HETEROPLASTIC PROPYLENE COPOLYMER, PROCESS FOR PREPARING A HETEROPLASTIC PROPYLENE COPOLYMER, AND, A

专利摘要:
heteroplastic propylene copolymer, process for preparing a heteroplastic propylene copolymer, and article. heteroplastic propylene copolymer comprising a propylene - c4 to c12 α-olefin copolymer as a matrix, in which an ethylene-propylene rubber is dispersed, said heteroplastic propylene copolymer has good mechanical properties and low extractables.
公开号:BR112016021834B1
申请号:R112016021834-5
申请日:2015-04-01
公开日:2021-07-13
发明作者:Jingbo Wang；Petar Doshev；Markus Gahleitner；Pauli Leskinen
申请人:Borealis Ag；
IPC主号:

专利说明:

[001] The present invention relates to the new heteroplastic propylene copolymer (RAHECO) to its preparation, as well as articles made from it.
[002] In the packaging area, polypropylene plays an important role. Very often so-called heterophasic polypropylene, i.e. a semi-crystalline polypropylene matrix in which rubber is dispersed, is used. Such material provides good hardness and impact; however, the optical properties can be highly dependent on the correct adjustment of the rubber dispersion in the matrix. Also, the amorphous part can cause high amounts of extractables. However, packaging material, especially in the food industry or for medical/health care products, needs to have low extractables. On the other hand, as mentioned, the packaging material can of course be mechanically stable. An additional key aspect of such a material is its optical performance, ie it must have acceptable turbidity values. Some required properties behave in a contradictory way, that is, they improve one property by decreasing the performance of another property.
[003] Consequently, it is an object of the present invention to provide a polypropylene with low extractables being mechanically stable and having good optical properties.
[004] The discovery of the present invention is a heteroplastic propylene copolymer having a propylene - C4 to C12 α-olefin copolymer as a matrix and an elastomeric ethylene propylene copolymer dispersed in said matrix. Preferably, said elastomeric ethylene propylene copolymer has a rather high ethylene content.
[005] Consequently, the present invention is directed to a heteroplastic propylene copolymer (RAHECO) comprising (i) a matrix (M) being a propylene - C4 to C12 α-olefin copolymer (C-PP), said propylene - C4 to C12 α-olefin copolymer (C-PP) comprises units derivable from (i.(1) propylene and (i.(2) at least one C4 to C12 α-olefin) and (ii) an elastomeric propylene copolymer (EC) dispersed in said matrix (M), said elastomeric propylene copolymer (EC) comprises units derivable from (ii.(1) propylene and (ii.(2) ethylene and optionally at least one C4 to C12 α-olefin) ;said heteroplastic propylene copolymer (RAHECO) has (a) an MFR2 melt flow rate (230°C) measured in accordance with ISO 1133 in the range of 2.5 to 200.0 g/10 minutes; (b ) a total comonomer content in the range of 12.0 to 35.0% by weight; (c) a cold soluble xylene fraction (XCS) determined in accordance with ISO 16152 (25°C) in an amount of 10, 0 to 40.0% by weight; pylene (RAHECO) still satisfies(d) the inequality (I)
where C2(total) is the ethylene content [in % by weight] of the heteroplastic propylene copolymer (RAHECO); Cx(total) is the α-olefin content C4 to C12 [in % by weight] of the heteroplastic propylene copolymer (RAHECO).
[006] From the phrasing of the previous paragraph it becomes evident that the propylene - C4 to C12 α-olefin copolymer (C-PP) and the elastomeric propylene copolymer (EC) are chemically different. It is therefore preferred that the propylene - C4 to C12 α-olefin copolymer (C-PP) does not comprise ethylene derivable units. more preferably the propylene - C4 to C12 α-olefin copolymer (C-PP) contains only one type of C4 to C12 α-olefin. On the other hand, the elastomeric propylene (EC) copolymer is preferably an ethylene-propylene rubber (EPR).
[007] Preferably, the ethylene content [in % by weight] of the total heteroplastic propylene copolymer (RAHECO) is in the range of 12.0 to 33.0% by weight and/or the content of α-olefin C4 to C12 [in % by weight] of the total heteroplastic propylene copolymer (RAHECO) is in the range of 0.5 to 6.0% by weight.
[008] The heteroplastic propylene copolymer of this invention is especially characterized by the properties of the cold soluble fraction in xylene (XCS) as well as the cold insoluble fraction in xylene (XCI). Consequently, the xylene soluble cold fraction (XCS) of the heteroplastic propylene copolymer (RAHECO) has a total comonomer content and/or xylene content based on the weight of the xylene soluble cold fraction (XCS) in the range of 30 to 90 % by weight and/or an intrinsic viscosity (IV) determined in accordance with DIN ISO 1628/1 (in Decalin at 135°C) of at least 1.2 dl/g.
[009] In a preferred embodiment, the cold insoluble fraction in xylene (XCI) of the heteroplastic propylene copolymer (RAHECO) has a total comonomer content [in % by weight] based on the weight of the cold insoluble fraction in xylene (XCI) in the range of 3.0 to 12.0% by weight and/or has a xylene content [in% by weight] based on the total weight of the cold insoluble fraction in xylene (XCI) in the range of 2.0 to 11, 0% by weight and/or a C4 to C12 α-olefin content [in% by weight] based on the total weight of the cold insoluble fraction in xylene (XCI) in the range of 0.5 to 6.0% by weight.
[0010] Even more preferably the cold insoluble fraction in xylene (XCI) of the heteroplastic propylene copolymer (RAHECO) satisfies inequality (II)
where C2(XCI) is the ethylene content [in % by weight] of the cold insoluble fraction in xylene (XCI) of the heteroplastic propylene copolymer (RAHECO); Cx(XCI) is the content of α-olefin C4 to C12 [in % by weight], preferably the 1-hexene content [in % by weight], of the cold xylene insoluble fraction (XCI) of the heteroplastic propylene copolymer (RAHECO).
[0011] In another preferred aspect, the heteroplastic propylene copolymer (RAHECO) according to this invention satisfies inequality (III)
whereC(XCS) the total comonomer content [in % by weight] of the xylene-soluble cold fraction (XCS) of the heteroplastic propylene copolymer (RAHECO); C(total) the total comonomer content [in % by weight] of the total heteroplastic propylene copolymer (RAHECO); and/or (b) the inequality (IV)
where C2(XCS) is the ethylene content [in % by weight] of the xylene-soluble cold fraction (XCS) of the heteroplastic propylene copolymer (RAHECO); C2(total) is the ethylene content [in % by weight] of the total heteroplastic propylene copolymer (RAHECO); and/or (c) the inequality (V)
where C2(XCS) is the ethylene content [in % by weight] of the xylene-soluble cold fraction (XCS) of the heteroplastic propylene copolymer (RAHECO); C(XCI) the total comonomer content [in % by weight] of the cold insoluble fraction in xylene (XCI) of the heteroplastic propylene copolymer (RAHECO); and/or (d) the inequality (VI)
where C2(XCS) is the ethylene content [in % by weight] of the xylene-soluble cold fraction (XCS) of the heteroplastic propylene copolymer (RAHECO); C2(XCI) is the ethylene content [in % by weight] of the cold insoluble xylene fraction (XCI) of heteroplastic propylene copolymer (RAHECO).
[0012] Preferably, the matrix (M) of the heteroplastic propylene copolymer (RAHECO) of the present invention comprises two different polymer fractions. Accordingly, it is preferred that the propylene - C4 to C12 α-olefin copolymer (C-PP) comprises, preferably consists of, a first polypropylene (PP1) fraction and a second propylene - C4 to C12 α-olefin copolymer fraction (C-PP2), preferably wherein the additional weight fraction between the first polypropylene fraction (PP1) and the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2) [(PP1)/(C -PP2)] is in the range of 30/70 to 70/30.
[0013] Preferably, the content of the comonomer, preferably the content of α-olefin C4 to C12, [in % by weight] in the propylene - α-olefin copolymer C4 to C12 (C-PP) is greater than in the first fraction of polypropylene (PP1) and/or the comonomer content, preferably the content of α-olefin C4 to C12, between the first fraction of polypropylene (PP1) and the propylene - α-olefin copolymer C4 to C12 (C-PP) differs by at least 1.5% by weight and/or the comonomer content, preferably the C4 to C12 α-olefin content, between the first polypropylene (PP1) fraction and the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2) differ by at least 2.5 wt%.
[0014] Even more preferably, the first polypropylene fraction (PP1) is a propylene homopolymer fraction (H-PP1) or especially preferred the first polypropylene fraction (PP1) is a first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), preferably said first propylene - C4 to C12 α-olefin copolymer fraction (C-PP1) has a C4 to C12 α-olefin content in the range of 0.5 to 4.0 % by weight.
[0015] In turn it is preferred that the second propylene - C4 to C12 α-olefin copolymer fraction (C-PP2) has a C4 to C12 α-olefin content in the range of 2.0 to 15.0% in Weight. Thus, in a specific modality, the propylene - C4 to C12 α-olefin copolymer (C-PP) has a comonomer content, preferably at a C4 to C12 α-olefin content, in the range of 1.5 to 9, 0% by weight.
[0016] Preferably, the elastomeric propylene copolymer (EC) of the heteroplastic propylene copolymer (RAHECO) has a comonomer content, preferably xylene content, in the range of 40 to 90% by weight.
[0017] In a preferred embodiment the heteroplastic propylene copolymer (RAHECO) satisfies inequality (VII)
whereC(XCS) is the total comonomer content [in mol%] of the heteroplastic propylene copolymer (RAHECO); XCS is the content [in weight%] of the xylene-soluble cold fraction (XCS) of the heteroplastic propylene copolymer ( RAHECO).
[0018] In yet another embodiment, the heteroplastic propylene copolymer (RAHECO) according to this invention has a first glass transition temperature Tg(1) and a second glass transition temperature Tg(2), wherein said first glass transition temperature Tg(1) is above the second glass transition temperature Tg(2), preferably the difference between the first glass transition temperature Tg(1) and the second glass transition temperature Tg(2) is at least 20 °C. Preferably, the first glass transition temperature Tg(1) is in the range of -5 to +12°C and/or the second glass transition temperature Tg(2) is in the range of -45 to -25°C.
[0019] In one aspect of the invention, the heteroplastic propylene copolymer (RAHECO) is α-nucleated.
[0020] Preferably, the heteroplastic propylene copolymer (RAHECO) has (a) a tensile modulus measured in accordance with ISO 527-1 of at least 500 MPa, and/or (b) an extractable hexane content determined in accordance with an FDA method on 100 µm cast films below 3.0% by weight.
[0021] The invention is also directed to an article comprising heteroplastic propylene copolymer (RAHECO) as defined herein, preferably, said article is selected from the group consisting of (medical) bags, food packaging articles, films and bottles .
[0022] Finally, the invention also describes a process for preparing a heteroplastic propylene copolymer (RAHECO) as defined herein to polymerize: (I) propylene and a C4 to C12 α-olefin, preferably 1-hexene, in order to form the matrix (M) being propylene - α-olefin copolymer C4 to C12 (C-PP) and subsequently polymerizing (II) propylene and ethylene optionally at least one α-olefin C4 to C12, preferably in the gas phase, in order of forming elastomeric propylene copolymer (EC) dispersed in said matrix (M); wherein both steps (I) and (II) take place in the presence of the same single-site solid particulate catalyst preferably free of an external carrier, more preferably a catalyst comprising (i) a transition metal compound of the formula (I) Rn(Cp')2MX2(I) wherein "M" is zirconium (Zr) or hafnium (Hf), each "X" is independently a monovalent anionic ligand, each "Cp'" is an organic cyclopentadienyl-type ligand independently s selected from the group consisting of substituted cyclopentadienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted or unsubstituted fluorenyl, said transition metal (M) coordinated organic ligands, "R" is a bridging group linking the said organic ligands (Cp'), "n" is 1 or 2, preferably 1 and (ii) a cocatalyst comprising a compound of a metal group, eg Al or boron compound.
[0023] More preferably, step (I) comprises polymerizing propylene and optionally a C4 to C12 α-olefin, preferably 1-hexene, in order to form the first polypropylene fraction (PP1) and subsequently polymerizing in another reactor propylene and C4 to C12 α-olefin, preferably 1-hexene, in order to form a second propylene - C4 to C12 α-olefin copolymer fraction (C-PP2), the first polypropylene fraction (PP1) and the second propylene - α-olefin copolymer C4 to C12 (C-PP2) fraction forms the propylene - α-olefin copolymer C4 to C12 n (C-PP).
[0024] Next, the first and second modalities will be described in more detail together.
[0025] The present invention is directed to a heteroplastic propylene copolymer (RAHECO). More precisely, the present invention is directed to a heteroplastic propylene copolymer (RAHECO) comprising a matrix (M) being a propylene - C4 to C12 α-olefin copolymer (C-PP) and dispersed here an elastomeric propylene copolymer ( EC). In this way, the matrix (M) contains inclusions dispersed (finely) not being part of the matrix (M) and said inclusions contain the elastomeric propylene copolymer (EC). The term "inclusion" according to this invention should preferably indicate that the matrix and the inclusion form different phases within the heteroplastic propylene copolymer (RAHECO), said inclusions are, for example, visible by high resolution microscopy such as electron microscopy or atomic force microscopy or dynamic thermal mechanical analysis (DMTA). Specifically, in DMTA, the presence of a multiphase structure can be identified by the presence of at least two distinct glass transition temperatures.
[0026] Preferably, the heteroplastic propylene copolymer (RAHECO) according to this invention comprises as polymeric components only propylene - C4 to C12 α-olefin copolymer (C-PP) and elastomeric propylene copolymer (EC). In other words, the heteroplastic propylene copolymer (RAHECO) may contain additional additives, but not another polymer in an amount that exceeds 5.0% by weight, more preferably that exceeds 3.0% by weight, which exceeds approximately 1.0% by weight, based on total heteroplastic propylene copolymer (RAHECO). An additional polymer that can be present in such low amounts is a polyethylene which is a sub-reaction product obtained by preparing the heteroplastic propylene copolymer (RAHECO). Consequently, in particular, it is estimated that the present heteroplastic propylene copolymer (RAHECO) contains only propylene - C4 to C12 α-olefin copolymer (C-PP), elastomeric propylene copolymer (EC) and optionally polyethylene in amounts with mentioned in this paragraph.
[0027] The heteroplastic propylene copolymer (RAHECO) according to this invention is characterized by a moderate melt flow rate. Consequently, the heteroplastic propylene copolymer (RAHECO) has a melt flow rate MFR2 (230°C) in the range of 2.5 to 200.0 g/10 minutes, preferably in the range of 5.0 to 100.0 g /10 min, more preferably in the range 8.0 to 80.0 g/10 min, as in the range 8.0 to 50.0 g/10 min.
[0028] Preferably, it is desired that the heteroplastic propylene copolymer (RAHECO) be thermomechanically stable. Accordingly, it is preferred that the heteroplastic propylene copolymer (RAHECO) has a dominant melting temperature that represents more than 50% of the total melting enthalpy of at least 135°C, more preferably in the range of 137 to 155°C, still more preferably in the range of 139 to 150°C.
[0029] Preferably, the heteroplastic propylene copolymer (RAHECO) has a crystallization temperature Tc greater than 105°C (if not α-nucleated) and a crystallization temperature Tc of at least 110°C (if α-nucleated) .
[0030] As mentioned above, the multiphase structure of the heteroplastic propylene copolymer (RAHECO) (elastomeric propylene copolymer (EC) dispersed in the matrix (M)) can be identified by the presence of at least two distinct glass transition temperatures. The higher first glass transition temperature (Tg(1)) represents the matrix (M), that is, propylene - α-olefin copolymer C4 to C12 (C-PP), whereas the second glass transition temperature (Tg) (2)) bottom reflects elastomeric propylene copolymer (E) of heteroplastic propylene copolymer (RAHECO).
[0031] Consequently, the heteroplastic propylene copolymer (RAHECO) according to this invention has a first glass transition temperature Tg(1) and a second glass transition temperature Tg(2), wherein said first glass transition temperature Tg(1) is above the second glass transition temperature Tg(2), preferably the difference between the first glass transition temperature Tg(1) and the second glass transition temperature Tg(2) is at least 20°C. Even more preferably the difference between the first glass transition temperature Tg(1) and the second glass transition temperature Tg(2) is at least 24°C, even more preferably in the range of 20 to 45°C, even more preferably in the range. range from 24 to 40°C. Preferably, the first glass transition temperature Tg(1) is in the range of -5 to +12°C and/or the second glass transition temperature Tg(2) is in the range of -45 to -25°C.
[0032] Preferably, the second glass transition temperature Tg(2) is at or below -25°C, more preferably is in the range of -45 to equal to or below -25°C, even more preferably in the range of -40 at -28°C.
[0033] It is further estimated that the heteroplastic propylene copolymer (RAHECO) according to this invention additionally has the first glass transition temperature Tg(1) (which represents the matrix (M) of the heteroplastic propylene copolymer (RAHECO)) in the range from -5 to +12°C, more preferably in the range from 0 to +10°C, such as in the range from +2 to +8°C.
[0034] The heteroplastic propylene copolymer (RAHECO) according to this invention is preferably α-nucleated, i.e. comprises an α-nucleating agent. Even more preferred, the present heteroplastic propylene copolymer (RAHECO) is free of e-nucleating agents. The α-nucleating agent, if present, is preferably selected from the group consisting of (i) salts of monocarboxylic acids and monocarboxylic acids, for example, sodium benzoate or aluminum tert-butylbenzoate and (ii) dibenzylidenesorbitol (for example, 1,3 : 2,4dibenzylidenesorbitol) and C1-C8 alkyl substituted dibenzylidenesorbitol derivatives, such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g., 1,3 :2,4 di(methylbenzylidene)sorbitol), or substituted nonitol derivatives, such as 1,2,3,-trideoxy- 4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol and (iii) salts of phosphoric acid diesters, e.g. ,2'-methylenebis(4,6,-di-tert-butylphenyl)sodium or aluminum-hydroxy-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate] and(iv) vinylcycloalkane polymer and vinylalkane polymer (as discussed in more detail below) and (v) mixtures thereof.
[0035] Such additives are generally commercially available and are described, for example, in "Plastic Additives Handbook", 6th edition, 2009 of Hans Zweifel (pages 967 to 990).
[0036] The ester of the heteroplastic propylene copolymer a-nucleating agent (RAHECO) is preferably up to 5.0% by weight. In a preferred embodiment, the heteroplastic propylene copolymer (RAHECO) contains no more than 3000 ppm, more preferably 1 to 2000 ppm of an α-nucleating agent, in particular selected from the group consisting of dibenzylidenesorbitol (for example, 1.3 : 2.4 dibenzylidene sorbitol), dibenzylidene sorbitol derivative, preferably dimethyldibenzylidene sorbitol (for example 1.3 : 2.4 di(methylbenzylidene) sorbitol), or substituted nonitol derivatives such as 1,2,3,- trideoxy- 4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer and mixtures thereof.
[0037] In a preferred embodiment, the heteroplastic propylene copolymer (RAHECO) contains a vinylcycloalkane, such as vinylcyclohexane (VCH), vinylalkane polymer and/or polymer, as the preferred α-nucleating agent. Preferably, in this embodiment the propylene copolymer contains a vinylcycloalkane such as vinylcyclohexane (VCH), vinylalkane polymer and/or polymer, preferably vinylcyclohexane (VCH). more preferably the amount of vinylcycloalkane, such as vinylcyclohexane (VCH), polymer and/or vinylalkane polymer, more preferably vinylcyclohexane (VCH) polymer, in the heteroplastic propylene copolymer (RAHECO) is not greater than 500 ppm, more preferably from 1 to 200 ppm, more preferably 5 to 100 ppm.
[0038] The a-nucleating agent can be introduced as a masterbatch. Alternatively, some α-nucleating agents as defined in the present invention can also be introduced by BNT technology.
[0039] The a-nucleation agent can be introduced to the heteroplastic propylene copolymer (RAHECO), for example, during the polymerization process of the heteroplastic propylene copolymer (RAHECO) or can be incorporated into the heteroplastic propylene copolymer (RAHECO) in the masterbatch form (MB) together with, for example, a carrier polymer.
[0040] In the case of the masterbatch (MB) incorporation modality, the masterbatch (MB) contains an α-nucleating agent, which is preferably a polymeric α-nucleating agent, more preferably a vinylcycloalkane such as vinylcyclohexane ( VCH), polymer and/or vinylalkane polymer, preferably vinylcyclohexane (VCH) polymer, as defined above or below, in an amount of not greater than 500 ppm, more preferably from 1 to 200 ppm and even more preferably from 5 at 100 ppm, based on the weight of the masterbatch (MB) (100% by weight). In this embodiment, more preferably, said masterbatch (MB) is present in an amount of not greater than 10.0% by weight, more preferably not greater than 5.0% by weight and most preferably not greater than 3, 5% by weight, with the preferred amount of masterbatch (MB) being from 1.5 to 3.5% by weight, based on the total amount of the heteroplastic propylene copolymer (RAHECO). More preferably, the masterbatch (MB) comprises, preferably consists of homopolymer or copolymer, preferably homopolymer, of propylene which has been nucleated according to BNT technology as known in the art. With respect to BNT technology, reference is made to international applications WO 99/24478, WO 99/24479 and particularly WO 00/68315.
[0041] In another preferred aspect, the heteroplastic propylene copolymer (RAHECO) of the invention has a tensile modulus measured in accordance with ISO 527-1 at 23°C of at least 500 MPa, more preferably in the range of 500 to 900 MPa, even more preferably in the range of 520 to 800 MPa;e/orb) soluble hexane content determined according to an FDA method in 100 µm cast films below 3.0% by weight, more preferably in the range above 0 .8 to below 3.0% by weight, even more preferably in the range of 1.0 to 2.8% by weight.
[0042] The heteroplastic propylene copolymer (RAHECO) also comprises, apart from propylene, other comonomers. Therefore it is preferred that the total comonomer content of the heteroplastic propylene copolymer (RAHECO) is in the range of 12.0 to 35.0% by weight, more preferably in the range of 15.0 to 30.0% by weight, even more preferably in the range of 18.0 to 28.0% by weight, such as in the range of 19.0 to 25.0% by weight.
[0043] As mentioned above and explained in more detail below the heteroplastic propylene copolymer (RAHECO) comprises a matrix (M) being a propylene - C4 to C12 α-olefin copolymer (C-PP) and an elastomeric propylene copolymer ( EC) comprising units derivable from propylene and at least ethylene. Accordingly, the heteroplastic propylene copolymer (RAHECO) according to this invention is understood to be a polypropylene comprising, preferably consisting of, units derivable from (a) propylene, (b) ethylene, and (c) α-olefin C4 to C12 , preferably α-olefin C4 to C8, more preferably at least one, similar to an α-olefin selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, still more preferably at least one similar to an α-olefin selected from the group consisting of 1-butene, 1-hexene and 1-octene, even more preferably 1-butene and/or 1-hexene, such as 1-hexene.
[0044] Thus, when specifying the total comonomer content of the heteroplastic propylene copolymer (RAHECO), the total number of units (based on the total weight of the heteroplastic propylene copolymer (RAHECO)) derivable from ethylene and α-olefin C4 to C12, more preferably derivable from ethylene and 1-butene and/or 1-hexene, as derivable from ethylene and 1-hexene, is understood.
[0045] Preferably, the heteroplastic propylene copolymer (RAHECO) according to the invention preferably satisfies inequality (I), more preferably inequality (Ia), even more preferably inequality (Ib), even more preferably inequality (Ic);
where C2(total) is the ethylene content [in % by weight] of the heteroplastic propylene copolymer (RAHECO); Cx(total) is the content of α-olefin C4 to C12, preferably content of 1-butene and/or 1 -hexene, [in % by weight] of the heteroplastic propylene copolymer (RAHECO).
[0046] It is therefore preferred that the ethylene content of the heteroplastic propylene copolymer (RAHECO) is in the range of 12.0 to 33.0% by weight, more preferably in the range of 15.0 to 30.0% by weight, even more preferably in the range of 16.0 to 25.0% by weight.
[0047] In addition or alternatively to the ethylene content, it is preferred that the α-olefin content C4 to C12, preferably 1-butene and/or 1-hexene content, as the 1-hexene content, of the copolymer of heteroplastic propylene (RAHECO) is in the range of 0.5 to 6.0% by weight, more preferably in the range of 1.0 to 5.0% by weight, even more preferably in the range of 1.2 to 4.5% by weight, even more preferably in the range of 1.5 to 4.0% by weight.
[0048] The cold soluble xylene fraction (XCS) measured in accordance with ISO 16152 (25°C) of the heteroplastic propylene copolymer (RAHECO) is in the range of 10.0 to equal to or below 40.0% by weight, preferably in the range of 12.0 to 30.0% by weight, more preferably in the range of 12.0 to 25.0% by weight, even more preferably in the range of 12.0 to 23.0% by weight.
[0049] The remaining part is the cold insoluble fraction in xylene (XCI) of the heteroplastic propylene copolymer (RAHECO). Consequently, the xylene cold insoluble fraction (XCI) of the heteroplastic propylene copolymer (RAHECO) is in the range of equal to or below 60.0 to 90.0% by weight, preferably in the range of 70.0 to 88.0% by weight. weight, more preferably in the range of 75.0 to 88.0% by weight, even more preferably in the range of 77.0 to 88.0% by weight.
[0050] The total comonomer content, that is, ethylene and α-olefin content C4 to C12 together, of the cold insoluble fraction in xylene (XCI) of the heteroplastic propylene copolymer (RAHECO) is in the range of 3.0 to 12 0.0% by weight, more preferably in the range of 4.0 to 10.0% by weight, even more preferably in the range of 5.0 to 9.5% by weight, even more preferably in the range of 5.5 to 9 0.0% by weight.
[0051] The comonomers present in the cold insoluble fraction in xylene (XCI) are those defined above, i.e. (i) ethylene and (ii) α-olefin C4 to C12, preferably α-olefin C4 to C8, more preferably at least one, similar to an, α-olefin selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, even more preferably at least one, similar to one, α-olefin selected from the group consisting of 1-butene, 1-hexene and 1-octene, even more preferably 1-butene and/or 1-hexene, such as 1-hexene.
[0052] Preferably, the ethylene content of the cold insoluble fraction in xylene (XCI) of the heteroplastic propylene copolymer (RAHECO) is in the range of 2.0 to 11.0% by weight, more preferably in the range of 3.0 to 9.0% by weight, even more preferably in the range of 3.5 to 8.0% by weight, even more preferably in the range of 4.0 to 7.0% by weight, such as in the range of 4.5 to 6 .5% by weight.
[0053] Preferably, the content of α-olefin C4 to C12, for example, the content of 1-butene and/or content of 1-hexene, of the cold insoluble fraction in xylene (XCI) of the heteroplastic propylene copolymer (RAHECO) is in the range of 0.5 to 6.0% by weight, more preferably in the range of 1.0 to 5.5% by weight, even more preferably in the range of 1.5 to 5.0% by weight, even more preferably in the range from 1.8 to 4.5% by weight, such as in the range from 2.0 to 4.0% by weight.
Therefore, it is especially preferred that the heteroplastic propylene copolymer (RAHECO) satisfies inequality (II), more preferably inequality (IIa), even more preferably inequality (IIb), even more preferably inequality (IIc);
where C2(XCI) is the ethylene content [in % by weight] of the cold insoluble fraction in xylene (XCI) of the heteroplastic propylene copolymer (RAHECO); Cx(XCI) is the content of α-olefin C4 to C12 [in % by weight], preferably the 1-hexene content [in % by weight], of the cold xylene insoluble fraction (XCI) of the heteroplastic propylene copolymer (RAHECO).
[0055] With respect to the xylene-soluble cold fraction (XCS) of the heteroplastic propylene copolymer (RAHECO) the following is especially preferred.
[0056] Preferably, the cold soluble xylene fraction (XCS) of the heteroplastic propylene copolymer (RAHECO) has an intrinsic viscosity (IV) measured in accordance with ISO 1628/1 (at 135°C in dekaline) of at least 1 .2 dl/g, more preferably in the range of 1.2 to 2.5 dl/g, more preferably in the range of 1.4 to 2.2 dl/g, even more preferably in the range of 1.5 to 2, 0 dl/g.
[0057] Additionally, it is preferred that the total comonomer content and/or xylene content of the xylene-soluble cold fraction (XCS) of the heteroplastic propylene copolymer (RAHECO) is in the range of 30.0 to 90.0% by weight even more preferably in the range of 50.0 to 90.0% by weight, even more preferably in the range of 60.0 to 90.0% by weight, such as in the range of 70.0 to 85.0% by weight. The comonomers present in the cold xylene soluble fraction (XCS) are those defined above, i.e. (i) ethylene and optionally (ii) C4 to C12 α-olefin, preferably C4 to C8 α-olefin, more preferably at least one, similar to an α-olefin selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, even more preferably at least one, similar to an α-olefin selected from the group which it consists of 1-butene, 1-hexene and 1-octene, even more preferably 1-butene and/or 1-hexene, such as 1-hexene.
[0058] Additionally, it is preferred that the heteroplastic propylene copolymer (RAHECO) according to the invention satisfies inequality (III), more preferably inequality (IIIa), even more preferably inequality (IIIb),
whereC(XCS) the total comonomer content [in % by weight] of the xylene-soluble cold fraction (XCS) of the heteroplastic propylene copolymer (RAHECO); C(total) the total comonomer content [in % by weight] of the heteroplastic propylene copolymer (RAHECO).
[0059] In addition or alternatively to inequality (III) it is preferred that the heteroplastic propylene copolymer (RAHECO) satisfies inequality (IV), more preferably inequality (IVa), even more preferably inequality (IVb), even more preferably inequality (IVc),
where C2(XCS) is the ethylene content [in % by weight] of the cold xylene fraction (XCS) of the heteroplastic propylene copolymer (RAHECO); C2(total) is the ethylene content [in % by weight] of the copolymer of heteroplastic propylene (RAHECO).
[0060] Additionally, it is preferred that the heteroplastic propylene copolymer (RAHECO) satisfies inequality (V), more preferably inequality (Va), even more preferably inequality (Vb),
where C2(XCS) is the ethylene content [in % by weight] of the xylene-soluble cold fraction (XCS) of the heteroplastic propylene copolymer (RAHECO); C(XCI) is the total comonomer content [in % by weight], that is, the ethylene content and α-olefin content C4 to C12 together, of the cold insoluble fraction in xylene (XCI) of the heteroplastic propylene copolymer (RAHECO).
[0061] In a specific preferred embodiment the heteroplastic depropylene copolymer (RAHECO) satisfies inequality (VI), more preferably inequality (VIa), even more preferably inequality (VIb), even more preferably inequality (VIc),
where C2(XCS) is the ethylene content [in % by weight] of the cold-soluble xylene fraction (XCS) of the heteroplastic propylene copolymer (RAHECO); C2(XCI) is the ethylene content [in % by weight] of the insoluble fraction cold in xylene (XCI) of the heteroplastic propylene copolymer (RAHECO).
[0062] Finally, it is preferred that the heteroplastic propylene copolymer (RAHECO) according to the invention preferably satisfies inequality (VIII), more preferably inequality (VIIIa), even more preferably inequality (VIIIb),
whereC(XCS) is the total comonomer content, i.e. the ethylene and α-olefin content C4 to C12 together, [in % by weight] of the propyleneheteroplastic copolymer (RAHECO); XCS is the content [in % by weight] weight] of the xylene-soluble cold fraction (XCS) of the heteroplastic propylene copolymer (RAHECO).
[0063] In addition, the a-nucleating agent, heteroplastic propylene copolymer (RAHECO) as defined in the present invention may preferably contain up to 5.0% by weight of additives such as antioxidants, acid decontaminants, stabilizers. UV as well as processing aids such as slip agents and anti-blocking agents. Preferably, the additive content (without α-nucleating agents) is below 3.0% by weight, such as below 1.0% by weight.
[0064] As mentioned above, the heteroplastic propylene copolymer (RAHECO) comprises as main components, the matrix (M) being a propylene - a-olefin copolymer C4 to C12 (C-PP) and the elastomeric propylene copolymer (EC ) dispersed in said matrix (M). Consequently, the heteroplastic propylene copolymer (RAHECO) can still be defined by these individual components, that is, by the propylene - C4 to C12 α-olefin copolymer (C-PP) and the elastomeric propylene copolymer (EC).
Accordingly, the propylene - C4 to C12 α-olefin copolymer (C-PP) according to this invention comprises units derivable from (i) propylene and (ii) at least one, preferably one, C4 to α-olefin C12, as 1-hexene. Thus, propylene - C4 to C12 α-olefin copolymer (C-PP) comprises, consists of monomers copolymerizable with propylene, i.e. C4 to C12 α-olefins, in particular C4 to C8 α-olefins, such as -C4 to C6 olefins, for example 1-butene and/or 1-hexene. Preferably, the propylene - C4 to C12 α-olefin copolymer (C-PP) according to this invention comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of 1-butene, 1-hexene, 1-octene. More specifically, the propylene - C4 to C12 α-olefin copolymer (C-PP) of this invention comprises - apart from propylene - units derivable from 1-butene and/or 1-hexene, preferably from 1-hexene. In a preferred embodiment the propylene - C4 to C12 α-olefin copolymer (C-PP) comprises derivable units of propylene and 1-hexene only, i.e. it is a propylene- 1-hexene copolymer (C6-PP).
[0066] The comonomer content, preferably the content of α-olefin C4 to C12, more preferably the content of 1-butene and/or 1-hexene, such as the content of 1-hexene, of propylene - α-copolymer C4 to C12 olefin (C-PP) is in the range of 1.5 to 9.0% by weight, even more preferably in the range of 2.0 to 6.0% by weight, even more preferably in the range of 2.5 to 5.0% by weight.
[0067] Preferably, the propylene - C4 to C12 α-olefin copolymer (C-PP) has a melt flow rate MFR2 (230°C) in the range of 5.0 to 100.0 g/10 minutes, preferably in the range of 10.0 to 80.0 g/10 min, more preferably in the range of 20.0 to 60.0 g/10 min.
[0068] The cold soluble xylene fraction (XCS) measured according to according to ISO 16152 (25°C) of the propylene - C4 to C12 α-olefin copolymer (C-PP) preferably is below 10.0 % by weight, more preferably in the range of 0.2 to equal to or below 7.0% by weight, even more preferably in the range of 0.8 to 5.0% by weight, more preferably in the range of 0.8 to 2 .5% by weight.
[0069] The propylene copolymer (R-PP) preferably comprises at least two polymer fractions, such as two or three polymer fractions; at least one of these is a propylene - C4 to C12 α-olefin copolymer. Even more preferred, the propylene - C4 to C12 α-olefin copolymer (C-PP) comprises, preferably consists of, a first polypropylene (PP1) fraction and a second propylene - C4 to C12 α-olefin copolymer fraction ( C-PP2). It is especially preferred that the propylene - C4 to C12 α-olefin copolymer (C-PP) comprises, preferably consists of, a first polypropylene (PP1) fraction and a second propylene - C4 to C12 α-olefin copolymer fraction ( C-PP2), wherein the comonomer content in the first polypropylene fraction (PP1) is mostly 4.0% by weight.
[0070] The weight ratio between the first polypropylene fraction (PP1), for example, the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), and the second propylene - α copolymer fraction -C4 to C12 olefin (C-PP2) [(PP1)/(C-PP2)] is in the range of 30/70 to 70/30, more preferably in the range of 35/65 to 65/35, as in the range of 40/60 to 55/45.
[0071] It is preferred that the first fraction of polypropylene (PP1), for example, the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), is the weak fraction of comonomer, for example, the fraction weak α-olefin C4 to C12, whereas the second propylene - α-olefin C4 to C12 copolymer fraction (C-PP2) is the rich comonomer fraction, eg the rich α-olefin fraction C4 to C12 . Consequently, in a preferred embodiment, the comonomer content, as the content of α-olefin C4 to C12, [in % by weight] in the propylene - α-olefin copolymer C4 to C12 (C-PP) is greater than in the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1).
[0072] In this way, it is preferred that the first fraction of polypropylene (PP1), eg the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), has instead low comonomer content , for example, instead of low content of α-olefin C4 to C12.
[0073] It is therefore preferred that the first polypropylene (PP1) fraction of the heteroplastic propylene copolymer (RAHECO) is (a) a propylene homopolymer (H-PP1) fraction; or (b) a first propylene - C4 to C12 α-olefin copolymer fraction (C-PP1), preferably said first propylene - C4 to C12 α-olefin copolymer fraction (C-PP1) has a content of α -C4 to C12 olefin in the range of 0.5 to 4.0% by weight.
[0074] It is especially preferred that the first polypropylene (PP1) fraction is a first propylene - C4 to C12 α-olefin copolymer fraction (C-PP1) as defined herein.
[0075] The expression homopolymer of propylene, for example, the first homopolymer of propylene (fraction) (H-PP1), used in the present invention refers to a polypropylene consisting substantially, that is, of more than 99.0 mol%, such as at least 99.5 mol%, even more preferably at least 99.7 mol%, of propylene units. In a preferred embodiment, only propylene units in the propylene homopolymer, e.g., the first propylene homopolymer (fraction) (H-PP1), are detectable.
[0076] In this case, the first polypropylene fraction (PP1) is a first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), comprises units derivable from (i) propylene and (ii) at least one is preferably a C4 to C12 α-olefin such as 1-hexene. In this way, the first propylene - α-olefin C4 to C12 copolymer fraction (C-PP1) comprises, consists of monomers copolymerizable with propylene, i.e., α-olefins C4 to C12, in particular α-olefins C4 to C8 , as C4 to C6 α-olefins, for example 1-butene and/or 1-hexene. Preferably, the first propylene - C4 to C12 α-olefin copolymer fraction (C-PP1) according to this invention comprises, consists especially of monomers copolymerizable with propylene from the group consisting of 1-butene, 1-hexene, 1 -octene. More specifically, the first propylene - C4 to C12 α-olefin copolymer (C-PP1) fraction of this invention comprises - apart from propylene - units derivable from 1-butene and/or 1-hexene, preferably from 1-hexene. In a preferred embodiment the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1) comprises derivable units of propylene and 1-hexene only, i.e. is a first fraction of propylene-copolymer of 1-hexene fraction (C6-PP1).
[0077] The comonomer content, preferably the content of α-olefin C4 to C12, more preferably the content of 1-butene and/or 1-hexene, such as the content of 1-hexene, of the first propylene - copolymer fraction of C4 to C12 α-olefin (C-PP1) is in the range of 0.5 to 4.0% by weight, even more preferably in the range of 0.5 to 3.5% by weight, even more preferably in the range of 0.7 to 3.0% by weight.
[0078] It is further preferred that the amount of the xylene-soluble cold fraction (XCS) of the first polypropylene fraction (PP1), for example, of the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), is at or below 4.0% by weight, more preferably is in the range of 0.5 to 3.5% by weight, even more preferably is in the range of 0.8 to 2.5% by weight.
[0079] Preferably, the first polypropylene fraction (PP1), for example the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), has a melt flow rate MFR2 (230°C) in the range of 5.0 to 100.0 g/10 minutes, preferably in the range of 10.0 to 80.0 g/10 min, more preferably in the range of 20.0 to 60.0 g/10 minutes.
[0080] The second fraction of propylene - α-olefin copolymer C4 to C12 (C-PP) is the fraction copolymer, that is, the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2), having a higher comonomer content, preferably higher content of α-olefin C4 to C12, more preferably higher content of 1-butene and/or 1-hexene, such as higher content of 1-hexene, than the first polypropylene fraction (PP1 ).
[0081] It is especially preferred that the difference in comonomer content, preferably the content of α-olefin C4 to C12, more preferably the content of 1-butene and/or 1-hexene, as the content of 1-hexene, between propylene - α-olefin copolymer C4 to C12 (C-PP) and the first polypropylene fraction (PP1), for example, the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), [ (C-PP) — (PP1)] differs by at least 1.5% by weight; more preferably by 1.5 to 6.0% by weight, even more preferably by 1.5 to 4.0% by weight, even more preferably by 1.8 to 3.5% by weight.
[0082] In this way, it is preferred that the second propylene - C4 to C12 α-olefin copolymer fraction (C-PP2) has a comonomer content, preferably C4 to C12 α-olefin content, more preferably 1- content butene and/or 1-hexene, as 1-hexene content, equal to or above 2.0% by weight, more preferably in the range of 2.0 to 15.0% by weight, such as 2.0 to 10.0 % by weight, even more preferably in the range of 3.0 to 8.0% by weight.
[0083] Consequently, it is still preferred that the docomonomer content. preferably the content of α-olefin C4 to C12, more preferably the content of 1-butene and/or 1-hexene, as the content of 1-hexene, between the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2) and the first polypropylene fraction (PP1), for example, the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), [(R-PP2) - (PP1)] differs by at least 2.5% by weight, more preferably by 2.5 to 10.0% by weight, such as by 3.0 to 10.0% by weight, even more preferably by 3.0 to 8.0% by weight. weight, even more preferably from 3.0 to 6.0% by weight.
[0084] The second propylene - C4 to C12 α-olefin copolymer fraction (C-PP2) comprises units derivable from (i) propylene and (ii) at least one, preferably one, C4 to C12 α-olefin, such as 1 -hexene. In this way, the second propylene - α-olefin C4 to C12 copolymer fraction (C-PP2) comprises, consists of monomers copolymerizable with propylene, i.e., α-olefins C4 to C12, in particular α-olefins C4 to C8 , as C4 to C6 α-olefins, for example 1-butene and/or 1-hexene. Preferably, the second propylene - C4 to C12 α-olefin copolymer fraction (C-PP2) according to this invention comprises, consists especially of monomers copolymerizable with propylene from the group consisting of 1-butene, 1-hexene, 1 -octene. More specifically, the second propylene - C4 to C12 α-olefin copolymer (C-PP2) fraction of this invention comprises - apart from propylene - units derivable from 1-butene and/or 1-hexene, preferably from 1-hexene. In a preferred embodiment the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2) comprises derivable units of propylene and 1-hexene only, i.e. it is a second propylene-copolymer of 1-hexene fraction (C6 -PP2).
[0085] In a particular preferred embodiment, the propylene - α-olefin copolymer C4 to C12 (C-PP) comprises, preferably consists of, the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1) and the second propylene - C4 to C12 α-olefin copolymer fraction (C-PP2), wherein both fractions comprise, consist of, derivable units of propylene and at least one C4 to C12 α-olefin, more preferably of propylene and a C4 to C12 α-olefin, even more preferably from propylene and 1-hexene or from propylene and 1-butene. In a specific preferred embodiment the propylene - α-olefin copolymer C4 to C12 (C-PP) comprises, preferably consists of, the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1) and the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2), both fractions comprising, consisting of, propylene and 1-hexene only.
[0086] Preferably, the weight ratio between the first matrix (M), i.e. the propylene - α-olefin copolymer C4 to C12 (C-PP), and the elastomeric propylene copolymer (EC) is in the range of 15/1 to 2/1, more preferably in the range of 10/1 to 5/2, even more preferably in the range of 8/1 to 3/1.
[0087] Consequently, in a preferred embodiment, the heteroplastic propylene copolymer (RAHECO) preferably comprises 65 to 95% by weight, more preferably 70 to 90% by weight, of the matrix (M), i.e. of the propylene - copolymer of α-olefin C4 to C12 (C-PP), based on the total weight of the heteroplastic propylene copolymer (RAHECO).
[0088] Additionally, the heteroplastic propylene copolymer (RAHECO) preferably comprises 5 to 35% by weight, more preferably 10 to 30% by weight, of the elastomeric (EC) propylene copolymer, based on the total weight of the heteroplastic propylene copolymer (RAHECO).
[0089] In this way, it is estimated that the heteroplastic propylene copolymer (RAHECO) preferably comprises, more preferably consists of, 65 to 95% by weight, more preferably 70 to 90% by weight, of the matrix (M), i.e. of the propylene - C4 to C12 α-olefin copolymer (C-PP) and 5 to 35% by weight, more preferably 10 to 30% by weight, of the elastomeric (EC) propylene copolymer, based on the total weight of the copolymer of heteroplastic propylene (RAHECO).
[0090] Consequently, another component of the heteroplastic propylene copolymer (RAHECO) is the elastomeric propylene copolymer (EC) dispersed in the matrix (M). The elastomeric (EC) propylene copolymer comprises units derivable from (i) propylene and (ii) ethylene and optionally at least one C4 to C12 α-olefin.
[0091] Consequently, the elastomeric propylene copolymer (EC) comprises monomers copolymerizable with propylene, i.e., ethylene and optionally at least one C4 to C12 α-olefin, such as a C4 to C12 α-olefin, in particular ethylene and optionally one α-olefin C4 to C6, for example 1-butene and/or 1-hexene. Preferably, the elastomeric (EC) propylene copolymer comprises, consists especially of, propylene, ethylene, and optionally 1-butene and 1-hexene. More specifically, the elastomeric propylene (EC) copolymer comprises - apart from propylene - derivable units of ethylene and optionally 1-hexene. Thus, in one embodiment the elastomeric propylene copolymer (EC) comprises derivable units of ethylene and propylene only, that is, it is an ethylene-propylene rubber (EPR).
[0092] The comonomer content, preferably the ethylene and α-olefin content C4 to C12 together, more preferably the ethylene content, of the elastomeric propylene copolymer (EC) preferably is in the range of 40.0 to 95.0% by weight, even more preferably in the range of 40.0 to 90.0% by weight, even more preferably in the range of 50.0 to 90.0% by weight, such as in the range of 70.0 to 90.0% by weight. Weight.
[0093] The present invention is not only directed to the present heteroplastic propylene copolymer (RAHECO) but also to articles, preferably to an article selected from the group consisting of bag (medical), food packaging article, film, such as non-oriented film and bottle. Accordingly, in a further embodiment, the present invention is directed to an article, especially an article selected from the group consisting of bag (medical), food packaging article, film, such as non-oriented film (i.e. cast film or film inflated, for example, or air-cooled inflated film), and bottle, which comprises at least 70.0% by weight, preferably which comprises at least 80.0% by weight, more preferably which comprises at least 90.0% by weight weight, even more preferably comprising at least 95.0% by weight, even more preferably comprising at least 99.0% by weight, of the present heteroplastic propylene copolymer (RAHECO).
[0094] One distinguishes between unoriented and oriented films (see eg polypropylene handbook, Nello Pasquini, 2nd edition, Hanser). Oriented films are typically monoaxial or biaxially oriented films, whereas unoriented films are cast or blown films. Consequently, an unoriented film is not withdrawn intensively in the machine and/or transverse direction as performed by the oriented films. In this way, the unoriented film according to this invention is not a monoaxial or biaxially oriented film. Preferably, the unoriented film according to the present invention is an inflated film or cast film.
[0095] In a specific embodiment, the unoriented film is a cast film or an air-cooled inflated film.
[0096] Preferably, the unoriented film has a thickness of 10 to 1000 µm, more preferably 20 to 700 µm, such as 40 to 500 µm.
[0097] The present invention is also directed to the use of heteroplastic propylene copolymer (RAHECO) in the manufacture of an article selected from the group consisting of bags (medical), food packaging systems, films, such as non-oriented films (i.e., cast film or blown film, such as either blown films cooled with air or blown films quenched with water) and bottles.
[0098] The present heteroplastic propylene copolymer (RAHECO) is preferably produced in a multi-stage process comprising at least two reactors, preferably at least three reactors, connected in series.
[0099] Consequently, the heteroplastic propylene copolymer (RAHECO) according to this invention is produced by polymerizing: (I) propylene and at least one C4 to C12 α-olefin, preferably a C4 to C12 α-olefin, more preferably 1 -butene and/or 1-hexene, such as 1-hexene, in order to form the matrix (M) with propylene - α-olefin copolymer C4 to C12 (C-PP) and subsequently polymerize (II) propylene and ethylene and optionally at least one C4 to C12 α-olefin, preferably propylene and ethylene, in the gas phase to form the elastomeric propylene copolymer (EC) dispersed in said matrix (M); wherein preferably both steps (I) and (II) take place in the presence of the same solid, single-site particulate catalyst preferably free of an external carrier, more preferably a catalyst comprising (i) a complex of formula (I) as defined in details below.
[00100] Preferably, the heteroplastic propylene copolymer (RAHECO) is obtained by a sequential polymerization process comprising the steps of (a) polymerizing in a first reactor (i) propylene and (ii) optionally at least one C4 α-olefin to C12, preferably a C4 to C12 α-olefin, more preferably 1-butene and/or 1-hexene, such as 1-hexene, thereby obtaining a first fraction of polypropylene (PP1), for example a first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1),(b) transferring said first polypropylene fraction (PP1), preferably said first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1 ), in a second reactor, (c) polymerize in said second reactor in the presence of the first polypropylene fraction (PP1), preferably in the presence of the first propylene - C4 to C12 α-olefin copolymer fraction (C-PP1), ( i) propylene and (ii) at least one C4 to C12 α-olefin, preferably a C4 to C12 α-olefin, more preferably preferably 1-butene and/or 1-hexene, as 1-hexene, obtain a second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2), said first polypropylene fraction (PP1), preferably said first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), and said second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2) forms the matrix (M), ie, propylene - α-olefin copolymer C4 to C12 (C-PP), (d) transfer said matrix (M) to a third reactor, (e) polymerize in said third reactor, in the presence of matrix (M), propylene and ethylene and optionally at least one C4 to C12 α-olefin, preferably propylene and ethylene, to obtain an elastomeric propylene copolymer (EC), said matrix (M) and said elastomeric propylene copolymer (EC) form the propylene copolymer heteroplastic (RAHECO), wherein the steps preferably take place in the presence of the same single-site solid particulate catalyst preferably free of an external carrier. o, more preferably a catalyst comprising (i) a complex of formula (I) as defined in detail below.
[00101] For the preferred embodiments of heteroplastic propylene copolymer (HECO), propylene - α-olefin copolymer C4 to C12 (C-PP), the first polypropylene fraction (PP1), as the first propylene - copolymer fraction of α-olefin C4 to C12 (C-PP1), the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2) and the elastomeric copolymer (EC) reference is made to the definitions given above.
[00102] The term "sequential polymerization process" indicates that heteroplastic propylene copolymer (HECO) is produced in at least two, such as three, reactors connected in series. Consequently, the present process comprises at least a first reactor, a second reactor and optionally a third reactor. The term “polymerization process” should indicate that the main polymerization takes place. Thus, in this case, the process consists of three polymerization reactors, this definition does not exclude the option that the total process comprises, for example, a pre-polymerization step, for example a pre-polymerization step in a pre-polymerization reactor. -polymerization. The term “consists of” is just a closing formulation in view of the main polymerization process.
[00103] The first reactor is preferably a slurry reactor and may be any continuous or simple stirred batch tank reactor or arc reactor operating in bulk or slurry. Mass means a polymerization in a reaction medium comprising at least 60% (w/w) of monomer. According to the present invention, the pulp reactor is preferably an arc (mass) reactor.
[00104] The second reactor and the third reactor are preferably gas phase reactors. Such gas phase reactors can be any mechanically mixed or fluid bed reactors. Preferably, the gas phase reactors comprise a mechanically stirred fluid bed reactor with gas velocities of at least 0.2 m/sec. In this way, it is estimated that the gas phase reactor is a fluidized bed type reactor preferably with a mechanical stirrer.
[00105] In this way, in a preferred embodiment the first reactor is a slurry reactor, such as arc reactor, since the second reactor and the third reactor are gas phase reactors (GPR). Consequently, for the present process at least three, preferably three polymerization reactors, i.e. a slurry reactor such as arc reactor, a first gas-phase reactor and a second gas-phase reactor are connected in series. If required from the slurry reactor a pre-polymerization reactor is placed.
[00106] A preferred multi-stage process is a "gas arc-phase" process as developed by Borealis A/S, Denmark (known as BORSTAR® technology) described, for example, in the patent literature 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.
[00107] Another suitable gas-phase paste process is the Spheripol® process from Basell.
[00108] Preferably, in the present process to produce the heteroplastic propylene copolymer (RAHECO) as defined above the conditions for the first reactor, that is, the slurry reactor, such as an arc reactor, 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 65 and 95°C, - the pressure is within the range of 20 bar to 80 bar, preferably between 40 bar at 70 bar, hydrogen can be added to control the molar mass in a manner known to you.
[00109] Subsequently, the reaction mixture from the first reactor is transferred to the second reactor, i.e. gas phase reactor, where the conditions are preferably as follows:- the temperature is within the range of 50°C to 130°C, preferably between 60°C and 100°C, - the pressure is within the range of 5 bar to 50 bar, preferably between 15 bar to 35 bar, - hydrogen can be added to control the molar mass in a manner known per se.
[00110] The condition in the third reactor is similar to the second reactor.
[00111] Residence time may vary in the three reactors.
[00112] In one embodiment of the process for producing heteroplastic propylene copolymer (RAHECO) the residence time in the mass reactor, for example, arc is in the range of 0.1 to 2.5 hours, for example, from 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 0.3 to 4.0 hours.
[00113] If desired, polymerization can be carried out in a known manner under supercritical conditions in the first reactor, that is, in the slurry reactor, as in the arc reactor and/or as a condensed mode in gas phase reactors.
[00114] In the following, the catalyst component is defined in more detail. Preferably, the catalyst comprises (i) a complex of the formula (I): (i) a transition metal compound of the formula (I) Rn(Cp')2MX2(I) wherein "M" is zirconium (Zr) or hafnium (Hf), each "X" is independently a monovalent anionic o-ligand, each "Cp'" is a cyclopentadienyl-type organic ligand independently selected from the group consisting of substituted cyclopentadienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted fluorenyl or unsubstituted, said transition metal coordinated organic ligands (M), "R" is a bridging group linking said organic ligands (Cp'), "n" is 1 or 2, preferably 1 and( ii) a cocatalyst comprising a compound of a metal group 13, for example Al or boron compound.
[00115] In a specific embodiment, the single-site solid particulate catalyst has a porosity measured in accordance with ASTM 4641 less than 1.40 ml/g and/or a surface area measured in accordance with ASTM D 3663 less than 25 m2/g.
[00116] Preferably, the single site solid particulate catalyst has a surface area less than 15 m2/g, even less than 10 m2/g and preferably less than 5 m2/g, which is the lower measurement limit . The surface area in accordance with this invention is measured in accordance with ASTM D 3663 (N2).
[00117] Alternatively or additionally, the single site solid particulate catalyst is estimated to have a porosity less than 1.30 ml/g and more preferably less than 1.00 ml/g. Porosity was measured according to ASTM 4641 (N2). In another preferred embodiment, porosity is not detectable when determined with the applied method in accordance with ASTM 4641 (N2).
[00118] Furthermore, the single-site solid particulate catalyst typically has an average particle size not greater than 500 µm, i.e. preferably in the range of 2 to 500 µm, more preferably 5 to 200 µm. In particular, it is preferred that the average particle size is below 80 µm, even more preferably below 70 µm. A preferred range for the average particle size is 5 to 70 µm or even 10 to 60 µm.
[00119] As stated above, the transition metal (M) is zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).
[00120] The term "o-ligand" is understood in the full description in a known manner, that is, a group bonded to the metal via a sigma bond. In this way, the “X” anionic ligands can be independently halogen or be selected from the group consisting of the group R', OR', SiR'3, OSiR'3, OSO2CF3, OCOR', SR', NR'2 or PR' 2 wherein R' is independently hydrogen, a C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C3 to C12 cycloalkyl, C6 to C20 aryl, C7 to C20 arylalkyl, C7 to C20 alkylaryl, C8 to C20 linear arylkenyl u branched, cyclic or acyclic, wherein the R' group may optionally contain one or more heteroatoms belonging to groups 14 to 16. In a preferred embodiment, the anionic linkers "X" are identical and halogen, such as Cl or methyl or benzyl .
[00121] A preferred monovalent anionic ligand is halogen, in particular chlorine (Cl).
[00122] Substituted cyclopentadienyl type linkers may have one or more substituents being selected from the group consisting of halogen, hydrocarbyl (for example, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C3 to C20 cycloalkyl, such as alkyl C1 to C20 substituted C5 to C20 cycloalkyl, C6 to C20 aryl, C1 to C20 alkyl substituted by C5 to C20 cycloalkyl wherein the cycloalkyl residue is substituted by C1 to C20 alkyl, C7 to C20 arylalkyl, C3 to C12 cycloalkyl containing 1, 2, 3 or 4 heteroatoms in the ring portion, C6 to C20 heteroaryl, C1 to C20 haloalkyl, -SiR"3 , -SR", -PR"2 or -NR"2, each R'' is independently hydrogen or hydrocarbyl (for example, C1 to C20 alkyl, C1 to C20 alkenyl, C2 to C20 alkynyl, C3 to C12 cycloalkyl, or C6 to C20 aryl) or, for example, in the case of -NR"2, the two R" substituents can form a ring, eg five- or six-membered ring, together with the nitrogen atom to which they are attached.
[00123] Still the "R" of formula (I) is preferably a bridge of 1 to 4 atoms, such atoms being independently carbon atoms (C), silicon (Si), germanium (Ge) or oxygen (O), seen that each of the bridged atoms may carry substituents independently, such as C1 to C20 hydrocarbyl, tri(C1 to C20 alkyl)silyl, tri(C1 to C20 alkyl)siloxy and more preferably "R" is an atomic bond such as, -SiR"'2-, wherein each R"'' is independently C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C3 to C12 cycloalkyl, C6 to C20 aryl, alkylaryl or arylalkyl, or tri( C1 to C20 alkylsilyl-, such as trimethylsilyl-, or both R''' may be part of a ring system including the Si linking atom.
[00124] In a preferred embodiment, the transition metal compound has formula (II)
wherein M is zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr), X are binders with an o bond to the metal "M", preferably those as defined above for formula (I), preferably chlorine (Cl) or methyl (CH3), the first especially preferred, R1 is equal to or different from each other, preferably equal to and are selected from the group consisting of saturated linear C1 to C20 alkyl, unsaturated linear C1 to C20 alkyl, saturated branched C1-C20 alkyl , unsaturated branched C1 to C20 alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl and C7 to C20 arylalkyl, optionally containing one or more heteroatoms from groups 14 to 16 of the Periodic Table (IUPAC), preferably is equal to or different from each other, preferably equal to and are C1 to C10 linear or branched hydrocarbyl, more preferably is equal to or different from each other, preferably equal to and are C1 to C6 linear or branched alkyl, R2 to R6 is equal to or different from one on the other and are selected s from the group consisting of hydrogen, saturated linear C1-C20 alkyl, unsaturated linear C1-C20 alkyl, saturated branched C1-C20 alkyl, unsaturated branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 arylalkyl, optionally containing one or more heteroatoms from groups 14 to 16 of the Periodic Table (IUPAC), preferably is the same as or different from each other and are C1 to C10 linear or branched hydrocarbyl, more preferably is the same as or different from each other. from each other and are linear or branched C1 to C6 alkyl, R7 and R8 are the same as or different from each other and selected from the group consisting of hydrogen, linear saturated C1 to C20 alkyl, linear unsaturated C1 to C20 alkyl, C1 to alkyl saturated branched C20, unsaturated branched C1 to C20 alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, C7 to C20 arylalkyl, optionally containing one or more heteroatoms from groups 14 to 16 of the Periodic Table (IUPAC), SiR103 , GeR103, OR10, SR10 and NR102, wherein R10 is selected from the group consisting of saturated linear C1-C20 alkyl, unsaturated linear C1 to C20 alkyl, saturated branched C1 to C20 alkyl, unsaturated branched C1 to C20 alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl and C7 to C20 arylalkyl, optionally containing one or more heteroatoms from groups 14 to 16 of the Periodic Table (IUPAC), and/or R7 and R8 optionally being part of a C4 to C20 carbon ring system together with the indenyl carbons to which these are attached, preferably a C5 ring, optionally a carbon atom may be replaced by a nitrogen, sulfur or oxygen atom, R9 is equal to or different from each other and is selected from the group consisting of hydrogen , saturated linear C1 to C20 alkyl, unsaturated linear C1 to C20 alkyl, saturated branched C1 to C20 alkyl, unsaturated branched C1 to C20 alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 alkylaryl, C7 to C20 arylalkyl, OR10 and SR10, pref Preferably R9 is the same as or different from each other and are H or CH3, wherein R10 is defined as above, L is a bivalent group linking the two indenyl linkers, preferably being a C2R114 unit or a SiR112 or GeR112 unit, wherein, R11 is selected from the group consisting of H, saturated linear C1 to C20 alkyl, unsaturated linear C1 to C20 alkyl, saturated branched C1 to C20 alkyl, unsaturated branched C1 to C20 alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 alkylaryl to C20 or aryl C7 to C20 alkyl, optionally containing one or more heteroatoms from groups 14 to 16 of the Periodic Table (IUPAC), preferably Si(CH3)2, SiCH3C6H11, or SiPh2, wherein C6H11 is cyclohexyl.
[00125] Preferably, the transition metal compound of formula (II) is C2-symmetric or pseudo-C2-symmetric. With regard to the definition of symmetry, it refers to Resconi et al. Chemical Reviews, 2000, Vol. 100, No. 4,1263 and references cited therein.
Preferably, the residues R1 are the same as or different from each other, more preferably the same and are selected from the group consisting of saturated linear C1 to C10 alkyl, unsaturated linear C1 to C10 alkyl, saturated branched C1 to C10 alkyl, alkyl C1 to C10 unsaturated branched and C7 to C12 arylalkyl. Even more preferably, the residues R1 are the same as or different from each other, more preferably the same, and are selected from the group consisting of saturated linear C1 to C6 alkyl, unsaturated linear C1 to C6 alkyl, saturated branched C1 to C6 alkyl, C1 alkyl unsaturated branched C6 and C7 to C10 arylalkyl. Even more preferably, the residues R1 are the same as or different from one another, more preferably the same, and are selected from the group consisting of linear or branched C1 to C4 hydrocarbyl, such as, for example, methyl or ethyl.
[00127] Preferably, the residues R2 to R6 are the same or different from each other and saturated linear C1 to C4 alkyl or saturated branched C1 to C4 alkyl. Even more preferably, the residues R2 to R6 are the same as or different from each other, more preferably the same and are selected from the group consisting of methyl, ethyl, iso-propyl and tert-butyl.
[00128] Preferably, R7 and R8 are the same as or different from each other and are selected from hydrogen and methyl or are part of a 5-methylene ring which includes two carbons of the indenyl ring to which they are attached. In another preferred embodiment, R7 is selected from OCH3 and OC2H5 and R8 is tert-butyl.
In a preferred embodiment the transition metal compound is rac-methyl(cyclohexyl)silanediyl bis(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconium dichloride.
[00130] In a second preferred embodiment, the transition metal compound is rac-dimethylsilanediyl bis(2-methyl-4-phenyl-1,5,6,7-tetrahydro-s-indacen-1-yl dichloride) )zirconium.
In a third preferred embodiment, the transition metal compound is rac-dimethylsilanediyl bis(2-methyl-4-phenyl-5-methoxy-6-tert-butylindenyl)zirconium dichloride.
[00132] As a further requirement, the single-site solid particulate catalyst according to this invention should comprise a cocatalyst comprising a compound of a metal group 13, for example, Al or boron compound
[00133] The borate cocatalysts of B(C6F5)3,C6H5N(CH3)2H:B(C6F5)4, (C6H5)3C:B(C6F5)4 or Ni(CN)4[B(C6F5)3]42 - are especially preferred. Suitable cocatalysts are described in WO2013/007650.
[00134] Examples of Al cocatalysts are organoaluminium compounds, such as aluminoxane compounds.
Such Al compounds, preferably aluminoxanes, can be used as the only compound in the cocatalyst or together with other cocatalyst compounds. In this way, except or in addition to Al compounds, ie aluminoxanes, other cocatalyst compounds that form the cation complex, such as boron compounds, can be used. Such cocatalysts are commercially available or can be prepared according to prior art literature. Preferably, however, in the fabrication of the solid catalyst system only Al compounds as a cocatalyst are used.
In particular preferred cocatalysts are the aluminoxanes, in particular the C1 to C10 alkylaluminoxanes, more particularly methylaluminoxane (MAO).
[00137] Preferably, the organo-zirconium compound or the organohafnium compound of formula (I) or (II) and the single site solid particulate catalyst cocatalyst represent at least 70% by weight, more preferably at least 80 % by weight, even more preferably at least 90 % by weight %, even more preferably at least 95 % by weight of the single site solid particulate catalyst. In this way it is estimated that the single-site solid particulate catalyst is characterized by the fact that it is self-supporting, that is, it does not comprise any catalytically inert support material, such as silica, alumina or MgCl2 or porous polymeric material, which is otherwise way commonly used in heterogeneous catalyst systems, i.e. the catalyst is not supported on the external support or carrier material. As a consequence the single site solid particulate catalyst is self-supporting and has a preferably low surface area.
[00138] In one embodiment the single site solid particulate catalyst is obtained by emulsion solidification technology, the basic principles of which are disclosed in WO 03/051934. This document is attached in its entirety by reference.
[00139] Since the single-site solid particulate catalyst is preferably in the form of solid catalyst particles, obtained by a process comprising the steps of a) Preparation of a solution of one or more catalyst components; b) Dispersion of said solution in a second solvent to form an emulsion wherein said one or more catalyst components are present in the dispersed phase droplets, c) Solidification of said dispersed phase to convert said droplets to solid particles and optionally recover said particles to obtain the said catalyst.
[00140] Preferably, a first solvent, more preferably a first organic solvent, is used to form said solution. Even more preferably the organic solvent is selected from the group consisting of a linear alkane, cyclic alkane, aromatic hydrocarbon and halogen containing hydrocarbon.
[00141] In addition, the second solvent that forms the continuous phase is an inert solvent toward the catalyst components. The second solvent must be immiscible towards the solution of the catalyst components at least under the conditions (such as temperature) during the dispersion step. The term "immiscible with the catalyst solution" means that the second solvent (continuous phase) is either totally immiscible or partly immiscible, i.e. not totally miscible with the dispersed phase solution.
[00142] Preferably, the immiscible solvent comprises a fluorinated organic solvent and/or a functionalized derivative thereof, even more preferably the immiscible solvent comprises a semi, highly or perfluorinated hydrocarbon and/or a functionalized derivative thereof. It is particularly preferred that said immiscible solvent comprises a perfluorohydrocarbon or a functionalized derivative thereof, preferably C3-C30 perfluoroalkanes, -alkenes or -cycloalkanes, more preferred C4-C10 perfluoroalkanes, -alkenes or -cycloalkanes, perfluorohexane particularly Preferred is perfluoroheptane, perfluorooctane or perfluoro (methylcyclohexane) or perfluoro (1,3-dimethylcyclohexane) or a mixture thereof.
[00143] Furthermore, it is preferred that the emulsion comprising said continuous phase and said dispersed phase is a bi- or multiphase system as known in the art. An emulsifier can be used for formation and stabilization of the emulsion. After formation of the emulsion system, said catalyst is formed in situ from catalyst components in said solution.
[00144] In principle, the emulsifying agent can be any suitable agent that contributes to the formation and/or stabilization of the emulsion and that does not have any adverse effect on the catalytic activity of the catalyst. The emulsifying agent may be, for example, a surfactant based on hydrocarbons optionally interrupted with (a) heteroatoms, preferably halogenated hydrocarbons optionally having a functional group, preferably semi-, highly or perfluorinated hydrocarbons as known in the art. Alternatively, the emulsifying agent can be prepared during the preparation of the emulsion, for example, by reacting a precursor with a compound from the catalyst solution. Said surfactant precursor may be a halogenated hydrocarbon with at least one functional group, for example a highly fluorinated C1-n alcohol (suitably C4-30- or C5-15) (for example heptanol, octanol or highly fluorinated nonanol) , oxide (eg, propenoxide) or acrylate ester which react, for example, with a cocatalyst component such as aluminoxane to form the "current" surfactant.
[00145] In principle, any solidification method can be used to form the solid particles from the dispersed droplets. According to a preferred embodiment, solidification is effected by the temperature change treatment. Since the emulsion undergoes gradual temperature change of up to 10°C/min, preferably 0.5 to 6°C/min and more preferably 1 to 5°C/min. Even more preferred the emulsion is subjected to a temperature change of more than 40°C, preferably more than 50°C within less than 10 seconds, preferably less than 6 seconds.
[00146] For further details, the modalities and examples of the continuous and dispersed phase system, emulsion formation method, emulsifying agent and the reference of solidification methods are made, for example, to the International application cited above in WO 03 /051934.
[00147] All or part of the preparation steps can be done in a continuous manner. Reference is made to WO 2006/069733 describing the principles of such a method of continuous or semi-continuous preparation of solid catalyst types prepared by means of the emulsion/solidification method.
[00148] The catalyst components described above are prepared according to the methods described in WO 01/48034.
[00149] Below, the present invention is further illustrated by means of examples. EXAMPLES1. measurement methods
[00150] The following definitions of terms and methods of determination apply to the above general description of the invention, as well as to the examples below unless otherwise defined.
[00151] Calculation of the comonomer content of the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2):
where w(PP1) is the weight fraction [in % by weight] of the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), w(PP2) is the weight fraction [in % by weight] of the secondpropylene - α-olefin copolymer fraction C4 to C12 (C-PP2), C(PP1) is the comonomer content [in % by weight] of the firstpropylene - α-olefin copolymer fraction C4 to C12 (C- PP1),C(PP) is the comonomer content [in % by weight] of the propylene - α-olefin copolymer fraction C4 to C12 (C-PP), C(PP2) is the calculated comonomer content [in % by weight] of the second propylene copolymer fraction (R-PP2).Calculation of cold soluble xylene content (XCS)propylene - α-olefin copolymer fraction C4 to C12 (C-PP2):
where w(PP1) is the weight fraction [in % by weight] of the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), w(PP2) is the weight fraction [in % by weight] of the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2), XS(PP1) is the cold soluble xylene (XCS) content [in % by weight] of the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1),XS(PP) is the cold soluble xylene (XCS) content [in % by weight] of propylene - α-olefin copolymer C4 to C12 (C-PP),XS(PP2) is the calculated cold soluble xylene (XCS) content [in wt.%] of the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2). MFR2 (230°C) melt flow rate calculation secondpropylene - α-olefin copolymer fraction C4 to C12 (C-PP2):
where w(PP1) is the weight fraction [in % by weight] of the first propylene - α-olefin copolymer fraction C4 to C12 (C-PP1), w(PP2) is the weight fraction [in % by weight ] of the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2), MFR(PP1) is the melt flow rate MFR2 (230°C) [in g/10 minutes] the first propylene - fraction of α-olefin copolymer C4 to C12 (C-PP1),MFR(PP) is the melt flow rate MFR2 (230°C) [in g/10 minutes] of propylene - α-olefin copolymer C4 to C12 (C-PP),MFR(PP2) is the calculated melt flow rate MFR2 (230°C) [in g/10 minutes] of the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2) .Calculation of the comonomer content of the elastomeric (EC) copolymer, respectively:
where w(PP) is the weight fraction [in % by weight] of propylene - fraction of α-olefin copolymer C4 to C12 (C-PP), ie polymer produced in the first and second reactor (R1 + R2) ,w(E) is the weight fraction [in % by weight] of the elastomeric propylene copolymer (EC), i.e. polymer produced in the third and optionally fourth reactor (R3 + R4)C(PP) is the comonomer content [in % by weight] of propylene - α-olefin copolymer C4 to C12 (C-PP), that is, comonomer content [in % by weight] of the polymer produced in the first and second reactor (R1 + R2),C (RAHECO) is the comonomer content [in % by weight] of the heteroplastic propylene copolymer (RAHECO), C(E) is the calculated comonomer content [in % by weight] of the elastomeric propylene copolymer (EC), i.e. , of the polymer produced in the third and optionally fourth reactor (R3 + R4).MFR2 (230°C) is measured in accordance with ISO 1133 (230°C, 2.16 kg load).
[00152] The number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (MWD) are determined by Gel Permeation Chromatography (GPC) according to the following method:
[00153] The weighted average molecular weight Mw and the molecular weight distribution (MWD = Mw/Mn where Mn is the number average molecular weight and Mw is the weighted average molecular weight) are measured by a method based on ISO 16014-1 :2003 and ISO 16014-4:2003. A Waters Alliance GPCV 2000 instrument equipped with refractive index detector and online viscometer was used with 3 x TSK-gel (GMHXL-HT) columns from TosoHaas and 1,2,4-trichlorobenzene (TCB, stabilized at 200 mg/L of 2,6-Di tert-butyl-4-methyl-phenol) as the solvent at 145 °C and at a constant flow rate of 1 ml/minute. 216.5 μL of sample solution was injected per analysis. Column fit was calibrated using relative calibration with 19 MWD narrow polystyrene standards in the range of 0.5 kg/mol to 11,500 kg/mol and a series of well-characterized broad polypropylene standards. All samples were prepared by dissolving 5 to 10 mg of polymer in 10 mL (at 160°C) of stabilized TCB (even as mobile phase) and holding for 3 hours with continuous agitation before sampling on the GPC instrument. Comonomer content by NMR spectroscopy
[00154] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the tacticity, regio-regularity and comonomer contents of the polymer.
[00155] Quantitative 13C{1H} NMR spectra recorded in the molten state using a Bruker Advance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for 1H and 13C respectively. All spectra were recorded using a 7mm Magic Angle Rotary Probe (MAS) head optimized by 13C (MAS) at 180°C using nitrogen gas for all tyres. Approximately 200 mg of material was packed in a 7 mm OD zirconia MAS rotor and rotated at 4 kHz. This setting was chosen primarily for the high sensitivity required for fast identification and accurate quantification. Standard single pulse excitation was used using the NOE at short recycling delays and the RS-HEPT shutdown scheme. A total of 1024 (1k) transients were acquired per spectrum.
[00156] Quantitative 13C{1H} NMR spectra were processed, integrated and the relevant quantitative properties determined from integrals. All chemical changes are internally referred to the isotactic methyl quinquenium (mmmm) at 21.85 ppm.
[00157] The characteristic signs corresponding to regio and comonomer defects have been observed.
[00158] The tacticity distribution was quantified by integrating the methyl region between 23.6 and 19.7 ppm correcting for any sites not related to the stereo sequences of interest.
[00159] Specifically, the influence of regio and comonomer defects in the quantification of tacticity distribution was corrected by subtracting representative regio defect and comonomer integrals from the specific integral regions of the stereo sequences.
[00160] Isotacticity was determined at the triad level and reported as the percentage of isotactic triad sequences (mm) with respect to all triad sequences: [mm] % = 100 * ( mm / (mm + mr + rr) ) where mr represents the sum of the reversible mr and rm triad sequences.
[00161] The presence of 2.1 erythro regius defects was indicated by the presence of the two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites.
[00162] The characteristic signs that correspond to other types of regio defects were not observed.
[00163] The amount of 2.1 erythro regius defects was quantified using the mean integral of the two characteristic methyl loci at 17.7 and 17.2 ppm: P21e = ( Ie6 + Ie8) / 2
[00164] The amount of 1,2 propene inserted primarily was quantified based on the methyl region with correction performed for sites included in this region not related to the primary insertion and for primary insertion sites excluded from this region: P12= ICH3 + P12e
[00165] The total amount of propene was quantified as the sum of primary inserted propylene (1.2) and all other region defects present: Ptotal = P12 + P21e
[00166] The percentage in mol of 2.1 defects in the erythro region was quantified with respect to all propenes: [21e] mol% = 100 * ( P21e / Ptotal )
[00167] The characteristic signals corresponding to the incorporation of alpha-olefin C5-12 were observed. The amount of isolated C5-12 alpha-olefin incorporated into PPC5-12PP sequences was quantified using the integral of the corresponding sites taking into account the number of reporting sites per comonomer.
[00168] The amount of isolated 1-hexene incorporated into the PPHPP sequences was quantified using the integral of the αB4 sites at 44.1 ppm taking into account the reporting sites by comonomer: H = I[αB4] / 2
[00169] With locations indicative of consecutive incorporation not observed, the total 1-hexene content of comonomer was calculated only in this amount: Htotal = H
[00170] The amount of isolated 1-octene incorporated into PPPP sequences was quantified using the integral of αB6 sites at 44.0 ppm taking into account the number of reporting sites per comonomer:O = I[αB6] / 2
[00171] With the locations indicative of consecutive incorporation, it was not observed that the total 1-octene content of comonomer was calculated only in this amount: Ototal = O
[00172] The characteristic signs corresponding to the incorporation of ethylene were observed.
[00173] The amount of isolated ethylene incorporated into the PPEPP sequences was quantified using the integral of the SαY sites at 37.8 ppm taking into account the number of reporting sites per comonomer: E = I[Sαy] / 2
[00174] The amount of ethylene consecutively incorporated into PPEEPP sequences was quantified using the SβY site integral at 26.9 ppm taking into account the number of reporting sites per comonomer: EE = ISβY
[00175] The sites indicative of other types of ethylene incorporation, for example, PPEPEPP and PPEEEPP were quantified from characteristic signals such as EPE and EEE and calculated for a similar pathway as PPEEPP sequences. The total ethylene content of comonomer was calculated based on the sum of ethylene isolated, consecutive and not consecutively incorporated: Etotal = E + EE + EPE + EEE
[00176] The total mole fraction of the comonomer in the polymer was calculated as: fE = ( Etotal / ( Etotal + Ptotal + C5-12; total ) fC5-12 = ( Etotal / ( Etotal + Ptotal + C5-12; total )
[00177] The percentage in mol of polymer incorporation into the polymer was calculated from the fraction in mol according to: [C5-12] mol% = 100 * fC5-12[E] mol% = 100 * fE
[00178] The percentage by weight of incorporation of 1-hexene and ethylene in the polymer was calculated from the fraction in mol according to: [H] wt% = 100 * ( fH * 84.16 ) / ( (fE * 28.05 ) ) + (fH * 84.16) + ((1-(fE+fH)) * 42.08) )[E] wt% = 100 * (fE * 28.05 ) / ( (fE * 28.05) + (fH * 84.16) + ((1-(fE+fH)) * 42.08))
[00179] The percentage by weight of incorporation of 1-octene and ethylene in the polymer was calculated from the fraction in mol according to: [O] wt% = 100 * ( fO * 112.21 )/( (fE * 28 ) .05)+(fO * 112.21) + ((1-(fE+fO)) * 42.08) )[E] wt% = 100 * (fE * 28.05 ) / ( (fE * 28, 05) + (fO * 112.21) + ((1-(fE+fO)) * 42.08) )
[00180] Intrinsic viscosity is measured according to DIN ISO 1628/1, October 1999 (in Decalina at 135°C).
[00181] Solubles of xylene (XCS, % by weight): The content of cold solubles of xylene (XCS) is determined at 25°C according to ISO 16152; first edition; 2005-07-01. The part that remains insoluble is the cold insoluble xylene fraction (XCI).
[00182] The extractable fraction of hexane is determined according to an FDA method (Federal registration, title 21, Chapter 1, part 177, section 1520, n. Annex B) on cast films 100 μm thick in a cast monolayer film with a melting temperature of 220°C and a cold roll temperature of 20°C. The extraction was carried out at a temperature of 50°C and an extraction time of 30 minutes.
[00183] Melting temperature (Tm) and heat of melting (Hf), temperature of crystallization (Tc) and heat of crystallization (Hc): measured with Mettler TA820 differential scanning calorimetry (DSC) on samples from 5 to 10 mg. DSC is performed in accordance with ISO 11357-3:1999 in a heat / cold / heat cycle with a scan rate of 10°C/minute in the temperature range of +23 to +210°C. The crystallization temperature and heat of crystallization (Hc) are determined from the cooling step, while the melting temperature and heat of fusion (Hf) are determined from the second heating step. All materials have more than one melting point, but a dominant represents more than 50% of the total melting enthalpy.
[00184] The glass transition temperature Tg is determined by dynamic mechanical analysis according to ISO 6721-7. Measurements are performed in torsional mode on compression molded samples (40x10x1 mm3) between -100°C and +150°C with a heating rate of 2°C/min and a frequency of 1 Hz.
[00185] The tensile modulus on the machine and the transverse direction was determined in accordance with ISO 527-1 at 23°C on 50 μm thick cast films produced on a monolayer cast film line with a melting temperature of 220° C and a cold roll temperature of 20°C. The test was performed at a crosshead speed of 1 mm/minute.
[00186] Charpy notch impact force is determined in accordance with ISO 179 1eA at 23°, and at -20°C using 80x10x4 mm3 test bars molded in line with EN ISO 1873-2.
The stress bleaching was determined as described in detail in EP 1 860 147 A1 on injection molded UL94 specimens having the dimension 125 x 12.5 x 2 mm (length x width x thickness).
[00188] The measurement of stress whitening is carried out in a reverse three-point bending test on a universal testing machine (Zwick Z010) with a test speed of 50 mm/minute. Definitions of technical terms (eg, deflection, support, loading edge) in this particular test method are as described in ISO 178 (bending test).
[00189] Two different parameters are determined:i. Stress bleaching angle [°] is the bending angle at which stress bleaching takes place. The occurrence of stress bleaching corresponds to a pronounced drop in the typical response during bending at a specific deflection value.ii. 90° residual stress bleaching [mm] is the residual size of the reddening zones immediately after a 90° bending. The bending test is conducted at a bending angle of 90°. The specimen is then released with a crosshead speed of 400 mm/minute. The length of the reddening area (measured parallel to the direction of the length of the sample) measured immediately after release is the whitening can residual stress 90°.
[00190] Mean particle size (d50) is measured with Coulter Counter LS200 at room temperature with n-heptane as mean particle sizes below 100 nm by transmission electron microscopy.2. Examples
[00191] The catalyst used in the polymerization processes for the heteroplastic propylene copolymer (RAHECO) of the inventive examples IE1 and IE2 was the metallocene catalyst as described in example 10 of WO 2010/052263 A1.
[00192] CE1 is the commercial random propylene copolymer “Borpact SH950MO” from Borealis AG.
[00193] CE2 is the commercial random propylene copolymer “BorPure RG466MO” from Borealis AG.
[00194] CE3 is the commercial random heteroplastic copolymer “BorSoft SD233CF” from Borealis AG.Table 1: Polymerization conditions
C2 ethyleneC6 1-hexeneH2/C3 ratio hydrogen / propylene ratio C6/C3 ratio 1-hexene / propylene 1/2 GPR 1/2 gas phase reactor Arc Arc reactorTable 2: Properties
IE 1a is seeded with 0.2 wt% 1.3:2.4 di(methylbenzylidene)sorbitol (DMDBS, commercially available as Millad 3988 from Milliken Co., USA) IE 2a is seeded with 0.2 wt% of a blend of aluminum-hydroxy-bis[2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate] and lithium myristate (commercially available as Adekastab NA-21 from Adeka Palmarole, France) nd - not determined
[00195] All polymer powders were compounded in a Coperion ZSK 57 co-rotating twin screw extruder at 220°C with 0.2% by weight of Irganox B225 (1:1-combination of Irganox 1010 (Pentaerythryl-tetraquis)(3 - (3',5'-di-tert.butyl-4-hydroxytoluyl)-propionate and tris (2,4-di-t-butylphenyl) phosphate) phosphite) from BASF AG, Germany), 0.1% by weight of calcium stearate and if present with 0.2% by weight of the nucleating agent Millad 3988 or Adekastab NA-21.

权利要求:
Claims (18)
[0001]
1. Heteroplastic propylene copolymer (RAHECO), characterized in that it comprises (i) a matrix (M) being a propylene - α-olefin copolymer C4 to C12 (C-PP), said propylene - α-copolymer C4 to C12 olefin (C-PP) comprises units derivable from (i.(1) propylene and (i.(2) at least one C4 to C12 α-olefin) and (ii) an elastomeric propylene (EC) copolymer dispersed in the said matrix (M), said elastomeric propylene copolymer (EC) comprises units derivable from (ii.(1) propylene and (ii.(2) ethylene) and optionally at least one α-olefin C4 to C12; wherein said heteroplastic propylene copolymer (RAHECO) has (a) an MFR2 melt flow rate (230°C) measured in accordance with ISO 1133 in the range of 2.5 to 200.0 g/10 minutes; (b) a content of total comonomer in the range of 12.0 to 35.0% by weight; (c) a cold soluble fraction of xylene (XCS) determined in accordance with ISO 16152 (25°C) in an amount of 10.0 to 40 .0% by weight; (d) a total comonomer content of the soluble fraction and m xylene (XCS) in the range of 50.0 to 90.0% by weight where the heteroplastic propylene copolymer (RAHECO) satisfies inequality (I)
[0002]
2. Heteroplastic propylene copolymer (RAHECO) according to claim 1, characterized in that (a) the ethylene content of the total heteroplastic propylene copolymer (RAHECO) is in the range of 12.0 to 33.0% in weight, based on the weight of the heteroplastic propylene copolymer (RAHECO); (b) the C4 to C12 α-olefin content of the total heteroplastic propylene copolymer (RAHECO) is in the range of 0.5 to 6.0% by weight, based on the weight of the heteroplastic propylene copolymer (RAHECO); or a combination of them.
[0003]
3. Heteroplastic propylene copolymer (RAHECO) according to claim 1 or 2, characterized in that one or more of the following are satisfied: (a) propylene - C4 to C12 α-olefin copolymer (C-PP) is a propylene - 1-hexene copolymer (C6-PP); (b) the elastomeric propylene copolymer (EC) is an ethylene-propylene rubber (EPR); or a combination of them.
[0004]
4. Heteroplastic propylene copolymer (RAHECO) according to any one of claims 1 to 3, characterized in that the xylene-soluble cold fraction (XCS) of the heteroplastic propylene copolymer (RAHECO) has a determined intrinsic viscosity (IV) according to DIN ISO 1628/1 (in Decaline at 135°C) of at least 1.2 dl/g.
[0005]
5. Heteroplastic propylene copolymer (RAHECO) according to any one of claims 1 to 4, characterized in that it satisfies one or more of: (a) inequality (III)
[0006]
6. Heteroplastic propylene copolymer (RAHECO) according to any one of claims 1 to 5, characterized in that propylene - C4 to C12 α-olefin copolymer (C-PP) comprises a first fraction of polypropylene (PP1) and a second propylene - C4 to C12 α-olefin copolymer fraction (C-PP2).
[0007]
7. Heteroplastic propylene copolymer (RAHECO) according to claim 6, characterized in that one or more of the following are satisfied: (a) the comonomer content [in % by weight] in propylene - α-olefin copolymer C4 to C12 (C-PP) is greater than the first fraction of polypropylene (PP1); (b) the comonomer content between the first fraction of polypropylene (PP1) and propylene - α-olefin copolymer C4 to C12 (C -PP) differs by at least 1.5% by weight; (c) the comonomer content between the first polypropylene fraction (PP1) and the second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2) differs by at least 2.5% by weight; or combinations thereof.
[0008]
8. Heteroplastic propylene copolymer (RAHECO) according to claim 6 or 7, characterized in that the first polypropylene fraction (PP1) is (a) a propylene homopolymer fraction (H-PP1); or (b) a first propylene - C4 to C12 α-olefin copolymer fraction (C-PP1).
[0009]
9. Heteroplastic propylene copolymer (RAHECO) according to claim 6 or 7, characterized in that one or more of the following are satisfied: (a) the content of α-olefin C4 to C12 in the second propylene - copolymer fraction of α-olefin C4 to C12 (C-PP2) is in the range of 2.0 to 15.0% by weight; (b) the comonomer content in propylene - copolymer of α-olefin C4 to C12 (C-PP) is in the range of 1.5 to 9.0% by weight; or combinations
[0010]
10. Heteroplastic propylene copolymer (RAHECO) according to any one of claims 1 to 9, characterized in that the elastomeric propylene copolymer (EC) has a comonomer content in the range of 40 to 90% by weight.
[0011]
11. Heteroplastic propylene copolymer (RAHECO) according to any one of claims 1 to 10, characterized in that it satisfies inequality (VIII)
[0012]
12. Heteroplastic propylene copolymer (RAHECO) according to any one of claims 1 to 11, characterized in that it has a first glass transition temperature Tg(1) and a second glass transition temperature Tg(2), wherein said first glass transition temperature Tg(1) is above the second glass transition temperature Tg(2).
[0013]
13. Heteroplastic propylene copolymer (RAHECO) according to any one of claims 1 to 12, characterized in that it has one or more of the following: (a) a first glass transition temperature Tg(1) in the range of -5 at +12°C; (b) a second glass transition temperature Tg(2) in the range of -45 to -25°C; or combinations thereof.
[0014]
14. Heteroplastic propylene copolymer (RAHECO) according to any one of claims 1 to 13, characterized in that said heteroplastic propylene copolymer (RAHECO) is α-nucleated.
[0015]
15. Heteroplastic propylene copolymer (RAHECO) according to any one of claims 1 to 14, characterized in that it has a tensile modulus measured in accordance with ISO 527-1 at 23°C of at least 500 MPa,
[0016]
16. Process for preparing a heteroplastic propylene copolymer (RAHECO) as defined in any one of claims 1 to 15, characterized in that it comprises the steps of polymerizing: (I) propylene and a C4 to C12 α-olefin in order of forming the matrix (M) being the propylene - α-olefin copolymer C4 to C12 (C-PP) and subsequently polymerizing (II) propylene; ethylene; and optionally at least one C4 to C12 α-olefin in order to form the elastomeric propylene copolymer (EC) dispersed in said matrix (M); wherein both steps (I) and (II) take place in the presence of the same particulate catalyst single site solid, the catalyst comprising (i) a complex of the formula (I):Rn(Cp')2MX2(I) wherein "M" is zirconium (Zr) or hafnium (Hf), each "X" is independently a monovalent anionic o-ligand, each "Cp'" is an organic cyclopentadienyl-type ligand independently selected from the group consisting of substituted cyclopentadienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted or unsubstituted fluorenyl, said metal-coordinated organic ligands transition (M), "R" is a bridging group linking said organic ligands (Cp'), "n" is 1 or 2, and (ii) a cocatalyst comprising a compound of a metallic group 13 .
[0017]
17. Process according to claim 16, characterized in that step (I) comprises polymerizing propylene and optionally a C4 to C12 α-olefin in order to form the first polypropylene fraction (PP1) and subsequently polymerizing in another propylene from the reactor and α-olefin C4 to C12, in order to form a second propylene - α-olefin copolymer fraction C4 to C12 (C-PP2), the first polypropylene fraction (PP1) and the second propylene - fraction of α-olefin copolymer C4 to C12 (C-PP2) forms propylene - α-olefin copolymer C4 to C12 (C-PP).
[0018]
18. Article, characterized in that it comprises heteroplastic propylene copolymer (RAHECO) as defined in any one of claims 1 to 15, wherein the article is selected from the group consisting of a bag, medical bag, food packaging, film , bottle, and combinations thereof.

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法律状态:
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