• 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 multi-stage polymer, its composition and method of preparation. In particular, the present invention relates to a multi-stage polymer, its composition and method of preparation and its use as impact modifier in thermoplastic compositions. More particularly, the present invention relates to a method of manufacturing a polymeric composition comprising a multi-stage polymer and its use as a shock modifier in thermoplastic compositions.
    公开号:FR3028859A1
    申请号:FR1461388
    申请日:2014-11-24
    公开日:2016-05-27
    发明作者:Christophe Navarro；Aline Couffin；Rosangela Pirri；Frederic Malet
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION [001] The present invention relates to a multi-stage polymer, its composition and method of preparation. More particularly, the present invention relates to a multi-stage polymer, its composition and method of preparation and its use as impact modifier in thermoplastic compositions. More particularly, the present invention relates to a process for producing a polymer composition comprising a multi-stage polymer and its use as a shock modifier in thermoplastic compositions. [Technical Problem] [004] Shock modifiers are widely used to improve the impact resistance of thermoplastic compositions in order to compensate for their intrinsic brittleness or embrittlement occurring at temperatures below zero, notch sensitivity. and the propagation of cracks. Therefore, an improved impact-resistant polymer is a polymeric material whose impact resistance has been increased by the incorporation of a phase consisting of 30 microdomains of an elastomeric material. [005] This is generally done by introducing sub-microscopic elastomer particles into a polymer matrix that can absorb the energy of a shock or dissipate it. One possibility is to introduce the elastomeric particles as core-shell particles. These core-shell particles, which generally have an elastomeric core and a polymeric bark, have the advantage of an appropriate particle size of the elastomeric core for effective reinforcement and grafted bark to obtain the adhesion and compatibility with the thermoplastic matrix. [006] Shock reinforcement performance is a function of the particle size, in particular of the elastomer part of the particle, and its quantity. There is an optimum average particle size for obtaining the highest impact strength for a given amount of added impact modifier particles. [007] These primary impact modifiers are generally added to the thermoplastic material in the form of a particle powder. This powder consists of agglomerated primary shock modifying particles. During the mixing of the thermoplastic material with the powder particles, the primary impact modifier particles are found and are dispersed more or less homogeneously in the thermoplastic material. [008] Although the particle size of the impact modifier particles is in the nanometer range, the size of the agglomerated powder particles is in the micrometer range. Agglomeration during recovery can be achieved by several methods, such as, for example, spray drying, coagulation by salt addition or shearing, lyophilization or a combination of spray drying and coagulation techniques. . It is important to have a shock modifying powder which has no negative influence on the thermoplastic polymer. As a negative influence, it is understood, for example, the color stability, the thermal stability, the hydrolytic stability of the thermoplastic polymer comprising the impact modifier, either as a function of time or temperature. or both. [010] "These influences can occur because of the core-bark architecture but, more particularly, the impurities and by-products used during the synthesis and treatment of the impact modifier powder. There is no particular purification step of the impact modifier, but only a solid / liquid separation, therefore more or less significant amounts of any chemical compound (impurities, by-products) used are still incorporated in the modifier. These quantities may vary, however, these chemical compounds should have no influence or only minor influence on the thermoplastic material, generally such as, for example, degradation of optical and / or mechanical properties. and / or rheological over time and / or temperature and / or hygrometry. [011] Careful washing or purification may be certain compounds from impurities or products used during the synthesis which could have a negative influence of the impact modifier powder on the performance of the thermoplastic polymer composition. [012] On the other hand, all the processes are extremely cost sensitive. A slight improvement in a process can lead to a significant commercial advantage. [013] The objective of the present invention is to provide a multi-stage polymer having a satisfactory thermal stability. [014] An additional object of the present invention is also to produce a multistage polymer having satisfactory thermal stability and which can be used as an impact modifier. [015] Another additional objective of the present invention is to provide a multi-step manufacturing process of a polymer having a satisfactory thermal stability. [016] An additional object of the present invention is a thermoplastic composition comprising a multi-step polymer, said composition having satisfactory thermal stability. BACKGROUND OF THE INVENTION [017] JP-A1-2005-248096 discloses a process for manufacturing a transparent thermoplastic resin having improved color. A graft polymer latex is prepared by graft polymerization followed by coagulation of the latex with an inorganic salt of alkaline earth metal to recover a product in powder form. An alkali metal salt of phosphoric acid is added previously in said graft polymer latex. [018] US5290867 discloses a process for producing an emulsion graft copolymer, which comprises grafting a vinyl aromatic monomer and a comonomer onto a rubber latex in the presence of an iron redox system ( II) as a polymerization catalyst and coagulation of the graft with an alkaline earth metal compound characterized in that the pH of the coagulated concentrated suspension is adjusted to a value in the range of 8 to 12. [019] ] Document WO2009 / 126373 describes functional MBS impact modifiers synthesized by multistage emulsion polymerization. At the end of the synthesis, the resulting reaction mixture is coagulated to separate the polymer. The coagulation treatment is carried out by contacting the reaction mixture with a saline solution (calcium chloride or aluminum chloride - CaCl 2 or AlCl 3) or an acidified solution with concentrated sulfuric acid and then for separation, by filtration. solid product resulting from coagulation, and the solid product is then washed and dried to obtain a graft copolymer in the form of a powder. [020] EP2465882 discloses improved impact resistant thermoplastic compositions. The thermoplastic compositions comprise a polymeric impact modifier with a core-shell structure made by a multi-step process and recovered by a special process by controlling and adjusting the pH value. Coagulation is performed with salts and, preferably, magnesium sulfate. [021] EP2189497 discloses polymer compositions containing phosphates and in particular the process for obtaining them. The polymer composition is a polymer obtained by a multi-step process and is a shock modifier. The phosphate salts are introduced to reduce or eliminate the deleterious effects of the multivalent cations that are present in the polymer obtained by a multi-step process. The use of such a method allows a coagulated polymer to be used as an impact modifying additive added to a matrix without causing the deleterious effects of the multivalent cations that would otherwise occur. [022] WO2009 / 118114 discloses a modified impact polycarbonate composition having a good combination of color stability, hydrolysis and melting. The elastomeric core is based on polybutadiene. For the preparation of the grafted elastomer polymer, salts of fatty acids, in particular carboxylic acids, are used. The yellow index of the compositions obtained with an injection temperature of 260 ° C. is very high: 20 or more. [023] In the prior art, coagulation was performed with multivalent cations since the polymer is much more easily coagulated. The present invention utilizes alkali metal cations for coagulation. [BRIEF DESCRIPTION OF THE INVENTION] [024] Unexpectedly, it has been discovered that a method of making a polymeric composition comprising a multi-stage polymer comprising the steps of a) emulsion polymerization of a monomer or mixture of monomers (Am) to obtain during this step a layer (A) comprising a polymer (A1) having a glass transition temperature of less than 0 ° C, b) polymerization by emulsion polymerization in the presence of the polymer obtained in step a) of a monomer or mixture of monomers (Bm) to obtain during this next step a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 45 ° C, c) coagulation of the multi-stage polymer with an alkali metal salt, d) washing the multi-step polymer, e) adjusting the pH value after coagulation to between 5 and 10, f) add an aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V, produces a polymer powder having satisfactory thermal aging properties. [025] Unexpectedly, it has also been found that a thermoplastic composition comprising a polymer obtained by a multi-step manufacturing process, comprising the steps of a) polymerization by emulsion polymerization of a monomer or mixture of monomers (Am ) to obtain during this step a layer (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C, b) polymerization by emulsion polymerization in the presence of the polymer obtained in step a) of a monomer or mixture of monomers (Bm) to obtain during this next step a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 45 ° C, c) coagulation of the polymer obtained by multistage 20 with an alkali metal salt, d) washing the multi-step polymer, e) adjusting the pH value after coagulation to between 5 and 10, f) adding a solution or dissolving aqueous persion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V, produces a thermoplastic composition having satisfactory thermal aging properties. In a first aspect, the present invention relates to a process for producing a polymeric composition comprising a multi-stage polymer, comprising the steps of: a) emulsion polymerization polymerization; a monomer or mixture of monomers (Am) for producing a layer (A) comprising a polymer (Al) having a glass transition temperature below 0 ° C., b) polymerization-by emulsion polymerization in the presence of the polymer obtained in step a) of a monomer or mixture of monomers (Bm) to obtain during this next step a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 45 ° C (C) coagulation of the multi-stage polymer with an alkali metal salt; (d) washing of the multi-stage polymer; (e) adjustment of the pH value after coagulation to a given value. ur between 5 and 10, f) adding an aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V. [027] According to a second aspect, the present invention relates to a thermoplastic composition comprising a multi-step polymer obtained by a process for producing a polymer composition comprising said multi-stage polymer comprising the steps of a) polymerization by polymerization. in emulsion of a monomer or mixture of monomers (Am) to obtain during this step a layer (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C. b) polymerization by emulsion polymerization in presence of the polymer obtained in step a) of a monomer or mixture of monomers (Bm) to obtain during this next step a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 45 ° C, c) coagulation of the multi-stage polymer with an alkali metal salt, 3028859 d) washing of the multi-stage polymer, e) adjustment the pH value after coagulation to a value between 5 and 10, f) adding an aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus is in the oxidation state of + III or + V, The term "polymer powder" in the present context refers to a polymer comprising powder grains of the order of at least 1 micron (μm) obtained by agglomeration of primary particles comprising a polymer of the invention. nanometer order. [029] The term "primary particle" in the present context refers to a particle comprising a copolymer of the order of one nanometer. Preferably, the primary particle has a weight average particle size of between 50 nm and 500 nm. [030] The term "particle size" in the present context refers to the volume average diameter of a particle considered to be spherical. The term "copolymer" in the present context means that the polymer consists of at least two different monomers. [032] "Multistage polymer" in the present context refers to a polymer formed sequentially by a multi-step polymerization process. It is preferred a multi-step emulsion polymerization process in which the first polymer is a first stage polymer and the second polymer is a second stage polymer, i.e. the second polymer is formed by polymerization. in emulsion in the presence of the first emulsion polymer, with at least two steps which are different in terms of composition. [033] The term "(meth) acrylic" in the present context refers to all types of acrylic and methacrylic monomers. [034] The term "(meth) acrylic polymer" in the present context means that the (meth) acrylic polymer essentially comprises polymers comprising (meth) acrylic monomers which constitute 50% by weight or more of the polymer (meth) )acrylic. The term "impact modifier" in the present context refers to a compound comprising an elastomer or a rubber that can be added or incorporated into a thermoplastic compound in order to improve its impact resistance. The term "elastomer" in this context refers to the thermodynamic state of the polymer above its glass transition. [037] With regard to the multistage polymer of the invention, it is a polymer particle having a multilayer structure comprising at least one layer (A) comprising a polymer (Al) having a temperature of glass transition below 0 ° C and at least one further layer (B) comprising a polymer (B1) having a glass transition temperature greater than 45 ° C. [038] The layer (A) / layer (B) ratio in the multilayered polymer is not particularly limited, but is preferably in a weight range between 10/90 and 95/5, more preferably 40 / 60 and 95/5 preferably 60/40 to 90/10 and most preferably between 70/30 and 90/10. The polymer particle having a multilayer structure is spherical. The polymer particle having a multilayer structure is also referred to as the primary particle. The primary particle has a weight average particle size of between 20 nm and 500 nm. Preferably, the weight average particle size of the polymer particle is between 50 nm and 400 nm, more preferably between 75 nm and 350 nm and advantageously between 80 nm and 300 nm. The polymer particle of the invention is obtained by a multi-step process, for example two or three steps or more. [041] Preferably, the polymer (A1) having a glass transition temperature of less than 0 ° C in layer (A) is not manufactured in the last step of the multi-step process. The polymer (A1) having a glass transition temperature below 0 ° C in the layer (A) never forms the outer layer or outer shell of the polymer particle having the multilayer structure. [042] Preferably the polymer (B1) having a glass transition temperature greater than 45 ° C in the layer (B) is the outer layer of the polymer particle having the multilayer structure. [043] There may be additional intermediate layers made by intermediate steps between the polymer (A1) having a glass transition temperature of less than 0 ° C in the layer (A) and the layer (B) comprising a polymer (B1 ) having a glass transition temperature above 45 ° C. This would lead to a multilayer particle. [044] The glass transition temperature (Tg) of the polymer (Al) is less than 0 ° C, preferably less than -10 ° C, preferably less than -20 ° C and most preferably less than -25 ° C and most preferably less than -40 ° C. [045] More preferably, the glass transition temperature Tg of the polymer (A1) is between -120 ° C. and 0 ° C., more preferably between -90 ° C. and -10 ° C. and advantageously between -80 ° C. and -25 ° C. [046] Preferably, the glass transition temperature Tg of the polymer (B1) is between 45 ° C and 150 ° C. The glass transition temperature of the polymer (B1) is more preferably from 60 ° C to 150 ° C, still more preferably from 80 ° C to 150 ° C and preferably from 90 ° C to 150 ° C. [047] The glass transition temperature Tg can be estimated, for example, by dynamic processes such as thermomechanical analysis. [048] The polymer composition of the invention in the form of polymer particles of a multi-layered polymer may also be in the form of a polymer powder. The polymer powder comprises agglomerated primary polymer particles made by the multi-step process. [049] As regards the polymer powder of the invention, it has a median particle size in volume D50 of between 1 μm and 500 μm. Preferably, the volume median 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. [50] The D10 of the volume particle size distribution is at least 7 μm and preferably 10 μm. [51] The D90 of the volume particle size distribution is at most 800 μm and preferably 500 μm, more preferably at most 350 μm. [052] Regarding the polymer (A1), there may be mentioned homopolymers and copolymers comprising monomers with double bonds and / or vinyl monomers. [053] In a first embodiment, the polymer (Al) is chosen from isoprene homopolymers or butadiene homopolymers, isoprene-butadiene copolymers and isoprene copolymers with at most 98% by weight. vinyl monomer and butadiene copolymers with at most 98% by weight of a vinyl monomer. the vinyl monomer may be styrene, alkylstyrene, acrylonitrile, alkyl (meth) acrylate, or butadiene or isoprene. In a specific embodiment, the polymer (Al) is a homopolymer of butadiene. [054] In a second embodiment, the polymer (Al) is a (meth) acrylic polymer. A (meth) acrylic polymer according to the invention is a polymer comprising at least 50% by weight, preferably at least 60% by weight and more preferably at least 70% by weight of monomers derived from acrylic or methacrylic monomers. The (meth) acrylic polymer according to the invention comprises less than 50% by weight, preferably less than 40% by weight and more preferably less than 30% by weight of non-acrylic or methacrylic monomers, which can be copolymerized with the monomers acrylic or methacrylic. [055] More preferably, the polymer (A1) of the second embodiment comprises at least 70% by weight of 20 monomers selected from (C1-C12) alkyl (meth) acrylates. Even more preferably, the polymer (A1) comprises at least 80% by weight of C1 to C4 alkyl methacrylate monomers and / or C1 to C8 alkyl acrylate monomers. [056] Most preferably, the acrylic or methacrylic monomers of the polymer (Al) are selected from methyl acrylate. ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, provided that the polymer (A1) has a glass transition temperature of less than 0 ° C. [057] The polymer (Al) can be fully or partially crosslinked. The only operation necessary is the addition of at least one difunctional monomer during the preparation of the polymer (A1). These difunctional monomers may be chosen from poly (meth) acrylic esters of polyols, such as butanediol di (meth) acrylate and trimethylolpropane trimethacrylate. Other multifunctional monomers are, for example, divinylbenzene, trivinylbenzene, and triallyl cyanurate. The core may also be crosslinked by introducing into the latter, by grafting or as a comonomer during the polymerization, unsaturated functional monomers such as unsaturated carboxylic acid anhydrides, unsaturated carboxylic acids and unsaturated epoxides. Mention may be made, for example, of maleic anhydride, (meth) acrylic acid and glycidyl methacrylate.
    [0002] The crosslinking can also be carried out using the intrinsic reactivity of the monomers, for example in the case of diene monomers. [058] With regard to the polymer (Bi), there may be mentioned homopolymers and copolymers comprising monomers with double bonds and / or vinyl monomers. [059] The polymer (131) is selected from homopolymers of styrene, homopolymers of alkylstyrene or homopolymers of methyl methacrylate, or copolymers comprising at least 70% by weight of one of the above monomers and from minus one comonomer selected from the other monomers above, another alkyl (meth) acrylate, vinyl acetate and acrylonitrile. The bark 30 can be functionalized by introducing into the latter, by grafting or as a comonomer during the polymerization, unsaturated functional monomers such as unsaturated carboxylic acid anhydrides, unsaturated carboxylic acids and unsaturated epoxides.
    [0003] Mention may be made, for example, of maleic anhydride, (meth) acrylic acid, glycidyl methacrylate, hydroxyethyl methacrylate and alkyl (meth) acrylamides. [060] Preferably, the polymer (B1) is also a (meth) acrylic polymer. [061] Preferably, the polymer (B1) comprises at least 70% by weight of monomers selected from (C1-C12) alkyl (meth) acrylates. Even more preferably, the polymer (B1) comprises at least 80% by weight of C1 to C4 alkyl methacrylate monomers and / or C1 to C8 alkyl acrylate monomers. [062] In a preferred manner, all 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 mixtures thereof, provided that the polymer (B1) has a glass transition temperature of at least 60 ° C. [063] Advantageously, the polymer (B1) comprises at least 70% by weight of monomer units derived from methyl methacrylate. [064] The polymer (B1) can be crosslinked by adding at least one multifunctional monomer during the preparation of the polymer (B1). [065] The multistage polymer of the invention having a multilayer structure comprising at least one layer (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C and another layer (B) comprising a polymer (B1) having a glass transition temperature above 45 ° C, does not include alkaline earth metals or intentionally added salt ions. [066] Without intentional addition means that traces of alkaline earth metals in the form of ions or salts can be accidentally added as minor impurities with other ions or salts in the composition. For example, in particular, calcium impurities in sodium compounds are mentioned. The trace or minor impurity alkaline earth metals are less than 30 ppm, preferably less than 20 ppm and more preferably less than 10 ppm and preferably less than 9 ppm of the layered polymer composition. multiple. In addition, the multivalent cations represent less than 50 ppm, preferably less than 40 ppm, more preferably less than 30 ppm and desirably less than 20 ppm of the multi-layer polymer composition. The multivalent cations have the general formula Mb +, where M represents the cation, with b> 1, and preferably 5> b> 1. The multivalent cations comprising the alkaline earth metals in the composition can be analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES). [070] The multi-step polymer of the invention having a multilayer structure has a pH value between 5 and 10 and preferably between 6 and 9, more preferably between 6 and 7.5 and advantageously between 6 and 7. [071] The multistage polymer of the invention comprises a phosphorus-containing compound wherein the phosphorus has the oxidation state of + III or + V. [072] The multi-stage polymer comprises at least 350 ppm, preferably at least 360 ppm, more preferably at least 370 ppm, still more preferably at least 380 ppm, more preferably at least 390 ppm, and more preferably at least 400 ppm. phosphorus which has the oxidation state of + III or + V. Phosphorus is part of a phosphorus-containing compound. The content of the phosphorus-containing compound is calculated and expressed as phosphorus in view of the composition of the multi-layer polymer composition and not the phosphorus-containing compound. [073] The multi-stage polymer comprises at most 2000 ppm, preferably at most 1900 ppm and more preferably at most 1800 ppm phosphorus which has the oxidation state of + III or + V. Phosphorus is part of a phosphorus-containing compound. [074] The multi-stage polymer comprises between 350 ppm and 2000 ppm, preferably between 370 ppm and 1900 ppm and more preferably between 390 ppm and 1800 ppm phosphorus which has the oxidation state of + III or + V. Phosphorus is part of a phosphorus-containing compound. [075] The amount of phosphorus in the multi-stage polymer can be estimated by inductively coupled plasma atomic emission spectrometry (ICP-AES). [076] The oxidation state is related to the nature of the phosphorus-containing compound added to the composition. Preferably, there is no voluntary addition of reducing or oxidizing agents in order to modify the oxidation state of the phosphorus in the phosphorus-containing compound. [077] The phosphorus-containing compound is preferably selected from an organophosphorus compound, a phosphate salt, phosphoric acid, phosphonate salts, phosphonic acid and their respective esters and mixtures thereof. [078] An organophosphorus compound in the present invention refers to compounds with PC and POC bonds [079]. More preferably, the phosphorus-containing compound is selected from an organophosphorus compound having a POC bond, a phosphate salt, phosphoric acid, phosphonate salts, phosphonic acid and esters and mixtures thereof. [080] Phosphate salts are salts which have as anion dihydrogen phosphate (H2PO4), hydrogen phosphate (HP042-) or phosphate (P043). [081] Phosphonate salts are salts which have as anion dihydrogenphosphonate (H2PO3), or hydrogenphosphonate (HP032-). [082] With regard to the method of manufacturing a polymeric composition comprising a multistage polymer comprising the steps of a) emulsion polymerization polymerization of a monomer or mixture of monomers (Am) to obtain during this step a layer (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C, b) polymerization by emulsion polymerization in the presence of the polymer obtained in step a) of a monomer or mixture of monomers (Bm) to obtain during this next step a layer (B) comprising a polymer (81) having a glass transition temperature of at least 45 ° C, c) coagulation of the multi-step polymer with an alkali metal salt (d) washing the polymer obtained by multistage steps; e) adjusting the pH value after coagulation to a value between 5 and 10; f) adding an aqueous solution comprising a compound containing ph phosphorus in which the phosphorus has the oxidation state of + III or + V. [083] Preferably, the method of making a polymeric composition comprising the multi-stage polymer comprises the steps in the indicated order. [084] Preferably, in step d), the pH value is adjusted between 6 and 9, more preferably between 6 and 7.5 and advantageously between 6 and 7. [085] The method may comprise the step additional g) drying of the polymer composition. A dry polymer composition according to the invention is a composition which comprises less than 1% moisture or water. The moisture content of a polymeric composition can be measured with a thermobalance. The drying of the polymer can be carried out in an oven or vacuum oven with heating of the composition for 48 hours at 50 ° C. [087] The respective monomers or monomer mixtures (Am) and (Bm) to form the layers (A) and (B) respectively comprising the polymers (A1) and (B1) respectively and the characteristics of the respective polymers (A1) and (B1) are the same as those defined above for the definition of the polymers (A1) and (B1) for the composition. [088] The emulsion polymerization during the step for layer (A) may be a semicontinuous monomer addition process, a semicontinuous addition process of monomers or a micro-agglomeration process. [089] Chain transfer agents are also useful in forming the polymer (Al). Useful chain transfer agents include those known in the art, including, but not limited to, terdodecylmercaptan, n-dodecylmercaptan, noctylmercaptan, and mixtures of chain transfer agents. The chain transfer agent is used at levels of 0 to 2 percent by weight, based on the total content of core monomers in the monomer mixture (Am). [090] Preferably, the polymer (B1) is grafted onto the polymer prepared in the previous step. [091] Polymerization initiators useful in the production of polymers (A1) and (B1) include, but are not limited to, a persulfate salt such as potassium persulfate, ammonium persulfate, and persulfate sodium; an organic peroxide such as tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, p-menthane hydroperoxide, and diisopropylbenzene hydroperoxide; an azo compound such as azobisisobutyronitrile, and azobisisovaleronitrile; or an oxidoreducing initiator. However, it is preferable to use oxidation-reduction type catalyst systems formed by the combination of a peroxide compound, for example as mentioned above, with a reducing agent, in particular such as an alkali metal sulfite. , an alkali metal bisulfite, sodium formaldehyde sulfoxylate (NaHSO2HCHO), an alkaline salt of an organic sulfinic acid derivative, ascorbic acid, glucose, and in particular those of said catalyst systems which are water-soluble, e.g. potassium persulfate / sodium metabisulfite or alternatively, diisopropylbenzene hydroperoxide / sodium formaldehyde sulfoxylate or even more complicated systems such as, for example, ferrous sulfate / dextrose / sodium pyrophosphate. [092] The initiators do not contain alkaline earth metals (Group IIA of the Periodic System of Elements) intentionally added. The initiator may, however, contain other multivalent cations that are not alkaline earth metals. [093] For the emulsion polymerization, during the two steps to form the layer (A) comprising the polymer (Al) and the layer (B) comprising a polymer (B1), as an emulsifying agent, one Any of the known surfactants, whether anionic, nonionic or even cationic, may be used. In particular, the emulsifying agent may be chosen from anionic emulsifying agents, such as sodium or potassium salts of fatty acids, in particular sodium laurate, sodium stearate, sodium palmitate, sodium oleate, mixed sodium or potassium sulphates and fatty alcohols, in particular sodium lauryl sulphate, sodium or potassium salts of sulphosuccinic esters, sodium or potassium salts of alkylarylsulphonic acids , especially sodium dodecylbenzenesulfonate, and sodium or potassium salts of fatty acid monoglyceride monosulfonates, or dodecyl-diphenyl-ether-disulphonic acid, potassium dodecyl-diphenyl ether-disulfonate, dodecyl ammonium di-phenyl ether-disulfonate and sodium dodecyl-diphenyl ether-disulfonate, or alternatively from nonionic surfactants, such as the reaction products of ethylene oxide and alkylphenol or aliphatic alcohols, alkylphenols. Mixtures of such surfactants may also be used, if necessary. [094] More preferably, the emulsifying agent is selected from an anionic surfactant. The coagulation in step c) of the process of the invention is carried out by aggregation of the primary polymer particles at the end of the emulsion polymerization by adding an aqueous electrolyte solution with stirring. Multivalent cations should be avoided in the electrolyte solution. No multivalent cation is intentionally added to the electrolyte solution. [096] Preferably, the coagulation is performed with a solution comprising an alkali metal salt. More preferably, coagulation is effected with a solution comprising an alkali metal salt which has a solubility in water of at least 10 g / l. [097] More preferably, the alkali metal salt is a sodium or potassium salt. For example, the alkali metal salt may be selected from NaCl, KCl, Na2SO4, Na3PO4 Na2F1PO4, but is not limited to this list. [098] The washing in step d) of the process of the invention is carried out with water, dilute aqueous solutions or aqueous buffer solutions. [099] The pH adjustment in step e) of the process of the invention is preferably carried out by adding sodium or potassium hydroxide or aqueous buffer solution after the coagulation step. After the adjusting step, the pH is between 5 and 10, preferably between 6 and 9, more preferably between 6 and 7.5, and advantageously between 6 and 7. [0103] Step f) relates to addition of an aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus is in the oxidation state of 15 + III or + V. Preferably, step f) concerning the addition of an aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V is carried out after the coagulation step c). [0102] In order to add a solution or dispersion comprising a phosphorus-containing compound, solution or dispersion is prepared by simply a known defined amount of the phosphorus-containing compound with water. In one embodiment, the aqueous solution or dispersion comprising the phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V is added by washing the multi-layered polymer which contains less 60% by weight of water with said aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V. In a second embodiment, the aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V is added to the wet cake after the aqueous step. said coagulation mixture and the filtration step. After filtration, a wet cake is obtained which contains less than 60% by weight of water. Then the wet cake is dried. In a third embodiment, the aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V is added during the drying step of the polymer obtained. in multi-steps, when the multi-stage polymer composition further comprises at least 10% by weight of water. No further separation between the liquid phase which may contain solids or salts and the solid phase occurs. The entire phosphorus added remains with the multi-stage polymer. The phosphorus-containing compound is preferably selected from an organophosphorus compound, a phosphate salt, phosphoric acid, phosphonate salts, phosphonic acid and their respective esters and mixtures thereof. The general structure of the phosphate ester P (= O) (OR) 2, wherein at least one R group is an alkyl group. The phosphonates are phosphonic acid esters and have the general formula RP (= O) (O121) 2, wherein at least one R or R 'group is an alkyl group. [0108]. An organophosphorus compound in the present invention refers to compounds with P-C and P-O-C bonds. More preferably, the phosphorus-containing compound is selected from an organophosphorus compound having a POC bond, a phosphate salt, phosphoric acid, phosphonate salts, phosphonic acid and esters and mixtures thereof. this. The phosphate salts are salts which have as anion dihydrogenphosphate (H 2 PO 4 -), hydrogen phosphate (HPO 4 -) or phosphate (PO 4 -). Phosphonate salts are salts which have as anion dihydrogenphosphonate (H 2 PO 3 -), or hydrogenophosphonate (HPO 32-). The present invention further relates to the use of the multistage polymer as impact modifier in thermoplastic polymers. The present invention further relates to a thermoplastic composition comprising the multi-stage polymer and a thermoplastic polymer. As regards the thermoplastic polymer which is part of the thermoplastic composition according to the invention, this may be chosen from polyvinyl chloride (PVC), chlorinated polyvinyl chloride (C15 PVC), polyesters such as that, for example, poly (ethylene terephthalate) (PET) or poly (butylene terephthalate) (PBT), polyhydroxyalkanoates (PHA) or polylactic acid (PLA), cellulose acetate, polystyrene (PS) polycarbonates (PC), polyethylene, poly (methyl methacrylates) (PMMA), copolymers of (meth) acrylic acid, thermoplastic poly (methyl methacrylate-co-acrylate), poly (alkylene terephthalates), polyvinylidene fluoride, polyvinylidene chloride, polyoxymethylene (POM), semi-crystalline polyamides, amorphous polyamides, semi-crystalline copolyamides, amorphous copolyamides, polyetheramides, polyesteramides, copolymers of styrene and acrylonitrile (SAN), and their respective mixtures or alloys. According to a preferred embodiment, the thermoplastic resin composition comprises polycarbonate (PC) and / or polyester (PET or PBT) or PC or polyester alloys. The alloys, for example, may be PC / ABS (poly (acrylonitrile-co-butadiene-co-styrene), PC / ASA, PC / polyester or PC / PLA. [0115] Preferably, if the thermoplastic polymer in the thermoplastic polymer composition comprises polycarbonate (PC) and / or polyester (PET or PBT) or PC or polyester alloys, the polymer (A) of the multi-layer polymer is selected from homopolymers of isoprene or homopolymers of butadiene, copolymers of isoprene-butadiene, copolymers of isoprene with not more than 98% by weight of a vinyl monomer and butadiene copolymers with not more than 98% by weight of a vinyl monomer. In the case of polycarbonate (PC), it can be aromatic, semi-aromatic and / or aliphatic (in particular based on isosorbide). [0117] As regards the thermoplastic composition comprising the polymer obtained by multistage and a thermoplastic polymer, the prop ortions between the multi-layer polymer of the invention and the thermoplastic polymer are between 0.5 / 99.5 and 50/50, preferably between 1/98 and 30/70, more preferably between 2/98 and 20/80 and advantageously between 2/98 and 15/85. [Evaluation methods] [0118] Glass transition temperature The glass transition (Tg) of the polymers is measured with a material capable of thermomechanical analysis. An RDAII "RHEOMETRICS DYNAMIC ANALYZER" analyzer provided by Rheometrics Company was used. Thermo-mechanical analysis accurately measures the viscoelastic changes of a sample as a function of temperature, stress or strain applied. The apparatus continuously records the deformation of the sample, maintaining the fixed stress, during a controlled program of temperature variation. The results are obtained by graphical representation, as a function of temperature, of the elastic modulus (G '), the loss modulus and tan delta. The Tg is the higher temperature value read in the tan delta curve when the tan delta derivative is zero. Particle Size Analysis The particle size of the primary particles after the multi-step polymerization is measured with a MALVERN Zetasizer Nano S90. The particle size of the polymer powder is measured with a Malvern Mastersizer 3000 from MALVERN. For estimating the weight average particle size, particle size and proportion of fine particles, a Malvern Mastersizer 3000 apparatus with 300 mm objectives, measuring a range of 0.5 to 880 pm is used. D (v, 0.5) or a shorter D50 is the particle size at which 50% of the sample is smaller in size and 50% of the sample is larger than this size, or in other words, the volume equivalent diameter at 0% cumulative volume. This size is also called median volume diameter, which is related to the mass median diameter by the density of the particles assuming a size-independent density for the particles. D (v, 0,1) or D10 is the particle size at which 10% of the sample is smaller, or in other words, the volume equivalent diameter at 10% cumulative volume D (v, 0) , 9) or D90 is the particle size at which 90% of the sample is smaller. [Examples] [0120] Example 1 10121] First step: polymerization of core 1 and core 2 In a 20-liter high pressure reactor are charged: demineralized water 116.5 parts, a salt emulsifier 0.1 part sodium dodecylbenzenesulfonic acid, 20 parts 1,3-butadiene, 0.1 part t-dodecyl-mercaptan, and 0.1 part p-menthane hydroperoxide as initial charge. . The solution is heated with stirring to 43 ° C after which a reductant catalyst solution is charged (water 4.5 parts, sodium tetrapyrophosphate 0.3 part, ferrous sulfate 0.004 part and dextrose 0.3 part ), which effectively primes the polymerization. Then, the solution is further heated to 56 ° C and maintained at this temperature for a period of three hours.
    [0004] Three hours after initiation of the polymerization, a second charge of monomer (BD 71 parts, t-dodecyl mercaptan 0.2 part), an additional charge of emulsifier and reducer (demineralized water 30.4 parts, salt emulsifier). 0.9 part sodium dodecylbenzenesulfonic acid, 0.5 part dextrose) and additional initiator (0.8 part p-menthane hydroperoxide) are added continuously over eight hours. After completion of the second monomer addition, the residual emulsifier and reducing agent feedstock and the initiator are added continuously for an additional five hours. Thirteen hours after initiation of the polymerization, the solution is heated to 68 ° C, additional initiator (0.09 part p-menthane hydroperoxide) and additional styrene (0.9 part) are added continuously for 25 hours. Additional 3 hours, and allowed to react until at least twenty hours have elapsed since initiation of the polymerization, so as to produce a latex with a butadiene core and a gradient core in BD / ST ( R1).
    [0005] The resulting polybutadiene elastomer latex (R1) contains 40.3% by weight solids and has a weight average particle size of about 180 nm. Second step: polymerization of the bark 1 In a reactor of 3.9 liters are charged 80.75 parts, on a solids basis, of polybutadiene elastomer latex R1, 1.3 parts of water demineralized, and 0.004 part of sodium formaldehyde sulfoxylate. The solution is stirred, purged with nitrogen, and heated to 55 ° C. When the solution reaches 62 ° C., continuously for 60 minutes, 7.1 parts of styrene, 0.09 part of divinylbenzene and 0.03 part of t-butyl hydroperoxide are added. Then, the temperature is increased to 75 ° C for 40 minutes. In batch form, a mixture of 1.4 parts of demineralized water, 0.003 parts of sodium formaldehyde sulphoxylate is added, then continuously, 10.5 parts of methyl methacrylate, 0.13 parts of divinylbenzene and 0.04 parts t-butyl hydroperoxide initiator are added in 30 minutes. Thirty minutes after the previous addition, 0.1 part t-butyl hydroperoxide was added to the reactor at one time, followed by a 60 minute hold period. After the 60 minute holding period, a stabilizing emulsion is added to the graft copolymer latex. The stabilizing emulsion is prepared by mixing 5.4 parts of demineralized water (based on the weight of the graft copolymer), 0.1 part of sodium salt of dodecylbenzenesulfonic acid and 0.38 part of 3 parts. Octadecyl 5-di-tert-butyl-4-hydroxy-octylcycloamine. The resulting core-shell latex (El) has an average particle size of about 190 nm. EXAMPLE OF Coagulation In a 3 1 jacketed vessel equipped with a stirrer, 500 g of core-bark particle latex are successively placed to obtain a solids content of 14.1%. With stirring at 300 rpm, the heating of the latex dispersion is increased to 50 ° C and then the salt solution (27.1 g of sodium chloride in 245 ml of deionized water) is injected. Coagulation occurs very quickly. After 15 minutes, at 50 ° C. with stirring, the temperature is raised to 85 ° C. and maintained for 30 minutes at this temperature. It is then cooled to 30 ° C. Then, the coagulated material is filtered through a centrifuge, washed with demineralized water and filtered to produce a powder. Pl. Addition of phosphate buffer solution. 750 g of graft copolymer (solids content 60% by weight) P1 are placed in a calibrated 2 liter flask and 99 ml of an aqueous solution of Na2HPO4 (disodium hydrogenphosphate) and KH2PO4 (potassium dihydrogenphosphate) comprising , expressed as phosphorus, a concentration of 2.97 mg / ml, so as to be between 6 and 7.5. [0125] Drying. The PP1 powder is placed in a ventilated oven for 48 hours at 50 ° C. and recovered after complete drying. Example 2 [0127] Example 1 is repeated until the powder P1 is obtained at the end of the coagulation. No phosphate buffer solution is added. The powder is dried as described in Example 1. Example 3 is repeated with respect to synthesis but coagulation is carried out with magnesium sulfate (MgSO 4). An aqueous solution of Na2HPO4 (disodium hydrogen phosphate) is added. The powder is dried as described in Example 1. Example 4 [0131] Example 1 is repeated for synthesis but coagulation is performed with calcium chloride (CaCl 2). An aqueous solution of Na2HPO4 (disodium hydrogen phosphate) is added. The powder is dried as described in Example 1.
    [0006] Table - coagulation recovery conditions Example Final Coagulation Adjustment Agent pH to obtain a neutral pH Example 1 NaCl Yes, with a solution of Na2HPO4 and KH2PO4 Example 2 NaCl no Example 3 MgSO4 Yes, with Na2HPO4 Example 4 CaCl2 Yes, with Na2HPO4 [0132] The multi-stage polymer dry powders of Examples 1-4 were formulated with 5 wt.% polycarbonate to produce compounds 1-4. [0133] Preparation of modified impact-resistant compound compositions The respective impact modifier powders of Examples 1 to 4 were mixed with the SABIC Lexan ML5221 thermoplastic polycarbonate resin (5% by weight using a Clextral type extruder (double diameter 25 mm, length 700 mm). ) using temperatures between 100 ° C and 320 ° C depending on the respective zones throughout the extruder The respective compounds obtained are thermally Illis at 120 ° C. The optical properties of the compounds are evaluated. The color change is observed by measuring the parameter b *. The b * value is used to characterize the main yellowing of the 20 samples. The value b * measures the blue and yellow of the color. The yellow tending colors have a positive b * value while the blue tending ones have a negative b * value. The b * values are measured using a colorimeter (particularly according to ASTM E 308). The color change is observed as a function of time: samples stored at 120 ° C for 4 days. If the initial color is close to zero, it is considered that the thermoplastic composition comprising the impact modifiers of the invention is acceptable. The value b * must not be greater than 10 after 4 days of thermal aging. Table 2 - Optical properties expressed by b * of modified PC impact composition modified with respective multi-layer polymers Example b * initial b * after 4 days at 120 ° C Example 1 -0.63 3.5 Example 2 - 0.6 7.2 Example 3 -2.4 2.3 Example 4 0.1 4.5 Table 3 - Izod impact strength of impact modified polycarbonate composition with polymers obtained by respective multi-stages Impact resistance IZOD [kJ / m2] at Example 23 ° C -30 ° C Example 1 49.2 31.8 Example 2 44.0 31.7 Example 3 35.3 17.4 (-20 ° C) Example 4 52.0 32.3
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. A process for producing the polymeric composition comprising the steps of a) polymerization by emulsion polymerization of a monomer or mixture of monomers (Am) to obtain during this step a layer (A) comprising a polymer (A1) having a glass transition temperature below 0 ° C, b) polymerization by emulsion polymerization in the presence of the polymer obtained in step a) of a monomer or mixture of monomers (Bm) to obtain during this next step a layer (B) comprising a polymer ( B1) having a glass transition temperature of at least 45 ° C, c) coagulating the multi-stage polymer with an alkali metal salt, d) washing the multi-stage polymer, e) adjusting the pH value after coagulation at a value between 5 and 10, f) adding an aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V.
    [0002]
    2. Method according to claim 1, characterized in that steps a) and b) use, in the emulsion polymerization, a surfactant selected from an anionic surfactant.
    [0003]
    3. Method according to claim 1 or 2, characterized in that the alkali metal salt is a sodium or potassium salt.
    [0004]
    4. Process according to any one of claims 1 to 3, characterized in that the process comprises an additional g) drying of the polymer composition.
    [0005]
    5. Method according to any one of claims 1 to 4, characterized in that the polymeric composition comprises at least 350 ppm of phosphorus.
    [0006]
    6. Process according to any one of claims 1 to 5, characterized in that the adjusted pH after coagulation is between 6 and 9.
    [0007]
    7. Process according to any one of Claims 1 to 6, characterized in that the phosphorus-containing compound is preferably chosen from an organophosphorus compound, a phosphate salt, phosphoric acid, phosphonate salts and phosphonic acid and their respective esters and mixtures thereof. 20
    [0008]
    8. Process according to any one of claims 1 to 7, characterized in that in step f), the aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V is added by washing the multi-stage polymer which contains less than 60% by weight of water, said aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III 30 or + V.
    [0009]
    9. Process according to any one of claims 1 to 7, characterized in that in step f), the aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V is added to the cake wet cake after the coagulation step the filtration step.
    [0010]
    10. Process according to any one of claims 1 to 7, characterized in that in step f), the aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of or + V is added during the step of drying the multi-stage polymer, when the multi-stage polymer composition further comprises at least 10% by weight of water.
    [0011]
    11. Use of the polymeric composition obtained by the process according to any one of claims 1 to 10 as impact modifier for thermoplastic polymers.
    [0012]
    12. Use of the polymeric composition according to claim 11 characterized in that the thermoplastic polymer is selected from polyvinyl chloride (PVC), chlorinated polyvinyl chloride (C-PVC), polyesters such as, for example, poly ethylene terephthalate (PET) or poly (butylene terephthalate) (PBT), polyhydroxyalkanoates (PHA) or (PLA), cellulose acetate, polycarbonates (PC), polyethylene, poly (methacrylates), methyl) (PMMA), copolymers of (meth) acrylic acid, thermoplastic poly (methyl methacrylate-co-ethyl acrylate), poly (alkylene terephthalates), poly (vinylidene fluoride), poly ( vinylidene chloride), polyoxymethylene (POM), semi-crystalline polyamides, amorphous polyamides, semi-crystalline copolyamides, amorphous copolyamides, polyetheramides, polylactic acid, polystyrene (PS), Polyesteramides, copolymers of styrene and acrylonitrile (SAN), and their respective blends or alloys and the thermoplastic polymer composition preferably comprises polycarbonate (PC) and / or polyester (PET or PBT) or PC or polyester alloys. The alloys, for example, can be PC / ABS (poly (acrylonitrile-co-butadiene-co-styrene), PC / ASA, PC / polyester or PC / PLA.
    [0013]
    A thermoplastic polymer composition comprising the polymeric composition obtained by the process of any one of claims 1 to 10.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3028859A1|2016-05-27|
    FR2969158A1|2012-06-22|METHOD FOR CHOCY MODIFIERS AND SHOCK MODIFIED THERMOPLASTIC COMPOSITION HAVING IMPROVED HYDROLYTIC RESISTANCE
    FR2969167A1|2012-06-22|MODIFIED THERMOPLASTIC COMPOSITION IMPROVED SHOCK
    FR3028861A1|2016-05-27|
    JP2017538814A5|2019-01-10|
    FR2969161A1|2012-06-22|NOVEL HEART-ECORCE MULTI-STEP POLYMER POWDER, PROCESS FOR PRODUCING THE SAME, AND COMPOSITION COMPRISING THE SAME
    KR20120067316A|2012-06-25|Impact modified thermoplastic composition with hydrolytic sensitivity to obtain higher fluidity while keeping high impact strength
    JP2017535658A5|2019-01-10|
    JP2005200502A|2005-07-28|Impact resistance improver and resin composition
    KR100477944B1|2005-03-21|Acrylate-styrene-acrylonitrile graft copolymer composition and method for preparing thereof
    FR3078068A1|2019-08-23|MULTI-LAYER POLYMER COMPRISING A FRAGMENT COMPRISING PHOSPHORUS, PROCESS FOR PREPARING SAME, USE THEREOF, AND COMPOSITION COMPRISING THE SAME
    KR101602531B1|2016-03-10|Manufacturing method of transparent thermoplastic resin having no mold deposit
    FR2750995A1|1998-01-16|COMPOSITION OF RESIN CONTAINING RUBBER AND COMPOSITION OF STYRENE RESIN CONTAINING IT
    KR20210049573A|2021-05-06|Mabs based graft copolymer, method for preparing thereof and transparent thermoplastic resin comprising the same
    CA2032760C|1997-06-03|Production process for a thermoplastic resin-based cast plate
    FR3052168A1|2017-12-08|
    JP2010013533A|2010-01-21|Acrylic multistage polymer composition, methacrylic resin composition and molded article
    同族专利:
    公开号 | 公开日
    US10316127B2|2019-06-11|
    SG11201704039XA|2017-06-29|
    CN107075044A|2017-08-18|
    FR3028859B1|2018-02-16|
    RU2017121983A3|2018-12-26|
    KR20170087922A|2017-07-31|
    WO2016083383A1|2016-06-02|
    BR112017010685A2|2018-02-14|
    RU2692244C2|2019-06-24|
    JP2017538814A|2017-12-28|
    EP3224289A1|2017-10-04|
    US20170355802A1|2017-12-14|
    RU2017121983A|2018-12-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP0900827A2|1997-09-04|1999-03-10|General Electric Company|Impact modified carbonate polymer composition|
    EP2189497A1|2008-11-21|2010-05-26|Rohm and Haas|Polymer compositions containing phosphates|
    EP2465882A1|2010-12-15|2012-06-20|Arkema France|Improved impact modified thermoplastic composition|
    DE2503966B1|1975-01-31|1975-08-07|Basf Ag|Impact-resistant thermoplastic molding compounds|
    EP0540470B1|1991-11-01|1997-06-04|Ciba SC Holding AG|Process for producing an emulsion graft copolymer|
    DE10260065A1|2002-12-19|2004-07-01|Röhm GmbH & Co. KG|Core-shell particles for toughening of poly acrylate molding compounds|
    JP4698156B2|2004-03-08|2011-06-08|日本エイアンドエル株式会社|Method for producing transparent thermoplastic resin having improved hue|
    DE102007032836A1|2007-07-12|2009-01-15|Evonik Röhm Gmbh|Emulsion polymer containing activators, processes for its preparation and its use in two- or multi-component systems|
    MX337457B|2008-03-22|2016-03-03|Bayer Materialscience Ag|Impact-resistant modified polycarbonate compositions with a good combination of raw talc, hydrolysis- and melt stability.|
    WO2009126373A2|2008-04-07|2009-10-15|Arkema Inc.|Functional mbs impact modifiers for use in engineering resins|
    FR2969161B1|2010-12-15|2014-06-06|Arkema France|NOVEL HEART-ECORCE MULTI-STEP POLYMER POWDER, PROCESS FOR PRODUCING THE SAME, AND COMPOSITION COMPRISING THE SAME|
    FR3028861B1|2014-11-24|2018-02-16|Arkema France|MULTI-STEP POLYMER, ITS COMPOSITION, PREPARATION METHOD, USE AND COMPOSITION COMPRISING THE SAME|FR3019549B1|2014-04-07|2020-10-02|Arkema France|MULTI-STAGE POLYMER POWDER COMPOSITION, ITS PREPARATION PROCESS AND ITS USE|
    BR112019004868A2|2016-09-22|2019-07-16|Rohm & Haas|processes for producing a polymer composition and a matrix composition.|
    US10920067B2|2016-09-22|2021-02-16|Rohm And Haas Company|Polymer compositions containing phosphates|
    WO2018147142A1|2017-02-09|2018-08-16|日本ゼオン株式会社|Acrylic rubber|
    FR3078068B1|2018-02-16|2020-11-06|Arkema France|MULTI-LAYER POLYMER COMPRISING A FRAGMENT INCLUDING PHOSPHORUS, ITS PREPARATION PROCESS, ITS USE AND COMPOSITION INCLUDING THE SAME|
    WO2021110739A1|2019-12-06|2021-06-10|Basf Se|Release coating composition|
    法律状态:
    2015-10-08| PLFP| Fee payment|Year of fee payment: 2 |
    2016-05-27| PLSC| Publication of the preliminary search report|Effective date: 20160527 |
    2016-10-14| PLFP| Fee payment|Year of fee payment: 3 |
    2017-10-12| PLFP| Fee payment|Year of fee payment: 4 |
    2018-10-11| PLFP| Fee payment|Year of fee payment: 5 |
    2019-10-14| PLFP| Fee payment|Year of fee payment: 6 |
    2020-10-13| PLFP| Fee payment|Year of fee payment: 7 |
    2021-11-09| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1461388|2014-11-24|
    FR1461388A|FR3028859B1|2014-11-24|2014-11-24|METHOD FOR MANUFACTURING A MULTIPURPOSE OF A POLYMER, ITS COMPOSITION, USE THEREOF, AND COMPOSITION COMPRISING THE SAME|FR1461388A| FR3028859B1|2014-11-24|2014-11-24|METHOD FOR MANUFACTURING A MULTIPURPOSE OF A POLYMER, ITS COMPOSITION, USE THEREOF, AND COMPOSITION COMPRISING THE SAME|
    CN201580063559.1A| CN107075044A|2014-11-24|2015-11-24|Manufacture method, its composition, its purposes and the composition comprising it of more grades of polymers|
    RU2017121983A| RU2692244C2|2014-11-24|2015-11-24|Method of producing a composition containing multistage polymer , and use of said composition as modifier of impact strength of thermoplastic polymers|
    SG11201704039XA| SG11201704039XA|2014-11-24|2015-11-24|Process of manufacturing a multistage polymer, its composition, its use and composition comprising it|
    KR1020177016898A| KR20170087922A|2014-11-24|2015-11-24|Process of manufacturing a multistage polymer, its composition, its use and composition comprising it|
    PCT/EP2015/077515| WO2016083383A1|2014-11-24|2015-11-24|Process of manufacturing a multistage polymer, its composition, its use and composition comprising it|
    US15/527,406| US10316127B2|2014-11-24|2015-11-24|Process of manufacturing a multistage polymer, its composition, its use and composition comprising it|
    EP15800797.1A| EP3224289A1|2014-11-24|2015-11-24|Process of manufacturing a multistage polymer, its composition, its use and composition comprising it|
    JP2017527582A| JP2017538814A|2014-11-24|2015-11-24|Method for producing multistage polymer, composition thereof, use thereof and composition comprising the same|
    BR112017010685A| BR112017010685A2|2014-11-24|2015-11-24|multistage polymer manufacturing process, its composition, its use and composition comprising the same|
    [返回顶部]