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    • 专利摘要:
    The present invention relates to a composition comprising a thermoplastic polymer, a multiphase polymer and a (meth) acrylic polymer. The present invention also relates to an impact resistant composition comprising a thermoplastic polymer, a multiphase polymer and a (meth) acrylic polymer. In particular, the present invention relates to a method of making an impact resistant composition comprising a multiphase polymer and a (meth) acrylic polymer and its use in thermoplastic polymers.
    公开号:FR3053349A1
    申请号:FR1656102
    申请日:2016-06-29
    公开日:2018-01-05
    发明作者:Aline COUFFIN；Rosangela Pirri；Raber Inoubli；Philippe Hajji
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [Field of the invention] The present invention relates to a composition comprising a thermoplastic polymer, a multi-phase polymer and a (meth) acrylic polymer.
    The present invention also relates to a composition whose impact resistance has been modified, comprising a thermoplastic polymer, a multi-phase polymer and a (meth) acrylic polymer.
    In particular, the present invention relates to a process for producing an impact modifier composition comprising a multi-phase polymer and a (meth) acrylic polymer as well as its use in thermoplastic polymers.
    [Technical problem] [004] Impact additives or modifiers are widely used to improve the impact resistance of thermoplastic compositions, with the aim of compensating for their brittleness, their sensitivity to notching and the propagation of inherent cracks. Thus, a polymer whose impact resistance has been modified is a polymer material whose impact resistance and solidity have been increased by the incorporation of phase microdomains of an elastomeric material. This is usually achieved by the introduction into the polymer matrix of microscopic particles of elastomers capable of absorbing or dissipating impact energy.
    A known practice consists in adding an impact modifier which modifies the impact resistance, comprising an elastomer or an elastomeric phase. Such an elastomer can be part of a multi-phase polymer in the form of core-shell particles, with a phase which is an elastomer or the elastomeric phase. These particles are prepared by emulsion polymerization in order to form a dispersion and can, for example, be recovered in the form of a powder. They generally include a succession of "hard" and "soft" layers. We can thus find particles with two layers (soft-hard) or three layers (hard-soft-hard). The particle size is generally less than 1 μm and more particularly between 50 nm and 500 nm. The outer layer or a grafted envelope is necessary for adhesion and compatibility with the thermoplastic matrix.
    The performance of the impact modifier is a function of the size of the particles, in particular of the elastomeric part of the particle, and of its quantity. There is an optimal average particle size to obtain the highest impact resistance for a given amount of added impact modifying particles.
    These primary impact modifier particles are generally added in the form of powder particles to the thermoplastic material. These powder particles are agglomerated primary particles modifying impact. During the homogenization of the thermoplastic material with the powder particles, the primary impact-modifying particles are recovered and are more or less homogeneously dispersed in the thermoplastic polymer material.
    [008] While the particle size of the impact modifier particles is in the nanometer range, that of the agglomerated powder particles is in the micrometer range.
    It is important to have an impact modifier powder devoid of any negative influence on the thermoplastic polymer composition and its processing capacity. A negative influence is in particular the fluidity or the viscosity of the thermoplastic polymer comprising the impact modifier. The fluidity or viscosity should not change considerably in order to be identical to that of the pure thermoplastic polymer, without modifying impact.
    A decrease in fluidity or an increase in viscosity of the polymer composition means either a longer treatment at identical temperature, or that the temperature of the polymer composition must be increased, in order to regain the level of fluidity or viscosity, this which involves a risk of increased thermal exposure of the polymer composition.
    The objective of the present invention is to obtain a polymer composition which comprises a thermoplastic polymer and a multi-phase polymer, and which can be transformed and / or treated like the pure thermoplastic polymer, while increasing the resistance to shocks.
    An objective of the present invention also consists in obtaining a polymer composition whose impact resistance has been modified, which comprises a thermoplastic polymer and a multi-phase polymer, and which can be transformed and / or treated like the thermoplastic polymer pure.
    [013] An additional objective of the present invention is a process for preparing a polymer composition which comprises a thermoplastic polymer, a multi-phase polymer and a (meth) acrylic polymer, said polymer composition being able to be transformed and / or treated as pure thermoplastic polymer. Another objective of the present invention is to find an impact modifier composition comprising a multi-phase polymer in a thermoplastic polymer to increase its impact resistance without increasing its viscosity.
    Another additional objective of the present invention is to find a method of introducing a multi-phase polymer into a thermoplastic polymer to increase its impact resistance without increasing its viscosity.
    Yet another object of the present invention is the use of a multi-phase polymer in an impact modifying composition in a thermoplastic polymer without considerably increasing the viscosity of the thermoplastic polymer.
    [Background of the invention] prior art [017] The document EP1963416 describes polyester compositions with high fluidity. The composition includes at least one polyester and at least one fluidity-enhancing ingredient and includes
    I also have other impact modifiers and a property-improving thermoplastic such as polycarbonate.
    Document EP 2465881 describes a thermoplastic composition whose impact resistance has been modified with a sensitivity to hydrolysis to obtain increased fluidity while retaining a high impact resistance. The thermoplastic polymer is polycarbonate with a core-shell impact modifier as a multi-phase polymer.
    [019] None of the documents of the prior art describes a composition, a process or a use in accordance with the present invention.
    [Brief description of the invention] [020] Surprisingly, it has been found that a polymer composition comprising
    a) a thermoplastic polymer (TPI) and
    b) a multi-phase polymer and
    c) a (meth) acrylic polymer (Pl), in which the amount of multi-phase polymer in the composition is between 0.1% by weight and 50% by weight and the (meth) acrylic polymer (Pl) has a average molecular mass of mass Mw of less than 100,000 g / mole, produces a polymer composition with increased impact resistance without increasing the viscosity of the composition.
    [021] Surprisingly, it has also been found that a polymer composition comprising
    a) a thermoplastic polymer (TPI) and
    b) a multi-phase polymer and
    c) a (meth) acrylic polymer (Pl), in which the amount of multi-phase polymer in the composition is between 0.1% by weight and 50% by weight and the (meth) acrylic polymer (Pl) has a molecular mass: average mass Mw of less than 100,000 g / mol, can be used to increase impact resistance without increasing its viscosity.
    [022] Surprisingly, it has also been found that a process for manufacturing a polymer composition comprising the step of
    a) mixing a thermoplastic polymer (TPI) with a polymer composition (PCI) comprising a multi-phase polymer and a (meth) acrylic polymer (Pl), in which the quantity of multi-phase polymer in the composition is between 0.1% by weight and 50% by weight and the (meth) acrylic polymer (Pl) having an average molecular mass of mass Mw of less than 100,000 g / mole, produces a polymer composition with increased impact resistance without increase in the viscosity of the composition.
    [Detailed description of the invention] [023] According to a first aspect, the present invention relates to a polymer composition comprising
    a) a thermoplastic polymer (TPI) and
    b) a multi-phase polymer,
    c) a (meth) acrylic polymer (Pl), in which the quantity of multi-phase polymer in the composition is between 0.1% by weight and 50% by weight and the (meth) acrylic polymer (Pl) having a average molecular mass of mass Mw of less than 100,000 g / mole.
    According to a second aspect, the present invention relates to a process for manufacturing a polymer composition comprising the step of
    a) mixture of a thermoplastic polymer (TPI) with a multi-phase polymer and a (meth) acrylic polymer Pl) which has a mean molecular mass Mw of less than 100,000 g / mole, in which the quantity of polymer to Multiple phases in the polymer composition is between 0.1% by weight and 50% by weight.
    [025] According to a third aspect, the present invention relates to a process for manufacturing a polymer composition comprising the step of
    a) mixture of a thermoplastic polymer (TPI) with a polymer composition (PCI) comprising a multi-phase polymer and a (meth) acrylic polymer (Pl) which has an average molecular mass of mass Mw of less than 100,000 g / mole , wherein the amount of multi-phase polymer in the polymer composition is between 0.1% by weight and 50% by weight.
    In a fourth aspect, the present invention relates to the use of a polymer composition comprising
    a) a thermoplastic polymer (TPI) and
    b) a multi-phase polymer,
    c) a (meth) acrylic polymer (Pl), in which the amount of multi-phase polymer in the polymer composition is between 0.1% by weight and 50% by weight and the (meth) acrylic polymer (Pl) has an average molecular mass of mass Mw of less than 100,000 g / mol to increase the impact resistance of the composition without increasing its viscosity.
    [027] In a fifth aspect, the present invention relates to the use of an impact modifier composition comprising
    b) a multi-phase polymer,
    c) a (meth) acrylic polymer (Pl), in a thermoplastic polymer (TPI) in which the amount of multi-phase polymer in the composition is between 0.1% by weight and 50% by weight and the polymer (meth ) acrylic (Pl) has an average molecular mass of mass Mw of less than 100,000 g / mol to increase the impact resistance of the thermoplastic polymer (TPI) without increasing the viscosity of the thermoplastic polymer (TPI) comprising the multi-phase polymer and the (meth) acrylic polymer (Pl).
    The term “polymer powder” as used, denotes a polymer comprising grains of powder in the range of at least 1 micrometer (pm) obtained by agglomeration of a polymer or of primary polymers or oligomers comprising particles in the nanometric range.
    The term "primary particle" as used, denotes a spherical polymer comprising particles in the nanometric range. Preferably, the primary particle has an average particle size by weight between 20 nm and 800 nm.
    The term "particle size" as used, denotes the average diameter of the volume of a particle considered to be spherical.
    The term "copolymer" as used, indicates that the polymer consists of at least two different monomers.
    [032] "Multi-phase polymer" as used, denotes a polymer formed sequentially by a multi-phase polymerization process. A multi-phase emulsion polymerization process is preferred, 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 emulsion in the presence of the first emulsion polymer.
    The term "(meth) acrylic" as it is used, designates all kinds of acrylic and methacrylic monomers.
    The term “(meth) acrylic polymer” as it is 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 “impact modifier” as it is used designates a material which, once incorporated in a polymer material, increases the impact resistance and the solidity of this polymer material by phase microdomains of a rubbery material or elastomeric or a rubber or elastomeric polymer.
    The term “elastomer” as used, denotes the thermodynamic state of the polymer above its glass transition.
    The term “polymer elastomer” as it is used designates a polymer which has a glass transition temperature (Tg) below 0 ° C.
    The composition according to the invention is a thermoplastic polymer (TPI), a multi-phase polymer and a (meth) acrylic polymer (Pl) having an average molecular mass of mass Mw of less than 100,000 g / mole, in which the amount of the multi-phase polymer in the composition comprising the three components is from 0.1% by weight to 50% by weight.
    [039] Preferably, the amount of the multi-phase polymer in the composition is at least 0.3% by weight, more preferably at least 0.8% by weight, even more preferably at least 1% by weight and advantageously at least 1.5% by weight. [040] Preferably, the quantity of the multi-phase polymer in the composition is at most 40% by weight, more preferably at most 30% by weight, even more preferably at most 28% by weight and advantageously at most 25% by weight .
    [041] Preferably, the quantity of multi-phase polymer in the composition is between 0.3% by weight and 40% by weight and more preferably between 0.8% by weight and 30% by weight, more preferably still between 1 % by weight and 28% by weight and advantageously between 1.5% by weight and 25% by weight.
    [042] Preferably, the amount of (meth) acrylic polymer (Pl) in the composition is between 0.005% by weight and 47.5% by weight, preferably between 0.015% by weight and 45% by weight, more preferably between 0.04% by weight and 27% by weight, more preferably still between 0.05% by weight and 25% by weight and advantageously between 0.075% by weight and 22.5% by weight.
    [043] As regards the (meth) acrylic polymer (Pl), it has an average molecular mass of mass Mw of less than 100,000 g / mole, preferably less than 90,000 g / mole, more preferably less than 80,000 g / mole, even more preferably less than 70,000 g / mole, advantageously less than 60,000 g / mole, more preferably less than 50,000 g / mole and even more advantageously less than 40,000 g / mole.
    (meth) acrylic [044] The (meth) acrylic polymer (Pl) has an average molecular mass of mass Mw greater than 2000 g / mole, preferably greater than 3000 g / mole, more preferably greater than 4000 g / mole, again more preferably greater than 5000 g / mole, advantageously greater than 6000 g / mole, more advantageously greater than 6500 g / mole and even more advantageously greater than 7000 g / mole, even more advantageously greater than 10 000 g / mole and most advantageously greater than 12,000 g / mole.
    The average molecular weight of mass (Pl) is between
    Mw of the polymer 2000 g / mole and
    100,000 g / mole, preferably between 3,000 g / mole and 90,000 g / mole and more preferably between 4,000 g / mole and 80,000 g / mole, advantageously between advantageously between
    5000 g / mole and 70,000 g / mole, plus 6000 g / mole and 50,000 g and most advantageously between 10,000 g / mole and 40,000 g / mole.
    [046] Preferably, the (meth) acrylic polymer (Pl) 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 chosen from C1 to C12 alkyl (meth) acrylates. Advantageously preferably, the (meth) acrylic polymer (Pl) comprises at least 50% by weight of monomers chosen from C1 to C4 alkyl methacrylate and C1 to C8 alkyl acrylate monomers and mixtures thereof. this. The other optional monomers are copolymerized.
    [047] Preferably, the glass transition temperature Tg of the (meth) acrylic polymer (Pl) is between 30 ° C and 150 ° C. The glass transition temperature of the (meth) acrylic polymer and
    150 ° C, (Pl) is more preferably between between 45 ° C and 150 ° C and more preferably between 50 ° C and 150 ° C. The other optional monomers which are copolymerized are chosen so that the Tg is between these limits.
    [048] Preferably, the (meth) acrylic polymer (Pl) is not crosslinked.
    ίο [049] Preferably, the (meth) acrylic polymer (Pl) is not grafted on any other polymer.
    In a first preferred embodiment, the (meth) acrylic polymer (Pl) comprises from 50% by weight to 100% by weight of methyl methacrylate, preferably from 80% by weight to 100% by weight of methacrylate methyl, even more preferably from 80% by weight to 99.8% by weight of methyl methacrylate and from 0.2% by weight to 20% by weight of a C1 to C8 alkyl acrylate monomer. The C1 to C8 alkyl acrylate monomer is advantageously chosen from methyl acrylate, ethyl acrylate or butyl acrylate.
    [051] In a second preferred embodiment, the polymer
    (meth) acrylic (Pl) understands between 0 % by weight and 50% in weight of a monomer functional Of preference, the polymer (meth) acrylic (Pl) understands between 0 % by weight and 30 % in weight
    of the functional monomer, more preferably between 1% by weight and 30% by weight, even more preferably between 2% by weight and 30% by weight, advantageously between 3% by weight and 30% by weight, more advantageously between 5% by weight and 30% by weight and most advantageously between 5% by weight and 30% by weight.
    [052] Preferably, the functional monomer of the second preferred embodiment is a (meth) acrylic monomer. The functional monomer has the formula (1) or (2):
    Ri
    Y — r 5 (1)
    Ri
    Y — r 3 [053] Ri being chosen from one and the other of formulas (1) and (2) from H or CH3; and in formula (1) Y is O, R 5 is H or an aliphatic or aromatic radical having at least one atom which is not C or H; and in formula (2) Y is N and R 4 and / or R3 is H or an aliphatic or aromatic radical.
    [054] 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 made quaternary, acrylate or methacrylate monomers comprising a phosphonate or phosphate group, alkyl imidazolidinone (meth) acrylates, (meth) acrylates of polyethylene glycol. Preferably, the polyethylene glycol group of polyethylene glycol (meth) acrylates has a molecular weight ranging from 400 g / mole to 10,000 g / mole.
    [055] The multi-phase polymer according to the invention has at least two layers which are different in their polymer composition.
    [056] The multi-phase polymer is preferably in the form of spherical polymer particles. These particles are also called core-shell particles. The first layer forms the heart, the second or all of the following phases form the respective barks.
    Regarding the spherical polymer particle, it has an average diameter of particles by weight between 20 nm and 800 nm. Preferably, the mean particle diameter by weight of the polymer particle is between 25 nm and 600 nm, more preferably between 30 nm and 550 nm, even more preferably between 35 nm and 500 nm, advantageously between 40 nm and 400 nm, even more advantageously between 50 nm and 400 nm, even more advantageously between 75 nm and. 350 nm and most advantageously between 80 nm and 300 nm.
    The primary polymer particles can be agglomerated, giving a polymer powder comprising either the multilayer polymer or the (meth) acrylic polymer (Pl) and the multilayer polymer.
    [059] The polymer particle is obtained by a multi-phase process such as a process comprising two, three or more than three phases.
    The polymer particle has a multilayer structure comprising at least one layer (Aj comprising a polymer (Al) having a glass transition temperature below 0 ° C and another layer (B) comprising a polymer (B) having a glass transition temperature above 30 ° C.
    [061] In a first preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30 ° C is the outer layer of the polymer particle having the multilayer structure.
    [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 multilayer structure.
    [063] Preferably, phase (A) is the first phase and phase (B) comprising the polymer (B1) is grafted onto the layer (A) comprising the polymer (Al) or another intermediate layer. First phase means that phase (A) comprising the polymer (Al) is carried out before phase (B) comprising the polymer (B1).
    [064] The polymer (Al) having a glass transition temperature below 0 ° C in the layer (A) is never produced during the last phase of the multi-phase process. This means that the polymer (Al) is never in the outer layer of the multilayer structure 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.
    [065] Preferably, the polymer (Al) having a glass transition temperature below 0 ° C in the layer (A) is produced during the first phase of the multi-phase process forming the core for the polymer particle having the structure with multiple layers and / or before the polymer (B1) having a glass transition temperature greater than 60 ° C. 13 Preferably, the polymer (Al) has a glass transition temperature below -5 ° C, more preferably less than 15 ° C, preferably below -25 ° C.
    [066] In a first preferred embodiment, the polymer (B1) having a glass transition temperature above 60 ° C. is produced during the last step of the multistage process forming the outer layer of the polymer particle having the structure with multiple layers.
    [067] In a second preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30 ° C is an intermediate layer of the polymer particle having the multilayer structure, which is produced during a step after the step of forming the polymer (Al) of the multi-step process.
    [068] There could be an additional intermediate layer or layers obtained by an intermediate step or intermediate steps.
    [069] The glass transition temperature Tg of the respective polymers can be estimated for example by dynamic methods and thermomechanical analysis.
    To obtain a sample of the respective polymers (Al) and (B1), they can be prepared alone, and not by a multi-phase process, to more easily estimate and measure the glass transition temperature Tg of the respective polymers of the respective phases.
    [071] 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.
    [072] More preferably, the polymer (Al) comprises a comonomer or comonomers which are copolymerizable with the alkyl acrylate, provided that the polymer (Al) has a glass transition temperature of less than 0 ° C.
    The comonomer or comonomers in the polymer (Al) are preferably chosen from (meth) acrylic monomers and / or vinyl monomers.
    [074] The (meth) acrylic comonomer in the polymer (Al) comprises monomers chosen from C1 to C12 alkyl (meth) acrylates. Even more preferably, the (meth) acrylic comonomer in the polymer (Al) comprises C1 to C4 alkyl methacrylate monomers and / or C1 to C8 alkyl acrylate monomers.
    [075] 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 (Al) has a glass transition temperature below 0 ° C. [076] Preferably, the polymer (Al) is crosslinked. This means that a crosslinking agent is added to the other monomer (s). A crosslinking agent comprises at least two groups which can be polymerized.
    [077] In a specific embodiment, the polymer (Al) is a butyl acrylate homopolymer.
    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.
    [079] More preferably, the glass transition temperature Tg of the polymer (Al) of the first embodiment is between -100 ° C and 0 ° C, even more preferably between -100 ° C and 5 ° C, advantageously between - 90 ° C and -15 ° C, and more advantageously between -90 ° C and -25 ° C.
    With regard to the polymer (Al), in a second embodiment, the polymer (Al) is a polymer based on silicone elastomer. The silicone elastomer, par. example, is the,. polydimethylsiloxane. More preferably, the glass transition temperature Tg of the polymer (Al) of the second embodiment is between -150 ° C and 0 ° C, even more preferably between -145 ° C and -5 ° C, advantageously between 140 ° C and -15 ° C, and more preferably between -135 ° C and -25 ° C.
    As regards the polymer (Al), in a third embodiment, the polymer (Al) having a glass transition temperature of less than 0 ° G comprises at least 50% by weight of polymer units originating from the isoprene or butadiene and layer (A) is the innermost layer of the polymer particle having the multilayer structure. In other words, the layer (A) comprising the polymer (Al) is the heart of the polymer particle.
    By way of example, the polymer (Al) at the heart of the second embodiment, mention may be made of isoprene homopolymers or butadiene homopolymers, isoprenebutadiene copolymers, isoprene copolymers with at most 98% by weight of a vinyl monomer and butadiene copolymers with at most 98% by weight of a vinyl monomer. The vinyl monomer can be styrene, an alkylstyrene, acrylonitrile, an alkyl (meth) acrylate, or butadiene or isoprene. In one embodiment, the core is a butadiene homopolymer.
    [083] More preferably, the glass transition temperature Tg of the polymer (Al) of the third embodiment comprising at least 50% by weight of polymer units originating from isoprene or butadiene is between -100 ° C. and 0 °. C, even more preferably between -100 ° C and -5 ° C, advantageously between 90 ° C and -15 ° C and even more advantageously between -90 ° C and 25 ° C.
    [084] 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.
    [085] 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 of C1 to C8 alkyl acrylate monomers.
    [086] The polymer (B1) can be crosslinked.
    [087] Ideally, the acrylic or methacrylic monomers of the polymer (B1) are chosen 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.
    [088] Advantageously, the polymer (B1) comprises at least 50% by weight, more advantageously at least 60% by weight, and even more advantageously at least 70% by weight of monomer units originating from methyl methacrylate.
    [089] 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, even more preferably between 70 ° C and 150 ° C, advantageously between 90 ° C and 150 ° C and more advantageously between 90 ° C and 130 ° C.
    In another embodiment, the multi-phase polymer as described above has an additional phase, which is the (meth) acrylic (PI) polymer. The primary particle of polymers according to this embodiment of the invention has a multilayer structure comprising at least one layer (A) comprising a polymer (Al) having a glass transition temperature below 0 ° C, at least one layer (B ) comprising a polymer (B1) having a glass transition temperature greater than 30 ° C and at least one layer (P) comprising the (meth) acrylic polymer (PI) having a glass transition temperature between 30 ° C and 150 ° C .
    [091] Preferably, the (meth) acrylic polymer (PI) is not grafted onto any of the polymers (Al) or (B1).
    [092] As regards the process for manufacturing the multi-layer polymer according to the invention, it comprises the steps consisting in:
    a) polymerize by emulsion polymerization of a monomer or a mixture of monomers (A m ) to obtain at least one to obtain a layer (B) having a layer temperature (A) comprising the polymer (Al) having a glass transition temperature below 0 ° C.
    b) polymerizing by emulsion polymerization of a monomer or a mixture of monomers (B c comprising a polymer (B1 glass transition of at least 30 ° C.) the monomer or the mixture of monomers (A m ) and the monomer or the mixture of monomers (B m ) are chosen from the monomers according to the composition of the polymer (Al) and of the polymer (Bl) given above.
    [093] 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.
    Advantageously, the process for manufacturing the multilayer 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 a mixture of monomers (B m ) for layer (B) comprising a polymer (Bl) glass transition temperature of at least 30 ° C.
    [095] The monomers or mixtures of monomers (A m ) and respective ones to form the layers (A) and (B) respectively comprising the polymers (Al) and (Bl) respectively and the characteristics of the respective polymers (Al) and (Bl ) are the same as those defined above.
    [096] The process for manufacturing the multilayer polymer may include additional steps for additional phases between steps a) and b).
    [097] The process for manufacturing the multilayer polymer may also comprise additional steps for additional phases before steps a) and b). A seed could be used for the polymerization by emulsion polymerization of the monomer or of the mixture of monomers (A m ) to obtain having a (Bm) to obtain the layer (A) comprising the polymer (Al) having a glass transition temperature below −0 ° C. The seed is preferably a thermoplastic polymer having a glass transition temperature of at least 20 ° C.
    The multi-phase polymer is obtained in the form of an aqueous dispersion of polymer particles. The solid content of the dispersion is between 10% by weight and 65% by weight.
    As regards the process for manufacturing the (meth) acrylic polymer (Pl) according to the invention, it comprises the step of polymerization of the respective (meth) acrylic monomers (Pl m ) and of the other optional comonomers. The respective (meth) acrylic monomers (Plm) are the same as those defined previously for the (meth) acrylic polymer (Pl) and the two preferred embodiments of the (meth) acrylic polymer (Pl).
    The (meth) acrylic (Pl) homopolymer or copolymer could be produced according to a batch or semi-continuous process:
    for the batch process, the mixture of monomers is introduced at once just before or after the introduction of the initiator system or a part thereof for the semi-continuous process, the mixture of monomers is added in several stages or continuously, in addition to adding the initiator (the initiator is also added in batches or continuously) for a defined period of addition which could be in the range of 30 to 500 minutes.
    The method for preparing the polymer composition according to the invention comprising the thermoplastic polymer (TPI), the (meth) acrylic polymer (Pl) and the multi-phase polymer comprises two preferred embodiments.
    In both cases, concerning the preferred embodiments of the method, the thermoplastic polymer (TPI) is mixed with the (meth) acrylic polymer (Pl) and the multi-phase polymer. The (meth) acrylic polymer (Pl). and the multi-phase polymer are added together in a polymer composition (PCI) which is also called an impact modifier composition. The polymer composition (PCI) can be obtained by two preferred methods.
    In a first preferred embodiment of the process, the (meth) acrylic polymer (Pl) is polymerized in the presence of the multi-phase polymer. The (meth) acrylic polymer (Pl) is produced as an additional layer of the multi-phase polymer to give the polymer composition (PCI).
    In a second preferred embodiment of the method, the (meth) acrylic polymer (Pl) is polymerized separately and mixed or combined with the multi-phase polymer to give the polymer composition (PCI).
    As regards the method according to the first preferred embodiment for the preparation of the polymer composition (PCI) comprising the (meth) acrylic polymer (Pl) and the multilayer polymer, it comprises the steps consisting in:
    a) polymerize by emulsion polymerization of a monomer or a mixture of monomers (A m ) to obtain a layer in the layer (A) comprising the polymer (Al) having a glass transition temperature below 0 ° C.
    b) polymerizing by emulsion polymerization of a monomer or a mixture of monomers (B m ) in order to obtain a layer in the layer (B) comprising a polymer (Bl) having a glass transition temperature of at least 30 ° VS
    c) polymerizing by emulsion polymerization of a monomer or of a mixture of monomers (Pim) in order to obtain a layer at this additional stage comprising the (meth) acrylic polymer (Pl) having a glass transition temperature of at least 30 ° C characterized in that the (meth) acrylic polymer (Pl) has an average molecular weight of mass Mw of less than 100,000 g / mole.
    [0106] Preferably, step â) ’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 manufacturing the polymer composition (PCI) comprising the (meth) acrylic polymer (Pl) and the multi-layer 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 (A m ) to obtain a layer in the 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 (B m ) to obtain a layer in the layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° VS
    c) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Pim) in order to obtain a layer in this additional step comprising the (meth) acrylic polymer (Pl) having a glass transition temperature of at least 30 ° C characterized in that the (meth) acrylic polymer (Pl) has an average molecular weight of mass Mw of less than 100,000 g / mole.
    The respective monomers or mixtures of monomers (A m ), (B m ) and (Pim) to form the layers (A), (B) and the additional layer respectively comprising the polymers (Al), (Bl) and (Pl) respectively, are the same as those defined above. The characteristics of the polymers (Al), (Bl) and (Pl) respectively, are the same as those defined above.
    The polymer composition (PCI) is obtained in the form of an aqueous dispersion of polymer particles. The solid content of the dispersion is between 10% by weight and 65% by weight.
    Optionally, the process for manufacturing the polymer composition comprising the (meth) acrylic polymer (Pl) and the multi-layer polymer comprises the additional step d) of recovering this polymer composition.
    By recovery is meant 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.
    Spray drying is the preferred recovery and / or drying process for the process for 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 originating from the alkyl acrylate and the layer (A) is the innermost layer of the polymer particle having the multilayer structure.
    Coagulation is the preferred recovery and / or drying process for the manufacturing process for a polymer powder composition of (PCI) if the polymer (Al) having a glass transition temperature below 0 ° C comprises at at least 50% by weight of polymer units originating from isoprene or butadiene and the layer (A) is the innermost layer of the polymer particle having the multilayer structure.
    The method of manufacturing the polymer composition (PCI) can optionally comprise the additional step e) of drying the polymer composition (PCI).
    Preferably, the drying step e) is carried out if the step
    d) recovery of the polymer composition (PCI) is carried out by coagulation.
    Preferably, after the drying step e), the polymer composition (PCI) comprises less than 3% by weight, more preferably less than 1.5% by weight, advantageously less than 1% of moisture or d 'water.
    The humidity of a polymer composition can be measured with a thermobalance.
    The polymer can be dried in an oven or a vacuum oven with heating of the composition for 48 hours at 50 ° C.
    As regards the method according to the second preferred embodiment for the preparation of the polymer composition (PCI) comprising the (meth) acrylic polymer (Pl) and the multi-layer polymer, it comprises the steps of
    a) mixing the (meth) acrylic polymer (Pl) and the multi-phase polymer,
    b) optionally, the recovery of the mixture obtained from the first step in the form of a polymer powder, the (meth) acrylic polymer (Pl) and the multi-phase polymer of step a) being in the form of a dispersion in aqueous phase. The quantities of the aqueous dispersion of the (meth) acrylic polymer (Pl) and of the aqueous dispersion of the multilayer polymer are chosen so that the weight ratio of the multilayer 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 advantageously at least 50% by weight.
    The amounts of the aqueous dispersion of the (meth) acrylic polymer (Pl) and of the aqueous dispersion of the multi-layer polymer are chosen so that the weight ratio of the multi-layer polymer based on the solid fraction only in the mixture obtained is at most 99% by weight, preferably at most 95% by weight, and more preferably at most 90% by weight.
    The quantities of the aqueous dispersion of the (meth) acrylic polymer (Pl) and of the aqueous dispersion of the multilayer polymer are chosen so that the weight ratio of the multilayer 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 polymer composition (PCI) is obtained in the form of an aqueous dispersion of polymer particles if the recovery step b) does not take place. The solid content of the dispersion is between 10% by weight and 65% by weight.
    In one embodiment, the recovery step b) of the process for manufacturing the polymer composition comprising the (meth) acrylic polymer (Pl) and the multi-layer polymer is not optional and is carried out preferably by coagulation or by spray drying.
    The method of manufacturing the polymer composition (PCI) comprising the (meth) acrylic polymer (Pl) and the multi-phase 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.
    The humidity can be measured by a thermobalance which heats the polymer composition and measures the weight loss. The method of manufacturing the polymer composition comprising the (meth) acrylic polymer (Pl) and the multi-layer 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 (Pl).
    As regards the polymer powder comprising the (meth) acrylic polymer (P1) and the multi-layer polymer according to the two embodiments of the process for preparing the polymer composition (PCI), it has a median size of particles by volume D50 of between 1 μm and 500 μm. Preferably, the median particle size by volume 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 distribution of the particle size by volume is at least 7 μm and preferably 10 μm.
    The D90 of the distribution of the particle size 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 (Pl) relative to the multilayer polymer is at least 5% by weight, more preferably at least 7% by weight, and even more preferably at least 10% by weight.
    According to the invention, the ratio r of the (meth) acrylic polymer (Pl) relative to the multi-layer polymer is at most 95% by weight.
    Preferably, the weight ratio of the (meth) acrylic polymer (Pl) relative to the multi-layer polymer is between 5% by weight and 95% by weight, and preferably between 10% by weight and 90% by weight. weight.
    As regards the thermoplastic polymer (TPI) which is part of the thermoplastic composition according to the invention, it can be chosen from the following components, without limitation, polyvinyl chloride (PVC), polyesters such as, for example, poly ( ethylene terephthalate) (PET) or poly (butylene terephthalate) (PBT) or polylactic acid (PLA), polystyrene (PS), polycarbonates (PC), polyethylene, poly (methyl methacrylate-coethylacrylates) thermoplastic, poly (alkylene terephthalates), polyvinylidene fluoride, poly (vinylidenchloride), polyoxymethylene (POM), semi-crystalline polyamides, amorphous polyamides, semi-crystalline copolyamides, amorphous copolyamides, polyetheramides, polyesteramides, styrene and acrylonitrile copolymers and their respective mixtures. According to a preferred embodiment, the thermoplastic resin composition comprises polycarbonate (PC) and / or polyester (PET or PBT) or PC and polyester alloys. The alloys can be, for example, PC / ABS (poly (Acrylonitrile-co-butadiene-co-styrene), PC / polyester or PC / PLA to name a few.
    The thermoplastic polymer which is part of the thermoplastic composition according to the invention can also be chosen from polyurethanes; polyaromatic ketones such as polyether ketone, polyether ether ketone, polyether ketone ketone, polyketone; poly (phenylene ethers); poly (phenylene sulfides); phenoxy resins; polysulfones such as poly (ether sulfone), poly (aryl sulfone)., polysulfone; poly (ether imides); poly (ether imide esters); copoly (ether imide esters); poly (carbonate ester); polyarylates such as poly (bisphenol A isophthalate); polyimides such as poly (glutarimides); aromatic polyimides; acrylatestyrene-acrylonitrile resins; acrylonitrile-butadiene-styrene resins; poly (amide imides); nitrile resins; poly (methyl pentene); modified olefin styrene-acrylonitrile; styrenebutadiene resins; chlorinated polyethylene-styrene acrylonitrile resins; thermoplastic elastomers such as poly (ether esters), poly (ether amides), poly (styrene butadiene styrenes) and poly (styrene ethylene-butylene styrenes); and copolymers and blends of the above.
    The thermoplastic polymer (TPI) has a melt index (at
    300 ° C / 1.2 kg) between 3 and 65 g / 10 min, preferably between 4 and 50 g / 10 min.
    In a first preferred embodiment, the thermoplastic polymer (TPI) is chosen from polycarbonate and its mixtures. Advantageously, the thermoplastic polymer (TPI) is chosen from polycarbonate, mixtures of polycarbonate and polyester or polycarbonate alloys. Preferably, the polyester is PET or PBT.
    In a second preferred embodiment, the thermoplastic polymer (TPI) is chosen from polyester and mixtures comprising polyesters. Preferably, the polyester is chosen from polylactide acid, polyethylene terephthalate or polybutylene terephthalate and their mixtures.
    Regarding the constituents of the composition, the proportions by weight between the part of phase (A) comprising a polymer (Al) having a glass transition temperature below 0 ° C of the multi-phase polymer (core-shell polymer) and the thermoplastic polymer are between 0.5 / 99.5 and 30/87, preferably between 1/98 and 12/75.
    As regards the process for manufacturing the composition according to the invention, it comprises the step of
    a) mixing the thermoplastic polymer (TPI with the multi-phase polymer and a (meth) acrylic polymer (Pl), in which the amount of the multi-phase polymer is between 0.5% by weight and 50% by weight of the composition and the (meth) acrylic polymer (Pl) has an average molecular mass of mass Mw of less than 100,000 g / mole.
    Preferably, the multi-phase polymer and a (meth) acrylic polymer (Pl) are in the form of the polymer composition (PCI) as described above.
    Preferably, the mixing is carried out by mixing (“compounding” in English). The mixing is carried out by passage through an extruder.
    The invention also relates to the use of the thermoplastic composition according to the invention for producing molded bodies.
    The invention also relates to molded bodies comprising the thermoplastic composition according to the invention.
    [0148] [Evaluation Methods] [0149] Analysis of the Particle Size
    The particle size of the primary particles after the multilayer polymerization is measured with a Zetasizer Nano S90 from MALVERN.
    The particle size of the polymer powder is measured with a Mastersizer 3000 Malvern from MALVERN. For the estimation of the average particle size by volume D50, a Mastersizer 3000 Malvern apparatus with 300 mm optics, measuring a range of 0.5 to 880 pm is used.
    Glass transition temperature
    The glass transitions (Tg) of multi-phase polymers are measured with equipment capable of performing a thermomechanical analysis. An RDAII analyzer "RHEOMETRICS DYNAMIC ANALYSER" proposed by Rheometrics Company was used. Thermomechanical analysis measures precisely the viscoelastic changes of a sample as a function of temperature, stress or applied deformation. The device continuously records the deformation of the sample, in. 27 now the fixed constraint, during a controlled temperature variation program. The results are obtained by plotting, as a function of the temperature, the elastic modulus (G '), the loss modulus (G' ') and the tangent delta. The Tg is the highest temperature value read in the tan delta curve, when the derivative of tan delta is equal to zero.
    Molecular mass
    The mass average molecular weight (Mw) of the polymers is measured by size exclusion chromatography (SEC).
    Impact resistance
    The impact resistance is measured by a split pendulum of 5.5 J leA of ISO180 standard IZOD type.
    Fluidity index (MFI)
    The melt index (MFI) is measured according to ISO 1133 at 300 ° C / 1.2 kg.
    [Examples] The following materials are used or prepared:
    Polycarbonate is used as a thermoplastic polymer (TPI), caliber 300-10 from the company TRINSEO.
    As a multi-phase polymer for a composition outside the invention, a polymeric impact modifier (IM1) is prepared according to the technique described in document EP 1 844 086, which uses a standard emulsion polymerization technique. This multi-phase polymer is used in Comparative Example 2.
    As a multi-phase polymer for the composition according to the invention in the polymer composition (PCI), an impact modifier composition (IM2) is prepared. According to the example of sample 1 of document WO2012 / 038441, a multi-phase polymer 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 glassy at least 30 ° C (consisting essentially of methyl methacrylate). The multi-phase polymer CS1 is stored as an aqueous dispersion for later use.
    The synthesis of a type of (meth) acrylic polymer (P1) can be carried out according to two embodiments: first, the (meth) acrylic polymer (P1) is polymerized in the presence of the polymer with multiple phases · CS1. The (meth) acrylic polymer (Pl) is produced as an additional layer of the multi-phase polymer CS. And in a second embodiment, the (meth) acrylic polymer (Pl) is polymerized separately and mixed or combined with the multi-phase polymer after the polymerization of the (meth) acrylic polymer (Pl) has ended.
    For example 1: The (meth) acrylic polymer (Pl) is produced as an additional layer of the multi-phase polymer CSl. A semi-continuous process is used: loading into a reactor, with stirring of 6,400 g of multi-phase polymer (CSl) in deionized water, 0.01 g of FeSO4 and 0.032 g of sodium salt of the ethylenediaminetetraacetic acid, (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 emulsifier potassium salt of fatty acid from beef tallow (dissolved in 139.44 g of water), and the mixture was stirred until complete dissolution of the raw materials added with the exception of the core-shell polymer. Three vacuum nitrogen purges were carried out in succession and the reactor was left under moderate vacuum. The reactor was then heated. At the same time, a mixture comprising 960.03 g of methyl methacrylate, 106.67 g of dimethylacrylamide 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 mixture of monomers was introduced into the reactor in 180 minutes in parallel, a pump solution.
    In of 5.33 g using a tert-butyl hydroperoxide (dissolved in 100 g of deionized water) is introduced (same addition time). The tubes were rinsed with 50 g and 20 g of water. Then the reaction mixture was heated to a temperature of 80 ° C and the polymerization was then allowed to terminate for 60 minutes after the addition of the monomers was completed. The reactor was cooled to 30 ° C. The mass average molecular weight of the (meth) acrylic polymer Pl is M w = 28,000 g / mole.
    The final polymer composition was then recovered, the polymer composition being dried by spray drying.
    The two impact modifiers IM1 and IM2 are mixed with the polycarbonate according to the ratios given in table 1.
    Table 1 Prepared compositions
    Polymer with phasesmultiples in thepolymerthermoplastic(TPI)[% in weight] Phase (A)including thepolymer (Al) inthe polymer.thermoplastic(TPI)[% in weight] Comparative example 1without modifying shock 0 0 Comparative example 2with IMl 4.35 3.35 Example 1 with IM2 5.00 3.35
    The compositions prepared in Comparative Examples and Examples' in Table 1 are compared over the same% by weight. Of the rubber phase (phase (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C) impact modifier with respect to the thermoplastic polymer (TPI).
    Table 2 - Evaluation of the impact properties and of the melt index of the respective examples and comparative examples of Table Ί
    Impact resistance at 23 ° C [kJ / m 2 ] MFI a)(300 ° C / 1.2 kg)[g / 10 min] Comparative example 1without modificationimpact - 12.2 Comparative example 2with IM1 63.0 9.6 Example 1 with IM2 61, 6 12.5
    a) The MFI is measured after 7 min of residence time.
    Example 1 represents a comparative level in impact resistance as Comparative Example 2 and at the same time retains the same fluidity (expressed as MFI) as the thermoplastic polymer without modification of impact.
    Comparative Example 2 has a decrease in MFI, which means increased viscosity.
    权利要求:
    Claims (18)
    [1" id="c-fr-0001]
    1. Polymer composition comprising:
    a) a thermoplastic polymer (TPI) and
    b) a multi-phase polymer and
    c) a (meth) acrylic polymer (Pl), in which the amount of multi-phase polymer is between 0.1% by weight and 50% by weight of the composition comprising a), b), c) and the polymer (meth) acrylic (Pl) has an average molecular mass of mass Mw less than
    100,000 g / mole.
    [2" id="c-fr-0002]
    2. Composition according to claim 1, characterized in that the (meth) acrylic polymer (Pl) has a lower average molecular mass Mw of between 5000 g / mole and 70,000 g / mole.
    [3" id="c-fr-0003]
    3. Composition according to claim 1 or 2, characterized in that the amount of (meth) acrylic polymer (Pl) is between 0.005% by weight and 47.5% by weight.
    [4" id="c-fr-0004]
    4. Composition according to any one of claims 1 to 3, characterized in that the thermoplastic polymer (TPI) is chosen from polyvinyl chloride (PVC), polyesters such as for example poly (ethylene terephthalate) (PET) or poly ( butylene terephthalate) (PBT) or polylactic acid (PLA), polystyrene (PS), polycarbonates (PC), polyethylene, poly (methyl methacrylate-coethylacrylates) thermoplastic, poly (alkylene terephthalates), polyvinylidene fluoride, poly (vinylidene chloride) ), polyoxymethylene (POM), semi-crystalline polyamides, amorphous polyamides, semi-crystalline copolyamides, amorphous copolyamides, polyetheramides, polyesteramides, styrene and acrylonitrile copolymers (SAN) and their respective mixtures.
    [5" id="c-fr-0005]
    5. Composition according to any one of claims 1 to 4, characterized in that the thermoplastic polymer (TPI) is chosen from polycarbonate and polycarbonate blends.
    [6" id="c-fr-0006]
    6. Composition according to any one of claims 1 to 4, characterized in that the thermoplastic polymer (TPI) is chosen from polycarbonate, mixtures of polycarbonate with polyester or polycarbonate alloys.
    [7" id="c-fr-0007]
    7. Composition according to any one of claims 1 to 4, characterized in that the thermoplastic polymer (TPI) is chosen from polyester and mixtures comprising polyesters.
    [8" id="c-fr-0008]
    8. Composition according to any one of claims 1 to 7, characterized in that the thermoplastic polymer (TPI) has a melt index at 300 ° C / 1.2 kg) between 3 and 65 g / 10 min.
    [9" id="c-fr-0009]
    9. Composition according to any one of claims 1 to 8, characterized in that the multi-phase polymer is preferably in the form of particles of spherical polymers having an average particle size of mass between
    20 nm and 800 nm.
    [10" id="c-fr-0010]
    10. Composition according to any one of claims 1 to 9, characterized in that the multi-phase polymer comprises
    a) a phase (A) comprising a polymer (Al) having a glass transition temperature below 0 ° C.
    b) a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C.
    [11" id="c-fr-0011]
    11. Composition according to Claim 10, characterized in that the polymers (Al) and (Bl) are acrylic or methacrylic polymers.
    [12" id="c-fr-0012]
    12. Composition according to claim 10, characterized in that the polymer (Al) is a polymer based on silicone elastomer.
    [13" id="c-fr-0013]
    13. Composition according to claim 10, characterized in that the polymer (Al) comprises at least 50% by weight of polymer units originating from isoprene or butadiene.
    [14" id="c-fr-0014]
    14. Composition according to any one of claims 10 to 13, characterized in that phase (A) is the first phase and phase (B) comprising the polymer (Bl) is grafted onto phase (A) comprising the polymer (Al).
    [15" id="c-fr-0015]
    15. Method for manufacturing the composition according to any one of claims 1 to 14, said method comprising the step of
    a) mixing the thermoplastic polymer (TPI) with a multi-phase polymer and a (meth) acrylic polymer (Pl).
    [16" id="c-fr-0016]
    16. The method of claim 15, characterized in that the multi-phase polymer and the (meth) acrylic polymer (Pl) are in the form of a polymer composition (PCI) comprising the multi-phase polymer and the polymer (meth ) acrylic (Pl).
    [17" id="c-fr-0017]
    17. The method of claim 16, characterized in that the polymer composition (PCI) is a polymer powder having a volume average particle size D50 between 1 pm and 500 pm.
    [18" id="c-fr-0018]
    18. Use of the composition according to any one of claims 1 to 10 or obtained by a process according to any one of claims 11 to 15, for transforming or treating the polymer composition without significant increase in viscosity.
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    同族专利:
    公开号 | 公开日
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    引用文献:
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    WO2010099160A1|2009-02-26|2010-09-02|Arkema Inc.|Composite polymer modifiers|
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    FR2964970B1|2010-09-22|2013-11-01|Arkema France|NEW MODIFYING SHOCKS AND IMPROVED THERMOPLASTIC COMPOSITIONS SHOCK|
    FR2969159B1|2010-12-15|2013-01-11|Arkema France|SHOCK MODIFIED THERMOPLASTIC COMPOSITION HAVING HYDROLYTIC SENSITIVITY TO OBTAIN HIGH FLUIDITY WHILE MAINTAINING HIGH SHOCK RESISTANCE|WO2020001835A1|2018-06-26|2020-01-02|Arkema France|Curable compositions based on multistage polymers|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1656102A|FR3053349B1|2016-06-29|2016-06-29|COMPOSITION COMPRISING A THERMOPLASTIC POLYMER, A MULTI-PHASE POLYMER AND AACRYLIC POLYMER, ITS PREPARATION METHOD AND ITS USE|
    FR1656102|2016-06-29|FR1656102A| FR3053349B1|2016-06-29|2016-06-29|COMPOSITION COMPRISING A THERMOPLASTIC POLYMER, A MULTI-PHASE POLYMER AND AACRYLIC POLYMER, ITS PREPARATION METHOD AND ITS USE|
    PCT/EP2017/066217| WO2018002273A1|2016-06-29|2017-06-29|Composition comprising a thermoplastic polymer, a multistage polymer and aacrylic polymer, its method of preparation and its use|
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