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    • 专利摘要:
    high flow polyolefin composition with low shrinkage and clte, automotive article comprising said composition and method for preparing said composition polyolefin composition comprising (a) a heterophasic propylene copolymer comprising a polypropylene (pp) with a fluidity index mfr 2 ( 230 ° c) of 30-350 g / 10 min, and an elastomeric propylene copolymer (e) with an intrinsic viscosity (iv) in the range of 1.5 to 3.0 dl / g, and (b) a polyethylene with a melt flow index mfr 2 (190 ° c) of 15 to 100 g / 10 min, where (i) the total polyolefin composition has a melt drop rate mfr 2 (230 ° c) of more than 15 to 200 g / 10min, and (ii) the weight ratio of elastomeric propylene copolymer to polyethylene is less than 2.0.
    公开号:BR112014000551B1
    申请号:R112014000551-6
    申请日:2012-07-11
    公开日:2020-03-03
    发明作者:Markus Gahleitner；Georg Grestenberger；Christelle Grein；Cornelia Tranninger
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    HIGH FLOW COMPOSITION OF POLYOLEFINE WITH LOW
    SHRINK AND CLTE, AUTOMOTIVE ARTICLE UNDERSTANDING THE
    REFERRED COMPOSITION AND METHOD FOR PREPARING
    COMPOSITION
    [001] A present invention is addressed to an new composition polyolefin with low shrinkage and coefficient expansion thermal linear (CLTE), good how to your manufacturing.[002] O polypropylene is the material of choice in many applications, once can be adapted for ends specific needed. Per example, polypropylenes
    heterophasics are widely used in the automotive industry (for example, bumper applications), as 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 a ethylene propylene diene monomer polymer (EPDM). In addition, heterophasic polypropylene contains crystalline polyethylene to some extent. In the automobile 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 reactors in the gaseous phase or added externally to the matrix by means of a composition.
    [003] In the field of automotive exterior applications the contraction and thermal expansion of a polymer are of great
    Petition 870190131906, of 11/12/2019, p. 14/69
    2/51 importance. While shrinkage influences part processing (especially in injection molding), the linear thermal expansion coefficient (CLTE) is important during the life of the parts. The linear thermal expansion coefficient (CLTE) determines the minimum width of the space between two parts. Most of the time the parts are made of different materials. To avoid large gaps and high stresses in the parts, the linear thermal expansion coefficient (CLTE) should be as low as possible.
    [004] The conventional way to reduce both shrinkage and the linear thermal expansion coefficient (CLTE) in automotive compounds is to incorporate inorganic fillers (usually at high loads, ie 10 to 30% by weight). The reduction of thermal expansion and contraction of the load through addition are based on two different mechanisms, which most of the time act simultaneously:
    • dilution of the volume with a material of less contraction / CLTE • mechanical restriction by a dispersed phase with low CLTE and high modulus. For this purpose, loads with a high aspect ratio are normally used.
    [005] A disadvantage of this method is that the materials may suffer from poor strength, poor appearance and processing difficulties. In addition, the weight of these parts increases through the incorporation of cargo. In order to minimize the need to incorporate a charge of the polymer itself, it must have a high dimensional stability.
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    3/51 [006] Thus, the object of the present invention is to provide a polyolefin composition with a low coefficient of linear thermal expansion (CLTE), low shrinkage and very low weight, without compromising the strength and stiffness of said composition. In addition, it is desired to increase the scratch resistance of parts made from the polyolefin composition.
    [007] The discovery of the present invention is to provide a polyolefin composition comprising (a) a heterophasic propylene copolymer (HECO), said heterophasic propylene copolymer (HECO) comprising (a1) a polypropylene (PP) with a fluidity index MFR2 ( 230 ° C) from 30 to 350 g / 10min, and (a2) an elastomeric propylene copolymer (E) with an intrinsic viscosity (IV) in the range 1.5 to 3.0 dL / g measured as the intrinsic viscosity ( IV) (XCS) of the heterophasic propylene copolymer (HECO), and
    (B) one polyethylene (PE) with an index of fluidity MFR2 (190 ° C) in 15 to 100 g / 10min in what(i) The composition total in polyolefin (PO) has a index in fluidity MFR2 (230 ° C) in more than 15 to 200 g / 10min, and (ii) the reason in Weight in copolymer propylene
    elastomeric (E) for polyethylene (PE) is less than 2.0.
    [008] To further improve the properties of the polyolefin composition (PO) an inorganic filler (F)
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    4/51 and / or a second polyethylene (PE2) other than the first polyethylene (PE), mentioned above, can be incorporated into the polyolefin (PO) composition.
    [009] It has been surprisingly found that such a polyolefin (PO) composition has superior properties compared to the known compositions in this technical field. In particular, the contraction, as well as the values of the coefficient of linear thermal expansion (CLTE) very low, without compromising the mechanical properties, such as strength and stiffness (see examples). In addition, the risk resistance was performed positively.
    [0010] In the following, the invention will be described in more detail below.
    [0011] As mentioned above, the polyolefin composition can be used, in particular, in the automotive field. In this area there is a tendency for larger articles. The problem with such articles is that high pressures are required during manufacture. To reduce the pressure, the fluidity of the material used must be very low. Therefore, the polyolefin composition of the present invention should have an MFR2 melt index (230 ° C) of more than 15 to 200 g / 10min, preferably 20 to 150 g / 10min, more preferably 20 to 80 g / min. 10min, however more preferably, from 22 to 80 g / 10min.
    [0012] Another important aspect of the present invention is that polyethylene (PE) is, in very high amounts, present in the polyolefin composition. It was observed that, with small amounts of polyethylene (PE), the desired improvement in expansion and / or contraction
    Petition 870190131906, of 11/12/2019, p. 17/69
    5/51 thermal cannot be obtained. 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.
    It is therefore preferred that the amount of polyethylene (PE) in the total polyolefin composition (PO) is at least 10% by weight, more preferably in the range of 10 to 30% by weight, even more preferably in the range from 12 to 20% by weight.
    Therefore, in a preferred aspect, the polyolefin (PO) composition comprises (a) 50 to 90% by weight, more preferably 60 to 80% by weight of the heterophasic propylene copolymer (HECO), (b) 10 to 30 % by weight, more preferably 12 to 20% by weight of polyethylene (PE), (c) 0 to 30% by weight, more preferably from 1 to 30% by weight, even more preferably from 1 to 9% by weight, of inorganic filler (F), and (d) 0 to 15% by weight, more preferably 3 to 9% by weight, of polyethylene (PE2), based on the total polyolefin composition (PO), preferably based on the total amount of polymers present in the composition of polyolefin (PO) and inorganic filler (F).
    [0015] In addition, the polyolefin (PO) composition can comprise, in small amounts, that is, no more than 10% by weight of another second copolymer of
    Petition 870190131906, of 11/12/2019, p. 18/69
    6/51 heterophasic propylene (HECO2). Said second heterophasic propylene copolymer (HECO2) differs from the first heterophasic propylene copolymer (HECO) especially in the fluidity index. Therefore, the second heterophasic propylene copolymer (HECO2) - if present - has an MFR2 melt index (230 ° C) of less than 20 g / 10 min.
    [0016] Thus, in a very specific embodiment the polyolefin (PO) composition comprises (a) 50 to 90% by weight, more preferably 60 to 80% by weight of the heterophasic propylene copolymer (HECO), (b) 10 to 30% by weight, more preferably from 12 to 20% by weight, of polyethylene (PE), (c) 0 to 30% by weight more preferably from 1 to 30% by weight, even more preferably 1 to 9% by weight inorganic load (F)
    (d) 0 to 15% in Weight, more preferably 3 to 9% in weight, polyethylene (PE2) , and (e) 0 to 10% in Weight, more preferably 3 to 9% in weight, second copolymer heterophasic propylene
    (HECO2), based on the total polyolefin composition (PO), preferably based on the total amount of polymers present in the polyolefin composition (PO) and the inorganic filler (F), more preferably, based on the total amount of the heterophasic propylene copolymer (HECO), polyethylene (PE), the second polyethylene (PE2), the second heterophasic propylene copolymer (HECO2) and the inorganic filler (F).
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    [0017] As mentioned above, the polyolefin composition of the present invention is characterized by its good mechanical properties. Therefore, it is preferable that the polyolefin (PO) composition has an elastic modulus of at least 900 MPa, more preferably of at least 1000 MPa, even more preferably in the range of between 950 and 1600 MPa, even more preferably in the range of 1000 to 1450 MPa =. These values are, in particular, applicable if the polyolefin composition (PO) does not comprise more than 10% by weight, that is, not more than 9% by weight of inorganic filler (F).
    [0018] In addition, the impact must also be quite high. Therefore, it is understood that the polyolefm (PO) composition has an impact resistance at 23 ° C of at least 10 kJ / m 2 , more preferably at least 14 kJ / m 2 , more preferably in the range of 10 to 70 kJ / m 2 , even more preferably in the range of 14 to 60 kJ / m 2 , and / or has a temperature impact resistance of -20 ° C, of at least 2.2 kJ / m 2 , more preferably at least minus 3.0 kJ / m 2 , more preferably still in the range of 2.2 to 10.0 kJ / m 2 , even more preferably in the range of 3.0 to 7.0 kJ / m 2 . The method of measuring impact resistance is defined in the example section.
    [0019] With regard to thermal expansion, it is preferred that the polyolefin composition (PO) has a linear thermal expansion coefficient (CLTE) carried out in a temperature range of -30 to + 80 ° C of not more than 100 pm / mK, more preferably not more than 96 pm / mK, even more preferably in the range of 70 to 100 pm / mK,
    Petition 870190131906, of 11/12/2019, p. 20/69
    8/51 even more preferably in the range of 78 to 96 pm / mK. These values are, in particular, applicable when the polyolefin composition (PO) does not comprise more than 10% by weight, that is, not more than 9% by weight of inorganic filler (F).
    [0020] The polyolefin (PO) composition according to the present invention can be prepared by mixing the components in melt mixing devices suitable for the preparation of polymeric compounds, including, in particular, extruders, such as single screw extruders , as well as twin screw extruders. Other suitable fusion mixing devices include planetary extruders and individual screw co-knenders. Especially preferred are twin screw extruders including high mixing intensity 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.
    [0021] In the sequence the individual components are defined in more detail.
    Hypophasic propylene copolymer [0022] 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 the
    Petition 870190131906, of 11/12/2019, p. 21/69
    9/51 said inclusions contain the elastomeric propylene copolymer (E). The term inclusion according to this invention will preferably indicate that the matrix 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 force microscopy. scanning.
    [0023] In addition, it is preferred that the heterophasic propylene copolymer (HECO) before mixing with the other components mentioned herein as polymer components comprises only polypropylene (PP) and elastomeric propylene (E) copolymer. In other words, the propylene heterophasic copolymer (HECO) may contain additional additives, but no other polymer in an amount greater than 5% by weight, more preferably greater than 3% by weight, as exceeding 1% by weight based on the total of heterophasic propylene copolymer (HECO), more preferably based on polymers present in the propylene copolymer (HECO). An additional polymer that can be present in such low amounts is a polyethylene, which is a product of the reaction obtained by preparing the heterophasic propylene copolymer (HECO). Therefore, 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 in accordance with mentioned in this paragraph.
    [0024] In addition, the polyolefin composition (PO)
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    10/51 of the present invention can be considered as a heterophasic system. Therefore, the polypropylene (PP) of the heterophasic propylene copolymer (HECO) also forms the matrix of the total polyolefin composition (PO). The elastomeric propylene copolymer (E) and polyethylene (PE), and optionally also the inorganic filler (F) and the second polyethylene (PE2), are (finely) dispersed in said matrix. In this way, the elastomeric propylene copolymer (E) and polyethylene (PE) can form separate inclusions in the matrix, that is, in polypropylene (PP) or polyethylene (PE), they can form an inclusion within the inclusion of the propylene copolymer elastomeric (E). In the case of the total polyolefin composition (PO) it also comprises a second heterophasic propylene copolymer (HECO2), then the matrix of the second heterophasic propylene copolymer (HECO2) forms together with the matrix, that is, polypropylene (PP), from the first heterophasic propylene copolymer (HECO) the matrix of the total polyolefin composition (PO). The elastomeric phase of the second heterophasic propylene copolymer (HECO2) also forms inclusions within the total polyolefin composition (PO).
    [0025] An important aspect of the present invention is that the polyolefin composition has a relatively high melt index. Therefore, it is preferred that the heterophasic propylene copolymer (HECO) has an MFR2 melt index (230 ° C) of at least 15 g / 10min, more preferably in the range of 15 to 300 g / 10min, even more preferably in the range from 20.0 to 100 g / 10 min, still
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    11/51 more preferably in the range of 20 to 80 g / 10min.
    [0026] Preferably, it is desirable that the heterophasic propylene copolymer (HECO) is mechanically thermostable. Thus, the heterophasic propylene copolymer (HECO) is considered to have a melting temperature (Tm) of at least 135 ° C, more preferably in the range of 135 to 168 ° C.
    [0027] Preferably, the propylene content in the heterophasic propylene copolymer (HECO) is 82.0 to 94.0% by weight, more preferably 86.0 to 92.0% by weight, based on the total copolymer of heterophasic propylene (HECO), more preferably based on the amount of the polymer components of the heterophasic propylene copolymer (HECO), even more preferably, based on the amount of the polypropylene (PP) and the elastomeric propylene copolymer (E) together. The remaining part constitutes the comonomers as defined for polypropylene (PP) being a random propylene copolymer (R-PP) and an elastomeric propylene copolymer (E), respectively, preferably ethylene. Accordingly, the comonomer content, preferably ethylene content, is in the range of 6.0 to 18.0% by weight, more preferably in the range of 8.0 to 14.0% by weight.
    [0028] As stated above, the heterophasic propylene copolymer (HECO) matrix is polypropylene (PP).
    [0029] The polypropylene (PP) according to this invention must have a melt flow index MFR2 (230 ° C) of 30 to 350 g / 10min, preferably in the range of 60 to 250 g / 10min, more preferably in the range from 80 to 150 g / 10min.
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    Therefore, it is preferred that polypropylene (PP) has an average weight molecular weight (M w ) of 100,000 to 300,000 g / mol, more preferably 150,000 to 250,000 g / mol.
    [0031] 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 to 10.0, even more preferably in the range of 3.0 to 8.0.
    [0032] Polypropylene (PP) can be a random propylene copolymer (R-PP) or a propylene homopolymer (H-PP), the latter is preferred.
    In this way it is appreciated that polypropylene (PP) has a comonomer content equal to or less than 10.0% by weight, more preferably equal to or less than 7.0% by weight.
    [0034] The term 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 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.
    [0035] In the case of polypropylene (PP) it is a random propylene copolymer (R-PP) comprising
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    13/51 monomers copolymerizable with propylene, for example, comonomers such as ethylene and / or C4 to C12 α-olefins, in particular ethylene and / or C4 to C10 α-olefins, for example, 1butene and / or 1-hexene . Preferably, the random propylene copolymer (R-PP) comprises, in particular, consists of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1hexene. More specifically, the random propylene copolymer (R-PP) comprises - in addition to propylene derivatives of ethylene and / or 1-butene. In a preferred embodiment, the random propylene copolymer (R-PP) includes derivable ethylene and propylene units only. The comonomer content in the random propylene copolymer (R-PP) is preferably in the range of more than 0.5 to 10.0% by weight, even more preferably in the range of more than 0.5 to 7.0% in weight.
    [0036] 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 have no neighboring comonomer units, compared to the total amount of comonomers in the polymer chain.
    [0037] Preferably, polypropylene (PP) is isotactic. Therefore, it is understood that the homopolymer
    propylene (H-PP) has one quintet in concentration quite high, or be , more in 90%, more preferably more of that 92% , still more preferably more of that 93% and still more
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    14/51 preferably more than 95%, such as at least 97%. On the other hand, it is preferred that the random propylene copolymer (R-PP) of a concentration triad of more than 90%, more preferably more than 92%, even more preferably more than 93% and even more preferably more than than 95%, like at least 97%.
    [0038] Furthermore, it is preferred that the polypropylene has a crystallinity of at least 40%, more preferably in the range of 40 to 65%, as in the range of 45 to 60%.
    [0039] Polypropylene (PP) can have a content of soluble in cold xylene (XCS) in a wide range, that is, up to 6.0% by weight. Therefore, polypropylene (PP) can have a content of soluble in cold xylene (XCS) in the
    0.3 to 6.0% by weight, such as 0.5 and 5.0% by weight.
    [0040] However, in preferred embodiments, polypropylene (PP), in particular in the case of polypropylene (PP) is a propylene homopolymer (H-PP), has a soluble cold xylene (XCS) content in the range from 0.5 to 4.5% by weight, more preferably in the range of 1.0 to 4.0% by weight, even more preferably from 1.5 to 3.5% by weight.
    [0041] Another essential component of the heterophasic propylene copolymer (HECO) is the elastomeric propylene copolymer (E).
    [0042] The elastomeric propylene copolymer (E) preferably 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 C10
    Petition 870190131906, of 11/12/2019, p. 27/69
    15/51 α-olefins, for example, 1-butene and / or 1-hexene. Preferably, the elastomeric propylene copolymer (E) comprises, in particular, consists of copolymerizable monomers 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 - units derivable from ethylene and / or 1-butene. Thus, in an especially preferred embodiment, the elastomeric propylene copolymer (E) phase comprises derivatives of ethylene and propylene only.
    [0043] In the case polypropylene (PP) is 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.
    [0044] The phase properties of the elastomeric propylene copolymer (E) mainly influences the cold soluble xylene content (XCS) of the heterophasic propylene copolymer (HECO). Thus according to the present invention the soluble cold xylene fraction (XCS) of the heterophasic propylene copolymer (HECO) is considered to be the elastomeric propylene copolymer (E) of the heterophasic propylene copolymer (HECO).
    Therefore, the amount of elastomeric propylene copolymer (E), that is, the soluble cold xylene fraction (XCS), of the heterophasic propylene copolymer (HECO) is preferably in the range of 20 to 50% by weight , more preferably in the range of 25 to 40% by weight, even more preferably in the range of 25 to 38% by weight. These values
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    16/51 are based on the heterophasic propylene copolymer (HECO) and not on the polyolefin composition (PO).
    [0046] An important requirement of the present invention is that the elastomeric propylene copolymer (E) has a balanced average weight molecular weight. Small particles are formed in the case of the matrix and the elastomeric phase has 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 to have a high fluidity index and, therefore, a slightly lower average molecular weight. Therefore, also the elastomeric propylene copolymer (E) must have a low 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 average molecular weight for the elastomeric propylene copolymer (E), which has a negative impact on the mechanical properties. Therefore, the intrinsic viscosity has to be carefully chosen.
    [0047] Values of low intrinsic viscosity (IV) reflect a low 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 3.0 dL / g, more preferably in the range equal to or greater than 1.8, equal to or less than 2.8 dL / g, even more preferably in the range equal to or greater than 2.0 and less or equal to
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    17/51
    2.6 dL / g.
    [0048] The comonomer content, preferably the ethylene content, in the elastomeric propylene (E) copolymer phase should preferably also be in a specific range. 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 75% or less by weight, more preferably in the range of 15 to 75% by weight, even more preferably in the range of 20 to 50% by weight, even more preferably in the range of 25 to 40% by weight. Therefore, it is appreciated that the propylene 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 greater than 25% by weight,
    more preferably at banner in 25 to 85% by weight, still more preferably at banner in 50 to 80% by weight, still more preferably at banner in 60 a equal to or less than
    75% by weight.
    [0049] 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 process of sequential steps using reactors in a configuration in
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    18/51 series 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.
    [0050] The heterophasic propylene copolymer (HECO) according to the present invention is preferably produced in a sequential polymerization process, that is, in a multistage 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).
    [0051] Therefore, it is preferred that O copolymer of heterophasic propylene (HECO) is produced on one process of sequential polymerization which comprises at steps of (a) polymerization of propylene and,
    optionally, at least one of ethylene and / or C4 to C12 α-olefin in a first reactor (R1) obtaining the first polypropylene (PP), preferably said first polypropylene fraction is a first propylene homopolymer, (b) transfer of the first polypropylene fraction for a second reactor (R2), (c) polymerization in the second reactor (R2) and in the presence of said first polypropylene propylene fraction and,
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    19/51 optionally, at least one ethylene and / or C4 to C12 α-olefin thus obtaining the second polypropylene fraction, preferably said second polypropylene fraction is a second propylene homopolymer, said first polypropylene fraction and the said second polypropylene fraction forms the polypropylene (PP), that is, the heterophasic propylene copolymer matrix (HECO), (d) transferring the polypropylene (PP) from step (c) to a third reactor (R3), (e) polymerization in the third reactor (R3) and in the presence of polypropylene (PP) obtained in step (c) propylene and at least one ethylene and / or C4 to C12 α-olefin thus obtaining a first fraction of elastomeric propylene copolymer, the first fraction of elastomeric propylene copolymer is dispersed in polypropylene (PP), (f) transferring 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), propylene and at least one of ethylene and / or C4 to C12 α-olefin thus obtaining the second fraction of elastomeric propylene copolymer, polypropylene (PP), a first fraction of elastomeric propylene copolymer, and the second fraction of elastomeric propylene copolymer forms the heterophasic propylene copolymer (HECO).
    [0052] Of course, 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 produced
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    20/51 be obtained. The same is true 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.
    [0053] 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 displayed outside.
    [0054] 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, in the case the process consists of four polymerization reactors, this definition does not exclude the possibility that the total process comprises, for example, a prepolymerization step in a prepolymerization reactor. The term made up of is only a closing formulation, considering the main polymerization reactors.
    [0055] The first reactor (R1) is preferably a suspension reactor (SR) and can be any continuous or simple agitated tank reactor or batch reactor.
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    21/51 closed circuit operating in bulk or in suspension. Mass means polymerization in a reaction medium that comprises at least 60% monomer (w / w). According to the present invention, the suspension reactor (SR) is preferably a closed loop (ground) (LR) reactor.
    [0056] 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 or fluidized bed reactors. Preferably, the gas phase reactors (GPR) comprise a mechanically agitated fluidized bed reactor with gas velocities of at least 0.2 m / sec. Thus, the gas phase reactor is considered to be a fluidized bed type reactor, preferably with a mechanical stirrer.
    [0057] 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 reactor gases (GPR). Therefore, for the present process, at least four, preferably four polymerization reactors, that is, a suspension reactor (SR), such as a closed circuit 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, a prepolymerization reactor is placed before the suspension reactor (SR).
    [0058] A preferred multistage process
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    22/51 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 WO 00/68315.
    [0059] A more suitable suspension-gas phase process is Basell's Spheripol® process.
    [0060] Preferably, in the present process to produce the heterophasic propylene copolymer (HECO) as defined above the conditions for the first reactor (R1), 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 within the range of 20 bar to 80 bar (2000 kPa to 8000 kPa), preferably between 40 bar to 70 bar (4000 kPa to 7000 kPa),
    - hydrogen can be added to control molar mass in a manner known per se.
    [0061] Subsequently, the reaction mixture of
    stage (a) is transferred to second reactor (R2), or be, phase reactor gaseous (GPR-1), that is, for The stage (c), where conditions of step (c) are in preferably as follows - the temperature is inside interval 50 ° C The 130 ° C, preferably between 60 ° C and 100 ° C, - the pressure is on interval from 5 bar to 50 bar (500
    Petition 870190131906, of 11/12/2019, p. 35/69
    23/51 kPa to 5000 kPa), preferably between 15 bar and 35 bar (1500 kPa to 3500 kPa),
    - hydrogen can be added to control molar mass in a manner known per se.
    [0062] 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 (GPR3), is similar to that of the second reactor ( R2).
    [0063] The residence time may vary in the three zones of the reactor.
    [0064] In an embodiment of the process for the production of polypropylene the residence time in the mass reactor, for example, cycle 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.
    [0065] If desired, polymerization can be carried out in a known manner, under supercritical conditions in the first reactor (R1), that is, in the
    suspension (SR), as in the reactor in closed circuit (LR), and / or as a mode of condensate we reactors gas phase (GPR).[0066] In preferably, O process comprises equally an prepolymerization how system of catalyst, as described in detail Next,
    comprising a Ziegler-Natta pro-catalyst, an external donor and, optionally, a cocatalyst.
    [0067] In a preferred embodiment, prepolymerization is conducted as suspension polymerization
    Petition 870190131906, of 11/12/2019, p. 36/69
    24/51 in bulk liquid propylene, that is, the liquid phase mainly comprises propylene, with a small amount of other reagents and, optionally, inert components dissolved in it.
    [0068] 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.
    [0069] 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 (2000 to 10,000 kPa), for example, 30 to 70 bar (3000 to 7000 kPa).
    [0070] The catalyst components are preferably all introduced in the prepolymerization step. However, when the solid catalyst component (i) and the cocatalyst (ii) can be fed separately, it is possible that only a part of the cocatalyst is introduced in the prepolymerization phase and the remainder in subsequent polymerization steps. In addition, in such cases, it is necessary to introduce so much cocatalyst for the prepolymerization phase that a sufficient polymerization reaction is obtained therein.
    [0071] 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 the particles from adhering to each other or to the reactor walls.
    Petition 870190131906, of 11/12/2019, p. 37/69
    25/51 [0072] Precise control of prepolymerization conditions and reaction parameters is within the skill of the art.
    [0073] 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.
    [0074] The pro-catalyst used according to the invention is prepared by
    a) reaction of an adduct by cystallized spray or solidified emulsion of MgC12 and a C1-C2 alcohol with T1CI4
    b) reaction of step a) with a dialkylphthalate product of formula
    R 2 'are, where R 1 ' and independently, at least one alkyl group
    C 5 under conditions in which a transesterification between said Ci to C2 alcohol and said dialkyl phthalate of formula (I) 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 TCICI4.
    Petition 870190131906, of 11/12/2019, p. 38/69
    26/51 [0075] 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 included by reference .
    [0076] Firstly an adduct of MgCl2 and a C1C2 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.
    [0077] The adduct, which is first melted and then crystallized spray or solidified emulsion, is used as a catalyst support.
    [0078] In the next step, the crystallized spray adduct or solidified emulsion of formula MgCl2 * nROH, where R is methyl or ethyl, preferably ethyl and n is 1 to 6, is contacted with TiCl4 to form a titanized vehicle, followed by steps of • adding to said titanized vehicle (i) a dialkylphthalate of formula (I) with R 1 'and R 2 ' being, independently, at least one C5-alkyl, such as at least one Cs-alkyl, or preferably ( ii) a dialkylphthalate of formula (I) with R 1 ' and R 2' being the same and being at least one C5-alkyl, such as at least one Cs-alkyl, or more preferably (iii) a dialkylphthalate 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
    Petition 870190131906, of 11/12/2019, p. 39/69
    27/51 dialkyl phthalate of formula (I) is a dioctyl phthalate (DOP), such as diiso-dioctyl phthalate 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 formula (I) to form preferably at least 80 mol%, more preferably 90 mol%, more preferably 95 mol%, of a dialkyl phthalate of formula (II)
    where R 1 and R 2 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 procatalyst (component (i)).
    [0079] The adduct of formula MgC12 * nROH, where R is methyl or ethyl and n is 1 to 6, is in a preferred melt embodiment and then the melt is preferably injected by a gas in a cooled solvent or a cooled gas, whereby the adduct is crystallized in a morphologically advantageous form, as described for example in WO 87/07620.
    Petition 870190131906, of 11/12/2019, p. 40/69
    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.
    [0081] As the catalyst residue is removed by extraction, an adduct from the titanized vehicle and the internal donor is obtained, in which the resulting group from the ester alcohol has changed.
    [0082] In case sufficient titanium remains in the vehicle, it will act as an active element of the procatalyst.
    [0083] Otherwise, titanization is repeated after the above treatment, in order to ensure a sufficient concentration of titanium and, therefore, the activity.
    [0084] 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.
    [0085] 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 diethyl phthalate (DEP) as the internal donor compound. .
    [0086] Even more preferably, the catalyst used according to the invention is Borealis BCF20P catalyst (prepared according to WO
    Petition 870190131906, of 11/12/2019, p. 41/69
    29/51
    92/19653 as disclosed in WO 99/24479, especially with the use of dioctyl phthalate as the dialkylphthalate of formula (I) according to WO 92/19658) or the Polytrack 8502 catalyst, commercially available from Grace.
    [0087] 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 procatalyst an organometallic cocatalyst as component (ii).
    [0088] Therefore, it is preferred to select the cocatalyst from the group consisting of trialkylaluminium, such as triethylaluminium (TEA), dialkyl aluminum chloride and alkyl aluminum aluminum sesquichloride.
    [0089] Component (iii) of the catalyst system used is an external donor represented by the formula (IIIa) or (IIIb). Formula (IIIa) is defined by
    Si (OCH3) 2R2 5 (IIIa) where R 5 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.
    [0090] It is in particular preferred that R 5 is selected from the group consisting of iso-propyl, iso-butyl, iso-pentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyla.
    [0091] Formula (IIIb) is defined by
    Petition 870190131906, of 11/12/2019, p. 42/69
    30/51
    Si (OCH2CH3) 3 (NR x Ry) (IIIb) where R x and R y can be the same or different represent a hydrocarbon group with 1 to 12 carbon atoms.
    [0092] R x and R y are independently selected from the group consisting of the linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. In particular, it is preferred that R x and R y 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.
    [0093] More preferably both R x and R y are O really, still more preferably both R x and R y are one ethyl group.[0094] More preferably the donor external in
    formula (IIIb) is diethylaminotriethoxysilane.
    [0095] 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) 2] .
    [0096] In another embodiment, the Ziegler-Natta procatalyst 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 cocatalyst
    Petition 870190131906, of 11/12/2019, p. 43/69
    31/51 (component (iii)), which vinyl compound has the formula:
    CH2 = CH-CHR3R4 where R 3 and R4 together form a saturated, unsaturated or aromatic 5- or 6-membered ring 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. The polymerized vinyl compound can act as an α-nucleating agent.
    [0097] Regarding the modification of the catalyst reference, international applications WO 99/24478, WO 99/24479 and in particular WO 00/68315, are 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.
    [0098] Thus, the heterophasic propylene copolymer (HECO) is considered to be α-nucleated. In the case αnucleation is not performed by a vinylcycloalkane polymer or a vinylalkane polymer as indicated above, the following α-nucleating agents (N) may be present (i) salts of monocarboxylic acids and polycarboxylic acids, for example, sodium benzoate or aluminum tert-butylbenzoate, and (ii) dibenzylidenosorbitol (e.g., 1,3: 2,4 dibenzylidenosorbitol) and C1-C8-substituted alkyl derivatives dibenzylidenosorbitol, such as
    Petition 870190131906, of 11/12/2019, p. 44/69
    32/51 methyldibenzylidenosorbitol, ethyldibenzylidenosorbitol or dimethyldibenzylidenesorbitol (eg 1,3: 2,4 di (methylbenzylidene) sorbitol), or substituted nonitol derivatives, such as 1,2,3-tridesoxy-4,6: 5,7- bis-O - [(4propylphenyl) -methylene] -nonitol, and (iii) salts of phosphoric acid diesters, for example, and 2,2'-methylenebis (4,6, di-tert-butylphenyl) sodium or hydroxy-phosphate aluminum bis [2,2'-methylenobis (4,6-di-t-butylphenyl) phosphate], and (iv) mixtures thereof.
    Polyethylene [0099] As mentioned above, the polyolefin (PO) composition must comprise a (first) polyethylene (PE) and, optionally, a second polyethylene (PE2). Preferably polyethylene (PE2) differs at least from (first) polyethylene (PE) in density and / or melt index. The (first) polyethylene (PE) and the second polyethylene (PE2), are well known in the art and are commercially available.
    [00100] According to the present invention, polyethylene (PE), must have a melt flow index MFR2 (190 ° C) in the range of 15 to 100 g / l0min, preferably in the range of more than 15 to 100 g / 10min, more preferably in the range of 18.0 to 100.0, even more preferably in the range of 20.0 to 100.0 g / 10min, even more preferably in the range of 10.0 to 80.0 g / 10min, such as 25 to 50 g / l0min.
    [00101] Preferably, the (first) polyethylene (PE) is a high density polyethylene (HDPE). Thus, it is considered that the (first) polyethylene (PE) has a
    Petition 870190131906, of 11/12/2019, p. 45/69
    33/51 density of at least 945 kg / m 3 , more preferably at least 955 kg / m 3 , even more preferably in the range of 945 to 975 kg / m 3 , yet, however, more preferably, in the range of 955 to 968 kg / m 3 .
    [00102] The second polyethylene (PE2) - if present, differs preferably from the (first) polyethylene (PE), by the fluidity index. Therefore, it is preferable that the second polyethylene (PE2), has a lower melt index MFR2 (190 ° C) than the (first) polyethylene (PE). More preferably, the second polyethylene (PE2), has an MFR2 flow rate (190 ° C) in the range of 0.5 to 30 g / 10min, more preferably in the range of 0.5 to less than 15 g / 10min, still more preferably in the range of 0.5 to 10 g / 10min.
    [00103] Preferably, the second polyethylene (PE2), is a low density polyethylene (900 less than 940 kg / m 3 , that is, 910 less than 940 kg / m 3 ) or a linear low density polyethylene (LLDPE) (820 for below 900 kg / m 3 ), the latter preferred.
    The second polyethylene (PE2) is a homopolymer of ethylene or a copolymer of ethylene, the latter being preferred. Therefore, the ethylene content in low density polyethylene (LDPE) is at least 80% by weight, more preferably at least 90% by weight.
    [00105] The term homopolymer of ethylene used in the present invention refers to a polyethylene that consists substantially, that is, of more than 99.7% by weight, even more preferably of at least 99.8% by weight, of ethylene units. In one embodiment
    Petition 870190131906, of 11/12/2019, p. 46/69
    Preferred, only the ethylene units in the ethylene homopolymer are detectable.
    [00106] In the case of the second polyethylene (PE2), that is, the linear low density polyethylene (LLDPE), it is a copolymer of ethylene it is preferred that it contains, as units of mostly ethylene derivatives. Therefore, it is understood that the second polyethylene (PE2), i.e., linear low density polyethylene (LLDPE), being an ethylene copolymer comprises at least 55% by weight of derivable ethylene units, more preferably, at least, 60% by weight of ethylene-derived units. Thus, the second polyethylene (PE2), i.e., linear low density polyethylene (LLDPE), is considered to be an ethylene copolymer comprising 60 to 99.5% by weight, more preferably 90 to 99% by weight of units derivable from ethylene. The comonomers present in such a second polyethylene (PE2), that is, linear low density polyethylene (LLDPE), are C4 to C20 α-olefins, such as 1-butene, 1-hexene and 1-octene, the latter being especially preferred, or dienes, preferably α, unconjugated ωalcadienes, that is, C5 to C20 α, ω-alkadienes, such as 1,7-octadiene. Thus, in a specific embodiment of the second polyethylene (PE2), that is, the linear low density polyethylene (LLDPE), being an ethylene copolymer is an ethylene-1,7octadiene polymer with the amounts indicated in this paragraph.
    [00107] As mentioned above, the (first) polyethylene (PE) and optionally the second polyethylene (PE2) are preferably also dispersed in the matrix, or
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    35/51 is, in the polypropylene (PP), the heterophasic propylene copolymer (HECO) and thus forming the total polyolefin composition.
    Inorganic filler [00108] In addition to the polymer components the polyolefin composition may contain an inorganic filler (F), in amounts up to 30% by weight, preferably in the range of 1 to 30% by weight, even more preferably in the range of 3 to 9% by weight. Preferably, the inorganic filler (F) is a phyllosilicate, mica or wollastonite. Even more preferred to the inorganic filler (F) is selected from the group consisting of mica, wollastonite, kaolinite, smectite, montmorillonite and talc. The most preferred inorganic filler (F) is talc.
    [00109] The mineral filler (F) preferably has a cutting particle size d95 [weight percent] of 20 pm or less, more preferably in the range of 2.5 to 10pm, as in the range of 2 , 5 to 8.0 pm.
    [00110] Typically, inorganic filler (F) has a surface area measured according to the BET method, commonly known, with N2 gas, such as adsorption analysis of less than 22 m 2 / g, more preferably less than 20 m 2 / g, even more preferably less than 18 m 2 / g. Inorganic fillers (F) that meet these requirements are mineral fillers preferably anisotropic (F), such as talc, mica and volastonite.
    Other components [00111] As mentioned above, a second heterophasic propylene copolymer (HECO2) may be present in the
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    36/51 polyolefin composition (PO) for fine adjustment of properties. It is preferable that the second heterophasic propylene copolymer (HECO2) is present in small amounts, that is, not more than 10% by weight. Said second heterophasic propylene copolymer (HECO2) differs from the first heterophasic propylene copolymer (HECO) especially in the fluidity index. Therefore, the second heterophasic propylene copolymer (HECO2) - if present - has an MFR2 melt index (230 ° C) of less than 20 g / 10min, more preferably in the range of 1 to 15 g / 10min, even more preferably in the range of 3 to 10 g / 10min.
    [00112] Regarding the definition of a heterophasic reference system, the information provided above is made. In this way also the second heterophasic propylene copolymer (HECO2) comprises a polypropylene matrix, in which an elastomeric propylene copolymer (E2) is dispersed.
    [00113] The matrix of the second heterophasic propylene copolymer (HECO2) is a second random propylene copolymer (R-PP2). This second random propylene copolymer (R-PP2) 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 C10 α-olefins, for example example, 1-butene and / or 1-hexene. Preferably, the second random propylene copolymer (R-PP2) comprises, in particular, consists of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More
    Petition 870190131906, of 11/12/2019, p. 49/69
    37/51 specifically, the second random propylene copolymer (R-PP2) comprises - in addition to propylene - units derivable from ethylene and / or 1-butene. In a preferred embodiment, the second random propylene copolymer (R-PP2) comprises derivable ethylene and propylene units only. The comonomer content in the second random propylene copolymer (R-PP2) is preferably in the range of more than 0.5 to 10.0% by weight, even more preferably in the range of more than 0.5 to 7.0 % by weight.
    [00114] The second random propylene copolymer (R-PP2) preferably has an MFR2 melt index (230 ° C) of 1 to 20 g / 10min, preferably in the range of 3 to 15 g / 10min, more preferably in the range of 5 to 10 g / 10min.
    [00115] An additional component of the second heterophasic propylene copolymer (HECO2) is the second elastomeric propylene copolymer (E2).
    [00116] The second elastomeric propylene copolymer (E2) preferably 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 C10 α- olefins, for example, 1-butene and / or 1-hexene. Preferably, the second elastomeric propylene copolymer (E2) comprises, in particular, consisting of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the second elastomeric propylene copolymer (E2) comprises - in addition to propylene - units derivable from ethylene and / or 1-butene. So, in a
    Petition 870190131906, of 11/12/2019, p. 50/69
    38/51 especially preferred embodiment the second phase of elastomeric propylene copolymer (E2) comprises units derivable from ethylene and propylene only.
    [00117] The comonomer content, preferably the ethylene content, in the elastomeric propylene copolymer (E) phase should preferably also be within a specific range. Therefore, in a preferred embodiment, the comonomer content, more preferably the ethylene content, of the propylene elastomeric copolymer (E) of the propylene copolymer
    heterophasic (HECO), is equal or less than 45% in Weight, more preferably at banner in 5 to 40% by weight, still more preferably at banner in 12 to 35% by weight, still more preferably at banner in 18 to 30% by weight . Per
    It is therefore understood that the propylene content of the elastomeric propylene copolymer (E) of the second heterophasic propylene copolymer (HECO2) is equal to or greater than 15% by weight, more preferably in the range of 20 to 85% by weight, still more preferably in the range of 30 to 80% by weight, even more preferably in the range of 50 to equal to or less than 75% by weight.
    [00118] It is especially preferred that the second random propylene copolymer (R-PP2) and the second elastomeric propylene copolymer (E2) contain the same comonomers, such as ethylene.
    [00119] The cold xylene-soluble fraction (XCS) of the second heterophasic propylene copolymer (HECO2) is preferably in the range of 15 to 50% by weight
    Petition 870190131906, of 11/12/2019, p. 51/69
    39/51 preferably in the range of 18 to 40% by weight, even more preferably in the range of 20 to 3% by weight. These values are based on the second heterophasic propylene copolymer (HECO2) and not on the polyolefin composition (PO).
    [00120] Finally, the polyolefin composition (PO) can include 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 well as not more than 3.5% by weight, within the composition.
    Articles made from the polyolefin (PO) composition [00121] The polyolefin (PO) composition of the present invention is preferably used for the production of automotive articles, such as injection molded automobile articles, preferably automotive articles molded. Even more preferred is the use for the production of automobile interiors and exteriors, such as bumpers, side moldings, step aids, body panels, spoilers, panels, interior finishes and the like.
    [00122] 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.
    Petition 870190131906, of 11/12/2019, p. 52/69
    40/51 of the inventive polyolefin composition (PO). Thus, the present invention is especially directed to automotive articles, especially for automotive interiors and exteriors, such as bumpers, side moldings, step assistants, 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 consisting of the inventive polyolefin (PO) composition.
    [00123] The present invention will now be described in more detail by the examples presented below.
    EXAMPLES
    1. Definitions / Methods of measurement [00124] 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.
    NMR spectroscopy measurements:
    [00125] The 13 C-NMR spectra of polypropylenes were recorded on a Bruker 400 MHz spectrometer at 130 ° C from samples dissolved in 1,2,4-trichlorobenzene / benzene-d6 (90/10 w / w). For the analysis of the triad, the assignment is made according to the methods described in the literature: (T. Hayashi, Y. Inoue, R. Chujo, and T. Asakura, Polímero 29 138-43 (1988) and Chujo R, et al ., polymer 35 339 (1994).
    [00126] NMR measurement was used to determine the mmmm pentade concentration and mm triad concentration of
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    41/51 a form well known in the art.
    Melting temperature (Tm) and melting heat (Hf), crystallization temperature (Tc) and crystallization heat (Hc):
    [00127] Measured with Mettler TA820 differential scanning calorimetry (DSC) 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 from +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.
    Density [00128] It is measured according to ISO 1183-1 method A (2004). Sample preparation is done by
    molding by compression in wake up with the ISO 1872 standard 2: 2007.MFR2 (230 ° Ç) [00129] IS measured in wake up with the ISO 1133 (230 ° C, 2.16 charge kg) • MFR2 (190 ° Ç) [00130] IS measured in wake up with the ISO 1133 (190 ° C,
    2.16 kg load).
    Average numerical molecular weight (M n ), average molecular weight (Mw) and molecular weight distribution (MWD) [00131] They are determined by gel permeation chromatography (GPC), according to the following method: O
    Petition 870190131906, of 11/12/2019, p. 54/69
    42/51 average molecular weight Mw and the molecular weight distribution (MWD = Mw / Mn where Mn is the average numerical molecular weight and Mw is the average molecular weight) is measured by a method based on ISO 16014-1 : 2003 and ISO 16014-4: 2003. A Waters Alliance GPCV 2000 instrument, equipped with a refractive index detector and in-line viscometer was used with 3 x TosoHaas TSK-gel (GMHXLHT) columns and 1,2,4-trichlorobenzene (TCB, stabilized at 200 mg / l 2,6-di tert-butyl-4-methyl-phenol) as a solvent at 145 ° C and at a constant flow rate of 1 ml / min. 216.5 pl of sample solution was injected by analysis. The column assembly was calibrated using relative calibration with 19 MWD narrow polystyrene (PS) standards in the range of 0.5 kg / mol to 11500 kg / mol and a set of well characterized wide polypropylene standards. All samples were prepared by dissolving 5 to 10 mg of polymer in 10 ml (at 160 ° C) of stabilized TCB (the same as a mobile phase) and maintaining for 3 hours with continuous agitation before sampling from inside the GPC instrument. .
    Quantification of the comonomer content by FTIR spectroscopy:
    [00132] The comonomer content is determined by quantitative Fourier transform infrared spectroscopy (FTIR) after the basic assignment calibrated using quantitative 13 C nuclear magnetic resonance (NMR) in a manner well known in the art. Thin films are pressed to a thickness of between 100 to 500 pm and spectra recorded in transmission mode. Specifically, the ethylene content of a
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    43/51 polypropylene-co-ethylene copolymer is determined using the corrected baseline of the peak area of the quantitative bands found at 720-722 and 730-733 cm -1 . Quantitative results were obtained based on the reference for the film thickness.
    Soluble in cold xylene (XCS,% by weight):
    [00133] Content soluble in cold xylene (XCS) is determined at 25 ° C according to ISO 16152; first edition; 2005-07-01
    Intrinsic viscosity [00134] It is measured according to DIN ISO 1628/1, October 1999 (in decal at 135 ° C).
    Modulus of elasticity; Breaking stress [00135] They are measured according to ISO 527-2 (crosshead speed = 1 mm / min, 23 ° C) using injected samples as described in EN ISO 1873-2 (dog bone shape, 4 mm ).
    Charpy impact test:
    [00136] Resistance to notched Charpy impact (Charpy NIS) is measured according to ISO 179 2C / DIN 53453 at 23 ° C, -20 ° C, using injected bar specimens of 80x10x4 mm 3 mm 3 prepared from according to ISO 294-1: 1996.
    Coefficient of linear thermal expansion:
    [00137] The linear thermal expansion coefficient (CLTE) was determined according to the ISO 113592: 1999 standard in cut pieces 10 mm in length from the same injected specimens as used for determining the modulus of elasticity. The measurement was
    Petition 870190131906, of 11/12/2019, p. 56/69
    44/51 carried out in a temperature range of -30 to + 80 ° C at a heating rate of 1 ° C / min.
    Contraction:
    [00138] Contraction is determined with injection-molded circular discs, closed center (diameter 180 mm, three mm thick, with a flow angle of 355 ° and a cut of 5 °). Two specimens are molded by applying different holding pressure twice (10s and 20s, respectively). The melting temperature at the gate is 260 ° C, and the average flow speed in front of the mold is 100mm / s. Tool temperature: 40 ° C, return pressure: 600 bar (60000 kPa).
    [00139] After the samples are stored at room temperature for 96 hours, the radial and tangential dimensional changes to the flow direction are measured on both discs. The average of the respective values of both disks are reported as the final results.
    [00140] To determine the scratch resistance a model of Cross Hatch cutter 420P, manufactured by Erichsen, was used. For the tests, the 70x70x4 mm size plates were cut from a molded ground plate (grain parameters: average grain size = 1 mm, grain depth = 0.12 mm, taper = 6 °, also known as Grain VW K09) size 140x200x3 mm. The period between sample injection molding and risk testing was 7 days.
    [00141] To test the samples they must be fixed in a suitable device, as described above. The risks
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    45/51 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.
    [00142] A minimum of 20 scratches parallel to each other were created with a load of 10 N, with a distance of 2 mm. The application of the scratches was repeated perpendicular to each other, so that the result was a scratched canvas. The direction of the scratches must be unidirectional. Scratch resistance is assessed as the difference between the AL luminance of the non-scratched areas from the scratched areas. AL values were measured using a spectrophotometer that meets the requirements for DIN 5033. Light source for quantification of AL D65 / 10 °. Measured AL values must be below a maximum of 1.5.
    [00143] A detailed description of the test the test method (Erichsen's cross hatch cutter method) can be found in the article Assessment of scratch resistance in multiphase PP mixtures by Thomas Koch and
    Doris Machl, published in POLYMER OF TEST 26 (2007), P. 927-936.Brightness[00144] It was measured on samples molded granules by injection sprinkles in according to DIN 67530 standard one
    60 ° angle. The grain for measurements of gloss was identical to the grain used in the assessment of scratch resistance.
    D95 cutting particle size (sedimentation)
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    46/51 [00145] It is calculated from the particle size distribution [mass percent] as determined by gravitational sedimentation of liquid according to ISO 13317-3 (Sedigraph)
    Specific surface area [00146] It is determined as the BET surface according to DIN 66131/2.
    2. Examples [00147] The two experimental HECO heterophasic propylene copolymers were produced in a Borstar pilot plant with a prepolymerization reactor, a closed loop suspension reactor and three gas phase reactors. The Catalyst Polytrack 8502, commercially available from Grace (USA) was used in combination with diethylaminotriethoxysilane [Si (OCH 2 CH3) 3 (N (CH 2 CH3) 2 )] as external donor and triethyl aluminum (TEAL) as activator and eliminator in the proportions indicated in table 1. The catalyst was modified by polymerization of a vinyl compound, in the presence of the catalyst system.
    Table 1: Preparation of heterophasic propylene copolymers (HECO)
    Parameter unity HECO Prepolymerization temperature (° C) 30 pressure (kPa) 5200 Al / donor ratio (mol / mol) 10 residence time (H) 0.5 circuit
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    47/51
    temperature (° C) 70 pressure (kPa) 5500 residence time (H) 0.5 ethylene feed (kg / h) 0 H2 / C3 ratio (mol / kmol) 20 GPR1 temperature (° C) 80 pressure (kPa) 1600 residence time (H) 1.7 ethylene feed (kg / h) 0.2 H2 / C3 ratio (mol / kmol) 130 GPR2 temperature (° C) 80 pressure (kPa) 2700 residence time (H) 2.3 ethylene feed (kg / h) 32.2 H2 / C3 ratio (mol / kmol) 21 C3 / C3 ratio (mol / kmol) 300 GPR3 temperature (° C) 85 pressure (kPa) 2600 residence time (H) 1.2 ethylene feed (kg / h) 17 H2 / C3 ratio (mol / kmol) 70 C3 / C3 ratio (mol / kmol) 300
    Table 2: Heterophasic polypropylenes (HECO)
    HECO HECO 2 Matrix MFR (g / 10 min) 250 8 Matrix XCS (% by weight) 2.5 -
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    48/51
    Matrix C2 (% by weight) 0 - MFR (g / 10 min) 35 7 XCS (% by weight) 31.0 23 Total C2 (% by weight) 11.0 8 C2 in XCS (% by weight) 33 25 XCS IV (dL / g) 2.4 1.2
    [00148] HECO 2 commercial heterophasic propylene copolymer product SD 233 CF from Borealis AG
    Table 3: Comparative examples
    Example*CE1 CE2 CE3 CE4 CE5 CE6 HECO (% inWeight) 97.5 91.5 81.5 90 75.5 86.5 Baby powder (% inWeight) - - - 7.0 7.0 - PE-A (% inWeight) -- - 14.5 - PE-B (% inWeight) -- - - 11 PE-C (% inWeight) - 6 16 - - - PE2 (% inWeight) - - - - - - HECO2 (% inWeight) - - - - -MRF (g / 10min) 35.1 35.5 35.3 36.2 32.0 31.1 Module ofelasticity (MPA) 1197 1081 1001 1481 1061 1083 Voltage to (%) 17 15 34.2 14 114 22.1
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    49/51
    break Impact resistance + 23 ° C (kJ / m 2 ) 13 19 13 11 10 14 Impact resistance 20 ° C (kJ / m 2 ) 5.4 6.9 5.7 2.8 3.7 6.7 Radial SH (%) 1.8 1.8 1.5 1.5 1.1 1.7 CLTE-30/80 (pm / mK) 110 110 111 97 89 113 Scratch resistance 10N AL 1.8 - - 4.8 3.6 - Brightness (60 °) (%) 2.7 - - 2.3 2.3 -
    [00149] Remaining to 100% by weight are additives such as antioxidants and pigments (eg carbon black) [00150] Talc is the commercial Jetfine 3CA talc from Luzenac having a cut-off D95 particle size of 3.3 pm ( sedigraph), as well as a specific surface area of 14.5 m 2 / g, [00151] PE-A is the commercial product Engage 8400 from Dow Elastomers having an MFR2 (190 ° C / 2.16 kg) of 30 g / 10min and a density of 870 kg / m3, [00152] pe-B is the commercial product of high density polyethylene MG 9601 from Borealis AG with an MFR2 (190 ° C / 2.16 kg) of 31 g / 10min and a density of 960 kg / m 3 , [00153] pe-C is the commercial product of linear low density polyethylene Superpass Ifs932-R from Nova Chemicals having an MFR2 (190 ° C / 2.16 kg) of 150 g / 10min and a density of 932 kg / m 3 ,
    Petition 870190131906, of 11/12/2019, p. 62/69
    50/51 [00154] PE2 is the commercial product Engage 8100 from Dow Elastomers with an MFR2 (190 ° C / 2.16 kg) of 1 g / 10 min and a density of 870 kg / m 3 ,
    Table 4: Inventive examples
    Example*E1 E2 E3 E4 HECO (% by weight) 81.5 75.5 69.0 62.5 Baby powder (% inWeight) - 7.0 7.0 7 PE-A (% inWeight) - - - - PE-B (% inWeight) 16.0 14.5 14.0 15.5 PE2 (% inWeight) - - - 5.0 HECO 2 (% inWeight) - - 7.0 7.0 MFR (g / 10min) 31.6 29.9 24.7 22.3 Module ofelasticity (Mpa) 1076 1327 1311 1219 Voltage tobreak (%) 22 19 37 159 Impact resistance + 23 ° C (kJ / m 2 ) 14 10 45 54 Impact resistance 20 ° C (kJ / m 2 ) 6.0 2.3 3.7 6.4
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    51/51
    Radial SH (%) 1.5 1.3 1.3 1.1 CLTE-30/80 (pm / mK) 96 84 83 89 Scratch resistance 10N AL2.1 2.3 2.8 Brightness (60 °) (%)3.2 3.3 3.4
    [00155] Remaining at 100% by weight are additives, such as antioxidants and pigments (carbon black).
    权利要求:
    Claims (14)
    [1]
    1. Polyolefin (PO) composition characterized by comprising (a) a heterophasic propylene copolymer (HECO) comprising (a1) a polypropylene (PP) with an MFR2 (230 ° C) fluidity index of 30 to 350 g / 10min, measured with ISO 1133, and (a2) an elastomeric propylene copolymer (E) with an intrinsic viscosity (IV) in the range of 1.5 to 3.0 dL / g measured as the intrinsic viscosity (IV) of the soluble fraction in cold xylene (XCS) of the heterophasic propylene copolymer (HECO), measured according to DIN ISO 1628/1, and
    (b) a polyethylene (PE) with an index of fluidity MFR2 (190 ° C) from 20 to 80 g / 10min on what (i) the composition total in polyolefin (PO) has a fluidity index MFR2 1230 ° C) in more than 15 to 200 g / 10min, and (ii) the reason for Weight in copolymer propylene
    elastomeric (E) for polyethylene (PE) is less than 2.0.
    [2]
    2. Polyolefin composition (PO), according to
    claim 1, characterized by the fact what (a) the amount of copolymer in propylene elastomeric (AND) inside of copolymer in propylene heterophasic (HECO) it's 20 to 50% by weight, and / or
    (b) the elastomeric propylene copolymer (E) has a comonomer content of 15 to 75% by weight, the comonomers are ethylene and / or a C4 to C12 α-olefin.
    Petition 870190131906, of 11/12/2019, p. 65/69
    2/4
    [3]
    3. Polyolefin (PO) composition according to claim 1 or 2, characterized by the fact that polypropylene (PP) has (a) a melting temperature of at least 135 ° C, and / or (b) a comonomer content equal to or less than 10% by weight, the comonomers are ethylene and / or a C4 to C12 αolefin.
    [4]
    Polyolefin (PO) composition according to any one of claims 1 to 3, characterized by the fact that polypropylene (PP) is a propylene homopolymer (H-PP).
    [5]
    5. Polyolefin (PO) composition according to any one of claims 1 to 4, characterized by the fact that the heterophasic propylene copolymer (HECO) has
    (a) an MFR2 fluidity index (230 ° C) too much from 15 to 300 g / 10min, and / or (b) a content of comonomer in banner in 6.0 a 18% in weight, comonomers are ethylene and / or an C4 a C12 α-
    olefin.
    [6]
    6. Polyolefin (PO) composition according to any one of claims 1 to 5, characterized in that the polyethylene (PE) (a) has a density of at least 945 kg / m 3 , and / or (b ) polyethylene (PE) is an ethylene homopolymer.
    [7]
    7. Polyolefin composition (PO), according to
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    3/4 any one of claims 1 to 6, characterized in that the polyolefin (PO) composition comprises up to 30% by weight of an inorganic filler.
    [8]
    8. Polyolefin (PO) composition according to claim 7, characterized by the fact that the inorganic filler has a cut-off particle size d95 [mass percentage] of 20 pm or less.
    [9]
    Polyolefin composition (PO) according to any one of claims 1 to 8, characterized in that the polyolefin composition (PO) comprises up to 30% by weight of a polyethylene (PE2) having (a) a density less than 940 kg / m 3 , and / or (b) an MFR2 fluidity index (190 ° C) of 0.5 to 30 g / 10 min, with the proviso that polyethylene (PE2) differs from polyethylene (PE ) in density and / or fluidity index.
    [10]
    10. Polyolefin composition (PO) according to any one of claims 1 to 9, characterized in that the polyolefin composition (PO) has (a) modulus of elasticity of at least 900 MPa, and / or (b ) resistance to impact at 23 ° C of at least 10 kJ / m 2 , and / or (c) a linear thermal expansion coefficient (CLTE) performed in a temperature range of -30 to + 80 ° C of no more than than 100 pm / mK.
    [11]
    11. Automotive article characterized by understanding
    Petition 870190131906, of 11/12/2019, p. 67/69
    4/4 a polyolefin (PO) composition as defined in any one of claims 1 to 10.
    [12]
    12. Automotive article, according to claim
    11, characterized by the fact that the article is an exterior automotive article.
    [13]
    13. Process for the preparation of the polyolefin (PO) composition, as defined in any one of claims 1 to 10, characterized in that it is by means of extrusion of the heterophasic propylene copolymer (HECO), polyethylene (PE), and optionally the inorganic filler (F) and polyethylene (PE2), in an extruder.
    [14]
    14. Process according to claim 13, characterized by the fact that the heterophasic propylene copolymer (HECO) is obtained through the production of polypropylene (PP) in a reactor, transferring said polypropylene (PP) in a subsequent reactor, where in the presence of polypropylene (PP), the elastomeric propylene copolymer (E) is produced.
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-01-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-03-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/07/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11174132|2011-07-15|
    EP11174132.8|2011-07-15|
    PCT/EP2012/063595|WO2013010879A1|2011-07-15|2012-07-11|High flow polyolefin composition with low shrinkage and clte|
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