material, for example a fibrous substrate.
• Syrup a melt thermoplastic polymer resin
• a syrup answering this problem has been developed by the Applicant and is described in the patent applications No. FR1159553, or its PCT extension WO2013 / 056845 and in the patent application No. FR1256929 or its PCT extension WO2014 / 013028.
• the thermoplastic polymer syrup constitutes the matrix of the composite material.
• the viscosity of the impregnating syrup must be controlled and adapted so as not to be too fluid or too viscous, so as to correctly impregnate each fiber of the fibrous substrate.
• wetting is partial, depending on whether the syrup is too fluid or too viscous, respectively "bare" zones, that is to say non-impregnated zones, appear and zones where polymer drops form on the fibers that are causing the creation of bubbles. These "bare" zones and these bubbles cause the appearance of defects in the final composite material which cause, among other things, a loss of mechanical strength of the final composite material.
• thermosetting polymer a material sold under the trademark Acrylit G10 may be mentioned.
• this composite material consists of a polyester acrylic resin reinforced with glass fibers.
• the material is a thermosetting composite that is neither thermoformable nor recyclable.
• this composite material is very resistant to UV radiation since it turns yellow after about a year of exposure. This material is not suitable for outdoor use, especially for the realization of roofing elements or building facades.
• the invention therefore aims to remedy at least one of the disadvantages of the prior art.
• the invention aims in particular to provide a piece of transparent / translucent thermoplastic composite material.
• the invention also aims to wet completely, correctly and homogeneously the fibrous substrate during impregnation. Any defect in the wetting of the fibers for example by bubbles and voids decreases the mechanical performance of the final composite part and its ability to obtain a total transmission of light (losses due to the diffusion of light by the defects of the material).
• Another object of the present invention is to provide a method which can be achieved at low cost and which allows the manufacture, on an industrial scale, of thermoplastic composite parts. Furthermore, the process should be easy and simple to implement using commercially available compounds. The manufacture of composite parts must also be reproducible and fast, which means short cycle times.
• a liquid (meth) acrylic syrup for impregnating a fibrous substrate said fibrous substrate being constituted by long glass fibers of refractive index, or said syrup of impregnation being characterized in that it comprises:
• said (meth) acrylic syrup having an index of refraction n4 which tends to nl and 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, provides a complete and correct impregnation of the fibrous substrate and a transparency of the composite material obtained after polymerization of said pre-impregnated substrate, the light transmission rate being between 50% and 100%, preferably greater than 70%.
• an impregnating process for impregnating a fibrous substrate said fibrous material consisting of long glass fibers, the fibers having a form factor of from at least 1000, preferably at least 1500, more preferably at least 2000, preferably at least 3000, most preferably at least 5000, more preferably at least 6000 still more preferably at least 7500 and most preferably at least 10000 and said method comprising a step of impregnating said fibrous substrate with said liquid (meth) acrylic impregnating syrup, provides complete and correct impregnation of the fibrous substrate and a transparent substrate after polymerization, the light transmission rate being between 50% and 100%, preferably greater than 70%.
• thermoplastic composite parts having transparency properties, with a light transmission rate of between 50% and 100%, preferably greater than 70%, and very resistant to UV radiation.
• fibrous substrate refers to fabrics, felts or nonwovens which may be in the form of strips, webs, braids, locks or pieces.
• long fiber refers to fibers having a form factor of at least 1000, preferably at least 1500, more preferably at least 2000, advantageously at least 3000, most preferably at least 5000, still more preferably at least 6000, still more advantageously at least 7500 and most preferably at least 10,000.
• (meth) acrylic refers to any type of acrylic and methacrylic monomers.
• PMMA methyl methacrylate
• SMA styrene maleic anhydride copolymer
• polymerization refers to the process of converting a monomer or a mixture of monomers into a polymer.
• thermoplastic polymer refers to a polymer that turns into a liquid or becomes more liquid or less viscous when heated and that can take on new forms through the application of heat and pressure.
• thermosetting polymer refers to a prepolymer in a soft, solid or viscous state which irreversibly turns into an insoluble and infusible polymer network by firing.
• polymer composite 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.
• transparent or translucent as used relates to a material having a total transmission rate of visible light of between 50% and 100%, preferably greater than 70%, according to the light transmission measurements defined. by the measurement standard ASTM D 1003
• transmission of light includes the transmission of visible and infra-red spectrum waves namely light whose wavelength is between 380nm and 780nm.
• refractive index is relative to the refractive indexes n1, n2, n3, n4 of the media traversed by the light visible spectrum.
• the present invention relates to a liquid (meth) acrylic syrup for impregnating a fibrous substrate, said fibrous substrate consisting of long glass fibers of refractive index n i and said syrup being characterized in what he understands:
• said (meth) acrylic syrup having an index of refraction n4 which tends to nl and 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 monomer is selected from acrylic acid, methacrylic acid, hydroxyalkyl acrylic monomers, hydroxyalkyl methacrylic monomers, acrylic alkyl monomers, methacrylic alkyl monomers and mixtures thereof.
• the monomer is chosen from acrylic acid, methacrylic acid, hydroxyalkyl acrylic monomers, hydroxyalkyl methacrylic monomers, alkyl acrylic monomers, alkyl methacrylic monomers and their derivatives. mixtures, the alkyl group containing 1 to 22 carbons, linear, branched or cyclic; the alkyl group preferably containing 1 to 12 carbons, linear, branched or cyclic.
• 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 monomer is methyl methacrylate.
• % by weight of the monomer is a mixture of methyl methacrylate with isobornyl acrylate and / or acrylic acid.
• the (meth) acrylic polymer mention may be made of alkyl polymethacrylates or alkyl polyacrylates. According to a preferred embodiment, the (meth) acrylic polymer is polymethyl methacrylate (PMMA).
• PMMA polymethyl methacrylate
• PMMA refers to a homopolymer or copolymer of methyl methacrylate (MMA) or mixtures thereof.
• the homopolymer or copolymer of methyl methacrylate comprises at least 70%, preferably at least 80%, advantageously at least 90% and more advantageously at least 95% by weight. of methyl methacrylate.
• the PMMA is a mixture of at least one homopolymer and at least one MMA copolymer, or a mixture of at least two homopolymers or two MMA copolymers having an average molecular weight different, or a mixture of at least two MMA copolymers having a different monomer composition.
• the methyl methacrylate (MMA) copolymer comprises from 70% to 99.7% by weight of methyl methacrylate and from 0.3 to 30% by weight of at least one monomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate.
• These monomers are well known and may include acrylic and methacrylic acids and (meth) acrylates in which the alkyl group contains from 1 to 12 carbon atoms.
• 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 preferably 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 weight average molecular weight of the (meth) acrylic polymer must be high, which means greater than 50,000 g / mol, preferably greater than 100,000 g / mol.
• the weight average molecular weight can be measured by steric exclusion chromatography (SEC).
• the refractive index n2 of the (meth) acrylic polymer is from 1.48 to 1.50, preferably from 1.485 to 1.495 and more preferably from 1.487 to 1.493.
• the (meth) acrylic polymer is completely soluble in the (meth) acrylic monomer or in the (meth) acrylic monomer mixture. It makes it possible to increase the viscosity of the (meth) acrylic monomer or the mixture of (meth) acrylic monomers.
• the solution obtained is generally called “syrup” or "prepolymer”.
• the value of the dynamic viscosity of the liquid (meth) acrylic syrup is 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 1 mPa * s. 000 mPa * s.
• the viscosity of the syrup can easily be measured with a rheometer or viscometer.
• the dynamic viscosity is measured at 25 ° C.
• the liquid (meth) acrylic syrup has a Newtonian behavior, which means that there is no dilution under shear, so that the dynamic viscosity is independent of the shear in a rheometer or the speed of the shear. mobile in a viscometer.
• Such a syrup viscosity obtained allows proper impregnation of the fibers of the fibrous substrate.
• the liquid (meth) acrylic syrup does not contain added voluntarily additional solvent.
• the liquid (meth) acrylic syrup according to the invention intended to impregnate the fibrous substrate, comprises in particular a) a (meth) acrylic monomer or a mixture of (meth) acrylic monomers, and b) at least one compound intended to to make the thermoplastic polymer matrix obtained after polymerization of the syrup, transparent.
• component b) it is chosen from components having a refractive index n3, such that n3> n2 and which can be mixed with the (meth) acrylic polymer or the (meth) acrylic and monomeric polymer mixture ( meth) acrylic and having 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 .
• This component b) is chosen from:
• styrene maleic anhydride (SMA) polymer present at a level of at least 10% by weight, preferably at least 15%, advantageously at least 20% and more preferably at least 25% by weight of the syrup ( meth) acrylic liquid total, - to be completely miscible in the syrup (meth) acrylic and keep this miscibility during the polymerization of the syrup, that is to say have a transparent thermoplastic resin, the styrene polymer maleic anhydride must contain between 15 and 50% of maleic anhydride monomer, preferably between 20 and 35%
• styrene present at least 10% by weight, preferably at least 15%, preferably at least 20% and more preferably at least 25% by weight of the total liquid (meth) acrylic syrup .
• the syrup component (s) are incorporated with the following percentages by mass:
• the (meth) acrylic monomer or the (meth) acrylic monomers in the liquid (meth) acrylic syrup are present in at least 90% by weight, preferably 85% by weight, advantageously 80% by weight. weight and more preferably 75% by weight of the syrup
• 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 20% or more. advantageously at least 25% by weight of the total liquid (meth) acrylic syrup.
• the syrup more particularly comprises:
• a first step consists in preparing a first syrup comprising the (meth) acrylic monomer or (meth) acrylic monomer mixture;
• the SMA styrene maleic anhydride polymer is then added to the monomer, in the proportions indicated above, to maintain a dynamic viscosity of between 10 mPa.s and 10,000 mPa.s, preferably between 50 mPa.s and 5000 mPa.s. * s and advantageously between 100 mPa * s and 1000 mPa * s.
• This polymer thanks to the presence of its maleic anhydride functionalities, is miscible in the (meth) acrylic polymer.
• Its refractive index n3 is 1.565 to 1.585, preferably 1.57 to 1.582 and more preferably 1.574 to 1.580 and greater than n2, where n2 is the index of the (meth) acrylic polymer.
• Their mixture in the proportions above allows to obtain a syrup (meth) acrylic of refractive index n4.
• this polymer has a viscosity similar to the (meth) acrylic polymer.
• the syrup more particularly comprises:
• the syrup comprises:
• the syrup comprises:
• a first step consists of preparing a first syrup comprising the (meth) acrylic monomer or mixture of (meth) acrylic monomers and a (meth) acrylic polymer;
• styrene and the (meth) acrylic monomer then form a (meth) acrylic-styrene copolymer, whose refractive index n3 varies according to the number of styrene units in the chain. polymer of the (meth) acrylic polymer in formation.
• styrene is incorporated in the (meth) acrylic syrup
• this copolymer is polymethacrylate-co-styrene, comprising from 10% to 50% by weight of styrene.
• the liquid (meth) acrylic impregnating syrup also comprises an initiator or an initiator system for starting the polymerization of the monomer or monomers. Initiators or initiator systems that are activated by heat may be mentioned.
• the heat-activated initiator is preferably a radical initiator.
• radical initiator it may be chosen from diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals or azo compounds.
• the initiator or initiator system is selected from isopropyl carbonate, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, tert-butyl per (2-ethylhexanoate), cumyl hydroperoxide, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butyl peroxyisobutyrate , tert-butyl peracetate, tert-butyl perpivalate, amyl perpivalate, tert-butyl peroctoate, azobisisobutyronitrile (AIBN), azobisisobutyramide, 2,2'-azobis (2, 4 dimethylvaleronitrile) or 4, 4'-azobis (4-cyanopentanoic acid).
• AIBN azobisisobutyronitrile
• the initiator or the initiator system is selected from peroxides containing 2 to 20 carbon atoms.
• the process for impregnating the fibrous substrate comprises a step of impregnating the fibrous substrate, based on long glass fibers, with the liquid (meth) acrylic syrup described above. This impregnation step is done in a closed mold.
• glass fabrics comprising glass fibers obtained from silica or molten mixtures after passing through a die.
• the substrate may be in the form of strips, webs, braids, locks or parts.
• 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 continuous, their assembly forms tissues.
• the one-dimensional form corresponds to long linear fibers.
• the fibers may be discontinuous or continuous.
• the fibers may be arranged randomly or in parallel with each other in the form of a continuous filament.
• a fiber is defined by its form factor, which is the ratio of the length and diameter of the fiber.
• the fibers used in the The present invention is long fibers or continuous glass fibers.
• the fibers have a form factor of at least 1000, preferably at least 1500, more preferably at least 2000, preferably at least 3000, most preferably at least 5000. 000, still more preferably at least 6000, still more preferably at least 7500 and most preferably at least 10,000.
• the two-dimensional form corresponds to fibrous mats or non-woven or woven reinforcements or bundles of fibers, which may also be braided. Even though the two-dimensional shape has a certain thickness and therefore has in principle a third dimension, it is considered two-dimensional according to the present invention.
• 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 fiber and banana fiber.
• Animal fibers are for example wool or hair.
• polymeric fibers selected 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 selected fibrous substrate comprises glass fibers, especially of type E, R or S2, whose refractive index ni varies from 1.52 to 1.6.
• the selected fibers are fibers S2 with a refractive index of 1.52.
• the fibers of the fibrous substrate have a diameter between 0.005 ⁇ and ⁇ , preferably between ⁇ and 50 ⁇ , more preferably between 5 ⁇ and 30 ⁇ and advantageously between ⁇ and 25 ⁇ .
• the fibers of the fibrous substrate of the present invention are chosen from continuous fibers (which means that the form factor is not necessarily applicable as for long fibers) for the one-dimensional form, or for fibers long or continuous for the two-dimensional or three-dimensional form of the fibrous substrate.
• the invention relates to a transparent polymeric composite material comprising a matrix
• thermoplastic (meth) acrylic and a fibrous substrate used as reinforcement wherein the fibrous substrate is made of long glass fibers, said composite material being characterized in that the thermoplastic (meth) acrylic matrix is obtained after polymerization of said fibrous substrate having impregnated with said syrup
• Another aspect of the present invention is a method of manufacturing mechanical or structured parts or products comprising the following steps:
• step a) 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.
• thermoplastic matrix has an index of refraction n4 which tends towards that neither of the fiberglass substrate.
• refractive index n4 of the thermoplastic matrix is identical to that of the fiberglass substrate.
• the method of manufacturing composite parts is selected from resin transfer molding or infusion.
• All methods include the step of impregnating the fibrous substrate with the liquid (meth) acrylic syrup prior to the polymerization step in a 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 syrup introduction.
• Resin transfer molding includes many varieties that differ in mechanics introducing the liquid (meth) acrylic syrup into 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.
• the composite part is in particular a room a building or building part (facades, panels, roofs), automobile, a bus room, a boat part, a train piece, a sports article, a part of a plane or helicopter, a piece of spaceship or rocket, a piece of photovoltaic module, a material for construction or building, a piece of wind turbine, a piece of furniture, a piece of telephone or cell phone, a computer or television room, a printer and photocopier room.
• a room a building or building part (facades, panels, roofs), automobile, a bus room, a boat part, a train piece, a sports article, a part of a plane or helicopter, a piece of spaceship or rocket, a piece of photovoltaic module, a material for construction or building, a piece of wind turbine, a piece of furniture, a piece of telephone or cell phone, a computer or television room, a printer and photocopier room.
• thermoplastic (meth) acrylic matrix is highly resistant to UV radiation so that these parts can be used outdoors without any problem. In this which relates to the recycling of the thermoplastic composite part, it can be achieved by grinding or depolymerization of the thermoplastic polymer.
• the grinding is performed mechanically to obtain smaller parts of the workpiece. Since the part comprises a thermoplastic polymer, this polymer can be heated, and the parts again transformed to a certain extent to obtain a recycled object.
• thermoplastic composite is heated to pyrolyze or thermally decompose PMMA and recover methyl methacrylate as a monomer.
• At least 50% by weight of the MMA present in the polymer are recovered by thermal decomposition.
• the piece is brought to a temperature of at least 200 ° C and less than or equal to 400 ° C.
• Example Manufacture of a transparent thermoplastic composite material.
• the syrup is prepared by dissolving 25% by weight PMMA (from Xiran ® SMA28110 society Polyscope Polymers BV, a copolymer comprising MMA methyl methacrylate, 75% by weight of methyl acrylate, which is stabilized with MEHQ (hydroquinone monomethyl ether).
• a 100% by weight of syrup are incorporated 2% by weight of benzolique peroxide (Luperox ® A75 PBO- of Arkema) and 0.2% by weight of DMT (N, -dimethyl-p-toluidine Sigma-Aldrich).
• the syrup has a dynamic viscosity of 520 mPa * 25 ° C.
• the syrup is injected into a closed mold comprising a glass fabric as fibrous and polymeric material at 25 ° C for 80 minutes.
• a syrup is prepared by dissolving 25% by weight of SMA (styrene maleic anhydride) containing 28% of maleic anhydride in 75% by weight of methyl methacrylate, which is stabilized with MEHQ (hydroquinone monomethyl ether). ).
• SMA styrene maleic anhydride
• MEHQ hydroquinone monomethyl ether
• a fiberglass fibrous substrate having a refractive index of not more than 1.52 is placed in a closed mold.
• the (meth) acrylic syrup is injected into the closed mold comprising the glass fabric and polymerized at 25 ° C. for 80 minutes.
• thermoplastic composite part obtained has a contact transparency, passes more than 50% of the light and has no defects.
• this piece is very resistant to UV radiation and can therefore be used intensively outdoors. It is therefore perfectly adapted to equip roofs, or facades of buildings.

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