• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a liquid composition comprising a monomer, a (meth) acrylic polymer and a multiphase polymer. In particular, the present invention relates to a liquid composition, comprising a monomer, a (meth) acrylic polymer and a multiphase polymer, which can be used as a syrup. More particularly, the present invention also relates to a process for preparing a liquid composition comprising a monomer, a (meth) acrylic polymer and a multiphase polymer.
    公开号:FR3046605A1
    申请号:FR1650191
    申请日:2016-01-11
    公开日:2017-07-14
    发明作者:Raber Inoubli；Philippe Hajji；Rosangela Pirri
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    LIQUID COMPOSITION COMPRISING A MULTIPHASE POLYMER, METHOD FOR PREPARING SAME AND USE THEREOF
    FIELD OF THE INVENTION [001] The present invention relates to a liquid composition comprising a monomer, a (meth) acrylic polymer and a multiphase polymer.
    In particular, the present invention relates to a liquid composition, comprising a monomer, a (meth) acrylic polymer and a multiphase polymer, which can be used as a syrup.
    More particularly, the present invention also relates to a process for preparing a liquid composition comprising a monomer, a (meth) acrylic polymer and a multiphase polymer.
    [Technical problem] [004] Impact modifiers 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 room temperature, but also and particularly at temperatures less than zero, notch sensitivity and crack propagation. Thus, a reinforced polymer may be a polymeric material whose impact strength and toughness have been increased by incorporating phase microdomains of an elastomeric material.
    [005] This is usually accomplished by introducing into the polymer matrix microscopic particles of elastomers that can absorb the energy of a shock or dissipate it. One possibility is to introduce the elastomer particles in the form of core-shell particles. These core-bark particles, which typically have an elastomeric core and a polymeric bark, have the advantage of an adequate particle size for the elastomeric core for effective cure 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 elastomeric part of the particle and its quantity. There is an optimum average particle size for obtaining the highest impact resistance for a given amount of added impact modifier particles.
    [007] These primary impact modifier particles are generally added as powder particles to the polymeric material. These powder particles are agglomerated primary impact modifier particles. During homogenization of the thermoplastic material with the powder particles, the primary impact modifier particles are recovered and dispersed more or less homogeneously in the thermoplastic material.
    While the particle size of the impact modifier 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.
    [009] For many polymers, thermoplastic or thermosetting polymers, it is very difficult or nearly impossible to properly disperse these multi-phase polymers in the form of core-shell particles into agglomerated dry powders. An ideal homogeneous dispersion of the core-bark particle. does not have agglomerates after dispersion in the matrix.
    The object of the present invention is to obtain a liquid composition comprising a monomer, a (meth) acrylic polymer and a multiphase polymer, with a homogeneous dispersion of the multiphase polymer.
    [011] An object of the present invention is also to obtain a liquid composition comprising a monomer, a (meth) acrylic polymer and a multiphase polymer, which can be used in a polymerization.
    Another object of the present invention is to avoid or significantly reduce the agglomeration of the multiphase polymer.
    [013] An additional objective is to obtain a process for preparing a liquid composition comprising a monomer, a (meth) acrylic polymer and a multiphase polymer, with a homogeneous dispersion of the multiphase polymer.
    [014] Yet another object is the use of the composition comprising a monomer, a (meth) acrylic polymer for the impact resistance of polymers.
    Background of the Invention [015] WO2014 / 013028 discloses an impregnation method 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 modifier in the form of fine particles.
    [016] No prior art document describes a composition as claimed or a method for obtaining it.
    [BRIEF DESCRIPTION OF THE INVENTION] [017] Surprisingly, it has been found that a liquid composition comprising a) a (meth) acrylic polymer (PI), b) a multiphase polymer and c) a 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, is less viscous than a composition not comprising the (meth) acrylic polymer (PI) .
    [018] Surprisingly, it has also been found that a liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a monomer (M1) in which the weight ratio of Multiphase polymer 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 (P1).
    [019] Surprisingly, it has also been found that a liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a monomer (M1) in which the weight ratio of multi-phase 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 comprising the (meth) acrylic polymer (P1).
    [020] Surprisingly, it has also been found that a method of 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 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, provides a liquid composition which is less viscous than a composition not comprising the (meth) acrylic polymer (P1).
    [021] Surprisingly, it has also been found that a liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a monomer (M1) in which the weight ratio of Multi-phase polymer monomer (M1) in the liquid composition is between 1/99 and 25/75, can be used for the preparation of impact-modified polymers.
    According to a first aspect, the present invention relates to a liquid composition comprising a) a (meth) acrylic polymer (PI), b) a multiphase polymer and c) a monomer (M1). wherein the weight ratio of the multiphase polymer to the monomer in the liquid composition is from 1/99 to 25/75.
    [023] 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 a (meth) acrylic polymer (P1) and a multiphase polymer b) mixing the composition of the preceding step with a 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.
    According to a third aspect, the present invention relates to the use of a liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a monomer (M1) in which the weight ratio of the multiphase polymer to the monomer (M1) in the liquid composition is from 1/99 to 25/75, for resistance to impregnancy on impact of polymers.
    [025] The term "polymer powder" as used refers to a grain of powder in the range of at least 1 micron (μm) obtained by agglomeration of primary polymers in the nanometer range.
    [026] The term "primary particle" as used refers to a spherical polymer comprising particles in the nanoscale range. Preferably, the primary particle has an average particle size by weight between 20 nm and 800 nm.
    [027] The term "particle size" as used, refers to the average diameter of the volume of a particle considered spherical.
    [028] The term "copolymer" as used indicates that the polymer consists of at least two different monomers.
    [029] "Multiphase Polymer" as used refers to a polymer formed sequentially by a multiphase polymerization process. A preferred method is a multiphase emulsion polymerization process wherein 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.
    [030] 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.
    [033] The term "(meth) acrylic resin" as used refers to adhesives based on acrylic and methacrylic monomers.
    [034] 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.
    The term "impact modifier" as used means a material that when incorporated into a polymeric material increases the impact resistance and strength of that polymeric material by phase microdomains of a material. elastomeric.
    The term "elastomer" as used refers to the thermodynamic state of the polymer above its glass transition.
    [037] The term "elastomeric polymer" as used refers to a polymer that has a glass transition temperature (Tg) of less than 0 ° C.
    [038] 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 to 300,000 mPa.s. The viscosity of the liquid composition (sometimes also called syrup) can be easily measured with a rheometer with a shear force 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 force of 1 s-1.
    [039] As regards 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. still more preferably less than 70,000 g / mol, preferably less than 60,000 g / mol and still more preferably less than 50,000 g / mol and still more preferably less than 40,000 g / mol.
    [040] The (meth) acrylic polymer (PI) has a weight 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 5000 g / mol, preferably greater than 6000 g / mol, more preferably greater than 6500 g / mol and even more preferably greater than 7000 g / mol and most preferably greater than 10 000 g / mol.
    [041] 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 4000 g / mole and 80,000 g / mole, advantageously between 5000 g / mole and 70,000 g / mole, more preferably between 6000 g / mole and 50,000 g / mole and most preferably between 10,000 g / mole and 40,000 g / mole. g / mol.
    [042] 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.
    [043] 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.
    [044] Preferably, the (meth) acrylic polymer (P1) is not crosslinked.
    [045] Preferably, the (meth) acrylic polymer (P1) is not grafted onto any other polymer (s).
    [046] 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-C8 alkyl acrylate monomer is advantageously chosen from methyl acrylate, ethyl acrylate or butyl acrylate.
    [047] In a second preferred embodiment, the (meth) acrylic polymer (PI) 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.
    [048] 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) [049] R1 being selected in either of formulas (1) and (2) from H or CH3; and in formula (1) Y is 0, 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.
    [050] 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.
    [051] The multiphase polymer according to the invention has at least two phases which are different in their polymer composition.
    [052] The multiphase polymer is preferably in the form of polymer particles considered as spherical particles. These particles are also called heart-bark particles. The first layer forms the heart, the second or all subsequent phases form the respective barks.
    [053] 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.
    [054] The polymer particle is obtained by a multi-phase process such as a process comprising two, three or more than three phases.
    [055] 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 (B1). ) having a glass transition temperature greater than 30 ° C.
    [056] 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.
    [057] 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).
    [058] Preferably, the phase (A) is the first phase and the phase (B) comprising the polymer (B1) is grafted onto the layer (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).
    [059] Polymer (A1) having a glass transition temperature below 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.
    [060] Preferably, the polymer (Al) 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.
    [061] In a first preferred embodiment, the polymer (B1) having a glass transition temperature above 60 ° C is produced during the last phase of the multi-step process forming the outer layer of the polymer particle having the structure. multi-layered.
    [062] 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 of a phase after the polymer formation phase (Al) of the multi-step process.
    [063] There could be an additional layer or layers obtained by an intermediate phase or intermediate phases.
    [064] The glass transition temperature Tg of the respective polymers can be estimated for example by dynamic processes and thermomechanical analysis.
    [065] 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.
    [066] 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.
    [067] 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.
    [068] The comonomer or comonomers in the polymer (Al) are preferably selected from (meth) acrylic monomers and / or vinyl monomers.
    [069] The (meth) acrylic comonomer in the polymer (A1) comprises monomers selected from C1 to C12 (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.
    [070] 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.
    [071] 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.
    [072] In a specific embodiment, the polymer (Al) is a homopolymer of butyl acrylate.
    [073] 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.
    [074] 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.
    [075] With regard to the polymer (Al), in a second embodiment, the polymer (Al) is a polymer based on silicone elastomer. Silicone, 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.
    [076] With regard to the polymer (A1), in a third embodiment, the polymer (A1) having a glass transition temperature of less than 0 ° C. comprises at least 50% by weight of polymer units originating from the polymer. isoprene or butadiene and layer (A) is the innermost layer of the polymer particle having the multilayered structure. In other words, the layer (A) comprising the polymer (Al) is the core of the polymer particle.
    [077] 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, copolymers of isoprene-butadiene, 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.
    [078] 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.
    [079] With regard to the polymer (B1), mention may be made of homopolymers and copolymers comprising monomers with double bonds and / or vinyl monomers. Preferably, the polymer (B1) is a (meth) acrylic polymer.
    [080] 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.
    [081] The polymer (B1) can be crosslinked.
    [082] 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.
    [083] Advantageously, the polymer (B1) comprises at least 50% by weight, more advantageously at least 60% by weight, and still more advantageously at least 70% by weight of monomer units derived from methyl methacrylate.
    [084] 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.
    [085] 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 .
    [086] Preferably, the (meth) acrylic polymer (P1) is grafted onto none of the polymers (A1) or (B1).
    [087] As regards the method of manufacturing 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 of less than 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 mixture of monomers (An) and the monomer or mixture of monomers (Bm) are chosen from the monomers according to the composition of the polymer (Al) and the polymer (B1) ) given previously.
    [088] Preferably, step a) is performed 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.
    [089] Advantageously, the process for producing 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 (An) to obtain at least one 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 a mixture of monomers (Bm) to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C
    [090] The respective monomers or monomer mixtures (Am) and (Bm) to form the layers (A) and (B) respectively comprising the polymers (A1) and (B1) respectively and the characteristics of the respective polymers (A1) and (B1) are the same as previously defined.
    [091] The method of manufacturing the multiphase polymer may comprise additional steps for additional phases between steps a) and b).
    [092] The method of manufacturing the multiphase polymer may also include additional steps for additional phases 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.
    [093] 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.
    [094] Regarding the process for manufacturing the (meth) acrylic polymer (P1) according to the invention, it comprises the step of polymerization of the respective (meth) acrylic monomers (Plm). The respective (meth) acrylic monomers (Plm) are the same as previously defined for the (meth) acrylic polymer (P1) and the two preferred embodiments of the (meth) acrylic polymer (P1).
    [095] The (meth) acrylic homopolymer or copolymer (P1) could be produced in a batch or semi-batch process: for the batch process, the monomer mixture is introduced in a single addition just before or after the introduction of the initiator system or a part thereof 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) for a defined period of addition that could be in the range of 30 to 500 minutes.
    [096] The process for preparing the polymer composition comprising the (meth) acrylic polymer (PI) and the multiphase polymer has two preferred embodiments.
    [097] 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.
    [098] In a second preferred embodiment of the process, the (meth) acrylic polymer (PI) is polymerized separately and mixed or combined with the multiphase polymer.
    [099] 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 a mixture of monomers (Plm) to obtain a layer in 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.
    [0100] 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 a mixture of monomers (Plm) to obtain a layer in this additional phase comprising the (meth) acrylic polymer (PI) having a glass transition temperature of at least 30 Characterized in that the (meth) acrylic polymer 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 layer respectively comprising the polymers (Al), (Bl) 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 above.
    Preferably, the method of manufacturing the polymer composition comprising the (meth) acrylic polymer (PI) 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 (A1) having a glass transition temperature below 0 ° C comprises at least 50% by weight of polymeric units from isoprene or butadiene and layer (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 recovering 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% 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 a furnace or a vacuum oven with heating of the composition for 48 hours at 50.degree.
    With regard to the method according to the second 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) mixing the (meth) acrylic polymer (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 (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 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 (PI) and the multiphase polymer is preferably carried out by coagulation or spray-drying.
    The process for producing 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 moisture and preferably less than 1.5% by weight moisture and more preferably less than 1.2% by weight. '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 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 a multi-step process and the (meth) acrylic polymer (P1).
    With regard to the polymer powder comprising the (meth) acrylic polymer (P1) 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 (P1) 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 (P1) 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.
    As regards the monomer (M1), it is a liquid monomer at least in the temperature range between 0 ° C and 60 ° C. The monomer (M1) comprises a C = C carbon double bond.
    The monomer (M1) according to the invention is a monomer which is a solvent for the (meth) acrylic polymer (P1). In other words, the (meth) acrylic polymer (P1) is soluble in the monomer (M1).
    Soluble means that in a certain period of time, the (meth) acrylic polymer (P1) in contact with the thermodynamically compatible monomer (M1) is dissolved and a solution of the (meth) acrylic polymer (P1) in the monomer (M1) is obtained.
    The solubility of the (meth) acrylic polymer (P1) in the monomer (M1) can be tested simply by mixing the two compounds with stirring at 25 ° C. For those skilled in the art, solvents comprising monomers such as 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 monomer (M1) is preferably selected from (meth) acrylic monomers and / or vinyl monomers and mixtures thereof. If the monomer (M1) is a mixture of several monomers, the (meth) acrylic polymer (PI) is soluble in the mixture comprising the monomer (s) (M1).
    The monomer (M1) is more preferably selected from (C1-C12) alkyl (meth) acrylates, styrenic monomers, and mixtures thereof.
    In a first preferred embodiment, the monomer (M1) comprises at least 50% by weight of methyl methacrylate.
    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 liquid composition not comprising the (meth) acrylic polymer (PI).
    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 monomer (M1) the weight ratio of the multiphase polymer to the monomer (M1) in the liquid composition being 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 / mol. The (meth) acrylic polymer (PI) is the same as that defined previously.
    The composition comprising the (meth) acrylic polymer (P1) 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 process provides a liquid composition which has a better dispersion of the multiphase polymer than a composition not comprising the (meth) acrylic polymer (P1).
    The agglomerated polymer powder is better dispersed in the solvent when the (meth) acrylic polymer (P1) 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 monomer (M1) in which the weight ratio of the polymer the monomer (M1) in the liquid composition is between 1/99 and 25/75, may be used to prepare a better dispersion of the multiphase polymer in the monomer (M1) than a composition not comprising the (meth) acrylic polymer (P1).
    Another further aspect of the invention is that the liquid composition comprising a) a (meth) acrylic polymer (P1), b) a multiphase polymer and c) a monomer (M1) in which the weight ratio of Multiphase monomer (M1) polymer 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 monomer (M1).
    The liquid composition according to the invention may also be mixed with other monomers and polymers which are not part of the composition before the polymerization of the monomer (M1). 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 than using a composition not comprising the (meth) acrylic polymer (P1).
    [Methods of Evaluation] [0149] 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.
    [0150] 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 (G1), 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.
    [0151] Molecular Weight
    The weight average molecular weight (Mw) of the polymers is measured by steric exclusion chromatography (SEC). Particle Size Analysis [0152]
    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] [0153] 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 a (meth) acrylic polymer type (PI) is carried out according to two embodiments: first, 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 (PI) is polymerized separately and mixed or combined with the multiphase polymer after completion of the polymerization of the (meth) acrylic polymer (PI).
    Comparative Example 1: The multiple phase 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 (PI) is produced as an additional layer of the multiple phase polymer CS1. A semi-continuous process is used: loading into a reactor, with stirring of 6400 g of multiphase polymer (CS1) in 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 sulfoxylate formaldehyde dissolved in 110 g of deionized water and 21.33 g of emulsifier potassium salt of beef tallow fatty acids (dissolved in 139.44 g of water), and the mixture was stirred until complete dissolution of the added raw materials except the core-shell polymer. 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 weight average molecular weight of the (meth) acrylic polymer PI is Mw = 28,000 g / mol.
    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 with respect 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 multiphase 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 fatty acid 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 (P1) 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 ( Pl) 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 (P1) and the multistage polymer CS1 is 25/75.
    The viscosity of the respective liquid compositions is measured.
    Table 1 - viscosity results of the liquid compositions
    As indicated in Table 1, the overall solid content of the polymer increases while the ratio of the multiphase polymer remains constant at 15% by weight relative to the monomer M1 = MMA, 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 (PI) is present.
    权利要求:
    Claims (20)
    [1" id="c-fr-0001]
    A liquid composition comprising: a) a (meth) acrylic polymer (P1); b) a multiphase polymer; and c) a 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 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 (C 1 -C 12) alkyl (meth) acrylates, styrenic monomers or mixtures thereof.
    [5" id="c-fr-0005]
    5. Composition according to any one of claims 1 to 4, 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.
    [6" id="c-fr-0006]
    6. Composition according to claim 5, 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).
    [7" id="c-fr-0007]
    7. Composition according to any one of claims 5 to 6 characterized in that the polymers (Al) and (Bl) are acrylic or methacrylic polymers.
    [8" id="c-fr-0008]
    8. Composition according to any one of claims 5 to 6 characterized in that the polymer (Al) comprises at least 50% by weight of polymer units from isoprene or butadiene.
    [9" id="c-fr-0009]
    9. Composition according to any one of claims 1 to 8 characterized in that the (meth) acrylic polymer (P1) comprises at least 50% by weight of monomers selected from (C 1 to C 12) alkyl (meth) acrylates.
    [10" id="c-fr-0010]
    10. Composition according to any one of claims 1 to 8 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.
    [11" id="c-fr-0011]
    11. Composition according to any one of claims 1 to 8 characterized in that the (meth) acrylic polymer (P1) comprises between 0% by weight and 50% by weight of a functional monomer.
    [12" id="c-fr-0012]
    12. Composition according to any one of claims 1 to 8 characterized in that the (meth) acrylic polymer (P1) comprises between 1% by weight and 30% by weight of a functional monomer.
    [13" id="c-fr-0013]
    13. Composition according to claim 11 or 12, 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.
    [14" id="c-fr-0014]
    14. A method of manufacturing a liquid composition according to any one of claims 1 to 13 comprising the steps of a) preparation of a composition comprising a polymer (meth) acrylic (PI) and a polymer with multiple phases b) mixture of the composition of the preceding step with a monomer (M1) the ratio of the multiphase polymer to the monomer in the liquid composition being between 1/99 and 25/75.
    [15" id="c-fr-0015]
    15. The method of claim 14, characterized in that the (meth) acrylic polymer (PI) has a mass average molecular weight Mw of less than 100,000 g / mol.
    [16" id="c-fr-0016]
    16. The method of claim 14 or 15, characterized in that the (meth) acrylic polymer (PI) is formed as an additional layer of the multiphase polymer.
    [17" id="c-fr-0017]
    17. The method of claim 14 or 15, characterized in that the composition comprising the (meth) acrylic polymer (PI) and the multiphase polymer is produced by 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 polymerization in emulsion 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 polymerization in emulsion of a monomer or a mixture of monomers (Plm) to obtain a layer in this additional phase comprising the (meth) acrylic polymer (PI) having a glass transition temperature of the ego ns 30 ° C
    [18" id="c-fr-0018]
    18. The method of claim 14 or 15, characterized in that the (meth) acrylic polymer (PI) is polymerized separately and mixed or combined with the multiphase polymer.
    [19" id="c-fr-0019]
    19. Use of the liquid composition according to any one of claims 1 to 13, or obtained by the process according to any one of claims 14 to 18 for preparing 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 13 or obtained by the method according to any one of claims 14 to 18 for the preparation of impact-modified polymers.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3046605B1|2019-09-06|LIQUID COMPOSITION COMPRISING A MULTIPHASE POLYMER, METHOD FOR PREPARING SAME AND USE THEREOF
    FR3046606B1|2019-09-06|LIQUID | ACRYLIC COMPOSITION COMPRISING A MULTIPHASE POLYMER AND A | ACRYLIC MONOMER, PROCESS FOR PREPARING THE SAME AND USE THEREOF
    FR3031108A1|2016-07-01|
    FR3053350A1|2018-01-05|LIQUID OR SYRUP COMPOSITION COMPRISING A MULTI-PHASE POLYMER AND A | ACRYLIC POLYMER, SYRUP FOR IMPREGNATION PROCESS, IMPREGNATION PROCESS FOR A FIBROUS SUBSTRATE, DEPOLYMERIZATION PROCESS AND STRUCTURAL ARTICLE THEREOF
    FR3031106A1|2016-07-01|
    FR2497811A1|1982-07-16|AQUEOUS DISPERSIONS OF POLYMERS AND THEIR APPLICATION IN PARTICULAR AS COATING COMPOSITIONS
    CA2364551A1|2000-10-12|Cross-linked microparticles, method for the production and use thereof
    FR3005057A1|2014-10-31|LIQUID | ACRYLIC SYRUP, ITS POLYMERIZATION PROCESS, ITS USE AND MOLDED OBJECT OBTAINED THEREFROM
    CA2788447A1|2011-09-01|Associative monomer based on oxo alcohols, acrylic polymer containing this monomer, use of said polymer as thickener in an aqueous formulation, and formulation obtained
    CA2895440A1|2014-06-26|Organic resin bearing cyclic carbonate groups and aqueous dispersion for crosslinked polyurethanes
    FR3053348A1|2018-01-05|COMPOSITION COMPRISING A MULTI-PHASE POLYMER AND TWO DIFFERENT | ACRYLIC POLYMERS, METHOD FOR PREPARING THE SAME AND ARTICLE THEREOF
    FR3053349A1|2018-01-05|COMPOSITION COMPRISING A THERMOPLASTIC POLYMER, A MULTI-PHASE POLYMER AND A | ACRYLIC POLYMER, METHOD FOR THE PREPARATION THEREOF AND USE THEREOF
    EP0890621B1|2005-12-21|Coating
    FR3068977A1|2019-01-18|COMPOSITION COMPRISING A MULTIPHASE POLYMER AND A | ACRYLIC POLYMER, PROCESS FOR PREPARING THE SAME AND USE THEREOF
    FR3019549A1|2015-10-09|
    FR2850661A1|2004-08-06|A method of preparing a composite material used for injection molded, extruded or press formed articles consisting of a matrix of a thermoplastic polymer, especially poly| containing metallic nanoparticles
    FR2520372A1|1983-07-29|HIGH SOLIDS COATING COMPOSITION
    FR3064267A1|2018-09-28|CROSS-LINKING COMPOUND, PROCESS FOR THE SYNTHESIS, LIQUID COMPOSITION COMPRISING SAID CROSS-LINKING COMPOUND, ITS POLYMERIZATION PROCESS, AND MATERIAL OBTAINED AFTER POLYMERIZATION OF SAID COMPOSITION
    FR3068979A1|2019-01-18| ACRYLIC ADHESIVE COMPOSITION, PROCESS FOR PREPARING THE SAME, AND USE THEREOF
    FR3097866A1|2021-01-01|A composition comprising a compound having two polymerizable groups, a multistage polymer and a thermoplastic polymer, its method of preparation, its use and article comprising the same
    FR3103817A1|2021-06-04|A composition comprising a multistage polymer and a | acrylic polymer, its method of preparation and its use
    FR3068980A1|2019-01-18|EPOXY ADHESIVE COMPOSITION COMPRISING MULTI-STAGE POLYMER AND | ACRYLIC POLYMER, PROCESS FOR PREPARING THE SAME, AND USE THEREOF
    FR3038612A1|2017-01-13|
    FR3038611A1|2017-01-13|
    BE654986A|1965-04-28|
    同族专利:
    公开号 | 公开日
    KR20180102133A|2018-09-14|
    FR3046605B1|2019-09-06|
    EP3402830A1|2018-11-21|
    CN108779218A|2018-11-09|
    SG11201805898RA|2018-08-30|
    RU2018129183A|2020-02-13|
    BR112018014026A2|2018-12-11|
    RU2018129183A3|2020-03-24|
    US20190023890A1|2019-01-24|
    US10968341B2|2021-04-06|
    JP6983163B2|2021-12-17|
    WO2017121749A1|2017-07-20|
    JP2019501267A|2019-01-17|
    RU2736487C2|2020-11-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP0985692A2|1998-09-09|2000-03-15|Rohm And Haas Company|Improved MBS impact modifier|
    WO2007135344A1|2006-05-23|2007-11-29|Arkema France|Multi-layer coextrusion method|
    WO2009126373A2|2008-04-07|2009-10-15|Arkema Inc.|Functional mbs impact modifiers for use in engineering resins|
    WO2012038441A1|2010-09-22|2012-03-29|Arkema France|New impact modifier and impact modified thermoplastic composition|
    EP2881436A1|2012-07-31|2015-06-10|Teijin Limited|Resin composition and molded article formed from same|
    WO2014135815A1|2013-03-08|2014-09-12|Arkema France|Liquid acrylic syrup for impregnating a fibrous substrate and method for the production thereof, method for impregnating a fibrous substrate, and composite material produced after polymerisation of said pre-impregnated substrate|
    WO2014135816A1|2013-03-08|2014-09-12|Arkema France|Liquid acrylic syrup for impregnating a fibrous substrate, method for impregnating a fibrous substrate, and composite material produced after polymerisation of said pre-impregnated substrate|WO2021105507A1|2019-11-29|2021-06-03|Arkema France|Porous polymer powder, its composition, its use and composition comprising it|US3793402A|1971-11-05|1974-02-19|F Owens|Low haze impact resistant compositions containing a multi-stage,sequentially produced polymer|
    GB2039496B|1979-01-12|1982-11-10|Du Pont|Cored acrylic polymers|
    DE4114641A1|1991-05-04|1992-11-05|Basf Ag|EMULSION PROPFCOPOLYMERISATE|
    EP0725092A3|1995-02-06|1997-08-27|Chemie Linz Gmbh|Redispersible, core-shell polymer powder, its preparation and use|
    EP0745622A1|1995-05-24|1996-12-04|Imperial Chemical Industries Plc|Impact modified acrylic polymers|
    JP3527565B2|1995-06-27|2004-05-17|三菱マテリアル神戸ツールズ株式会社|Gear measuring method and NC gear cutting machine|
    ES2135916T3|1995-08-31|1999-11-01|Basf Ag|THERMOPLASTIC MOLDING MASSES WITH A LOW DISPERSION RATIO OF LIGHT.|
    JPH09111086A|1995-10-13|1997-04-28|Mitsubishi Rayon Co Ltd|Resin composition, acrylic premix and production of acrylic artificial marble|
    JPH09110496A|1995-10-13|1997-04-28|Mitsubishi Rayon Co Ltd|Resin composition, and productions of acryl based premix and acryl based artificial marble|
    JPH09111084A|1995-10-13|1997-04-28|Mitsubishi Rayon Co Ltd|Resin composition, acrylic premix and production of acrylic artificial marble|
    JPH09110497A|1995-10-13|1997-04-28|Mitsubishi Rayon Co Ltd|Resin composition, and productions of acryl based premix and acryl based artificial marble|
    JPH09111085A|1995-10-13|1997-04-28|Mitsubishi Rayon Co Ltd|Resin composition, acrylic premix and production of acrylic artificial marble|
    US5688870A|1996-04-10|1997-11-18|Air Products And Chemicals, Inc.|Process for preparing water dispersible polymer powders|
    DE10203565C1|2002-01-29|2003-07-10|Roehm Gmbh|Production of polymethyl methacrylate casting, used for making acoustic insulation panels and balcony cladding, involves adding impact modified of core-shell I-shell II type as masterbatch in polymethyl methacrylate|
    DE10260089A1|2002-12-19|2004-07-01|Röhm GmbH & Co. KG|Process for the preparation of aqueous dispersions|
    FR2993581B1|2012-07-18|2016-01-22|Arkema France|IMPREGNATION PROCESS FOR A FIBROUS SUBSTRATE, LIQUID ACRYLIC SYRUP FOR THE IMPREGNATION PROCESS, ITS POLYMERIZATION PROCESS AND STRUCTURE PRODUCT OBTAINED THEREFROM|
    CN105073804B|2013-03-25|2018-01-19|赢创罗姆有限公司|With impact resistance and with the PMMA of improved optical property|
    FR3019549B1|2014-04-07|2020-10-02|Arkema France|MULTI-STAGE POLYMER POWDER COMPOSITION, ITS PREPARATION PROCESS AND ITS USE|FR3053350B1|2016-06-29|2020-03-27|Arkema France|LIQUID OR SYRUP COMPOSITION COMPRISING A MULTI-PHASE POLYMER AND AACRYLIC POLYMER, SYRUP FOR IMPREGNATION PROCESS, IMPREGNATION PROCESS FOR A FIBROUS SUBSTRATE, DEPOLYMERIZATION PROCESS AND STRUCTURAL ARTICLE THEREOF|
    WO2020001835A1|2018-06-26|2020-01-02|Arkema France|Curable compositions based on multistage polymers|
    GB2575056A|2018-06-27|2020-01-01|Hexcel Composites Ltd|Curable compositions comprising filled multistage polymers|
    CN114144163A|2019-07-31|2022-03-04|阿科玛法国公司|Nail coatings based on photocurable compositions|
    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
    FR1650191A|FR3046605B1|2016-01-11|2016-01-11|LIQUID COMPOSITION COMPRISING A MULTIPHASE POLYMER, METHOD FOR PREPARING SAME AND USE THEREOF|
    FR1650191|2016-01-11|FR1650191A| FR3046605B1|2016-01-11|2016-01-11|LIQUID COMPOSITION COMPRISING A MULTIPHASE POLYMER, METHOD FOR PREPARING SAME AND USE THEREOF|
    KR1020187023030A| KR20180102133A|2016-01-11|2017-01-11|LIQUID COMPOSITION COMPRISING MULTI-TERM POLYMERS, PROCESS FOR PRODUCING THE SAME,|
    CN201780015099.4A| CN108779218A|2016-01-11|2017-01-11|Include the liquid composition of more grades of polymers, preparation method and its purposes|
    BR112018014026A| BR112018014026A2|2016-01-11|2017-01-11|liquid composition comprising a multistage polymer, its method of preparation and use|
    EP17701056.8A| EP3402830A1|2016-01-11|2017-01-11|Liquid composition comprising a multistage polymer, its method of preparation and its use|
    US16/068,954| US10968341B2|2016-01-11|2017-01-11|Liquid composition comprising a multistage polymer, its method of preparation and its use|
    JP2018536202A| JP6983163B2|2016-01-11|2017-01-11|Liquid composition containing multi-stage polymer, method of preparation thereof and use thereof|
    RU2018129183A| RU2736487C2|2016-01-11|2017-01-11|Liquid composition containing a multistage polymer, a method for production thereof and use|
    PCT/EP2017/050460| WO2017121749A1|2016-01-11|2017-01-11|Liquid composition comprising a multistage polymer, its method of preparation and its use|
    SG11201805898RA| SG11201805898RA|2016-01-11|2017-01-11|Liquid composition comprising a multistage polymer, its method of preparation and its use|
    [返回顶部]