HIGH FLOW POLYOLEFIN COMPOSITION WITH HIGH RIGIDITY AND RESISTANCE AND AUTOMOTIVE ITEMS

专利摘要:
The present invention relates to a polyolefin composition comprising two heterophasic propylene copolymers which differ in the intrinsic viscosity of their soluble xylene fractions.
公开号:BR112016003128B1
申请号:R112016003128-8
申请日:2014-08-18
公开日:2021-08-24
发明作者:Martina Sandholzer；Georg Grestenberger；Susanne Kahlen
申请人:Borealis Ag；
IPC主号:

专利说明:

[001] The present invention is directed to a polyolefin composition having improved properties, such as an excellent balance of stiffness, hardness and fluidity. The polyolefin composition according to the present invention comprises a blend of two defined heterophasic propylene copolymers.
[002] Polypropylene is the material of choice in many applications as it can be adapted for specific purposes required. For example, heterophasic polypropylenes are widely used in the automotive industry (eg in adhesive applications) as they combine good stiffness with reasonable impact strength 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 a crystalline polyethylene to some extent. In the automotive industry, such heterophasic polypropylene grades 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 through a step of composition.
[003] Automotive parts are increasingly produced by means of injection molding. Injection molding of large automotive parts, such as bumpers, casing panels, or instrument panels, requires the polymers to have a sufficiently low viscosity (ie, a sufficiently high melt flow rate), but still acceptable and balanced. the mechanical performance. However, polymers of higher melt flow rate (ie, greater fluidity) generally have a lower molecular weight and, therefore, lower mechanical properties. The reduction in molecular weight not only reduces viscosity and increases fluidity, but also alters or deteriorates mechanical properties such as toughness. Thus, polymeric compositions exhibiting a combination of high fluidity and excellent mechanical properties are not trivial to supply. Invention Summary
[004] The purpose of the present invention is to provide a polyolefin composition having high fluidity in addition to excellent mechanical properties, so that the composition can be used for the production of automotive parts, in particular, large automotive parts, for example , using injection molding.
[005] The inventors of the present invention have found that the above objective can be achieved by combining two different heterophasic propylene copolymers having the defined characteristics.
[006] Thus, the present invention provides a polyolefin composition comprising (a) a first heterophasic propylene copolymer (HECO1) having (i) a melt flow rate MFR2 (230°C) measured in accordance with ISO 1133 in the range from 15.0 to 55.0 g/10 min, and (ii) a cold soluble xylene content (XCS) determined in accordance with ISO 16152 (25°C) in the range of 24 to 38% by weight, in which additionally (iii) the intrinsic viscosity (IV) determined according to DIN ISO 1628/1 (in decalin at 135°C) of the cold soluble xylene fraction (XCS) of the heterophasic propylene copolymer (HECO1) is in the range of 2.0 at 3.5 dl/g, and (b) a second heterophasic propylene copolymer (HECO2) comprising a homopolymer of propylene (H-PP2) and an elastomeric propylene copolymer (E2), wherein (i) said homopolymer of propylene (H-PP2) has an MFR2 melt flow rate (230°C) measured according to ISO 1133 in the range of 15 to 400 g/10 min, such as above 30 to 120 g/10 min;(ii ) the cold soluble fraction of xylene (XCS) of the second heterophasic propylene copolymer (HECO2) has an intrinsic viscosity determined according to DIN ISO 1628/1 (in decalin at 135°C) in the range of 3.7 to 9.0 dl/g; and (iii) the comonomer content of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2) is in the range of 10.0 to 40.0% by weight, such as in the range of 12.0 to 30.0% by weight.
[007] Preferably, the second heterophasic propylene copolymer (HECO2) has a cold soluble xylene content (XCS) determined in accordance with ISO 16152 (25°C) below 40% by weight, preferably in the range of 8 to 35% by weight.
[008] In a preferred embodiment, the second heterophasic propylene copolymer (HECO2) completes equation (IV)
where C is the comonomer content in % by weight of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2), and IV is the intrinsic viscosity in dl/g of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2).
[009] Other preferred embodiments of the present invention are described in the appended dependent claims. Detailed Description
[0010] As mentioned above, the polyolefin composition according to the present invention comprises two specific heterophasic propylene copolymers.
[0011] The expression "heterophasic propylene copolymer" or "heterophasic" as used in the present invention indicates that an elastomeric propylene copolymer is (finely) dispersed in a (semi)crystalline polypropylene. In other words, the (semi)crystalline polypropylene constitutes a matrix, in which the elastomeric propylene copolymer forms the inclusions in the matrix, that is, in the (semi)crystalline polypropylene. Thus, the matrix contains (finely) dispersed inclusions which are not part of the matrix and said inclusions contain the elastomeric propylene copolymer. The term "inclusion" according to this invention should preferably indicate that the matrix and the inclusion form different phases within the heterophasic system, said inclusions are, for example, visible by high resolution microscopy, such as microscopic electron or atomic force microscopy, or by dynamic mechanical thermal analysis (DMTA). Specifically in DMTA, the presence of a multiphase structure can be identified by the presence of at least two distinct glass transition temperatures.
[0012] The first heterophasic propylene copolymer (HECO1) and the second heterophasic propylene copolymer (HECO2) as employed in accordance with the present invention are described in greater detail below. First Heterophasic Propylene Copolymer (HECO1)
[0013] As stated above, the polyolefin composition according to the present invention comprises a first heterophasic propylene copolymer (HECO1) as an essential component. It is preferred that the first heterophasic propylene copolymer (HECO1) above mixed with the other components mentioned herein as polymer components comprises only the matrix polypropylene (PP1) and dispersed therein the elastomeric propylene copolymer (E1). In other words, the first heterophasic propylene copolymer (HECO1) may contain other additives, but no other polymer in an amount greater than 5% by weight, more preferably greater than 3% by weight, such as greater than 1% by weight , based on the total amount of the first heterophasic propylene copolymer (HECO1), more preferably based on polymers present in the first heterophasic propylene copolymer (HECO1). An additional polymer that can be present in such low amounts is a polyethylene, which is a reaction product obtained by preparing the first heterophasic propylene copolymer (HECO1). Thus, it is particularly appreciated that a first heterophasic propylene copolymer (HECO1) as defined in the present invention contains only a polypropylene (PP1), an elastomeric propylene copolymer (E1) and optionally a polyethylene in amounts as mentioned. in this paragraph.
[0014] An important aspect of the present invention is that the first heterophasic propylene copolymer (HECO1) has a relatively high melt flow rate, i.e., it has an MFR2 melt flow rate (230°C) of at least, 15.0 g/10 min, more preferably in the range 15.0 to 55.0 g/10 min, even more preferably in the range 20.0 to 50.0 g/10 min, even more than preferably in the range of 20.0 to 45.0 g/10 min.
[0015] Preferably, it is desirable that the first heterophasic propylene copolymer (HECO1) is term mechanically stable. In this way, it is appreciated that the first heterophasic propylene copolymer (HECO1) has a melting temperature (Tm) of at least 135°C, more preferably in the range of 135 to 168°C.
[0016] Preferably, the propylene content in the heterophasic propylene copolymer (HECO1) is 83.0 to 94.0% by weight, more preferably 85.0 to 93.0% by weight, based on the total amount of the first heterophasic propylene copolymer (HECO1), more preferably, based on the amount of the polymer components of the first heterophasic propylene copolymer (HECO1), even more preferably, based on the amount of the polypropylene (PP1) and the copolymer of elastomeric propylene (E1) together. The remaining part constitutes the comonomers as defined for polypropylene (PP1) being a copolymer of propylene (R-PP1) and the copolymer of elastomeric propylene (E1), respectively, preferably ethylene. In this way, the comonomer content, preferably the ethylene content, is in the range of 6.0 to 17.0% by weight, more preferably in the range of 7.0 to 15.0% by weight.
[0017] As mentioned above, the matrix of the first heterophasic propylene copolymer (HECO1) is polypropylene (PP1).
[0018] The polypropylene (PP1) according to the present invention constitutes the matrix of the first heterophasic copolymer (HECO1) should have a melt flow rate MFR2 (230°C) of 60 to 400 g/10 min, preferably, in the range 100 to 350 g/10 min, more preferably in the range 150 to 300 g/10 min.
[0019] Polypropylene (PP1) can be a copolymer of propylene (R-PP1) or a homopolymer of propylene (H-PP1), the latter being preferred.
[0020] In this way, it is appreciated that polypropylene (PP1) has a comonomer content equal to or below 9.0% by weight), more preferably equal to or below 7.0% by weight, even more preferably , equal to or below 4.0% by weight.
[0021] The expression of homopolymer of propylene, for example, the expressions of homopolymer of propylene (H-PP1) and homopolymer of propylene (H-PP2), used in the present invention refer to a polypropylene consisting substantially, i.e. , from more than 99.0% by weight, such as at least 99.5% by weight, even more preferably, from at least 99.7% by weight, such as at least 99.8% by weight , from propylene units. In the case, other monomeric units are present in small amounts, the units are selected from ethylene and/or a C4 to C12 α-olefin, as described below. In a preferred embodiment, only propylene units in the propylene homopolymer are detectable.
[0022] In this case, polypropylene (PP1) is a copolymer of propylene (R-PP1) comprising monomers copolymerizable with propylene, for example, comonomers, such as ethylene and/or C4 to C12 α-olefin, in particular, ethylene and/or C4 to C10 α-olefin, for example 1-butene and/or 1-hexene. Preferably, the propylene copolymer (R-PP1) comprises, in particular, it consists of monomers copolymerizable with propylene, from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the propylene copolymer (R-PP1) comprises - in addition to propylene - units derivable from ethylene and/or 1-butene. In a preferred embodiment, the propylene copolymer (R-PP1) comprises units derivable from only ethylene and propylene. The comonomer content in the propylene copolymer (R-PP1) is preferably in the range of greater than 1.0 to 9.0% by weight, even more preferably in the range of greater than 1.0 to 7.0% by weight.
[0023] Polypropylene (PP1) can have a cold soluble content of xylene (XCS) in a wide range, ie up to 5.0% by weight. In this way, the polypropylene (PP1) may have a cold soluble xylene content (XCS) in the range of 0.3 to 5.0% by weight, preferably in the range of 0.5 to 4.5% by weight, as in the range of 1.0 to 4.0% by weight.
[0024] However, in preferred embodiments, polypropylene (PP1), in particular in the case of polypropylene (PP1) is a homopolymer of propylene (H-PP1), has a cold soluble xylene content (XCS) in the range of 0 0.5 to 5.0% by weight, more preferably in the range of 1.0 to 4.0% by weight, even more preferably 1.5 to 3.5% by weight.
[0025] Another essential component of the first heterophasic propylene copolymer (HECO1) is its elastomeric propylene copolymer (E1).
[0026] The elastomeric propylene copolymer (E1) preferably comprises monomers copolymerizable with propylene, for example, comonomers such as ethylene and/or C4 to C12 α-olefin, in particular ethylene and/or C4 to C10 α- olefin, for example 1-butene and/or 1-hexene. Preferably, the elastomeric propylene copolymer (E1) comprises, in particular, it consists of monomers copolymerizable with propylene, from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the elastomeric propylene copolymer (E1) comprises - in addition to propylene - units derivable from ethylene and/or 1-butene. Thus, in an especially preferred embodiment, the elastomeric propylene copolymer phase (E1) comprises the units derivable from only ethylene and propylene.
[0027] In the case, polypropylene (PP1) is a copolymer of propylene (R-PP1) is preferred, in which the comonomers of the copolymer of propylene (R-PP1) and the copolymer of elastomeric propylene (E1) are the same.
[0028] The properties of the elastomeric propylene copolymer phase (E1) mainly influence the cold soluble xylene content (XCS) of the first heterophasic propylene copolymer (HECO1). Thus, according to the present invention, the cold soluble xylene fraction (XCS) of the first heterophasic propylene copolymer (HECO1) is considered as the elastomeric propylene copolymer (E1) of the first heterophasic propylene copolymer (HECO1).
[0029] In this way, the amount of the elastomeric propylene copolymer (E1), that is, the cold soluble fraction of xylene (XCS), of the first heterophasic propylene copolymer (HECO1) is preferably in the range of 24 to 38 % by weight, more preferably in the range of 25 to 37% by weight, even more preferably in the range of 26-36% by weight. These values are based on the first heterophasic propylene copolymer (HECO1) and not the total polyolefin composition.
[0030] An important requirement of the present invention is that the elastomeric propylene copolymer (E1) has a balanced weight average molecular weight. Small particles are formed in the case where the matrix and 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 tends towards a high melt flow rate and thus a low weight average molecular weight. In this way, also the elastomeric propylene copolymer (E1) must have a low weight average molecular weight in order to obtain small particles. On the other hand, this would mean, in the present case, a severe reduction in the low weight average molecular weight for the elastomeric propylene copolymer (E1), which has a negative impact on the mechanical properties. In this way, the intrinsic viscosity has to be carefully chosen.
[0031] Low intrinsic viscosity (IV) values reflect a low weight average molecular weight. Thus, it is appreciated that the elastomeric propylene copolymer phase (E1), i.e. the cold soluble xylene fraction (XCS) of the first heterophasic propylene copolymer (HECO1), has an intrinsic viscosity (IV) determined in accordance with DIN ISO 1628/1 (in decalin at 135°C) in the range of 2.0 to 3.5 dl/g, more preferably in the range equal to or more than 2.1 to 3.2 dl/g, even more preferably in the range equal to or greater than 2.3 to 3.0 dl/g.
[0032] The comonomer content, preferably the ethylene content, within the elastomeric propylene copolymer phase (E1) should preferably also be in a specific range. Thus, in a preferred embodiment, the comonomer content, more preferably the ethylene content, of the elastomeric propylene copolymer (E1), i.e., the cold soluble xylene fraction (XCS) of the first heterophasic propylene copolymer ( HECO1) is in the range of 26 to 40% by weight, even more preferably in the range of 28 to 38% by weight, even more preferably in the range of 31 to 38% by weight. In this way, it is appreciated that the propylene content of the elastomeric propylene copolymer (E1), i.e., the cold soluble xylene fraction (XCS) of the first heterophasic propylene copolymer (HECO1), is preferably in the range of 60 to 74% by weight, even more preferably in the range of 62 to 72% by weight, even more preferably in the range of 62 to equal to or less than 69% by weight.
[0033] As will be explained below, the first heterophasic polypropylene (HECO1) as well as its individual components (matrix and elastomeric copolymer) can be produced by mixing different types of polymer, that is, of different molecular weight and/or content of comonomer. However, it is preferred that the first heterophasic polypropylene (HECO1) as well as its individual components (matrix and elastomeric copolymer) are produced in a sequential step process, using reactors in series configuration and operating under different reaction conditions. As a consequence, each fraction prepared in a specific reactor will have its own molecular weight distribution and/or comonomer content distribution.
[0034] The first heterophasic propylene copolymer (HECO1) 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 ( PP1) is produced in at least one slurry reactor, preferably in a slurry reactor and optionally in a subsequent gas phase reactor, and subsequently the elastomeric propylene copolymer (E1) is produced , in at least one, i.e. one or two gas-phase reactors.
[0035] In this way, it is preferred that the first heterophasic propylene copolymer (HECO1) is produced in a sequential polymerization process comprising the steps of (a) polymerization of propylene and optionally at least one ethylene and/or C4 the C12 α-olefin in a first reactor (R1) obtaining the first polypropylene fraction from polypropylene (PP1), preferably, said first polypropylene fraction is a first homopolymer of propylene, (b) transfer of the first polypropylene fraction to a second reactor (R2), (c) polymerization in the second reactor (R2) and in the presence of said first fraction of polypropylene propylene and optionally at least one ethylene and/or C4 to C12 α-olefin thus obtaining the second fraction of polypropylene, preferably said second polypropylene fraction is a second homopolymer of propylene, said first polypropylene fraction and said second polypropylene fraction form polypropylene (PP1), i.e. the heterophasic propylene copolymer matrix (HECO1), (d) transfer of polypropylene (PP1) from step (c) in a third reactor (R3), (e) polymerization in the third reactor (R3) and in the presence of polypropylene (PP1 ) obtained in step (c) propylene and at least one ethylene and/or C4 to C12 α-olefin thus obtaining a first elastomeric propylene copolymer fraction, the first elastomeric propylene copolymer fraction is dispersed in polypropylene (PP1) ,(f) transfer of polypropylene (PP1) 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) propylene and at least one ethylene and/or C4 to C12 α-olefin thus obtaining the second elastomeric propylene copolymer fraction, polypropylene (PP1), the first elastomeric propylene copolymer fraction, and the second fraction of elastomeric propylene copolymer form propylene copolymer h and terophasic (HECO1).
[0036] 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 is true for the elastomeric propylene copolymer phase. In this way, in the third reactor (R3) the second elastomeric propylene copolymer fraction can be produced, while in the fourth reactor (R4) the first elastomeric propylene copolymer fraction is made.
[0037] 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 bright.
[0038] The term "sequential polymerization process" indicates that the first heterophasic propylene copolymer (HECO1) is produced in at least two, such as three or four reactors connected in series. In this way, 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 takes place. Thus, in case the process consists of four polymerization reactors, this definition does not exclude the option that the overall process comprises, for example, a prepolymerization step in a prepolymerization reactor. The term “consists of” is only a closure formulation, in view of the main polymerization reactors.
[0039] The first reactor (R1) is preferably a slurry reactor (SR) and can be any simple or continuous stirred batch tank reactor or closed loop reactor operating in volume or slurry. Volume means a polymerization in a reaction medium comprising at least 60% (w/w) monomer. According to the present invention, the slurry reactor (SR) is preferably a closed loop (volume) reactor (LR).
[0040] 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 fluid bed or mechanically mixed reactors. Preferably, gas phase reactors (GPR) comprise a mechanically stirred fluid bed reactor with gas velocities of at least 0.2 m/sec. Thus, it is appreciated that the gas phase reactor is a fluidized bed type reactor, preferably with a mechanical stirrer.
[0041] Thus, in a preferred embodiment, the first reactor (R1) is a slurry reactor (SR), like a closed loop reactor (LR), whereas the second reactor (R2), the third reactor ( R3) and the fourth reactor (R4) are gas phase reactors (GPR). Thus, during the present process, at least four, preferably four polymerization reactors, i.e. a slurry 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 slurry reactor (SR) a pre-polymerization reactor is placed.
[0042] A preferred multistage process is a "closed loop gas phase" process as developed by Borealis A/S, Denmark (known as BORSTAR® technology) described, for example, in the patent literature, such 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.
[0043] An additional suitable gas-phase-slurry process is the Spheripol® process from Basell.
[0044] Preferably, in the present process for the production of heterophasic propylene copolymer (HECO), as defined above, the conditions for the first reactor (R1), that is, the slurry reactor (SR), as a reactor Closed loop (LR) of 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 within the range of 20 bar (2 MPa) to 80 bar (8 MPa), preferably between 40 bar (4 MPa) to 70 bar (7 MPa), - hydrogen can be added to control the molar mass in a manner known per se.
[0045] Subsequently, the reaction mixture from step (a) is transferred to the second reactor (R2), i.e. the gas phase reactor (GPR-1), i.e. to step (c), wherein the conditions in 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 from the range of 5 bar (0.5 MPa) to 50 bar (5 MPa), preferably between 15 bar (1.5 MPa) to 35 bar (3.5 MPa), - hydrogen can be added to control the molar mass in a manner known per se.
[0046] 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 the second reactor (R2).
[0047] The residence time can vary in the three zones of the reactor.
[0048] In one modality of the process for the production of polypropylene, the residence time in the bulk reactor, for example, closed circuit 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.
[0049] If desired, polymerization can be carried out in a known manner under supercritical conditions in the first reactor (R1), that is, in the slurry reactor (SR), as in the closed loop reactor (LR), and/or as a condensed mode in gas phase reactors (GPR).
[0050] Preferably, the process also comprises a pre-polymerization with the catalyst system, as described in detail below, comprising a Ziegler-Natta pro-catalyst, an external donor and optionally a co-catalyst.
[0051] In a preferred embodiment, the prepolymerization is carried out as bulk slurry polymerization in liquid propylene, i.e., the liquid phase mainly comprises propylene, with a smaller amount of other reactants and, optionally, inert components dissolved therein .
[0052] The prepolymerization reaction is typically carried out at a temperature from 10 to 60°C, preferably from 15 to 50°C, and more preferably from 20 to 45°C.
[0053] The pressure in the prepolymerization reactor is not critical, but it should be high enough to keep the reaction mixture in liquid phase. Thus, the pressure can be from 20 to 100 bar (2 to 10 MPa), for example 30 to 70 bar (3 to 7 MPa).
[0054] The catalyst components are preferably all introduced to the prepolymerization step. However, where the solid catalyst component (i) and the co-catalyst (ii) can be fed separately, it is possible that only a part of the co-catalyst is introduced in the pre-polymerization stage and the remaining part in the stages of subsequent polymerization. Furthermore, in such cases, it is necessary to introduce so much co-catalyst to the prepolymerization stage that a sufficient polymerization reaction is obtained therein.
[0055] It is possible to add other components also to the pre-polymerization stage. In this way, hydrogen can be added at the prepolymerization stage to control the molecular weight of the prepolymer, as is known in the art. In addition, the anti-static additive can be used to prevent the particles from sticking to each other or to the reactor walls.
[0056] Precise control of prepolymerization conditions and reaction parameters is within the skill of the art.
[0057] According to the invention, the first heterophasic propylene copolymer (HECO1) is obtained by a multistage polymerization process, as described above, in the presence of a catalyst system comprising as component (i) a procatalyst from Ziegler-Natta which contains a transesterification product of a lower alcohol and a phthalic ester.
[0058] The procatalyst used according to the invention for the preparation of the first heterophasic propylene copolymer (HECO1) is prepared by) reacting a crystallized spray or solidified adduct by emulsion of MgCl2 and a C1-C2 alcohol with TiCl4,b ) reacting the product of stage a) with a dialkylphthalate of formula (I)
wherein R1' and R2' are independently at least one C5 alkyl under conditions where a transesterification between said C1 to C2 alcohol and said dialkylphthalate of formula (I) occurs to form the internal donor, c) wash the product from stage b) or, d) optionally reacting the product of step c) with additional TiCl4.
The procatalyst 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 incorporated herein by reference.
[0060] First, an adduct 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 the alcohol.
[0061] The adduct, which is first melted and then spray crystallized or solidified emulsion, is used as a catalyst vehicle.
[0062] In the next step, the spray crystallized or emulsion solidified adduct of the formula MgCl2 * nROH, where R is methyl or ethyl, preferably, ethyl and n is 1 to 6, is in contact with TiCl4 to form a titanized vehicle, followed by the steps of adding to said titanized vehicle (i) a dialkylphthalate of formula (I) with R1' and R2' independently being at least a C5-alkyl such as at least a C8-alkyl, or preferably ,(ii) a dialkylphthalate of formula (I) with R1' and R2' being the same and being at least a C5-alkyl such as at least a C8-alkyl, or more preferably, (iii) a formula (I) dialkylphthalate selected from the group consisting of propylhexylphthalate (PrHP), dioctylphthalate (DOP), di-iso-decylphthalate (DIDP), and ditridecylphthalate (DTDP), even more preferably, the formula (I) dialkylphthalate ) is a dioctylphthalate (DOP), such as di-iso-octylphthalate or diethylhexylphthalate, in particular diethylhexylphthalate, to form a first product,• subme having said first product at suitable transesterification conditions, i.e. at a temperature above 100°C, preferably between 100 to 150°C, more preferably between 130 to 150°C, such that said methanol or ethanol is transesterified with said ester groups of said dialkylphthalate of formula (I) to preferably form at least 80 mol%, more preferably 90 mol%, more preferably 95 mol%, of a dialkylphthalate of formula (II)
with R1 and R2 being methyl or ethyl, preferably ethyl, the dialkylphthalate of formula (II) being the internal donor and recovering said transesterification product as the procatalyst composition (component (i)).
[0063] The adduct of formula MgCl2 * nROH, where R is methyl or ethyl and n is 1 to 6, is in a preferred embodiment molten and then the molten mass is preferably injected by a gas to a cooled solvent or a cooled gas, in which the adduct is crystallized in a morphologically advantageous form, as for example described in WO 87/07620.
[0064] This crystallized adduct is preferably used as the catalyst carrier and reacted with the procatalyst useful in the present invention, as described in WO 92/19658 and WO 92/19653.
[0065] As the catalyst residue is removed by extraction, an adduct of the titanized carrier and the internal donor are obtained, in which the group derived from alcohol ester has changed.
[0066] In case enough titanium remains in the vehicle, it will act as an active element of the procatalyst.
[0067] Otherwise, titanization is repeated after the above treatment in order to ensure sufficient titanium concentration and thus activity.
[0068] Preferably, the procatalyst used according to the invention contains 2.5% by weight of titanium at most, preferably 2.2% by weight at most, and more preferably 2.0% by weight maximum. Its donor content is preferably between 4 to 12% by weight and more preferably between 6 and 10% by weight.
[0069] Most preferably, the procatalyst used according to the invention was produced using ethanol as the alcohol and dioctylphthalate (DOP) as the dialkylphthalate of formula (I), obtaining diethylphthalate (DEP) as the internal donor compound .
[0070] Even more preferably, the catalyst used according to the invention is the catalyst as described in the example section; especially with the use of dioctylphthalate as the dialkylphthalate of formula (I).
[0071] During the production of heterophasic propylene copolymer (HECO1), according to the invention, the catalyst system used preferably comprises, in addition to the special Ziegler-Natta procatalyst, an organometallic co-catalyst as a component (ii ).
[0072] Therefore, it is preferred to select the co-catalyst from the group consisting of aluminum trialkyl, such as aluminum triethyl (TEA), aluminum dialkyl chloride and aluminum alkyl sesquichloride.
[0073] The component (iii) of the catalyst system used is an external donor represented by formula (IIIa) or (IIIb). Formula (IIIa) is defined as Si(OCH3)2R25(IIIa) wherein 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 cyclo. alkyl having 4 to 12 carbon atoms, preferably a cycloalkyl having 5 to 8 carbon atoms.
[0074] It is in particular 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 cycloheptyl.
[0075] Formula (IIIb) is defined by Si(OCH2CH3)3(NRxRy)(IIIb)wherein Rx and Ry can be the same or different, a represents a hydrocarbon group having 1 to 12 carbon atoms.
[0076] Rx and Ry are independently selected from the group consisting of linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms, and a cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. carbon. It is, in particular, 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.
[0077] More preferably, both Rx and Ry are the same, even more preferably, both Rx and Ry are an ethyl group.
More preferably, the external donor is of formula (IIIa), such as dicyclopentyl dimethylsilane [Si(OCH3)2(cyclopentyl)2] or diisopropyl dimethylsilane [Si(OCH3)2(CH(CH3) 2)2].
[0079] Most preferably, the external donor of formula (IIIb) is diethylaminotriethoxysilane.
[0080] In another embodiment, the Ziegler-Natta procatalyst can be modified by polymerization of a vinyl compound in the presence of the catalyst system, comprising the special Ziegler-Natta procatalyst (component (i)), an external donor (component (iii) and optionally a co-catalyst (component (iii)), wherein the vinyl compound has the formula: CH2=CH-CHR3R4 wherein R3 and R4 together form a saturated, unsaturated or 5- or 6-membered aromatic 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 the present invention. as an a-nucleating agent.
[0081] With respect to catalyst modification, reference is made to international applications WO 99/24478, WO 99/24479 and particularly WO 00/68315, incorporated herein by reference with respect to reaction conditions relating to catalyst modification as well. how, with respect to the polymerization reaction.
[0082] In this way, it is appreciated that the first heterophasic propylene copolymer (HECO1) is α-nucleated. In the case, the α-nucleation is not effected by a vinylcycloalkane polymer or a vinylalkane polymer as indicated above, the following α-nucleation agents may be present (i) salts of monocarboxylic acids and polycarboxylic acids, e.g. sodium or aluminum tert-butylbenzoate, and(ii) dibenzylidenesorbitol (eg 1.3:2.4 dibenzylidenesorbitol) and C1-C8-alkyl substituted dibenzylidenesorbitol derivatives such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (eg 1, 3:2,4 di(methylbenzylidene)sorbitol), or substituted nonitol derivatives such as 1,2,3-trideoxy- 4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol , and (iii) salts of phosphoric acid diesters, for example 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate sodium or aluminum-hydroxy-bis[2,2'-methylene-bis (4.6-di-t-butylphenyl)phosphate)], and (iv) mixtures thereof. Second Heterophasic Propylene Copolymer (HECO2)
[0083] As mentioned above, the polyolefin composition according to the present invention further comprises a second heterophasic propylene copolymer (HECO2) as an essential component.
[0084] The second heterophasic propylene copolymer (HECO2) typically has a lower melt flow rate MFR2 than the first heterophasic propylene copolymer (HECO1). In addition, the intrinsic viscosity (IV) of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2) must be significantly higher than that of the first heterophasic propylene copolymer (HECO1).
[0085] In this way, it is preferable that the ratio of melt flow rate MFR2 (230°C) of the first heterophasic propylene copolymer (HECO1) to the second heterophasic propylene copolymer (HECO2) completes equation (I), more preferably, equation (Ia), even more preferably, equation (Ib), even more preferably, equation (Ic)
where MFR(1) is the melt flow rate MFR2 (230°C) of the first heterophasic propylene copolymer (HECO1) and MFR(2) is the melt flow rate MFR2 (230°C) of the second heterophasic propylene copolymer (HECO2).
[0086] In another embodiment, it is preferable that the ratio of the intrinsic viscosity (IV) of the soluble content of cold xylene (XCS) of the second heterophasic propylene copolymer (HECO2) to the intrinsic viscosity (IV) of the soluble content of cold xylene (XCS) of the first heterophasic propylene copolymer (HECO1) completes equation (II), more preferably, equation (IIa), even more preferably, equation (IIb), even more preferably, equation (IIc)
where IV (1) is the intrinsic viscosity (IV) of the soluble cold xylene content (XCS) of the first heterophasic propylene copolymer (HECO1) and V V (2) is the intrinsic viscosity (IV) of the soluble cold xylene content (XCS) ) of the second heterophasic propylene copolymer (HECO2).
[0087] The second heterophasic propylene copolymer (HECO2) of the present invention is a heterophasic system with intrinsic viscosity ratio / comonomer balanced in the cold soluble xylene fraction (XCS) thereof.
[0088] In this way, the second heterophasic polypropylene composition (HECO2) of the present invention comprises a propylene homopolymer (H-PP2) and an elastomeric propylene copolymer (E2), wherein (i) said propylene homopolymer (H) -PP2) has an MFR2 melt flow rate (230°C) measured according to ISO 1133 in the range above 15 to 400 g/10 min; (ii) the cold soluble xylene fraction (XCS) of the second copolymer of heterophasic propylene (HECO2) has an intrinsic viscosity determined according to DIN ISO 1628/1 (in decalin at 135°C) in the range of more than 3.7 to 9.0 dl/g; and (iii) the comonomer content of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2) is in the range of 10.0 to 40.0% by weight.
[0089] Preferably, the second heterophasic propylene copolymer (HECO2) has a cold soluble xylene content (XCS) determined in accordance with ISO 16152 (25°C) below 40% by weight, preferably below 35% by weight, more preferably in the range of 8.0 to 35% by weight, even more preferably in the range of 15 to 35% by weight, such as in the range of 20 to 35% by weight.
[0090] In a preferred embodiment, the second heterophasic propylene copolymer (HECO2) completes equation (III)
where C is the comonomer content in % by weight of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2), and IV is the intrinsic viscosity in dl/g of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2).
[0091] Preferably, the second heterophasic propylene copolymer (HECO2) as defined above has a melt flow rate MFR2 (230°C) measured according to ISO 1133 in the range of 1.0 to 150 g/10 min preferably in the range 1.0 to 80 g/10 min, more preferably in the range 2.0 to 50 g/10 min, such as in the range 3.0 to 20 g/10 min.
[0092] The second heterophasic propylene copolymer (HECO2) comprises a matrix (M2) being a homopolymer of propylene (H-PP2) and dispersed therein the elastomeric propylene copolymer (E2). Thus, the matrix (M2) contains (finely) dispersed inclusions that are not part of the matrix (M2) and said inclusions contain the elastomeric propylene copolymer (E2). Relatively, another definition of the term "heterophasic propylene copolymer" is referred to for the information given above.
[0093] As mentioned above, the second heterophasic propylene copolymer (HECO2) comprises a propylene homopolymer (H-PP2). Said propylene homopolymer (H-PP2) constitutes the matrix (M2) of the second heterophasic propylene copolymer (HECO2).
[0094] As the homopolymer of propylene (H-PP2) is almost insoluble cold xylene and the elastomeric propylene copolymer (E2) is predominantly soluble in cold xylene, the properties of the cold insoluble xylene fraction (XCI) of the second copolymer of heterophasic propylene (HECO2) and propylene homopolymer (H-PP2) are quite similar.
[0095] In this way, the cold insoluble xylene (XCI) of the second heterophasic propylene copolymer (HECO2) and the propylene homopolymer (H-PP2) has a melt flow rate MFR2 (230°C) measured in accordance with ISO 1133 in the range of 15 to 400 g/10 min, preferably in the range of 20 to 300 g/10 min, more preferably in the range of 30 to 120 g/10 min, even more preferably in the range of 45 at 95 g/10 min.
[0096] The homopolymer of propylene (H-PP2) can be monomodal or multimodal, such as bimodal, in its molecular weight fraction.
[0097] In this case, the homopolymer of propylene (H-PP2) is multimodal, such as bimodal, in its molecular weight, which comprises at least two fractions, preferably consists of two fractions, the fractions are a first fraction of propylene homopolymer (H-PP2a) and a second fraction of propylene homopolymer (H-PP2b). Preferably, the two fractions differ in the MFR2 melt flow rate (230°C).
[0098] In this way, it is appreciated that the first fraction of propylene homopolymer (H-PP2a) differs by a melt flow rate MFR2 (230°C) of at least 10 g/10 min, more preferably, at least 20 g/10 min, even more preferably in a range of 10 to 200 g/10 min, even more preferably in a range of 20 to 150 g/10 min, from the second homopolymer fraction of propylene (H-PP2b). Preferably, the MFR2 melt flow rate (230°C) of the first propylene homopolymer fraction (H-PP2a) is greater than the MFR2 melt flow rate (230°C) of the second propylene homopolymer fraction (H-PP2b).
[0099] The elastomeric propylene copolymer (E2) of the second heterophasic propylene copolymer (HECO2) mainly influences the properties and amount of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2). Thus, in a first approximation, the properties of the elastomeric propylene copolymer (E2) can be equated with the properties of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2). However, in preferred embodiments, the amount of elastomeric propylene copolymer (E2) is greater than the cold soluble total xylene content (XCS) of the second heterophasic propylene copolymer (HECO2).
[00100] In this way, the amount of elastomeric copolymer (E2) of the second heterophasic propylene copolymer (HECO2) is preferably below 40.0% by weight, more preferably equal to or below 38.0% by weight weight, even more preferably in the range of 15.0 to 40% by weight, even more preferably in the range of 17.0 to less than 38% by weight.
[00101] On the other hand, the amount of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2) is preferably below 40.0% by weight, more preferably equal to or below 35 0.0% by weight, even more preferably in the range of 8.0 to 35.0% by weight, even more preferably in the range of 15.0 to 35.0% by weight, such as in the range of 20, 0 to 35.0% by weight.
[00102] Elastomeric propylene copolymer (E2) comprises monomers copolymerizable with propylene, for example, comonomers such as ethylene and/or C4 to C12 α-olefins, in particular ethylene and/or C4 to C12 α-olefins, by example, 1-butene and/or 1-hexene. Preferably, the elastomeric propylene copolymer (E2) comprises, especially, consists of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the elastomeric propylene copolymer (E2) comprises - in addition to propylene - units derivable from ethylene and/or 1-butene. Thus, in an especially preferred embodiment, the elastomeric propylene copolymer phase (E2) comprises units derivable from ethylene and propylene alone, i.e. it is an ethylene-propylene rubber (EPR).
[00103] The comonomer content, preferably the ethylene content, of the elastomeric propylene copolymer (E2) based on the total weight of the elastomeric propylene copolymer (E2) is preferably no more than 40.0% by weight, even more preferably not more than 35.0% by weight, even more preferably in the range of 10.0 to 40.0% by weight, even more preferably in the range of 12.0 to 35.0% by weight, even more preferably in the range of 14.0 to 30.0% by weight.
[00104] In turn, it is preferable that the comonomer content, preferably the ethylene content, of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2) is not more than 40.0% by weight, even more preferably not more than 35.0% by weight, even more preferably in the range of 10.0 to 40.0% by weight, even more preferably in the range of 12.0 to 30.0% by weight, even more preferably in the range of 13.0 to 28.0% by weight, such as in the range of 14.0 to 25.0% by weight.
[00105] Furthermore, it is necessary that the molecular weight of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2) is in a specific range. In this way, it is appreciated that the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2) has an intrinsic viscosity (IV) determined in accordance with DIN ISO 1628/1 (in decalin at 135°C) in the range from more than 3.7 to 9.0 dl/g, more preferably in the range from 4.0 to 8.5 dl/g, even more preferably in the range from 4.2 to 8.0 dl/g , such as in the range of 4.5 to 7.0 dl/g.
[00106] An essential aspect of the present invention is that the intrinsic viscosity (IV) and the comonomer content, preferably the ethylene content, of the cold soluble xylene fraction of the second heterophasic propylene copolymer (HECO2) are aligned with one another. the others.
[00107] In this way, it is necessary that the second heterophasic propylene copolymer (HECO2) completes equation (III), preferably, equation (IIIa), more preferably, equation (IIIb), even more preferably, equation (IIIc ),
where C is the comonomer content in % by weight of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2), and IV is the intrinsic viscosity in dl/g of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2).
[00108] As can be seen from the above equations, the values of comonomer content and intrinsic viscosity are used without dimension, as they are divided by the respective unit, that is, by "% by weight" and "dl/ g", respectively.
[00109] As mentioned above, the second heterophasic propylene copolymer (HECO2) comprises the propylene homopolymer (H-PP2) and the elastomeric propylene copolymer (E2). In this way, the comonomers of the second heterophasic propylene copolymer (HECO2) are preferably the same as for the elastomeric propylene copolymer (E2). Thus, the second heterophasic propylene copolymer (HECO2) comprises in addition to propylene comonomers, such as ethylene and/or C4 to C12 α-olefins, in particular ethylene and/or C4 to C10 α-olefins, for example, 1 -butene and/or 1-hexene. Preferably, the second heterophasic propylene copolymer (HECO2) comprises, in particular, consists of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the second heterophasic propylene copolymer (HECO2) comprises - in addition to propylene - units derivable from ethylene and/or 1-butene. Thus, in an especially preferred embodiment, the second heterophasic propylene copolymer (HECO2) comprises units derivable from ethylene and propylene only.
[00110] The comonomer content, preferably the ethylene content, of the second heterophasic propylene copolymer (HECO2) is preferably below 20.0% by weight, more preferably not more than 16.0 % by weight, even more preferably in the range of 3.5 to 16.0% by weight, even more preferably in the range of greater than 4.0 to 14.0% by weight.
[00111] Preferably, it is desirable that the second heterophasic propylene copolymer (HECO2) is thermomechanically stable. In this way, it is appreciated that the second heterophasic propylene copolymer (HECO2) has a melting temperature (Tm) of at least 135°C, more preferably in the range of 135 to 168°C.
[00112] The second heterophasic propylene copolymer (HECO2) as defined in the present invention may contain up to 5.0% by weight of additives (excluding α-nucleating agents) such as antioxidants and slip agents as well like, the antiblocking agents. Preferably, the additive content is below 3.0% by weight, such as below 1.0% by weight.
[00113] Preferably, the second heterophasic propylene copolymer (HECO2) comprises an α-nucleating agent. Even more preferred, the present invention is free of β-nucleating agents. In this way, the α-nucleating agent is preferably selected from the group consisting of (i) salts of monocarboxylic acids and polycarboxylic acids, for example, sodium benzoate or aluminum tert-butyl benzoate, and (ii) dibenzylidenesorbitol (eg 1.3:2.4 dibenzylidenesorbitol) and C1-C8-alkyl substituted dibenzylidenesorbitol derivatives such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (eg 1,3:2.4 di(methylbenzylidene)sorbitol), or substituted nonitol derivatives such as 1,2,3-trideoxy-4.6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol, and (iii) salts of phosphoric acid diesters, for example, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate or aluminum-hydroxy-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate ], and(iv) vinylcycloalkane polymer and vinylalkane polymer (as discussed in more detail below), and(v) mixtures thereof.
[00114] Such additives are generally commercially available and are described, for example, in "Plastic Additives Handbook", 5th edition, 2001 of Hans Zweifel, pages 871 to 873.
[00115] Preferably, the second heterophasic propylene copolymer (HECO2) contains up to 5% by weight of the α-nucleating agent. In a preferred embodiment, the second heterophasic propylene copolymer (HECO2) contains no more than 200 ppm, more preferably 1 to 200 ppm, most preferably 5 to 100 ppm of an α-nucleating agent, in particular, selected from the group consisting of dibenzylidenesorbitol (eg 1.3:2.4 dibenzylidene sorbitol), dibenzylidenesorbitol derivative, preferably dimethyldibenzylidenesorbitol (eg 1.3:2.4 di(methylbenzylidene)sorbitol) , or substituted nonitol derivatives, such as 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer, and mixtures of the same.
[00116] It is especially preferred, that the second heterophasic propylene copolymer (HECO2) contains a vinylcylcoalkane, such as vinylcyclohexane (VCH), polymer and/or vinylalkane polymer. In a specific embodiment, the second heterophasic propylene copolymer (HECO2) contains a vinylcylcoalkane, such as vinylcyclohexane (VCH), vinylalkane polymer and/or polymer. Preferably, the vinylcycloalkane is vinylcyclohexane polymer (VCH) is introduced into the second heterophasic propylene copolymer (HECO2) by BNT technology.
[00117] The second heterophasic propylene copolymer (HECO2) is preferably obtained by a specific process. In this way, the second heterophasic propylene copolymer (HECO2) is preferably obtained by a sequential polymerization process in the first reactor (1st R') and optionally in a second reactor (2nd R'), the homopolymer of propylene (H-PP2) is produced, while in the third reactor (3° R'), and optionally in a fourth reactor (4° R'), the elastomeric propylene copolymer (E2) of the second heterophasic propylene copolymer ( HECO2) is obtained.
[00118] The term "sequential polymerization process" indicates that the second heterophasic propylene copolymer (HECO2) is produced in at least two reactors, preferably in three or four reactors, connected in series. Thus, the present process comprises at least a first reactor (1st R'), an optional second reactor (2nd R'), a third reactor (3rd R') and an optional fourth reactor (4th R' '). The term "polymerization reactor" should indicate that the main polymerization takes place. Thus, in case the process consists of three or four polymerization reactors, this definition does not exclude the option that the overall process comprises, for example, a prepolymerization step in a prepolymerization reactor. The term “consists of” is only a closure formulation, in view of the main polymerization reactors.
[00119] As indicated above, in the first (1st R') or in the first two reactors (1st and 2nd R'), the matrix (M2), that is, the homopolymer of propylene (H-PP2) is produced. In this case, the two reactors are used for the preparation of the propylene homopolymer (H-PP2), in each reactor, a fraction of the propylene homopolymer (H-PP2a) and (H-PP2b) is produced, which may be different at the melt flow rate as indicated above. Preferably, the first fraction of homopolymer of propylene (H-PP2b) is produced in the first reactor (1st R'), whereas the second fraction of homopolymer of propylene (H-PP2b) is produced in the second reactor (2nd R').
[00120] Preferably, the weight ratio between the first fraction of homopolymer of propylene (H-PP2a) and second fraction of homopolymer of propylene (H-PP2b) is from 20/80 to 80/20, more preferably 30 /70 to 70/30, even more preferably 40/60 to 65/35.
[00121] After the first reactor (1st R') or optional second reactor (2nd R'), the matrix (M2), that is, the homopolymer of propylene (H-PP2), of the second heterophasic propylene copolymer ( HECO2), is obtained. This matrix (M2) is subsequently transferred to the third reactor (3rd R') and the optional fourth reactor (4th R'), in which the elastomeric propylene copolymer (E2) is produced and therefore the second copolymer of heterophasic propylene (HECO2) of the present invention is obtained.
[00122] Preferably, the weight ratio between the matrix (M2), i.e. the homopolymer of propylene (H-PP2), and the copolymer of elastomeric propylene (E2) [(M2)/(E2)] is 91 /9 to 60/40, more preferably 90/10 to below 70/30.
[00123] The first reactor (1° R') is preferably a slurry reactor (SR) and can be any simple or continuous stirred batch tank reactor or closed loop reactor operating in volume or slurry. Slurry means a polymerization in a reaction medium comprising at least 60% (w/w) monomer.
[00124] According to the present invention, the slurry reactor (SR) is preferably a closed loop reactor (volume) (LR).
[00125] The second reactor (2° R'), the third reactor (3° R') and the fourth reactor (4° R') are preferably gas phase reactors (GPR). Such gas phase reactors (GPR) can be any mechanically fluid or mixed bed reactors. Preferably, gas phase reactors (GPR) comprise a mechanically stirred fluidized bed reactor with gas velocities of at least 0.2 m/sec. Thus, it is appreciated that the gas phase reactor is a fluidized bed type reactor, preferably with a mechanical stirrer.
[00126] Thus, in a preferred embodiment, the first reactor (1° R') is a slurry reactor (SR), such as a closed loop reactor (LR), whereas the second reactor (2° R' ), the third reactor (3rd R'), and the optional fourth reactor (4th R'), are gas phase reactors (GPR). Thus, for the present process, at least two, preferably two or three polymerization reactors, i.e. a slurry reactor (SR) such as a closed loop reactor (LR), a first gas phase reactor (GPR-1), a second gas-phase reactor (GPR-2) and optionally a third gas-phase reactor (GPR-3) connected in series are used. If necessary, before the slurry reactor (SR) a pre-polymerization reactor is placed.
[00127] A preferred multistage process is a "closed loop gas phase" process as developed by Borealis A/S, Denmark (known as BORSTAR® technology) described, for example, in the patent literature, such 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.
[00128] An additional suitable slurry gas phase process is the Spheripol® process from Basell.
[00129] Preferably, in the present process for the production of the second heterophasic propylene copolymer (HECO2), as defined above, the conditions for the first reactor (1st R'), i.e., the slurry reactor (SR ), such as a closed loop reactor (LR), can be as follows:- the temperature is within the range of 40°C to 110°C, preferably between 60°C and 100°C, such as 68 to 95°C, - pressure is within the range of 20 bar to 80 bar (2 MPa to 8 MPa), preferably between 40 bar to 70 bar (4 MPa to 7 MPa), - hydrogen can be added to control the molar mass in a manner known per se.
[00130] Subsequently, the reaction mixture from the first reactor (1st R') is transferred to the second reactor (2nd R'), that is, gas phase reactor (GPR-1), where the conditions 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 to 50 bar (0, 5 MPa to 5 MPa), preferably between 15 bar to 35 bar (1.5 MPa to 3.5 MPa), hydrogen can be added to control the molar mass in a manner known per se.
[00131] The condition in the third reactor (3rd R') and the fourth reactor (4th R'), preferably in the second gas phase reactor (GPR-2) and the third gas phase reactor (GPR-3 ), are similar to those of the second reactor (2°R').
[00132] The residence time may vary in the three or four zones of the reactor.
[00133] In an embodiment of the process for the production of the second heterophasic propylene copolymer (HECO2), the residence time in the first reactor (1st R'), that is, the slurry reactor (SR), such as a closed loop reactor (LR) is in the range of 0.2 to 4 hours, eg 0.3 to 1.5 hours and the residence time in gas phase reactors will generally be 0.2 to 6.0 hours, such as 0.5 to 4.0 hours.
[00134] If desired, polymerization can be carried out in a known manner under supercritical conditions in the first reactor (1° R'), i.e. in the slurry reactor (SR) such as in the closed loop reactor (LR) , and or as a condensed method in gas phase reactors (GPR).
[00135] Preferably, the process also comprises a pre-polymerization, with the catalyst system, as mentioned below, comprising a Ziegler-Natta procatalyst, an external donor and, optionally, a co-catalyst.
[00136] In a preferred embodiment, the prepolymerization is carried out as bulk slurry polymerization in liquid propylene, i.e., the liquid phase mainly comprises propylene, with a smaller amount of other reactants and, optionally, inert components, there dissolved.
[00137] The prepolymerization reaction is typically carried out at a temperature from 0 to 50°C, preferably from 10 to 45°C, and more preferably from 15 to 40°C.
[00138] The pressure in the prepolymerization reactor is not critical, but it should be high enough to keep the reaction mixture in liquid phase. Thus, the pressure can be from 20 to 100 bar (2 to 10 MPa), for example 30 to 70 bar (3 MPa to 7 MPa).
[00139] The catalyst components are preferably all introduced to the pre-polymerization step. However, where the solid catalyst component (i) and the co-catalyst (ii) can be fed separately, it is possible that only a part of the co-catalyst is introduced in the pre-polymerization stage and the remaining part in the stages of subsequent polymerization. Furthermore, in such cases, it is necessary to introduce co-catalyst both to the prepolymerization stage that a sufficient polymerization reaction is obtained therein.
[00140] It is also possible to add other components to the pre-polymerization stage. Thus, hydrogen can be added at the prepolymerization stage to control the molecular weight of the prepolymer, as is known in the art. In addition, the anti-static additive can be used to prevent the particles from sticking to each other or to the reactor walls.
[00141] Precise control of prepolymerization conditions and reaction parameters is within the skill of the art.
[00142] According to the invention, the second heterophasic propylene copolymer (HECO2) is obtained by a sequential polymerization process, as described above, in the presence of a catalyst system comprising a Ziegler-Natta catalyst and optionally a donor external, preferably, a catalyst system comprising three components, namely, as component (i) a Ziegler-Natta procatalyst, and optionally, as component (ii) an organometallic co-catalyst, and as component (iii) an external donor represented by formula (IIIa) or (IIIb), preferably represented by formula (IIIa), as described above, according to the preparation of the first heterophasic propylene copolymer (HECO1).
More preferably, the external donor is of formula (IIIa), such as dicyclopentyl dimethyl silane [Si(OCH3)2(cyclopentyl)2] or diisopropyl dimethyl silane [Si(OCH3)2(CH(CH3) 2)2].
[00144] The additives as mentioned above are added to the second heterophasic propylene copolymer (HECO2), preferably by extrusion. For mixing/extrusion, a conventional composition or mixing apparatus, for example a Banbury mixer, a 2-roll rubber mill, Buss co-kneader or a twin screw extruder can be used. Polymeric materials recovered from the extruder are generally in the form of pellets. Polyolefin Composition and Its Use
[00145] The first heterophasic propylene copolymer (HECO1) and the second heterophasic propylene copolymer (HECO2) are combined to form the polyolefin composition of the invention. Mixing can be achieved in any conventional manner, such as, for example, in an extruder.
[00146] In order to obtain the desired properties, the heterophasic propylene copolymers are preferably mixed in a specific mixing ratio. Thus, the polyolefin composition of the invention preferably comprises the first heterophasic propylene copolymer (HECO1) and the second heterophasic propylene copolymer (HECO2) in a weight ratio [(HECO1):(HECO2)] of 1.2 :1 to 15:1, more preferably from 1.3:1 to 10:1, even more preferably in the range from 1.4.1 to 8:1. The polyolefin composition of the invention may comprise other polymers, however, it is preferable that the two heterophasic propylene copolymers (HECO1) and (HECO2) constitute the major amount of the composition. Therefore, it is preferred that the two heterophasic propylene copolymers (HECO1) and (HECO2) become up to at least 50 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt. % by weight of the polyolefin composition of the invention. The remaining part can be additives, fillers, polymers used as a vehicle for the additives or elastomers.
[00147] The polyolefin 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 use for the production of car interiors and exteriors, such as bumpers, side trims, auxiliary step, body panels, spoilers, instrument panels, interior trims and the like.
[00148] The present invention also provides (automotive) articles, 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 consisting of the polyolefin composition of the invention. In this way, the present invention is especially directed to automotive articles, especially for car interiors and exteriors, such as bumpers, side linings, auxiliary stage, body panels, spoilers, instrument panels, interior linings and the like, which comprise at least 60% by weight, more preferably at least 80% by weight, even more preferably at least 95% by weight, as consisting of the polyolefin composition of the invention.
[00149] The present invention will now be described in more detail by the Examples provided below. EXAMPLES 1. Definitions/Measurement Methods
[00150] The following definitions of the terms and methods of determination apply to the above general description of the present invention, as well as, to the examples below, unless otherwise defined.
[00151] Calculation of the comonomer content of the second fraction of the propylene copolymer (R-PP2) of the first heterophasic propylene copolymer (HECO1):
where W(PP1) is the fraction by weight [in % by weight] of the first fraction of the propylene copolymer (R-PP1), W(PP2) is the fraction by weight [in % by weight] of the second fraction of the copolymer of propylene (R-PP2),C(PP1) is the comonomer content [in % by weight] of the first fraction of the propylene copolymer (R-PP1),C(PP) is the comonomer content [in % by weight] of the propylene copolymer (R-PP), C(PP2) is the calculated comonomer content [in % by weight] of the second fraction of the propylene copolymer (R-PP2).
[00152] Calculation of the cold soluble xylene content (XCS) of the second fraction of the propylene copolymer (R-PP2) of the first heterophasic propylene copolymer (HECO1):
where W(PP1) is the fraction by weight [in % by weight] of the first fraction of the propylene copolymer (R-PP1), W(PP2) is the fraction by weight [in % by weight] of the second fraction of the copolymer of propylene (R-PP2),XS (PP1) is the cold soluble content of xylene (XCS) [in % by weight] of the first fraction of the propylene copolymer (R-PP1),XS(PP) is the cold soluble content of xylene (XCS) [in % by weight] of the propylene copolymer (R-PP), XS(PP2) is the calculated cold soluble xylene content (XCS) [in % by weight] of the second fraction of the propylene copolymer (R -PP2).
[00153] Calculation of the melt flow rate MFR2 (230°C) of the second fraction of the propylene copolymer (R-PP2) of the first heterophasic propylene copolymer (HECO1):
where W(PP1) is the fraction by weight [in % by weight] of the first fraction of the propylene copolymer (R-PP1), W(PP2) is the fraction by weight [in % by weight] of the second fraction of the copolymer of propylene (R-PP2),MFR(PP1) is the melt flow rate MFR2 (230°C) [in g/10 min] of the first fraction of the propylene copolymer (R-PP1),MFR(PP) is the melt flow rate MFR2 (230°C) [in g/10 min] of the propylene copolymer (R-PP), MFR(PP2) is the calculated melt flow rate MFR2 (230°C) [in g/ 10 min] of the second fraction of the propylene copolymer (R-PP2).
[00154] Calculation of the melt flow rate MFR2 (230°C) of the second fraction of the propylene copolymer (H-PP2b) of the second heterophasic propylene copolymer (HECO2):
where W(PP1) is the fraction by weight [in % by weight] of the first fraction of the propylene copolymer (H-PP2), i.e. of the first fraction of the homopolymer of propylene (H-PP2a), W(PP2) is the fraction by weight [in % by weight] of the second fraction of the propylene copolymer (H-PP2), i.e. of the second fraction of the homopolymer of propylene (H-PP2b),MFR(PP1) is the melt flow rate MFR2 (230°C) [in g/10 min] of the first fraction of propylene copolymer (H-PP2), that is, of the first fraction of propylene homopolymer (H-PP2a), MFR(PP) is the rate of melt flow MFR2 (230°C) [in g/10 min] of the homopolymer of propylene (H-PP2), MFR(PP2) is the calculated melt flow rate MFR2 (230°C) [in g/10 min ] of the second fraction of propylene copolymer (H-PP2), that is, of the second fraction of propylene homopolymer (H-PP2b).
[00155] Calculation of the comonomer content of the elastomeric propylene copolymer (E) of the first heterophasic propylene copolymer (HECO1):
where W(PP) is the fraction by weight [in % by weight] of the propylene copolymer (R-PP), i.e. polymer produced in the first and second reactors (R1 + R2), W(E) is the fraction in weight [in % by weight] of the elastomeric propylene copolymer (E), i.e. polymer produced in the third and fourth reactors (R3 + R4), C(PP) is the comonomer content [in % by weight] of the copolymer of propylene (R-PP), ie the comonomer content [in % by weight] of the polymer produced in the first and second reactors (R1 + R2), C(HECO) is the comonomer content [in % by weight] of the propylene copolymer, ie is the comonomer content [in % by weight] of the polymer obtained after polymerization in the fourth reactor (R4), C(E) is the calculated comonomer content [in % by weight] of the copolymer of Elastomeric propylene (E), ie, the comonomer content [in % by weight] of the polymer produced in the third and fourth reactors (R3 + R4). Quantification of Microstructure by NMR Spectroscopy
[00156] Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of polymers. Quantitative 13C{1H}NMR spectra were recorded in the solution state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1H and 13C, respectively. All spectra were recorded using a 13C optimized at 10mm to raise the probe head temperature to 125°C using nitrogen gas for all tires. Approximately 200 mg of the material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) together with chromium-(III)-acetylacetonate (Cr(acac)3) resulting in a 65 mM solution of the agent. relaxation in solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogeneous solution, after initial sample preparation on a heating block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion into the magnet, the tube was centrifuged at 10 Hz. This configuration was chosen primarily for the high resolution and quantitatively needed to ensure quantification of the ethylene content. The single standard pulse excitation was employed without NOE, using an optimized tip angle, 1 s recycling delay and a WALTZ16 bilevel of the dissociation scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag Reson 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R. ., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128). A total of 6144 transients (6k) were acquired by spectra.
[00157] Quantitative 13C{1H}NMR spectra were processed, integrated and relevant quantitative properties determined from the integers using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the solvent chemical shift. This approach allowed for comparable reference, even when this structural unit was not present. The characteristic signs corresponding to ethylene incorporation were observed in Cheng, H.N., Macromolecules 17(1984), 1950).
[00158] With characteristic signs corresponding to 2.1 regio erythro defects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100(4), 1253, in Cheng , HN, Macromolecules 1984, 17, 1950, and in WJ. Wang and S. Zhu, Macromolecules 2000, 33 1157) correction for the influence of regio defects on certain properties was necessary. The characteristic signs corresponding to other types of regio defects were not observed.
[00159] The comonomer fraction was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33(2000), 1157) by integrating multiple signals from the entire spectral region into the 13C{1H} spectra. This method was chosen for its robust nature and ability to account for the presence of regio defects when necessary. Integral regions were slightly tweaked to increase applicability across the range of comonomer content found.
[00160] During systems, where only ethylene isolated in PPEPP sequences was observed, the method of Wang et. al. has been modified to reduce the influence of non-zero integers from places that are known not to be present. This approach reduced the overestimation of the ethylene content for such systems and was achieved by reducing the number of sites used to determine the absolute ethylene content to: E = 0.5 (Sββ + SβY + Sβδ + 0.5 (Sαβ + SαY ))
[00161] Through the use of this set of places, the corresponding integral equation became: E = 0.5 (IH + IG + 0.5 (IC + ID)) using the same notation used in the article by Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33(2000), 1157). Equations used for absolute propylene content were not modified.
[00162] Comonomer incorporation in percent in mol was calculated from the fraction in mol:E [% in mol] = 100 * fE
[00163] Comonomer incorporation in percent by weight was calculated from the fraction in mol:E [% by weight] = 100 * (fE * 28.06)/((fE * 28.06) + ((1 - fE) * 42.08))
[00164] The distribution of the comonomer sequence at the triad level was determined using the method of analysis of Kakugo et al. (Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150). This method was chosen for its robust nature and slightly adjusted integration regions to increase the applicability of a wider range of comonomer contents.
[00165] Analyzes of DSC, melting temperature (Tm) and heat of melting (Hf), temperature of crystallization (Tc) and heat of crystallization (Hc): measured with a TA Instrument Q2000 differential scanning calorimeter (DSC) on samples 5 to 7 mg. DSC is performed according to ISO 11357/part 3/method C2 in a heat/cold/heat cycle with a scan rate of 10°C/min, in the temperature range of -30 to +225°C. Crystallization temperature and heat of crystallization (Hc) are determined from the cooling step, while the melting temperature and heat of fusion (Hf) are determined from the second heating step.
[00166] MFR2 (230°C) is measured according to ISO 1133 (230°C, 2.16 kg load).
[00167] Cold xylene solubles (XCS, % by weight): cold xylene solubles (XCS) content is determined at 25°C according to ISO 16152; first edition; 2005-0701.
Intrinsic viscosity is measured according to DIN ISO 1628/1, October 1999 (in decalin at 135°C).
[00169] Traction Modules; Break tensile strains are measured in accordance with ISO 527-2 (crosshead speed = 1 mm/min; 23°C) using injection molded samples as described in EN ISO 1873-2 (form of dog bone, 4 mm thick).
[00170] Charpy Impact Test: Charpy notched impact strength (Charpy NIS) is measured in accordance with ISO 179 2C/DIN 53453 at 23°C and -20°C using injection molded bar test samples of 80x10x4 mm3mm3 prepared in accordance with ISO 294-1:1996. 2. Examples
[00171] The catalyst used in the polymerization processes was produced as follows: First, 0.1 mol of MgCl2 x 3 of EtOH was suspended under inert conditions in 250 ml of decane in a reactor at atmospheric pressure. The solution was cooled to a temperature of -15°C and 300 ml of cold TiCl4 was added while keeping the temperature at this level. Then, the slurry temperature was slowly increased to 20°C. At this temperature, 0.02 mol of dioctylphthalate (DOP) was added to the slurry. After the addition of phthalate, the temperature was raised to 135°C over 90 minutes and the slurry was allowed to stand for 60 minutes. Then another 300 ml of TiCl4 was added and the temperature was maintained at 135°C for 120 minutes. After this, the catalyst was filtered from the liquid and washed six times with 300 ml of heptane at 80°C. Then, the solid catalyst component was filtered and dried. Catalyst and its concept of preparation are described in general, for example, in patent publications EP491566, EP591224 and EP586390. The catalyst was prepolymerized with vinyl cyclohexane in an amount to obtain a concentration of 200 ppm poly(vinyl cyclohexane) (PVCH) in the final polymer (see EP 1183307 A1). As triethylaluminum co-catalyst (TEAL) and as dicyclopentyl dimethoxy silane donor (D-donor) (HECO2a and Heco 2b) and diethylaminotriethoxysilane [U-Donor] (HECO1), respectively, were used. Aluminum for the donor ratio is indicated in Table 1. Table 1: Preparation of heterophasic propylene copolymers (HECO)

nd = not determined Table 2: Heterophasic polypropylenes (HECO)

na = undetermined
[00172] The polyolefin compositions according to the present invention were produced by melt blending two heterophasic propylene copolymers. Table 3: Properties of invention examples and examples

[00173] The characterization of the base polymers is summarized in Table 2. The properties of the invention examples and comparatives are summarized in Table 3. CE1 refers to a first heterophasic propylene copolymer (HECO1), CE2 refers to to a second heterophasic propylene copolymer (HECO2a) and CE3 refers to another second heterophasic propylene copolymer (HECO2b). The results described in Table 3 show an improvement in the fluidity of balance, strength, stiffness, impact and rupture strain.

权利要求:
Claims (16)
[0001]
1. Polyolefin composition characterized in that it comprises (a) a first heterophasic propylene copolymer (HECO1) having (i) a melt flow rate MFR2 (230°C) measured in accordance with ISO 1133 in the range of 15.0 to 55 .0 g/10 min, and (ii) a cold soluble xylene content (XCS) determined in accordance with ISO 16152 (25°C) in the range of 24 to 38% by weight, wherein in addition (iii) the intrinsic viscosity (IV) determined in accordance with DIN ISO 1628/1 (in decalin at 135°C) of cold soluble xylene fraction (XCS) of heterophasic propylene copolymer (HECO1) is in the range of 2.0 to 3.5 dl/ g, e(b) a second heterophasic propylene copolymer (HECO2) comprising a propylene homopolymer (H-PP2) and an elastomeric propylene copolymer (E2), wherein (i) said propylene homopolymer (H-PP2) has an MFR2 melt flow rate (230°C) measured according to ISO 1133 in the range above 15 to 400 g/10 min; (ii) the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2) has an intrinsic viscosity determined according to DIN ISO 1628/1 (in decalin at 135°C) in the range of more than 3.7 to 9.0 dl/g; and (iii) the comonomer content of the cold soluble xylene fraction (XCS) of the second heterophasic propylene copolymer (HECO2) is in the range of 10.0 to 40.0% by weight.
[0002]
2. Polyolefin composition according to claim 1, characterized in that the second heterophasic propylene copolymer (HECO2) has a cold soluble xylene content (XCS) determined in accordance with ISO 16152 (25°C) ) below 40% by weight, and/or (b) an MFR2 melt flow rate (230°C) measured in accordance with ISO 1133 in the range of 1.0 to 150 g/10 min.
[0003]
3. Polyolefin composition according to claim 1, characterized in that the second heterophasic propylene copolymer (HEC02) completes equation (IV)
[0004]
4. Polyolefin composition according to claim 1, characterized in that (i) the first heterophasic propylene copolymer (HECO1) has a comonomer content in the range of 6.0 to 17.0% by weight, and /or (ii) the comonomer content of the cold soluble xylene fraction (XCS) of the first heterophasic propylene copolymer (HECO1) is in the range of 26 to 40% by weight.
[0005]
5. Polyolefin composition according to claim 1, characterized in that the second heterophasic propylene copolymer (HECO2) has a comonomer content below 20.0% by weight.
[0006]
6. Polyolefin composition according to claim 1, characterized in that the first heterophasic propylene copolymer (HECO1) comprises a polypropylene (PP1) as matrix and an elastomeric propylene copolymer (E1) dispersed in said matrix.
[0007]
7. Polyolefin composition according to claim 1, characterized in that (i) the polyolefin composition comprises the first heterophasic propylene copolymer (HECO1) and the second heterophasic propylene copolymer (HECO2) in a weight ratio [(HECO1):(HECO2)] from 1.2:1 to 15:1, and/or (ii) the two heterophasic propylene copolymers (HECO1) and (HECO2) become at least 50% by weight preferably at least 70% by weight of the polyolefin composition of the invention.
[0008]
8. Automotive articles characterized in that they comprise at least 60% by weight of the polyolefin composition as defined in claim 1.
[0009]
9. Automotive article according to claim 8, characterized in that it is selected from the group consisting of bumpers, side trims, auxiliary stage, body panels, spoilers, instrument panels, and interior trims.
[0010]
10. Polyolefin composition according to claim 2, characterized in that the second heterophasic propylene copolymer (HECO2) has (a) a cold soluble xylene content (XCS) determined in accordance with ISO 16152 (25°C) ) from 8% by weight to 35% by weight, and/or (b) an MFR2 melt flow rate (230°C) measured in accordance with ISO 1133 in the range of 1.0 to 150 g/10 min.
[0011]
11. Polyolefin composition according to claim 6, characterized in that (i) polypropylene (PP1) is a homopolymer of propylene (H-PP1), and/or (ii) polypropylene (PP1) has a MFR2 melt flow rate (230°C) measured according to ISO 1133 from 60 to 400 g/10 min.
[0012]
12. Polyolefin composition according to claim 2, characterized in that the second heterophasic propylene copolymer (HEC02) completes equation (IV)
[0013]
13. Polyolefin composition according to claim 2, characterized in that (i) the first heterophasic propylene copolymer (HECO1) has a comonomer content in the range of 6.0 to 17.0% by weight, and /or (ii) the comonomer content of the cold soluble xylene fraction (XCS) of the first heterophasic propylene copolymer (HECO1) is in the range of 26 to 40% by weight.
[0014]
14. Polyolefin composition according to claim 2, characterized in that the second heterophasic propylene copolymer (HECO2) has a comonomer content below 20.0% by weight.
[0015]
15. Polyolefin composition according to claim 2, characterized in that the first heterophasic propylene copolymer (HECO1) comprises a polypropylene (PP1) as matrix and an elastomeric propylene copolymer (E1) dispersed in said matrix.
[0016]
16. Polyolefin composition according to claim 2, characterized in that (i) the polyolefin composition comprises the first heterophasic propylene copolymer (HECO1) and the second heterophasic propylene copolymer (HECO2) in a weight ratio [(HECO1):(HECO2)] from 1.2:1 to 15:1, and/or (ii) the two heterophasic propylene copolymers (HECO1) and (HECO2) become at least 50% by weight preferably at least 70% by weight of the polyolefin composition of the invention.

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JP2017508032A|2014-02-06|2017-03-23|ボレアリス エージー|Soft copolymer with high impact strength|

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JP6474417B2|2014-02-06|2019-02-27|ボレアリス エージー|Soft and transparent impact copolymers|

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EP2907841A1|2014-02-14|2015-08-19|Borealis AG|Polypropylene composite|

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EP2947118B1|2014-05-20|2017-11-29|Borealis AG|Polypropylene composition for automotive interior applications|EP3033389B1|2013-08-14|2017-10-11|Borealis AG|Propylene composition with improved impact resistance at low temperature|

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US9670293B2|2013-10-29|2017-06-06|Borealis Ag|Solid single site catalysts with high polymerisation activity|

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CN105722872B|2013-11-22|2017-10-13|博里利斯股份公司|Low emission Noblen with high melt flows|

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US9828698B2|2013-12-04|2017-11-28|Borealis Ag|Phthalate-free PP homopolymers for meltblown fibers|

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MX2016007438A|2013-12-18|2016-10-03|Borealis Ag|Bopp film with improved stiffness/toughness balance.|

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CN105829364B|2014-01-17|2017-11-10|博里利斯股份公司|Method for preparing the butylene copolymer of propylene/1|

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JP2017508032A|2014-02-06|2017-03-23|ボレアリス エージー|Soft copolymer with high impact strength|

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JP6474417B2|2014-02-06|2019-02-27|ボレアリス エージー|Soft and transparent impact copolymers|

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EP2907841A1|2014-02-14|2015-08-19|Borealis AG|Polypropylene composite|

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法律状态:
2020-01-14| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/08/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP13181231|2013-08-21|

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EP13181231.5|2013-08-21|

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PCT/EP2014/067533|WO2015024887A1|2013-08-21|2014-08-18|High flow polyolefin composition with high stiffness and toughness|

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