• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a polymer composition comprising an epoxy resin and a multi-step polymer. In particular, the present invention relates to a polymer composition comprising an epoxy resin and a multi-step polymer that can be used as a masterbatch. More particularly, the present invention also relates to a process for preparing a polymer composition comprising an epoxy resin and a multi-stage polymer by spray drying or coagulation.
    公开号:FR3031109A1
    申请号:FR1463304
    申请日:2014-12-24
    公开日:2016-07-01
    发明作者:Raber Inoubli；Rosangela Pirri；Philippe Hajji
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a polymer composition comprising an epoxy resin and a multi-step polymer. In particular, the present invention relates to a polymer composition comprising an epoxy resin and a multi-stage 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 an epoxy resin and a multi-stage polymer by spray drying or coagulation. [Technical problem] [004] Thermoset polymers are the most widely used as matrices 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 curing agent. 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 material is added to increase the impact resistance. Such an elastomer may be a polymer made in multi-stage form of core-shell particles, a phase of which (step) is an elastomer. [008] The multi-stage polymer in the form of core-shell particles is in the form of an agglomerated dry powder, 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 polymer particles made in multi-step is very difficult or almost impossible. [009] There is also a complex technology for incorporating a polymer produced in multi-step form. of core-shell particles, without drying the polymer made in multi-step after its synthesis process, in an epoxy resin by the gradual change of the continuous dispersion medium of the core-shell particles of water into organic solvent. The object of the present invention is to obtain a polymer composition comprising a multi-step polymer which can be easily dispersed in uncured epoxy resins. [011] An objective of the present invention also lies in obtaining an effective and homogeneous distribution of the polymer made in multi-step in epoxy resins. Another object of the present invention is to avoid agglomerated particles of polymer made in multi-steps. [013] A further object of the present invention is the strengthening of the cured epoxy resin matrix by homogeneous distribution of the impact modifier in the form of a multi-step polymer. Still another object of the present invention is a process for the production of a polymer composition comprising a multi-step polymer which can be easily dispersed in uncured epoxy resins. [015] Yet another additional object is a process for the preparation of a polymer composition comprising a multi-stage polymer which can be readily dispersed in uncured epoxy resins and having an efficient and homogeneous distribution. of the polymer made in multi-step in epoxy resins. Still another object is the use of a polymer composition comprising a multi-step polymer which is in the form of a masterbatch for modifying the impact resistance of epoxy resins. Still another object of the present invention is to provide a process for producing a free-flowing dry powder polymer composition comprising an epoxy resin and a multi-stage polymer for use as a masterbatch for the modification of the impact resistance of epoxy resins having a homogeneous distribution of the polymer made in multi-steps. (BACKGROUND OF THE INVENTION) Background Art [018] EP 0 228 450 discloses elastomer-modified epoxy compounds The composition comprises a continuous phase of epoxy resin and a discontinuous phase of dispersed rubber particles in the continuous phase The rubber particles are grafted rubber particles The rubber particles are dispersed in the epoxy phase by a mixing or shearing device [019] EP 0 911 358 discloses the use of copolymers However, block copolymers are relatively expensive and it is preferred to disperse standard core-shell shock modifiers in the epoxy resin. [2020] FR 2934866 discloses a blister pack in the form of epoxy resin. a specific core-shell polymer having a functional shell comprising hydrophilic monomers. used as impact modifiers in thermoset polymers. [021] EP 1 632 533 discloses a process for the production of a modified epoxy resin. The epoxy resin composition has rubber-like polymer particles dispersed therein by a process which brings the particles into contact with an organic medium which disperses the rubber 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 rubbery polymer particles dispersed therein and a corresponding production process. [024] None of the documents of the prior art discloses 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) an epoxy resin E1, said E1 epoxy resin being solid at a temperature below 25 ° C and b) a multi-step polymer wherein the multi-step polymer of at least 20% by weight of the composition can be readily dispersed in an E2 epoxy resin. [026] Surprisingly, it has also been found that a polymer composition comprising: a) an epoxy resin E1, said epoxy resin E1 being solid at a temperature below 25 ° C, and b) a polymer made of The multi-step polymer comprising at least 20% by weight of the composition can be used as the masterbatch for epoxy resins. [027] Surprisingly, it has also been found that a method for producing a polymer composition comprising the steps of: a) mixing an epoxy resin El, said epoxy resin E1 being solid at a temperature below 25 ° C, and a polymer made in multi-step b) recovering the mixture obtained from the previous step the epoxy resin (El) and the polymer made in multi steps in step a) being in the form of a dispersion in aqueous phase, provides a polymer composition which can be used as a masterbatch for epoxy resins. [028] Surprisingly, it has also been found that a polymer composition comprising: a) an epoxy resin E1, said epoxy resin E1 being solid at a temperature below 25 ° C, and b) a polymer obtained by a multi-step process having a) a step (A) comprising a polymer (A1) having a glass transition temperature of less than 0 ° C (b) a step (B) comprising a polymer (B1) having a glass transition temperature at least 30 ° C the polymer obtained by the multi-step process representing at least 20% by weight of the composition a) + b), can be easily dispersed in an epoxy resin E2 and can be used as a masterbatch for epoxy resins. According to a first aspect, the present invention relates to a polymer composition comprising an epoxy resin E1, said epoxy resin E1 being solid at a temperature below 25 ° C, and a polymer the multi-step polymer is at least 20% by weight, preferably at least 30% by weight, more preferably at least 40% by weight and advantageously at least 50% by weight of the composition. 030] According to a second aspect, the present invention relates to a polymer composition comprising an epoxy resin El, said epoxy resin El being solid at a temperature below 25 ° C, and a polymer made in multi stages, said polymer made in multi steps comprising a) a step (A) comprising a polymer (A1) having a glass transition temperature of less than 0 ° C (b) a step (B) comprising a polymer e (B1) having a glass transition temperature of at least 30 ° C the multi-step polymer comprising at least 20% by weight, preferably at least 30% by weight, more preferably at least 40% by weight, and advantageously at least 50% by weight of the composition. [031] In a third aspect, the present invention relates to a process for producing a polymer composition comprising the steps of a) mixing an epoxy resin El, said epoxy resin El being solid at a temperature below 25 ° C. C, and a polymer made in multi steps b) recovering the mixture obtained from the previous step the epoxy resin El and the polymer made in multi steps in step a) being in the form of a dispersion in aqueous phase. [032] In a fourth aspect, the present invention relates to the use of a polymer composition comprising an epoxy resin E1, said epoxy resin being solid at a temperature below 25 ° C, and a polymer made in multi steps, the multi-step polymer being 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 composition, as a masterbatch for epoxy resins. [033] In a fifth aspect, the present invention relates to a process for producing a polymer composition comprising the steps of a) mixing an epoxy resin E1, said epoxy resin E1 being solid at a temperature below 25 ° C. and a multi-step polymer b) recovering the mixture obtained from the preceding step the epoxy resin El and the multi-step polymer in step a) being in the form of an aqueous dispersion, for use as a masterbatch for epoxy resins. [034] In a sixth aspect, the present invention relates to a process for producing a masterbatch polymer composition comprising the steps of a) mixing an El epoxy resin, said El epoxy resin being solid to a temperature below 25 ° C, and a polymer made in multi steps b) recovering the mixture obtained from the previous step epoxy resin El and the polymer made in multi steps in step a) being in the form of a dispersion in aqueous phase. [035] The term "polymer powder" as used refers to a powder grain 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. [036] The term "primary particle" as used refers to a spherical particle comprising a polymer in the nanoscale range. Preferably, the primary particle has an average particle size of between 20 nm and 800 nm. [037] The term "particle size" as used refers to the average volume diameter of a particle considered spherical. The term "copolymer" as used means that the polymer consists of at least two different monomers. [039] The term "multi-stage polymer" as used refers to a polymer formed in a sequential manner by a multiple step polymerization process. A multi-stage emulsion polymerization process is preferred in which the first polymer is that obtained in the first steps and the second polymer is that obtained in the second step, i.e. the second polymer is formed by emulsion polymerization. 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 comprises essentially polymers comprising (meth) acrylic monomers which represent up to 50% by weight or more of the polymer (meth) acrylic acid. By the term "epoxy resin" as used is meant any organic compound having at least two oxirane functional groups which can be ring-opened polymerized. [043] By the expression "epoxy resin which is solid below a certain temperature", it is meant that the epoxy resin has either a melting point Tm greater than this certain temperature, or a glass transition temperature Tg greater than this certain temperature. [044] By the term "masterbatch" as used is meant a composition which comprises an additive at a high concentration in a support material. The additive is dispersed in the support material. As regards the epoxy resin E1 according to the invention, it is solid at a temperature below 25 ° C, preferably below 50 ° C and more preferably below 70 ° C. [046] These epoxy resins can, on the one hand, be monomers or polymers and on the other hand be aliphatic, cycloaliphatic, heterocyclic or aromatic. Examples of such epoxy resins are resorcinoliglycidyl ether, bisphenol A-diglycidyl ether, triglycidyl-p-aminophenol, bromobisphenol F-diglycidyl ether, m-aminophenol triglycidyl ether, tetraglycidylmethylenedianiline, triglycidyl ether resins. (trihydroxyphenyl) methane, phenol formaldehyde novolac polyglycidyl ethers, ortho-cresol novolak polyglycidyl ethers and tetraphenylethane tetraglycidyl ethers. Blends of at least two of these resins may also be used. [047] The multi-stage polymer according to the invention has at least two synthesis steps which are different in terms of polymer composition. [048] The polymer obtained in multi-stage is preferably in the form of spherical particles of polymer. These particles are also called core-shell particles. The first step or phase forms the core, the second step or phase or all subsequent steps or phases form the respective barks. [049] 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 50 nm and 400 nm, more preferably between 75 nm and 350 nm and advantageously between 80 nm and 300 nm. [050] The polymer particle has a multilayer structure 35 comprising at least one layer (A) comprising a polymer (Al) having a glass transition temperature below 0 ° C and another layer (B) comprising a polymer (B1) having a glass transition temperature above 30 ° C. Preferably, the polymer (B1) having a glass transition temperature above 30 ° C is the outer layer of the polymer particle having a multilayer structure. Preferably, the layer (A) is the first layer and the layer (B) comprising the polymer (B1) is grafted onto the layer (A) comprising the polymer (Al). [51] The polymer particle is obtained by a multi-step process such as a process comprising two, three or more steps. The polymer (Al) having a glass transition temperature below 0 ° C in the layer (A) is never prepared during the last step of the multi-step process. This means that the polymer (Al) is never in the outer layer of the particle having a multilayer structure.
    [0002] The polymer (A1) 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. [52] Preferably, the polymer (A1) having a glass transition temperature of less than 0 ° C in the layer (A) is prepared in the first step of the multi-step 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. [053] Preferably, the polymer (B1) having a glass transition temperature above 30 ° C is prepared in the last step of the multi-step process, forming the outer layer of the polymer particle having a multilayer structure. [054] There may be one or more additional intermediate layers obtained by one or more intermediate steps. [055] The glass transition temperature Tg can be estimated for example by dynamic processes such as thermomechanical analysis. [056] With regard to the polymer (A1), in a first embodiment, it is a (meth) acrylic polymer comprising at least 50% by weight of alkyl acrylate monomers. [057] More preferably, the polymer (Al) 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. [058] The comonomer (s) in the (Al) polymer are preferably selected from (meth) acrylic monomers and / or vinyl monomers. [059] The (meth) acrylic comonomer in the polymer (Al) comprises monomers selected from C1-C12 alkyl (meth) acrylates.
    [0003] 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. [060] Most preferably, the acrylic or methacrylic comonomers of the polymer (Al) are chosen from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, acrylate and the like. tert-butyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as the polymer (Al) has a glass transition temperature below 0 ° C. [061] Preferably the polymer (Al) is crosslinked. This means that a crosslinking agent is added to the other monomer (s). A crosslinker comprises at least two groups that can be polymerized. [062] In a specific embodiment, the polymer (Al) is a homopolymer of butyl acrylate. [063] In another specific embodiment, the polymer (Al) is a copolymer of butyl acrylate and at least one crosslinking agent. The crosslinking agent represents less than 5% by weight of this copolymer. [064] More preferably, the glass transition temperature Tg of the polymer (A1) of the first embodiment is 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. [065] In a second embodiment, the polymer (Al) is a silicone rubber-based polymer. The silicone rubber is for example polydimethylsiloxane. More preferably, the glass transition temperature Tg of the polymer (A1) of the second embodiment is between -150 ° C and 000, still more preferably between -145 ° C and -5 ° C, preferably between -140 ° C. and -15 ° C and more preferably between -135 ° C and -25 ° C. [066] In a third embodiment, the polymer (A1) having a glass transition temperature of less than 0 ° C comprises at least 50% by weight of polymeric units derived from isoprene or butadiene and the 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. [68] More preferably, the glass transition temperature Tg of the polymer (Al) 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. [69] Regarding 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. [070] 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. [071] Most preferably, the acrylic or methacrylic monomers of the polymer (B1) are chosen from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methacrylate and the like. ethyl, butyl methacrylate and the corresponding mixtures, as long as the polymer (B1) has a glass transition temperature of at least 30 ° C. [072] Advantageously, the polymer (B1) comprises at least 70% by weight of monomeric units derived from methyl methacrylate. [073] 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 60 ° C and 150 ° C, still more preferably between 80 ° C and 150 ° C, preferably between 90 ° C and 150 ° C and more preferably between 100 ° C and 100 ° C. ° C and 150 ° C. [074] With regard to the process for producing the multi-step polymer according to the invention, it comprises the steps of a) polymerizing, by emulsion polymerization, a monomer or a mixture of monomers (Am) for to obtain a 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 or mixture of monomers (Bm) being selected from the respective monomers according to the composition for the polymer (Al) and the polymer (B1) indicated above. [075] Preferably, step a) is performed before step b). More preferably, step b) is carried out in the presence of the polymer (A1) obtained in step a), if there are only two steps. [076] Advantageously, the process for producing the multi-step polymer composition according to the invention is a multi-step process comprising the following steps of a) polymerizing, by emulsion polymerization, a monomer or a mixture of monomers (Am) to obtain a 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. [077] The monomers or monomer mixtures (Am) and (Bm) respectively for forming respectively the layers (A) and (B) respectively comprising the polymers (Al) and (B1) and the characteristics of the polymers (Al) and (B1) are identical to those described above. [078] The process for producing the multi-step polymer may comprise additional steps for additional phases between steps a) and b). [079] The process for producing the multi-step 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 30 is preferably a thermoplastic polymer having a glass transition temperature of at least 20 ° C. [080] The multi-step 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. [081] With regard to the process for producing the polymer composition according to the invention, it comprises the steps of a) mixing an epoxy resin El, said epoxy resin El 5 being solid at a lower temperature at 25 ° C., and the polymer made in multi-step steps b) recovering the mixture obtained from the preceding step in the form of a polymer powder and the epoxy resin El, and the polymer produced in multi-step in step a) being in the form of a dispersion in aqueous phase. [082] The quantities of aqueous dispersion of the epoxy resin E1 and of the aqueous dispersion of the polymer produced in multi-stage are chosen so that the weight ratio of the polymer produced in multi-stage on the basis of the solid part only in the mixture obtained is at least 5% by weight, preferably at least 10% by weight, more preferably at least 20% by weight and preferably at least 50% by weight. [83] The amounts of the aqueous dispersion of the epoxy resin E1 and the aqueous dispersion of the polymer made in multi-stage are chosen such that the weight ratio of the multiphase polymer based on the solid part 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. [84] The quantities of the aqueous dispersion of the epoxy resin E1 and the aqueous dispersion of the polymer made in multi-stage are chosen such that the weight ratio of the multiphase polymer based on the solid part only in 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. [085] 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. [086] If the epoxy resin E1 according to the invention is solid at a temperature below 25 ° C, the recovery step is preferably carried out by coagulation. If the epoxy resin E1 according to the invention is solid at a temperature below 7000, the recovery step is carried out by spray drying or coagulation. [88] The process for producing the polymer composition according to the invention may optionally include the additional step c) for drying the polymer composition. [89] Drying means that the polymer composition according to the present invention comprises less than 3% by weight of moisture and preferably less than 1.5% by weight of moisture and more preferably less than 1.2% by weight. % by weight of moisture. [90] Moisture can be measured by a thermal balance that heats the polymer composition and measures weight loss. [091] 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. One particle of polymer powder comprises agglomerated primary polymer particles prepared by the multi-step process and the El epoxy resin. [092] With respect to the polymer powder of the invention, it has an average volume size particle size D50 between 1 μm and 500 μm. Preferably, the average particle volume 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. [093] The D10 of the volume distribution of the particle sizes is at least 7 μm and preferably at least 10 μm. [094] The D90 of the particle size volume distribution is at most 950 μm and preferably at most 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 in thermosetting resins. Preferably, the thermosetting resin is an epoxy resin E2. [096] The masterbatch is mixed with the other resin. The ratio of the masterbatch used is at most 90% by weight in view of the composition containing the thermosetting resin 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 and the polymer composition according to the invention. [097] In another embodiment, the polymer composition according to the invention can also be used as it is. The present invention relates, as a further aspect, to a polymer composition comprising an epoxy resin. [099] As regards the composition of polymers comprising an epoxy resin according to the invention, it comprises a) an epoxy resin E2 and b) an epoxy resin El, said epoxy resin El being solid at a temperature below 25 ° C, and c) a polymer produced in multi-steps, and is characterized in that the multi-stage polymer represents at least 5% by weight of the composition. [100] Preferably, the polymer composition comprising an epoxy resin according to the invention comprises a) an epoxy resin E2 and b) an epoxy resin El, said epoxy resin E1 being solid at a temperature below 25 ° C, and C) a polymer obtained by a multi-step process comprising -a step (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C -a step (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C and characterized in that the multi-stage polymer is at least 5% by weight of the composition. [101] The multistep polymer and the epoxy resin E1 are the same as those defined above. [102] 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. [103] With regard to the epoxy resin E2, according to the invention, it can be any organic compound having at least two oxirane functional groups which can be polymerized by ring opening. [104] The epoxy resin E2 could be identical to the epoxy resin El. [105] The epoxy resin E2 could be different from the epoxy resin El. The epoxy resin E2 could be solid or liquid. By the term "epoxy resin which is liquid below a certain temperature" it is meant that the epoxy resin has either a melting point Tm lower than this certain temperature, or a glass transition temperature Tg lower than this temperature. certain temperature. [106] This epoxy resin E2 can be on the one hand monomer or polymer and on the other hand be aliphatic, cycloaliphatic, heterocyclic or aromatic. [107] Preferably, the epoxy resin E2 is selected from epoxy resins based on resorcinoldiglycidyl ether, bisphenol adiglycidyl ether, triglycidyl-p-aminophenol, bromobisphenol F-diglycidyl ether, triglycidyl ether m-aminophenol, tetraglycidylmethylenedianiline, triglycidyl ether of (trihydroxyphenyl) methane, polyglycidyl ethers of phenol formaldehyde novolac, ortho-cresol novolak polyglycidyl ethers and tetraphenylethane tetraglycidyl ethers. Mixtures of at least two of these resins may also be used. [108] The polymer composition comprising an epoxy resin according to the invention comprises between 1% and 90% of the polymer obtained by the multi-step process. [109] With regard to the process for producing the polymer composition comprising an epoxy resin according to the invention, it comprises the steps of [110] mixing the epoxy resin E2 with a master mix [111] said mixture master being a polymer composition comprising an epoxy resin El and a polymer made in multi steps. [112] The multistage polymer and the epoxy resin E1 are the same as those defined above. [113] The epoxy resin comprising the polymer composition can be cured. [114] In yet another aspect, the present invention relates to a thermoset resin obtained by curing the polymer composition comprising an epoxy resin according to the invention. [115] [Figures] [116] Figure 1 - Microscopy of Comparative Example 1: AFM and Optical Microscopy. Optical microscopy of the surface of a sample cutout shows visible heterogeneities thanks to white dots. AFM analysis in white dot areas shows a large number of aggregates of polymer particles made in multi-steps. In other areas, there are significantly fewer polymer particles made in multi-stage, occasionally having aggregates. [117] Figure 2 - Microscopy of Example 1: AFM and Optical Microscopy. Optical microscopy of the surface of a sample cut shows homogeneity. AFM analysis shows a good distribution of the polymer particles made in multi-steps. [118] [Methods of Evaluation] [119] Optical microscopy is performed with a ZEISS model [120] Atomic Force Microscopy (AFM) is performed with a VEECO D3100 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. [121] For AFM, the sample is broken and to obtain a thin, more or less smooth surface, the sample is cooled to -90 ° C and cut with a microtome. The cut slices of the sample have a thickness of about 100 nm. [122] [Examples] [123] Comparative Example 1: Multi-stage polymer latex (MP1) was prepared according to the technique described in US Pat. No. 4,278,576, which uses standard emulsion polymerization technology. In other words, the acrylic core / shell polymer is prepared using 84.2 parts of butyl acrylate, 0.4 part of butylene glycol diacrylate and 0.4 part of allyl methacrylate as the elastomeric core, and then polymerizes with 15 parts of methyl methacrylate. The solids content is 40%. The multi-stage polymer latex is spray-dried and a powder having less than 1% residual volatiles is obtained. [124] The polymer made in multi-stage MP1 comprises a (meth) acrylic polymer core having a Tg <-20 ° C as the first phase and a (meth) acrylic polymeric shell having a Tg> 30 ° C as the last phase. [125] The multi-stage polymer MP1 powder is dispersed at room temperature (25 ° C) with an epoxy resin (Huntsman LY556). A polyetheramine hardener (Huntsman, Jeffamine T403) is added at room temperature. The mixture is cured in an oven at 120 ° C for 2 hours. [126] As shown in Figure 1, microscopy shows an inhomogeneous distribution of multi-step polymer particles within the cured epoxy resin. There are sites where there are virtually no particles and sites where there are many particles and agglomerated particles due to the poor dispersibility within the epoxy resin. [127] Example 1: The multi-stage polymer latex (MP1) is prepared according to the technique described in US Pat. No. 4,227,576, which uses standard emulsion polymerization technology. In other words, the acrylic core / shell polymer is prepared using 84.2 parts of butyl acrylate, 0.4 part of butylene glycol diacrylate and 0.4 part of allyl methacrylate as the elastomeric core, and then polymerizes with 15 parts of methyl methacrylate. The solids content is 40%. [128] 2421 g of the multi-stage polymer latex (40% solids content) were mixed with 2096 g of an aqueous dispersion of a solid epoxy resin (EPI-REZ7 resin 3522-W-60). Momentive Specialty Chemicals Inc. (59.2% solids) and 4054 g deionized water The dispersion mixture has a solids content of 30.6% and is spray dried to obtain a powder having less than 1% residual volatiles [129] This powder is dispersed at room temperature (25 ° C) in the same epoxy resin (Huntsman LY556) and with the same polyetheramine hardener (Huntsman, Jeffamnine T403) as those used in Comparative Example 1. The mixture is cured in an oven at 120 ° C for 2 hours [130] As shown in Figure 2, microscopy shows a homogeneous distribution of the multiphase polymer particles within hardened epoxy resin, this is due to the good the dispersion of the composition according to the invention within the epoxy resin
    权利要求:
    Claims (16)
    [0001]
    REVENDICATIONS1. A polymer composition, comprising an epoxy resin E1, said epoxy resin E1 being solid at a temperature below 25 ° C, and a polymer made in multi-stage, the multi-stage polymer representing at least 20% by weight of the composition.
    [0002]
    2. Polymer composition according to claim 1, characterized in that the epoxy resin is solid at a temperature below 50 ° C and preferably below 70 ° C.
    [0003]
    3. Composition of polymers according to claim 1 or 2, characterized in that the composition comprises at least 30% by weight of the polymer produced in multi steps.
    [0004]
    4. Composition of polymers according to any one of claims 1 to 3, characterized in that the epoxy resin is chosen from resorcinoldiglycidylether, bisphenol A-diglycidylether, triglycidyl-p-aminophenol, bromobisphenol F-diglycidylether, triglycidylether aminophenol, tetraglycidylmethylenedianiline, trihydroxyphenylmethane triglycidyl ether, phenolformaldehyde novolac polyglycidyl ethers, ortho-cresol novolac polyglycidyl ethers and tetraphenylethane tetraglycidyl ethers or mixtures thereof.
    [0005]
    5. Polymer composition according to any one of claims 1 to 4, characterized in that the polymer produced in multi-stage comprises a) a layer (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° (B) a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C. 5
    [0006]
    6. Polymer composition according to claim 5, characterized in that the polymers (Al) and (B1) are acrylic or methacrylic polymers.
    [0007]
    7. Polymer composition according to claim 5, characterized in that the polymer (Al) is a polymer based on silicone rubber.
    [0008]
    8. Polymer composition according to claim 5, characterized in that the polymer (A1) comprises at least 50% by weight of polymer units derived from isoprene or butadiene.
    [0009]
    9. Polymer composition according to any one of claims 5 to 8, characterized in that the layer (A) is the first layer and the layer (B) comprising the polymer (B1) is grafted onto the layer (A). comprising the polymer (Al).
    [0010]
    A process for producing a polymer composition, comprising the steps of a) mixing an epoxy resin E1, said epoxy resin E1 being solid at a temperature below 25 ° C, and a polymer made in multi-step b ) recovering the mixture obtained from the previous step, the epoxy resin El and the polymer made in multi-step in step a) being in the form of a dispersion in aqueous phase.
    [0011]
    11. A process according to claim 10, characterized in that the multi-stage polymer is at least 20% by weight of the polymer composition. 3031109 24
    [0012]
    12. Method according to any one of claims 10 to 11, characterized in that the recovery step b) is carried out by coagulation or spray drying. 5
    [0013]
    13. Use of the polymer composition according to any one of claims 1 to 9 or obtained by the process according to any one of claims 10 to 12 as a masterbatch in thermosetting resins. 10
    [0014]
    14. Use according to claim 13, characterized in that the thermosetting resin is an epoxy resin E2.
    [0015]
    15. A polymer composition comprising an epoxy resin, comprising a) an epoxy resin E2 and b) the polymer composition according to any one of claims 1 to 9 or obtained by the process according to any one of claims 10 to 12 20
    [0016]
    A process for producing a polymer composition comprising an epoxy resin, comprising the step of: a) mixing the epoxy resin E2 with a masterbatch characterized in that said masterbatch comprises a polymer composition according to any of claims 1 to 9 or obtained by the process according to any one of claims 10 to 12.
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    同族专利:
    公开号 | 公开日
    EP3237501B1|2021-07-21|
    FR3031109B1|2018-08-17|
    EP3237501A1|2017-11-01|
    BR112017013703A2|2018-03-13|
    RU2017126036A3|2019-05-16|
    CN107250266B|2021-10-29|
    US10597499B2|2020-03-24|
    CN107250266A|2017-10-13|
    RU2017126036A|2019-01-24|
    US20170362395A1|2017-12-21|
    SG11201705085UA|2017-07-28|
    RU2703620C2|2019-10-21|
    BR112017013703B1|2022-02-01|
    JP2018500439A|2018-01-11|
    KR20170101254A|2017-09-05|
    WO2016102658A1|2016-06-30|
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    法律状态:
    2015-11-10| PLFP| Fee payment|Year of fee payment: 2 |
    2016-07-01| PLSC| Publication of the preliminary search report|Effective date: 20160701 |
    2016-11-11| PLFP| Fee payment|Year of fee payment: 3 |
    2017-11-13| PLFP| Fee payment|Year of fee payment: 4 |
    2019-11-14| PLFP| Fee payment|Year of fee payment: 6 |
    2020-11-12| PLFP| Fee payment|Year of fee payment: 7 |
    2021-11-15| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1463304A|FR3031109B1|2014-12-24|2014-12-24|POLYMER COMPOSITION, PROCESS FOR PREPARING THE SAME, USE THEREOF, AND COMPOSITION COMPRISING THE SAME|
    FR1463304|2014-12-24|FR1463304A| FR3031109B1|2014-12-24|2014-12-24|POLYMER COMPOSITION, PROCESS FOR PREPARING THE SAME, USE THEREOF, AND COMPOSITION COMPRISING THE SAME|
    KR1020177020410A| KR20170101254A|2014-12-24|2015-12-23|Polymer composition, its method of preparation, its use and composition comprising it|
    JP2017534198A| JP2018500439A|2014-12-24|2015-12-23|Polymer composition, process for its preparation, use thereof and composition comprising it|
    RU2017126036A| RU2703620C2|2014-12-24|2015-12-23|Polymer composition, method for production thereof, use thereof and composition containing thereof|
    US15/536,168| US10597499B2|2014-12-24|2015-12-23|Polymer composition, its method of preparation, its use and composition comprising it|
    SG11201705085UA| SG11201705085UA|2014-12-24|2015-12-23|Polymer composition, its method of preparation, its use and composition comprising it|
    BR112017013703-8A| BR112017013703B1|2014-12-24|2015-12-23|Polymer composition, its method of preparation, its use and composition comprising the same|
    EP15820161.6A| EP3237501B1|2014-12-24|2015-12-23|Polymer composition, its method of preparation, its use and composition comprising it|
    PCT/EP2015/081142| WO2016102658A1|2014-12-24|2015-12-23|Polymer composition, its method of preparation, its use and composition comprising it|
    CN201580076837.7A| CN107250266B|2014-12-24|2015-12-23|Polymer composition, method for the production thereof, use thereof and composition comprising the same|
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