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    • 专利摘要:
    A liquid (meth) acrylic composition comprising a multiphase polymer and a (meth) acrylic monomer, its method of preparation and its use. The present invention relates to a liquid (meth) acrylic composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multiphase polymer. In particular, the present invention relates to a liquid composition, comprising a (meth) acrylic monomer, a meth (acrylic) polymer and a multiphase polymer, which can be used as a syrup and particularly as a syrup for impregnation. More particularly, the present invention also relates to a process for preparing a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multiphase polymer.
    公开号:FR3046606A1
    申请号:FR1650195
    申请日:2016-01-11
    公开日:2017-07-14
    发明作者:Raber Inoubli；Philippe Hajji；Rosangela Pirri；Pierre Gerard
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    LIQUID (METH) ACRYLIC COMPOSITION COMPRISING A MULTIPHASE POLYMER AND A (METH) ACRYLIC MONOMER, PROCESS FOR PREPARING THE SAME AND USE THEREOF
    FIELD OF THE INVENTION [001] The present invention relates to a liquid (meth) acrylic composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multiphase polymer.
    In particular, the present invention relates to a liquid composition, comprising a (meth) acrylic monomer, a meth (acrylic) polymer and a multiphase polymer, which can be used as a syrup and particularly as a syrup for 1 '. impregnation.
    [003] More particularly, the present invention also relates to a process for preparing a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multiphase polymer.
    [Technical problem] [004] Impact additives are used to a large extent to improve the impact resistance for polymer compositions in order to compensate for their inherent brittleness or friability which occurs at ambient temperature, but also and particularly at temperatures below zero, notch sensitivity and crack propagation. Thus, an impact modified polymer is a polymeric material whose impact strength and toughness have been increased by the incorporation of phase microdomains of an elastomer material.
    This is usually achieved by introducing into the polymer matrix microscopic particles of elastomer that can absorb the energy of a shock or dissipate it. One possibility is to introduce the elastomeric particles in the form of core-shell particles. These core-bark particles, which generally have an elastomer core and a polymeric bark, have the advantage of an adequate particle size for the elastomer core for efficient curing and the grafted bark for adhesion. and compatibility with the thermoplastic matrix.
    [006] The performance of the impact resistance is a function of the particle size, in particular of the elastomer part of the particle and its quantity. There is an optimum average particle size for obtaining the highest impact strength for a given amount of added impact additive particles.
    [007] These primary particles of impact additives are generally added in the form of powder particles to the polymer material. These powder particles are agglomerated primary particles of impact additive. During the homogenization of the thermoplastic material with the powder particles, the primary particles of impact additive are recovered and are dispersed more or less homogeneously in the thermoplastic material.
    While the particle size of the impact additive particles is in the range of nanometers, the range of agglomerated powder particles is in the range of micrometers. The latter is much more convenient for handling.
    For many polymers, thermoplastic or thermosetting polymers, it is very difficult or almost impossible to properly disperse these multi-layer polymers in the form of core-shell particles into agglomerated dry powders. An ideal homogeneous dispersion of the core-bark particle. has no agglomerates after dispersion in the thermoplastic material also called matrix.
    [010] This is even more difficult if the multilayer polymers are to be homogeneously distributed in a polymer matrix which also comprises a fibrous substrate such as, for example, fiber-reinforced polymer composites.
    [011] The fibrous substrate is usually impregnated with a liquid composition, either a molten polymer or a liquid composition comprising monomers, oligomers and / or polymers.
    The object of the present invention is to obtain a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multiphase polymer, with a homogeneous dispersion of the multiphase polymer.
    [013] An object of the present invention is also to obtain a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multiphase polymer, with a homogeneous dispersion of the multiphase polymer, which can to be used in a polymerization process.
    Another object of the present invention is to avoid or significantly reduce the agglomeration of the multiphase polymer.
    [015] Another additional objective is to obtain a process for preparing a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multiphase polymer, with a homogeneous dispersion of the multiphase polymer. .
    [016] Yet another objective is the use of the composition comprising a monomer, a (meth) acrylic polymer for the impact modification of polymers.
    [017] Yet another object is to obtain a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multiphase polymer, with a homogeneous dispersion of the multiphase polymer as an impregnating liquid for a fibrous substrate or the use of the liquid composition in an impregnation process for impregnating a fibrous substrate.
    [018] Yet another object of the present invention is to thoroughly, correctly and homogeneously wet a fibrous substrate during impregnation with a liquid composition comprising a multiphase polymer.
    BACKGROUND OF THE INVENTION [0008] WO01414 / 013028 discloses an impregnation process for a fibrous substrate, a liquid (meth) acrylic syrup for the impregnation process, its polymerization process and a structured article that is obtained. The syrup comprises a (meth) acrylic monomer, a (meth) acrylic polymer and optionally an impact additive in the form of fine particles.
    [020] No prior art document describes a composition as claimed or a process for obtaining it or its use.
    [BRIEF DESCRIPTION OF THE INVENTION] [021] Surprisingly, it has been found that a liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a monomer (meth) ) acrylic (M1) in which the weight ratio of the multiphase polymer to the monomer (M1) in the liquid composition is between 1/99 and 25/75, is less viscous than a composition not comprising the polymer (meth) acrylic (Pl).
    [022] Surprisingly, it has also been found that a liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a (meth) acrylic monomer (M1) in which the weight ratio of the multiphase polymer to the monomer (M1) in the liquid composition is between 1/99 and 25/75, has a better dispersion of the multiphase polymer than a composition not comprising the (meth) acrylic polymer (Pl).
    [023] Surprisingly, it has also been found that a liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a (meth) acrylic monomer (M1) in which the weight ratio of the multiphase polymer to the monomer (M1) in the liquid composition is between 1/99 and 25/75, can be used to prepare a better dispersion of the multiphase polymer in the monomer (M1) than composition not comprising the (meth) acrylic polymer (P1).
    [024] Surprisingly, it has also been found that a method for manufacturing a liquid composition comprising the steps of a) preparing a composition comprising the (meth) acrylic polymer (P1) and a multiphase polymer b mixture of the composition of the preceding step with a (meth) acrylic monomer (MI) in which the weight ratio of the multiphase polymer to the monomer (M1) in the liquid composition is between 1/99 and 25/75, provides a liquid composition which is less viscous than a composition not comprising the (meth) acrylic polymer (P1).
    [025] Surprisingly, it has also been found that a method for manufacturing a liquid composition comprising the steps of a) preparing a composition comprising the (meth) acrylic polymer (P1) and a multiphase polymer b ) mixing the composition of the preceding step with a (meth) acrylic monomer (M1) the weight ratio of the multiphase polymer to the monomer (M1) in the liquid composition being between 1/99 and 25/75, provides a liquid impregnation in the form of a (meth) acrylic syrup.
    [026] Surprisingly, it has also been found that a liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a (meth) acrylic monomer (M1) in which the weight ratio of the multiphase polymer to the monomer in the liquid composition is from 1/99 to 25/75, can be used to impregnate a fibrous substrate.
    [027] Surprisingly, it has also been found that a liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a (meth) acrylic monomer (M1) in which the ratio of the weight ratio of the multiphase polymer to the monomer in the liquid composition is from 1/99 to 25/75, can be used in an impregnation process for impregnating a fibrous substrate, said fibrous substrate consisting of long fibers .
    [028] According to a first aspect, the present invention relates to a liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a monomer (meth) ) acrylic (M1) in which the weight ratio of the multiphase polymer to the monomer in the liquid composition is between 1/99 and 25/75.
    [029] According to a second aspect, the present invention relates to a method for manufacturing a liquid composition comprising the steps of a) preparing a composition comprising the (meth) acrylic polymer (P1) and a multiphase polymer b) mixing the composition of the preceding step with a (meth) acrylic monomer (M1) in which the weight ratio of the multiphase polymer to the monomer in the liquid composition is between 1/99 and 25/75.
    [030] According to a third aspect, the present invention relates to the use of a liquid composition comprising a) a (meth) acrylic polymer (PI), b) a multi-phase polymer and c) a (meth) acrylic monomer ( M1) in which the weight ratio of the polymer to the monomer in the liquid composition is between 1/99 and 25/75, for impregnating a fibrous substrate.
    [031] In a fourth aspect, the present invention relates to the use of a liquid composition comprising a) a (meth) acrylic polymer (PI), b) a multiphase polymer and c) a (meth) acrylic monomer ( M1) in which the weight ratio of the multiphase polymer to the monomer in the liquid composition is from 1/99 to 25/75 in an impregnating process for impregnating a fibrous substrate, said fibrous substrate being long fibers.
    The term "polymeric powder" as used refers to a grain of powder comprising polymer in the range of at least 1 micron (μm) obtained by agglomeration of primary particles comprising polymer in the nanometer range.
    [033] The term "primary particle" as used refers to a spherical particle comprising polymer in the nanometer range. Preferably, the primary particle has an average particle size by weight between 20 nm and 800 nm.
    [034] The term "particle size" as used, refers to the average diameter of the volume of a particle considered spherical.
    [035] The term "copolymer" as used indicates that the polymer consists of at least two different monomers.
    [036] "multi-phase polymer" as used means a polymer formed sequentially by a multi-layer polymerization process. A preferred method is a multiple layer emulsion polymerization process in which the first polymer is a first phase polymer and the second polymer is a second phase polymer, i.e. the second polymer is formed by polymerization. in emulsion in the presence of the first emulsion polymer.
    [037] The term "(meth) acrylic" as used refers to all kinds of acrylic and methacrylic monomers.
    The term "(meth) acrylic polymer" as used indicates that the (meth) acrylic polymer consists essentially of polymers comprising (meth) acrylic monomers which represent up to 50% by weight or more (meth) acrylic polymer.
    The term "epoxy resin" as used refers to any organic compound having at least two oxyrane functional groups that can be ring-opened polymerized.
    [040] The term "(meth) acrylic resin" as used refers to adhesives based on acrylic and methacrylic monomers.
    [041] The term "masterbatch" as used refers to a composition that includes an additive at a high concentration in a carrier material. The additive is dispersed in the carrier material.
    [042] The term "impact additive" as used refers to a material that when incorporated into a polymeric material increases the impact resistance and strength of that polymeric material by phase microdomains of a rubbery material or material. an elastomeric polymer.
    [043] The term "elastomer" as used refers to the thermodynamic state of the polymer above its glass transition.
    [044] The term "polymeric elastomer" as used refers to a polymer that has a glass transition temperature (Tg) of less than 0 ° C.
    [045] The dynamic viscosity of the liquid composition according to the invention is in a range from 10 mPa.s to 1,000,000 mPa.s, preferably from 10 mPa.s to 500,000 mPa.s, and advantageously from 50 mPa. * s at 300,000 mPa.s. The viscosity of the liquid composition (sometimes also called syrup) can be easily measured with a rheometer with a shear rate of between 0.1 s-1 and 100 s-1. The dynamic viscosity is measured at 25 ° C. If there is shear fluidization, the viscosity is measured at a shear rate of 1 s-1.
    [04 6] With regard to the (meth) acrylic polymer (PI), it has a mass 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.
    [047] The (meth) acrylic polymer (P1) has a mass average molecular weight Mw greater than 2000 g / mol, preferably greater than 3000 g / mol, more preferably greater than 4000 g / mol, still more preferably greater than 4000 g / mol 5000 g / mol, preferably greater than 6000 g / mol, more preferably greater than 6 500 g / mol and even more preferably greater than 7000 g / mol and most preferably greater than 10 000 g / mol.
    [048] The weight average molecular weight Mw of the (meth) acrylic polymer (P1) is between 2000 g / mol and 100,000 g / mol, preferably between 3000 g / mol and 90,000 g / mol and more preferably between 4,000 g / mol and 80,000 g / mol, more preferably between 5,000 g / mol and 70,000 g / mol, more preferably between 6,000 g / mol and 50,000 g and most preferably between 10,000 g / mol and 40,000 g /mole.
    [049] Preferably, the (meth) acrylic polymer (P1) is a copolymer comprising (meth) acrylic monomers. More preferably, the (meth) acrylic polymer (P1) is a (meth) acrylic polymer. Even more preferably, the (meth) acrylic polymer (P1) comprises at least 50% by weight of monomers selected from (C1-C12) alkyl (meth) acrylates. Advantageously, the (meth) acrylic polymer (P1) comprises at least 50% by weight of monomers selected from C1 to C4 alkyl methacrylate and C1 to C8 alkyl acrylate monomers and mixtures thereof. this.
    [050] 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 between 40 ° C and 150 ° C, preferably between 45 ° C and 150 ° C and more preferably between 50 ° C and 150 ° C.
    [051] Preferably, the (meth) acrylic polymer (P1) is not crosslinked.
    [052] Preferably, the (meth) acrylic polymer (P1) is not grafted onto any other polymer (s).
    [053] 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 methacrylate of methyl, more preferably 80 wt.% to 99.8 wt.% methyl methacrylate and 0.2 wt.% to 20 wt.% of a C1 to C8 alkyl acrylate monomer. The C1 to C8 alkyl acrylate monomer is advantageously selected from methyl acrylate, ethyl acrylate or butyl acrylate.
    [054] 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 (P1) 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.
    [055] 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) [056] wherein for both formulas (1) and (2) R1 is selected from H or CH3; and in formula (1) Y is O, R5 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.
    [057] Preferably, the functional monomer (1) or (2) is chosen from the group consisting of: glycidyl (meth) acrylate, acrylic or methacrylic acid, amides derived from these acids such as, for example, dimethylacrylamide, acrylate or 2-methoxyethyl methacrylate, 2-aminoethyl acrylates or methacrylates which are optionally quaternized, acrylate or methacrylate monomers comprising a phosphonate or phosphate group, alkyl imidazolidinone (meth) acrylates, polyethylene glycol (meth) acrylates. Preferably, the polyethylene glycol group of polyethylene glycol (meth) acrylates has a molecular weight ranging from 400 g / mol to 10,000 g / mol.
    [058] The multiphase polymer according to the invention has at least two layers which are different in their polymer composition.
    [059] The multiphase polymer is preferably in the form of polymer particles considered as spherical particles. These particles are also called core-shell particles. The first phase forms the core, the second or all subsequent layers form the respective barks.
    As regards the polymer particle according to the invention, which is the primary particle, it has an average particle size by weight of between 15 nm and 900 nm. . Preferably, the average particle size by weight of the polymer is between 20 nm and 800 nm, more preferably between, more preferably between 25 nm and 600 nm, still more preferably between 30 nm at 550 nm, still more preferably between 35 nm. and 500 nm, advantageously between 40 nm and 400 nm, even more advantageously between 75 nm and 350 nm and advantageously between 80 nm and 300 nm. The primary polymer particles can be agglomerated, yielding a polymer powder comprising either the multiphase polymer or the (meth) acrylic polymer (PI) and the multiphase polymer.
    [061] The polymer particle is obtained by a multi-step process such as a process comprising two, three or more than three phases.
    [062] The polymer particle has a multilayered 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 (B1). ) having a glass transition temperature greater than 30 ° C.
    [063] 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 multilayered structure.
    [064] 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 multilayered structure, before the polymer to multiple phases are brought into contact with the monomer (M1).
    [065] Preferably, the phase (A) is the first phase and the phase (B) comprising the polymer (B1) is grafted onto the phase (A) comprising the polymer (Al) or another intermediate layer. First phase means that the phase (A) comprising the polymer (Al) is carried out before the phase (B) comprising the polymer (B1).
    [066] Polymer (A1) having a glass transition temperature of less than 0 ° C in layer (A) is never produced during the last phase of the multiphase process. This means that the polymer (Al) is never in the outer layer of the multi-layered particle. The polymer (Al) having a glass transition temperature below 0 ° C in the layer (A) is either in the core of the polymer particle or in one of the inner layers.
    [067] Preferably, the polymer (A1) having a glass transition temperature below 0 ° C in the layer (A) is produced during the first phase of the multiphase process forming the core for the particle of polymers having the structure multilayer and / or before the polymer (B1) having a glass transition temperature above 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.
    [068] In a first preferred embodiment, the polymer (B1) having a glass transition temperature above 60 ° C is produced during the last phase of the multiphase process forming the outer layer of the polymer particle having the structure. multi-layered.
    [069] 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 multilayered structure, which is produced during one phase after the polymer formation phase (Al) of the multiphase process.
    [070] There could be an additional layer or layers obtained by an intermediate phase or intermediate phases.
    [071] The glass transition temperature Tg of the respective polymers can be estimated, for example, by dynamic processes and thermomechanical analysis.
    [072] To obtain a sample of the respective polymers (A1) and (B1), they can be prepared alone, and not by a multiphase process, to more easily estimate and measure the individual glass transition temperature Tg of the polymers of the respective polymers. respective phases.
    [073] 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.
    [074] 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 of less than 0 ° C.
    [075] The comonomer or comonomers in the polymer (Al) are preferably selected from (meth) acrylic monomers and / or vinyl monomers.
    [076] The (meth) acrylic comonomer in the polymer (A1) comprises 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.
    [077] More preferably, the acrylic or methacrylic comonomers of the polymer (Al) are chosen from the group consisting of: methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate , ethyl methacrylate, butyl methacrylate and mixtures thereof, provided that the polymer (A1) has a glass transition temperature of less than 0 ° C.
    [078] 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.
    [079] In a specific embodiment, the polymer (Al) is a homopolymer of butyl acrylate.
    [080] 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.
    [081] 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.
    [082] As regards the polymer (Al), in a second embodiment, the polymer (Al) is a polymer based on silicone elastomer. The silicone elastomer, 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.
    [083] With regard to the polymer (Al), in a third embodiment, the polymer (Al) having a glass transition temperature of less than 0 ° C. comprises at least 50% by weight of polymer units originating from the isoprene or butadiene and the (A) phase is the innermost layer of the polymer particle having the multilayered structure. In other words, the phase (A) comprising the polymer (Al) is the core of the polymer particle.
    [084] By way of example, the polymer (Al) of the core of the second embodiment, mention may be made of homopolymers of isoprene or homopolymers of butadiene, of isoprene-butadiene copolymers, of copolymers of isoprene 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.
    [085] More preferably, the glass transition temperature Tg of the polymer (Al) 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, still 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.
    [086] Regarding 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.
    [087] 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.
    [088] The polymer (B1) can be crosslinked.
    [089] Ideally, the acrylic or methacrylic monomers of the polymer (B1) are selected from the group consisting of: methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof, provided that the polymer (B1) has a glass transition temperature of at least 30 ° C.
    [090] Advantageously, the polymer (B1) comprises at least 50% by weight, more preferably at least 60% by weight, and still more advantageously at least 70% by weight of monomer units derived from methyl methacrylate.
    [091] 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 and 130 ° C.
    [092] In another embodiment, the multiphase polymer as previously described has an additional phase, which is the (meth) acrylic polymer (PI). The primary polymer particle according to this embodiment of the invention has a multilayer structure comprising at least one phase (A) comprising a polymer (Al) having a glass transition temperature below 0 ° C, at least one phase (B). ) comprising a polymer (B1) having a glass transition temperature above 30 ° C and at least one phase (P) comprising the (meth) acrylic polymer (P1) having a glass transition temperature between 30 ° C and 150 ° C .
    [093] Preferably, the (meth) acrylic polymer (P1) is grafted onto any of the polymers (A1) or (B1).
    [094] As regards the process for the manufacture of the multiphase polymer according to the invention, it comprises the steps of:
    a) polymerization by emulsion polymerization of a monomer or a 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 a 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 the monomer mixture (Am) and the monomer or the mixture of monomers (Bm) are chosen from the monomers according to the composition of the polymer (Al) and the polymer (B1) given previously.
    [095] Preferably, step a) is carried out before step b). More preferably, step b) is carried out in the presence of the polymer (Al) obtained in step a), if there are only two steps.
    [096] Advantageously, the method of manufacturing the multiphase polymer composition according to the invention is a multi-step process comprising the successive steps of
    a) polymerization by emulsion polymerization of a monomer or a 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 monomer mixture (Bm) to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C.
    [097] The respective monomers or mixtures of monomers (Am) and (Bm) to form the layers (A) and (B) respectively comprising the polymers (Al) and (Bl) respectively and the characteristics of the respective polymers (Al) and (B1) are the same as previously defined.
    [098] The process for making the multiphase polymer may comprise additional steps for additional steps between steps a) and b).
    [099] The process for making the multiphase polymer may also include additional steps for additional steps before steps a) and b). A seed could 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 multiphase polymer is obtained in the form of an aqueous dispersion of polymer particles. The solids content of the dispersion is between 10% by weight and 65% by weight.
    As regards the process for the manufacture of the (meth) acrylic polymer (PI) according to the invention, it comprises the polymerization steps of the respective (meth) acrylic monomers (Plm). The respective (meth) acrylic monomers (Plm) are the same as previously defined for the (meth) acrylic polymer (PI) and the two preferred embodiments of the (meth) acrylic polymer (PI).
    The (meth) acrylic homopolymer or copolymer (PI) could be produced according to a batch or semi-continuous process: for procedébatch, the monomer mixture is introduced in a single addition just before or after the introduction of the system. initiator or part of it for the semi-continuous process, the monomer mixture is added in several times or continuously, parallel to the addition of armor (the armorcer is also added in several times or in continuous) during a defined period of addition which could be in the range of 30 to 500 minutes.
    The process for preparing the polymer composition comprising the (meth) acrylic polymer (PI) and the multiphase polymer comprises two preferred embodiments.
    In a first preferred embodiment of the process, the (meth) acrylic polymer (PI) is polymerized in the presence of the multiphase polymer. The (meth) acrylic polymer (PI) is produced as an additional phase of the multiphase polymer.
    In a second preferred embodiment of the process, the (meth) acrylic polymer (PI) is polymerized separately and mixed or combined with the multiphase polymer.
    With regard to the method according to the first preferred embodiment for the preparation of the polymer composition comprising the (meth) acrylic polymer (PI) and the multiphase polymer, it comprises the steps of
    a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in the phase (A) comprising the polymer (Al) having a glass transition temperature below 0 ° C.
    b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in the phase (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C
    c) polymerization by emulsion polymerization of a monomer or monomer mixture (Plm) to obtain a layer at this additional phase 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 mass average molecular weight Mw of less than 100,000 g / mole.
    [0107] Preferably, step a) is carried out before step b).
    More preferably, step b) is carried out in the presence of the polymer (Al) obtained in step a).
    Advantageously, the process for producing the polymer composition comprising the (meth) acrylic polymer (PI) and the multiphase polymer is a multi-step process and comprises the consecutive steps of
    a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in the phase (A) comprising the polymer (Al) having a glass transition temperature below 0 ° C.
    b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in the phase (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C
    c) polymerization by emulsion polymerization of a monomer or monomer mixture (Plm) to obtain a layer at this additional phase comprising the (meth) acrylic polymer (PI) having a glass transition temperature of at least 30 ° C characterized in that the (meth) acrylic polymer (PI) has a mass 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 the additional phase respectively comprising the polymers (Al), (B1) and ( PI) respectively, are the same as those defined above. The characteristics of the polymers (Al), (B1) and (P1), respectively, are the same as those defined previously.
    Preferably, the method of manufacturing the polymer composition comprising the (meth) acrylic polymer (P1) and the multiphase polymer comprises the additional step d) of recovering this polymer composition.
    By recovery means a partial or complete separation between the aqueous phase and the solid phase, the latter comprising the polymer composition.
    According to the invention, the recovery of the polymer composition is more preferably carried out by coagulation or by spray drying.
    The spray drying is the preferred method for recovery and / or drying for the method of manufacturing 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 the alkyl acrylate and the phase (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 below 10 ° C comprises at least 50% by weight of polymeric units from isoprene or butadiene and phase (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 e), the polymer composition comprises less than 3% by weight, more preferably less than 1.5% by weight, advantageously 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 embodiment for preparing the polymer composition comprising the (meth) acrylic polymer (PI) and the multiphase polymer, it comprises the steps of a) mixing the polymer (meth) ) acrylic (PI) and multiphase polymer b) recovering the mixture obtained from the first step in the form of a polymer powder the (meth) acrylic polymer (PI) and the multiphase polymer of step a) being in the form of a dispersion in aqueous phase.
    The amounts of the aqueous dispersion of the (meth) acrylic polymer (PI) and the aqueous dispersion of the multiphase polymer are chosen so that the weight ratio of the multiphase polymer based on the solid fraction 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 preferably at least 50% by weight.
    The amounts of the aqueous dispersion of the (meth) acrylic polymer (P1) and the aqueous dispersion of the multiphase polymer are chosen so that the weight ratio of the multiphase polymer based on the solid fraction only in the mixture obtained is 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 multiphase polymer are chosen so that the weight ratio of the multiphase polymer based on the solid fraction 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 recovery step b) of the process for producing the polymer composition comprising the (meth) acrylic polymer (P1) and the multiphase polymer is preferably carried out by coagulation or by spraying.
    The method of making the polymer composition comprising the (meth) acrylic polymer (P1) and the multiphase polymer may optionally include the additional step c) for drying the polymer composition.
    Dry means that the polymer composition according to the present invention contains 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 (PI) and the multiphase polymer preferably gives a polymer powder. The polymer powder of the invention is in the form of particles. A polymer powder particle comprises primary particles of agglomerated polymers produced by the multi-step process and the (meth) acrylic polymer (PI).
    With regard to the polymer powder comprising the (meth) acrylic polymer (PI) and the multiphase polymer according to the two embodiments of the preparation process, it has a median particle size by volume D50 of between 1 pm and 500 pm. Preferably, the median volume 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 distribution is at least 7 μm and preferably 10 μm.
    The D90 of the particle size distribution by volume is at most 950 μm and preferably 500 μm, more preferably at most 400 μm.
    The weight ratio r of the (meth) acrylic polymer (PI) relative to the multiphase polymer is at least 5% by weight, more preferably at least 7% by weight, and still more preferably at least 5% by weight. at least 10% by weight.
    According to the invention, the ratio r of the (meth) acrylic polymer (P1) relative to the multiphase polymer is at most 95% by weight.
    Preferably, the weight ratio of the (meth) acrylic polymer (PI) relative to the multiphase polymer is between 5% by weight and 95% by weight, and preferably between 10% by weight and 90% by weight. weight.
    With regard to the (meth) acrylic monomer (M1) it is a liquid monomer at least in the temperature range between 0 ° C and 60 ° C. The (meth) acrylic monomer (M1) comprises a C = C carbon double bond.
    The (meth) acrylic monomer (MI) according to the invention is a monomer which is a solvent for the (meth) acrylic polymer (PI). In other words, the (meth) acrylic polymer (PI) is soluble in the (meth) acrylic monomer (M1).
    Soluble means that in a certain period of time, the (meth) acrylic polymer (PI) in contact with the thermodynamically compatible (meth) acrylic monomer (M1) is dissolved and a solution of (meth) acrylic polymer (PI) in the (meth) acrylic monomer (M1) is obtained.
    The solubility of the (meth) acrylic polymer (PI) in the (meth) acrylic monomer (M1) can be tested simply by mixing the two compounds with stirring at 25 ° C. For those skilled in the art, solvents including monomers such as (meth) acrylic monomer (M1) for a large number of polymers are known. On the other hand, solubility parameter values are given for a large number of polymers and solvents, the latter comprising a large number of monomers for example in Polymer Handbook (4th edition) Ed. J. Brandrup, EH Immergut and EA Grulke; Pub. : John Wiley and Sons Inc. 1999, Chapter "Solubility Parameter Value" by Eric A. Gulke VII / 675 to VII / 714.
    The (meth) acrylic monomer (M1) is preferably selected from (meth) acrylic monomers and mixtures thereof. If the (meth) acrylic monomer (M1) is a mixture of several monomers, the (meth) acrylic polymer (PI) is soluble in the mixture comprising the (meth) acrylic monomer (s) (M1) The (meth) acrylic monomer (M1) is more preferably selected from acrylic acid, methacrylic acid, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof.
    Still more preferably, the (meth) acrylic monomer (M1) is selected from acrylic acid, methacrylic acid, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof, the alkyl group having from 1 to 22 carbons, being either linear, branched or cyclic; preferably, the alkyl group has 1 to 12 carbons, being either linear, branched or cyclic.
    Advantageously, the (meth) acrylic monomer (M1) is chosen from the group consisting of: methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, n-acrylate and the like. butyl, isobutyl acrylate, n-butyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof.
    More preferably, the (meth) acrylic monomer (M1) is selected from methyl methacrylate, isobornyl acrylate or acrylic acid and mixtures thereof.
    In a first most advantageous embodiment, at least 50% by weight, preferably at least 60% by weight of the (meth) acrylic monomer (M1) is methyl methacrylate.
    In a second most advantageous embodiment, at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, and advantageously at least 80% by weight and even more advantageously 90% by weight of the (meth) acrylic monomer (M1) is a mixture of methyl methacrylate with isobornyl acrylate and / or acrylic acid.
    The liquid composition of the present invention is less viscous than a composition not comprising the (meth) acrylic polymer (PI).
    The liquid composition of the present invention can be used to prepare a better dispersed multiphase polymer instead of a composition not comprising the (meth) acrylic polymer (P1).
    As regards the method of manufacturing the liquid composition, it comprises the steps of a) preparing a composition comprising a (meth) acrylic polymer (PI) and a multiphase polymer b) mixing the composition from the previous step with a (meth) acrylic monomer (M1) in which the weight ratio of the multiphase polymer to the (meth) acrylic monomer (M1) in the liquid composition is between 1/99 and 25/75.
    Preferably, the (meth) acrylic polymer (PI) has a mass average molecular weight Mw of less than 100,000 g / mole. The (meth) acrylic polymer (PI) is the same as that defined previously.
    The composition comprising the (meth) acrylic polymer (PI) and a multiphase polymer may be in the form of the polymer powder as obtained by the two preferred embodiments of the preparation.
    The process provides a liquid composition which is less viscous than a composition not comprising the (meth) acrylic polymer (PI).
    The method provides a liquid composition which has a better dispersion of the multiphase polymer than a composition not comprising the (meth) acrylic polymer (PI).
    The agglomerated polymer powder is better dispersed in the solvent when the (meth) acrylic polymer (PI) is present.
    The process of the invention for the manufacture of the liquid composition can be used to prepare a more dispersed multi-phase polymer than a composition not comprising the (meth) acrylic polymer (P1).
    A further aspect of the invention is that the liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a (meth) acrylic monomer (M1) in which the weight ratio of the multiphase polymer to the monomer (M1) in the liquid composition is between 1/99 and 25/75, can be used to prepare a better dispersion of the multiphase polymer in the monomer (M1) than a composition not including the (meth) acrylic polymer (PI).
    Another further aspect of the invention is that the liquid composition comprising a) a (meth) acrylic polymer (PI), b) a multiphase polymer and c) a (meth) acrylic monomer (Ml) in which the weight ratio of the multiphase polymer to the monomer in the liquid composition is between 1/99 and 25/75, can be used for the preparation of impact-modified polymers, by polymerization of the (meth) acrylic monomer (M1).
    The liquid composition according to the invention may also be mixed with other monomers and polymers which are not part of the liquid composition before the polymerization. The liquid composition according to the invention can be used as a liquid masterbatch.
    The multiphase polymer is better distributed in the polymer matrix after the polymerization rather than using a composition not comprising the (meth) acrylic polymer (PI).
    Another further aspect of the invention is that the liquid composition comprising a) a (meth) acrylic polymer (PI), b) a multiphase polymer and c) a (meth) acrylic monomer (Ml) in which the weight ratio of the multiphase polymer to the monomer in the liquid composition is between 1/99 and 25/75, can be used as a liquid (meth) acrylic impregnating syrup, preferably for a fibrous substrate.
    Another further aspect of the invention is a method of manufacturing a liquid composition comprising the steps of a) preparing a composition comprising the (meth) acrylic polymer (PI) and a multiphase polymer b) mixing the composition of the preceding step with a (meth) acrylic monomer (M1) in which the weight ratio of the multiphase polymer to the monomer (M1) in the liquid composition is between 1/99 and 25/75, for a liquid impregnation in the form of a (meth) acrylic syrup, preferably an impregnating liquid for a fibrous substrate.
    Another further aspect of the invention relates to an impregnation process for impregnating a fibrous substrate, wherein said fibrous substrate comprises long fibers and said method comprises a step of impregnating said fibrous substrate with a liquid composition comprising a) a (meth) acrylic polymer (PI), b) a multiphase polymer and c) a (meth) acrylic monomer (M1) in which the weight ratio of the multiphase polymer to the monomer in the liquid composition is included between 1/99 and 25/75.
    Another further aspect of the invention relates to the use of a liquid composition comprising a) a (meth) acrylic polymer (PI), b) a multiphase polymer and c) a (meth) acrylic monomer ( M1) in which the weight ratio of the multiphase polymer to the monomer in the liquid composition is from 1/99 to 25/75, in an impregnating process for impregnating a fibrous substrate.
    [0164] Preferably, said fibrous substrate comprises long fibers.
    The liquid composition according to the invention can be used as a liquid masterbatch for use as a liquid (meth) acrylic impregnating syrup or in an impregnation process for impregnating a fibrous substrate. The liquid composition is diluted with another monomer.
    As regards the fibrous substrate, there may be mentioned fabrics, felts or nonwovens which may be in the form of strips, sheets, braids, locks or pieces. The fibrous material can have different shapes and sizes, either 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 fabric.
    The one-dimensional form is long linear fibers. The fibers may be discontinuous or continuous. The fibers may be arranged randomly or in a continuous filament parallel to each other. A fiber is defined by its aspect ratio, 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 an aspect ratio 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 non-woven reinforcements or roving fabric or bundles of fibers that can also be braided.
    The three-dimensional shapes are, for example, stacked or folded fibrous mats or non-woven reinforcements or bundles of fibers or mixtures thereof, an assembly of the two-dimensional form in the third dimension.
    The origin of the fibrous material may be natural or synthetic. As natural material can be mentioned plant fibers, wood fibers, animal fibers or mineral fibers.
    The natural fibers are, for example, sisal, jute, hemp, flax, cotton, coconut fibers and banana fibers. Animal fibers are for example wool or hair.
    As synthetic material may be mentioned polymeric 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 type E, R or S2, carbon fibers, boron fibers or silica fibers.
    The fibrous substrate of the present invention is chosen from vegetable fibers, wood fibers, animal fibers, mineral fibers, synthetic polymer fibers, glass fibers, carbon fibers or mixtures thereof. this.
    Preferably, the fibrous substrate is chosen from mineral fibers.
    [Methods of Evaluation] [0177] Viscosity Measurements
    The viscosity is measured with an Anton Paar MCR 301 rheometer. Couette geometry is used. The temperature is 25 ° C and with a shear rate of 0.1 s-1 to 100 s-1.
    [0178] Glass transition temperature
    The glass transitions (Tg) of the polymers are measured with equipment capable of performing a thermomechanical analysis. A RDAII "RHEOMETRICS DYNAMIC ANALYZER" analyzer from Rheometrics Company was used. Thermomechanical analysis accurately measures the viscoelastic changes of a sample as a function of temperature, stress or applied deformation. The apparatus continuously records the deformation of the sample, maintaining the fixed stress, during a controlled program of temperature variation.
    The results are obtained by plotting, as a function of temperature, the elastic modulus (G '), the loss modulus and the delta tan. The Tg is the highest temperature value read in the tan delta curve when the tan delta derivative is zero.
    [0179] Molecular Weight
    The weight average molecular weight (Mw) of the polymers is measured by steric exclusion chromatography (SEC).
    [0180] Analysis of the particle size
    The particle size of the primary particles after the multiple layer polymerization is measured with a Zetasizer. The particle size of the polymer powder after recovery is measured with a MALVERN Mastersizer 3000 Malvern.
    For estimating the average particle size of powder by weight, the particle size distribution and the ratio of fine particles, a Mastersizer 3000 Malvern device with 300 mm optics, measuring a range of 0.5 to 880 pm is used.
    [Examples] [0181] The synthesis of the multiphase polymer (core-shell particles) is carried out according to the example of the sample 1 of WO2012 / 038441 to obtain a multiphase polymer. The multiphase polymer CS1 is obtained. It comprises a phase (A) comprising a polymer (Al) having a glass transition temperature below 0 ° C (consisting essentially of butyl acrylate) and a phase (B) comprising a polymer (B1) having a transition temperature vitreous of at least 30 ° C (consisting essentially of methyl methacrylate). The multiple phase polymer CS1 is preserved as an aqueous dispersion for later use.
    The synthesis of one type of (meth) acrylic polymer (PI) is carried out according to two embodiments: firstly, the (meth) acrylic polymer (PI) is polymerized in the presence of the multiple-phase polymer CS1. The (meth) acrylic polymer (PI) is produced as an additional layer of the multiple-phase polymer CS. And in a second embodiment, the (meth) acrylic polymer (P1) is polymerized separately and mixed or combined with the multiphase polymer after completion of the polymerization of the (meth) acrylic polymer (P1).
    Comparative Example 1: The multiphase polymer CS1 is mixed with methyl methacrylate (MMA) at 20 ° C with stirring so that 15% by weight of CS1 are in the liquid composition relative to the MMA.
    EXAMPLE 1 The (meth) acrylic polymer (P1) is produced as an additional layer of the multiphase polymer CS1. The weight average molecular weight of the (meth) acrylic polymer P1 is M "= 28,000 g / mole.
    The final polymer composition was then recovered, the polymer composition being dried by spray drying. The polymer composition obtained is mixed with methyl methacrylate (MMA) at 20 ° C. with stirring so that 15% by weight of CS1 relative to the MMA are in the liquid composition comprising MMA, the polymer (meth) acrylic (P1) and the multiple phase polymer CS1.
    EXAMPLE 2 The (meth) acrylic polymer (P1) is polymerized separately and mixed or combined with the multiple phase polymer CS1. Synthesis of the (meth) acrylic polymer (P1): semi-continuous process: charge in a reactor, with stirring, of 1700 g of deionized water, 0.01 g of FeSO4 and 0.032 g of ethylenediaminetetraacetic acid, sodium salt ( dissolved in 10 g of deionized water), 3.15 g of sodium formaldehyde sulfoxylate dissolved in 110 g of deionized water and 21.33 g of potassium tallow potassium emulsifier (dissolved in 139.44 g of water), and the mixture was stirred until complete dissolution. Three vacuum nitrogen purges were carried out sequentially and the reactor was left under a moderate vacuum. The reactor was then heated. At the same time, a mixture comprising 960.03 g of methyl methacrylate, 106.67 g of dimethyl acrylamide and 10.67 g of n-octyl mercaptan was degassed with nitrogen for 30 minutes. The reactor is heated to 63 ° C and maintained at this temperature. Then, the monomer mixture was introduced into the reactor in 180 minutes using a pump. In parallel, a solution of 5.33 g of tert-butyl hydroperoxide (dissolved in 100 g of deionized water) is introduced (same addition time). The tubings were rinsed with 50 g and 20 g of water. Then the reaction mixture was heated to a temperature of 80 ° C and then the polymerization was allowed to terminate for 60 minutes after the end of the addition of the monomers. The reactor was cooled to 30 ° C. The solids content obtained is 34.2%. The weight average molecular weight of the (meth) acrylic polymer PI is Mw = 28,000 g / mol.
    The aqueous dispersion of the multiple-phase polymer CS1 and the (meth) acrylic polymer (PI) are mixed in such quantities that the weight ratio based on the solid polymer between the (meth) acrylic polymer (PI) and the polymer to multiple phases CS1 is 15/85. The mixture was recovered as a powder by spray drying.
    The mixture obtained is mixed with methyl methacrylate at 20 ° C. with stirring so that 15% by weight of CS1 with respect to the MMA are in the liquid composition comprising MMA, the (meth) acrylic polymer ( PI) and the multiphase polymer CS1.
    Example 3: Example 2 is repeated, but the weight ratio based on the solid polymer between the (meth) acrylic polymer (PI) and the multistage polymer CS1 is 25/75.
    The viscosity of the respective liquid compositions is measured.
    Table 1 - viscosity results
    As indicated in Table 1, the overall solids content of the polymer increases while the ratio of the core-shell polymer remains constant at 15% by weight relative to the monomer, but the dynamic viscosity of the composition decreases.
    The core-shell particles are dispersed more efficiently by having a lower effective volume in the liquid composition, when the methacrylic polymer is present.
    权利要求:
    Claims (22)
    [1" id="c-fr-0001]
    A liquid composition comprising: a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a (meth) acrylic monomer (M1) wherein the weight ratio of the multiphase polymer to the monomer in the liquid composition is between 1/99 and 25/75.
    [2" id="c-fr-0002]
    2. Composition according to claim 1, characterized in that the (meth) acrylic polymer (P1) has a mass average molecular weight Mw of less than 100,000 g / mole.
    [3" id="c-fr-0003]
    3. Composition according to claim 1 or 2, characterized in that the (meth) acrylic polymer (P1) is soluble in the (meth) acrylic monomer (M1).
    [4" id="c-fr-0004]
    4. Composition according to any one of claims 1 to 3, characterized in that the monomer (MI) is selected from the group consisting of: acrylic acid, methacrylic acid, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof. ci, the alkyl group having 1 to 22 carbons, either linear, branched or cyclic; preferably, the alkyl group having 1 to 12 carbons, either linear, branched or cyclic.
    [5" id="c-fr-0005]
    5. Composition according to any one of claims 1 to 3, characterized in that the monomer (MI) is selected from the group consisting of: methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, acid methacrylic acid, acrylic acid, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof.
    [6" id="c-fr-0006]
    6. Composition according to any one of claims 1 to 5, characterized in that the multiphase polymer comprises a) a phase (A) comprising a polymer (Al) having a glass transition temperature below 0 ° C b) a phase (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 phase (A) is the first phase and the phase (B) comprising the polymer (B1) is grafted onto the phase (A) comprising the polymer (Al).
    [8" id="c-fr-0008]
    8. Composition according to any one of claims 6 to 7 characterized in that the polymers (Al) and (Bl) are acrylic or methacrylic polymers.
    [9" id="c-fr-0009]
    9. Composition according to any one of claims 6 to 7 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 1 to 9 characterized in that the (meth) acrylic polymer (PI) comprises at least 50% by weight of monomers selected from (C1 to C12) alkyl (meth) acrylates.
    [11" id="c-fr-0011]
    11. Composition according to any one of claims 1 to 10 characterized in that 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 alkyl acrylate monomer, C1 to C8.
    [12" id="c-fr-0012]
    12. Composition according to any one of claims 1 to 10 characterized in that the (meth) acrylic polymer (P1) comprises between 0% by weight and 50% by weight of a functional monomer.
    [13" id="c-fr-0013]
    13. Composition according to any one of claims 1 to 10 characterized in that the (meth) acrylic polymer (PI) comprises between 1% by weight and 30% by weight of a functional monomer.
    [14" id="c-fr-0014]
    14. Composition according to Claim 12 or 13, characterized in that the functional comonomer is chosen from the group consisting of: glycidyl (meth) acrylate, acrylic or methacrylic acid, amides derived from these acids, acrylate or methacrylate of 2- methoxyethyl, 2-aminoethyl acrylates or methacrylates are optionally quaternized, acrylate or methacrylate monomers comprising a phosphonate or phosphate group, alkyl imidazolidinone (meth) acrylates, polyethylene glycol (meth) acrylates.
    [15" id="c-fr-0015]
    15. The method of manufacturing a liquid composition according to any one of claims 1 to 14 comprising the steps of a) preparing a composition comprising a (meth) acrylic polymer (P1) and a multiphase polymer b) mixture of the composition of the preceding step with a (meth) acrylic monomer (M1) the ratio of the multiphase polymer to the monomer in the liquid composition being between 1/99 and 25/75.
    [16" id="c-fr-0016]
    16. The method of claim 15, characterized in that the (meth) acrylic polymer (P1) has a mass average molecular weight Mw of less than 100,000 g / mole.
    [17" id="c-fr-0017]
    An impregnation method for impregnating a fibrous substrate, wherein said fibrous substrate comprises long fibers and said method comprising a step of impregnating said fibrous substrate with a liquid composition comprising: a) a (meth) acrylic polymer (P1) b) a multiphase polymer and c) a (meth) acrylic monomer (M1) in which the weight ratio of the multiphase polymer to the monomer in the liquid composition is between 1/99 and 25/75.
    [18" id="c-fr-0018]
    18. Impregnation process according to claim 17, characterized in that the (meth) acrylic polymer (PI) has a mass average molecular weight Mw of less than 100,000 g / mol.
    [19" id="c-fr-0019]
    19. Use of the liquid composition according to any one of claims 1 to 14, or obtained by the process according to any one of claims 15 to 16 to prepare a better dispersion of the multiphase polymer in the monomer (M1).
    [20" id="c-fr-0020]
    20. Use of the liquid composition according to any one of claims 1 to 14 or obtained by the process according to any one of claims 15 to 16 for the preparation of impact-modified polymers.
    [21" id="c-fr-0021]
    21. Use of the liquid composition according to any one of claims 1 to 14 or obtained by the method according to any one of claims 15 to 16 as a liquid (meth) acrylic impregnating syrup, preferably for a fibrous substrate.
    [22" id="c-fr-0022]
    22. Use of the liquid composition according to any one of claims 1 to 14 or obtained by the method according to any one of claims 15 to 16 in an impregnation process for impregnating a fibrous substrate.
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    FR3068979A1|2019-01-18| ACRYLIC ADHESIVE COMPOSITION, PROCESS FOR PREPARING THE SAME, AND USE THEREOF
    FR3038612A1|2017-01-13|
    FR3053693A1|2018-01-12|LIQUID COMPOSITION COMPRISING A PHOSPHORUS-BASED ADDITIVE, USE THEREOF AND MATERIAL OR COMPOSITION OBTAINED AFTER POLYMERIZATION OF THE COMPOSITION
    FR3038611A1|2017-01-13|
    FR3068980A1|2019-01-18|EPOXY ADHESIVE COMPOSITION COMPRISING MULTI-STAGE POLYMER AND | ACRYLIC POLYMER, PROCESS FOR PREPARING THE SAME, AND USE THEREOF
    FR3053045A1|2017-12-29|
    同族专利:
    公开号 | 公开日
    CN108779316A|2018-11-09|
    BR112018014029A2|2018-12-11|
    US10815370B2|2020-10-27|
    WO2017121750A1|2017-07-20|
    EP3402843A1|2018-11-21|
    KR20180102132A|2018-09-14|
    JP2019506487A|2019-03-07|
    FR3046606B1|2019-09-06|
    US20190031875A1|2019-01-31|
    CA3010993A1|2017-07-20|
    US20210040305A1|2021-02-11|
    MX2018008508A|2019-01-21|
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    法律状态:
    2016-12-15| PLFP| Fee payment|Year of fee payment: 2 |
    2017-07-14| PLSC| Publication of the preliminary search report|Effective date: 20170714 |
    2017-12-11| PLFP| Fee payment|Year of fee payment: 3 |
    2018-12-13| PLFP| Fee payment|Year of fee payment: 4 |
    2019-12-16| PLFP| Fee payment|Year of fee payment: 5 |
    2020-12-10| PLFP| Fee payment|Year of fee payment: 6 |
    2021-12-17| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1650195A|FR3046606B1|2016-01-11|2016-01-11|LIQUIDACRYLIC COMPOSITION COMPRISING A MULTIPHASE POLYMER AND AACRYLIC MONOMER, PROCESS FOR PREPARING THE SAME AND USE THEREOF|
    FR1650195|2016-01-11|FR1650195A| FR3046606B1|2016-01-11|2016-01-11|LIQUIDACRYLIC COMPOSITION COMPRISING A MULTIPHASE POLYMER AND AACRYLIC MONOMER, PROCESS FOR PREPARING THE SAME AND USE THEREOF|
    EP17700245.8A| EP3402843A1|2016-01-11|2017-01-11|Liquidacrylic composition comprising a multistage polymer and aacrylic monomer, its method of preparation and its use|
    US16/068,993| US10815370B2|2016-01-11|2017-01-11|Liquid acrylic composition comprising a multistage polymer and a acrylic monomer, its method of preparation and its use|
    CA3010993A| CA3010993A1|2016-01-11|2017-01-11|Liquidacrylic composition comprising a multistage polymer and aacrylic monomer, its method of preparation and its use|
    JP2018536166A| JP2019506487A|2016-01-11|2017-01-11|Liquidacrylic composition comprising multi-stage polymer andacrylic polymer, method of preparation thereof and use thereof|
    BR112018014029A| BR112018014029A2|2016-01-11|2017-01-11|liquid composition comprising a multistage polymer and aacrylic monomer, its method of preparation and use|
    MX2018008508A| MX2018008508A|2016-01-11|2017-01-11|Liquidacrylic composition comprising a multistage polymer and aacrylic monomer, its method of preparation and its use.|
    CN201780015089.0A| CN108779316A|2016-01-11|2017-01-11|Including more grades of polymers and（Methyl）The liquid of acrylic monomer（Methyl）Acrylic composition, preparation method and its purposes|
    KR1020187023026A| KR20180102132A|2016-01-11|2017-01-11|Liquidacrylic compositions comprising a multistage polymer andacrylic monomers, processes for their preparation, and uses thereof|
    PCT/EP2017/050462| WO2017121750A1|2016-01-11|2017-01-11|Liquidacrylic composition comprising a multistage polymer and aacrylic monomer, its method of preparation and its use|
    US17/078,144| US20210040305A1|2016-01-11|2020-10-23|Liquid acrylic composition comprising a multistage polymer and a acrylicmonomer, its method of preparation and its use|
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