POLYOLEFINE COMPOSITION, ARTICLE UNDERSTANDING A POLYOLEFINE COMPOSITION, PROCESS FOR PREPARING THE

专利摘要:
heterophasic system with improved surface properties the present invention relates to a polyolefin composition comprising a heterophasic propylene copolymer having an mfr2 of at least 5 g / 10 min and a polyethylene (pe) having a density of at least 935 kg / m3 and a melt flow index mfr5 (190 ° c) of less than 1.5 g / 10min.
公开号:BR112014003238B1
申请号:R112014003238-6
申请日:2012-08-14
公开日:2020-12-15
发明作者:Georg Grestenberger；Christelle Grein；Cornelia Kock
申请人:Borealis Ag；
IPC主号:

专利说明:

[0001] The present invention relates to a new polyolefin composition comprising a heterophasic propylene copolymer and a polyethylene. The present invention also relates to an article comprising said polyolefin composition, a process for preparing the polyolefin composition and the uses thereof.
[0002] Polypropylene is the material of choice in many applications since it can be adapted for specific, necessary purposes. For example, heterophasic polypropylenes are widely used in the automotive industry (for example, in adhesive applications) because they combine good rigidity with reasonable impact resistance behavior. Heterophasic polypropylenes contain a polypropylene matrix in which an amorphous phase is dispersed. The amorphous phase contains a propylene copolymer rubber, such as an ethylene propylene rubber (EPR) or an ethylene propylene diene monomer polymer (EPDM). In addition, heterophasic polypropylene contains crystalline polyethylene to some extent. In the automotive industry, such grades of heterophasic polypropylene contain an amount of about 30% by weight of propylene copolymer rubber, which is normally produced directly in one or two gas-phase reactors or added externally to the matrix by means of a composition.
[0003] Injection molded parts are widely used in the automotive field. Automotive interior parts, such as panels, door trim, trim, etc. are commonly made of polymers. Especially propylene-based resins are widely used for these applications. These parts often try to imitate a leather-like or fabric-like surface and feel in order to give occupants a high-quality car impression. As a result, the materials used should provide a low level of surface gloss and good touch. The automotive industry especially asks for a good balance of mechanical performance and superior surface characteristics. In particular, formulations that show impact resistance, high scratch resistance and low gloss to reasonable stiffness are highly desired. Thus, in addition, to maintain the perception of high quality parts until the end of the car's useful life, the polymer must provide a high resistance to scratches, for example, keys, nails, rings etc.
[0004] Due to the low rigidity and surface hardness of polymers compared to metals they are much more prone to scratches. Therefore, in addition to design material and charge addition, additives are typically used to overcome this disadvantage. It is known to those skilled in the art that the scratch resistance of polypropylene / talc impact compounds can be improved by the addition of slip agents. Sliding agents such as fatty acid amides (Erucamide, Oleamide, Stearamide, Beenamide, etc.) reduce the friction coefficient of polymeric surfaces by migration of the mass to the surface. In addition, the addition of polyethylenes with a defined density and molecular weight to improve the surface durability of polypropylene compounds, as described, for example, in WO 2007/139622, WO 02 / 22731A2 or WO 2005 / 111145A1, affects the morphology of the dispersed rubber phase stabilizing the surface and the immediate subsurface layer of injection molds.
[0005] In combination both mechanisms lead to cost-effective scratch-resistant material formulations. However, in addition to high scratch resistance, low gloss and balanced mechanical performance are required for automotive interior applications. None or only one of the latter two features is considered in the prior art available. Thus, a simple solution that provides balanced mechanics and balanced surface properties at the same time is highly desired.
[0006] Thus, the object of the present invention is to provide a modified heterophasic polypropylene being characterized by good impact performance and surface properties on the one hand, and also a high modulus on the other hand.
[0007] The present inventors have surprisingly found that polyethylene (PE) with a high density and a low melt index (MFR) can improve impact performance and surface properties, while maintaining the material modulus at a high level. Polyethylene typically has a high molecular weight, and is preferably bimodal or multimodal. In particular, the composition claimed here uses grades of polyethylene which combine a high hardening potential with a high modulus and resistance to scratches and a low surface gloss.
[0008] In a first aspect, the present invention relates to a polyolefin (PO) composition, which comprises (a) a heterophasic propylene copolymer (HECO) comprising (a1) a polypropylene (PP), and (a2) a elastomeric propylene copolymer (E), wherein the heterophasic propylene copolymer (HECO) has an MFR2 (230 ° C) fluidity index of at least 5 g / 10min, and (b) a polyethylene (PE), with a density of at least 935 kg / m3, and an MFR5 flow rate (190 ° C) of less than 1.5 g / 10min.
[0009] Optionally, the polyolefin composition comprises an inorganic filler (F).
[00010] The present invention further relates to an article comprising the above polyolefin composition (PO). The article is preferably an automotive article.
[00011] Another aspect of the present invention is a process for preparing the above polyolefin composition (PO) by extruding the heterophasic propylene copolymer (HECO), polyethylene (PE), and optionally the inorganic filler (M) in a extrusion machine.
[00012] The present invention also relates to the use of a polyethylene (PE) having a density of at least 935 kg / m3, and an MFR5 fluidity index (190 ° C) of less than 1.5 g / 10min in a heterophasic propylene copolymer (HECO) for the supply of an article, preferably an automotive article, having a brightness at 60 ° which is at least 10% less than the brightness at 60 ° of an article made using the same heterophasic propylene copolymer (HECO) but without polyethylene (PE).
[00013] Other preferred embodiments of the present invention are described in the appended claims.
[00014] In the following, the invention will be described in more detail below.
[00015] The polyolefin (PO) composition of the present invention comprises in a preferred embodiment (a) at least 50% by weight, at least 60% by weight, more preferably from 50 to 90% by weight, even more preferably 60 to 80% by weight, of the heterophasic propylene copolymer (HECO); (b) at least 5% by weight, such as at least 10% by weight, more preferably 10 to 30% by weight, even more preferably 12 to 20% by weight, of polyethylene (PE); and (c) optionally at least 3% by weight, such as at least 5% by weight, more preferably from 5 to 30% by weight, even more preferably from 7 to 25% by weight, of inorganic filler (F), based on the total polyolefin composition (PO), preferably based on the total amount of polymers present in the polyolefin composition (PO) and inorganic filler (F), more preferably based on the heterophasic propylene copolymer (HECO), polyethylene (PE) and inorganic filler (F).
[00016] Preferably, the polyolefin (PO) composition does not contain a linear low density polyethylene. More preferably, polyethylene (PE) is the only polyethylene in the polyolefin (PO) composition. In another preferred embodiment, the polyolefin (PO) composition comprises the heterophasic propylene copolymer (HECO) and polyethylene (PE), as the only polymeric components.
[00017] Furthermore, it is understood that polyethylene (PE) is, in quite high amounts, present in the polyolefin composition. It is therefore preferable that the weight ratio of elastomeric propylene copolymer (E) to polyethylene (PE) [(E) / (PE)] is less than 2.0, more preferably below 1.8, even more preferably in the range of 1.0 to 2.0, even more preferably in the range of 1.2 to 1.8, and even more preferably in the range of 1.2 to below 1.6.
[00018] The flow rate MFR2 (230 ° C) of the total polyolefin composition (PO) is preferably at least 3.0 g / 10min, more preferably at least 5.0 g / 10min, even more preferably at range from 3.0 to 20.0 g / 10min, more preferably from 5.0 to 15.0 g / 10min.
[00019] As mentioned above, the polyolefin composition of the present invention is characterized by its good mechanical properties. Therefore, it is preferable that the polyolefin composition (PO) has an elastic modulus (ISO 527-2) of at least 1,000 MPa, more preferably in the range of 1,000 to 2,200 MPa, even more preferably in the range of 1,100 to 2,000 MPa and even more preferably in the range of 1,150 to 1,800 MPa. The method of measuring the modulus of elasticity is defined in the example section.
[00020] Furthermore, the impact must also be quite high. Therefore, it is understood that the polyolefin (PO) composition has a notched Charpy impact resistance (ISO 179 1eA) at 23 ° C of at least 35 kJ / m2, more preferably of at least 40 kJ / m2. m2, even more preferably in the range of 45 to 90 kJ / m2, even more preferably in the range of 50 to 70 kJ / m2, and / or has an impact resistance at -20 ° C of at least 5.5 kJ / m2, more preferably at least 6.0 kJ / m2, even more preferably in the range of 6.0-15.0 kJ / m2, even more preferably in the range of 7.0 to 13.0 kJ / m2 . The method of measuring impact resistance is defined in the example section.
[00021] The polyolefin (PO) composition, in accordance with the present invention, can be prepared by mixing the components in melting mixing devices suitable for the preparation of polymeric compounds, including, in particular, extruder machines, such as extruders. single screw as well as double screw extruders. Other suitable fusion mixing devices include planetary extruders and single screw co-kneaders. Especially preferred are twin screw extruders, including high intensity mixing and kneading sections. Suitable melting temperatures for preparing the compositions are in the range of 170 to 300 ° C, preferably in the range of 200 to 260 ° C.
[00022] In the following, the individual components are defined in more detail. Heterophasic Propylene Copolymer
[00023] The term "heterophasic" as used in the present invention indicates that the elastomeric propylene copolymer (E) is (finely) dispersed in the polypropylene (PP). In other words, polypropylene (PP) constitutes a matrix in which the elastomeric propylene copolymer (E) forms inclusions in the matrix, that is, in polypropylene (PP). Thus, the matrix contains (finely) dispersed inclusions that are not part of the matrix and said inclusions contain the elastomeric propylene copolymer (E). The term "inclusion", according to this invention, should preferably indicate that the matrix of and the inclusion form different phases in the heterophasic system, said inclusions are, for example, visible by high resolution microscopy, such as electron microscopy or scanning force microscopy.
[00024] Furthermore, it is preferable that the heterophasic propylene copolymer (HECO), before mixing with the other components mentioned here, comprises as polymer components only polypropylene (PP) and elastomeric propylene (E) copolymer. In other words, the heterophasic propylene copolymer (HECO) may contain additional additives, but no other polymer in an amount greater than 7.5% by weight, more preferably greater than 5% by weight, based on the total propylene copolymer heterophasic (HECO), more preferably, based on the polymers present in the propylene copolymer (HECO). An additional polymer that may be present in such low amounts is a polyethylene, which is a product of the reaction obtained by preparing the heterophasic propylene copolymer (HECO). Thus, it is particularly appreciated that a heterophasic propylene copolymer (HECO), as defined in the present invention, has only one polypropylene (PP), an elastomeric propylene copolymer (E) and, optionally, a polyethylene in quantities as mentioned in this paragraph.
[00025] Furthermore, the polyolefin (PO) composition of the present invention can be considered as a heterophasic system. Therefore, the polypropylene (PP) of the heterophasic propylene copolymer (HECO) also constitutes the matrix of the polyolefin composition in general (PO). The elastomeric propylene copolymer (E) and polyethylene (PE), and optionally also the inorganic filler (C) are (finely) dispersed in said matrix. Thus, the elastomeric propylene copolymer (E) and polyethylene (PE), can form separate inclusions in the matrix, that is, in which polypropylene (PP) or polyethylene (PE), can form an inclusion within the inclusion of the elastomeric propylene copolymer (E).
[00026] The heterophasic propylene copolymer (HECO) has an MFR2 fluidity index (230 ° C) of at least 5 g / 10min, more preferably in the range of 5 to 40 g / 10min, even more preferably in the range of 8, 0 to 25.0 g / 10 min, even more preferably in the range of 10 to 20 g / 10 min.
[00027] Preferably, it is desirable that the heterophasic propylene copolymer (HECO) is mechanically stable. Thus, the heterophasic propylene copolymer (HECO) is considered to have a melting temperature (Tm) of at least 135 ° C, more preferably in the innerval of 135 to 170 ° C, even more preferably in the range of 145 to 168 ° Ç.
[00028] Preferably, the propylene content in the heterophasic propylene copolymer (HECO) is 75.0 to 95.0% by weight, more preferably 80.0 to 90.0% by weight, based on the total of heterophasic propylene copolymer (HECO), more preferably based on the amount of polymer components of the heterophasic propylene copolymer (HECO), even more preferably based on the amount of polypropylene (PP) and elastomeric propylene copolymer (E) together. The remaining part constitutes the comonomers, as defined for polypropylene (PP), being a random propylene copolymer (PP-R) and the elastomeric propylene copolymer (E), respectively, preferably ethylene. Therefore, the comonomer content, preferably the ethylene content, is in the range of 5.0 to 25.0% by weight, more preferably in the range of 10.0 to 20.0% by weight.
[00029] As stated above, the heterophasic propylene copolymer (HECO) matrix is polypropylene (PP).
[00030] The polypropylene (PP) according to this invention preferably has a melt index MFR2 (230 ° C) of 20 to 100 g / 10min, preferably in the range of 30 to 80 g / 10min.
[00031] Therefore, it is preferable that polypropylene (PP) has an average molecular weight by weight (Mw) of 100,000 to 350,000 g / mol, more preferably from 150,000 to 300,000 g / mol.
[00032] A wide molecular weight distribution (MWD) improves the processability of polypropylene. Thus, the molecular weight distribution (MWD) of polypropylene (PP) is considered to be at least 2.8, more preferably at least 3.0, such as at least 3.3. In a preferred embodiment, the molecular weight distribution (MWD) is preferably between 2.8 and 10.0, even more preferably in the range of 3.0 to 8.0.
[00033] Polypropylene (PP) can be a random propylene copolymer (PP-R) or a propylene homogen (PP-H), the latter being preferred.
[00034] Thus, polypropylene (PP) is considered to have a comonomer content equal to or less than 5.0% by weight, more preferably equal to or less than 3.0% by weight.
[00035] The expression propylene homopolymer used in the present invention refers to a polypropylene that consists substantially, that is, of more than 99.5% by weight, even more preferably of at least 99.7% by weight, such as at least 99.8% by weight of propylene units. In a preferred embodiment, only the propylene units in the propylene homopolymer are detectable.
[00036] In the case of polypropylene (PP) being a random propylene copolymer (R-PP) it comprises monomers copolymerizable with propylene, for example, comonomers such as ethylene and / or α-olefins C4 to C12, in particular ethylene and / or α-olefins C4 to C10, for example, 1-butene and / or 1-hexene. Preferably, the random propylene copolymer (PP-R) comprises, in particular, consists of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the random propylene copolymer (PP-R) comprises - in addition to propylene - derivable units of ethylene and / or 1-butene. In a preferred embodiment, the random propylene copolymer (PP-R) includes derivatives of ethylene and propylene only. The comonomer content in the random propylene copolymer (PP-R) is preferably in the range of more than 0.5 to 5.0% by weight, even more preferably in the range of more than 0.5 to 3.0% in weight Weight.
[00037] The term "random copolymer" indicates that the comonomers within the propylene copolymer (PP) are distributed at random. Randomness defines the number of isolated comonomer units, that is, those that do not have neighboring comonomer units compared to the total amount of comonomers in the polymer chain.
[00038] Polypropylene (PP) can have a content of soluble in cold xylene (XCS) in the range of up to 6.0% by weight. Consequently, polypropylene (PP) can have a content of soluble in cold xylene (XCS) in the range of 0.5 to 4.5% by weight, as well as 0.7 to less than 3.0% by weight.
[00039] Another essential component of the heterophasic propylene copolymer (HECO) is the elastomeric propylene copolymer (E).
[00040] The elastomeric propylene copolymer (E) preferably comprises monomers copolymerizable with propylene, for example, comonomers such as ethylene and / or α-olefins C4 to C12, in particular ethylene and / or α-olefins C4 to C10, for example, 1-butene and / or 1-hexene. Preferably, the elastomeric propylene copolymer (E) comprises, in particular, consists of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the elastomeric propylene copolymer (E) comprises - in addition to propylene - derivable units of ethylene and / or 1-butene. Thus, in an especially preferred embodiment, the propylene elastomeric copolymer phase (E) comprises derivable units of ethylene and propylene only.
[00041] In the case of polypropylene (PP) being a random propylene copolymer (R-PP) it is preferred that the comonomer (s) of the random propylene copolymer (R-PP) and the elastomeric propylene copolymer (E) are the themselves.
[00042] The properties of the elastomeric propylene copolymer (E) phase mainly influences the cold soluble xylene (XCS) content of the heterophasic propylene copolymer (HECO). Thus, according to the present invention, the cold xylene soluble fraction (XCS) of heterophasic propylene copolymer (HECO) is considered to be the elastomeric propylene copolymer (E) of the heterophasic propylene copolymer (HECO). In the context of the present invention, the fraction soluble in cold xylene (XCS) is also referred to as "amorphous fraction".
[00043] Therefore, the amount of elastomeric propylene copolymer (E), i.e. the cold xylene-soluble fraction (XCS), of the heterophasic propylene copolymer (HECO) is preferably at least 20% by weight , most preferably it is in the range of 20 to 45% by weight, even more preferably in the range of 25 to 35% by weight. These values are based on the heterophasic propylene copolymer (HECO) and not on the polyolefin composition (PO).
[00044] In addition, the molecular weight of the elastomeric propylene copolymer (E) has an impact on the properties of the heterophasic propylene copolymer (HECO). Small particles are formed in the case of the matrix and the elastomeric phase have a similar molecular weight. Small particles are generally preferred, as this improves the overall properties of the heterophasic system. However, in the present invention, the matrix preferably has a tendency to have a very high flow rate, and therefore a slightly lower average molecular weight. Therefore, also the elastomeric propylene copolymer (E) must have a low molecular weight average in order to obtain small particles. On the other hand, this would mean, in the present case, a severe reduction in the average molecular weight of low weight for the elastomeric propylene copolymer (E), which has a negative impact on the mechanical properties. Therefore, the intrinsic viscosity has to be chosen carefully.
[00045] Low intrinsic viscosity (IV) values reflect a low molecular weight average molecular weight. Thus, the elastomeric propylene copolymer (E) phase, that is, the cold xylene soluble fraction (XCS) of the heterophasic propylene copolymer (HECO), is considered to have an intrinsic viscosity (IV) in the range of 1, 5 to 3.5 dL / g, more preferably in the range equal to or greater than 1.7, to equal to or less than 3.0 dL / g, even more preferably in the range equal to or greater than 1.8 and less or equal to 2.8 dL / g.
[00046] The comonomer content, preferably the ethylene content, in the elastomeric propylene (E) copolymer phase should preferably be also at a specific interval. Therefore, in a preferred embodiment, the comonomer content, more preferably the ethylene content, of the elastomeric propylene copolymer (E), that is, of the cold xylene soluble fraction (XCS) of the heterophasic propylene copolymer (HECO ), is equal to or less than 50.0% by weight, more preferably in the range of 25.0 to 50.0% by weight, even more preferably in the range of 30.0 to 46.0% by weight. Thus, the propylene content of the elastomeric propylene copolymer (E), that is to say, of the soluble cold xylene fraction (XCS) of the heterophasic propylene copolymer (HECO), is considered to be more than 50.0% by weight, more preferably in the range of more than 50.0 to 75.0% by weight, even more preferably in the range of 54.0 to 70.0% by weight.
[00047] As will be explained below, heterophasic polypropylene (HECO) as well as its individual components (matrix and elastomeric copolymer) can be produced by mixing different types of polymer, that is, of different molecular weights and / or the comonomer content . However, it is preferred that the heterophasic polypropylene (HECO) as well as its individual components (matrix and elastomeric copolymer) are produced in a sequential step process, using reactors in a series configuration and operating under different reaction conditions. As a consequence, each of the fractions prepared in a specific reactor will have its own molecular weight distribution and / or comonomer content distribution.
[00048] The heterophasic propylene copolymer (HECO) according to the present invention is preferably produced in a sequential polymerization process, that is, in a multi-stage process, known in the art, in which polypropylene (PP) is produced in at least one suspension reactor, preferably in a suspension reactor and, optionally, in a subsequent gas phase reactor, and subsequently the elastomeric propylene copolymer (E) is produced in at least one, that is, one or two, gas phase reactor (s).
[00049] It is therefore preferable that the heterophasic propylene copolymer (HECO) is produced in a sequential polymerization process comprising the steps of (a) polymerization of propylene and, optionally, at least one ethylene and / or α-olefin C4 to C12 in a first reactor (R1) obtaining the first polypropylene (PP), preferably, said first polypropylene fraction is a first propylene homopolymer, (b) transferring the first polypropylene fraction in a second reactor (R2) , (c) polymerization in the second reactor (R2) and in the presence of said first fraction of propylene and polypropylene, optionally at least one ethylene and / or α-olefin C4 to C12 thus obtaining the second fraction of polypropylene, preferably , said second fraction of polypropylene being a second homopolymer of propylene, said first fraction of polypropylene and said second fraction of polypropylene form polypropylene (PP), that is, the matrix of the copolymer of pr heterophasic opylene (HECO), (d) transferring the polypropylene (PP) from step (c) in a third reactor (R3), (e) polymerization in the third reactor (R3) and, in the presence of the polypropylene (PP) obtained in step (c), propylene and at least one ethylene and / or α-olefin C4 to C12 thus obtaining a first fraction of elastomeric propylene copolymer, the first fraction of elastomeric propylene copolymer being dispersed in polypropylene (PP), (f) transfer of polypropylene (PP), in which the first fraction of elastomeric propylene copolymer is dispersed in the fourth reactor (R4), and (g) polymerization in the fourth reactor (R4), and in the presence of the mixture obtained in step ( e), of propylene and at least one ethylene and / or α-olefin C4 to C12 thus obtaining the second fraction of elastomeric propylene copolymer, polypropylene (PP), the first fraction of elastomeric propylene copolymer, and the second fraction of elastomeric propylene copolymer forms the heterophasic propylene copolymer (HE CO).
[00050] It is clear that in the first reactor (R1) the second fraction of polypropylene can be produced and in the second reactor (R2) the first fraction of polypropylene can be obtained. The same goes for the elastomeric propylene copolymer phase. Thus, in the third reactor (R3) the second fraction of elastomeric propylene copolymer can be produced while in the fourth reactor (R4), the first fraction of elastomeric propylene copolymer is made.
[00051] Preferably, between the second reactor (R2) and the third reactor (R3) and, optionally, between the third reactor (R3) and fourth reactor (R4), the monomers are thrown out.
[00052] The term "sequential polymerization process" indicates that the heterophasic propylene copolymer (HECO) is produced in at least two, like three or four reactors connected in series. Thus, the present process comprises at least a first reactor (R1) and a second reactor (R2), more preferably, a first reactor (R1), a second reactor (R2), a third reactor (R3) and a fourth reactor (R4). The term "polymerization reactor" will indicate that the main polymerization occurs. Thus, if the process consists of four polymerization reactors, this definition does not exclude the possibility that the overall process comprises, for example, a prepolymerization step in a prepolymerization reactor. The term "constitutes by" is only a final formulation, taking into account the main polymerization reactors.
[00053] The first reactor (R1) is preferably a suspension reactor (SR) and can be any continuous or simple agitated batch tank reactor or closed circuit reactor operating in bulk or in suspension. Mass means polymerization in a reaction medium that comprises at least 60% monomer (w / w).
[00054] According to the present invention, the suspension reactor (SR) is preferably a (loose) closed loop reactor (LR).
[00055] The second reactor (R2), the third reactor (R3) and the fourth reactor (R4) are preferably gas phase reactors (GPR). Such gas phase reactors (GPR) can be any mechanically mixed bed or fluid reactors. Preferably, the gas phase reactors (GPR) comprise a mechanically stirred fluidized bed reactor with gas velocities of at least 0.2 m / sec. Thus, the gas phase reactor is considered to be a type of fluidized bed reactor, preferably with a mechanical stirrer.
[00056] Thus, in a preferred embodiment, the first reactor (R1) is a suspension reactor (SR), like a closed loop reactor (LR), while the second reactor (R2), the third reactor (R3) and the fourth reactor (R4) are gas phase reactors (GPR). Therefore, for the present process, at least four, preferably four polymerization reactors, that is, a suspension reactor (SR), such as a closed loop reactor (LR), a first gas phase reactor (GPR- 1), a second gas phase reactor (GPR-2) and a third gas phase reactor (GPR-3) connected in series are used. If necessary, before the suspension reactor (SR), a prepolymerization reactor is placed.
[00057] A preferred multistage process is a "cycle-gas phase" process, as developed by Borealis A / S, Denmark (known as BORSTAR® technology) described in the patent literature, for example, as in EP 0 887 379, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
[00058] A more suitable suspension-gas phase process is Basell's Spheripol® process.
[00059] Preferably, in the present process to produce the heterophasic propylene copolymer (HECO) as defined above under the conditions for the first reactor (RI), that is, the suspension reactor (SR), as a closed circuit reactor ( LR), from step (a) can be as follows: - the temperature is within the range of 50 ° C to 110 ° C, preferably between 60 ° C and 100 ° C, more preferably between 68 and 95 ° C, - the pressure is in the range of 20 bar to 80 bar (2,000 to 8,000 kPa), preferably between 40 bar to 70 bar (4,000 to 7,000 kPa), - hydrogen can be added to control the molecular mass in a manner known to you.
[00060] Subsequently, the reaction mixture from step (a) is transferred to the second reactor (R2), that is, the gas phase reactor (GPR-1), that is, to step (c), where the The conditions of step (c) are preferably as follows: - the temperature is within the range of 50 ° C to 130 ° C, preferably between 60 ° C and 100 ° C, - the pressure is within the range of 5 bar at 50 bar (500 to 5,000 kPa), preferably between 15 bar and 35 bar (1,500 to 3,500 kPa), - hydrogen can be added to control molecular mass in a manner known to you.
[00061] The condition in the third reactor (R3) and the fourth reactor (R4), preferably in the second gas phase reactor (GPR-2) and third gas phase reactor (GPR-3), is similar to that of the second reactor (R2).
[00062] The residence time may vary in the three reactor zones.
[00063] In an embodiment of the process for the production of polypropylene, the residence time in the bulk reactor, for example, closed loop, is in the range of 0.1 to 2.5 hours, for example, 0 , 15 to 1.5 hours and the residence time in the gas phase reactor will generally be 0.2 to 6.0 hours, such as 0.5 to 4.0 hours.
[00064] If desired, polymerization can be carried out in a known manner, under supercritical conditions, in the first reactor (R1), that is, in the suspension reactor (SR), as in the closed circuit reactor (LR), and / or as a condensed mode in the gas phase reactors (GPR).
[00065] Preferably, the process also comprises a prepolymerization, with the catalyst system, as described in detail below, comprising a Ziegler-Natta pro-catalyst, an external donor and, optionally, a co-catalyst.
[00066] In a preferred embodiment, prepolymerization is carried out as suspension polymerization in bulk liquid propylene, that is, the liquid phase comprises mainly propylene, with a small amount of other reagents and, optionally, inert components , dissolved there.
[00067] The prepolymerization reaction is typically carried out at a temperature of 10 to 60 ° C, preferably 15 to 50 ° C, and more preferably 20 to 45 ° C.
[00068] The pressure in the prepolymerization reactor is not critical, but it must be high enough to maintain the reaction mixture in liquid phase. Thus, the pressure can be 20 to 100 bar (2,000 to 10,000 kPa), for example, 30 to 70 bar (3,000 to 7,000 kPa).
[00069] The catalyst components are preferably all introduced in the prepolymerization step. However, when the solid catalyst component (I) and co-catalyst (ii) can be fed separately, it is possible that only a part of the co-catalyst is introduced in the prepolymerization phase and the remainder in stages of subsequent polymerization. In addition, in such cases, it is necessary to introduce so much co-catalyst in the prepolymerization phase that a sufficient polymerization reaction is obtained there.
[00070] It is also possible to add other components for the prepolymerization phase. Thus, hydrogen can be added in the prepolymerization phase to control the molecular weight of the prepolymer, as is known in the art. In addition, the antistatic additive can be used to prevent particles from adhering to each other or to the reactor walls.
[00071] Precise control of prepolymerization conditions and reaction parameters is within the skill of the art.
[00072] According to the invention, the heterophasic propylene copolymer (HECO) is obtained by a multi-stage polymerization process, as described above, in the presence of a catalyst system comprising as component (i) a pro-catalyst of Ziegler-Natta which contains a transesterification product of a lower alcohol and a phthalic ester.
[00073] The pro-catalyst used according to the invention is prepared by a) reaction of a spray crystallized addition product or solidified by MgCl2 emulsion and a C1-C2 alcohol with TiCl4 b) reaction of the product from step a) with a dialkylphthalate of formula (I)
wherein R1 'and R2' independently represent at least C5 alkyl under conditions where a transesterification between said C1 to C2 alcohol and said formula (I) dialkyl phthalate is carried out in order to form the internal donor c) washing the product from step b) or d) optionally reacting the product from step c) with additional TiCl4.
[00074] The pro-catalyst is produced as defined, for example, in patent applications WO 87/07620, WO 92/19653, WO 92/19658 and EP 0 491 566. The content of these documents is included here by reference.
[00075] First an addition product of MgCl2 and a C1-C2 alcohol of the formula MgCl2 * nROH, where R is methyl or ethyl and n is 1 to 6, is formed. Ethanol is preferably used as alcohol.
[00076] The addition product, which is first melted and then crystallized by spraying or solidified by emulsion, is used as a catalyst carrier.
[00077] In the next step, the addition product crystallized by spraying or solidified by emulsion of the formula MgCl2 * nROH, where R is methyl or ethyl, preferably ethyl and n is 1 to 6, is contact with TiCl4 to form a titanized carrier, followed by the steps of adding to said titanized vehicle (i) a dialkylphthalate of formula (I) with R1 'and R2', independently, being at least one C5 alkyl, such as at least one C8 alkyl, or preferably (ii) a dialkyl phthalate of formula (I) with R1 'and R2' being the same and being at least one C5 alkyl, such as at least one C8 alkyl, or more preferably (iii) a dialkyl phthalate of formula (I) selected from the group consisting of propylhexyl phthalate (PrHP), dioctyl phthalate (DOP), diisopropyl phthalate (DIDP), and ditridecyl phthalate (DTDP), even more preferably the dialkyl phthalate of formula (I) is a dioctyl phthalate (DOP), such as diisopropyl or diethylhexyl phthalate, in particular diethylhexyl phthalate, to form a first product, • subject said first product to suitable transesterification conditions, that is, at a temperature above 100 ° C, preferably between 100 and 150 ° C, more preferably between 130 and 150 ° C, such that said methanol or ethanol is transesterified with said ester groups of said dialkyl phthalate of formula (I) to preferably form at least 80 mol%, more preferably 90 mol%, more preferably 95 mol% of a dialkyl phthalate formula (II)
with R1 and R2 being methyl or ethyl, preferably ethyl, the dialkyl phthalate of formula (II), being the internal donor and • recovering said transesterification product as the composition of the pro-catalyst (component (i)).
[00078] The MgCl2 * nROH addition product, where R is methyl or ethyl and n is 1 to 6, is in a preferred melted embodiment and then the melt is preferably injected by a gas in a cooled solvent or a cooled gas, where the addition product is crystallized in a morphologically advantageous form, as described for example in WO 87/07620.
[00079] This crystallized addition product is preferably used as the catalyst carrier and reacted with the pro-catalyst useful in the present invention, as described in WO 92/19658 and WO 92/19653.
[00080] As the catalyst residue is removed by extraction, a product added from the titanized carrier and the internal donor is obtained, in which the resulting group of the alcohol ester has changed.
[00081] In case sufficient titanium remains in the operator, it will act as an active element of the pro-catalyst.
[00082] Otherwise, titanization is repeated after the above treatment, in order to ensure a sufficient concentration of titanium and, therefore, the activity.
[00083] Preferably the pro-catalyst used according to the invention contains a maximum of 2.5% by weight of titanium, preferably a maximum of 2.2% by weight and more preferably 2.0% by weight of maximum. Its donor content is preferably between 4 to 12% by weight and more preferably between 6 and 10% by weight.
[00084] More preferably, the pro-catalyst used according to the invention was produced using ethanol as the alcohol and dioctyl phthalate (DOP) as the dialkyl phthalate of formula (I), obtaining the diethyl phthalate (DEP) as the internal donor compound.
[00085] Even more preferably, the catalyst used according to the invention is Borealis BCF20P catalyst (prepared according to WO 92/19653 as disclosed in WO 99/24479, especially with the use of dioctyl phthalate as the dialkyl phthalate of formula (I ) according to WO 92/19658) or Polytrack 8502 catalyst, commercially available from Grace.
[00086] For the production of the heterophasic propylene copolymer (HECO) according to the invention, the catalyst system used preferably comprises, in addition to the special Ziegler-Natta pro-catalyst, an organometallic co-catalyst, as component (ii).
[00087] Therefore, it is preferred to choose the co-catalyst from the group consisting of trialkyl aluminum, such as triethyl aluminum (TEA), dialkyl aluminum chloride and alkyl aluminum sesquichloride.
[00088] The component (iii) of the catalyst system used is an external donor represented by the formula (IIIia) or (IIIb). Formula (IIIa) is defined by Si (OCH3) 2R25 (IIIa) where R5 represents a branched alkyl group having 3 to 12 carbon atoms, preferably a branched alkyl group having 3 to 6 carbon atoms, or a cycloalkyl having 4 to 12 carbon atoms, preferably a cycloalkyl having 5 to 8 carbon atoms.
[00089] In particular, it is preferred that R5 is selected from the group consisting of iso-propyl, iso-butyl, iso-pentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cyclohepty.
[00090] Formula (IIIb) is defined by Si (OCH2CH3) 3 (NRxRy) (IIIb) where Rx and Ry can be the same or different and represent a hydrocarbon group having from 1 to 12 carbon atoms.
[00091] Rx and Rysão independently selected from the group consisting of the group of linear aliphatic hydrocarbons having from 1 to 12 carbon atoms, group of branched aliphatic hydrocarbons having from 1 to 12 carbon atoms and group of cyclic aliphatic hydrocarbons having from 1 to 12 carbon atoms. In particular, it is preferred that Rx and Ry are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso-pentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
[00092] Most preferably both Rx and Rys are the same, even more preferably both Rx and Rys are an ethyl group.
[00093] More preferably, the external donor of formula (IIIb) is diethylaminyltriethoxysiloxane
[00094] More preferably, the external donor is of formula (IIIa), such as dicyclopentyl dimethoxy silane [Si (OCH3) 2 (cyclopentyl) 2] or diisopropyl dimethoxy silane [Si (OCH3) 2 (CH (CH3) 2) two].
[00095] In another embodiment, the Ziegler-Natta pro-catalyst can be modified by polymerizing a vinyl compound, in the presence of the catalyst system, comprising the special Ziegler-Natta pro-catalyst (component (i )), an external donor (component (iii) and, optionally a co-catalyst (component (iii)), which vinyl compound has the formula: CH2 = CH-CHR3R4 where R3 and R4 together form a saturated ring , unsaturated or aromatic 5- or 6-membered or independently represent an alkyl group comprising 1 to 4 carbon atoms, and the modified catalyst is used for the preparation of the heterophasic propylene copolymer according to this invention. polymerized can act as an a-nucleating agent.
[00096] With regard to the modification of catalyst, reference is made to international applications WO 99/24478, WO 99/24479 and in particular WO 00/68315, incorporated herein by reference with respect to the reaction conditions relating to the modification of the catalyst, as well as with respect to the polymerization reaction.
[00097] Thus, the heterophasic propylene copolymer (HECO) is considered to be α-nucleated. In the event that α-nucleation is not effected by a vinylcycloalkane polymer or a vinylalkane polymer as indicated above, the following α-nucleation agents (N) may be present: (i) salts of monocarboxylic acids and polycarboxylic acids, for example , sodium benzoate or aluminum tert-butylbenzoate, and (ii) dibenzylidenosorbitol (eg 1,3: 2,4 dibenzylidenosorbitol) and derivatives of dibenzylidenosorbitol substituted by C1-C8 alkyl, such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethylbenzyl or dimethylsorbitol or dimethyl , 1,3: 2,4 di (methylbenzylidene) sorbitol), or substituted nonitol derivatives, such as 1,2,3 tridesoxy-4,6: 5,7-bis-0 - [(4-propylphenyl) -methylene ] -nonitol, and (iii) salts of phosphoric acid diesters, for example, 2,2'-methylenebis (4,6, di-tert-butylphenyl) sodium phosphate or aluminum-hydroxy-bis 2,2'-methylene -bis (4,6-di-t-butylphenyl) phosphate], and (iv) mixtures thereof. Polyethylene (PE)
[00098] According to the present invention, polyethylene (PE), must have an MFR5 melt index (190 ° C) of less than 1.50 g / 10min, preferably 1.00 g / 10min or less, more preferably 0.80 g / 10 min or less, such as 0.60 g / 10 min or less. Thus, it is preferred that the polyethylene (PE) should have a melt flow index MFR5 (190 ° C) in the range of 0.08 to less than 1.50 g / 10min, more preferably in the range of 0.12 to 1.00 g / 10min, even more preferably in the range of 0.15 to 0.80 g / 10min.
[00099] Polyethylene (PE) is typically a high density polyethylene (HDPE). Thus, polyethylene (PE) is considered to have a density of at least 935 kg / m3, such as 935 to 975 kg / m3, more preferably to have a density of at least 940 kg / m3, such as 940 kg / m3 m3 to 965 kg / m3, even more preferably it has a density of at least 943 kg / m3, such as from 943 kg / m3 to 960 kg / m3.
[000100] As mentioned above, polyethylene (PE) is also dispersed in the matrix, that is, in polypropylene (PP), of the heterophasic propylene copolymer (HECO) and thus forming the total polyolefin composition.
[000101] In an especially preferred embodiment, polyethylene (PE), for example, high density polyethylene (HDPE), is bimodal or multimodal. More particularly, polyethylene (PE), for example, high density polyethylene (HDPE), is bimodal or multimodal, taking into account the distribution of molecular weight and / or the distribution of comonomers.
[000102] Therefore, polyethylene (PE), for example, high density polyethylene (HDPE), preferably comprises at least two fractions of different comonomer content and / or of different weight of average molecular weight Mw.
[000103] Thus, in a specific embodiment, polyethylene (PE), for example, high density polyethylene (HDPE), preferably comprises a fraction (A) and a fraction (B), said fraction (A) having a lower comonomer content and / or a lower weight of average molecular weight Mw measured according to ISO 16014 than fraction (B).
[000104] Thus, fraction (A) is an ethylene homopolymer or an ethylene copolymer with the proviso that if fraction (A) is an ethylene copolymer, the comonomer content is preferably lower in comparison with the comonomer content of the fraction (B). In turn, fraction (B) can also be an ethylene homopolymer, or alternatively an ethylene copolymer, the latter being preferred. In the case of polyethylene (PE), for example, high density polyethylene (HDPE), that is, the fraction (A) and / or the fraction (B), comprise comonomers (it is appreciated that the comonomers are selected from the group consisting of 1-butene, 1-octene, 1-hexene and 4-methyl-penetene.
[000105] Thus, the fraction (A) of polyethylene (PE), for example, high density polyethylene (HDPE), is preferably defined as follows: - It is an ethylene copolymer or an ethylene copolymer with a comonomer, such as 1-butene or 1-hexene, the content of 0.5 to 3.0% by weight. Furthermore, it is understood that the weight of the average molecular weight Mw measured according to the ISO 16014 standard of fraction (A) ranges from 200,000 to 500,000 g / mol, more preferably from 250,000 to 400,000 g / mol. In addition, the density measured according to ISO 1183-187 of the fraction (A) is preferably higher compared to the density of the fraction (B). Thus, it is especially preferred that the fraction (A) has a density measured according to the ISO 1183-187 standard in the range of 950-980 kg / m3, more preferably, from 955 to 965 kg / m3.
[000106] On the other hand, the fraction (B) of polyethylene (PE), for example, high density polyethylene (HDPE), is preferably defined as follows: - It is an ethylene copolymer with a comonomer, as 1- butene or 1-hexene, content from 1.5 to 6.0% by weight. Furthermore, it is understood that the weight of the average molecular weight Mw measured according to the ISO 16014 standard of the fraction (B) ranges from 350,000 to 600,000 g / mol, more preferably from 300,000 to 500,000 g / mol. In addition, the density measured according to ISO 1183-187 of the fraction (B) can vary from 920 to 950 kg / m3, more preferably from 925 to 940 kg / m3.
[000107] The weight ratio between the fraction (A) and the fraction (B) of polyethylene (PE), for example, high density polyethylene (HDPE), varies from 70:30 to 30:70, more preferably 60 : 40 to 40:60.
[000108] The total comonomer content other than ethylene from polyethylene (PE), for example, high density polyethylene (HDPE), is preferably 0.2 to 10% by weight, preferably 1.0 to 3 , 0% by weight, as measured by FTIR as defined in the example section.
[000109] High density polyethylene (HDPE), as defined in the present invention can be produced by mixing two or more monomodal polyethylene having maximum centered differently on its MWDs or with different comonomer content.
[000110] Alternatively and preferably, high density polyethylene (HDPE) can be produced by polymerization using conditions that create a bimodal or multimodal polymer product, using, for example, a catalyst system or mixture of two or more different sites catalytic, using the polymerization process in two or more stages with different process conditions in the different phases (for example, different temperatures, pressures, polymerization media, partial hydrogen pressures, comonomer content, etc.).
[000111] Such high density polyethylene (HDPE) can be produced relatively simply by a polymerization of ethylene, of several stages, for example, using a series of reactors, with the addition of comonomer only in the reactor (s) ) used for the production of the higher / higher molecular weight component (s). Examples of production of high density polyethylene (HDPE) are given in EP 0 778 289 and W0 92/12182.
[000112] If an ethylene homopolymer component is produced by suspension polymerization, involving the use of recycled diluent, the diluent may contain small amounts of higher α-olefins as contaminants. Likewise, in which a polymerization stage previously produced an ethylene copolymer component, small amounts of comonomer can be carried over to an ethylene homopolymerization phase.
[000113] Therefore, by ethylene homopolymer here is meant a polymer containing at least 99.9% by weight of ethylene units. Just as in multi-stage / multiple reactor polymerization using more than one catalyst system, homo-polymerization catalysts can be at least partially active during the copolymerization reaction, any copolymer component becoming less than 5% by weight of the total polymer should not be considered the lowest molecular weight component in a high density polyethylene (HDPE) according to the invention.
[000114] Polymerization reactions used for the production of high density polyethylene (HDPE) may involve homo-polymerization of ethylene or copolymerization of conventional reactions, for example, in gas phase, suspension phase, polymerizations in liquid phase, using conventional reactors, for example, closed circuit reactors, gas phase reactors, batch reactors, etc. (see for example WO 97/44371 and WO 96/18662). The catalyst systems used can also be any conventional system, for example, chromium catalysts, Ziegler-Natta and metallocene or metallocene / aluminoxane catalysts, catalysts either homogeneous or more preferably heterogeneous, for example, supported catalysts in organic or inorganic particles, in particular, magnesium halides or inorganic oxides such as silica, alumina or silica-alumina. For the preparation of the high molecular weight component, in particular, the use of supported Ziegler catalysts is especially desirable, as the molecular weight can be conveniently controlled using hydrogen. It is also possible to use the supported metallocene catalysts since it is particularly simple to select the desired molecular weights by the appropriate selection of certain metallocenes. The metallocenes used will typically be metals from group IVa to VIa (in particular, Zr or Hf) complexed by optionally substituted cyclopentadienyl groups, for example, groups that carry hanging or fused substituents optionally linked by bridge groups. Suitable metallocenes and aluminoxane co-catalysts are widely described in the literature, for example, in the patent publications of Borealis, Hoechst, Exxon, etc.
[000115] Normally and preferably, however, high density polyethylene (HDPE) will be prepared using multi-stage polymerization using a single catalyst system or a plurality of catalyst systems, for example, two or more metallocenes, from one or more metallocenes and one or more Ziegler catalysts, two or more chromium catalysts, one or more chromium catalysts and one or more Ziegler catalysts, etc. Especially preferably, the same catalyst system is used at different stages of polymerization, for example, a catalyst system, as described in EP 0 688 794. Inorganic cargo
[000116] In addition to the polymer components the polyolefin composition (PO) can comprise an inorganic filler (F), in amounts of up to 30% by weight, preferably in the range of 5 to 30% by weight, more preferably in the range of 7 to 25% by weight. Preferably, the inorganic filler (F) is a phyllosilicate, mica or wollastonite. Even more preferred the inorganic charge (C) is selected from the group consisting of mica, volastonite, kaolinite, smectite, montmorillonite and talc. The most preferred inorganic filler (F) is talc.
[000117] The mineral filler (F) preferably has a cut-off particle size d95 [weight percent] of 20 μm or less, more preferably in the range of 2.5 to 10 μm, as in the range of 2.5 to 8.0 μm.
[000118] Typically, the inorganic filler (F) has a surface area measured according to the commonly known BE method, with N2 gas as an adsorption analysis of less than 22 m2 / g, more preferably less than 20 m2 / g, even more preferably less than 18 m2 / g. Inorganic fillers (F) that meet these requirements are preferably anisotropic mineral fillers (F), such as talc, mica and wollastonite. Other components
[000119] The instant polyolefin (PO) composition can comprise typical additives, such as acid scavengers (AS), antioxidants (AO), nucleating agents (NA), hindered amine light stabilizers (HALS), sliding agents ( SA), and pigments. Preferably, the amount of additives, excluding the inorganic filler (F) should not exceed 7% by weight, more preferably it should not exceed 5% by weight, as no more than 3% by weight, within the instant composition. Articles made from the composition of polyolefins (PO)
[000120] The polyolefin (PO) composition of the present invention is preferably used for the production of automotive articles, such as molded automotive articles, preferably automotive injection molded articles. Even more preferred is the use for the production of car interiors and exteriors, such as bumpers, side strips, step assist, body panels, spoilers, panels, interior finishes and the like.
[000121] The present invention also provides articles (automobiles), such as injection molded articles, comprising at least 60% by weight, more preferably at least 80% by weight, even more preferably at least 95% by weight, as a compound , of the inventive polyolefin (PO) composition. Thus, the present invention is especially directed to automotive articles, especially for automobile interiors and exteriors, such as bumpers, side strips, step assist, body panels, spoilers, panels, interior finishes and the like, including at least 60% by weight, more preferably, at least 80% by weight, even more preferably at least 95% by weight, as a compound, of the inventive polyolefin (PO) composition. Uses according to the invention
[000122] The present invention also relates to the use of a polyethylene (PE), with a density of at least 935 kg / m3, and an MFR5 fluidity index (190 ° C) of less than 1.5 g / 10min in a heterophasic propylene copolymer (HECO) to reduce the gloss of said heterophasic propylene copolymer (HECO) or the article made from the heterophasic propylene copolymer (HECO) comprising polyethylene (PE), the improvement is determined as the brightness at 60 °, where the brightness of 60 ° in relation to the heterophasic propylene copolymer (HECO) comprising the polyethylene (PE) is at least 10% less, preferably 10 to 35% less, more preferably it is 12 to 30% lower than the 60 ° gloss of the same heterophasic propylene copolymer (HECO) but without polyethylene (PE), the percentage is determined by the following formula
where G (HECO) is the 60 ° gloss of heterophasic propylene copolymer (HECO) without polyethylene (PE), and G (HECO + PE) is the 60 ° gloss of heterophasic propylene copolymer (HECO) comprising polyethylene (PE).
[000123] That is, the addition of polyethylene (PE) to the heterophasic propylene copolymer (HECO) reduces its brightness, preferably without compromising the other optical or mechanical properties of the heterophasic propylene copolymer (HECO). Preferred embodiments of the polyethylene (PE) and / or the heterophasic propylene copolymer (HECO) are provided above in the discussion of the inventive polyolefin (PO) composition.
[000124] In a preferred embodiment, the claimed use further involves the following characteristics: the heterophasic propylene copolymer (HECO) comprising polyethylene (PE) (or its articles) in comparison with the same heterophasic propylene copolymer (HECO) ) without polyethylene (PE) (or its articles) has (a) zero visibility, which is at least 25% less, more preferably 25 to 50% less, even more preferably 30 to 45% less, the percentage being determined by the following formula
where S (HECO) is the zero visibility of the heterophasic propylene copolymer (HECO) without the polyethylene (PE), and S (HECO + PE) is the zero visibility of the heterophasic propylene copolymer (HECO) which comprises the polyethylene (PE) ); and / or (b) an impact resistance at 23 ° C, which is at least 90% higher, more preferably 90 to 150% higher, even more preferably 95 to 130% higher, where the impact force at 23 ° C, is measured as the impact force with Charpy notch according to ISO 179 1eA at 23 ° C, using test specimens of injection molded bars of 80x10x4 mm3 prepared according to ISO 294-1: 1996, the percentage being determined by the following formula
where I (HECO) is the impact force at 23 ° C of the heterophasic propylene copolymer (HECO) without polyethylene (PE), and I (HECO + PE) is the impact force at 23 ° C of the propylene copolymer heterophasic (HECO) comprising polyethylene (PE); and / or (c) an impact resistance at -20 ° C, which is at least 60% greater, more preferably at least 75%) greater, even more preferably 60 to 120% higher, even more preferably 75 to 120% higher, where impact strength at -20 ° C is measured as notched Charpy impact strength according to ISO 179 1eA at -20 ° C, using 80x10x4 mm3 injection molded bar test specimens prepared according to ISO 294-1: 1996, the percentage being determined by the following formula
where I (HECO) is the impact strength at -20 ° C of the heterophasic propylene copolymer (HECO) without polyethylene (PE), and I (HECO + PE) is the impact resistance at -20 ° C of the heterophasic propylene copolymer (HECO) which comprises polyethylene (PE).
[000125] In another preferred embodiment, the present invention relates to the use of a polyethylene (PE), with a density of at least 935 kg / m3, and an MFR5 (190 ° C) fluidity index of less than 1.5 g / 10min in a heterophasic propylene copolymer (HECO) for the supply of an article, preferably an automotive article, where the article in relation to an article made using the heterophasic propylene copolymer (HECO) without polyethylene (PE) has the following characteristics: (a) a brightness at 60 °, which is at least 10% less, preferably 10 to 35% less, more preferably 12 to 30% less; and / or (b) zero visibility, which is at least 25% less, more preferably 25 to 50% less, even more preferably 30 to 45% less, and and / or (c) an impact resistance at 23 ° C, which is at least 90% greater, more preferably 90 to 150% greater, and / or (d) an impact resistance at -20 ° C, which is at least 60% greater, more preferably 60 to 120% bigger.
[000126] Regarding the calculation of the percentage reference, it is done with the information provided above.
[000127] Preferred embodiments in the "use section" of the heterophasic propylene copolymer (HECO) comprising polyethylene (PE) are the preferred embodiments of the polyolefin (PO) composition according to the invention.
[000128] The present invention will now be described in more detail by the examples presented below. EXAMPLES 1. Measurement Definitions / Methods
[000129] The following definitions of the terms and methods of determination apply to the general description of the invention, above, as well as to the examples below, unless otherwise defined. Zero visibility
[000130] To determine zero visibility, a model cutter Cross Hatch 420P, manufactured by Erichsen, was used. For the tests, the 70x70x4 mm size plates were cut from a molded granulated plate (grain parameters: average grain size = 1 mm, grain depth = 0.12 mm, taper = 6 °) of size 140 x 200 x 4 mm. The minimum period between injection of sample molding and scratch test was 7 days. To test the samples they must be fixed in a suitable device, as described above. The streaks were applied with a force of 10 N, using a cylindrical metal pen with a ball-shaped tip (radius = 0.5 mm ± 0.01). A cutting speed of 1,000 mm / min was used. A minimum of 20 scratches parallel to each other were created with a 10 N load, with a distance of 2 mm. The application of the scratches was repeated perpendicular to each other, so that the result was a scratch screen. The scratch direction must be unidirectional.
[000131] Zero visibility is evaluated as the difference between the ΔL luminance of the non-scratched areas for the scratched ones. ΔL values were measured using a spectrophotometer that meets the requirements for DIN 5033. Light source for quantification of ΔL D65 / 10 °. Measured ΔL values must be below a maximum of 1.5.
[000132] A detailed test description of the test method (Erichsen transverse hairline cut method) can be found in the article "Evaluation of scratch resistance in multiphase PP blends" (Evaluation of risk resistance in multiphase PP mixtures) by Thomas Koch and Doris Machl, published in POLYMER TESTING 26 (2007), p. 927-936.
[000133] The brightness of 60 ° was measured in granulated samples injection molded according to DIN 67530 at an angle of 60 °. The grain for brightness measurements was identical to the grain used in the evaluation of zero visibility.
[000134] NMR spectroscopy measurements: The 13C NMR spectra of polypropylenes were recorded on a 400 MHz Bruker spectrometer at 130 ° C from samples dissolved in 1,2,4-trichlorobenzene / benzene-d6 (90/10 p /for). For the triad and penny analysis, the assignment is made according to the methods described in the literature: (T. Hayashi, Y. Inoue, R. Chujo, and T. Asakura, Polymer 29 13843 (1988) and Chujo R, et al , Polymer 35 339 (1994). NMR measurement was used to determine the penny mmmm and triad mm concentration in a manner well known in the art.
[000135] Melting temperature (Tm) and heat of melting (Hf), temperature of crystallization (Tc) and heat of crystallization (Hc): measured with differential scanning calorimetry (DSC) Mettler TA820 in samples of 5 to 10 mg. DSC is performed according to ISO 3146 / part 3 / method C2 in a heat / cold / heat cycle with a scanning speed of 10 ° C / min in the temperature range of 23 to 210 ° C. Crystallization temperature and crystallization heat (Hc) are determined from the cooling step, while the melting temperature and melting heat (Hf) are determined from the second heating phase.
[000136] Density is measured according to ISO 1183-1 - method A (2004). Sample preparation is done by compression molding according to ISO 1872-2: 2007.
[000137] MFR2 (230 ° C) is measured according to ISO 1133 (230 ° C, 2.16 kg load).
[000138] MFR2 (190 ° C) is measured according to ISO 1133 (190 ° C, 2.16 kg load).
[000139] MFR5 (190 ° C) is measured according to ISO 1133 (190 ° C, 5 kg load).
[000140] Average molecular weight (Mn) number, average molecular weight (Mw) and molecular weight distribution (MWD) are determined by gel permeation chromatography (GPC), according to the following method: The weight of average molecular weight Mw and the molecular weight distribution (MWD = Mw / Mn where Mn is the average molecular weight in number and Mw is the average molecular weight by weight) is measured by a method based on ISO 16014-1: 2003 and ISO 16014-4: 2003. A Waters 2000 Alliance GPCV instrument, equipped with a refractive index detector and a line viscometer, was used with 3 x TSK-gel (GMHXL-HT) columns from TosoHaas and 1,2,4-trichlorobenzene (TCB, stabilized with 200 mg / 2,6-di tert-butyl-4-methyl-phenol) as a solvent at 145 ° C and a constant flow rate of 1 ml / min. 216.5 μL of sample solution was injected by analysis. The column assembly was calibrated using relative calibration with 19 narrow MWD polystyrene (PS) standards in the range of 0.5 kg / mol to 11 500 kg / mol and a well-characterized broad set of polypropylene standards. All samples were prepared by dissolving 5 - 10 mg of polymer in 10 ml of (at 160 ° C) stabilized TCB (the same as a mobile phase) and maintaining for 3 hours with continuous agitation before sampling inside the GPC instrument . Quantification of comonomer content by FTIR spectroscopy
[000141] The comonomer content is determined by quantitative Fourier transform infrared spectroscopy (FTIR) after the quantitative basic assignment by quantitative 13C nuclear magnetic resonance (NMR) in a manner well known in the art. Thin films are pressed to a thickness of between 100-500 μm and spectra recorded in transmission mode.
[000142] Specifically, the ethylene content of a polypropylene-co-ethylene copolymer is determined using the peak area corrected baseline of the quantitative bands found at 720-722 and 730-733 cm-1. Specifically, the content of butane or hexene gas in a polyethylene copolymer is determined using the corrected baseline peak area of the quantitative bands found at 1377-1379 cm-1. Quantitative results were obtained based on the reference to the film thickness.
[000143] Soluble in cold xylene (XCS,% by weight): The content of soluble in cold xylene (XCS) is determined at 25 ° C according to ISO 16152; first edition; 2005-07-01.
[000144] Intrinsic viscosity is measured according to DIN ISO 1628/1, October 1999 (in decal at 135 ° C).
[000145] Traction module; Tensile stress in productivity and stress at break are measured according to ISO 527-2 (crosshead speed = 1 mm / min, 23 ° C), using injection molded samples, as described in EN ISO 1873-2 (dog bone shape, 4 mm).
[000146] Charpy impact test: Charpy notched impact resistance (Charpy NIS) is measured in accordance with ISO 1eA 179 at 23 ° C, -20 ° C, using prepared 80x10x4 mm3mm3 injection molded bar test samples according to ISO 294-1: 1996.
[000147] D95 cut particle size (sedimentation) is calculated from the particle size distribution [mass percent] as determined by gravitational liquid sedimentation in accordance with ISO 13317-3 (Sedigraphy).
[000148] The specific surface area is determined as the BET surface according to DIN 66131/2. 2. Examples
[000149] An experimental heterophasic propylene copolymer (HECO) was produced in a Borstar polypropylene factory with a prepolymerization reactor, a closed loop suspension reactor and three gas phase reactors. The Polytrack 8502 catalyst, commercially available from Grace (USA), was used in combination with dicyclopentyl dimethoxy silane [Si (OCH3) 2 (cyclopentyl) 2] as an external donor and triethyl aluminum (TEAL) as an activator and eliminator in the portions indicated in table 1. The catalyst was modified by polymerization of a vinyl compound, in the presence of the catalyst system.
[000150] The preparation of HECO is described in table 1 below. Table 1: Preparation of heterophasic propylene copolymer (HECO)

Table 2: Comparative examples

[000151] The Rest at 100% by weight are additives, such as antioxidants and pigments (for example, black carbon) "Talc" is the T1 CA commercial light talc from Luzenac, having a cut (de) particle size of 6.2 μm. "PE-1" is the commercial product Engage 8150 from Dow Elastomers having an MFR2 (190 ° C / 2.16kg) of 0.50 g / 10min and a density of 868 kg / m3, "PE-2" is the product commercial Engage 8100 from Dow Elastomers having an MFR2 (190 ° C / 2.16kg) of 1.0 g / 10min and a density of 870 kg / m3, "PE-3" is the commercial product FA3220 from Borealis AG having an MFR2 (190 ° C / 2.16kg) 0.3 g / 10min and density of 922 kg / m3, "PE-4" is the commercial product FA5224 from Borealis AG having an MFR2 (190 ° C / 2.16kg) 1.2 g / 10min and the density of 922 kg / m3, "PE-5" is the commercial product VL4580 from Borealis AG having an MFR2 (190 ° C / 2.16kg) of 0.6 g / 10min and the density of 958 kg / m3, "PE-6" is the commercial product MG9641 from Borealis AG having an MFR2 (190 ° C / 2.16 kg) of 8 g / 10min and a density of 964 kg / m3, "PE-A "is the commercial product HE3490-LS-H from Borealis AG, a MFR5 bimodal polyethylene (190 ° C / 2.16kg) of 0.24 g / 10min, the density of 959 kg / m3, and 2.3% in hexene weight, "PE-B" is the commercial product HE3490-LS from Borealis AG, a poly bimodal ethylene from MFR5 (190 ° C / 2.16kg) of 0.24 g / 10min, the density of 959 kg / m3, and 1.25% by weight of butene. Table 3: Inventive Examples
The rest at 100% by weight are additives, such as antioxidants and pigments (for example, black carbon)
[000152] The examples above show the benefits of preferred bimodal PE, with high density and low fluidity as an impact modifier in automotive interior compounds. The examples of the invention show a similar low gloss as the comparative examples C1 to C6 modified with LLDPE at much less zero visibility. In addition, the drop in the module is far less than when using LLDPE as an impact modifier. Although similar is true for HDPE, comparative examples C7 to C9 show a much greater brightness than the examples of the invention. The impact resistance of the examples of the invention is higher over the comparative examples, except for the comparative examples C1-C3. However, the latter suffers from a very poor surface feature and low modulus.

权利要求:
Claims (15)
[0001]
1. Polyolefin (PO) composition CHARACTERIZED by the fact that it comprises: (a) a heterophasic propylene copolymer (HECO) comprising (a1) a polypropylene (PP), which is a copolymer (PP-R) or more preferably a homopolymer propylene (PP-H), random propylene, and (a2) an elastomeric propylene copolymer (E), where the heterophasic propylene copolymer (HECO) has an MFR2 (230 ° C) fluidity index of at least 5 g / 10min, and (b) a polyethylene (PE) having a density of at least 935 kg / m3, and an MFR5 melt index (190 ° C) of less than 1.5 g / 10min.
[0002]
2. Polyolefin (PO) composition, according to claim 1, CHARACTERIZED by the fact that polyethylene (PE) (a) is bimodal or multimodal, and / or (b) has a density equal to or greater than 940 kg / m3, and / or (c) has an MFR5 (190 ° C) melt index of 1.0 g / 10min or less.
[0003]
3. Polyolefin (PO) composition, according to claim 1 or 2, CHARACTERIZED by the fact that the heterophasic propylene copolymer (HECO) has (a) the MFR2 fluidity index (230 ° C) from 5 to 40 g / 10min, and / or (b) a content of soluble in cold xylene (XCS) of at least 20% by weight based on the total weight of the heterophasic propylene copolymer (HECO), and / or (c) a comonomer content from 5.0 to 25.0% by weight based on the total weight of the heterophasic propylene copolymer (HECO), wherein the comonomers are preferably ethylene and / or an C4 to C12 olefin.
[0004]
4. Polyolefin (PO) composition according to any of claims 1 to 3, CHARACTERIZED by the fact that (a) the weight ratio of elastomeric propylene copolymer (E) to polyethylene (PE) [E / PE ] is less than 2.0; and / or (b) polypropylene (PP) has a melt index MFR2 (230 ° C) of 20 to 100 g / 10min.
[0005]
5. Polyolefin composition (PO) according to any one of claims 1 to 4, CHARACTERIZED by the fact that the elastomeric propylene copolymer (E) has (a) an intrinsic viscosity (IV) in the range of 1.0 to 3.5 dL / g, measured as the intrinsic viscosity (IV) of the cold xylene-soluble fraction (XCS) of the heterophasic propylene copolymer (HECO); and / or (b) a comonomer content of 25.0 to 50.0% by weight, based on the total weight of the cold xylene-soluble fraction of the heterophasic propylene copolymer (HECO), where the comonomers are preferably ethylene and / or a C4 to C12 olefin.
[0006]
6. Polyolefin (PO) composition according to any one of claims 1 to 5, CHARACTERIZED by the fact that polypropylene (PP) is a propylene homopolymer (H-PP).
[0007]
7. Polyolefin composition (PO) according to any one of claims 1 to 6, CHARACTERIZED by the fact that the polyolefin composition (PO) further comprises an inorganic filler (F), preferably in an amount of up to 30% by weight, based on the total weight of the polyolefin composition (PO).
[0008]
8. Polyolefin (PO) composition according to claim 7, CHARACTERIZED by the fact that the inorganic filler (F) has a cut particle size d95 [mass percent] equal to or less than 20 μm.
[0009]
9. Article CHARACTERIZED by the fact that it comprises a polyolefin (PO) composition, defined in any one of claims 1 to 8.
[0010]
10. Article, according to claim 9, CHARACTERIZED by the fact that the article is an automotive article.
[0011]
11. Process for the preparation of the polyolefin composition (PO), defined in any one of claims 1 to 8, CHARACTERIZED by the fact that it is by means of the extrusion of the heterophasic propylene copolymer (HECO), of the polyethylene (PE), and optionally inorganic load (F), in an extruder.
[0012]
12. Process, according to claim 11, CHARACTERIZED by the fact that the heterophasic propylene copolymer (HECO) is obtained through the production of polypropylene (PP) in at least one reactor system, the said system comprises, at least at least one reactor, transferring said polypropylene (PP) into a subsequent reactor system, said system comprises at least one reactor, in which, in the presence of polypropylene (PP), the elastomeric propylene copolymer (E) is produced.
[0013]
13. Use of a polyethylene (PE) having a density of at least 935 kg / m3 and an MFR5 fluidity index (190 ° C) of less than 1.5 g / 10min in a heterophasic propylene copolymer (HECO ) CHARACTERIZED by the fact that it is to reduce the gloss of said heterophasic propylene copolymer (HECO) or an article made from the heterophasic propylene copolymer (HECO) comprising polyethylene (PE), the improvement being determined as the gloss at 60 °, where the 60 ° brightness in relation to the heterophasic propylene copolymer (HECO) comprising polyethylene (PE) is at least 10% lower than the 60 ° brightness of the same heterophasic propylene copolymer (HECO ) but without polyethylene (PE), the percentage being determined by the formula
[0014]
14. Use according to claim 13, CHARACTERIZED by the fact that the heterophasic propylene copolymer (HECO) or an article made from the heterophasic propylene copolymer (HECO) comprising polyethylene (PE) has (a) a zero visibility, which is at least 25% lower than that of the same heterophasic propylene copolymer (HECO) but without polyethylene (PE) or articles made from them, the percentage being determined by the formula
[0015]
15. Use according to claim 13 or 14, CHARACTERIZED by the fact that the heterophasic propylene copolymer (HECO) with polyethylene (PE) is a polyolefin (PO) composition defined in any of claims 1 to 8.

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法律状态:
2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-05-05| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-10-13| B09A| Decision: intention to grant|

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2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/08/2012, OBSERVADAS AS CONDICOES LEGAIS. |

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