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    • 专利摘要:
    The present invention relates to an impregnation process for a fibrous substrate, a liquid composition for carrying out this process and the impregnated fibrous substrate obtained. The impregnated fibrous substrate is suitable for the manufacture of mechanical or structural parts or articles. The present invention relates in particular to an industrial process for impregnating a fibrous substrate or long fibers with a viscous liquid composition mainly containing methacrylic, vinyl or acrylic components, in the form of monomers or polymers. This viscous composition is hereinafter called liquid monomer syrup. The invention also relates to a fibrous substrate pre-impregnated with said syrup, which is useful for the manufacture of mechanical or structural parts or articles. More particularly, the impregnation of a fibrous substrate with the monomer syrup is carried out in a mold. The present invention also relates to a manufacturing method for the manufacture of mechanical or structural parts or articles, and three-dimensional mechanical or structural parts obtained by this method.
    公开号:FR3016642A1
    申请号:FR1450545
    申请日:2014-01-22
    公开日:2015-07-24
    发明作者:Pierre Gerard；Michel Glotin；Sebastien Taillemite
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] Process for impregnating a fibrous substrate, liquid monomer syrup for the impregnation process, its polymerization method and structural article obtained [Field of the invention] [1] The present invention relates to an impregnation process for a fibrous substrate , a liquid composition for carrying out this process and the impregnated fibrous substrate obtained.  The impregnated fibrous substrate is suitable for the manufacture of mechanical or structural parts or articles.  In particular, the present invention relates to an industrial process for impregnating a fibrous or long fiber substrate with a viscous liquid composition containing mainly methacrylic, vinyl or acrylic components in the form of monomers or polymers.  This viscous composition is hereinafter called liquid monomer syrup.  The invention also relates to a fibrous substrate pre-impregnated with said syrup, which is useful for the manufacture of mechanical or structural parts or articles.  [003] More particularly, the impregnation of a fibrous substrate with the monomer syrup is carried out in a mold.  [4] The present invention also relates to a manufacturing method for the manufacture of mechanical or structural parts or articles, and three-dimensional mechanical or structural parts obtained by this method.  [Technical problem] [5] Mechanical or structural parts or articles which must withstand high stresses during their use are largely made from composite materials.  A composite material is a macroscopic combination of two or more immiscible materials.  The composite material consists of at least one matrix material which forms a continuous phase for the cohesion of the structure and a reinforcing material having various architectures for the mechanical properties.  [6] The objective when using composite materials is to obtain from the composite material performance that is not available from its separate constituents if used alone.  As a result, composite materials are widely used in a number of industrial sectors such as building, automotive, aerospace, transportation, recreation, electronics and sports, notably because of their better mechanical performance ( higher tensile strength, higher tensile modulus, higher fracture toughness) compared to homogeneous materials and their low density.  [7] The most important class in terms of commercial scale commercial scale is that of organic matrix composites, in which the matrix material is generally a polymer.  The matrix or main continuous phase of a polymeric composite material is either a thermoplastic polymer or a thermosetting polymer.  [8] Thermosetting polymers consist of three-dimensional cross-linked structures.  Crosslinking is achieved by curing reactive groups in the so-called prepolymer compound.  Hardening can be achieved for example by heating the polymer chains to permanently cure and cure the material.  To prepare the polymeric composite material, the prepolymer is mixed with the other component, such as beads or glass fibers, or the other component is wetted or impregnated, and then cured.  Examples of prepolymers or matrix material for thermosetting polymers are unsaturated polyesters, vinyl esters, epoxies or phenolics.  [010] A major disadvantage of a thermosetting polymer matrix is its rigidity The matrix can not easily be shaped into other forms.  Once the polymer has hardened, the shape is fixed.  This also makes it difficult to recycle the thermosetting composite material and mechanical or structural parts or articles manufactured comprising said thermosetting composite material, which are burned in a cement plant or discarded in a landfill.  [011] The thermoplastic polymers consist of linear or branched polymers, which are generally not crosslinked.  The thermoplastic polymers are heated to mix the constituents necessary for the production of the composite material, and cooled for curing.  The limit to the use of thermoplastic polymers for the manufacture of composite materials is their high melt viscosity, for example to impregnate a fibrous substrate homogeneously.  The wetting or the correct impregnation of the fibers by the thermoplastic polymer can only be obtained if the thermoplastic resin is sufficiently fluid.  In order to have a low viscosity or a sufficient fluidity of the thermoplastic polymer, the length or the molecular weight of the chain must be reduced.  However, a too low molecular weight has a negative impact on the performance of the composite material and on the mechanical or structural parts, in particular their mechanical properties, such as the deformation module.  [012] Another way to reduce the viscosity of the thermoplastic polymer to a significant extent is to increase the temperature.  Therefore, the continuous working temperature is relatively high, higher than 200 ° C, which increases the economic costs of the composite material and mechanical or structural parts due to the involvement of high energy costs.  On the other hand, thermoplastic polymers tend to degrade if the temperature is too high, which is particularly true for semicrystalline thermoplastic polymers which have high melting points, such as for example polyamides such as PA6. 6, polyether sulphone (PES), polyether imide (PEI), polyether ether ketone (PEEK) or polyphenylene sulphide (PPS).  This thermally induced degradation causes a decrease in the molecular weight of the polymer matrix on the fibrous substrate, which is important for the cohesion of the composite material and the mechanical or structural parts.  [13] Another possibility for impregnating the fibrous substrate is to dissolve the thermoplastic polymer in an organic solvent.  This method, however, requires a large amount of solvent, which must be evaporated.  The use of large amounts of solvent presents environmental problems in terms of energy and pollution.  [14] Another possibility for impregnating the fibrous substrate is to use the respective monomers for impregnation and to perform polymerization to form the thermoplastic polymer after impregnation.  However, this method generally uses monomers that can evaporate in part or have an unpleasant odor.  The use of certain monomers in an open environment also presents environmental problems.  [15] These are the limitations or disadvantages of the preparation of thermoplastic composite materials, in particular with fibrous reinforcements, the process of impregnating a fibrous substrate, and mechanical or structural parts or articles manufactured comprising said thermoplastic composite material.  [16] The object of the present invention is to overcome the disadvantages mentioned above.  It is an object of the present invention to provide a structural part comprising a thermoplastic composite material which exhibits satisfactory mechanical properties such as high rigidity and Young's modulus of at least 8 GPa.  [18] Another object of the present invention is to provide a structural part comprising a thermoplastic composite material having a satisfactory UV resistance.  [019] Another object of the present invention is to provide a structural part comprising a thermoplastic composite material which can be transformed and shaped with some flexibility.  Another object of the present invention is to provide a structural part or part comprising a relatively large thermoplastic composite material, and the method of impregnating a large fibrous substrate.  Another object of the present invention is to thoroughly, correctly and evenly wet the fibrous substrate during impregnation.  Any defect in the wetting of the fibers, for example due to bubbles and voids, decreases the mechanical performance of the structural part.  Another object of the present invention is to provide a process for impregnating a fibrous substrate and a liquid impregnating syrup having a low or a low volatile organic compound (VOC) content.  It is another object of the present invention to provide a process for impregnating a fibrous substrate which can contain a large amount of additives and fillers.  [024] Another object of the present invention is the recycling of the structural part comprising the composite material or structural parts that do not meet the quality standards or worn structural parts.  "Recycling" is understood as the recovery of at least a portion of the raw materials used.  This means the grinding and reuse of the thermoplastic polymer.  This also means for example that the monomer of the thermoplastic matrix of the composite material can be recovered.  [025] Another object of the present invention is to provide a method which can be achieved at low cost and allows for large scale manufacture for the production of structural parts comprising the thermoplastic composite material of the invention.  Furthermore, the method must be easy and simple to implement using commercially available components.  Parts manufacturing also needs to be repeatable and fast, which means short cycle times.  BACKGROUND OF THE INVENTION [0007] FR1374046 discloses a process for the polymerization of acrylic monomers, especially methacrylic monomers, from monomeric-polymer syrups using a tin metal catalyst.  Glass fibers are impregnated with a methanol solution of the tin catalyst.  The fibers are then impregnated with a monomer-polymer syrup, then the composition is polymerized.  The process uses a metal catalyst and the impregnation is carried out with a liquid syrup based on methyl methacrylate.  [027] JP9085841 discloses the preparation of a composite thermoplastic plastic fabric-based element.  A thermoplastic polymer is dissolved in a volatile solvent and mixed with the fabric base material.  The solvent is evaporated and the prepreg is cut into shapes, then it is re-coated with the thermoplastic polymer solution in a solvent and cured by evaporation of the solvent.  In the example, a polymethyl methacrylate as a thermoplastic polymer is dissolved at 15% by weight in a solvent mixture of methanol, xylene and tetrahydrofuran to impregnate the fibrous material.  This method of preparation uses a large amount of solvent which evaporates.  [028] EP0796873 discloses a (meth) acrylic syrup, syrup preparation process and a process for preparing a syrup.  Molding material containing the (meth) acrylic syrup.  The main objective is to have a syrup with excellent storage stability.  The molding material may comprise a reinforcing material in the form of fibers.  The syrup mainly comprises methyl methacrylate and, in a lesser amount, a vinyl monomer.  [029] WO2013 / 056845 discloses a thermoplastic composite material obtained by in situ polymerization of a thermoplastic resin with a fibrous material.  More particularly, the present invention relates to a polymer composite material obtained by in situ polymerization of a thermoplastic (meth) acrylic resin and a fibrous material containing long fibers and its use, a method of manufacturing such a composite material and a mechanical or structural part or article manufactured comprising this polymeric composite material.  The (meth) acrylic resin mainly comprises methyl methacrylate as the main monomer which has a boiling point of about 101 ° C to 1013 mbar and a vapor pressure of about 26.7 mbar at 20 ° C .  [30] The prior art does not describe an impregnating process for impregnating a fibrous substrate as described according to which the fibrous substrate and the liquid monomer syrup are brought into contact prior to the polymerization according to the present invention, and impregnation method for impregnating a fibrous substrate mainly using a methyl methacrylate monomer as a main component in the syrup or other monomer having a boiling point below 115 ° C at 1013 mbar and a vapor pressure greater than 25 mbar at 20 ° C.  [31] The prior art discloses no manufacturing method for the manufacture of mechanical or structural parts or articles comprising the impregnation method for impregnating a fibrous substrate with the composition of a liquid monomer syrup and the polymerization according to the present invention.  [BRIEF DESCRIPTION OF THE INVENTION] [32] Surprisingly, it has been discovered that an impregnating process for impregnating a fibrous substrate, said fibrous substrate being made of long fibers and said method comprising a step of impregnating said fibrous substrate with a liquid monomer syrup comprising: a) a (meth) acrylic polymer, b) at least one monomer (A) selected from a (meth) acrylic monomer or a vinyl monomer or a mixture thereof, c) at least one initiator or initiation system for starting the polymerization of the monomer or monomers, d) optionally another (meth) acrylic monomer (B), the monomer (s) (A) selected from (meth) acrylic monomers or monomers vinyl having a boiling point of at least 115 ° C to 1013 mbar and / or a vapor pressure of less than 25 mbar at 20 ° C, and the other (meth) acrylic monomer (B) having a d boiling below 115 ° C at 1013 m bar and / or a vapor pressure greater than 25 mbar at 20 ° C, and said liquid monomer syrup having a dynamic viscosity of a value in the range of 10 mPa * s to 10,000 mPa * s, preferably 50 mPa * s at 5000 mPa * s and advantageously from 100 mPa * s to 1000 mPa * s, allows complete and correct impregnation of the fibrous substrate.  [033] Surprisingly, it has also been discovered that a liquid impregnating monomer syrup for carrying out the impregnation process for a fibrous substrate, said liquid monomer syrup comprising: a) a (meth) acrylic polymer, b) at least one monomer (A) selected from a (meth) acrylic monomer or a vinyl monomer or a mixture thereof, c) at least one initiator or initiation system for starting the polymerization of the monomer or monomers, d) ) optionally another (meth) acrylic monomer (B), the monomer (s) (A) selected from (meth) acrylic monomers or vinyl monomers having a boiling point of at least 115 ° C to 1013 mbar and / or a vapor pressure of less than 25 mbar at 20 ° C, and the other (meth) acrylic monomer (B) having a boiling point below 115 ° C at 1013 mbar and / or a vapor pressure greater than 25 mbar at 20 ° C, and said liquid monomer syrup having a e dynamic viscosity of a value in the range of 10 mPa * s to 10 000 mPa * s, preferably 50 mPa * s to 5000 mPa * s and preferably 100 mPa * s to 1000 mPa * s, allows complete and correct impregnation of the fibrous substrate.  Surprisingly, it has also been discovered that a manufacturing process for the manufacture of mechanical or structural parts or articles comprising the following steps: a) the impregnation of a fibrous substrate with a liquid monomer syrup, said liquid monomer syrup comprising: i) a (meth) acrylic polymer, ii) at least one monomer (A) selected from a (meth) acrylic monomer or a vinyl monomer or a mixture thereof, iii) at least one initiator or initiation system for starting the polymerization of the monomer or monomers, iv) optionally another (meth) acrylic monomer (B), the monomer or monomers (A) chosen from (meth) acrylic monomers or vinyl monomers having a point of boiling of at least 115 ° C at 1013 mbar and / or a vapor pressure of less than 25 mbar at 20 ° C, and the other (meth) acrylic monomer (B) having a boiling point below 115 ° C at 1013 mbar and / or a pressure of steam greater than 25 mbar at 20 ° C, and said liquid monomer syrup having a dynamic viscosity of a valedr in the range of 10 mPa * s to 10,000 mPa * s, preferably 50 mPa * s to 5,000 mPa * s * s and advantageously from 100 mPa * s to 1000 mPa * s, allows a complete and correct impregnation of the fibrous substrate, b) the polymerization of liquid monomer syrup impregnating said fibrous substrate, allows to obtain parts or mechanical or structural items manufactured having satisfactory mechanical properties having a high rigidity and a Young's modulus of at least 8 GPa.  [035] Furthermore, it has also been discovered that a three-dimensional mechanical or structural part obtained by the manufacturing method having a high rigidity and a Young's modulus of at least 8 GPa has practically no defects such as voids between the fibrous substrate and the polymer.  [036] According to a first aspect, the present invention relates to an impregnating process for impregnating a fibrous substrate, said fibrous substrate being constituted by long fibers and said method comprising a step impregnating said fibrous substrate with a liquid monomer syrup comprising: a) a (meth) acrylic polymer, b) at least one monomer (A) selected from a (meth) acrylic monomer or a vinyl monomer or a mixture thereof, c) at least one initiator or initiation system for starting the polymerization of the monomer or monomers, d) optionally another (meth) acrylic monomer (B), the monomer (s) (A) chosen from monomers (meth) acrylic or vinyl monomers having a boiling point of at least 115 ° C to 1013 mbar and / or a vapor pressure of less than 25 mbar at 20 ° C, and the other (meth) acrylic monomer (B ) having a boiling point less than 115 ° C at 1013 mbar and / or a vapor pressure greater than 25 mbar at 20 ° C, and said liquid monomer syrup having a dynamic viscosity of a value in the range of 10 mPa * s to 10,000 mPa * s, preferably from 50 mPa * s to 5,000 mPa * s and preferably from 100 mPa * s to 1,000 mPa * s.  [37] In another aspect, the method of impregnating the fibrous substrate of the present invention is made in a mold.  [38] In another aspect, the process for impregnating the fibrous substrate of the present invention is carried out with a liquid monomer syrup which comprises a (meth) acrylic polymer which is a homo- or copolymer of methyl methacrylate (MMA) or a mixture of these.  [39] The term "fibrous substrate" as used refers to fabrics, felts or nonwovens which may be in the form of strips, webs, braids, locks or pieces.  The term "vinyl monomer", as used, refers to all types of monomers that comprise a H2C = CHR structure.  [41] The term "(meth) acrylic", as used, refers to all types of acrylic and methacrylic monomers.  [42] The term "PMMA" as used refers to homo- and copolymers of methyl methacrylate (MMA), the proportion by weight of MMA in PMMA being at least 70% by weight for the MMA copolymer.  [43] The term "monomer" as used refers to a molecule that can undergo polymerization.  [044] The term "polymerization" as used refers to the process of converting a monomer or mixture of monomers to a polymer.  [45] The term "thermoplastic polymer" as used refers to a polymer which becomes liquid or which becomes more liquid or less viscous when heated and which can take on new forms by the application of heat. and pressure.  [46] The term "thermosetting polymer" as used refers to a prepolymer in a soft, solid or viscous state which irreversibly converts to an infusible and insoluble polymer network upon curing.  [47] The term "polymer composite" as used refers to a multicomponent material comprising a plurality of different phase domains, wherein at least one type of phase domain is a continuous phase and wherein at least one component is a polymer.  [48] The term "initiator" as used refers to a chemical species that reacts with a monomer to form an intermediate compound capable of successfully linking a large number of other monomers to a polymeric compound.  [049] Definition of "boiling point and" vapor pressure ", [50] With respect to the structural part or article, the part or article relates to a panel, a lid or an envelope in a composite material, or parts for aircraft, for boats (hull and deck), railway vehicles (hatch, bulkhead, body) and to automobile parts (car body, bonnet, door).  [51] With respect to the (meth) acrylic polymer, there may be mentioned alkyl polymethacrylates or alkyl polyacrylates.  According to a preferred embodiment, the (meth) acrylic polymer is polymethyl methacrylate (PMMA).  [52] The term "PMMA" refers to a homopolymer or copolymer of methyl methacrylate (MMA) or mixtures thereof.  [053] According to one embodiment, the methyl methacrylate (MMA) homo- or copolymer comprises at least 70%, preferably at least 80%, advantageously at least 90% and more preferably at least 95% by weight. weight of methyl methacrylate.  [054] According to another embodiment, 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 a molecular weight. different means, or a mixture of at least two MMA copolymers having a different monomer composition.  [055] 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.  [56] These monomers are well known, and 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.  As examples, mention may be made of methyl acrylate and ethyl, butyl or 2-ethylhexyl (meth) acrylate.  Preferably, the comonomer is an alkyl acrylate in which the alkyl group contains from 1 to 4 carbon atoms.  [57] According to a preferred embodiment, the methyl methacrylate (MMA) copolymer comprises from 70% to 99.7%, preferably from 80% to 99.7%, advantageously from 90% to 99.7% and more preferably from 90% to 99.5% by weight of methyl methacrylate, and from 0.3% to 30%, preferably from 0.3% to 20%, preferably from 0.3% to 10% and more preferably from 0.5% to 10% by weight of at least one monomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate.  Preferably, the comonomer is selected from methyl acrylate or ethyl acrylate or mixtures thereof.  [58] The weight average molecular weight of the (meth) acrylic polymer should be high, which means greater than 50,000 g / mol, preferably greater than 100,000 g / mol.  [059] The weight average molecular weight can be measured by size exclusion chromatography (CES).  [60] Regarding the monomer (A) of the syrup according to the invention, it is selected from a (meth) acrylic monomer or a vinyl monomer or a mixture thereof.  [61] The monomer (A) has a boiling point of at least 115 ° C to 1013 mbar and / or a vapor pressure of less than 25 mbar at 20 ° C.  [62] Preferably, the monomer (A) has a vapor pressure of less than 10 mbar at 20 ° C.  [63] Preferably, the monomer (A) has a boiling point of at least 135 ° C to 1013 mbar.  [64] Advantageously, the monomer (A) is chosen from cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, heptyl methacrylate, n-octyl acrylate and 2-acrylate. -octyl, isooctyl acrylate, 2-ethylhexyl methacrylate, butyldiglycol methacrylate, dicyclopentenyloxyethyl methacrylate, ethoxyethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, hydroxylpropyl methacrylate, styrene, alpha-methylstyrene, ortho-, beta- or para-methylstyrene, tert-butylstyrene, nitrostyrene, N-vinylpyrrolidone and their mixtures.  [65] With respect to the optional (meth) acrylic monomer (B), it is selected from alkyl acrylate monomers, alkyl methacrylic monomers and mixtures thereof.  [66] The monomer (B) has a boiling point of less than 115 ° C at 1013 mbar and / or a vapor pressure of at least 25 mbar at 20 ° C.  [67] Preferably, the monomer (B) is selected from alkyl acrylate monomers, alkyl group containing 1 to 4 carbons, linear or branched, or methyl methacrylate and mixtures thereof.  [68] Advantageously, the (meth) acrylic monomer is selected from methyl methacrylate, methyl acrylate, ethyl acrylate and mixtures thereof.  [69] According to a preferred embodiment, at least 50% by weight, preferably at least 60% by weight, of the monomer (B) is methyl methacrylate.  [70] According to a more preferred embodiment, at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight and preferably at least 80% by weight and even more preferably 90% by weight By weight of the monomer (B) is a mixture of methyl methacrylate with ethyl methacrylate, methyl acrylate, ethyl acrylate and iso-butyl acrylate or.  [71] With respect to the fibrous substrate, there may be mentioned fabrics, felts or nonwovens which may be in the form of strips, webs, braids, locks or pieces.  The fibrous material can have different shapes and sizes, i.e. it can be 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.  [72] The one-dimensional form corresponds to linear long fibers.  The fibers may be discontinuous or continuous.  The fibers may be arranged randomly or in the form of a continuous filament parallel to each other.  A fiber is defined by its ratio of length, which is the ratio of 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, more preferably at least 5000, more preferably more preferably at least 6,000, most preferably at least 7,500 and most advantageously at least 10,000.  [73] The two-dimensional form consists of fibrous mats or non-woven reinforcements or woven reinforcements or bundles of fibers, which may also be braided.  Even though these two-dimensional shapes have a certain thickness and therefore in principle a third dimension, they are considered two-dimensional according to the present invention.  [74] The three-dimensional shape corresponds, for example, to fibrous mats or non-woven reinforcements or bundles of fibers or their stacked or folded mixtures, an assembly of the two-dimensional form in the third dimension.  [75] The origins of the fibrous material may be natural or synthetic.  As a natural material, there may be mentioned vegetable fibers, wood fibers, animal fibers or mineral fibers.  [76] Natural fibers include, for example, sisal, jute, hemp, flax, cotton, coconut fiber and banana fiber.  Animal fibers are for example wool or hair.  As synthetic material, there may be mentioned polymeric fibers selected from thermosetting polymers, thermoplastic polymers or mixtures thereof.  [78] The polymeric fibers may consist of polyamide (aliphatic or aromatic), polyester, polyvinyl alcohol, polyolefins, polyurethanes, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins and vinyl esters.  [79] The mineral fibers may also be chosen from glass fibers, in particular of type E, R or S2, carbon fibers, boron fibers or silica fibers.  The fibrous substrate of the present invention is selected from vegetable fibers, wood fibers, animal fibers, mineral fibers, synthetic polymeric fibers, glass fibers, carbon fibers, or mixtures thereof.  [81] Preferably, the fibrous substrate is selected from mineral fibers.  [82] The fibers of the fibrous material have a diameter of between 0.005 μm and 100 μm, preferably between 1 μm and 50 μm, more preferably between 5 μm and 30 μm and advantageously between 10 μm and 25 μm.  [083] Preferably, the fibers of the fibrous material of the present invention are selected from continuous fibers (which means that the length ratio does not apply as for long fibers) for the one-dimensional form, or the fibers long or continuous forming the two- or three-dimensional form of the fibrous substrate.  [084] With regard to the initiator or initiator system for starting the polymerization of the monomer (A) and the optional (meth) acrylic monomer (B), initiators or initiation systems may be mentioned. which are activated by heat.  [85] The heat activated initiator is preferably a radical initiator.  [86] As for the radical initiator, it may be selected from diacyl peroxides, peroxy esters, dialkyl peroxides, peroxyacetals, hydroperoxides or azo compounds.  [87] The initiator or initiation system for starting the polymerization of the (meth) acrylic monomer 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, peroxyisobutyrate. tert-butyl, 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).  The use of a radical initiator mixture selected from the above list would not be outside the scope of the invention.  [88] Preferably, the initiator or initiation system for starting the polymerization of the monomer (A) and the optional (meth) acrylic monomer (B) is selected from peroxides containing 2 to 20 carbon atoms.  [089] The radical initiator content with respect to the monomer (A) and optional (meth) acrylic monomer (B) of the liquid monomer syrup is from 100 to 50,000 ppm by weight (50,000 ppm = 5% by weight) preferably between 200 and 40,000 ppm by weight and preferably between 300 and 30,000 ppm.  [090] The monomer (A) and the optional (meth) acrylic monomer (B) are generally one or more monomers as defined above, optionally containing a suitable inhibitor such as hydroquinone (HQ), methylhydroquinone and the like. (MEHQ), 2,6-di-tert. -butyl-4-methoxyphenol (Topanol O) and 2,4-dimethyl-6-tert. -butyl phenol (Topanol A).  [91] The inhibitor is present to prevent the monomer from spontaneously polymerizing.  [92] The liquid monomer syrup optionally also comprises an activator for the polymerization.  [093] The activator or polymerization accelerator is selected from tertiary amines such as N, N-dimethyl-p-toluidine (DMPT), N, N-dihydroxyethyl-p-toluidine (DHEPT), metal catalysts transition salts soluble in organic media or mixtures thereof.  [094] Advantageously, the liquid monomer syrup does not contain activators for catalytically accelerating the polymerization reaction, such as compounds based on cobalt or tin and in particular tin chloride.  [095] The activator content relative to the monomer (A) and the optional (meth) acrylic monomer (B) of the liquid monomer syrup is from 100 ppm to 20,000 ppm (by weight), preferably from 200 ppm to 10,000 ppm by weight and preferably from 300 ppm to 7000 ppm.  [096] The presence of activators or accelerators depends on the final application.  When "cold hardening" is needed or desired, an accelerator is generally required.  "Cold curing" means that the polymerization takes place at room temperature, which means less than 50 ° C or preferably less than 40 ° C.  [97] However, for industrial applications, the use of heat in "hot curing" systems is also possible.  [98] Another ingredient of the liquid resin may also be a chain-limiting agent for regulating the molecular weight, for example γ-terpinene or terpinolene, at levels of between 0 and 500 ppm and preferably between 0 and 500 ppm. 100 ppm, based on the monomers of the mixture.  [099] The impregnation process according to the invention for impregnating a fibrous substrate comprises a step of impregnating the fibrous substrate with a liquid monomer syrup.  A single monomer (A) and the optional (meth) acrylic monomer (B) or a mixture of monomers as a liquid monomer syrup are too liquid for the impregnation process of the present invention, especially for wetting and the correct and complete impregnation of the fibrous substrate.  The viscosity must therefore be adapted by increasing it.  As regards the liquid monomer syrup according to the invention which impregnates the fibrous substrate, it comprises a monomer (A), optionally a (meth) acrylic monomer (B) or a mixture of (meth) acrylic monomers (B). ), a (meth) acrylic polymer and at least one initiator or initiation system for starting the polymerization of the respective monomer or monomers.  According to the invention, the viscosity is increased by using a monomer (A) or a mixture of monomers (A) and optionally a (meth) acrylic monomer (B) with a (meth) acrylic polymer or polymers (meth) ) dissolved acrylics.  This solution is commonly called "syrup" or "prepolymer".  [0103] Advantageously, the liquid monomer syrup does not contain a deliberately added additional solvent.  [0104] The (meth) acrylic polymer is completely soluble in the monomer (A) or the monomer mixture (A) and (B).  This (meth) acrylic polymer is PMMA, which means the homo- or copolymer of methyl methacrylate (MMA) or a mixture thereof as defined above.  This monomer (A) and this (meth) acrylic monomer (B) are the same as previously defined.  The monomer (A) represents more than 30% by weight, preferably more than 50% by weight of the total sum of monomers (A) and (B) present in the liquid monomer syrup.  [0108] The (meth) acrylic monomer (B) represents less than 70% by weight, preferably less than 50% by weight of the total sum of the monomers (A) and (B) in the liquid monomer syrup.  The monomer (A) or the sum of the monomer (A) and the (meth) acrylic monomer (B) in the liquid monomer syrup represents at least 30% by weight, preferably 40% by weight, advantageously 50%. by weight and more preferably 60% by weight of the total weight of the compounds a) + b) + c) + d) liquid monomer syrup.  The monomer (A) or the sum of the monomer (A) and the (meth) acrylic monomer (B) in the liquid monomer syrup represents at most 95% by weight, preferably at most 90% by weight, advantageously at most 85% by weight and more preferably at most 80% by weight of the total weight of the compounds a) + b) + c) + d) of the liquid monomer syrup.  [0111] The (meth) acrylic polymer (s) in the liquid monomer syrup represent at least 5% by weight, preferably at least 10%, advantageously at least 15% and more advantageously at least 20% by weight of the total weight of the monomers. compounds a) + b) + c) + d) liquid monomer syrup.  [0112] The (meth) acrylic polymer (s) in the liquid monomer syrup represent at most 60% by weight, preferably at most 50%, advantageously at most 40% and more advantageously at most 35% by weight of the total weight of the monomers. compounds a) + b) + c) + d) liquid monomer syrup.  The monomer (A) or the sum of the monomer (A) and the (meth) acrylic monomer (B) in the liquid monomer syrup represents from 30% to 90% by weight, preferably from 40% to 90% by weight. by weight, preferably from 50% to 85% by weight and more preferably from 60% to 80% by weight of the total weight of the compounds a) + b) + c) + d) of the liquid monomer syrup.  [0114] Thus, the (meth) acrylic polymer (s) in the liquid monomer syrup represent from 60% to 5% by weight, preferably from 60% to 10% by weight, advantageously from 15% to 50% by weight and more preferably from 20% to 40% by weight of the total weight of the compounds a) + b) + c) + d) of the liquid monomer syrup.  The dynamic viscosity of the liquid monomer syrup is in the range of from 10 mPa.s to 10,000 mPa.s, preferably from 50 mPa.s to 5,000 mPa.s and preferably from 100 to 1 mPa.sup.-1. 000 mPa * s and more preferably 100 mPa * s to 500 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 monomer syrup has a Newtonian behavior, which means that it does not exhibit shear thinning, thus the dynamic viscosity being independent of shear in a rheometer or velocity of the moving part in a viscometer.  If the viscosity of the liquid monomer syrup at a given temperature is too high for the impregnation process and for the correct impregnation, it is possible to heat the syrup in order to obtain a more liquid syrup within the limits of the aforementioned dynamic viscosity range at the respective temperature at which impregnation takes place for sufficient wetting and correct and complete impregnation of the fibrous substrate.  The liquid syrup according to the present invention does not contain additional solvent added voluntarily.  The liquid monomer syrup may also comprise other additives and fillers.  A charge within the scope of the present invention is not considered an additive.  All additives and fillers can be added to the liquid monomer syrup prior to impregnation.  As additives, mention may be made of organic additives such as impact modifiers or block copolymers, thermal stabilizers, UV stabilizers, lubricants, dispersants, antifoaming agents, rheology modifiers, waxes, adhesion modifiers, mold release agents and mixtures thereof.  The impact modifier is in the form of fine particles comprising an elastomeric core and at least one thermoplastic shell, the size of the particles being generally less than 1 μm and advantageously between 50 and 300 nm.  The impact modifier is prepared by emulsion polymerization.  The impact modifier of the liquid monomer syrup is 0 to 50% by weight, preferably 0 to 25% by weight, and preferably 0 to 20% by weight.  As fillers, mention may be made of carbon nanotubes or mineral fillers, including mineral nanofillers (TiO 2, silica), and carbonates and hydrates.  The content of the fillers in the liquid monomer syrup is from 0% by weight to 60% by weight.  An additional aspect according to the present invention is the impregnation process, for the impregnation of a fibrous substrate, said fibrous substrate being constituted by long fibers and said method comprising a step of impregnating said fibrous substrate with a syrup. liquid (meth) acrylic composition comprising: a) from 5% by weight to 59.99% by weight of a (meth) acrylic polymer, b) from 30% by weight to 89.99% by weight of the sum of one monomer (A) and optionally a monomer (B), c) from 0.01% by weight to 5% by weight of an initiator or initiation system for starting the polymerization of the (meth) acrylic monomer, d) from 0% by weight to 1% by weight of an activator, e) from 0% by weight to 60% by weight of fillers, f) from 0% by weight to 20% by weight of additives, or the monomers (A) chosen from (meth) acrylic monomers or vinyl monomers having a boiling point of at least 115 ° C. to 1013 mbar and / or a vapor pressure less than 25 mbar at 20 ° C, and the other (meth) acrylic monomer (B) having a boiling point of less than 115 ° C at 1013 mbar and / or a vapor pressure greater than 25 mbar at 20 ° C, said liquid (meth) acrylic syrup having a dynamic viscosity of a value in the range of 10 mPa * s to 10 000 mPa * s, preferably 50 mPa * s to 5000 mPa * s and advantageously from 35 100 mPa * s to 1000 mPa * s.  The respective compounds are the same as previously defined.  Another additional aspect according to the present invention is the liquid (meth) acrylic impregnating syrup for carrying out the impregnation method according to any one of the preceding claims, said liquid (meth) acrylic syrup comprising: a) a (meth) acrylic polymer, b) at least one monomer (A) chosen from a (meth) acrylic monomer or a vinyl monomer or a mixture thereof, c) at least one initiator or initiation system for starting the polymerization of the (meth) acrylic monomer, d) optionally another (meth) acrylic monomer (B), the monomer (s) (A) chosen from (meth) acrylic monomers or vinyl monomers having a boiling point of from minus 115 ° C to 1013 mbar and / or a vapor pressure of less than 25 mbar at 20 ° C, and the other (meth) acrylic monomer (B) having a boiling point of less than 115 ° C to 1 013 mbar and / or a vapor pressure greater than 25 mba at 20 ° C, said liquid (meth) acrylic syrup having a dynamic viscosity of a value in the range of from 10 mPa * s to 10,000 mPa * s, preferably from 50 mPa * s to 5,000 mPa * s and advantageously from 100 mPa * s to 1000 mPa * s.  The respective compounds are the same as previously defined.  [0126] Another additional aspect according to the present invention is a liquid (meth) acrylic impregnating syrup comprising: 5% by weight to 59.99% by weight of a (meth) acrylic polymer, 30% by weight weight at 89.99% by weight of the sum of a monomer (A) and optionally a monomer (B), from 0.01% by weight to 5% by weight of an initiator or initiation system for starting the polymerization of the (meth) acrylic monomer, from 0% by weight to 1% by weight of an activator, from 0% by weight to 60% by weight of fillers, from 0% by weight to 20% by weight weight of additives.  Another aspect of the present invention is a manufacturing method for the manufacture of mechanical or structural parts or articles comprising the following steps: a) impregnation of a fibrous substrate with a liquid monomer syrup, b) the polymerization of the liquid monomer syrup impregnating said fibrous substrate.  The respective compounds are the same as previously defined.  Preferably, the impregnation of the fibrous substrate in step a) is carried out in a mold.  Advantageously, step a) and step b) are performed in the same mold.  The mold is opaque to visible and ultraviolet radiation on at least one side.  The use of the same mold avoids the transfer of the material after the impregnation.  The temperature of the polymerization at step b) is less than 120 ° C, preferably less than 80 ° C and more preferably less than 40 ° C.  [0134] No tin is present in manufactured mechanical or structural parts or articles from accelerators added for the polymerization step.  The manufactured mechanical or structural parts or articles do not contain any additional solvent added voluntarily since the syrup did not contain any additional solvent for the impregnation step.  As regards the manufactured mechanical or structural parts or articles of the present invention, they comprise at least 20% by weight of fibrous substrate, preferably at least 40% by weight of fibrous material, advantageously at least 50% by weight. by weight of fibrous material and preferably at least 55% by weight of fibrous material, based on the total composition.  The mechanical or structural parts or articles manufactured of the present invention comprise at most 99% by weight of fibrous material, preferably at most 95% by weight of fibrous material, advantageously at most 90% by weight of fibrous material and advantageously at most 80% by weight of fibrous material, based on the total composition.  Due to the manufacturing process for the manufacture of mechanical or structural parts or articles according to the invention, a complete, correct and homogeneous wetting of the fibrous substrate takes place during the impregnation.  The wetting of the fibers during the impregnation has no defects, for example due to bubbles and voids which reduce the mechanical performance of parts or mechanical or structured manufactured articles.  The mechanical or structural parts or articles manufactured according to the invention essentially do not comprise pores.  "Pore" means a spherical void with a diameter of at least 1 μm or more, or an elongated ellipsoidal void in the form of an oblate having a smallest major axis of at least 0.5 μm or more.  "Comprising essentially no pores" means that the pores represent less than 1% by volume, preferably less than 0.5% by volume and more preferably less than 0.2% by volume of the total volume of the mechanical parts or articles or manufactured structures.  With regard to the manufacturing process for the manufacture of mechanical or structural parts or articles comprising the polymeric composite material, several methods can be used to prepare three-dimensional mechanical or structural parts.  Examples include infusion, vacuum bag molding, pressure bag molding, autoclave bag molding, resin transfer molding (RTM), injection molding and reaction molding (RIM), molding injection and reinforced reaction (R-RIM) and its variants, press molding, compression molding or pultrusion, contact molding, simultaneous projection molding, filament winding, sheet prepreg or prepreg in bulk.  The preferred manufacturing methods for the manufacture of mechanical or structural parts or articles comprising the composite materials are the processes in which the liquid monomer syrup is transferred into the fibrous substrate by impregnating the fibrous substrate in a mold.  Advantageously, the impregnating step of the fibrous material is carried out in a mold.  Most advantageously, the manufacturing method for the manufacture of mechanical or structural parts or articles comprising the polymeric composite material is chosen from pultrusion, contact molding, simultaneous projection molding, resin transfer molding or infusion.  [0144] All the methods comprise the step of impregnating the fibrous substrate with the liquid monomer syrup before the polymerization step in a mold.  The polymerization step of the liquid monomer syrup impregnating said fibrous substrate takes place after the impregnation step in the same mold.  [0146] According to the pultrusion method, a continuous product of constant cross section is produced.  Fibers from creels are wetted and impregnated with the liquid resin in a resin bath, followed by preforming, shaping and polymerization.  Resin transfer molding is a method using a set of two-sided molds that shapes both surfaces of a composite material.  The lower side is a rigid mold.  The upper side may be a rigid or flexible mold.  The flexible molds may be of composite materials, silicone or extruded polymeric films such as nylon.  Both sides assemble to produce a mold cavity.  The distinctive feature of resin transfer molding is that the fibrous substrate is placed in this cavity and the set of molds is closed prior to introduction of the liquid monomer syrup.  Resin transfer molding includes many variations that differ in the mechanics of introducing the liquid (meth) acrylic syrup into the fibrous substrate in the mold cavity.  These variations range from vacuum infusion to vacuum assisted resin transfer molding (VARTM).  This process can be performed at room temperature or elevated.  "Ambient temperature" means between 10 ° C and 50 ° C.  "High temperature" means up to 200 ° C.  A preferred elevated temperature is 50 ° C to 160 ° C.  With the infusion method, the liquid monomer syrup does not have to have the viscosity suitable for this method of preparation of the polymer composite material.  The liquid monomer syrup is sucked into the fibrous substrate present in a special mold by application of a slight vacuum.  The fibrous substrate is infused and completely impregnated with the liquid monomer syrup.  An advantage of this method is the large amount of fibrous material in the composite.  With regard to the use of mechanical or structural parts or articles manufactured, mention may be made of automotive applications, nautical applications, railway applications, sports, aeronautical and aerospace applications, photovoltaic applications, applications related to computers, telecommunications applications and wind applications.  [0151] Particularly, the three-dimensional mechanical or structural part is an automobile part, a boat part, a train part, a sporting article, an airplane or helicopter part, a piece of spaceship or flare, a piece of photovoltaic module, a piece of wind turbine, a piece of furniture, a building or building part, a piece of telephone or cell phone, a computer or television room, a room printer and photocopier.  The impregnation method for impregnating a fibrous substrate or the process for manufacturing mechanical or structural parts or articles is used in the manufacture of recyclable mechanical and / or structural parts, which are recyclable by depolymerization. thermal, preferably at least 50% of the monomers being recovered.
    权利要求:
    Claims (29)
    [0001]
    An impregnation method for impregnating a fibrous substrate, said fibrous substrate consisting of long fibers and said method comprising a step of impregnating said fibrous substrate with a liquid monomer syrup comprising: a) a (meth) acrylic polymer b) at least one monomer (A) chosen from a (meth) acrylic monomer or a vinyl monomer or a mixture thereof, c) at least one initiator or initiation system for starting the polymerization of the (meth) acrylic monomer, d) optionally another (meth) acrylic monomer (B), the monomer (s) (A) selected from a (meth) acrylic monomer or vinyl monomers having a boiling point of at least 115 ° C to 1013 mbar and / or a vapor pressure of less than 25 mbar at 20 ° C, and the other (meth) acrylic monomer B having a boiling point of less than 115 ° C at 1013 mbar and / or a vapor pressure greater than 25 mbar at 20 ° C, and led liquid monomer syrup having a dynamic viscosity of a value in the range of 10 mPa * s to 10,000 mPa * s, preferably 50 mPa * s to 5,000 mPa * s and preferably 100 mPa * s to 1 000 mPa * s.
    [0002]
    2. Impregnation process according to claim 1, characterized in that the monomer (A) has a vapor pressure of less than 10 mbar at 20 ° C.
    [0003]
    3. Impregnation process according to claim 1, characterized in that the monomer (A) has a boiling point of at least 135 ° C to 1013 mbar.
    [0004]
    4. Impregnation process according to any one of claims 1 to 3, characterized in that the monomer syrup comprises the monomer (meth) acrylic (B).
    [0005]
    5. Impregnation process according to any one of claims 1 to 4, characterized in that the monomer or monomers (A) represent more than 30% by weight, preferably more than 50% by weight of the total sum of the monomers (A) and (B) present in the liquid monomer syrup.
    [0006]
    6. Impregnation process according to any one of claims 1 to 5, characterized in that the (meth) acrylic monomer (B) is less than 70% by weight, preferably less than 50% by weight of the total sum monomers (A) and (B) in the liquid monomer syrup.
    [0007]
    7. Impregnation process according to any one of claims 1 to 6, characterized in that the monomer (A) is selected from cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, methacrylate d. heptyl, n-octyl acrylate, 2-octyl acrylate, isooctyl acrylate, 2-ethylhexyl methacrylate, butyldiglycol methacrylate, dicyclopentenyloxyethyl methacrylate, ethoxyethyl methacrylate , isobutyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, hydroxylpropyl methacrylate, styrene, alpha-methylstyrene, ortho, beta or para-methylstyrene, tert-butylstyrene, nitrostyrene, N-vinylpyrrolidone and mixtures thereof.
    [0008]
    8. Impregnation process according to any one of claims 1 to 7, characterized in that the (meth) acrylic polymer is a homo- or copolymer of methyl methacrylate (MMA) or a mixture thereof.
    [0009]
    9. Impregnation process according to claim 8, characterized in that the methyl methacrylate (MMA) copolymer comprises at least 70%, preferably at least 80%, advantageously at least 90% and more advantageously at least 95% by weight. weight of methyl methacrylate (MMA).
    [0010]
    10. Impregnation process according to any one of claims 8 or 9, characterized in that the methyl methacrylate (MMA) copolymer comprises from 70% to 99.7% by weight, preferably from 80% to 99%, 7% by weight, preferably from 90% to 99.7% by weight and more preferably from 90% to 99.5% by weight of methyl methacrylate, and from 0.3% to 30% by weight, preferably from 0% to From 3% to 20% by weight, preferably 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 methacrylate of methyl.
    [0011]
    11. Impregnation method according to claim 10, characterized in that the comonomer is selected from methyl acrylate or ethyl acrylate and a mixture thereof.
    [0012]
    12. Impregnation process according to any one of claims 4 to 11, characterized in that the (meth) acrylic monomer (B) is selected from alkyl acrylic monomers, the alkyl group containing 1 to 4 carbons, linear or branched, methyl methacrylate and mixtures thereof.
    [0013]
    13. Impregnation process according to any one of claims 5 to 12, characterized in that the (meth) acrylic monomer (B) is selected from methyl methacrylate, methyl acrylate, ethyl acrylate and their mixtures.
    [0014]
    14. Impregnation process according to any one of claims 1 to 13, characterized in that the initiator or the initiation system for starting the polymerization of the monomer (A) and the (meth) acrylic monomer (B). ) generates radicals.
    [0015]
    15. Impregnation method according to any one of claims 1 to 14, characterized in that the initiator or the initiation system for starting the polymerization of the monomer (A) and the (meth) acrylic monomer (B). ) is selected from diacyl peroxides, peroxy esters, dialkyl peroxides, peroxyacetals, hydroperoxides, azo compounds or mixtures thereof.
    [0016]
    16. Impregnation method according to any one of claims 1 to 15, characterized in that the (meth) acrylic polymer in the liquid monomer syrup is at least 5% by weight, preferably at least 10%, preferably at least 15% and more preferably at least 20% by weight of the total weight of the compounds a) + b) + c) + d) liquid monomer syrup.
    [0017]
    17. Impregnation process according to any one of claims 1 to 16, characterized in that the (meth) acrylic polymer in the liquid (meth) acrylic syrup is at most 60% by weight, preferably at most 50%, advantageously at most 40% and more advantageously at most 35% by weight of the total weight of the compounds a) + b) + c) + d) of the liquid monomer syrup.
    [0018]
    18. Impregnation process according to any one of claims 1 to 17, characterized in that the monomer (A) and the monomer (B) in the liquid monomer syrup represent at least 30% by weight, preferably 40% by weight. weight, advantageously 50% by weight and more preferably 60% by weight of the total weight of the compounds a) + b) + c) + d) liquid monomer syrup.
    [0019]
    19. Impregnation process according to any one of claims 1 to 18, characterized in that the liquid monomer syrup comprises: a) from 5% by weight to 59.99% by weight of a (meth) acrylic polymer, b) from 30% by weight to 89.99% by weight of the sum of a monomer (A) and a monomer (B), c) from 0.01% by weight to 5% by weight of a initiator or initiation system for starting the polymerization of the monomer or monomers, d) from 0% by weight to 1% by weight of an activator, e) from 0% by weight to 60% by weight of fillers, f) from 0% by weight to 20% by weight of additives.
    [0020]
    20. An impregnating liquid monomer acrylic syrup for carrying out the impregnation process according to any one of the preceding claims, said liquid monomer syrup comprising: a) a (meth) acrylic polymer, b) at least one monomer ( A) chosen from a (meth) acrylic monomer or a vinyl monomer or their mixture, c) at least one initiator or initiation system for starting the polymerization of the (meth) acrylic monomer, d) optionally another monomer (meth) ) acrylic (B), the monomer (s) (A) chosen from a (meth) acrylic monomer or vinyl monomers having a boiling point of at least 115 ° C and / or a vapor pressure of less than 25 mbar; 20 ° C, and the other (meth) acrylic monomer B having a boiling point below 115 ° C and / or a vapor pressure greater than 25 mbar at 20 ° C, and said liquid monomer syrup having a dynamic viscosity a value in the range from 10 mPa * s to 10,000 mPa * s, preferably from 50 mPa * s to 5,000 mPa * s and preferably from 100 mPa * s to 1,000 mPa * s.
    [0021]
    21. A liquid impregnating monomer syrup according to claim 20, said syrup comprising: a) from 5% by weight to 59.99% by weight of a (meth) acrylic polymer, b) from 30% by weight to 89, 99% by weight of the sum of the monomer (A) and the monomer (B), c) from 0.01% by weight to 5% by weight of an initiator or initiation system for starting the polymerization of the monomer or monomers, d) from 0% by weight to 1% by weight of an activator, e) from 0% by weight to 60% by weight of filler, f) from 0% by weight to 20% by weight of additives.
    [0022]
    22. Process for the manufacture of mechanical or structural parts or articles comprising the following steps: a) impregnation of a fibrous substrate with a liquid monomer syrup according to any one of claims 1 to 19, b) polymerization liquid monomer syrup impregnating said fibrous substrate.
    [0023]
    23. The method of claim 22, characterized in that the impregnation of the fibrous substrate in step a) is performed in a mold.
    [0024]
    24. Method according to any one of claims 22 to 23, characterized in that step a) and step b) are carried out in the same mold.
    [0025]
    25. A method according to any one of claims 22 to 24, characterized in that the method is selected from pultrusion, contact molding, simultaneous projection molding, resin transfer molding or infusion. 35
    [0026]
    26. Process according to any one of claims 22 to 25, characterized in that the temperature of the polymerization in step b) is less than 120 ° C, preferably less than 80 ° C and more preferably less than 40 ° C. .
    [0027]
    27. Three-dimensional mechanical or structural parts obtained by the manufacturing method according to claims 22 to 26.
    [0028]
    28. Part according to claim 27, which is an automobile part, a boat part, a train piece, a sporting article, an airplane or helicopter part, a part of a spaceship or a rocket, a piece of photovoltaic module, a piece of wind turbine, a piece of furniture, a piece of construction or building, a piece of telephone or mobile phone, a computer or television part, a printer and photocopier.
    [0029]
    29. Use of the impregnation method according to any one of claims 1 to 19 or the manufacturing method according to any one of claims 22 to 26, in the manufacture of mechanical and / or structural recyclable parts, which are recyclable by thermal depolymerization, preferably at least 50% of the monomers being recovered.
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    同族专利:
    公开号 | 公开日
    EP3097138B1|2020-04-15|
    US20170009033A1|2017-01-12|
    US10500339B2|2019-12-10|
    CN106459434A|2017-02-22|
    FR3016642B1|2020-02-21|
    WO2015110534A1|2015-07-30|
    EP3097138A1|2016-11-30|
    CN106459434B|2020-04-21|
    ES2804100T3|2021-02-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO1993004141A1|1991-08-26|1993-03-04|Aristech Chemical Corporation|Polymethylmethacrylate syrup as medium for liquid crystals|
    EP1927603A1|2005-09-21|2008-06-04|Mitsubishi Rayon Co., Ltd.|Syrup composition, resin mortar composition and application method|
    EP1918309A1|2006-10-30|2008-05-07|Sika Technology AG|Radically curable composition comprising apolymerizable monomer and a radical-generating agent|
    WO2013056845A2|2011-10-21|2013-04-25|Arkema France|Composite material via in-situ polymerization of thermoplastic acrylic resins and its use|
    FR3002942A1|2013-03-11|2014-09-12|Arkema France|LIQUID ACRYLIC SYRUP FOR IMPREGNATING A FIBROUS SUBSTRATE, METHOD FOR IMPREGNATING A FIBROUS SUBSTRATE, COMPOSITE MATERIAL OBTAINED AFTER POLYMERIZATION OF SAID PRE-IMPREGNATED SUBSTRATE.|
    WO2014140467A1|2013-03-11|2014-09-18|Arkema France|Liquid acrylic syrup for impregnating a fibrous substrate, method of impregnating a fibrous substrate, composite material obtained following polymerisation of the pre-impregnated substrate|
    US2961364A|1954-12-09|1960-11-22|Rohm & Haas|Method of making bonded fibrous products|
    BE639628A|1962-11-08|
    US5242968A|1990-08-27|1993-09-07|Aristech Chemical Corporation|Acrylic-filled thermoformable acrylic sheet|
    JP3583205B2|1995-09-27|2004-11-04|トヨタ自動車株式会社|Manufacturing method of cloth-like substrate composite thermoplastic member|
    EP0796873A4|1995-10-06|1999-11-03|Nippon Catalytic Chem Ind|acrylic syrup, process for preparing the same, and process for preparing molding material containing acrylic syrup|
    US20100028710A1|2006-04-21|2010-02-04|Metafoam Technologies Inc.|Open cell porous material and method for producing same|
    FR2993581B1|2012-07-18|2016-01-22|Arkema France|IMPREGNATION PROCESS FOR A FIBROUS SUBSTRATE, LIQUID ACRYLIC SYRUP FOR THE IMPREGNATION PROCESS, ITS POLYMERIZATION PROCESS AND STRUCTURE PRODUCT OBTAINED THEREFROM|
    WO2014111129A1|2013-01-15|2014-07-24|Arkema France|Multilayer composite composition, its manufacturing process, and article obtained thereof|
    FR3002941B1|2013-03-08|2015-04-10|Arkema France|LIQUID ACRYLIC SYRUP FOR IMPREGNATING A FIBROUS SUBSTRATE, METHOD FOR IMPREGNATING A FIBROUS SUBSTRATE, COMPOSITE MATERIAL OBTAINED AFTER POLYMERIZATION OF SAID PRE-IMPREGNATED SUBSTRATE|
    FR3002943B1|2013-03-11|2015-03-27|Arkema France|LIQUID ACRYLIC SYRUP FOR IMPREGNATING A FIBROUS SUBSTRATE, METHOD FOR IMPREGNATING A FIBROUS SUBSTRATE, COMPOSITE MATERIAL OBTAINED AFTER POLYMERIZATION OF SAID PRE-IMPREGNATED SUBSTRATE.|
    FR3005057B1|2013-04-25|2015-05-15|Arkema France|LIQUID ACRYLIC SYRUP, ITS POLYMERIZATION PROCESS, ITS USE AND MOLDED OBJECT OBTAINED THEREFROM|WO2017115749A1|2015-12-28|2017-07-06|ヤマハ株式会社|Resin composition for frp, frp sheet and molded body|
    FR3060577B1|2016-12-21|2020-11-06|Arkema France|LIQUID COMPOSITION COMPRISING TWO INITIATORS, ITS POLYMERIZATION PROCESS, USE AND MATERIAL OR COMPOSITION OBTAINED AFTER POLYMERIZATION OF THE COMPOSITION|
    FR3082845B1|2018-06-21|2021-01-15|Arkema France|LIQUID COMPOSITION COMPRISING THREE INITIATORS, ITS POLYMERIZATION PROCESS, ITS USE AND MATERIAL OBTAINED AFTER POLYMERIZATION OF THE COMPOSITION|
    FR3093727B1|2019-03-11|2021-10-22|Arkema France|LIQUID COMPOSITION CONSISTING OF A WAX COMPOUND, ITS POLYMERIZATION PROCESS, USE AND MATERIAL OR COMPOSITION OBTAINED FOLLOWING THE POLYMERIZATION OF THE COMPOSITION|
    FR3105227A1|2019-12-18|2021-06-25|Arkema France|COMPOSITION INCLUDING A HEMIPEROXYACETAL, ITS POLYMERIZATION PROCESS, ITS USE AND COMPOSITION MATERIAL OBTAINED AFTER POLYMERIZATION OF THE COMPOSITION|
    法律状态:
    2015-12-08| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-15| PLFP| Fee payment|Year of fee payment: 4 |
    2017-12-11| PLFP| Fee payment|Year of fee payment: 5 |
    2018-12-13| PLFP| Fee payment|Year of fee payment: 6 |
    2019-12-16| PLFP| Fee payment|Year of fee payment: 7 |
    2020-12-10| PLFP| Fee payment|Year of fee payment: 8 |
    2021-12-17| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1450545A|FR3016642B1|2014-01-22|2014-01-22|IMPREGNATION PROCESS FOR A FIBROUS SUBSTRATE, LIQUID MONOMERIC SYRUP FOR THE IMPREGNATION PROCESS, ITS POLYMERIZATION METHOD AND STRUCTURAL ARTICLE OBTAINED|
    FR1450545|2014-01-22|FR1450545A| FR3016642B1|2014-01-22|2014-01-22|IMPREGNATION PROCESS FOR A FIBROUS SUBSTRATE, LIQUID MONOMERIC SYRUP FOR THE IMPREGNATION PROCESS, ITS POLYMERIZATION METHOD AND STRUCTURAL ARTICLE OBTAINED|
    US15/113,206| US10500339B2|2014-01-22|2015-01-22|Impregnation process for a fibrous substrate, a liquid monomer syrup for the impregnation process, its method of polymerization and structured article obtained thereof|
    ES15700886T| ES2804100T3|2014-01-22|2015-01-22|Impregnation process for a fibrous substrate, a liquid monomer syrup for the impregnation process, its polymerization method and structured article obtained therefrom|
    PCT/EP2015/051263| WO2015110534A1|2014-01-22|2015-01-22|Impregnation process for a fibrous substrate, a liquid monomer syrup for the impregnation process, its method of polymerization and structured article obtained thereof|
    EP15700886.3A| EP3097138B1|2014-01-22|2015-01-22|Impregnation process for a fibrous substrate, a liquid monomer syrup for the impregnation process, its method of polymerization and structured article obtained thereof|
    CN201580015450.0A| CN106459434B|2014-01-22|2015-01-22|Impregnation process for fibrous substrates, liquid monomer slurry for use in impregnation process, polymerization process thereof and structured articles obtained therefrom|
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