WO2016102884A1 - Procede d'impregnation d'un substrat fibreux avec un melange (meth)acrylique, composition dudit melange (meth)acrylique, et materiau composite obtenu apres polymerisation dudit melange (meth)acrylique - Google Patents
Procede d'impregnation d'un substrat fibreux avec un melange (meth)acrylique, composition dudit melange (meth)acrylique, et materiau composite obtenu apres polymerisation dudit melange (meth)acrylique Download PDFInfo
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- WO2016102884A1 WO2016102884A1 PCT/FR2015/053711 FR2015053711W WO2016102884A1 WO 2016102884 A1 WO2016102884 A1 WO 2016102884A1 FR 2015053711 W FR2015053711 W FR 2015053711W WO 2016102884 A1 WO2016102884 A1 WO 2016102884A1
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- WIPO (PCT)
- Prior art keywords
- meth
- acrylic
- μιτι
- weight
- mixture
- Prior art date
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 239000000203 mixture Substances 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000000758 substrate Substances 0.000 title claims abstract description 52
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- 239000003999 initiator Substances 0.000 claims abstract description 73
- 235000020357 syrup Nutrition 0.000 claims abstract description 63
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 30
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- 238000006116 polymerization reaction Methods 0.000 claims description 33
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 25
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 22
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
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- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
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- VDMLVOIDGSOUTA-UHFFFAOYSA-N 2-(4-methylanilino)ethane-1,1-diol Chemical compound CC1=CC=C(NCC(O)O)C=C1 VDMLVOIDGSOUTA-UHFFFAOYSA-N 0.000 description 4
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- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
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- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Polymerisation Methods In General (AREA)
- Reinforced Plastic Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/538,440 US20180002503A1 (en) | 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 |
JP2017533432A JP2017538844A (ja) | 2014-12-22 | 2015-12-22 | 繊維基材に(メタ)アクリル混合物を含浸させるための方法、前記(メタ)アクリル混合物の成分、及び前記(メタ)アクリル混合物の重合後に生成される複合材料 |
CA2971543A CA2971543A1 (fr) | 2014-12-22 | 2015-12-22 | Procede d'impregnation d'un substrat fibreux avec un melange (meth)acrylique, composition dudit melange (meth)acrylique, et materiau composite obtenu apres polymerisation dudit melange (meth)acrylique |
KR1020177020558A KR20170101264A (ko) | 2014-12-22 | 2015-12-22 | (메트)아크릴 혼합물로 섬유질 기재를 함침시키는 방법, 상기 (메트)아크릴 혼합물의 조성물, 및 상기 (메트)아크릴 혼합물의 중합 후에 생성된 복합 물질 |
EP15828360.6A EP3237505A1 (fr) | 2014-12-22 | 2015-12-22 | Procede d'impregnation d'un substrat fibreux avec un melange (meth)acrylique, composition dudit melange (meth)acrylique, et materiau composite obtenu apres polymerisation dudit melange (meth)acrylique |
MX2017008226A MX2017008226A (es) | 2014-12-22 | 2015-12-22 | Proceso de impregnacion de un sustrato fibroso con una mezcla (met)acrilica, composicion de la mezcla (met)acrilica, y material compuesto obtenido despues de la polimerizacion de la mezcla (met)acrilica. |
CN201580076635.2A CN107531977A (zh) | 2014-12-22 | 2015-12-22 | 用(甲基)丙烯酸系混合物浸渍纤维基材的方法、所述(甲基)丙烯酸系混合物的组合物和聚合所述(甲基)丙烯酸系混合物后制得的复合材料 |
BR112017013517A BR112017013517A2 (pt) | 2014-12-22 | 2015-12-22 | processo de impregnação de um substrato fibroso com uma mistura (met)acrílica, composição da referida mistura (met)acrílica, e material compósito obtido após polimerização da referida mistura (met)acrílica |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1463058 | 2014-12-22 | ||
FR1463058A FR3030585B1 (fr) | 2014-12-22 | 2014-12-22 | Procede d'impregnation d'un substrat fibreux avec un melange (meth)acrylique, composition dudit melange, et materiau composite obtenu apres polymerisation dudit melange. |
Publications (1)
Publication Number | Publication Date |
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WO2016102884A1 true WO2016102884A1 (fr) | 2016-06-30 |
Family
ID=53398137
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/FR2015/053711 WO2016102884A1 (fr) | 2014-12-22 | 2015-12-22 | Procede d'impregnation d'un substrat fibreux avec un melange (meth)acrylique, composition dudit melange (meth)acrylique, et materiau composite obtenu apres polymerisation dudit melange (meth)acrylique |
Country Status (10)
Country | Link |
---|---|
US (1) | US20180002503A1 (fr) |
EP (1) | EP3237505A1 (fr) |
JP (1) | JP2017538844A (fr) |
KR (1) | KR20170101264A (fr) |
CN (1) | CN107531977A (fr) |
BR (1) | BR112017013517A2 (fr) |
CA (1) | CA2971543A1 (fr) |
FR (1) | FR3030585B1 (fr) |
MX (1) | MX2017008226A (fr) |
WO (1) | WO2016102884A1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3053350B1 (fr) | 2016-06-29 | 2020-03-27 | Arkema France | Composition liquide ou sirop comprenant un polymere a phases multiples et un polymere (meth)acrylique, sirop pour procede d'impregnation, procede d'impregnation pour un substrat fibreux, procede depolymerisation et article structure obtenu de celui-ci |
FR3087203B1 (fr) * | 2018-10-15 | 2022-01-21 | Arkema France | Compositions polymeres (meth)acryliques pour composite, leur procede de preparation et leur utilisation |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
WO2010112534A1 (fr) | 2009-04-03 | 2010-10-07 | Akzo Nobel Chemicals International B.V. | Suspension aqueuse de peroxyde de diacyle solide |
WO2014013028A1 (fr) | 2012-07-18 | 2014-01-23 | Arkema France | Traitement d'imprégnation pour substrat fibreux, sirop (méth)acrylique liquide pour ce traitement d'imprégnation, procédé de polymérisation, et article structuré ainsi obtenu |
WO2014135816A1 (fr) | 2013-03-08 | 2014-09-12 | Arkema France | Sirop (meth) acrylique liquide d'impregnation d'un substrat fibreux, procede d'impregnation d'un substrat fibreux, materiau composite obtenu apres polymerisation dudit substrat pre-impregne |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6310156B1 (en) * | 1998-03-06 | 2001-10-30 | Nippon Shokubai Co., Ltd. | (Meth) acrylic acid polymer and manufacturing method thereof |
TWI506078B (zh) * | 2008-08-14 | 2015-11-01 | Lucite Int Uk Ltd | 可硬化雙組份丙烯酸組合物 |
US20140199397A1 (en) * | 2011-06-10 | 2014-07-17 | Daniel Levin | Benzoyl Peroxide Microparticle Process |
FR2981652B1 (fr) * | 2011-10-21 | 2015-03-27 | Arkema France | Composites via la polymerisation in-situ de resines thermoplastiques methacryliques |
-
2014
- 2014-12-22 FR FR1463058A patent/FR3030585B1/fr not_active Expired - Fee Related
-
2015
- 2015-12-22 US US15/538,440 patent/US20180002503A1/en not_active Abandoned
- 2015-12-22 EP EP15828360.6A patent/EP3237505A1/fr not_active Withdrawn
- 2015-12-22 BR BR112017013517A patent/BR112017013517A2/pt not_active Application Discontinuation
- 2015-12-22 CN CN201580076635.2A patent/CN107531977A/zh active Pending
- 2015-12-22 CA CA2971543A patent/CA2971543A1/fr not_active Abandoned
- 2015-12-22 KR KR1020177020558A patent/KR20170101264A/ko unknown
- 2015-12-22 WO PCT/FR2015/053711 patent/WO2016102884A1/fr active Application Filing
- 2015-12-22 JP JP2017533432A patent/JP2017538844A/ja not_active Withdrawn
- 2015-12-22 MX MX2017008226A patent/MX2017008226A/es unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
WO2010112534A1 (fr) | 2009-04-03 | 2010-10-07 | Akzo Nobel Chemicals International B.V. | Suspension aqueuse de peroxyde de diacyle solide |
WO2014013028A1 (fr) | 2012-07-18 | 2014-01-23 | Arkema France | Traitement d'imprégnation pour substrat fibreux, sirop (méth)acrylique liquide pour ce traitement d'imprégnation, procédé de polymérisation, et article structuré ainsi obtenu |
WO2014135816A1 (fr) | 2013-03-08 | 2014-09-12 | Arkema France | Sirop (meth) acrylique liquide d'impregnation d'un substrat fibreux, procede d'impregnation d'un substrat fibreux, materiau composite obtenu apres polymerisation dudit substrat pre-impregne |
Non-Patent Citations (1)
Title |
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See also references of EP3237505A1 |
Also Published As
Publication number | Publication date |
---|---|
FR3030585A1 (fr) | 2016-06-24 |
BR112017013517A2 (pt) | 2018-03-06 |
US20180002503A1 (en) | 2018-01-04 |
EP3237505A1 (fr) | 2017-11-01 |
CN107531977A (zh) | 2018-01-02 |
MX2017008226A (es) | 2017-10-06 |
CA2971543A1 (fr) | 2016-06-30 |
JP2017538844A (ja) | 2017-12-28 |
KR20170101264A (ko) | 2017-09-05 |
FR3030585B1 (fr) | 2017-02-03 |
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