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    • 专利摘要:
    The present invention relates to a polymer composition comprising a (meth) acrylic polymer and a multiphase polymer. In particular, the present invention relates to a polymer composition comprising a (meth) acrylic polymer and a multiphase polymer, which can be used as a masterbatch. More particularly, the present invention also relates to a process for preparing a polymer composition comprising a (meth) acrylic polymer and a multiphase polymer by spray drying or coagulation.
    公开号:FR3031108A1
    申请号:FR1463306
    申请日:2014-12-24
    公开日:2016-07-01
    发明作者:Raber Inoubli；Philippe Hajji；Rosangela Pirri
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to a polymer composition comprising a (meth) acrylic polymer and a multiphase polymer.  In particular, the present invention relates to a polymer composition comprising a (meth) acrylic polymer and a multiphase polymer, which may be used as a masterbatch.  [003] More particularly, the present invention also relates to a process for preparing a polymer composition comprising a (meth) acrylic polymer and a multiphase polymer by spray drying or coagulation.  [Technical problem] [004] Thermoset polymers are the most widely used matrix material in composite materials.  A thermoset polymer is an infusible and insoluble polymer network.  One possibility for obtaining a thermoset polymer is in a curing reaction of a thermosetting resin, such as an epoxy resin, with a hardener or a curing agent or a polyester resin.  Because of the high crosslinking density, the material has a high glass transition temperature, which makes it possible to obtain excellent thermomechanical properties of the material.  However, the impact properties of thermoset polymers are insufficient for many applications.  [006] Usually, an elastomeric type material is added to increase the impact resistance.  Such an elastomer may be a multi-phase polymer in the form of core-shell particles, at least one phase of which is an elastomer.  [008] The multi-phase polymer in the form of core-shell particles exists as agglomerated dry powders, the latter being dispersed in the matrix in order to obtain a homogeneous distribution.  For certain thermosetting resins, and in particular the epoxy resin, the correct dispersion of these multi-phase polymer particles is very difficult or almost impossible.  [009] There is also a complex technology for incorporating a multi-phase polymer in the form of core-shell particles, without drying the multiphase polymer after its synthesis process, in an epoxy resin by gradually changing the continuous medium. dispersion of the core-shell particles of water in an organic solvent.  The object of the present invention is to obtain a polymer composition, comprising a multiphase polymer, which can be easily dispersed in uncured resins, such as epoxy, polyester and (meth) acrylic resins.  [011] An object of the present invention is also to obtain an effective and homogeneous distribution of the multi-phase polymer in resins, such as epoxy, polyester and (meth) acrylic resins.  Another object of the present invention is to avoid agglomerated particles of multiphase polymer in resins, such as epoxy, polyester and (meth) acrylic resins.  [013] A further object of the present invention is the reinforcement of thermoset matrix based on epoxy, polyester or (meth) acrylic or thermoplastic matrix through a homogeneous distribution of the impact modifier in the form of a multiphase polymer.  [014] Yet another object of the present invention is a process for the production of a polymer composition comprising a multiphase polymer which can be easily dispersed in epoxy, polyester or (meth) resins. uncured acrylics.  [015] Yet another additional object is a process for the preparation of a polymer composition comprising a multiphase polymer which can be readily dispersed in uncured epoxy, polyester or (meth) acrylic resins having a efficient and homogeneous distribution of the multiphase polymer in the corresponding thermosetting resins.  Still another object is to use a polymer composition, comprising a multiphase polymer, which is in the form of a masterbatch for modifying the impact strength of thermoset polymers comprising the resins. epoxy, polyester or (meth) acrylic.  Still another object of the present invention is a process for the production of a free-flowing dry powder polymer composition comprising a (meth) acrylic polymer and a multiphase polymer for a use as a masterbatch for modifying the impact resistance of epoxy, polyester or thermoset (meth) acrylic resins having a homogeneous distribution of the multiphase polymer.  BACKGROUND OF THE INVENTION Prior Art [018] EP 0 228 450 discloses epoxy compounds modified with an elastomer.  The composition comprises a continuous phase of epoxy resin and a discontinuous phase of elastomer particles dispersed in the continuous phase.  The elastomer particles are grafted elastomer particles.  The elastomer particles are dispersed in the epoxy phase by a mixing or shearing device.  [019] EP 0 911 358 discloses the use of block copolymers as impact modifiers in an epoxy resin.  However, block copolymers are relatively expensive and it is preferred to disperse standard core-shell type impact modifiers in the epoxy resin.  [020] FR 2934866 (our AM 2509) discloses a preparation of core-shell-specific polymers having a functional shell comprising hydrophilic monomers.  The core-shell polymers are used as an impact modifier in thermoset polymers.  [021] EP 1 632 533 discloses a process for the production of a modified epoxy resin.  The epoxy resin composition has elastomeric polymer particles dispersed therein by a process that brings the particles into contact with an organic medium that disperses the elastomeric particles.  [022] EP 1 666 519 discloses a process for producing elastomeric polymer particles and a process for a resin composition containing them.  [023] EP 2 123 711 discloses a thermosetting resin composition having elastomeric polymer particles dispersed therein and a corresponding production process.  [024] None of the documents of the prior art disclose a composition as claimed or a process for obtaining it.  [BRIEF DESCRIPTION OF THE INVENTION] [025] Surprisingly, it has been found that a polymer composition comprising: a) a (meth) acrylic polymer (P1) and b) a multiphase polymer, the multiphase polymer representing at least 20% by weight of the composition can be easily dispersed in epoxy, polyester or (meth) acrylic resins.  [026] Surprisingly, it has also been found that a polymer composition comprising: a) a (meth) acrylic polymer (P1) and b) a multiphase polymer, the multiphase polymer representing at least 20 % by weight of the composition, can be used as a masterbatch for epoxy, polyester or (meth) acrylic resins.  [027] Surprisingly, it has also been found that a process for producing a polymer composition comprising the steps of: a) mixing a (meth) acrylic polymer (P1) and a multiphase polymer b ) recovering the mixture obtained from the preceding step the (meth) acrylic polymer (P1) and the multiphase polymer in step a) being in the form of an aqueous phase dispersion, makes it possible to obtain a composition of polymers that can be used as a masterbatch for epoxy, polyester or (meth) acrylic resins.  [028] Surprisingly, it has also been found that a polymer composition comprising: a) a (meth) acrylic polymer (P1) and b) a polymer obtained by a multiphase process having a) a phase (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C; b) a phase (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C the polymer obtained by the multiphase process representing at least 20% by weight of the composition a) + b), can be easily dispersed in epoxy, polyester or (meth) acrylic resins and can be used as a masterbatch for epoxy resins , polyester or (meth) acrylic.  According to a first aspect, the present invention relates to a polymer composition comprising a (meth) acrylic polymer (P1) and a multiphase polymer, wherein the multiphase polymer represents at least one less than 20% by weight, preferably at least 30% by weight, more preferably at least 40% by weight and preferably at least 50% by weight of the polymer composition.  According to a second aspect, the present invention relates to a polymer composition comprising a (meth) acrylic polymer (P1) and a multiphase polymer, said multiphase polymer comprising 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 the multiphase polymer representing at least 20% by weight, preferably at least 30% by weight, more preferably at least 40% by weight and preferably at least 50% by weight of the polymer composition.  [031] In a third aspect, the present invention relates to a process for producing a polymer composition comprising the steps of a) mixing a (meth) acrylic polymer (P1) and a multiphase polymer b) drying the mixture obtained from the preceding step the (meth) acrylic polymer (P1) and the multiphase polymer in step a) being in the form of an aqueous phase dispersion.  [032] In a fourth aspect, the present invention relates to the use of a polymer composition comprising a (meth) acrylic polymer (P1) and a multiphase polymer, the multiphase polymer accounting for at least 20% by weight. Weight, preferably at least 30% by weight, more preferably at least 40% by weight and advantageously at least 50% by weight of the composition, as the masterbatch for epoxy, polyester or (meth) acrylic resins.  [033] In a fifth aspect, the present invention relates to a process for producing a polymer composition comprising the steps of a) mixing a (meth) acrylic polymer (P) and a multiphase polymer b) recovering the mixture obtained from the preceding step, the (meth) acrylic polymer (P1) and the multiphase polymer in step a) being in the form of an aqueous phase dispersion, for use as a masterbatch for resins Epoxy, polyester or (meth) acrylic.  [034] In a sixth aspect, the present invention relates to a process for producing a masterbatch polymer composition comprising the steps of a) mixing a (meth) acrylic polymer (P1) and a phase polymer multiple b) recovering the mixture obtained from the preceding step the (meth) acrylic polymer (P1) and the multiphase polymer in step a) being in the form of an aqueous phase dispersion.  The term "polymer powder" as used refers to a grain of powder comprising a polymer in the range of at least 1 micron (μm), obtained by the agglomeration of primary particles comprising a polymer in the nanometric range.  The term "primary particle" as used refers to a spherical particle comprising a polymer in the nanometer range.  Preferably, the primary particle has an average particle size of between 20 nm and 800 nm.  [37] The term "particle size" as used refers to the average volume diameter of a particle considered spherical.  [38] The term "copolymer" as used means that the polymer consists of at least two different monomers.  [39] The term "multiphase polymer" as used refers to a polymer formed in a sequential fashion by a multiphase polymerization process.  A multiphase emulsion polymerization process is preferred in which the first polymer is a first phase polymer and the second polymer is a second phase polymer, i.e. the second polymer is formed by emulsion in the presence of the first polymer which is in emulsion.  [040] The term "(meth) acrylic" as used refers to any type of acrylic and methacrylic monomers.  [041] The term "(meth) acrylic polymer" as used means that the (meth) acrylic polymer essentially comprises polymers comprising (meth) acrylic monomers which represent up to 50% (meth) acrylic.  [042] By the expression by weight or more of the "epoxy resin" polymer as used is meant any organic compound having at least two oxirane functional groups which can be ring-opened polymerized.  [043] By the term "(meth) acrylic resin" as used is meant adhesives based on acrylic and methacrylic monomers.  [044] By the term "masterbatch" as used is meant a composition which comprises an additive at a high concentration in a carrier material.  The additive is dispersed in the support material.  [045] The multiphase polymer according to the invention has at least two phases which are different in terms of polymer composition.  [046] The multiphase polymer is preferably in the form of polymer particles believed to be spherical particles.  These particles are also called core-shell particles.  The first phase forms the core, the second phase or all subsequent phases form the respective barks.  [047] With regard to the spherical polymer particle, it has an average particle size of between 20 nm and 800 nm.  Preferably, the average particle weight of the polymer is between 40 nm and 400 nm, more preferably between 50 nm and 350 nm and advantageously between 80 nm and 300 nm.  [048] The polymer particle has a multilayer structure comprising at least one layer (A) comprising a polymer (A1) having a glass transition temperature of less than 0 ° C and another layer (B) comprising a polymer (B1) having a glass transition temperature above 60 ° C.  Preferably, the polymer (B1) having a glass transition temperature greater than 60 ° C is the outer layer of the polymer particle having a multilayer structure.  [49] The polymer particle is obtained by a multiple phase process such as a process comprising two, three or more phases.  [50] Preferably, the polymer (A1) having a glass transition temperature below 0 ° C in the layer (A) is prepared in the first phase of the multiphase process, forming the core for the polymer particle having a Multilayer structure.  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.  [051] Preferably, the polymer (B1) having a glass transition temperature above 60 ° C is prepared in the last phase of the multiphase process, forming the outer layer of the polymer particle having a multilayer structure.  [052] There could be one or more additional intermediate layers obtained by one or more intermediate phases.  [053] The glass transition temperature Tg can be estimated for example by dynamic processes such as thermomechanical analysis.  [054] With regard to the polymer (Al), in a first embodiment, it is a (meth) acrylic polymer comprising at least 50% by weight of alkyl acrylate monomers.  [055] More preferably, the polymer (A1) comprises one or more comonomers which are copolymerizable with the alkyl acrylate, as long as the polymer (A1) has a glass transition temperature of less than 0 ° C.  [056] The comonomer or comonomers in the polymer (A1) are preferably selected from (meth) acrylic monomers and / or vinyl monomers.  The (meth) acrylic comonomer in the polymer (A1) comprises monomers selected from C1-C12alkyl (meth) acrylates.  Even more preferably, the (meth) acrylic comonomer in the polymer (A1) comprises monomers of the C1-C4 alkyl methacrylate type and / or of the C1-C8 alkyl acrylate type.  [058] Most preferably, the acrylic or methacrylic comonomers of the polymer (Al) are selected from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, acrylate and the like. tert-butyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the corresponding mixtures, as long as the polymer (A1) has a glass transition temperature below 0 ° C.  [059] 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 that can be polymerized.  [060] In a specific embodiment, the polymer (Al) is a homopolymer of butyl acrylate.  [061] In another specific embodiment, the polymer (Al) is a butyl acrylate copolymer and at least one crosslinking agent.  The crosslinking agent represents less than 5% by weight of this copolymer.  [062] More preferably, the glass transition temperature Tg 10 of the polymer (Al) of the first embodiment is located between -100 ° C and 0 ° C, still more preferably between -100 ° C and -5 ° C, advantageously between -90 ° C and -15 ° C and more preferably between -90 ° C and -25 ° C.  [063] In a second embodiment, the polymer (Al) is a polymer based on silicone elastomer.  The silicone elastomer is, for example, polydimethylsiloxane.  More preferably, the glass transition temperature Tg of the polymer (A1) of the second embodiment is between -150 ° C and 0 ° C, still more preferably between -145 ° C and -5 ° C, preferably between -140 ° C. ° C and -15 ° C and more preferably between -135 ° C and -25 ° C.  [064] In a third embodiment, the polymer (A1) having a glass transition temperature of less than 0 ° C comprises at least one. less than 50% by weight of polymer units from isoprene or butadiene and phase (A) is the innermost layer of the polymer particle having the multilayer structure.  In other words, the phase (A) comprising the polymer (Al) is the core of the polymer particle.  By way of example, for the polymer (Al) of the core of the second embodiment, mention may be made of isoprene homopolymers or homopolymers of butadiene, isoprene-butadiene copolymers, copolymers of isoprene and not more than 98% by weight of a vinyl monomer and butadiene copolymers and 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.  [066] More preferably, the glass transition temperature Tg of the polymer (A1) of the third embodiment comprising at least 50% by weight of polymer units 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 more preferably between -90 ° C and -25 ° C.  [067] As regards the polymer (B1), there may be mentioned homopolymers and copolymers comprising monomers having double bonds and / or vinyl monomers.  Preferably the polymer (B1) is a (meth) acrylic polymer.  [68] Preferably, the polymer (B1) comprises at least 70% by weight of monomers selected from C1-C12alkyl (meth) acrylates.  Even more preferably, the polymer (B1) comprises at least 80% by weight of C1-C4 alkyl methacrylate monomers and / or C1-C8 alkyl acrylate type.  [69] Most preferably, the acrylic or methacrylic monomers of the polymer (B1) are selected from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methacrylate and the like. ethyl, butyl methacrylate and the corresponding mixtures as long as the polymer (B1) has a temperature of 30 ° C.  [070] Advantageously, the polymer weight of monomer units from the glass transition of at least (B1) comprises at least 70% of methyl methacrylate.  [071] Preferably, the glass transition temperature Tg of the polymer (B1) is between 30 ° C and 150 ° C.  The glass transition temperature of the polymer (B1) is more preferably between 50 ° C and 150 ° C, still more preferably between 70 ° C and 150 ° C, preferably between 90 ° C and 150 ° C and more preferably between 90 ° C. C and 130 ° C.  In one embodiment, 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).  [073] With respect to the process for producing the multiphase polymer according to the invention, it comprises the steps of a) polymerizing, by emulsion polymerization, a monomer or a mixture of monomers (Am) for obtaining at least one layer (A) comprising a polymer (Al) having a glass transition temperature below 0 ° C; b) polymerizing, by emulsion polymerization, 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 mixture of monomers (Am) and the monomer to the monomer mixture (Bm) being selected from the monomers according to the composition for the polymer (A1) and the polymer (B1) indicated above.  [074] 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 phases.  [075] Advantageously, the process for producing the multiphase polymer composition according to the invention is a multiphase process comprising the following steps of a) polymerizing, by emulsion polymerization, a monomer or a monomer mixture (Am) to obtain at least one layer (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C b) polymerizing, by emulsion polymerization, 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 [076] The monomers or monomer mixtures (Am) and (am) respectively for forming respectively the layers (A) and (B) respectively comprising the polymers (Al) and (B1) and the characteristics of the respective polymers (Al) and (B1) are identical to those described above.  [077] The process for producing the multiphase polymer may comprise additional steps for additional phases between steps a) and b).  [078] The process for producing the multiphase polymer may also include additional steps for additional phases before steps a) and b).  A seed could be used to polymerize, by emulsion polymerization, the monomer or monomer mixture (Am) to obtain the layer (A) comprising the polymer (A1) 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. [079] The multiphase polymer is obtained as an aqueous dispersion of polymer particles.  The solids content of the dispersion is between 10% by weight and 65% by weight.  [080] With regard to the (meth) acrylic polymer (P1), mention may be made of homopolymers. and copolymers of (meth) acrylic monomers.  Preferably, the (meth) acrylic polymer (P1) comprises (meth) acrylic monomers which represent up to 50% by weight or more of the (meth) acrylic polymer (P1).  More preferably, the (meth) acrylic polymer (P1) comprises at least 60% by weight of (meth) acrylic monomers and preferably at least 70% by weight.  [081] Still more preferably, the (meth) acrylic polymer (P1) comprises at least 70% by weight of monomers chosen from C1-C12 alkyl (meth) acrylates.  Advantageously preferably, the (meth) acrylic polymer (P1) comprises at least 80% by weight of C1-C4 alkyl methacrylate monomers and / or C1-C8 alkyl acrylate type monomers.  The methacrylate (meth) acrylic acid (P1) of 99.8 wt.% To 20 wt.% Is preferably selected from methyl methacrylate and 0.2 wt.% Acrylate monomer. Cl-C8-alkyl.  monomer of Cl-C8 alkyl acrylate type, methyl acrylate or butyl acrylate.  [082] In one embodiment, the polymer comprises from 80 wt% to 100 wt% methyl, preferably 80 wt% to 10 [083] In some embodiments, the (meth) acrylic polymer (P1) also includes a functional comonomer.  [084] The functional comonomer has the formula (1) O-R2 (1) O [85] wherein R1 is selected from H or CH3 and R2 is H or an aliphatic or aromatic radical having at least one atom which does not is not C or H.  [86] Preferably, the functional monomer is chosen from glycidyl (meth) acrylate, acrylic or methacrylic acid, amides derived from these acids, such as, for example, dimethylacrylamide, acrylate or methacrylate. Methoxyethyl, 2-aminoethyl acrylates or methacrylates optionally quaternized, acrylate or methacrylate monomers comprising a phosphonate or phosphate group, alkylimidazolidinone (meth) acrylates, polyethylene glycol (meth) acrylates.  Preferably, the polyethylene glycol group of polyethylene glycol (meth) acrylates has a molecular weight in the range of 400 g / mole to 10,000 g / mole.  [87] Preferably, the glass transition temperature Tg of the (meth) acrylic polymer (P1) of all embodiments 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.  [088] Preferably, the (meth) acrylic polymer (P1) of all embodiments is not crosslinked.  [089] The (meth) acrylic polymer (P1) is preferably in the form of spherical particles of polymer.  The spherical particles of the (meth) acrylic polymer (P1) have an average particle size of between 20 nm and 800 nm.  Preferably, the weight average particle size of the polymer is between 30 nm and 400 nm, more preferably between 30 nm and 350 nm and advantageously between 35 nm and 200 nm.  [090] Preferably, the (meth) acrylic polymer (P1) of all embodiments has a weight average molecular weight Mw of less than 100,000 g / mole, preferably less than 90,000 g / mole, more preferably less than 80,000 g / mol, more preferably less than 70,000 g / mol and more preferably less than 60,000 g / mol.  [91] Preferably, the (meth) acrylic polymer (P1) of all the embodiments has a weight average molecular weight Mw greater than 2000 g / mol, preferably greater than 3000 g / mol, more preferably greater than 4000 g / mole, still more preferably greater than 5000 g / mole, more preferably greater than 6000 g / mole, still more preferably greater than 6500 g / mole and still more preferably greater than 7000 g / mole.  [92] Advantageously, the average molecular weight Mw of the (meth) acrylic polymer (P1) of all the embodiments is between 2000 g / mol and 100,000 g / mol, preferably between 3000 g / mol and 90,000 g / mole and still more preferably between 4000 g / mole and 70,000 g / mole.  As regards the process for the production of the (meth) acrylic polymer (P1) according to the invention, it comprises the step of polymerization of the respective (meth) acrylic monomers.  [094] The (meth) acrylic homopolymer or copolymer (P1) could be prepared in a batch or semi-batch process: for the batch process, the monomer mixture is introduced at once just before or after the introduction of an initiator system or a part thereof for the semi-continuous process, the monomer mixture is added in multiples or continuously in parallel with the addition of the initiator (the initiator is also added multiple times or continuously) for a defined period of addition which may range from 30 to 500 minutes.  As to the process for producing the polymer composition according to the invention, it comprises the steps of a) mixing the (meth) acrylic polymer (P1) and the multiphase polymer b) recovering the mixture obtained from the previous step in the form of a polymer powder the (meth) acrylic polymer (P1) and the multiphase polymer in step a) being in the form of an aqueous phase dispersion.  The amounts of 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 part only in the 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 such that the weight ratio of the multiphase polymer based on the solid part 30 only in the 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.  [098] The amounts of 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 part only in the The mixture obtained is between 5% by weight and 99% by weight, preferably between 10% by weight and 95% by weight, more preferably between 20% by weight and 90% by weight.  [099] The recovery step b) of the process for the production of the polymer composition according to the invention is preferably carried out by coagulation or spray drying.  The process for the production of the polymer composition according to the invention may optionally comprise the additional step c) for drying the polymer composition.  By dry is meant that the polymer composition according to the present invention comprises less than 3% by weight of moisture and preferably less than 1.5% by weight of moisture and more preferably less than 1.2% by weight. % by weight of moisture.  Moisture can be measured by a thermal balance that heats the polymer composition and measures weight loss.  The process for producing the polymer composition according to the invention preferably makes it possible to obtain a polymer powder.  The polymer powder of the invention is in the form of particles.  A polymer powder particle comprises agglomerated primary polymer particles prepared by the multiphase process and the methacrylic polymer (P1).  As regards the polymer powder of the invention, it has an average particle size D50 of between 1 μm and 500 μm.  Preferably, the average 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 distribution of the particle sizes is at least 7 μm and preferably 10 μm.  The D90 of the volume distribution of particle sizes is at most 950 μm and preferably 500 μm, more preferably at most 400 μm.  The present invention also relates to the use of the polymer composition according to the invention in the form of the polymer powder as a masterbatch for thermosetting resins or thermoplastic polymers.  [0108] The masterbatch is mixed with the other resin or polymer.  The ratio of the masterbatch used is at most 90% by weight in view of the composition containing the thermosetting resin or the thermoplastic polymers and the polymer composition according to the invention.  The ratio of the masterbatch used is at least 10% by weight in view of the composition containing the thermosetting resin or the thermoplastic polymers and the polymer composition according to the invention.  The present invention relates, as a further aspect, to a modified impact-modified polymer composition.  As regards the composition of modified impact-resistant polymers according to the invention, it comprises a) a polymer (P2) and b) a (meth) acrylic polymer (P1) and c) a phase polymer multiple, and is characterized in that the multiphase polymer is at least 5% by weight of the composition.  Preferably, the modified impact-modified polymer composition according to the invention comprises a) a polymer (P2) and b) a (meth) acrylic polymer (P1) and c) a polymer obtained by a method of multiple phases having a phase (A) comprising a polymer (A1) having a glass transition temperature of less than 0 ° C; a phase (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C and it is characterized in that the multiphase polymer represents at least 5% by weight of the composition.  The multiphase polymer and the (meth) acrylic polymer (P1) are the same as those defined above.  The respective phases (A) and (B) respectively comprising the polymers (A1) and (B1) and the characteristics of the respective polymers (A1) and (B1) are identical to those described above.  With regard to the polymer (P2), according to the invention, it is a thermosetting resin R1 or a thermoplastic polymer.  The thermosetting resin R1 is preferably chosen from epoxy, polyester or (meth) acrylic resins.  As regards the epoxy resin according to the invention, it may be any organic compound having at least two oxirane functional groups which can be polymerized by ring opening.  This epoxy resin (abbreviated to E) can be on the one hand monomer or polymer and on the other hand be aliphatic, cycloaliphatic, heterocyclic or aromatic.  Examples of such epoxy resins are resorcinoldiglycidyl ether, bisphenol A-diglycidyl ether, triglycidyl-p-aminophenol, bromobisphenol F-diglycidyl ether, triglycidyl ether of m-aminophenol, tetraglycidylmethylenedianiline, triglycidyl ether of (trihydroxyphenyl) methane, phenol formaldehyde novolac polyglycidyl ethers, ortho-cresol novolak polyglycidyl ethers and tetraphenylethane tetraglycidyl ethers.  Mixtures of at least two of these resins may also be used.  In a more preferred embodiment, the modified impact-modified polymer composition of the invention comprises a) an epoxy resin E1 which has a Tg of 25 ° C or less and b) a polymer (meth). ) acrylic (P1) comprising from 80% by weight to 100% by weight of methyl methacrylate and c) a polymer obtained by a multiphase process having a phase (A) comprising a polymer (Al) having a vitreous transition temperature below 0 ° C - a phase (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C and characterized in that the multiphase polymer represents at least 5% by weight of the composition.  In a second and more preferred embodiment, the modified impact-modified polymer composition according to the invention comprises a) an epoxy resin E1 and b) a (meth) acrylic polymer (P1) comprising a functional comonomer and c) a polymer obtained by a multiphase process having a phase (A) comprising a polymer (A1) having a glass transition temperature of less than 0 ° C -a phase (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C and is characterized in that the multiphase polymer is at least 5% by weight of the composition.  Preferably, the epoxy resin El is chosen from resorcinoldiglycidyl ether, bisphenol A-diglycidyl ether, triglycidyl-p-aminophenol, bromobisphenol F-diglycidyl ether, triglycidyl ether of m-aminophenol, tetraglycidylmethylenedianiline, triglycidyl ether of trihydroxyphenyl) methane, phenol formaldehyde novolac polyglycidyl ethers, ortho-cresol novolac polyglycidyl ethers and tetraphenylethane tetraglycidyl ethers.  The modified impact-modified polymer composition according to the invention comprises between 1% and 90% of the polymer obtained by the multiphase process.  As regards the process for producing the modified impact-modified polymer composition according to the invention, it comprises the steps of: a) mixing the epoxy resin E1 with a master mixture said masterbatch being a polymer composition comprising a (meth) acrylic polymer (P1) and a multiphase polymer.  [0123] The multiphase polymer and the (meth) acrylic polymer (P1) are the same as those defined above.  [0124] The polymer composition comprising an epoxy resin may be cured.  In a third most preferred embodiment, the modified impact-modified polymer composition according to the invention comprises a) a methacrylic resin and b) a (meth) acrylic polymer (P1) comprising 80% by weight. weight at 100% by weight of methyl methacrylate and c) a polymer obtained by a multiphase process having a phase (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C. (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C and characterized in that the multiphase polymer is at least 5% by weight of the composition.  [0126] The modified impact-modified polymer composition comprising the methacrylic resin is preferably an adhesive composition.  [Evaluation Methods] Atomic Force Microscopy (AFM) is performed with a D3100 from VEECO in Tapping mode.  Two modes are used to acquire images: a height mode to obtain the topography of the surface and a phase contrast mode to obtain the viscoelastic properties.  For AFM, the sample is broken and to obtain a thin, more or less smooth surface, the sample is cooled to 23 ° -30 ° C. and cut with a microtome.  The cut slices of the sample have a thickness of about 100 nm.  [Examples] [0129] Comparative Example 1 [0130] Synthesis of the multi-phase polymer (core-shell particles) [0131] First phase - polymerization of the core: in a high-pressure reactor of 20 l: deionized water 116.5 parts, potassium salt of beef tallow fatty acid as an emulsifier 0.1 part, 1,3-butadiene 21.9 parts, t-dodecyl mercaptan 0.1 part and the p-menthane hydroperoxide 0.1 part as initial charge of vat.  The 43 ° C. solution, at which time a solution is heated, with stirring, with a redox-based catalyst is charged (water 4.5 parts, sodium tetrapyrophosphate 0.3 part, ferrous sulfate 0.004 part and dextrose 0.3 part ), which actually initiates the polymerization.  Then, the solution is further heated to 56 ° C and maintained at this temperature for a period of three hours.  Three hours after initiation of the polymerization, a second batch of monomers (77.8 parts of BD, tdodecyl mercaptan 0.2 part), one half of an additional charge of emulsifier and reducer (deionized water 30, 4 25 parts, potassium salt of beef tallow fatty acid as emulsifier 2.8 parts, dextrose 0.5 part) and additional initiator (p-menthane hydroperoxide 0.8 part) are added continuously for eight hours.  After completion of the addition of the second monomer, the residual charge of emulsifier and reductant plus initiator is added continuously for a further five hours.  Thirteen hours after initiation of the polymerization, the solution is heated to 68 ° C. and allowed to react until at least 20 hours have elapsed since the initiation of the polymerization, with production of polybutadiene elastomer latex, R1.  The resulting polybutadiene elastomer latex (R1) contains 38% solids and has a weight average particle size of about 160 nm.  Second phase - polymerization of bark 1 (outer bark): 75.0 parts, based on solids, of a polybutadiene elastomer latex R1 are charged to a 3.9 liter reactor, 37.6 parts of deionized water and 0.1 part of sodium formaldehyde sulfoxylate.  The solution is stirred, purged with nitrogen and heated to 77 ° C.  When the solution reaches 77 ° C., a mixture of 22.6 parts of methyl methacrylate, 1.4 parts of divinylbenzene and 0.1 part of t-butyl hydroperoxide initiator is continuously added in 70 minutes. the addition being followed by a holding period of 80 minutes.  Thirty minutes after the start of the holding period, 0.1 part of sodium formaldehyde sulfoxylate and 0.1 part of t-butyl hydroperoxide are added to the reactor in one portion.  After the 80 minute holding period, a graft copolymer latex stabilizer emulsion is added.  The stabilizing emulsion is prepared by mixing 3.2 parts of deionized water (based on the weight of the graft copolymer), 0.1 part of oleic acid, 0.1 part of potassium hydroxide and 0% of potassium hydroxide. 9 parts of octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.  The resulting core-shell latex (MP1 multiphase polymer) has a mean particle size of about 180 nm and a solids content of 38%.  Coagulation: In a 3 l jacketed vessel equipped with a stirrer, 500 g of core-shell particles (MP1 multi-phase polymer) are successively placed in order to obtain a solids content. 14.1%.  With stirring at 300 rpm, the heat of the solution is raised to 52 ° C and then 1.6% aqueous sulfuric acid solution is injected, resulting in a coagulated material which is heat-treated at 96 ° C. vs.  The pH is adjusted between 2 and 6 using NaOH during coagulation.  Then, the coagulated material is filtered on a centrifuge and washed with deionized water.  After filtration and drying, a powder with less than 1% residual volatiles is obtained.  [0134] This powder (at a ratio of 20%) is dissolved at room temperature in a DGEBA epoxy resin.  Then, the hardener component (Jeffamine) is added and mixed (so as to obtain the 10% coagulated material in the final resin) and cured at 120 ° C for 2 hours.  The dispersion of the additive is observed using an AFM equipment, the dispersion is not good and we can observe aggregates of particles (cf.  AFM snapshot in Figure 1).  Example 1: The same MP1 multiphase polymer was prepared as in Comparative Example 1.  Synthesis of the copolymer P1: semi-continuous process: 1700 g of deionized water, 0.01 g of Fe504 and 0.032 g of sodium salt of ethylenediaminetetraacetic acid (dissolved) are charged into a reactor with stirring. 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 salt of tallow fatty acid as an emulsifier (dissolved 44 g of water) and the mixture is stirred until complete dissolution.  Three purges are successively carried out with nitrogen under vacuum and the reactor is left under a slight vacuum.  The reactor is 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 is degassed with nitrogen for 30 minutes.  The reactor is heated to 63 ° C and maintained at this temperature.  Then, the monomer mixture is introduced into the reactor in 180 minutes using a pump.  A solution of 5.33 g of tert-butyl hydroperoxide (dissolved in 100 g of deionized water) is introduced in parallel (same addition time).  The pipes are rinsed with 50 g and 20 g of water.  Then, the reaction mixture is heated to a temperature of 80 ° C and then allowed to complete the polymerization for 60 minutes after the end of the addition of the monomers.  The reactor is cooled to 30 ° C.
    [0002] The solids content obtained is 34.2%. Coagulation: A mixture of 139.14 g of multiphase polymer latex MP1 and 51.54 g of copolymer latex P1 is diluted with 309.32 g of deionized water to obtain 500 g of a latex mixture having a solids content of 14.1%. In a 3-liter jacketed vessel equipped with a stirrer, the 500 g of the prepared mixing latex are introduced. With stirring at 5,300 rpm, the heat of the solution is raised to 52 ° C and then an aqueous solution of sulfuric acid is injected at 1.6%, which results in a coagulated material which is heat-treated at 96 ° C. vs. The pH is adjusted between 2 and 6 using NaOH during coagulation. Then, the coagulated material is filtered on a centrifuge and washed with deionized water. After filtration and drying, a powder having less than 1% of residual volatile substances is obtained. This powder (at a ratio of 20%) is dissolved at ambient temperature in a DGEBA epoxy resin. Then, the hardener component (Jeffamine) is added and mixed (so as to obtain the coagulated material at 10% in the final resin) and cured at 120 ° C for 2 hours. The dispersion of the additive is observed using an AFM equipment, the dispersion is very good and well-dispersed particles can be observed (see photograph).
    权利要求:
    Claims (23)
    [0001]
    REVENDICATIONS1. A polymer composition comprising a (meth) acrylic polymer (P1), a multiphase polymer, the multiphase polymer representing at least 20% by weight of the polymer composition.
    [0002]
    2. Polymer composition according to claim 1, characterized in that the (meth) acrylic polymer (P1) has a weight average molecular weight Mw less than 100,000 g / mol.
    [0003]
    3. Composition of polymers according to claim 1 or 2, characterized in that the composition comprises at least 30% of multiphase polymer.
    [0004]
    4. Polymer composition according to any one of claims 1 to 3, characterized in that the multiphase polymer comprises a) a phase (A) comprising a polymer (A1) having a glass transition temperature of less than 0 ° C b) a phase (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C.
    [0005]
    5. Polymer composition according to claim 4, 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).
    [0006]
    6. The polymer composition as claimed in claim 4, wherein the polymers (A1) and (B1) are acrylic or methacrylic polymers. 5 3031108 28
    [0007]
    7. Polymer composition according to any one of claims 4 to 5, characterized in that the polymer (A1) comprises at least 50% by weight of polymer units from isoprene or butadiene.
    [0008]
    8. Polymer composition according to any one of claims 1 to 7, characterized in that the (meth) acrylic polymer (P1) comprises from 80% by weight to 100% by weight of methyl methacrylate, preferably 80% by weight. 99.8% by weight of methyl methacrylate and 0.2% by weight to 20% by weight of a C1-C8 acrylate monomer.
    [0009]
    9. Polymer composition according to any one of claims 1 to 7, characterized in that the (meth) acrylic polymer (P1) also comprises a functional comonomer.
    [0010]
    Polymer composition according to claim 9, characterized in that the functional comonomer is selected from glycidyl (meth) acrylate, acrylic or methacrylic acid, amides derived from these acids, such as, for example, dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, optionally quaternized 2-aminoethyl acrylates or methacrylates, acrylate or methacrylate monomers comprising a phosphonate or phosphate group, alkylimidazolidinone (meth) acrylates, Polyethylene glycol (meth) acrylates, preferably the polyethylene glycol group, of polyethylene glycol (meth) acrylates have a molecular weight in the range of 400 g / mole to 10,000 g / mole.
    [0011]
    A process for producing a polymer composition, comprising the steps of a) mixing a (meth) acrylic polymer (P1) and a multiphase polymer b) recovering the mixture obtained from the previous step in the form of of a polymer powder, the (meth) acrylic polymer (P1) and the multiphase polymer in step a) being in the form of an aqueous phase dispersion. 5
    [0012]
    12. Process according to claim 11, characterized in that the multiphase polymer represents at least 20% by weight of the dry polymer composition.
    [0013]
    13. Method according to any one of claims 11 to 12, characterized in that the recovery step b) is carried out by coagulation or spray drying.
    [0014]
    14. Use of the polymer composition according to any one of claims 1 to 10 or obtained by the process according to any one of claims 11 to 13 as a masterbatch in thermosetting resins or a thermoplastic polymer.
    [0015]
    15. Use of the polymer composition according to any one of claims 1 to 10 or obtained by the process according to any one of claims 11 to 13 as a masterbatch in thermosetting resins, the resin being selected from epoxy resins. , polyester or (meth) acrylic. 25
    [0016]
    16. Use according to claim 15, characterized in that the thermosetting resin is an epoxy resin.
    [0017]
    17. A modified impact resistance polymer composition comprising a) a polymer (P2) and b) a (meth) acrylic polymer (P1) and c) a polymer obtained by a multiphase process having a phase ( A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C; a phase (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C characterized in that the multiphase polymer represents at least 5% by weight of the composition. 5
    [0018]
    18. Composition of impact-modified polymers according to claim 17, characterized in that the polymer (P2) is a thermosetting resin R1 which is preferably chosen from epoxy, polyester or (meth) acrylic resins.
    [0019]
    Modified impact-resistant polymer composition according to claim 17, characterized in that the polymer (P2) is a thermosetting resin R1 which is an epoxy resin El having a Tg of 25 ° C or less, the polymer (meth) ) acrylic (P1) comprising 80% by weight to 100% by weight of methyl methacrylate.
    [0020]
    20. A modified impact resistance polymer composition according to claim 17, characterized in that the polymer (P2) is a thermosetting resin R1 which is an epoxy resin El and the (meth) acrylic polymer (P1) comprises a functional comonomer . 25
    [0021]
    21. Composition of modified impact-resistant polymers according to claim 17, characterized in that the polymer (P2) is a methacrylic resin, the (meth) acrylic polymer (P1) comprising 80% by weight to 100% by weight of methacrylate. of methyl. 30
    [0022]
    22. Composition of impact-modified polymers according to any one of claims 17 to 21, characterized in that the (meth) acrylic polymer (P1) has a weight average molecular weight Mw less than 100,000 g / mol. 35
    [0023]
    23. A process for producing a modified impact-modified polymer composition, comprising the step of: a) mixing an epoxy resin E1 with a masterbatch characterized in that said masterbatch comprises a polymer composition according to any of claims 1 to 10 or obtained by the process of any of claims 11 to 13.
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    同族专利:
    公开号 | 公开日
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    US20180002520A1|2018-01-04|
    KR20170098913A|2017-08-30|
    BR112017013691A2|2018-03-13|
    CN107250260A|2017-10-13|
    RU2017126213A3|2019-05-08|
    FR3031108B1|2018-08-17|
    JP2018500441A|2018-01-11|
    EP3237500A1|2017-11-01|
    EP3237500B1|2022-01-26|
    RU2703621C2|2019-10-21|
    US10513603B2|2019-12-24|
    WO2016102666A1|2016-06-30|
    RU2017126213A|2019-01-24|
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    法律状态:
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    2016-07-01| PLSC| Publication of the preliminary search report|Effective date: 20160701 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1463306|2014-12-24|
    FR1463306A|FR3031108B1|2014-12-24|2014-12-24|COMPOSITION COMPRISING A MULTIPHASE POLYMER, METHOD FOR PREPARING THE SAME AND USE THEREOF|FR1463306A| FR3031108B1|2014-12-24|2014-12-24|COMPOSITION COMPRISING A MULTIPHASE POLYMER, METHOD FOR PREPARING THE SAME AND USE THEREOF|
    JP2017534209A| JP2018500441A|2014-12-24|2015-12-23|Composition comprising multi-stage polymer, process for its preparation and use thereof|
    RU2017126213A| RU2703621C2|2014-12-24|2015-12-23|Composition containing polymer obtained by multi-step method, method for production thereof and use thereof|
    EP15817865.7A| EP3237500B1|2014-12-24|2015-12-23|Composition comprising a multistage polymer, it method of preparation and its use|
    US15/537,465| US10513603B2|2014-12-24|2015-12-23|Composition comprising a multistage polymer, its method of preparation and its use|
    KR1020177020650A| KR20170098913A|2014-12-24|2015-12-23|Composition comprising a multistage polymer, it method of preparation and its use|
    CN201580076849.XA| CN107250260A|2014-12-24|2015-12-23|Composition, Its Preparation Method And Use comprising multistage polymerization thing|
    SG11201705040QA| SG11201705040QA|2014-12-24|2015-12-23|Composition comprising a multistage polymer, it method of preparation and its use|
    PCT/EP2015/081159| WO2016102666A1|2014-12-24|2015-12-23|Composition comprising a multistage polymer, it method of preparation and its use|
    BR112017013691A| BR112017013691A2|2014-12-24|2015-12-23|composition comprising a multistage polymer, its method of preparation and its use|
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