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    • 专利摘要:
    PROPYLENE COPOLYMER FOR FILMS OR ARTICLES MOLDED BY INJECTION Propylene copolymer having a fluidity index MFR2 (230 ° C) in the range of 2.5 to 12.0 g / 10min, a soluble content in cold xylene (XCS) in the range from 20.0 to 45.0% by weight, a co-monomer content in the range of 7.5 to 12.0% by weight, in the co-monomer content of the cold xylene soluble fraction (XCS) of the propylene copolymer is in the range of 16.0 to 28.0% by weight.
    公开号:BR112014014803B1
    申请号:R112014014803-1
    申请日:2012-12-18
    公开日:2020-12-08
    发明作者:Martina Sandholzer；Klaus Bernreitner；Katja Klimke；Markus Gahleitner
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    [001] The present invention is directed to a new soft propylene copolymer as well as articles made from it.
    [002] Polymers are increasingly used in different demanding applications. At the same time, there is a continuous search for bespoke polymers that meet the requirements of these applications. The demands can be challenging, since many properties of the polymers are directly or indirectly interconnected. For example, heterophasic systems are known for their good impact behavior. Such heterophasic propylene copolymers comprise a matrix being either a propylene homopolymer or a random propylene copolymer, in which an elastomeric copolymer is dispersed. Thus, the polypropylene matrix contains inclusions (finely) dispersed that are not part of the matrix and said inclusions contain the elastomeric copolymer. The term inclusion indicates that the matrix and the inclusion form different phases within the heterophasic propylene copolymer, said inclusions are visible, for example, through high-resolution microscopy, such as electron microscopy or force-scanning microscopy.
    [003] A specific soft heterophasic propylene copolymer is described in WO 2008/141934 A1. This heterophasic propylene copolymer has a relatively low melting temperature, which is detrimental in view of sterilization.
    [004] However, in the field of packaging soft materials with good optical properties are needed, which remain at a high level after sterilization.
    [005] It is therefore the object of the present invention to provide a soft heterophasic propylene copolymer with good optical properties, in particular, after sterilization. In addition, the heterophasic propylene copolymer must show temperature resistance and good fluidity.
    [006] The disclosure of the present invention is to provide a heterophasic propylene copolymer with a high co-monomer content and the content of soluble in cold xylene (XCS), in which the fraction of soluble in cold xylene is characterized by a high content of propylene. Especially good results are obtained in case the intrinsic viscosity of the soluble in cold xylene (XCS) is quite high.
    [007] Therefore, the present invention is directed to a propylene copolymer having (a) an MFR2 melt index (230 ° C) measured according to ISO 1133 in the range of more than 2.5 to 12.0 g / 10min, (b) a co-monomer content in the range of more than 7.5 to 12.0% by weight, and (c) a content of soluble in cold xylene (XCS) determined in accordance with ISO 16152 (25 ° C) in the range of 20.0 to 45.0% by weight, in which the co-monomer content of the fraction of soluble in cold xylene (XCS) of the propylene copolymer is in the range of 16.0 to 28.0 % by weight.
    [008] Preferably, the cold xylene soluble fraction (XCS) of the propylene copolymer has a co-monomer content in the range of 1.5 to 6.0% by weight and / or the intrinsic viscosity (IV) of the cold xylene-soluble fraction (XCS) of the propylene copolymer is at least 1.8 dl / g, more preferably in the range of 1.8 or more and less than 3.0 dl / g.
    [009] It has been surprisingly revealed that such a propylene copolymer has a low flexural modulus, high impact resistance and good optical properties before and after sterilization.
    [010] Next, the invention is defined in more detail.
    [011] The propylene copolymer comprises, in addition to propylene, also co-monomers. Preferably, the propylene copolymer comprises, in addition to propylene, ethylene and / or C4 to C12 α-olefins. Accordingly, the term "propylene copolymer" according to that invention is understood to mean a polypropylene preferably comprising units derived from (d) propylene and (e) ethylene and / or C4 to C12 α-olefins.
    [012] Thus, the propylene copolymer according to this invention comprises monomers copolymerizable with propylene, for example, co-monomers such as ethylene and / or C4 to C12 α-olefins, in particular ethylene and / or C4 to C8 α - olefins, for example, 1-butene and / or 1-hexene.
    [013] Preferably, the propylene copolymer according to this invention comprises, especially consists of, copolymerizable monomers with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the propylene copolymer of this invention comprises - in addition to propylene - derivable units of ethylene and / or 1-butene. In a preferred embodiment, the propylene copolymer according to this invention comprises derivable units of ethylene and propylene only.
    [014] Furthermore, it is understood that the propylene copolymer preferably has a very high total co-monomer content, which contributes to the softness of the material. Thus, the co-monomer content of the propylene copolymer is required to be at least 7.5% by weight, preferably in the range of 7.5 to 12.0% by weight, more preferably in the range equal to or above 8.0 to 11.0% by weight, as above 8.0 to 11.0% by weight, even more preferably in the range of 8.2 to 10.5% by weight.
    [015] The propylene copolymer of the present invention can be further defined by the amount of co-monomers within the fraction of soluble in cold xylene (XCS). It is therefore preferred that the co-monomer content of the cold xylene-soluble fraction (XCS) of the propylene copolymer is quite moderate. Thus, it is preferred that the co-monomer content of the cold xylene soluble fraction (XCS) of the propylene copolymer is in the range of 16.0 to 28.0% by weight, even more preferably in the range of 18.0 to 26.0% by weight, even more preferably in the range of 19.0 to 25.0% by weight, even more preferably in the range of 20.0 to 24.0% by weight.
    [016] As for the comonomers present in the fraction soluble in cold xylene (XCS), they refer to the information provided for the propylene copolymer. Consequently, in a specific embodiment, the fraction of soluble in cold xylene (XCS) comprises, in particular, it consists of the copolymerizable monomers with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the fraction of soluble in cold xylene (XCS) comprises - in addition to propylene - derivable units of ethylene and / or 1-butene. In a preferred embodiment, the fraction of soluble in cold xylene (XCS) comprises derivable units of ethylene and propylene only.
    [017] Considering the information provided above, it is preferred that the propylene copolymer satisfies the inequality (I), more preferably the inequality (Ia), even more preferably the inequality (Ib), even more preferably the inequality (Ic ),
    where Co (total) is the co-monomer content [% by weight] of the propylene copolymer Co (XCS) is the co-monomer content [% by weight] of the cold xylene soluble (XCS) copolymer fraction propylene.
    [018] In another preferred embodiment, the propylene copolymer is additionally or alternatively defined by the total co-monomer content in relation to its fraction of soluble in cold xylene (XCS). It is therefore preferable that the propylene copolymer satisfies inequality (II), more preferably inequality (IIa), even more preferably inequality (IIb),
    where Co (total) is the co-monomer content [% by weight] of the propylene copolymer Co (XCS) is the co-monomer content [% by weight] of the propylene copolymer fraction.
    [019] Furthermore, it is understood that the fraction of soluble in cold xylene (XCS) of the propylene copolymer is specified by its intrinsic viscosity. A low intrinsic viscosity (IV) value reflects a low average molecular weight. For the present invention it is preferably required that the fraction of soluble in cold xylene (XCS) of propylene copolymer has an intrinsic viscosity (IV) measured according to ISO 1628/1 (at 135 ° C in decalin) of equal or greater at 1.8 dl / g, more preferably in the range of 1.8 to below 3.0 dl / g, even more preferably in the range of 1.8 to 2.7 dl / g, such as in the range of 1, 9 to 2.6 dl / g.
    [020] Furthermore, it is understood that the propylene copolymer has a fraction of soluble in cold xylene in the range of 20 to 45% by weight, more preferably in the range of 23 to 40% by weight, even more preferably in the range of 25 to 39% by weight. The remainder of the propylene copolymer being non-soluble in cold xylene is the cold insoluble fraction (XCI) which is also defined below.
    [021] It is therefore preferred that the co-monomer content in the cold insoluble fraction (XCI) of the propylene copolymer is in the range of 1.5 to 6.0% by weight, even more preferably in the range of 2, 0 to 5.5% by weight, even more preferably in the range of 2.5 to 5.5% by weight, even more preferably in the range of 3.0 to 5.0% by weight.
    [022] In a preferred embodiment, the molecular weight distribution (MWD) of the cold insoluble fraction (XCI) of the propylene copolymer is in the range of 3.0 to 6.0, more preferably in the range of 3.5 to 5.7, as in the range of 3.7 to 5.5.
    [023] Furthermore, it is understood that the fraction of insoluble in cold xylene (XCI) of propylene copolymer has an intrinsic viscosity (IV) measured according to ISO 1628/1 (at 135 ° C in decaline) of equal or greater than 1.8 dl / g, more preferably in the range of 1.8 to below 3.0 dl / g, even more preferably in the range of 1.8 to 2.7 dl / g, even more preferably in the range of 1.9 to 2.6 dl / g, as in the range of 2.0 to 2.5 dl / g.
    [024] Also the properties between the fraction of soluble in cold xylene (XCS) and the fraction of insoluble in cold xylene (XCI) must be balanced.
    [025] Therefore, it is preferred that the intrinsic viscosity in the fraction of soluble in cold xylene (XCS) and in the fraction of insoluble in cold xylene (XCI) are quite similar. Thus, it is preferred that the propylene copolymer meets the inequality (III), more preferably the inequality (IIIa), even more preferably the inequality
    where IV (XCS) is the intrinsic (IV) [dl / g] viscosity of the cold xylene soluble (XCS) of the propylene copolymer IV (XCI) is a is the intrinsic (IV) viscosity [dl / g] of the insoluble in cold xylene (XCI) of the propylene copolymer.
    [026] In addition, it is preferred that the co-monomer content in both fractions is in a specific proportion to each other. Therefore, it is preferred that the propylene copolymer fulfills inequality (IV), more preferably inequality (IVa), even more preferably inequality (IVb),
    Where Co (XCS) is the co-monomer [% by weight] of the cold xylene soluble (XCS) of the propylene copolymer, Co (XCI) is the co-monomer [% by weight] of the insoluble in cold xylene (XCI) of the propylene copolymer.
    [027] Preferably, it is desired that the propylene copolymer is mechanically stable term, so that, for example, a thermal sterilization process can be carried out. Thus, the propylene copolymer is considered to have a melting temperature of at least 145 ° C, more preferably in the range of 145 to 160 ° C, even more preferably in the range of 150 to 159 ° C, as in the range of 150 to 158 ° C.
    [028] The propylene copolymer according to this invention can have a melt index MFR2 (230 ° C) in the range of 2.5 to 12.0 g / 10 min, more preferably in the range of 2.5 to 8, 5 g / 10 min, more preferably in the 2.5 to 8.5 g / 10 min range, even more preferably in the 2.5 to 5.0 g / 10 min range. In the case that the propylene copolymer is used as a blown film material it preferably has a melt index MFR2 (230 ° C) in the range of 2.5 to 4.5 g / 10 min, more preferably in the range of 3.0 to 4 , 0 g / 10 min. In turn, in case the propylene copolymer is used to mold film, or injection molding, it is preferred that the flow rate MFR2 (230 ° C) is in the range of 3 to 12 g / 10 min, as in the range of 4 to 10 g / 10 min.
    [029] The present propylene copolymer is especially characterized by its specific optical and mechanical properties.
    [030] It is therefore preferred that the propylene copolymer has a flexural modulus measured according to ISO 178 of no more than 600 MPa, more preferably in the range of 200 to 600 MPa, more preferably in the range of 250 to 550 MPa, more preferably in the range of 350 to 540 MPa.
    [031] In a preferred embodiment, the propylene copolymer performs well on impact. It is therefore preferred that the propylene copolymer has (a) an impact resistance determined in accordance with ISO 179 / leA at 23 ° C of at least 60.0 kJ / m2, more preferably in the range of 60.0 at 95.0 kJ / m2, even more preferably in the range of 62.0 to 90.0 kJ / m2, and / or (b) an impact resistance determined in accordance with ISO 179 / leA at -20 ° C at least minus 4.5 kJ / m2, more preferably in the range of 4.5 to 8.0 kJ / m2, even more preferably in the range of 4.6 to 7.5 kJ / m2.
    [032] Additionally and / or alternatively the propylene copolymer preferably has (a) turbidity before sterilization determined according to ASTM D 1003-07 (injection molded plates 60x60x1mm3) less than 50%, more preferably 20 at 50%, even more preferably from 25 to less than 50%, and / or (b) a turbidity after sterilization determined according to ASTM D 1003-07 (injection molded plates of 60x60x1mm3) to less than 65%, more preferably from 25 to less than 65%, still more preferably 35 to 63% and / or (c) a turbidity prior to sterilization, determined according to ASTM D1003-00 (50 μm molded film) to less than 15%, more preferably from 5 to less than 15%, even more preferably from 6 to 12%, and / or (d) a turbidity after sterilization determined in accordance with ASTM D 1003-00 (50 μm molded film) to less than 20% , more preferably 8 to 20%, even more preferably 10 to 16%.
    [033] As indicated above, the present propylene copolymer is characterized by a rather high amount of a fraction of soluble in cold xylene (XCS). On the other hand, the propylene copolymer is also preferably characterized by a rather high amount of a crystalline fraction that melts at a high temperature. Therefore, the present propylene copolymer is a mixture of a crystalline polymer and amorphous material. Such a type of polymer is classified as a heterophasic propylene copolymer. A heterophasic propylene copolymer comprises a polymer matrix, such as (semi) crystalline polypropylene, in which the amorphous material, such as an elastomeric propylene copolymer, is dispersed. Thus, in a preferred embodiment, the present propylene copolymer is a heterophasic propylene copolymer (RAHECO). More precisely, the present propylene copolymer is a heterophasic propylene copolymer (RAHECO) comprising a matrix (M) being a random propylene copolymer (R-PP) and an elastomeric propylene copolymer (E) dispersed therein. Thus, the matrix (M) contains inclusions (finely) dispersed that are not part of the matrix (M) and said inclusions contain the elastomeric propylene copolymer (E). The term "inclusion" according to this invention should preferably indicate that the matrix and the inclusion form different phases within the heterophasic propylene copolymer (RAHECO), said inclusions are, for example, visible by high resolution microscopy, such as electron microscopy or atomic force microscopy, or by dynamic mechanical thermal analysis (DMTA). Specifically in DMTA, the presence of a multi-phase structure can be identified by the presence of at least two different glass transition temperatures.
    [034] Preferably, the heterophasic propylene copolymer (RAHECO) according to this invention comprises as polymeric components only the random propylene copolymer (PP-R) and the elastomeric propylene copolymer (E). In other words, the heterophasic propylene copolymer (RAHECO) may contain other additives, but no other polymer in an amount that exceeds 5% by weight, more preferably that exceeds 3% by weight, as exceeding 1% by weight, based on the total heterophasic propylene copolymer (RAHECO). An additional polymer that can be present in such low amounts is a polyethylene which is a product of the sub-reaction obtained by preparing the heterophasic propylene copolymer (RAHECO) (see in detail below). Thus, it is considered, in particular, that the present heterophasic propylene copolymer (RAHECO) contains only the random propylene copolymer (PP-R), the elastomeric propylene copolymer (E) and optionally polyethylene in quantities as mentioned in that paragraph .
    [035] Preferably, the weight ratio between the matrix (M), that is, the random propylene copolymer (PP -R) and the elastomeric propylene copolymer (E) is 45/55 to 80/20, more preferably 50/50 to 75/25, even more preferably 52/48 to 70/30.
    [036] Next, the random propylene copolymer (PP-R) and the elastomeric propylene copolymer (E) are more precisely defined.
    [037] The random propylene copolymer (R-PP) comprises monomers copolymerizable with propylene, for example, co-monomers such as ethylene and / or C4 to C12 α-olefins, in particular ethylene and / or C4 to C8 α- olefins, for example, 1-butene and / or 1-hexene. Preferably, the random propylene copolymer (PP-R) according to this invention comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the random propylene copolymer (PP-R) of this invention comprises - in addition to propylene - units derivable from ethylene and / or 1-butene. In a preferred embodiment, the random propylene copolymer (R-PP) comprises units derivable from ethylene and propylene only.
    [038] The co-monomer content of the random propylene copolymer (PP-R) is preferably in the range of 1.0 to 9.0% by weight, even more preferably in the range of 1.5 to 8.0% by weight, even more preferably in the range of 1.5 to 7.5% by weight, as in the range of 2.0 to 7.0% by weight.
    [039] Furthermore, the propylene copolymer is considered to satisfy the inequality (V), more preferably the inequality (Va), even more preferably the inequality (Vb), even more preferably the inequality (Vc), even more preferably the inequality (Vd),
    where Co (total) is the co-monomer [% by weight] of the propylene copolymer, Co (RPP) is the co-monomer [% by weight] of the random propylene copolymer (R-PP).
    [040] The term "random" indicates that the co-monomers of the random propylene copolymer (R-PP), as well as the first fraction of propylene copolymer (R-PP1) and the second fraction of propylene copolymer (R- PP2) are randomly distributed within the propylene copolymers. The term random is understood according to IUPAC (Glossary of basic terms in polymer science; IUPAC recommendations 1996).
    [041] The co-monomer content of the matrix (M), that is, of the random propylene copolymer (R-PP), also has an impact on the amount of soluble in cold xylene in the matrix (M). Thus, it is preferred that the amount of the fraction of soluble in cold xylene (XCS) of the matrix (M), that is, of the random propylene copolymer (R-PP) is preferably in the range of 3.5 to 15.0 % by weight, even more preferably in the range of 4.0 to 12.0% by weight.
    [042] The random propylene copolymer (R-PP) preferably comprises at least two polymer fractions, such as two or three polymer fractions, all of which are propylene copolymers. Even more preferred, the random propylene copolymer (R-PP) preferably comprises a first fraction of propylene copolymer (R-PP1) and a second fraction of propylene copolymer (R-PP2). It is preferred that the first fraction of propylene copolymer (R-PP1) is the poor fraction of co-monomer while the second fraction of propylene copolymer (R-PP2) is the rich fraction of co-monomer.
    [043] Thus, it is preferred that the first fraction of random propylene copolymer (R-PP1) has a co-monomer content of 5.0% or less by weight, more preferably equal to or less than 4.0 by weight, even more preferably in the range of 0.5 to 5.0% by weight, even more preferably in the range of 0.5 to 4.0% by weight, as in the range of 1.0 to 3.5% in Weight.
    [044] As a co-monomer of the first fraction of random propylene copolymer (R-PP1) it is preferably quite low, also its soluble in cold xylene (XCS) are comparatively low. Thus, it is preferred that the amount of the fraction of soluble in cold xylene (XCS) of the first fraction of random propylene copolymer (R-PP1) is equal to or less than 12.0% by weight, more preferably it is in the range of 3, 0 to 12.0% by weight, even more preferably it is in the range of 4.0 to 11.0% by weight, even more preferably it is in the range of 5.0 to 10.0% by weight, as in the range of 4 , 5 to 9.0% by weight. The values of soluble in cold xylene (XCS) provided in that paragraph are especially applicable before viscorreduction as indicated in detail below.
    [045] On the other hand, the second fraction of random propylene copolymer (R-PP2) preferably has a co-monomer content of at least 0.5% by weight, more preferably in the range of 0.5 to 20, 0% by weight, even more preferably in the range of 1.0 to 19.0% by weight, even more preferably in the range of 1.5 to 18.0% by weight.
    [046] The co-monomers of the first fraction of random propylene copolymer (R-PP1) and a second fraction of random propylene copolymer (R-PP2), respectively, copolymerizable with propylene are ethylene and / or C4 to C12 α- olefins, in particular ethylene and / or C4 to C8 α-olefins, for example, 1-butene and / or 1-hexene. Preferably, the first fraction of random propylene copolymer (R-PP1) and a second fraction of random propylene copolymer (R-PP2), respectively, comprise, especially consist of, propylene copolymerizable monomers from the group consisting of ethylene , 1-butene and 1-hexene. More specifically, the first fraction of random propylene copolymer (R-PP1) and a second fraction of random propylene copolymer (R-PP2), respectively, comprise - in addition to propylene - units derivable from ethylene and / or 1- butene. In a preferred embodiment, the first fraction of random propylene copolymer (R-PP1) and a second fraction of random propylene copolymer (R-PP2), comprise the same co-monomers, that is, only ethylene.
    [047] Preferably, the weight ratio between the first fraction of random propylene copolymer (R-PP1) and the second fraction of random propylene copolymer (R-PP2) is from 20/80 to 80/20, more preferably from 30/70 to 70/30.
    [048] As mentioned above, an additional component of the heterophasic propylene copolymer (RAHECO) is the elastomeric propylene copolymer (E) dispersed in the matrix (M), that is, in the random propylene copolymer (R-PP). As for the co-monomers used in the elastomeric propylene copolymer (E), the information provided for the heterophasic propylene copolymer (RAHECO) and the random propylene copolymer (R-PP), respectively, is mentioned. Accordingly, the elastomeric propylene copolymer (E) comprises monomers copolymerizable with propylene, for example, co-monomers such as ethylene and / or C4 to C12 α-olefins, in particular ethylene and / or C4 to C8 α- olefins, for example, 1-butene and / or 1-hexene. Preferably, the elastomeric propylene copolymer (E) comprises, in particular, consists of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the elastomeric propylene copolymer (E) comprises - in addition to propylene - units derivable from ethylene and / or 1-butene. Thus, in an especially preferred embodiment the elastomeric propylene copolymer (E) comprises units derivable from ethylene and propylene only. It is especially preferred that the random propylene copolymer (PP-R) and the elastomeric propylene copolymer (E) comprise the same co-monomers. Consequently, in a specific embodiment the random propylene copolymer (R-PP) and the elastomeric propylene copolymer (E) comprise only propylene and ethylene.
    [049] The co-monomer content of the elastomeric propylene copolymer (E) is preferably not more than 30.0% by weight, more preferably not more than 25% by weight, even more preferably in the range 14.0 to 26.0% by weight, even more preferably in the range of 15.0 to 25.0% by weight.
    [050] The propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), as defined in the present invention, can contain up to 1.0% by weight of additives, such as nucleating agents and antioxidants, as well as slip and anti-blocking agents. Preferably, the amount of additives is less than 5.0% by weight, preferably less than 3.0% by weight, as less than 1.0% by weight.
    [051] The present invention is directed not only to the present propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), but also to the films made from it.
    [052] A distinction is made between non-oriented and oriented films (see, for example, Polypropylene handbook, Nello Pasquini, 2nd edition, Hanser). Oriented films are typically biaxially oriented films, while non-oriented films are molded or blown films. Thus, a non-oriented film is not stretched intensively in the machine and in a transversal direction as done by oriented films. Thus, the non-oriented film according to the present invention is not a biaxially oriented film. Preferably, the non-oriented film according to the present invention is a blown film or molded film, the latter being preferred.
    [053] Therefore, in another embodiment of the present invention it is directed to a film, preferably a non-oriented film comprising at least 70% by weight, preferably comprising at least 80% by weight, more preferably comprising at least minus 90% by weight, even more preferably it comprises at least 95% by weight, even more preferably, at least 99% by weight, of the present propylene copolymer, i.e. the heterophasic propylene copolymer (RAHECO). In a preferred embodiment, the film, preferably the non-oriented film, consists of the propylene copolymer, that is, it consists of the heterophasic propylene copolymer (RAHECO). Such a film can be a single layer film or it can be a layer, more preferably, a core layer of a multilayer film. Thus, the term "film" also encompasses a layer of a multilayer film. In the case where the present film is a layer of a multilayer film, it is preferred that the multilayer film preferably comprises three layers, wherein the film of the present invention is preferably the core layer.
    [054] Preferably, the film, that is, the non-oriented film, has a thickness of 5 to 2000 μm, preferably 10 to 1000 μm, more preferably 20 to 700 μm, such as 40 to 500 μm.
    [055] Typically, such as films, such as multilayer films, in particular, three-layer films, in which the present film is preferably the core layer of multilayer films, are used as pouches and / or bags. Thus, the present invention is also directed to pouches and bags made of the present film.
    [056] In another embodiment, the present invention is also directed to injection molded articles comprising at least 70% by weight, preferably comprising at least 80% by weight, more preferably comprising at least 90% by weight, more preferably comprising at least 95% by weight, even more preferably at least 99% by weight, of the present propylene copolymer, i.e., the heterophasic propylene copolymer (RAHECO). In a preferred embodiment, the injection molded articles consist of the propylene copolymer, that is, the heterophasic propylene copolymer compound (RAHECO). Typical items are caps, closures, (small) syringes, (small) bottles, such as powder and tablet bottles.
    [057] The present propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO) is preferably obtained through a specific process. Accordingly, the present propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO) is preferably obtained by a sequential polymerization process comprising the steps of (a) polymerization of a first reactor (R1), propylene and ethylene and / or C4 to C12 α-olefins, preferably ethylene, obtaining a first fraction of polymer, that is, a first fraction of random propylene copolymer (R-PPI), (b) transfer of the first polymer fraction, i.e. , the first fraction of random propylene copolymer (R-PP1), in a second reactor (R2), (c) polymerization in said second reactor (R2) in the presence of the first polymer fraction, that is, of the first copolymer fraction random propylene (R-PP1), propylene and ethylene and / or C4 to C12 α-olefins, preferably ethylene, obtaining a fraction of a second polymer, that is, a second fraction of random propylene copolymer (R-PP2), the first and second polymer fractions form a first mixture ura, that is, the random propylene copolymer (R-PP), (d) transferring said first mixture, the random propylene copolymer (R-PP), to a third reactor (R3), (e) said polymerization third reactor (R3) in the presence of the first mixture, that is, the random propylene copolymer (R-PP), propylene and ethylene and / or C4 to C12 α-olefins, preferably ethylene, obtaining a third polymer fraction, said third polymer fraction is preferably the first fraction of elastomeric propylene copolymer (E); the third polymer fraction and the first mixture, that is, the random propylene copolymer (R-PP) form a second mixture, (f) transferring said second mixture to the fourth reactor (R4), (g) said polymerization fourth reactor (R4) in the presence of the second mixture and propylene ethylene and / or C4 to C12 α-olefins, preferably ethylene, obtaining a fourth fraction of polymer, said fourth fraction of polymer is preferably the second fraction of copolymer of elastomeric propylene (E); the fourth polymer fraction and the second mixture form the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO); (h) removing the propylene copolymer from the fourth reactor (R4), (i) optionally reducing the viscosity of said propylene copolymer, that is, said heterophasic propylene copolymer (RAHECO).
    [058] Preferably, between the second reactor (R2), the third reactor (R3) and the fourth reactor (R4), the monomers are displayed.
    [059] The term "sequential polymerization process" indicates that the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), is produced in at least four reactors, preferably in four reactors connected in series. Thus, the present process comprises at least one first reactor (R1), a second reactor (R2), a third reactor (R3), and a fourth reactor (R4). The term "polymerization reactor" should indicate that the main polymerization occurs. Thus, in the case the process consists of four polymerization reactors, this definition does not exclude the option that the total process comprises, for example, a prepolymerization step in a prepolymerization reactor. The term "consists of" is just a formulation closer to the main polymerization reactors.
    [060] As stated above, in the first two reactors the matrix (M), that is, the random propylene copolymer (R-PP) is produced. More precisely, in the first reactor (R1), the first fraction of random propylene copolymer (R-PP1) is produced while in the second reactor (R2) the second fraction of random propylene copolymer (R-PP2).
    [061] The preferred co-monomers used in the first reactor (R1) are the same as indicated above, for the first fraction of random propylene copolymer (R-PP1). Consequently, especially preferred co-monomers are ethylene, 1-butene and 1-hexene. In a specific embodiment the co-monomer is ethylene.
    [062] Preferably, the weight ratio between the first fraction of random propylene copolymer (R-PP1) and the second fraction of random propylene copolymer (R-PP2) is 20/80 to 80/20, more preferably, 30/70 to 70/30.
    [063] Thus, in the first reactor (R1) a first fraction of random propylene copolymer (R-PP1) is produced with a co-monomer content of 5.0% or less by weight, more preferably equal to or less than 4.0% by weight, even more preferably in the range of 0.5 to 5.0% by weight, even more preferably in the range of 0.5 to 4.0% by weight, as in the range of 1.0 to 3.5% by weight.
    [064] In the second reactor (R2) the second fraction of random propylene copolymer (R-PP2) is produced thus obtaining the random propylene copolymer (R-PP).
    [065] The preferred co-monomers used in the second reactor (R2) are the same as indicated above, for the first reactor (R1). Consequently, especially preferred co-monomers are ethylene, 1-butene and 1-hexene. In a specific embodiment the co-monomer is ethylene.
    [066] The second fraction of random propylene copolymer (R-PP2) preferably has a co-monomer content of at least 0.5% by weight, more preferably in the range of 0.5 to 20.0% by weight, even more preferably in the range of 1.0 to 19.0% by weight, even more preferably in the range of 1.5 to 18.0% by weight.
    [067] Thus, the total co-monomer content in the second reactor (R2), that is, the co-monomer content of the random propylene copolymer (R-PP) is preferably in the range of 1.0 to 9.0% by weight, even more preferably in the range of 1.5 to 8.0% by weight, even more preferably in the range of 1.5 to 7.5% by weight, as in the range of 2.0 to 7 , 0% by weight.
    [068] The co-monomers of the random propylene copolymer (R-PP), the first fraction of random propylene copolymer (R-PP1), and the second fraction of random propylene copolymer (R-PP2) copolymerizable with propylene are ethylene and / or C4 to C12 α-olefins, in particular ethylene and / or C4 to C8 α-olefins, for example, 1-butene and / or 1-hexene. Preferably, the random propylene copolymer (R-PP), the first fraction of random propylene copolymer (R-PP1), and the second fraction of random propylene copolymer (R-PP2) comprise, especially consists of, copolymerizable monomers with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the random propylene copolymer (R-PP), the first fraction of random propylene copolymer (R-PP1) and the second fraction of random propylene copolymer (R-PP2) comprise - in addition to propylene - units derived from ethylene and / or 1-butene. In a preferred embodiment, the random propylene copolymer (R-PP), the first fraction of random propylene copolymer (R-PP1) and the second fraction of random propylene copolymer (R-PP2) comprise the same co-monomers, that is, only ethylene.
    [069] In addition, the first fraction of random propylene copolymer (R-PP1), that is, the polymer of the first reactor (R1), preferably has a fraction of soluble in cold xylene (XCS) equal to or less 12.0% by weight, more preferably in the range of 3.0 to 12.0% by weight, even more preferably in the range of 4.0 to 11.0% by weight, even more preferably in the range of 5.0 to 10.0% by weight, even more preferably in the range of 4.5 to 9.0% by weight.
    [070] On the other hand, the second fraction of random propylene copolymer (R-PP2), that is, the polymer produced in the second reactor (R2), preferably has a fraction of soluble in cold xylene (XCS) below 40% by weight, more preferably in the range of 2 to 35% by weight, even more preferably in the range of 3 to 30% by weight.
    [071] Therefore, the total content of soluble in cold xylene (XCS) in the second reactor, that is, the fraction of soluble in cold xylene (XCS) of the random propylene copolymer (R-PP) is, preferably, in the range of 3.5 to 15.0% by weight, even more preferably it is in the range of 4.0 to 12.0% by weight.
    [072] Preferably, the first fraction of random propylene copolymer (R-PP1) preferably has a melt index MFR2 (230 ° C) in the range of 0.5 to 3.0 g / 10 min, more preferably at range from 1.0 to 3.0 g / 10 min.
    [073] On the other hand, the second fraction of random propylene copolymer (R-PP2), that is, the polymer produced in the second reactor (R2), preferably has an MFR2 fluidity index (230 ° C) in the range from 0.4 to 3.0 g / 10 min, more preferably in the range of 0.4 to 2.5 g / 10 min.
    [074] Therefore, the total fluidity rate MFR2 (230 ° C) in the second reactor, that is, the fluidity MFR2 (230 ° C) of the random propylene copolymer (R-PP), is preferably in the range of 0.5 to 3.0 g / 10 min, more preferably in the range of 1.0 to 3.0 g / 10 min.
    [075] Thus, after the second reactor (R2) the matrix (M), that is, the random propylene copolymer (R-PP) of the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), is obtained . This matrix (M) is subsequently transferred to the third reactor (R3), in which the first fraction of elastomeric propylene copolymer (E) is produced (step (e)).
    [076] The preferred co-monomers used in the third reactor (R3) are the same, as indicated above for the first reactor (R1). Consequently, especially preferred co-monomers are ethylene, 1-butene and 1-hexene. In a specific embodiment the co-monomer is ethylene.
    [077] The second mixture obtained comprises the matrix (M), in which the first fraction of elastomeric propylene copolymer (E) is dispersed. Said second mixture preferably has a co-monomer content which is greater than the co-monomer content of the second reactor (R2). On the other hand, the co-monomer content should not be too high. Thus, it is preferred that the co-monomer content of the second mixture, that is, after step (e) is not greater than 20.0% by weight, preferably in the range of 4.0 to 20.0% in weight, more preferably in the range of 5.0 to 18.0% by weight.
    [078] Another characteristic feature of the second mixture is its content of soluble in cold xylene (XCS). Therefore, it is understood that the second mixture has a fraction of soluble in cold xylene (XCS) of at least 22% by weight, more preferably at least 25% by weight, even more preferably in the range of 22 to 50% by weight , even more preferably in the range of 25 to 45% by weight, even more preferably in the range 27 to 42% by weight.
    [079] The co-monomer content in the cold xylene soluble fraction (XCS) of the second mixture is preferably at least 16.0% by weight, more preferably in the range of 16.0 to 28.0% by weight , even more preferably in the range of 18.0 to 26.0% by weight, even more preferably in the range of 20.0 to 25.0% by weight.
    [080] In step (f), the second mixture is transferred to the fourth reactor (R4). In the fourth reactor (R4) the second fraction of elastomeric propylene copolymer (E) is produced (step (g)).
    [081] The preferred co-monomers used in the fourth reactor (R4) are the same as above for the first reactor (R1). Consequently, especially preferred co-monomers are ethylene, 1-butene and 1-hexene. In a specific embodiment the co-monomer is ethylene.
    [082] The polymer thus obtained is the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO) of the present invention.
    [083] Preferably, the heterophasic propylene copolymer (RAHECO) after step (g) has a flow rate MFR2 (230 ° C) in the range of 0.5 to 2.0 g / 10min, such as 0.5 to 1 , 9 g / 10min.
    [084] It is preferred that the co-monomer content of the cold xylene soluble fraction (XCS) after step (g), that is, the co-monomer content of the cold xylene soluble fraction (XCS) of the copolymer propylene, that is, the heterophasic propylene copolymer (RAHECO), is in the range of 16.0 to 28.0% by weight, even more preferably in the range of 18.0 to 26.0% by weight, even more preferably in the range of 20.0 to 25.0% by weight.
    [085] The amount of soluble in cold xylene (XCS) in the second mixture and in the propylene copolymer after step (g) is more or less the same. The same goes for the intrinsic viscosities of the respective fractions of soluble in cold xylene (XCS).
    [086] Therefore, the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), has a fraction of soluble in cold xylene (XCS) of at least 25% by weight, more preferably in the range of 25 to 50% by weight, even more preferably in the range of 25 to 45% by weight, even more preferably still in the range of 27 to 41% by weight.
    [087] In addition, the intrinsic viscosity (IV) measured according to ISO 1628/1 (at 135 ° C in decalin) of the cold xylene soluble fraction (XCS) of propylene copolymer after step (g) is preferably equal to or less than 3.7 dl / g, more preferably in the range of 1.6 to below 3.5 dl / g, even more preferably in the range of 1.8 to below 3.5 dl / g.
    [088] Regarding the melting temperature of the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), after step (g) it refers to the information provided above.
    [089] Preferably, the weight ratio between the matrix (M), that is, the random propylene copolymer (R-PP), after step (c) and the elastomeric propylene copolymer (E) produced in steps ( e) a (g) is 45/55 to 80/20, more preferably 50/50 to 75/25, even more preferably 52/48 to 70/30.
    [090] After step (g) the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), can optionally be subjected to the viscorreduction phase (step (i)) to obtain a propylene copolymer, ie , a heterophasic propylene copolymer (RAHECO), with a higher flow rate. Viscoreduction can be carried out in any known manner, but generally the present invention provides for viscoreduction by a chemical using a peroxide agent. Typical viscosity reducing agents are 2,5-dimethyl-2,5-bis (tert-butyl-peroxy) -hexane (DHBP) (for example, sold under the trade names Luperox 101 and Trigonox 101), 2,5- dimethyl-2,5-bis (tert-butyl-peroxy) hexino-3 (DYBP) (for example, sold under the trade names Luperox 130 and Trigonox 145), dicumyl peroxide (DCUP) (for example, sold under the names Luperox DC and Perkadox BC), di-tert-butyl peroxide (DTBP) (for example, sold under the trade names Trigonox B and Luperox Di), tert-butyl-cumyl peroxide (BCUP) (for example, sold under the trade names Trigonox T and Luperox 801) and bis (tert-butylperoxy-isopropyl) benzene (DIPP) (for example, sold under the trade names Perkadox 14S and Lupperox DC). The appropriate amounts of peroxide to be used in accordance with the present invention are, in principle, known to the skilled person and can be easily calculated based on the amount of propylene copolymer from step (g) to be subjected to viscoreduction, the value of MFR2 (230 ° C) of the propylene copolymer of step (g), to be subjected to viscoreduction and the desired target MFR2 (230 ° C) of the product to be obtained. Accordingly, typical amounts of viscorreducing peroxide agent are from 0.005 to 5% by weight, more preferably from 0.005 to 0.2% by weight, based on the amount of propylene copolymer employed.
    [091] Typically, the viscorreduction according to the present invention is carried out in an extruder, so that, under the appropriate conditions, an increase in the flow rate is obtained. During viscoreduction, larger molar mass chains of the starting product are often statistically reduced more than smaller molar mass molecules, resulting in a total decrease in average molecular weight and an increase in flow rate.
    [092] Due to viscorreduction the flow rate, the amount of soluble in cold xylene (XCS) and the intrinsic viscosity (IV) of the fraction of soluble in cold xylene (XCS) of the propylene copolymer, that is, of the propylene copolymer heterophasic (RAHECO), are affected. On the other hand, the melting temperature, the total co-monomer content and the co-monomer content of the cold xylene-soluble fraction (XCS) of the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), are not affected. Thus, the propylene copolymer that did not have viscoreduction (after step (g)) and the propylene copolymer that did not have viscoreduction (after step (i)) have the same melting temperature, the same total co-monomer content and the same co-monomer content of the cold xylene soluble fraction (XCS). Thus, with regard to these modalities, reference is made to the information provided above.
    [093] The propylene copolymer which has viscoreduction preferably has a flow rate, a fraction of soluble in cold xylene (XCS) and an intrinsic viscosity (IV) as specified above for the propylene copolymer than the propylene copolymer which there was no viscorreduction. Therefore, the propylene copolymer after step (i) preferably has an MFR2 flow rate (230 ° C) in the range of 2.5 to 12.0 g / 10 min, more preferably in the range of 2.5 to 10.0 g / 10 min, even more preferably in the 2.5 to 8.5 g / 10 min range, as in the 2.5 to 5.0 g / 10 min range.
    [094] Furthermore, it is preferred that the fraction of soluble in cold xylene (XCS) of propylene copolymer after step (i) is in the range of 20 to 45% by weight, even more preferably in the range of 23 to 40% by weight, even more preferably in the range of 25 to 39% by weight.
    [095] Preferably, the cold xylene soluble fraction (XCS) of propylene copolymer after step (i) has an intrinsic viscosity (IV) measured according to ISO 1628/1 (at 135 ° C in decaline) of equal to or greater than 1.8 dl / g, more preferably in the range of 1.8 to equal to or less than 3.0 dl / g, even more preferably in the range of 1.8 to 2.7 dl / g, even more preferably in the range of 1.9 to 2.6 dl / g, as in the range of 2.0 to 2.5 dl / g.
    [096] The first reactor (R1) is preferably a suspension reactor (SR) and can be any reactor with agitated tank in continuous or simple batch or recirculation reactor that operates in bulk or in suspension. Bulk 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 recirculation reactor (in bulk) (LR).
    [097] 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 fluid bed reactors. Preferably, the gas phase reactors (GPR) comprise a mechanically stirred fluidized bed reactor with gas velocities of at least 0.2 m / sec. Thus, the gas phase reactor is considered to be a type of fluidized bed reactor, preferably with a mechanical stirrer.
    [098] Thus, in a preferred embodiment, the first reactor (R1) is a suspension reactor (SR), as a recirculation reactor (LR), while the second reactor (R2), third reactor (R3) and the fourth reactor (R4) are gas phase reactors (GPR). Therefore, for the present process, at least four, preferably four, polymerization reactors, that is, a suspension reactor (SR), as a recirculation reactor (LR), a first gas phase reactor (GPR-1) , a second gas phase reactor (GPR-2) and a third gas phase reactor (GPR-3) connected in series are used. If necessary, before the suspension reactor (SR) a prepolymerization reactor is placed.
    [099] A preferred multi-step process is a "gas phase cycle" 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 and / or WO 00/68315.
    [100] Another more suitable gas phase / suspension process is the Basell Spheripol® process.
    [101] Preferably, in the present process for the production of the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), as defined above in the conditions for the first reactor (R1), that is, the suspension reactor ( SR), as a recirculation reactor (LR), from step (a), should 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 90 ° C, - the pressure is in the range of 2000 kPa (20 bar) to 8000 kPa (80 bar), preferably between 4000 kPa (40 bar) to 7000 kPa (70 bar), - hydrogen can be added to control molecular mass in a manner known per se.
    [102] Subsequently, the reaction mixture from step (a) is transferred to the second reactor (R2), that is, the gas phase reactor (GPR-1), that is, to step (c), in which the The conditions of step (c) are preferably as follows: - the temperature is within the range of 50 ° C to 130 ° C, preferably between 60 ° C and 100 ° C, - the pressure is within the range of 500 to 5000 kPa (5 bar to 50 bar), preferably between 1500 to 3500 kPA (15 bar to 35 bar), - hydrogen can be added to control molecular mass in a manner known per se.
    [103] The condition in the third reactor (R3), preferably in the second gas phase reactor (GPR-2), and the fourth reactor (R4), preferably in the third gas phase reactor (GPR-3), are similar to those of the second reactor (R2).
    [104] The residence time may vary in the three zones of the reactor.
    [105] In a process modality for the production of the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), the residence time in the first reactor (R1), that is, the suspension reactor (SR), as a recirculation reactor (LR), it is in the range of 0.2 to 4 hours, for example, 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.
    [106] If desired, polymerization can be carried out in a known manner under supercritical conditions in the first reactor (R1), that is, in the suspension reactor (SR), as in the recirculation reactor (LR), and / or as a condensed mode in the gas phase reactors (GPR).
    [107] Preferably, the process also comprises prepolymerization with the catalyst system as described in detail below, comprising a Ziegler-Natta pro-catalyst, an external donor and, optionally, a co-catalyst.
    [108] In a preferred embodiment, prepolymerization is conducted as bulk suspension polymerization in liquid propylene, that is, the liquid phase comprises mainly propylene, with a small amount of other reagents and, optionally, inert components dissolved in it.
    [109] The prepolymerization reaction is typically carried out at a temperature of 0 to 50 ° C, preferably 10 to 45 ° C, and more preferably 15 to 40 ° C.
    [110] The pressure in the prepolymerization reactor is not critical, but it must be high enough to keep the reaction mixture in the liquid phase. Thus, the pressure can be from 2,000 to 10,000 kPa (20 to 100 bar), for example, 3,000 to 7,000 kPa (30 to 70 bar).
    [111] The catalyst components are preferably all introduced in the prepolymerization step. However, when the solid catalyst component (i) and co-catalyst (ii) can be fed separately, it is possible that only a part of the co-catalyst is introduced in the prepolymerization phase and the remainder in stages of subsequent polymerization. In addition, in such cases, it is necessary to introduce so much co-catalyst for the prepolymerization phase that a sufficient polymerization reaction is obtained there.
    [112] 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 anti-static additive can be used to prevent particles from adhering to each other or to the reactor walls.
    [113] Precise control of prepolymerization conditions and reaction parameters is within the skill of the art.
    [114] According to the invention, the heterophasic propylene copolymer (RAHECO) 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, that is, as component (i) a Ziegler-Natta pro-catalyst, 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).
    [115] The process is performed especially efficiently using a Ziegler-Natta catalyst system, preferably by means of a Ziegler-Natta catalyst system, as defined in detail below, and a specific co-monomer / propylene ratio in second reactor (R2) and / or third (R3) and fourth reactor (R4), respectively. Therefore, it is preferable that (a) the proportion of co-monomer / propylene [Co / C3], as the proportion of ethylene / propylene [C2 / C3], in the second reactor (R2), that is, in step (c ), is in the range of 5 to 60 mol / kmol, more preferably in the range of 10 to 40 mol / kmol, and / or (b) the proportion of co-monomer / propylene [Co / C3], as the proportion of ethylene / propylene [C2 / C3], in the third reactor (R3), that is, in step (e), it is in the range of 160 to 200 mol / kmol, more preferably in the range of 170 to 190 mol / kmol, and / or (c) the proportion of co-monomer / propylene [Co / C3], as the proportion of ethylene / propylene [C2 / C3], in the fourth reactor (R4), that is, in step (g), is in the range of 160 to 200 mol / kmol, more preferably in the range of 170 to 190 mol / kmol.
    [116] In the following the catalyst used is defined in more detail.
    [117] The pro-catalyst used according to the invention is prepared by a) reacting a crystallized spray or adduct of solidified emulsion of MgCl2 and a C1-C2 alcohol with TiCl4. b) reaction of the product from step a) with a dialkylphthalate of formula (I)
    wherein R1 'and R2 are independently at least C5 alkyl under conditions in which a transesterification between said C1 to C2 alcohol and said dialkylphthalate of formula (I) occurs in order to form the internal donor c) washing of the product from step b) or d) optionally reacting the product from step c) with additional TiCl4.
    [118] The pro-catalyst is produced as defined, for example, in patent applications WO 87/07620, WO 92/19653, WO 92/19658 and EP 0.491,566. The content of these documents is included here by reference.
    [119] Firstly, 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.
    [120] The adduct, which is first melted and then crystallized by spraying or solidified into emulsion, is used as a catalyst support.
    [121] In the next step, the adduct crystallized by spraying or solidified in an emulsion of the formula MgCl2 * nROH, where R is methyl or ethyl, preferably ethyl, and n is 1 to 6, is contacting TiCl4 to form a vehicle with titanium, followed by the steps of • adding to said titanium vehicle (i) a dialkylphthalate of formula (I) with R1 'and R2 independently being at least one C5-alkyl, such as at least one C8-alkyl, or preferably (ii) a dialkylphthalate of formula (I) with R1'and R2 being the same and being at least one C5-alkyl, such as at least one C8-alkyl, or more preferably (iii) a 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 dialkyl phthalate of formula (I) is a dioctyl phthalate (DOP) , such as di-iso-dioctyl phthalate or diethylhexyl phthalate, in particular diethylhexyl phthalate, to form a first product to, • subject said first product to suitable transesterification conditions, that is, at a temperature above 100 ° C, preferably between 100 and 150 ° C, more preferably between 130 and 150 ° C, such that said methanol or ethanol is transesterified with said ester groups of said dialkyl phthalate of formula (I) to preferably form at least 80% by ml, more preferably 90% by mol, more preferably 95% by mol, of a dialkyl phthalate of formula (II)
    with R1 and R2 being methyl or ethyl, preferably ethyl, the dialkyl phthalate of formula (II), being the internal donor and • recovering this transesterification product as the pro-catalyst composition (component (i)).
    [122] The adduct of the formula MgCl2 * nROH, where R is methyl or ethyl and n is 1 to 6, is in a preferred melt mode and then the melt is preferably injected by a gas in a cooled solvent or a cooled gas, in that the adduct is crystallized in a morphologically advantageous form as, for example, described in WO 87/07620.
    [123] This crystallized adduct is preferably used as the catalyst carrier and reacted with the pro-catalyst useful in the present invention as described in WO 92/19658 and WO 92/19653.
    [124] As the catalyst residue is removed by extraction of an adduct from the titanium vehicle and the internal donor is obtained, in which the group derived from the ester alcohol has changed.
    [125] If sufficient titanium remains in the vehicle, it will act as an active element in the pro-catalyst.
    [126] Otherwise, titanization is repeated after the above treatment in order to ensure a sufficient titanium concentration and therefore activity.
    [127] Preferably the pro-catalyst used according to the invention contains 2.5% by weight of titanium at most, preferably 2.2% by weight at most and most preferably 2.0% by weight in the maximum. Its donor content is preferably between 4 to 12% by weight and more preferably between 6 and 10% by weight.
    [128] 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.
    [129] Even more preferably, the catalyst used according to the invention is the catalyst as described in the example section; especially with the use of dioctyl phthalate as the dialkyl phthalate of formula (I).
    [130] For the production of the propylene copolymer, ie the heterophasic propylene copolymer (RAHECO), according to the invention, the catalyst system used preferably comprises, in addition to the special Ziegler-Natta pro-catalyst, an organometallic co-catalyst as component (ii).
    [131] Therefore, it is preferred to select the co-catalyst from the group consisting of trialkylaluminium, such as triethylaluminium (TEA), dialkyl aluminum chloride and alkyl aluminum aluminum sesquichloride.
    [132] 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) 2R25 (IIIa) where R5 represents a branched alkyl group having 3 to 12 carbon atoms, preferably a branched alkyl group having 3 to 6 carbon atoms, or a cycloalkyl having 4 to 12 carbon atoms, preferably a cycloalkyl having 5 to 8 carbon atoms.
    [133] 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.
    [134] Formula (IIIb) is defined by Si (OCH2CH3) 3 (NRxRy) (IIIb) in which Rx and Ryp can be the same or different and represent a hydrocarbon group having 1 to 12 carbon atoms.
    [135] Rxe Rysão selected independently from the group consisting of the linear aliphatic hydrocarbon group having 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group having from 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group with 1 to 12 carbon atoms. In particular, it is preferred that Rx and Ry are selected independently from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, isopropyl, iso-butyl, iso-pentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
    [136] More preferably, both Rx and Rys are the same, even more preferably, both Rx and Rys are an ethyl group.
    [137] Most preferably, the external donor of formula (IIIb) is diethylaminotriethoxysilane.
    [138] More preferably, the external donor is selected from the group consisting of diethylaminotriethoxysilane [Si (OCH2CH3) 3 (N (CH2CH3) 2)], dicyclopentyl dimethoxy silane [Si (OCH3) 2 (cyclopentyl) 2], diisopropyl dimethoxy silane [Si (OCH3) 2 (CH (CH3) 2) 2], and mixtures thereof. More preferably, the external donor is dicyclopentyl dimethoxy silane [Si (OCH3) 2 (cyclopentyl) 2].
    [139] If desired, the Ziegler-Natta pro-catalyst is modified by the polymerization of a vinyl compound in the presence of the catalyst system, comprising the special Ziegler-Natta pro-catalyst (component (i)), the external donor (component (iii)) and, optionally, the co-catalyst (component (ii)), in which the vinyl compound has the formula: CH2 = CH - CHR3R4 in which R3 and R4 together form an aromatic or unsaturated, saturated, unsaturated ring 5- or 6-membered independently represent an alkyl group comprising 1 to 4 carbon atoms. The catalyst thus modified is used for the preparation of the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), according to this invention.
    [140] The aforementioned additives are added before or after viscorreduction to the propylene copolymer, ie the heterophasic propylene copolymer (RAHECO). These additives are preferably mixed in the propylene copolymer, that is, in the heterophasic propylene copolymer (RAHECO) before visceduction. In another preferred embodiment, the additives and the degrading agent (peroxide) are added in the same extrusion / mixing process, preferably in a co-rotating twin screw extruder as mentioned below.
    [141] For mixing, a conventional mixing device or composition, for example, a Banbury mixer, a 2-roller rubber mill, Buss co-kneader or a twin screw extruder can be used. The polymeric materials recovered from the extruder are generally in the form of pellets. These pellets are further processed, for example, by injection molding or a film-forming process as described below.
    [142] In the event that a film is produced, it can be obtained by blown or blown film technology. In fused film technology, the fused propylene copolymer, that is, the fused heterophasic propylene copolymer (RAHECO) is extruded through an extruded die with a groove in a cooling roll to cool the polymer in a solid film. Usually a propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO) is, firstly, compressed and liquefied in an extruder, making it possible for all additives to be already added to the polymer or introduced in this phase through a masterbatch. The melt is then forced through a flat film matrix (grooved matrix), and the extruded film is removed on one or more take-off rolls, during which it cools and solidifies. It has proved to be particularly favorable to keep the take-off roll or rollers, whereby the extruded film is cooled and solidified at a temperature of 10 to 50 ° C, preferably from 10 to 0 ° C, more preferably from 12 to 35 ° C. The product obtained is an unstretched film that can be desired to be biaxially stretched.
    [143] In the blown film process of the propylene copolymer, that is, the heterophasic propylene copolymer (RAHECO), the melt is extruded through an annular matrix and blown into a tubular film, forming a bubble, which is burst between the pressure cylinders after solidification. The extrusion of the melt can be carried out preferably at a temperature in the range 160 to 240 ° C, and cooled by water, or preferably by blowing gas (usually air) at a temperature of 10 to 50 ° C, to provide a height of the ice level from 0.5 to 8 times the diameter of the matrix. The blowing ratio should generally be in the range of 1.5 to 4, such as 2 to 4, preferably 2.5 to 3.5.
    [144] The preparation of injection molded articles is known to a knowledgeable person. Reference is made, in particular, to the “Propylene handbook”, Pasquini (Ed.), 2nd Edition, Hanser.
    [145] In the following the present invention is further illustrated by way of examples. EXAMPLES 1. Measurement methods
    [146] The following definitions of terms and methods of determination are applied to the above general description of the invention as well as the examples below unless otherwise defined.
    [147] Calculation of the co-monomer content of the second fraction of propylene copolymer (R-PP2):
    Where: w (PP1) is the fraction by weight [% by weight] of the first fraction of propylene copolymer (R-PP1), w (PP2) is the fraction by weight [% by weight] of the second fraction of copolymer of propylene (R-PP2), C (PP1) is the co-monomer content [% by weight] of the first fraction of propylene copolymer (R-PP1), C (PP) is the co-monomer content [% in weight] of the random propylene copolymer (R-PP), C (PP2) is the calculated co-monomer content [% by weight] of the second fraction of propylene copolymer (R-PP2).
    [148] Calculation of the content of soluble in cold xylene (XCS) of the second fraction of propylene copolymer (R-PP2):
    w (PP1) is the fraction by weight [% by weight] of the first fraction of propylene copolymer (R-PP1), w (PP2) is the fraction by weight [% by weight] of the second fraction of propylene copolymer (R -PP2), XS (PP1) is the content of soluble in cold xylene (XCS) [% by weight] of the first fraction of propylene copolymer (R-PP1), XS (PP) is the content of soluble in cold xylene ( XCS) [% by weight] of the random propylene copolymer (R-PP), XS (PP2) is the content of soluble in cold xylene (XCS) calculated [% by weight] of the second fraction of propylene copolymer (R-PP2 ), respectively.
    [149] Calculation of the fluidity index MFR2 (230 ° C) of the second fraction of propylene copolymer (R-PP2):
    w (PP1) is the fraction by weight [% by weight] of the first fraction of propylene copolymer (R-PP1), w (PP2) is the fraction by weight [% by weight] of the second fraction of propylene copolymer (R -PP2), MFR (PP1) is the flow rate MFR2 (230 ° C) [in g / 10min] of the first fraction of the first propylene copolymer (R-PP1), MFR (PP) is the flow rate MFR2 ( 230 ° C) [in g / 10min] of the random propylene copolymer (R-PP), MFR (PP2) is the fluidity index MFR2 (230 ° C) [in g / 10min] of the second fraction of the first propylene copolymer (R-PP2).
    [150] Calculation of the co-monomer content of the elastomeric propylene copolymer (E), respectively:
    w (PP) is the fraction by weight [% by weight] of the random propylene copolymer (R-PP), ie, polymer produced in the first and second reactors (Rl + R2), w (E) is the fraction by weight [% by weight] of the elastomeric propylene copolymer (E), ie, polymer produced in the third and fourth reactors (R3 + R4) C (PP) is the co-monomer content [% by weight] of the random propylene copolymer (R-PP), that is, the co-monomer content [% by weight] of the polymer produced in the first and second reactors (Rl + R2), C (RAHECO) is the co-monomer content [% by weight ] of the propylene copolymer, that is, it is the co-monomer content [% by weight] of the polymer obtained after polymerization in the fourth reactor (R4), C (E) is the calculated co-monomer content [% by weight ] of the elastomeric propylene copolymer (E), that is, the polymer produced in the third and fourth reactors (R3 + R4).
    [151] MFR 2 (230 ° C) is measured according to ISO 1133 (230 ° C, load 2.16 kg).
    [152] Average numerical molecular weight (Mo), average weight molecular weight (Mw) and molecular weight distribution (MWD) are determined by Gel Permeation Chromatography (GPC) according to the following method:
    [153] The 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) are measured by a method based on ISO 16014-1 : 2003 and ISO 16014-4: 2003. A GPCV 2000 Waters Alliance instrument equipped with a refractive index detector and in-line viscometer was used with 3 x TSK-gel (GMRXL-RT) columns from TosoHaas 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 a constant flow rate of 1 ml / min. 216.5 μl of sample solution was injected by analysis. The column assembly was calibrated using relative calibration with 19 narrow MWD polystyrene (PS) standards in the range of 0.5 kg / mol to 11,500 kg / mol and a set of well-characterized broad polypropylene standards. All samples were prepared by dissolving 5 - 10 mg of polymer in 10 ml (at 160 ° C) of stabilized TCB (even as a mobile phase) and maintaining for 3 hours with continuous agitation before sampling on the GPC instrument.
    [154] Co-monomer content, especially ethylene content, is measured with Fourier transform infrared spectroscopy (FTIR) calibrated with 13C-NMR. When measuring the content of ethylene in polypropylene, a thin film of the sample (thickness of about 250 μm) was prepared by hot pressing. The area of absorption peaks 720 and 733 cm-1 for propylene and ethylene copolymers was measured with a Perkin Elmer FTIR 1600 spectrometer. Propylene-1-butene copolymers were evaluated at 767 cm-1. The method was calibrated with the ethylene content data measured by 13C-NMR. See also "IR-Spektroskopie fur Anwender"; Wiley-VCR, 1997 and "Validierung in der Analytik", Wiley -VCR, 1997
    [155] Flexural module: The flexural module was determined in a 3-point curve at 23 ° C according to ISO 178 on test bars of 80x10x4 mm3 injection molded according to EN ISSO 1873-2.
    [156] Notched Charpy impact resistance is determined according to ISO 179 / l and at 23 ° C and -20 ° C using injection molded species as described in EN ISO 1873-2 (80 x 10 x 4 mm).
    [157] Intrinsic viscosity is measured according to DIN ISO 1628/1, October 1999 (in decal at 135 ° C).
    [158] Soluble in xylene (XCS,% by weight): the content of soluble in cold xylene (XCS) is determined at 25 ° C according to ISO 16152; first edition; 2005-07-01. The part that remains insoluble is the fraction of insoluble in cold xylene (XCI).
    [159] Melting temperature (Tm) and heat of fusion (Hf), temperature of crystallization (Tc) and heat of crystallization (Hc): measured with Mettler TA820 differential scanning calorimeter (DSC) in samples of 5 to 10 mg. DSC is performed according to ISO 3146 3 / part 3 / method C2 in a heat / cold / heat cycle with a scanning speed of 10 ° C / min in the temperature range 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.
    [160] Turbidity, transparency and clarity were determined according to ASTM D 1003-07 on 60x60x1 mm3 injection molded plates in line with EN ISO 1873-2 using a melting temperature of 200 ° C. Steam sterilization was performed as described below.
    [161] Turbidity, transparency and clarity were determined according to ASTM D1003-00 on 50 μm thick cast films produced on a monolayer film line with a melting temperature of 220 ° C and a temperature of the cooling roller of 15 ° C. 2.Examples
    [162] The catalyst used in the polymerization process for examples E1 to E5 and CE1 to CE3 was produced as follows: First, 0.1 mol of MgCl2 x 3 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 maintaining the temperature at that level. Then, the temperature of the suspension was slowly increased to 20 ° C. At that temperature, 0.02 mol of dioctyl phthalate (DOP) was added to the suspension. After the addition of phthalate, the temperature was raised to 135 ° C for 90 minutes and the suspension was left 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 that, 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 EP 491,566, EP 591,224 and EP 586,390. As a co-catalyst triethyl aluminum (TEAL) and as a donor pentyl dimethoxy silane (D- donor) were used. The aluminum to donor ratio is shown in tables 1 (a) and 1 (b).
    [163] The resulting polymers were viscored in a co-rotating twin screw extruder (type: Coperion ZSK 57) with adequate amounts of 2,5-dimethyl-2,5-di- (tercbutilperoxy) -hexane (Trigonox® supplied by Akzo Nobel, The Netherlands) added to the extruder in the form of a 1% by weight polypropylene powder concentrate. As additives 0.04% synthetic hydrotalcite (DHT-4A supplied by Kisuma Chemicals, Netherlands) and 0.15% by weight of Irganox B 215 (1: 2 mixture of Irganox 1010 (pentaerythrityl - tetrakis (3- (3 ', 5'-di-tert-butyl-4-hydroxytoluyl) - propionate and tris (2,4-di-t-butylphenyl) -phosphate) phosphite) from BASF AG, Germany were added to the polymers in the same step.
    [164] Steam sterilization was performed on a Systec D series machine (Systec Inc., USA). The samples were heated at a heating rate of 5 ° C / min from 23 ° C. After being held for 30 minutes at 121 ° C, they were immediately removed from steam sterilization and stored at room temperature until further processing.
    [165] Table 1 (a): Polymerization conditions (Comparative examples)


    [166] Table 1 (b): Polymerization conditions (Examples of the invention)

    C2 ethylene IV intrinsic viscosity H2 / C3 ratio hydrogen / propylene ratio C2 / C3 ratio ethylene / propylene ratio POX 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane 1/2/3 / GRP 1/2 / 3 gas phase reactors Loop recirculation reactor
    [167] Table 2 (a): Properties (comparative examples) after viscoreduction


    [168] Table 2 (b): Properties (Examples of the invention) after viscoreduction

    C2 ethylene XCS fraction of soluble in cold xylene XCI fraction of insoluble in cold xylene IV intrinsic viscosity H2 / C3 ratio hydrogen / propylene ratio C2 / C3 ratio ethylene / propylene POX 2,5-dimethyl-2,5-di- (terc - 1/2/3 gas phase reactors recirculation reactor transparency before transparency after turbidity before turbidity after sterilization turbidity before turbidity after sterilization
    权利要求:
    Claims (15)
    [0001]
    1. Propylene copolymer, characterized by the fact that it has: (a) an MFR2 fluidity index (230 ° C) measured according to ISO 1133 in the range of more than 2.5 to 12.0 g / 10min, (b ) a co-monomer content in the range of more than 7.5 to 12.0% by weight, (c) a content of soluble in cold xylene (XCS) determined according to ISO 16152 (25 ° C) in the range of 20.0 to 45.0% by weight, and (d) an intrinsic viscosity (IV) of the insoluble fraction in cold xylene (XCI) in the range equal to or more than 1.8 to equal to or below 2.7 dl / g, in which the intrinsic viscosity (IV) is determined according to DIN ISSO 1628/1 (in decalin at 135 ° C), in which still (e) the co-monomer content of the fraction soluble in cold xylene ( XCS) of the propylene copolymer is in the range of 16.0 to 28.0% by weight, and (f) the propylene copolymer satisfies the inequality (II)
    [0002]
    2. Propylene copolymer, according to claim 1, characterized by the fact that the propylene copolymer (a) has a flow rate MFR2 (230 ° C) measured according to ISO 1133 in the range of more than 2.5 a below 12.0 g / 10min and / or (b) satisfies inequality (I)
    [0003]
    3. Propylene copolymer according to any of the preceding claims, characterized by the fact that the cold xylene insoluble fraction (XCI) of the propylene copolymer has (a) a co-monomer content in the range of 1.5 at 6.0% by weight, and / or (b) molecular weight distribution (MWD) in the range of 3.0 to below 6.0.
    [0004]
    4. Propylene copolymer according to any one of the preceding claims, characterized by the fact that the propylene copolymer has an intrinsic viscosity (IV) of the cold xylene soluble fraction (XCS) in the range of 1 or more, 8 and less than or equal to 3.0 dl / g.
    [0005]
    5. Propylene copolymer according to any of the preceding claims, characterized by the fact that the propylene copolymer satisfies inequality (III)
    [0006]
    6. Propylene copolymer according to any of the preceding claims, characterized by the fact that the propylene copolymer has (a) a melting temperature Tm determined by differential scanning calorimetry (DSC) in the range of 145 to 160 ° C, and / or (b) a flexural module measured according to ISO 178 below 600 MPa.
    [0007]
    7. Propylene copolymer, according to any of the preceding claims, characterized by the fact that the propylene copolymer is a heterophasic propylene copolymer (RAHECO) comprising a matrix (M) and an elastomeric propylene copolymer (E) dispersed in said matrix (M), wherein said matrix (M) is a random propylene copolymer (R-PP).
    [0008]
    8. Propylene copolymer, according to claim 6, characterized by the fact that the weight ratio between the matrix (M) and the elastomeric propylene copolymer (E) is 45/55 to 80/20.
    [0009]
    9. Propylene copolymer according to either of claims 7 or 8, characterized by the fact that the co-monomer content of the random propylene copolymer (R-PP) is in the range of 1.0 to 9.0% in Weight.
    [0010]
    10. Propylene copolymer according to one of the preceding claims 7 to 9, characterized by the fact that the propylene copolymer satisfies the inequality (IV)
    [0011]
    11. Propylene copolymer, according to any of the preceding claims 7 to 10, characterized by the fact that the random propylene copolymer (R-PP) has a fraction of soluble in cold xylene (XCS) in the range of 3.5 to 15.0% by weight.
    [0012]
    12. Propylene copolymer according to any of the preceding claims 7 to 11, characterized by the fact that the random propylene copolymer (R-PP) comprises at least two distinct fractions, a first fraction of random propylene copolymer (R- PP1) and a second fraction of random propylene copolymer (R-PP2), which still optionally (a) the weight ratio between the first fraction of random propylene copolymer (R-PP1) and the second fraction of random propylene copolymer (R-PP2) is 20/80 to 80/20, and / or (b) the first fraction of random propylene copolymer (R-PP1) has a co-monomer content in the range of 0.5 to 5.0 % by weight, and / or (c) the second fraction of random propylene copolymer (R-PP2) has a co-monomer content in the range of 0.5 to 20.0% by weight.
    [0013]
    13. Propylene copolymer according to any of the preceding claims 6 to 12, characterized by the fact that the elastomeric propylene copolymer (E) has a co-monomer content in the range of 14.0 to 26.0% in Weight.
    [0014]
    14. Injection molded article, characterized by the fact that it comprises a propylene copolymer defined in any of the preceding claims.
    [0015]
    15. Film, characterized by the fact that it comprises a propylene copolymer defined in any one of the preceding claims 1 to 13.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-09-24| B09A| Decision: intention to grant|
    2020-12-08| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11195493|2011-12-23|
    EP11195493.9|2011-12-23|
    PCT/EP2012/076002|WO2013092620A1|2011-12-23|2012-12-18|Propylene copolymer for injection molded articles or films|
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