• 专利附录
  • 专利说明
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    • 专利摘要:
    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 in thermoplastic compositions. More particularly, the present invention relates to a multi-step method of manufacturing a polymer, said multi-stage polymer in a thermoplastic composition, producing a composition having a satisfactory thermal stability.
    公开号:FR3028861A1
    申请号:FR1461384
    申请日:2014-11-24
    公开日:2016-05-27
    发明作者:Aline Couffin；Rosangela Pirri；Frederic Malet
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The multi-step polymer, its composition, method of preparation, use and composition comprising the same [Field of the Invention] [001] The present invention relates to a multi-stage polymer, its composition and process. of preparation.  [2] More particularly, the present invention relates to a multi-stage polymer, its composition and method of preparation and its use in thermoplastic compositions.  [3] More particularly, the present invention relates to a multi-step method of manufacturing a polymer, said multi-stage polymer in a thermoplastic composition, producing a composition having a satisfactory thermal stability.  [Technical Problem] [4] 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 subzero temperatures, 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 nanodomains of an elastomeric material.  This is generally done by introducing the sub-microscopic elastomer particles into the polymer matrix that can absorb the energy of a shock or dissipate it.  One possibility is to introduce the elastomer particles in the form of core-shell particles.  These core-shell particles, which generally have an elastomeric core and a polymeric shell, have the advantage of an appropriate particle size of the elastomeric core for effective reinforcement and a grafted bark to achieve adhesion and stability. compatibility with the thermoplastic matrix.  [006] Shock reinforcement performance is a function of particle size, particularly of the elastomeric portion of the particle, and its amount.  There is an optimum average particle size for obtaining the highest impact resistance for a given amount of added impact modifier particles.  These primary impact modifier particles are generally added to the thermoplastic material in the form of a particle powder.  This powder consists of primary particles of agglomerated impact modifiers.  During the mixing of the thermoplastic material with the powder particles, the primary particles of impact modifiers are found and are dispersed more or less homogeneously in the thermoplastic material.  [8] Although the particle size of the impact modifiers is in the nanometer range, the size of the agglomerated powder particles is in the micrometer range.  [9] Agglomeration during recovery can be achieved by several methods, such as, for example, spray drying, coagulation, shearing, lyophilization or a combination of spray drying and coagulation techniques.  [10] It is important to have a shock modifying powder that does not have a 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, or as a function of time or temperature or both. .  [011] All these influences can occur due to the architecture of the core-bark but, more particularly, impurities and by-products used during the synthesis and treatment of the impact modifier powder.  Generally, there are no particular purification steps of the impact modifier, but only solid / liquid separation.  Therefore, more or less significant amounts of any chemical compound (impurities, by-products) used are still incorporated in the impact modifier.  These quantities in question may vary.  However, these chemical compounds should have no influence or only minor influence on the thermoplastic material, generally such as, for example, the degradation of optical and / or mechanical and / or rheological properties during the course of time. time and / or temperature and / or hygrometry.  [12] Careful washing or purification may remove some of the compounds from the impurities or products used during the synthesis which could negatively influence the impact modifier powder on the performance of the thermoplastic polymer composition.  [13] On the other hand, all processes are extremely cost sensitive.  A slight improvement in a process can lead to a significant commercial advantage.  [14] The object of the present invention is to provide a multi-step polymer having a satisfactory thermal stability.  [015] An additional object of the present invention is also to produce a multi-stage polymer having satisfactory thermal stability and which can be used as a shock modifier.  [016] Another additional object of the present invention is to provide a multi-step manufacturing method of a polymer having a satisfactory thermal stability.  [17] An additional object of the present invention is a thermoplastic composition comprising a multi-step polymer, said composition having a satisfactory thermal stability.  [18] An additional, additional objective is a multi-step process for manufacturing a polymer, said multi-stage polymer in a thermoplastic composition, producing a composition having a satisfactory thermal stability.  BACKGROUND OF THE INVENTION [019] EP0900827 discloses a modified impact modified carbonate polymer composition having improved resistance to degradation and improved thermal stability.  According to the document, the impact modifier must be essentially free of basic compounds from the emulsion polymerization, and more particularly the typical fatty acid emulsifiers present in the alkali metal carboxylate form.  The impact modifier preferably has a core-shell structure and is prepared by an emulsion polymerization process and has a pH of from about 3 to about 8.  A preferable emulsifier is an alkylsulfonate having a C6 to C6 alkyl group.  [020] EP2189497 discloses polymeric compositions containing phosphates and in particular the process for obtaining them.  The polymeric composition is a polymer obtained by a multi-step process and is a shock modifier.  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 modifier added to a matrix without causing the deleterious effects of the multivalent cations that would otherwise occur.  The process employs a water wash step to first remove the salts and ions, followed by the addition of an aqueous alkaline phosphate solution.  As a result, the process requires a large amount of water.  [021] EP 2465882 discloses modified modified 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 specific process by controlling and adjusting the pH value.  Coagulation is performed with salts and, preferably, magnesium sulfate.  [022] WO2009 / 118114 discloses a modified impact polycarbonate composition having a good combination of color stability upon hydrolysis and melting.  The elastomeric core is based on polybutadiene.  For the preparation of the grafted elastomer polymer, fatty acid salts, in particular carboxylic acid salts, are used.  The yellow index of the compositions obtained with an injection temperature of 260 ° C. is very high: 20 or more.  [023] WO2009 / 126373 discloses functional MBS impact modifiers synthesized by multi-stage 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 with aluminum chloride - CaCl 2 or AlCl 3) or an acidified solution with concentrated sulfuric acid and then for separation, by filtration of the solid product resulting from the coagulation and the solid product is then washed and dried to obtain a graft copolymer in powder form.  [24] The object of the present invention is to avoid at least one of the disadvantages of the state of the art.  [25] There is a need to improve the multi-step process of making a polymer, by optimizing the steps involved, while providing the multi-stage polymer with increased performance as a shock modifier. in thermoplastic compositions.  [Brief Description of the Invention] [26] Unexpectedly, it has been discovered that a polymer particle polymer composition made by a multi-step process comprising at least one layer forming step (A) comprising a polymer (A1) having a glass transition temperature of less than 0 ° C and at least one subsequent step forming a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 45 ° C, obtained by a multi-step process characterized by the polymeric composition comprising less than 50 ppm of multivalent cations and at least 350 ppm of phosphorus in the form of a compound containing 3028861 6 phosphorus, the phosphorus being in the oxidation state + III or + V, leads to a product having satisfactory thermal aging properties.  Unexpectedly, it has also been discovered that a method of manufacturing the polymeric composition comprising a multi-stage polymer 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 the 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 monomer mixture (B. ) 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 in multi-step d) adjusting the pH to a value between 5 and 10 e) washing the polymer obtained in multi-steps f) adding an aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V characterized by that the coagulation step is not conducted with multivalent cations, and that the polymer composition comprises at least 350 ppm of phosphorus in the form of a phosphorus-containing compound, the phosphorus being in the form of Oxidation + III or + V results in a product having satisfactory thermal aging properties.  [028] According to a first aspect, the present invention relates to a polymeric polymer particle composition of a polymer obtained by a multi-step process comprising at least one step forming a layer (A) comprising a polymer (A1) having a glass transition temperature of less than 0 ° C and at least one subsequent step forming a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 45 ° C., obtained by a multi-step process characterized in that the polymer composition comprises less than 50 ppm of multivalent cations and at least 350 ppm of phosphorus in the form of a compound containing phosphorus with phosphorus in the state oxidation + III or + V.  [029] According to a second aspect, the present invention relates to a process for producing a polymeric composition comprising a polymer obtained in multi-steps 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 the polymer (A1) having a 20 to 0 ° C b) polymerization by emulsion polymerization at lower glass transition temperature presence of the polymer obtained in step a) d) a monomer or mixture of monomers (B. ) 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 in multi-steps d) adjustment of the pH to a value between 5 and 10 e) washing the polymer obtained in multi-steps f) adding an aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V characterized by that the coagulation step is not conducted with multivalent cations, and that the polymer composition comprises at least 350 ppm of phosphorus in the form of a phosphorus-containing compound, the phosphorus being in the state oxidation + III or + V.  [30] The term "polymer powder" as used herein refers to a polymer comprising powder grains of the order of at least 1 micrometer (μm) obtained by agglomeration of primary particles comprising a polymer of the order of the nanometer.  [31] The term "primary particle" in this 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 20 nm and 500 nm.  The term "particle size" in the present context refers to the volume average diameter of a particle considered to be spherical.  [33] The term "copolymer" in the present context means that the polymer consists of at least two different monomers.  [34] "Multi-step polymer" in the present context refers to a polymer formed sequentially by a multi-step polymerization process.  It is preferred a multi-stage emulsion polymerization process wherein 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.  [035] The term "(meth) acrylic" in the present context refers to all types of acrylic and methacrylic monomers.  [36] 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.  [37] 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 to improve its impact resistance.  The term "elastomer" in this context refers to the thermodynamic state of the polymer above its glass transition.  [039] As regards the multi-step 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 glass transition temperature below 0 ° C and at least one other layer (B) comprising a polymer (B1) having a glass transition temperature greater than 45 ° C.  [40] 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 advantageously 60/40 to 90/10 and most preferably between 70/30 and 90/10.  [41] The polymer particle having a multilayer structure is spherical.  The polymer particle having a multilayer structure is also called 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.  [042] The polymer particle according to the invention is obtained by a multi-step process, for example two or three steps or more.  [043] Preferably, the polymer (A1) having a glass transition temperature of less than 0 ° C in the layer (A) is not manufactured in the last step of the multi-step process.  The polymer (Al) 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.  [044] 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.  [45] 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.  [46] The glass transition temperature (Tg) of the polymer (Al) 10 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.  [47] More preferably the glass transition temperature Tg of the polymer (Al) is from -120 ° C to 0 ° C, still more preferably from -90 ° C to -10 ° C and preferably from -80 ° C to -25 ° C.  [48] 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 between 60 ° C and 150 ° C, still more preferably between 80 ° C and 150 ° C and preferably between 90 ° C and 150 ° C.  [49] The glass transition temperature Tg can be estimated, for example, by dynamic methods such as thermo mechanical analysis.  [50] The polymeric composition of the invention in the form of polymer particles of a multi-step 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.  [51] 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.  [52] The D10 of the volume particle size distribution is at least 7 μm and preferably 10 μm.  [53] The D90 of the volume particle size distribution is at most 800 μm and preferably 500 μm, more preferably at most 350 μm.  As regards the (Al) polymer, there may be mentioned homopolymers and copolymers comprising monomers with double bonds and / or vinyl monomers.  [055] In a first embodiment, the polymer (A1) is chosen from isoprene homopolymers or homopolymers of butadiene, 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.  [56] In a second embodiment, the polymer (A1) 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.  [57] More preferably, the polymer (A1) of the second embodiment comprises at least 70% by weight of monomers selected from (C1-C12) alkyl (meth) acrylates.  Even more preferably, the polymer (Al) comprises at least 80% by weight of C1 to C4 alkyl methacrylate monomers and / or C1 to C8 alkyl acrylate monomers.  Most preferably, the acrylic or methacrylic monomers of the polymer (A1) are selected from methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, and the like. , butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, provided that the polymer (Al) has a glass transition temperature of less than 0 ° C.  [059] 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 (Al).  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.  The crosslinking can also be carried out using the intrinsic reactivity of the monomers, for example in the case of diene monomers.  [060] As regards the polymer (Ba), there may be mentioned homopolymers and copolymers comprising monomers with double bonds and / or vinyl monomers.  [061] The polymer (B1) 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 may be functionalized by introducing into the graft, or as a comonomer during 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, glycidyl methacrylate, hydroxyethyl methacrylate and alkyl (meth) acrylamides.  [62] Preferably, the polymer (B1) is also a (meth) acrylic polymer.  [63] Preferably, the polymer (B1) comprises at least 70% by weight of monomers selected from (C1 to 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 10 to C8 alkyl acrylate monomers.  [64] 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 and ethyl methacrylate. butyl methacrylate and mixtures thereof, provided that the polymer (B1) has a glass transition temperature of at least 60 ° C.  [65] Advantageously, the polymer (B1) comprises at least 70% by weight of monomer units derived from methyl methacrylate.  [66] The polymer (B1) can be crosslinked by adding at least one multifunctional monomer during the preparation of the polymer (B1).  [67] The multi-stage polymer of the invention having a multilayer structure comprising at least one layer (A) comprising a polymer (A1) having a glass transition temperature of less than 0 ° C and another layer (B) comprising a polymer (B1) having a glass transition temperature above 45 ° C, does not include alkaline earth metals or ions in the form of intentionally added sials.  The polymeric polymer particle composition of a polymer obtained by a multi-step process does not comprise any intentionally added multivalent cation selected from an alkaline earth metal.  [068] Without intentional addition means that traces of alkaline earth metals in the form of ions or salts may be accidentally added as minor impurities with other ions or salts to the composition.  For example, in particular, calcium impurities in sodium compounds are mentioned.  [69] The alkaline earth metals in the form of traces or minor impurities represent less than 30 ppm, preferably less than 20 ppm and more preferably less than 10 ppm, advantageously less than 9 ppm of the layered polymeric composition. multiple.  The multivalent cation is selected from Ca 2+ or Mg 2+.  [70] 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 10 Mb +, where M represents the cation, with b> 1, and preferably 5> b> 1.  [71] Multivalent cations comprising the alkaline earth metals in the composition can be analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES).  [072] The multi-stage multi-layered polymer of the invention having a multilayer structure has a pH value of between 5 and 10 and preferably between 6 and 9, more preferably between 6 and 7.5 and advantageously between 6 and 7.  [073] The multi-stage polymer of the invention comprises a phosphorus-containing compound in which the phosphorus is in the oxidation state of + III or + V.  [74] 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, preferably at least 390 ppm, and more preferably at least 400 ppm of 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.  [75] The polymer obtained in multi-stage comprises at most 2000 ppm, preferably at most 1900 ppm and more preferably at most 1800 ppm of phosphorus which has the oxidation state of + III or + V.  Phosphorus is part of a phosphorus-containing compound.  [76] The multilayer 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.  [77] The amount of phosphorus in the multi-stage polymer can be determined by inductively coupled plasma atomic emission spectrometry (ICP-AES).  [78] 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 to modify the state of oxidation of phosphorus in the phosphorus-containing compound.  [79] 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.  [080] An organophosphorus compound in the present invention refers to compounds with P-C and P-O-C bonds.  [81] 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.  [82] Phosphate salts are salts which have as anion dihydrogenphosphate (H 2 PO 4 -), hydrogen phosphate (HPO 4 -) or phosphate (PO 4 -).  1083] Phosphonate salts are salts which have as the anion dihydrogenphosphonate (H2PO3-), or hydrogenphosphonate (HP032- [084] With regard to the process for the manufacture of a polymeric composition comprising a polymer obtained in multi-steps 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 transition temperature vitreous lower 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) coagulating the polymer obtained in multi-steps, d) adjusting the pH to a value between 5 and 10, e) washing the polymer obtained in mu lti-steps, f) adding an aqueous solution comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V.  [85] Preferably, in step d), the pH value is adjusted to between 6 and 9, more preferably between 6 and 7.5 and advantageously between 6 and 7.  [86] The process may comprise the additional step g) of drying the polymeric composition.  A dry polymeric composition according to the invention is a composition which comprises less than 1% moisture or water.  The moisture of a polymeric composition can be measured with a thermobalance.  [87] 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.  [88] The respective monomers or monomer mixtures (Am) and (Bm) to form the layers (A) and (B) respectively comprising the polymers (A1) and (B1) respectively and the characteristics of the respective polymers (A1) and (B1) are the same as previously defined for the definition of polymers (A1) and (B1) for the composition.  [89] The emulsion polymerization during the step for the layer (A) may be a semi-continuous monomer addition process, a semicontinuous addition process of monomers or a micro-agglomeration process.  [90] 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).  [91] Preferably, the polymer (B1) is grafted to the polymer prepared in the preceding step and more preferably to the polymer (A1) prepared in the previous step.  [92] 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 oxidation-reducing 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 (NaHSO 2 HCHO), 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.  [93] The initiators do not contain any alkaline earth metals (Group IIA Periodic System of Elements) intentionally added.  The initiator may, however, contain other multivalent cations that are not alkaline earth metals.  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 emulsifying agent, the 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, oleate sodium, 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 alkylarylsulfonic acids, in particular particularly sodium dodecylbenzenesulfonate, and sodium or potassium salts of fatty acid monoglyceride monosulfonates, 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.  [095] More preferably, the emulsifying agent is selected from an anionic surfactant.  Advantageously, the emulsifying agent is chosen from anionic surfactants which comprise a carboxylate group or a phosphate group.  [96] More preferably, the emulsifier is a carboxylate or a carboxylic acid salt.  [97] 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 addition of an electrolyte aqueous solution with stirring.  Coagulation is not performed with multivalent cations.  Multivalent cations should be avoided in the electrolyte solution.  No multivalent cation is intentionally added to the electrolyte solution.  [98] Preferably, coagulation is performed with a solution comprising an inorganic acid or an alkali metal salt.  More preferably the inorganic acid is selected from, but not limited to, HC1, H2SO4, H3PO4.  Advantageously, a 1 molar aqueous solution of the inorganic acid has a pH 1.  [099] 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 Na2HPO4, but is not limited to this list.  The pH adjustment in step d) of the process of the invention is preferably carried out by addition of sodium or potassium hydroxide or aqueous buffer solution after the coagulation step.  The washing in step e) of the process of the invention is carried out with water, dilute aqueous solutions or aqueous buffer solutions.  After the washing step, the pH is between 5 and 10.  The polymer obtained by multi-step coagulated after step e) is in the form of a wet cake.  The wet cake contains less than 60% water.  [0102] Step f) relates to 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.  [0103] 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 coagulation step c).  In order to add an aqueous solution or dispersion comprising a phosphorus-containing compound, said solution or dispersion is prepared by simply mixing 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-stage polymer which contains less than 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 step coagulation and the filtration step.  After filtration, a wet cake is obtained which contains less is dried.  In a third weight mode of water.  Next, the wet cake of 60 being made, 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 to multiple layers, when the polymeric composition obtained by multi-step 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 polymer obtained by multi-steps.  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) 3, wherein at least one R group is an alkyl group.  The phosphonates are phosphonic acid esters and have the general formula RP (-O) (OR1) 2, wherein at least one R or R 'group is an alkyl group.  An organophosphorus compound in the present invention refers to compounds with P-C and P-O-C linkages.  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, as anion, have dihydrogen phosphate (H 2 PO 4 -), hydrogen phosphate (HPO 4 2-) or phosphate (P0 4 O). The salts of phosphonate are salts. which have as anion dihydrogenphosphonate (H2PO3-), or hydrogenphosphonate (HP032-).  The present invention further relates to the use of the multi-stage polymer as impact modifier in thermoplastic polymers.  The present invention further relates to a thermoplastic composition comprising the polymer obtained in multi-steps, and a thermoplastic polymer.  With regard to 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 (C-PVC), polyesters such as, 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), (meth) acrylic copolymers, thermoplastic poly (methyl methacrylates-co-acrylate), poly ( alkylene terephthalates), polyvinylidene fluoride, polyvinylidene chloride, polyoxymethylene (PO), semi-crystalline polyamides, amorphous polyamides, semi-crystalline copolyamides, amorphous copolyamides, polyetheramides , polyesteramides, copolymers of styrene and acrylonitrile (SAN), and their respective mixtures or alloys.  In 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, can be PC / ABS (poly (acrylonitrile-co-butadiene-co-styrene), PC / ASA, PC / polyester or PC / PLA.  [0117] Preferably, if the thermoplastic polymer in the thermoplastic polymer composition comprises polycarbonate (PC) and / or polyester (PET or PBT) or alloys of PC or polyester, the polymer (A) of the polymer with multiple layers is selected from isoprene homopolymers or butadiene homopolymers, isoprene-butadiene copolymers, isoprene copolymers with at most 98% by weight of a vinyl monomer and butadiene copolymers with at least plus 98% by weight of a vinyl monomer.  As regards the polycarbonate (PC), it may be aromatic, semi-aromatic and / or aliphatic (in particular based on isosorbide).  With regard to the thermoplastic composition comprising the polymer obtained in multi-steps, and a thermoplastic polymer, the proportions between the multilayer 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] [0120] Glass transition temperature The glass transition (Tg) of the polymers is measured with a material capable of performing a thermomechanical analysis.  A 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.  [0121] 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 after coagulation is measured with a Malvern Mastersizer 3000 from MALVERN.  For the estimation of the average particle size by weight, the particle size and the proportion of fine particles, a Malvern Mastersizer 3000 device with 300 mm objectives, measuring a range of 0.5 to 880 pm is used.
    [0002] 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 50% cumulative volume. This size is also referred to as the volume median 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. [0122] Analysis of the phosphorus content and multivalent cations. The phosphorus content is determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). The result is expressed in ppm on the basis of phosphorus (P) or the respective multivalent cation (Mb + with b> 1) relative to the polymer obtained in multi-steps. The analysis does not make it possible to obtain the structure of the composition containing phosphorus or a multivalent cation. PH value The pH value of the respective products is measured according to the procedure to obtain the pH of the final powder: 5 g of dried powder are dispersed in 20 ml of demineralized water with stirring for 10 minutes at 45 ° C. C. Then, the concentrated slurry is filtered on a Wattman paper filter. The pH of the filtered water is measured at room temperature. The pH value is obtained by using a Fisher Scientific glass probe connected to an Eutech pH Series pH meter 5 calibrated with standard buffer solutions. [Examples] [0124] Example 1 [0125] Polymer synthesis obtained in multi-steps, (core-shell type particles) [0125] First step - core polymerization: In a high-pressure reactor of 20 liters are charged: 116.5 parts demineralized water, 0.1% tallow beef fatty acid potassium emulsifier, 21.9 parts 1,3-butadiene, 0.1% t-dodecyl mercaptan, part, and 0.1 part p-menthane hydroperoxide as initial tank 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. Three hours after initiation of the polymerization, a second charge of monomer (BD 77.8 parts, 0.25 t-dodecylmercaptan 0.2 part), half an additional charge of emulsifier and reducing agent (demineralized water 30, 4 parts, emulsifier of potassium salt of beef tallow fatty acid 2.8 parts, dextrose 0.5 part) and the additional initiator (hydroperoxide of p-menthane 0.8 part) are added continuously in 30 parts. 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 polymerization, the solution is heated to 68 ° C and allowed to react until at least twenty hours have elapsed since initiation of the polymerization, to obtain a latex with polybutadiene core, R1. The resulting polybutadiene latex (R1) contains 38% solids and has a weight average particle size of about 160 nm. Second stage - Polymerization of bark 1 (outer bark): in a reactor of 3.9 liters are charged 75.0 parts, 5 on a solids basis, of polybutadiene elastomer latex R1, 37.6 parts of demineralised water, and 0.1 part of sodium formaldehyde sulfoxylate. The solution is stirred, purged with nitrogen, and heated to 77 ° C. When the solution reaches 77 ° C., a mixture of 22.6 parts of methyl methacrylate, 1.4 parts of divinylbenzene and 0.1 part of t-butyl hydroperoxide initiator is added continuously over 70 minutes. followed by a maintenance period of 80 minutes. Thirty minutes after the start of the holding period, 0.1 part of sodium formaldehyde sulfoxylate and 0.1 part of t-butyl hydroperoxide are added to the reactor at one time. After the 80 minute holding period, a stabilizing emulsion is added to the graft copolymer latex. The stabilizing emulsion is prepared by mixing 3.2 parts of demineralized water (based on the weight of graft copolymer), 0.1 part of oleic acid, 0.1 part of potassium hydroxide, and 0.9 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. The resulting core-shell latex (G1) has a weight average particle size of about 180 nm. Coagulation: In a 3 L jacketed vessel equipped with an agitator, 500 g of core-shell particles latex (G1) are successively placed in order to obtain a solids content of 14.1%. With stirring at 300 rpm, the heating of the solution was increased to 52 ° C and then 1.6% aqueous sulfuric acid solution was injected to obtain a coagulated material which was heat-treated at 96 ° C. The pH is adjusted with NaOH during coagulation between 2 and 6. Next, the coagulated material is filtered using a centrifuge and washed with deionized water. Then the pH is measured and adjusted with aqueous sodium hydroxide solution to be between 5 and 9. The resulting polymer (P1) has a neutral pH (6 <pH <7) and an average particle size about 141 pm. [0129] Addition of phosphate buffer solution: 750 g of graft copolymer P13028861 26 (solids content 60% by weight) are placed in a calibrated 2 liter flask and 99 ml of an aqueous solution of Na2HPO4 ( sodium hydrogenphosphate) and KH2PO4 (potassium dihydrogenphosphate) comprising, expressed as phosphorus, a concentration of 2.97 mg / ml. [0130] Drying. The final powder PP1 (P1 + phosphate) is placed in a ventilated oven for 48 hours at 50 ° C. and recovered after complete drying, moisture <1% by weight. EXAMPLE 2 Polymer synthesis obtained by multi-step (core-shell particles) is the same as in Example 1. Coagulation without adjustment of pH after coagulation: in a reaction vessel The double jacket of 3 L equipped with a stirrer is successively placed 500 g of core-bark particle latex (G1) 15 to obtain a solids content of 14.1%. With stirring at 300 rpm, the heating of the solution was increased to 52 ° C and then 1.6% aqueous sulfuric acid solution was injected to obtain a coagulated material which was heat-treated at 96 ° C. The pH is adjusted during coagulation between 2 and 6.
    [0003] Next, the coagulated material is filtered using a centrifuge and washed with deionized water to obtain P2. [0134] Addition of phosphate buffer solution: 750 g of graft copolymer (solids content 60% by weight), P2 are placed in a calibrated 2-liter flask and 99 ml of an aqueous solution of Na 2 HPO 4 ( sodium hydrogenphosphate) and KH2PO4 (potassium dihydrogenphosphate) comprising, expressed as phosphorus, a concentration of 2.97 mg / ml. [0135] Drying. The final powder PP2 is placed in a ventilated oven for 48 hours at 50 ° C. and recovered after drying. Example 3 (Comparative) Polymer synthesis obtained by multi-step (core-shell particles) is the same as in Example 1. Coagulation: in a jacketed vessel of 3 The equipped with a stirrer is successively placed 500 g of heart-shell particle latex (G1) of Example 1 to obtain a solids content of 14.1%. Under stirring at 300 rpm, the heating of the solution is increased to 52 ° C and then 1.6% aqueous sulfuric acid solution is injected to obtain a coagulated material which is heat-treated at 96 ° C. C. The pH is adjusted during coagulation between 2 and 6. Next, the coagulated material is filtered using a centrifuge and washed with deionized water. Then, the pH is measured and adjusted with an aqueous solution of sodium hydroxide so as to be between 5 and 9. The resulting polymer (P1) has a neutral pH (5 <pH <8) and a mean particle size of about 141 pm (method, same size as Example 1). Adding a phosphate buffer solution: 750 g of graft copolymer P1 (solids content 60% by weight) are placed in a calibrated 2 liter flask and 46 ml of an aqueous solution of Na 2 HPO 4 (hydrogen phosphate di sodium) and KH2PO4 (potassium dihydrogenphosphate) comprising, expressed in phosphorus, a concentration of 2.97 mg / ml. Drying: the final powder PP3 is placed in a ventilated oven for 48 h at 50 ° C. and recovered after drying. Example 4 (comparative) [0142] The multi-step polymer synthesis (core-shell particles) is the same as in Example 1. [0143] Coagulation: in a double jacket vessel 3 L equipped with a stirrer are successively placed 500 g of heart-shell particles latex (G1) of Example 1 to obtain a solids content of 14.1%. With stirring at 300 rpm, the heating of the solution was increased to 52 ° C and then 1.6% aqueous sulfuric acid solution was injected to obtain a coagulated material which was heat-treated at 96 ° C. The pH is adjusted during coagulation between 2 and 6. Next, the coagulated material is filtered using a centrifuge and washed with deionized water. Then the pH is measured and adjusted with aqueous sodium hydroxide solution to be between 5 and 9. The resulting polymer (P1) has a neutral pH (6 <pH <7) and an average particle size about 141 pm. [0144] Addition of a phosphate buffer solution: 750 g of graft copolymer Pl 3028861 28 (solids content 60% by weight) are placed in a calibrated 2-liter flask and 15 ml of an aqueous solution of Na2HPO4 ( sodium hydrogenphosphate) and KH2PO4 (potassium dihydrogenphosphate) comprising, expressed as phosphorus, a concentration of 2.97 mg / ml. Drying: The final powder PP4 is placed in a ventilated oven for 48 hours at 50 ° C. and recovered after drying. EXAMPLE 5 (COMPARATIVE) Polymer synthesis obtained by multi-step (core-shell particles) is the same as in Example 1. Coagulation: in a jacketed vessel of 3 L, equipped with an agitator are successively placed 500 g of core-bark particle latex (G1) of Example 1 to obtain a solids content of 14.1%. With stirring at 300 rpm, the heating of the solution is increased to 52 ° C and then 1.6% aqueous sulfuric acid solution is injected to obtain a coagulated material which is heat-treated at 96 ° C. . The pH is adjusted during coagulation between 2 and 6. Next, the coagulated material is filtered on a centrifuge and washed with deionized water. Then, the pH is measured and adjusted with an aqueous solution of sodium hydroxide so as to be between 5 and 9. The resulting polymer (P1) has a neutral pH (6 <pH <7) and a mean particle size of about 141 pm. [0149] No addition of phosphate buffer solution. Drying: The final powder P5 is placed in a ventilated oven for 48 hours at 50 ° C. and recovered after drying. The phosphorus content of all the powders is determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). The results are summarized in Table 1. Table 1 - Summary of Powder Characteristics Coagulation Agent P / [pm] Example 1 650 Sulfuric Acid Example 2 650 Sulfuric Acid Example 3 300 Sulfuric Acid Example 4 100 Sulfuric Acid Example 5 Sulfuric Acid [0153] Table 1 indicates that the phosphorus content decreases with Examples 3 and 4, since a smaller amount of the phosphate buffer solution is added to the polymer powder after coagulation. In Example 5, the phosphorus content is the lowest since no phosphate buffer solution is added to the polymer powder after coagulation.The phosphorus in Example 5 is due to the products used during the reaction. Synthesis of the multi-step polymer [0154] The dry powders obtained by multi-step P1 to P5 are formulated with 5% by weight polycarbonate to produce the compounds 1 to 5. modified impact-resistant compound compositions: the respective impact-modifying powders P1 to P6 are mixed with the SABIC Lexan ML5221 thermoplastic polycarbonate resin (at 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 areas throughout the extruder. The respective compounds obtained are thermally aged 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 samples. The value b * measures the blue and yellow of the color 3028861. 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 (in particular 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 * should not be greater than 10 after 4 days of thermal aging. Table 2 - Color of compounds after thermal aging Multiple layer polymer of initial b * b * after 4 days at 120 ° C Compound 1 Example 1 0.43 4.02 Compound 2 Example 2 -1.55 5.47 Compound 3 Example 3 0.73 13.77 Compound 4 Example 4 -2.45 15.34 Compound 5 Example 5 -0.84 20.74 Table 3 - Impact Resistance of Thermoplastic Compositions Layered Polymer Resistance to shocks Resistance to multiples of IZOD [kJ / m2] shocks IZOD [kJ / m2] at 23 ° C to -30 ° C Compound 1 Example 1 48.0 37.0 Compound 2 Example 3 - - Compound 3 Example 4 45.4 35.6 Compound 4 Example 5 - - Compound 5 Example 6 45.9 41.0
    权利要求:
    Claims (22)
    [0001]
    REVENDICATIONS1. Polymeric polymer particle composition of a multi-layered polymer manufactured by a multi-step process comprising at least one step forming a layer (A) comprising a polymer (Al) having a glass transition temperature of less than 0 ° C and at least one subsequent step forming a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 45 ° C, obtained by a multi-step process characterized in that the polymer composition comprises less 50 ppm of multivalent cations and at least 350 ppm of phosphorus as a phosphorus-containing compound with phosphorus in the + III or + V oxidation state.
    [0002]
    2. Polymeric composition according to claim 1, characterized in that the composition comprises phosphorus in the form of a compound containing phosphorus preferably at least 360 ppm, more preferably at least 370 ppm, still more preferably at least 380 ppm preferably at least 390 ppm and more preferably at least 400 ppm.
    [0003]
    3. The polymeric composition as claimed in claim 1, wherein the composition comprises phosphorus in the form of a compound containing phosphorus at most 2000 ppm, preferably at most 1900 ppm and more preferably at most 1800 ppm.
    [0004]
    4. Polymeric composition according to any one of claims 1 to 3 characterized in that the composition comprises phosphorus in the form of a phosphorus-containing compound at between 350 ppm and 2000 ppm, preferably between 370 ppm and 1900 ppm and more preferably between 390 ppm and 1800 ppm, preferably at most 1800 ppm of phosphorus which has the oxidation of + III or + V. 3028861 32
    [0005]
    5. Polymeric composition according to any one of claims 1 to 4 characterized in that the phosphorus-containing compound is selected from an organophosphorus compound, a phosphate salt, phosphoric acid, phosphonate salts, phosphonic acid and their respective esters and mixtures thereof.
    [0006]
    Polymeric composition according to any one of claims 1 to 5, characterized in that the composition does not comprise any intentionally added multivalent cation selected from an alkaline earth metal.
    [0007]
    7. A polymeric composition according to any one of claims 1 to 6 characterized in that the composition comprises less than 30 ppm, preferably less than 20 ppm and more preferably less than 10 ppm of multivalent cations selected from alkaline earth metals. earth. 20
    [0008]
    8. Polymeric composition according to claims 1 to 7 characterized in that the multivalent cation is selected from Ca2 + or Mg2 +.
    [0009]
    9. A polymeric composition according to any one of claims 1 to 8 characterized in that the multivalent cation is present at less than 40 ppm and more preferably less than 30 ppm of the composition comprising the multi-stage polymer. 30
    [0010]
    Polymeric composition according to any one of claims 1 to 9, characterized in that the polymer composition has a pH between 5 and 10, preferably between 6 and 9, more preferably between 6 and 7.5 and advantageously between 6 and 9. 7. 35
    [0011]
    11. Polymeric composition according to any one of claims 1 to 10 characterized in that the polymer (Al) is chosen 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. 5
    [0012]
    12. Polymeric composition according to any one of claims 1 to 9, characterized in that the polymer (B1) is chosen from homopolymers of styrene, homopolymers of alkylstyrene or homopolymers of methyl methacrylate, or copolymers comprising at least at least 70% by weight of one of the above monomers and at least one comonomer selected from the other monomers above, another alkyl (meth) acrylate, vinyl acetate or acrylonitrile. 15
    [0013]
    A process for producing a polymer composition in the form of polymeric particles of a multi-layered polymer comprising a multi-stage polymer comprising the steps of a) emulsion polymerization by 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) a monomer or mixture of monomers (B.) to obtain during this next step 25 a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 45 ° C c) coagulation of the polymer obtained by multi steps d) adjustment of the pH value after coagulation to a value between 5 and 10 e) washing of the polymer obtained by multi-step f) addition of an aqueous solution or dispersion comprising a phosphorus-containing compound in which the phosphorus has the oxidation state of + III or + V characterized in that the coagulation step is not conducted with multivalent cations, and the polymer composition comprises at least 350 ppm of phosphorus. 3028861 34
    [0014]
    14. Process according to claim 13, characterized in that the steps a) and b) use in the emulsion polymerization a surfactant chosen from an anionic surfactant and advantageously the emulsifying agent is chosen from anionic surfactants which comprise a carboxylate group or a phosphate group.
    [0015]
    15. Process according to claim 13 or 14, characterized in that the coagulation in step c) is carried out with an inorganic acid or an alkali metal salt.
    [0016]
    16. Process according to any one of claims 13 to 15, characterized in that the process comprises an additional step g) of drying the polymer composition. 15
    [0017]
    17. Process according to any one of claims 13 to 16, 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-layered polymer which contains less than 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. 25
    [0018]
    18. Process according to any one of claims 13 to 16, 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 wet cake after the coagulation step and the filtration step.
    [0019]
    19. A process according to any one of claims 13 to 16, 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 during the step of drying the multi-stage polymer when the multi-stage polymer composition further comprises at least 10% by weight of water.
    [0020]
    20. Use of the polymer composition according to any one of claims 1 to 12 or obtained by the process according to any one of claims 13 to 19 as impact modifier for thermoplastic polymers.
    [0021]
    Use of the polymer composition according to Claim 10, 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 polylactic acid (PLA), cellulose acetate, polystyrene (PS), polycarbonates (PC), polyethylene, poly (methyl methacrylates) (PMMA), (meth) acrylic copolymers, thermoplastic poly (methyl methacrylates-co-ethyl acrylates), poly (alkylene terephthalates), polyvinylidene fluoride, polyvinylidene chloride, polyoxymethylene (POM), semicrystalline polyamides, amorphous polyamides, semicrystalline copolyamides, amorphous copolyamides, polyetheramides, polyesteramides, styrene copolymers and the like. of acry lonitrile (SAN), and their respective blends or alloys and preferably a thermoplastic polymer composition 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.
    [0022]
    22. A thermoplastic polymeric composition comprising the polymeric composition of any one of claims 1 to 12 or obtained by the process of any one of claims 13 to 16.
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    法律状态:
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    申请号 | 申请日 | 专利标题
    FR1461384A|FR3028861B1|2014-11-24|2014-11-24|MULTI-STEP POLYMER, ITS COMPOSITION, PREPARATION METHOD, USE AND COMPOSITION COMPRISING THE SAME|
    FR1461384|2014-11-24|FR1461384A| FR3028861B1|2014-11-24|2014-11-24|MULTI-STEP POLYMER, ITS COMPOSITION, PREPARATION METHOD, USE AND COMPOSITION COMPRISING THE SAME|
    US15/527,415| US20170355801A1|2014-11-24|2015-11-24|Multistage polymer, its composition, its method of preparation, its use and composition comprising it|
    RU2017121870A| RU2017121870A3|2014-11-24|2015-11-24|
    SG11201704159SA| SG11201704159SA|2014-11-24|2015-11-24|Multistage polymer, its composition, its method of preparation, its use and composition comprising it|
    EP15800803.7A| EP3224290A1|2014-11-24|2015-11-24|Multistage polymer, its composition, its method of preparation, its use and composition comprising it|
    JP2017527717A| JP2017535658A|2014-11-24|2015-11-24|Multistage polymer, composition thereof, process for its preparation, use thereof and composition comprising it|
    CN201580063551.5A| CN107001545A|2014-11-24|2015-11-24|Multistage polymerization thing, its composition, its preparation method, its purposes and the composition comprising it|
    BR112017010804A| BR112017010804A2|2014-11-24|2015-11-24|multi-stage polymer, its composition, its method of preparation, its use and composition comprising the same|
    KR1020177017443A| KR20170088951A|2014-11-24|2015-11-24|Multistage polymer, its composition, its method of preparation, its use and composition comprising it|
    PCT/EP2015/077538| WO2016083396A1|2014-11-24|2015-11-24|Multistage polymer, its composition, its method of preparation, its use and composition comprising it|
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