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    • 专利摘要:
    The present invention relates to a composition comprising a fibrous material, a multi-stage polymer and a (meth) acrylic polymer. The composition may be in the form of a prepreg, a preform or a laminate. In particular, the present invention relates to a method of manufacturing a composition comprising a fibrous material, a multi-stage polymer and a (meth) acrylic polymer and its use in the manufacture of composite articles. More particularly, the present invention relates to a process for preparing a composition comprising a fibrous material, a multi-stage polymer and a (meth) acrylic polymer and its use for producing fiber reinforced modified impact strength composites.
    公开号:FR3053044A1
    申请号:FR1655832
    申请日:2016-06-23
    公开日:2017-12-29
    发明作者:Pierre Escale；Raber Inoubli；Pierre Gerard；Philippe Hajji
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    Composition comprising a fibrous material, a multi-stage polymer and a (meth) acrylic polymer, its method of preparation, its use and a composite comprising the same [Field of the invention] [001] The present invention relates to a composition comprising a fibrous material, a multi-stage polymer and a (meth) acrylic polymer. The composition may be in the form of a prepreg, a preform or a laminate.
    In particular, the present invention relates to a method of manufacturing a composition comprising a fibrous material, a multi-stage polymer and a (meth) acrylic polymer and its use in the manufacture of composite articles.
    More particularly, the present invention relates to a process for preparing a composition comprising a fibrous material, a multi-stage polymer and a (meth) acrylic polymer and its use for producing fiber reinforced modified impact resistant composites.
    [Technical problem] [004] Mechanical parts that have to withstand high stresses during use are frequently 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 material that forms the matrix, that is to say a continuous phase that ensures the cohesion of the structure, and a reinforcing material.
    [005] The objective of the use of composite materials is to obtain performance of the composite material that can not be obtained with its separate components if they are used alone. As a result, composite materials are widely used in several industrial sectors such as, for example, building, automotive, aerospace, transportation, recreation, electronics, and sports, particularly because of their performance. improved mechanical properties (higher tensile strength, higher tensile modulus and higher fracture toughness) compared to homogeneous materials and low density.
    [006] The largest class in terms of volume on a commercial industrial scale are composites with organic matrices, where the matrix material is generally a polymer. The main matrix or continuous phase of a polymeric composite material is a thermoplastic polymer or a thermosetting polymer.
    [007] Thermosetting polymers consist of three-dimensional crosslinked structures. Crosslinking is achieved by reactive curing groups within the prepolymer. Curing, for example, can be achieved by heating the polymer chains to permanently cure and cure the material.
    In order to prepare the polymeric composite material, the prepolymer is mixed with the other component such as glass beads or fibers (reinforcing material) or the other component which is wet or impregnated with a prepolymer and cured by the following. Examples of prepolymers or matrix material for thermosetting polymers are unsaturated polyesters, vinyl, epoxy or phenolic esters. After curing, a thermoset composite can not be reformed and remains in its predetermined form.
    [009] The thermoplastic polymers consist of linear or branched polymers, which are not crosslinked. The thermoplastic polymers are heated to mix the constituents necessary to produce the composite material and are cooled to thermoset. The limit of the use of thermoplastic polymers for the manufacture of composite materials is their high viscosity in the molten state in order to homogeneously impregnate, for example, a fibrous substrate. The wetting or correct impregnation of the fibers with the thermoplastic polymer can only be obtained if the thermoplastic resin is sufficiently fluid.
    [010] Another method of impregnating the fibrous substrate is the dissolution of the thermoplastic polymer in an organic solvent.
    The solution is used for impregnation and the solvent is evaporated.
    Another method of preparing a thermoplastic composite is the impregnation of the fibrous substrate with a liquid syrup which comprises a monomer and the polymerization of said monomer.
    [012] Nevertheless, many of the polymers used for the preparation of composite materials remain very fragile and do not have good mechanical properties, for example impact resistance. Although the fibrous substrate makes it possible to reinforce the mechanical properties of material by absorbing the energy due to an impact, since the matrix based on thermoplastic polymer is fragile, it can not prevent the propagation of cracks, for example and as such, the final composite material remains too fragile.
    [013] In order to improve the impact resistance of a polymer, it is known practice to add an impact-resistant additive, which modifies the impact resistance, comprising an elastomer phase or a rubber. Such rubber may be part of a multi-stage polymer in the form of core-shell particles, with a stage which is a rubber or elastomeric phase. These particles are prepared by emulsion polymerization to form a dispersion and can, for example, be recovered as a powder. They generally include a succession of "hard" and "soft" layers. Two-layer (soft-hard) or three-layer (hard-soft-hard) particles can thus be formed. The particle size is generally less than 1 p and more particularly between 50 nm and 500 nm.
    [014] The multi-stage polymer in the form of core-shell particles is available in the form of an agglomerated dry powder, the latter being dispersed in the matrix in order to obtain a homogeneous distribution of the initial core-shell particles. For certain thermosetting polymers or resins, such as, in particular, an epoxy resin, but also for thermoplastic polymers, it is very difficult or practically impossible to properly disperse these multi-stage polymer particles.
    [015] The dispersion of these discrete heart-bark particles generally weakly crosslinked in the liquid syrup or prepolymers in order to impregnate the fibrous reinforcement poses problems during the impregnation step. In fact, the particles swell in the syrup, which leads to the gelation of the syrup. The viscosity is then too high and it is no longer possible to impregnate the fibrous substrate without defects appearing. In order to avoid this gelling phenomenon, the content of these particles in the resin must be limited to a very low content. However, such a content remains too low and does not lead to the expected mechanical properties, in particular as regards the impact resistance.
    The object of the present invention is to obtain a composition which comprises a fibrous material, a multi-stage polymer and a (meth) acrylic polymer adapted for use in a polymeric composite material.
    It is also an object of the present invention to provide a stable composition that comprises a fibrous material, a multi-stage polymer, and a (meth) acrylic polymer that can be used to produce an impact-resistant polymer composite. changed.
    [018] An additional objective of the present invention is to obtain a stable preform which comprises a fibrous material, a multi-stage polymer and a (meth) acrylic polymer.
    Another additional object of the present invention is a process for preparing a composition which comprises a fibrous material, a multi-stage polymer and a (meth) acrylic polymer.
    Another object of the present invention is the discovery of a method of introducing a multi-stage polymer into a polymeric composite material or mechanical or structured parts or articles comprising the polymeric composite material.
    Another further object of the present invention is a method of obtaining a stable preform which comprises a fibrous material, a multi-stage polymer and a (meth) acrylic polymer.
    [022] An additional objective is the provision of a method for manufacturing a modified impact-modified polymeric composite material or mechanical or structured parts or articles comprising the modified impact-resistant polymeric composite material.
    BACKGROUND OF THE INVENTION [023] EP1085968 discloses composite articles comprising prepregs, preforms, laminates and sandwich moldings and methods of making them. In particular, one strand of a plurality of fibers coated with polymer particles is described. The polymer particle is a thermoplastic polymer or a crosslinked thermoplastic polymer.
    [024] EP1312453 discloses composite articles comprising prepregs, preforms, laminates and sandwich moldings and methods of making them. In particular, one strand of a plurality of fibers coated with polymer particles is described which has an average diameter of less than 5 μm. The polymer particle is a thermoplastic polymer or a crosslinked thermoplastic polymer. A polymer particle having a small size of from 0.1 μm to 0.25 μm having high molecular weights of at least 10,000 g / mol is mentioned.
    [025] None of the documents of the prior art describes a composition, a method or a use according to the present invention.
    [026] Unexpectedly, it has been discovered that a composition comprising a) a fibrous material and b) a multi-stage polymer and c) a (meth) acrylic polymer (PI), wherein the amount of multi-stage polymer in the composition is from 3 wt% to 50 wt% and the (meth) acrylic polymer (PI) has a weight average molecular weight M w of less than 100,000 g / mol, is adapted for use in a polymeric composite material.
    [027] Unexpectedly, it has been discovered that a preform comprising a) a fibrous material and b) a multi-stage polymer and c) a (meth) acrylic polymer (PI), where the amount of multi-stage polymer in the preform is between 3% by weight and 50% by weight and the (meth) acrylic polymer (PI) has a weight average molecular weight Mw of less than 100,000 g / mol, retains its shape.
    [028] Unexpectedly, it has also been observed that a composition comprising a) a fibrous material and b) a multi-stage polymer and c) a (meth) acrylic polymer (PI), where the amount of multistage polymer in the preform is between 3% by weight and 50% by weight and the (meth) acrylic polymer (PI) has a weight average molecular weight Mw of less than 100,000 g / mol, can be used to make a composite material polymer or mechanical or structured parts or articles comprising the polymeric composite material.
    [029] Unexpectedly, it has also been observed that a method of manufacturing a composition comprising the steps of a) contacting a fibrous material and a multi-stage polymer and a polymer ( meth) acrylic (PI) which has a weight average molecular weight Mw of less than 100,000 g / mol, wherein the amount of multi-stage polymer in the composition is from 3 wt.% to 50 wt. which can be used in a polymeric composite material.
    In a first aspect, the present invention relates to a composition comprising a) a fibrous material and b) a multi-stage polymer, c) a (meth) acrylic polymer (PI), wherein the amount of multi-stage polymer in the composition is from 3% by weight to 50% by weight and the (meth) acrylic polymer (PI) has a weight average molecular weight Mw of less than 100,000 g / mol.
    [031] According to a second aspect, the present invention relates to a method of manufacturing a preform comprising the steps of a) contacting a fibrous material and a multi-stage polymer and a polymer (meth) acrylic (PI) which has a weight average molecular weight Mw of less than 100,000 g / mol, wherein the amount of multi-stage polymer in the preform is from 3 wt% to 50 wt%.
    [032] According to a third aspect, the present invention relates to a preform comprising a) a fibrous material and b) a multi-stage polymer, c) a (meth) acrylic polymer (PI), wherein the amount of multi-stage polymer in the preform is between 3% by weight and 50% by weight and the (meth) acrylic polymer (PI) has a weight average molecular weight Mw of less than 100,000 g / mol.
    [033] In a fourth aspect, the present invention relates to the use of a preform comprising a) a fibrous material and b) a multi-stage polymer, c) a (meth) acrylic polymer (PI), where the amount of multi-stage polymer in the preform is from 3 wt% to 50 wt% and the (meth) acrylic polymer (PI) has a weight average molecular weight Mw of less than 100,000 g / mol to make a polymer composite material or mechanical or structured parts or articles comprising the polymeric composite material.
    [034] In a fifth aspect, the present invention relates to the use of a composition comprising a) a fibrous material and b) a multi-stage polymer, c) a (meth) acrylic polymer (PI), where the amount of polymer in the composition is between 3 wt% and 50 wt% and the (meth) acrylic polymer (PI) has a weight average molecular weight Mw of less than 100,000 g / mol to make a polymeric composite material or mechanical or structured parts or articles comprising the polymeric composite material.
    The term "polymer powder" as used herein refers to a polymer comprising powder grains in the range of at least 1 micron (μm) obtained by agglomeration of primary particles comprising a polymer or polymers or polymers. oligomers in the nanometer range.
    The term "primary particle" in the present context refers to a spherical polymer comprising particles in the nanoscale range. Preferably, the primary particle has a weight average particle size of between 20 nm and 800 nm.
    [037] The term "particle size" in the present context refers to the average volume diameter of a particle considered to be spherical.
    The term "copolymer" in the present context means that the polymer consists of at least two different monomers.
    The term "multi-stage polymer" as used herein refers to a polymer formed sequentially by a multistage polymerization process. It is preferred a multi-stage emulsion polymerization process wherein the first polymer is a first stage polymer and the second polymer is a second stage polymer, i.e. the second polymer is formed by emulsion in the presence of the first emulsion polymer.
    The term "(meth) acrylic" in this context refers to any type of acrylic and methacrylic monomers.
    [041] The term "(meth) acrylic polymer" in the present context means that the (meth) acrylic polymer essentially comprises polymers comprising (meth) acrylic monomers which represent 50% by weight or more of the polymer (meth) acrylic.
    [042] The term "impact modifier" in the present context refers to a material which, when incorporated into a polymeric material, increases the impact resistance and strength of that polymeric material by phase microdomains of a polymer of elastomeric material or rubber.
    [043] The term "rubber" in this context refers to the thermodynamic state of the polymer above its glass transition.
    [044] The term "polymeric rubber" as used herein refers to a polymer that has a glass transition temperature (Tg) of less than 0 ° C.
    [045] The term "preform" in this context refers to a preformed fiber reinforcement. It is a semi-finished fiber product that already has essentially the necessary external contours of a preform, which is rigid enough to be fully automated and precisely placed.
    [046] The term "prepreg" in the present context refers to a combination of a mat, a fabric, a nonwoven material, or a roving with a resin.
    [047] The composition according to the invention comprises a fibrous material, a multi-stage polymer and a (meth) acrylic polymer (P1) has a weight average molecular weight Mw of less than 100,000 g / mol, where the amount of polymer in the composition comprising three components is between 3% by weight and 50% by weight.
    [048] Preferably, the amount of multi-stage polymer in the composition is at least 4% by weight, more preferably at least 5% by weight and preferably at least <5% by weight.
    [049] Preferably, the amount of multi-stage polymer in the composition is at most 40% by weight, more preferably at most 30% by weight and preferably at least 25% by weight.
    [050] Preferably, the amount of multi-stage polymer in the composition is from 4% by weight to 40% by weight and more preferably from 5% by weight to 30% by weight and advantageously from 6% by weight to 25% by weight.
    [051] Preferably, the amount of (meth) acrylic polymer (PI) in the composition is between 0.15% by weight and 47.5% by weight and preferably between 0.3% by weight and 45% by weight. weight.
    [052] The composition of the present invention may also be in the form of a prepreg or a preform.
    [053] In a first preferred embodiment, the composition is in the form of a preform.
    [054] With regard to the (meth) acrylic polymer (PI), it has a weight average molecular weight Mw of less than 100,000 g / mol, preferably less than 90,000 g / mol, more preferably less than 80 000 g / mol, more preferably less than 70 000 g / mol, preferably less than 60 000 g / mol, more preferably less than 50 000 g / mol and even more preferably less than 40 000 g / mol.
    [055] The (meth) acrylic polymer (PI) has a weight average molecular weight Mw greater than 2,000 g / mol, preferably greater than 3,000 g / mol, more preferably greater than 4,000 g / mol, even more preferably higher at 5,000 g / mol, advantageously greater than 6,000 g / mol, more preferably greater than 6,500 g / mol and even more preferably greater than 7,000 g / mol, still more preferably greater than 10,000 g / mol and the most advantageously greater than 12,000 g / mol.
    [056] The weight average molecular weight Mw of the (meth) acrylic polymer (PI) is between 2,000 g / mol and 100,000 g / mol, preferably between 3,000 g / mol and 90,000 g / mol and more. preferably between 4,000 g / mol and 80,000 g / mol, advantageously between 5,000 g / mol and 70,000 g / mol, more advantageously between 6,000 g / mol and 50,000 g / mol and most advantageously between 10,000 g / mol and 40,000 g / mol.
    [057] Preferably, the (meth) acrylic polymer (PI) is a copolymer comprising (meth) acrylic monomers. More preferably, the (meth) acrylic polymer (PI) is a (meth) acrylic polymer. Even more preferably, the (meth) acrylic polymer (PI) comprises at least 50% by weight of monomers selected from (C1-C12) alkyl (meth) acrylates.
    Advantageously, preferably, the (meth) acrylic polymer (PI) comprises at least 50% by weight of monomers chosen from C1 to C4 alkyl methacrylate monomers and a C1 to C8 alkyl acrylate and mixtures of them.
    [058] Preferably, the glass transition temperature Tg of the (meth) acrylic polymer (P1) is between 30 ° C and 150 ° C. The glass transition temperature of the (meth) acrylic polymer (P1) is more preferably from 40 ° C to 150 ° C, preferably from 45 ° C to 150 ° C, and more preferably from 50 ° C to 150 ° C.
    [059] Preferably, the (meth) acrylic polymer (P1) is not crosslinked.
    [060] Preferably, the (meth) acrylic polymer (P1) is not grafted onto another polymer or other polymers.
    [061] In a first preferred embodiment, the (meth) acrylic polymer (P1) comprises from 50% by weight to 100% by weight of methyl methacrylate, preferably from 80% by weight to 100% by weight of methyl methacrylate, still more preferably from 80% by weight to 99.8% by weight of methyl methacrylate and from 0.2% by weight to 20% by weight of a C1 to C8 alkyl acrylate monomer . Advantageously, the C1-C8 alkyl acrylate monomer is chosen from methyl acrylate, ethyl acrylate or butyl acrylate.
    [062] In a second preferred embodiment, the (meth) acrylic polymer (P1) comprises between 0% by weight and 50% by weight of a functional monomer. Preferably, the (meth) acrylic polymer (PI) comprises between 0% by weight and 30% by weight of the functional monomer, more preferably between 1% by weight and 30% by weight, still more preferably between 2% by weight and 30% by weight. % by weight, advantageously between 3% by weight and 30% by weight, more preferably between 5% by weight and 30% by weight and most preferably between 5% by weight and 30% by weight.
    [063] Preferably, the functional monomer of the second preferred embodiment is a (meth) acrylic monomer. The functional monomer has the formula (1) or (2):
    (1) (2) [064] wherein in both formulas (1) and (2), Ri is selected from H or CH3 and in formula (1) Y is O, Rs is H or an aliphatic or aromatic radical having at least one non-C or H atom; and in formula (2) Y is N and R4 and / or R3 is H or an aliphatic or aromatic radical.
    [065] Preferably, the functional monomer (1) or (2) is chosen from glycidyl (meth) acrylate, acrylic or methacrylic acid, amides derived from these acids, such as, for example, dimethylacrylamide, 2-methoxyacrylate or ethyl methacrylate, 2-aminoethyl acrylates or methacrylates are optionally quaternized, monomers comprising a phosphonate or phosphate group, alkylimidazolidinone (meth) acrylates, polyethylene glycol (meth) acrylates. Preferably, the polyethylene glycol group of polyethylene glycol (meth) acrylates has a molecular weight in the range of 400 g / mol to 10,000 g / mol.
    [066] The multi-stage polymer according to the invention has at least two stages which are different in terms of polymer composition.
    [067] The multi-stage polymer is preferably in the form of spherical polymer particles. These particles are also called heart-bark particles. The first floor forms the heart, the second or all subsequent stages of the respective envelopes.
    As regards the spherical polymer particle, it has a mean particle diameter by weight of between 20 nm and 800 nm. Preferably, the weight average particle diameter of the polymer particle is between 25 nm and 600 nm, more preferably between 30 nm and 550 nm, still more preferably between 35 nm and 500 nm, advantageously between 40 nm and 400 nm. more preferably between 50 nm and 400 nm, still more preferably between 75 nm and 350 nm and most preferably between 80 nm and 30 nm.
    [069] The primary polymer particles can be agglomerated to obtain a polymer powder comprising the multi-stage polymer or the (meth) acrylic polymer (PI) and the multi-stage polymer.
    [070] The polymer particle is obtained by a multistage process such as a process comprising two, three or more stages.
    [071] The polymer particle has a multilayer structure comprising at least one layer (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C and another layer (B) comprising a polymer (B 1) having a glass transition temperature above 30 ° C.
    [072] In a first preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30 ° C is the outer layer of the polymer particle having the multilayer structure.
    [073] In a second preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30 ° C is an intermediate layer of the polymer particle having the multilayer structure.
    [074] Preferably, the stage (A) is the first stage and the stage (B) comprising the polymer (B1) is grafted onto the stage (A) comprising the polymer (Al) or another intermediate layer. The first stage means that the stage (A) comprising the polymer (Al) is formed before stage (B) comprising the polymer (B1).
    [075] Polymer (A1) having a glass transition temperature of less than 0 ° C in layer (A) is never performed in the last stage of the multistage process. This means that the polymer (Al) is never in the outer layer of the particle with the multilayer structure. The polymer (Al) having a glass transition temperature of less than 0 ° C in the layer (A) is in the core of the polymer particle or one of the inner layers.
    [076] Preferably, the polymer (A1) having a glass transition temperature below 0 ° C in the layer (A) is manufactured in the first stage of the multi-stage process forming the core for the polymer particle having the structure multilayer and / or before the polymer (B1) having a glass transition temperature greater than 60 ° C. Preferably, the polymer (A1) has a glass transition temperature of less than -5 ° C, more preferably less than -15 ° C, preferably less than -25 ° C.
    [077] In a first preferred embodiment, the polymer (B1) having a glass transition temperature above 60 ° C is manufactured in the last stage of the multi-stage process forming the outer layer of the polymer particle having the structure. multilayer.
    [078] In a second preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30 ° C is an intermediate layer of the polymer particle having the multilayer structure, is prepared in a stage after the Polymer formation stage (A1) of the multi-stage process.
    [079] An additional layer or layers obtained by an intermediate stage or intermediate stages may be present.
    [080] The glass transition temperature Tg of the respective polymers can be estimated, for example, by dynamic processes such as thermomechanical analysis.
    [081] In order to obtain a sample of the respective polymers (A1) and (B1), these can be prepared alone, and not by a multistage process, to estimate and measure more easily the individual glass transition temperature Tg. respective polymers of the respective stages.
    [082] As regards the polymer (Al), in a first embodiment, it is a (meth) acrylic polymer comprising at least 50% by weight of alkyl acrylate monomers.
    [083] More preferably the polymer (Al) comprises a comonomer or comonomers which are copolymerizable with the alkyl acrylate, as long as the polymer (Al) has a glass transition temperature below 0 ° C.
    [084] The comonomer or comonomers in the polymer (Al) are preferably selected from (meth) acrylic monomers and / or vinyl monomers.
    [085] The (meth) acrylic comonomer in the polymer (A1) comprises the monomers selected from (C1-C12) alkyl (meth) acrylates. Even more preferably, the (meth) acrylic comonomer in the polymer (A1) comprises C1 to C4 alkyl methacrylate monomers and / or C1 to C8 alkyl acrylate monomers.
    [086] Most preferably, the acrylic or methacrylic comonomers of the polymer (Al) are chosen from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate and acrylate. tert-butyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as the polymer (A1) 'has a glass transition temperature of less than 0 ° C.
    [087] Preferably, the polymer (Al) is crosslinked. This means that a crosslinking agent is added to the other monomer or monomers. A crosslinking agent comprises at least two groups that can be polymerized.
    [088] In a specific embodiment, the polymer (Al) is a homopolymer of butyl acrylate.
    [089] In another specific embodiment, the polymer (Al) is a copolymer of butyl acrylate and at least one crosslinking agent. The crosslinking agent has less than 5% by weight of this copolymer.
    [090] More preferably, the glass transition temperature Tg of the polymer (Al) of the first embodiment is between -100 ° C and 0 ° C, still more preferably between -100 ° C and -5 ° C, preferably between -90 ° C and -15 ° C and more preferably between -90 ° C and -25 ° C.
    [091] With regard to the polymer (Al), in a second embodiment, the polymer (Al) is a polymer based on silicone rubber. Silicone rubber, for example, is polydimethylsiloxane. More preferably, the glass transition temperature Tg of the polymer (A1) of the second embodiment is between -150 ° C. and 0 ° C., more preferably between -145 ° C. and -5 ° C., advantageously between -140 ° C. C and -15 ° C and more preferably between -135 ° C and -25 ° C.
    [092] With regard to the polymer (Al), in a third embodiment the polymer (Al) having a glass transition temperature below 0 ° C comprises at least 50% by weight of polymer units derived from isoprene or butadiene and stage (A) is the innermost layer of the polymer particle having the multilayer structure. In other words, the stage (A) comprising the polymer (Al) is the core of the polymer particle.
    [093] By way of example, the polymer (Al) of the core of the second embodiment, homopolymers of isoprene or homopolymers of butadiene, copolymers of isoprene-butadiene, copolymers of isoprene may be mentioned. with not more than 98% by weight of a vinyl monomer and butadiene copolymers with not more than 98% by weight of a vinyl monomer. The vinyl monomer may be styrene, alkylstyrene, acrylonitrile, alkyl (meth) acrylate, or butadiene or isoprene. In one embodiment, the core is a homopolymer of butadiene.
    [094] More preferably, the glass transition temperature Tg of the polymer (A1) of the third embodiment comprising at least 50% by weight of polymer units derived from isoprene or butadiene is between -100 ° C and 0 ° C more preferably between -100 ° C and -5 ° C, preferably between -90 ° C and -15 ° C and even more preferably between -90 ° C and -25 ° C.
    As regards the polymer (B1), there may be mentioned homopolymers and copolymers comprising monomers with double bonds and / or vinyl monomers. Preferably, the polymer (B1) is a (meth) acrylic polymer.
    [096] Preferably, the polymer (B1) comprises at least 70% by weight of monomers chosen from C1-C12 alkyl (meth) acrylates. Even more preferably, the polymer (B1) comprises at least 80% by weight of C1 to C4 alkyl methacrylate monomers and / or C1 to C8 alkyl acrylate monomers.
    [097] The polymer (B1) can be crosslinked.
    [098] Most preferably, the acrylic or methacrylic monomers of the polymer (B1) are chosen from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methacrylate and the like. ethyl, butyl methacrylate and mixtures thereof, as long as the polymer (B1) has a glass transition temperature of at least 30 ° C.
    [099] Advantageously, the polymer (B1) comprises at least 50% by weight, more preferably at least 60% by weight and still more preferably at least 70% by weight of monomer units derived from methyl methacrylate.
    Preferably, the glass transition temperature Tg of the polymer (B1) is between 30 ° C and 150 ° C. The glass transition temperature of the polymer (B1) is more preferably between 50 ° C and 150 ° C, still more preferably between 70 ° C and 150 ° C, preferably between 90 ° C and 150 ° C and more preferably between 90 ° C. C and 130 ° C.
    In another embodiment, the multi-stage polymer as described above, has an additional stage, which is the (meth) acrylic polymer (P1). The primary polymer particle according to this embodiment of the invention has a multilayer structure comprising at least one stage (A) comprising a polymer (Al) having a glass transition temperature below 0 ° C, at least one stage (B). ) comprising a polymer (B1) having a glass transition temperature above 30 ° C and at least one stage (P) comprising the (meth) acrylic polymer (P1) having a glass transition temperature between 30 ° C and 150 ° C .
    Preferably, the (meth) acrylic polymer (PI) is not grafted onto any of the polymers (A1) or (B1).
    As regards the method of manufacturing the multi-stage polymer according to the invention, this comprises the steps of
    a) polymerization by emulsion polymerization of a monomer or mixture of monomers (Am) to obtain at least one layer (A) comprising the polymer (Al) having a glass transition temperature below 0 ° C.
    b) polymerization by emulsion polymerization of a monomer or mixture of monomers (Bm) to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C the monomer or mixture of monomers (Am) and the monomer or mixture of monomers (Bm) are chosen from monomers according to the composition for the polymer (A1) and the polymer (B1) previously described.
    [0104] Preferably, step a) is carried out before step b). More preferably, step b) is conducted in the presence of the polymer (Al) obtained in step a), if there are only two stages.
    Advantageously, the process for producing the multi-stage polymer composition according to the invention is a multistep process which comprises the successive stages of
    a) polymerization by emulsion polymerization of a monomer or mixture of monomers (Am) to obtain a layer (A) comprising the polymer (Al) having a glass transition temperature of less than 0 ° C. b) polymerization by emulsion polymerization of a monomer or mixture of monomers (Bm) to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C.
    The monomers or respective monomer mixtures (Am) and (Bm) for forming the layers (A) and (B) respectively comprising the polymers (Al) and (B1) respectively and the characteristics of the respective polymers (Al) and (Bl) are the same as those defined above.
    The multi-stage polymer manufacturing process may comprise additional steps for additional stages between steps a) and b).
    The method for manufacturing the multi-stage polymer may further comprise additional steps for additional stages before steps a) and b). A seed may be used for the emulsion polymerization polymerization of the monomer or monomer mixture (Am) to obtain the layer (A) comprising the polymer (Al) having a glass transition temperature of less than 0 ° C. The seed is preferably a thermoplastic polymer having a glass transition temperature of at least 20 ° C.
    The multi-stage polymer is obtained in the form of an aqueous dispersion of the polymer particle. The solid content of the dispersion is between 10% by weight and 65% by weight.
    As regards the manufacturing process of the (meth) acrylic polymer (P1) according to the invention, it comprises the step of polymerization of the respective (meth) acrylic monomers (Plm). The monomers (meth) ) respective acrylics (Plm) are the same as those previously defined for the (meth) acrylic polymer (P1) and two preferred embodiments of the (meth) acrylic polymer (P1).
    The (meth) acrylic homo or copolymer (P1) may be prepared in a batch or semi-continuous process: for the batch process, the monomer mixture is introduced at one time just before or after the introduction of the of a part of the initiator system for the semi-continuous process, the monomer mixture is added in several times or continuously in parallel with the addition of initiator (the initiator is also added in several times or continuously) during a defined addition period that may be in the range of 30 to 500 min.
    The process for preparing the composition according to the invention comprising the fibrous material, the (meth) acrylic polymer (PI) and the multi-stage polymer has two preferred embodiments.
    In both cases, the fibrous material is brought into contact with the (meth) acrylic polymer (PI) and the multi-stage polymer. The (meth) acrylic polymer (PI) and the multi-stage polymer may be separated or added together in a polymer composition (PCI). The polymer composition (PCI) can be obtained by two preferred methods.
    In a first preferred embodiment of the process, the (meth) acrylic polymer (PI) is polymerized in the presence of the multi-stage polymer. The (meth) acrylic polymer (PI) is prepared as an additional stage of the multi-stage polymer to obtain the polymer composition (PCI).
    In a second preferred embodiment of the process, the (meth) acrylic polymer (PI) is polymerized separately and mixed or incorporated with the multi-stage polymer to obtain the polymer composition (PCI).
    With respect to the method according to the first preferred embodiment for preparing the polymer composition (PCI) comprising the (meth) acrylic polymer (PI) and the multi-stage polymer, this comprises the steps of
    a) polymerization by emulsion polymerization of a monomer or mixture of monomers (Am) to obtain a layer in the stage (A) comprising the polymer (Al) having a glass transition temperature below 0 ° C.
    b) polymerization by emulsion polymerization of a monomer or mixture of monomers (Bm) to obtain the layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C (c) polymerization by emulsion polymerization of a monomer or mixture of monomers (Plm) to obtain a layer in this additional stage comprising the polymer
    (Meth) acrylic (PI) having a glass transition temperature of at least 30 ° C, characterized in that the (meth) acrylic polymer (PI) has a weight average molecular weight Mw of less than 100,000 g / mol.
    [0117] Preferably, step a) is carried out before step b).
    More preferably, step b) is conducted in the presence of the polymer (Al) obtained in step a).
    Advantageously, the method of manufacturing the polymer composition (PCI) comprising the (meth) acrylic polymer (PI) and the multi-stage polymer is a multi-step process and comprises the successive steps of
    a) polymerization by emulsion polymerization of a monomer or mixture of monomers (Am) to obtain a layer in the stage (A) comprising the polymer (Al) having a glass transition temperature below 0 ° C.
    b) polymerization by emulsion polymerization of a monomer or mixture of monomers (Bm) to obtain the layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C.
    c) polymerization by emulsion polymerization of a monomer or mixture of monomers (Plm) to obtain a layer in this additional stage comprising the (meth) acrylic polymer (PI) having a glass transition temperature of at least 30 ° C characterized in that the (meth) acrylic polymer (P1) has a weight average molecular weight Mw of less than 100,000 g / mol.
    The respective monomers or monomer mixtures (Am), (Bm) and (Plm) for forming the layers (A), (B) and an additional stage respectively comprising the polymers (Al), (B1) and (P1) ) respectively, are identical to those previously defined. The characteristics of the polymers (Al), (B1) and (P1), respectively, are identical to those defined previously.
    The polymer composition (PCI) is obtained in the form of an aqueous dispersion of the polymer particles. The solid content of the dispersion is between 10% by weight and 65% by weight.
    Optionally, the method of manufacturing the polymer composition comprising the (meth) acrylic polymer (PI) and the multi-stage polymer comprises the additional step d) of recovering this polymer composition.
    Recovery means a partial or total separation between the aqueous and solid phase, the latter comprising the polymer composition.
    More preferably, according to the invention, the recovery of the polymer composition is carried out by coagulation or by spray drying.
    The spray drying is the preferred method for recovery and / or drying for the manufacturing process for a polymer powder composition according to the present invention if the polymer (Al) having a glass transition temperature of less than 0. ° C comprises at least 50% by weight of polymer units derived from alkyl acrylate and stage (A) is the innermost layer of the polymer particle having the multilayer structure.
    Coagulation is the preferred method for recovery and / or drying for the manufacturing process for a polymer powder composition according to the present invention if the polymer (Al) having a glass transition temperature of less than 0 ° C. comprises at least 50% by weight of polymeric units derived from isoprene or butadiene and stage (A) is the innermost layer of the polymer particle having the multilayer structure.
    The process for producing the polymer composition according to the invention may optionally comprise the additional step e) of drying the polymer composition.
    Preferably, the drying step e) is carried out if the step d) of recovery of the polymer composition is carried out by coagulation.
    Preferably, after the drying step in e) the polymer composition comprises less than 3% by weight, more preferably less than 1.5% by weight, preferably less than 1% of moisture or water. .
    The moisture of a polymer composition can be measured with a thermobalance.
    The drying of the polymer can be carried out in an oven or a vacuum oven with heating of the composition for 48 hours at 50 ° C.
    With regard to the method according to the second preferred embodiment for preparing the polymer composition (PCI) comprising the (meth) acrylic polymer (PI) and the multi-stage polymer, it comprises the steps of a ) mixing the (meth) acrylic polymer (P1) and the multi-stage polymer b) optionally recovering the mixture obtained from the previous step in the form of a polymer powder where the (meth) acrylic polymer (P1) and the multi-stage polymer in step a) are in the form of a dispersion in aqueous phase.
    The amounts of the aqueous dispersion of the (meth) acrylic polymer (P1) and the aqueous dispersion of the multi-stage polymer are chosen such that the weight ratio of the multi-stage polymer on the basis of a solid portion only in the mixture obtained is at least 5% by weight, preferably at least 10% by weight, more preferably at least 20% by weight and advantageously at least 50% by weight.
    The amounts of the aqueous dispersion of the (meth) acrylic polymer (P1) and the aqueous dispersion of the multi-stage polymer are chosen such that the weight ratio of the multi-stage polymer on the basis of the solid part only in the mixture obtained not more than 99% by weight, preferably not more than 95% by weight and more preferably not more than 90% by weight.
    The amounts of the aqueous dispersion of the (meth) acrylic polymer (P1) and the aqueous dispersion of the multi-stage polymer are chosen such that the weight ratio of the multi-stage polymer based on the solid portion only in the mixture obtained is between 5% by weight and 99% by weight, preferably between 10% by weight and 95% by weight and more preferably between 20% by weight and 90% by weight.
    The polymer composition (PCI) is obtained in the form of an aqueous dispersion of the polymer particles, if the recovery step b) is not carried out. The solid content of the dispersion is between 10% by weight and 65% by weight.
    In one embodiment, the recovery step b) of the process for producing the polymer composition comprising the (meth) acrylic polymer (P1) and the multi-stage polymer is not optional and is preferably conducted by coagulation or spray drying.
    The method of making the polymer composition comprising the (meth) acrylic polymer (P1) and the multi-stage polymer may optionally include the additional step c) of drying the polymer composition.
    Dry means that the polymer composition according to the present invention comprises less than 3% by weight of moisture and preferably less than 1.5% by weight of moisture and more preferably less than 1.2% by weight of 'humidity.
    Moisture can be measured by a thermobalance which heats the polymer composition and measures the weight loss.
    The process for producing the polymer composition comprising the (meth) acrylic polymer (P1) and the multi-stage polymer preferably produces a polymer powder. The polymer powder of the invention is in the form of particles. A polymer particle powder comprises agglomerated primary polymer particles made by the multi-stage process and the (meth) acrylic polymer (P1).
    With regard to the polymer powder comprising the (meth) acrylic polymer (P1) and the multi-stage polymer according to the two embodiments of the preparation process, the latter has a median particle size by volume D50 between 1 pm and 500 pm. Preferably, the volume median particle size of the polymer powder is between 10 μm and 400 μm, more preferably between 15 μm and 350 μm and advantageously between 20 μm and 300 μm.
    The D10 of the volume particle size is at least 7 μm and preferably 10 μm.
    The D90 of the volume particle size is at most 950 μm and preferably 500 μm, more preferably at most 400 μm.
    The ratio by weight of the (meth) acrylic polymer (P1) with respect to the multi-stage polymer is at least 5% by weight, more preferably at least 7% by weight and still more preferably at least 10% by weight. in weight.
    According to the invention, the ratio r of the (meth) acrylic polymer (P1) relative to the multi-stage polymer is at most 95% by weight.
    Preferably, the ratio by weight of the (meth) acrylic polymer (P1) relative to the multi-stage polymer is between 5% by weight and 95% by weight and preferably between 10% by weight and 90% by weight. in weight.
    As regards the fibrous material, there may be mentioned fabrics, felts or nonwovens which may be in the form of strips, loops, braids, flakes or parts. The fibrous material may have different one-dimensional, two-dimensional, or three-dimensional shapes and dimensions. A fibrous material comprises a set of one or more fibers. When the fibers are continuous, their assembly forms tissues.
    The unidimensional shape consists of long linear fibers. The fibers may be discontinuous or continuous. The fibers may be arranged randomly or in the form of continuous parallel filaments. A fiber is defined by its form factor, which is the ratio of the length and diameter of the fiber. The fibers used in the present invention are long fibers or continuous fibers. The fibers have a form factor of at least 1000, preferably at least 1500, more preferably at least 2000, preferably at least 3000 and most preferably at least 5000.
    The two-dimensional shapes are fibrous mats or nonwoven reinforcements or a woven roving or bundles of fibers, which may also be braided.
    The three-dimensional shapes are, for example, stacked or folded fibrous mats or non-woven reinforcements or bundles or bundles of fibers or mixtures thereof, an assembly of the two-dimensional form in the third dimension.
    The origins of the fibrous material may be natural or synthetic. As a natural material, mention may be made of vegetable fibers, wood fibers, animal fibers or mineral fibers.
    The natural fibers are, for example, sisal fibers, jute, hemp, linen, cotton, coconut, and banana fibers. Animal fibers are, for example, wool or hair.
    As synthetic material, mention may be made of polymer fibers selected from thermosetting polymer fibers, thermoplastic polymers or mixtures thereof.
    The polymer fibers may consist of polyamide (aliphatic or aromatic), polyester, polyvinyl alcohol, polyolefins, polyurethanes, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins and vinyl esters.
    The mineral fibers may also be chosen from glass fibers, in particular of the E, R or S2 type, carbon fibers, boron fibers or silica fibers.
    The fibrous material of the present invention is selected from vegetable fibers, wood fibers, animal fibers, mineral fibers, synthetic fibers, glass fibers, carbon fibers or mixtures thereof. -this.
    [0158] Preferably, the fibrous material is two- or three-dimensional.
    As regards the method of manufacturing the composition according to the invention, it comprises the steps of a) contacting a fibrous material and a multi-stage polymer and a polymer ( meth) acrylic (PI), wherein the amount of the multi-stage polymer is between 3 wt.% and 50 wt.% of the composition and the (meth) acrylic polymer (Pl) has a weight average molecular weight Mw less than 100,000 g / mol.
    Step a) of said process may be conducted by immersion, infusion or impregnation of the fibrous material with an aqueous dispersion comprising the multi-stage polymer and the (meth) acrylic polymer (P1) or by spraying the fibrous material with a powder comprising the multi-stage polymer and the (meth) acrylic polymer (PI). Preferably, the multi-stage polymer and the (meth) acrylic polymer (PI) are in the form of the polymer composition (PCI) as previously described.
    If the polymer composition (PCI) is in the form of an aqueous dispersion, the process comprises the additional step b) drying the product of step a). In addition, a step c) heating the dried product of b) can be added.
    Step b) is conducted by evaporation of the aqueous phase or by heating slightly. Preferably, step b) is conducted by heating to at least 45 ° C.
    If the polymer composition (PCI) is in the form of a dry powder, the process comprises the additional step c) heating the composition.
    Step c) is conducted in a mold at a temperature of between 100 ° C and 250 ° C. Preferably between 125 ° C and 225 ° C. The mold may be under pressure.
    The method of manufacturing the composition, in particular in the form of a preform, may further comprise the step of transforming the preform. This can be done during step c), whether the heating is conducted in a mold having a certain shape, or that the preform is converted into another form again under heating after step c).
    The composition or preform of the invention may be used to manufacture a polymeric composite material or mechanical or structured parts or articles comprising the polymeric composite material.
    The composition or preform of the invention is used in a process such as infusion, vacuum bag molding, pressure bag molding, autoclaving, resin transfer molding ( RTM), injection reaction molding (RIM), reinforced injection reaction molding (R-RIM) and variants thereof, press molding or compression molding.
    Preferably, the process is a resin transfer molding.
    During this process, a matrix or continuous phase is added to the composition or preform and a modified impact-modified polymeric composite material or mechanical or structured parts or articles comprising the polymeric composite material is obtained.
    The matrix or continuous phase of the polymer composite material is a thermosetting polymer or a thermoplastic polymer.
    As an example, the method of manufacturing the modified impact-resistant polymer composite material is conducted by a molding method. The methods generally perform the steps of forming the preform to match the contours of a mold, placing the preform formed in a mold, injecting an uncured or fused molding resin or a syrup to a mold. polymerizing in the mold, and then curing or cooling the molding resin or polymerization as required to form a solid molded polymer composite.
    [0172] [Methods of Evaluation] [0173] Particle Size Analysis
    The particle size of the primary particles after the multi-stage polymerization is measured with a MALVERN Zetasizer Nano S90.
    The particle size of the polymer powder is measured with a Malvern Mastersizer 3000 from MALVERN. For the estimation of the volume median particle size D50 a Malvern Mastersizer 3000 with a 300 mm lens, measuring a range of 0.5 to 880 μm is used.
    [0174] Glass transition temperature
    The glass transitions (Tg) of multistage polymers are measured with equipment capable of thermomechanical analysis. A RHEOMETRICS DYNAMIC ANALYZER RDAII proposed by Rheometrics Company was used. Thermomechanical analysis accurately measures the viscoelastic changes of a sample as a function of temperature, stress or strain applied. The apparatus continuously records the deformation of the sample, maintaining the fixed stress, during a controlled temperature variation program. The results are obtained by plotting, as a function of temperature, the modulus of elasticity (G '), the loss modulus and the delta tangent. The Tg is the upper temperature value observed in the delta tangent curve, when the delta tangent derivative is zero.
    [0175] Molecular Weight
    The weight average molecular weight (Mw) of the polymers is measured by exclusion chromatography (SEC).
    权利要求:
    Claims (16)
    [1" id="c-fr-0001]
    claims
    A composition comprising a) a fibrous material and b) a multi-stage polymer and c) a (meth) acrylic polymer (PI) wherein the amount of multi-stage polymer is from 3 wt.% To 50 wt.% of the composition and the (meth) acrylic polymer (PI) has a weight average molecular weight Mw of less than 100,000 g / mol.
    [2" id="c-fr-0002]
    2. Composition according to claim 1 characterized in that the (meth) acrylic polymer (PI) has a weight average molecular weight Mw between 5000 g / mol and 70 000 g / mol.
    [3" id="c-fr-0003]
    3. Composition according to claim 1 or 2 characterized in that the amount of (meth) acrylic polymer (PI) is between 0.15% by weight and 47.5% by weight.
    [4" id="c-fr-0004]
    4. Composition according to any one of claims 1 to 3 characterized in that the composition is in the form of a preform.
    [5" id="c-fr-0005]
    5. Composition according to any one of claims 1 to 4 characterized in that the multi-stage polymer is preferably in the form of spherical polymer particles having a mean particle size by weight of between 20 nm and 800 nm.
    [6" id="c-fr-0006]
    6. Composition according to any one of claims 1 to 5 characterized in that the multi-stage polymer comprises a) a stage (A) comprising a polymer (Al) having a glass transition temperature below 0 ° C b) a stage (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C.
    [7" id="c-fr-0007]
    7. Composition according to claim 6 characterized in that the polymers (Al) and (Bl) are acrylic or methacrylic polymers.
    [8" id="c-fr-0008]
    8. Composition according to claim 6 characterized in that the polymer (Al) is a polymer based on silicone rubber.
    [9" id="c-fr-0009]
    9. Composition according to claim 6 characterized in that the polymer (Al) comprises at least 50% by weight of polymer units from isoprene or butadiene.
    [10" id="c-fr-0010]
    10. Composition according to any one of claims 5 to 8 characterized in that the stage (A) is the first stage and the stage (B) comprising the polymer (B1) is grafted on the stage (A). comprising the polymer (Al).
    [11" id="c-fr-0011]
    11. The method of manufacturing the composition according to any of claims 1 to 10, said method comprising the step of a) contacting a fibrous material and a multi-stage polymer and a polymer ( meth) acrylic (PD ·
    [12" id="c-fr-0012]
    12. The method of claim 11, characterized in that step a) is conducted by immersion, infusion or impregnation of the fibrous material with an aqueous dispersion comprising the multi-stage polymer and the (meth) acrylic polymer (PI).
    [13" id="c-fr-0013]
    13. The method of claim 12, characterized in that the method comprises the additional step b) drying the product of step a).
    [14" id="c-fr-0014]
    The method of claim 11, characterized in that step a) is conducted by spraying the fibrous material with a powder comprising the multi-stage polymer and the (meth) acrylic polymer (PI).
    [15" id="c-fr-0015]
    15. Method according to any one of claims 11 to 14, characterized in that the method comprises the additional step c) heating the composition.
    [16" id="c-fr-0016]
    16. Use of the composition according to any one of claims 1 to 10 or obtained by a process according to any one of claims 11 to 15 for manufacturing a polymer composite material or mechanical or structured parts or articles comprising the polymer composite material. .
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    同族专利:
    公开号 | 公开日
    WO2017220791A1|2017-12-28|
    JP2019518857A|2019-07-04|
    SG11201811018SA|2019-01-30|
    EP3475346A1|2019-05-01|
    KR20190022664A|2019-03-06|
    FR3053044B1|2019-11-01|
    US20190248968A1|2019-08-15|
    US10815344B2|2020-10-27|
    BR112018075917A2|2019-03-26|
    CN109563291A|2019-04-02|
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    法律状态:
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    2021-05-13| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1655832A|FR3053044B1|2016-06-23|2016-06-23|COMPOSITION COMPRISING A FIBROUS MATERIAL, A STAGE POLYMER AND AACRYLIC POLYMER, PROCESS FOR PREPARING THE SAME, USE THEREOF, AND COMPOSITE COMPRISING THE SAME|
    FR1655832|2016-06-23|FR1655832A| FR3053044B1|2016-06-23|2016-06-23|COMPOSITION COMPRISING A FIBROUS MATERIAL, A STAGE POLYMER AND AACRYLIC POLYMER, PROCESS FOR PREPARING THE SAME, USE THEREOF, AND COMPOSITE COMPRISING THE SAME|
    US16/311,712| US10815344B2|2016-06-23|2017-06-23|Composition comprising a fibrous material, a multistage polymer and aacrylic polymer, its method of preparation and its use|
    CN201780051276.4A| CN109563291B|2016-06-23|2017-06-23|Composition comprising a fibrous material, a multistage polymer and aacrylic polymer, method for the preparation thereof and use thereof|
    EP17731184.2A| EP3475346A1|2016-06-23|2017-06-23|Composition comprising a fibrous material, a multistage polymer and aacrylic polymer, its method of preparation and its use|
    JP2018567255A| JP2019518857A|2016-06-23|2017-06-23|Composition comprising fibrous material, multistage polymer andacrylic polymer, preparation method thereof, use thereof|
    KR1020197001828A| KR20190022664A|2016-06-23|2017-06-23|Compositions comprising fiber materials, multistage polymers andacrylic polymers, processes for their preparation, and uses thereof|
    SG11201811018SA| SG11201811018SA|2016-06-23|2017-06-23|Composition comprising a fibrous material, a multistage polymer and aacrylic polymer, its method of preparation and its use|
    BR112018075917-1A| BR112018075917A2|2016-06-23|2017-06-23|composition comprising a fibrous material, a multistage polymer and aacrylic polymer, its method of preparation and its use|
    PCT/EP2017/065566| WO2017220791A1|2016-06-23|2017-06-23|Composition comprising a fibrous material, a multistage polymer and aacrylic polymer, its method of preparation and its use|
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