• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    low emission propylene homopolymer with high melt index propylene homopolymer with low emission value and high melt index.
    公开号:BR112016009549B1
    申请号:R112016009549-9
    申请日:2014-11-19
    公开日:2021-07-27
    发明作者:Timo Leinonen；Markus Gahleitner；Peter Denifl；Thomas Horill；Jingbo Wang；Johanna LILJA
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    [001] The present invention is directed to a new homopolymer of propylene with reduced emissions as well as its manufacture and use.
    [002] Polypropylene is used in many applications. Depending on its final applications the properties of polypropylene must be adapted accordingly. For example, some end applications require very rigid material. Furthermore, today's polymer processors require low-emission material to meet the consistently increasing demands of regulatory authorities as well as consumers.
    [003] Typically, adsorbent additives are used to achieve low emission values. For example, in WO 2011/023594 melamine is employed to obtain polymer material with reduced emission values. In WO 92/13029 Alzeolites are used for the same purpose. Two disadvantages of these solutions employing adsorbent additive particles are the parallel absorption of antioxidants and the unsuitability for film and fiber applications.
    [004] Thus, the object of the present invention is to provide a polymer material that is quite rigid and characterized by low emissions.
    [005] The disclosure of the present invention is that a propylene homopolymer has to be produced with a Ziegler-Natta catalyst containing an internal donor (ID) not belonging to the phthalic acid ester class. With such a catalyst propylene homopolymer can be produced having excellent stiffness and low emission values.
    [006] Thus, the present invention is directed to a homopolymer of propylene having (a) melt index MFR2 (230°C/2.16 kg) measured according to ISO 1133 in the range of 75.0 to 500 g/10 min; and (b) a pentate isotacticity (mmmm) of more than 90.0%, determined by 13C-NMR; wherein further (c) the homopolymer of propylene fulfills inequality (I) VOC <. (MFR x 0.08) + 201.0 whereVOC is the amount of volatile organic compounds (VOC) [in ppm] measured according to VDA 278:2002 for the homopolymer of propylene; MFR is the melt index MFR2 (230°C /2.16 kg) measured according to ISO 1133 of the propylene homopolymer, and (d) the propylene homopolymer preferably has a melting temperature Tm of equal to or greater than 160°C.
    [007] In a preferred embodiment, the propylene homopolymer according to the present invention has a VOC value measured in accordance with VDA 278:2002 of equal to or less than 210 ppm.
    [008] In addition to or alternatively to the VOC value, the propylene homopolymer according to this invention can also be characterized by its FOG value. Therefore, it is preferable that the homopolymer of propylene meets the inequality (II)FOG < (MFR x 1.26) + 350.0 where FOG is the amount of fogging compounds (FOG) [in ppm] measured according to VDA 278: 2002 of the homopolymer of propylene, preferably of the homopolymer of propylene in the form of granules; eMFR is the melt index MFR2 (230°C/2.16 kg) measured in accordance with ISO 113 of the homopolymer of propylene.
    [009] In a preferred embodiment, the propylene homopolymer according to the present invention has a FOG value measured in accordance with VDA 278:200, of not more than 580 ppm.
    [010] Preferably, the propylene homopolymer according to this invention has a crystallization temperature equal to or greater than 114°C.
    [011] In another preferred embodiment, the propylene homopolymer according to the present invention has a content of solubles in cold xylene (XCS) determined in accordance with ISO 16152 (25°C) of at least 1.8% by weight, preferably in the range of from 1.8 to 5.5% by weight.
    [012] It is particularly preferred that the homopolymer of propylene according to this invention has 2.1 erythro regio-defects of equal to or less than 0.4% in mol determined by 13 C-NMR spectroscopy and/or a pentate isotacticity ( mmmm) of more than 93.0%.
    [013] It is further preferred that the propylene homopolymer according to this invention has a strain modulus measured at 23°C in accordance with ISO 527-1 (pull speed of 1 mm/min) of at least 1500 MPa.
    [014] The present invention is also directed to an article comprising the homopolymer of propylene as described herein.
    [015] The present invention is also directed to the manufacture of propylene homopolymer as defined herein, wherein said propylene homopolymer is obtained by polymerization of propylene in the presence of (a) a Ziegler-Natta (ZN-C) catalyst comprising the (TC) compounds of an IUPAC Group 4 to 6 transition metal, a Group 2 metal compound (MC) and an internal donor (ID), wherein said internal donor (ID) is a compound non-phthalic, preferably is a non-phthalic acid ester; (b) optionally a co-catalyst (Co), and (c) optionally an external donor (ED).
    [016] It is particularly preferred that (a) the internal donor (ID) is selected from malonates, maleates, succinates, glutarates, cyclohexene-1,2-dicarboxylates, benzoates and derivatives and/or mixtures thereof, preferably the internal donor ( ID) is a citraconate; and/or(b) the mole ratio of cocatalyst (Co) to external donor (ED) [Co/ED] is 5 to 45.
    [017] In a preferred embodiment, the propylene homopolymer is produced in a sequential polymerization process comprising at least two reactors (Rl) and (R2), in the first reactor (Rl) a fraction of the first propylene homopolymer (H-PP1 ) is produced and subsequently transferred to the second reactor (R2), in the second reactor (R2) a second fraction of homopolymer of propylene (H-PP2) is produced in the presence of the first fraction of homopolymer propylene (H-PP1), wherein a catalyst is used as defined above and in more detail below.
    [018] Next, the invention is described in more detail.
    [019] According to the present invention, the term "propylene homopolymer" refers to a polypropylene consisting substantially, i.e., of at least 99.0% by weight, more preferably of at least 99.5% of weight, even more preferably at least 99.8% by weight, such as at least 99.9% by weight of propylene units. In another embodiment only propylene units are detectable, i.e. only propylene has polymerized.
    [020] A requirement of the propylene homopolymer according to the present invention is its melt index. Therefore, the propylene homopolymer has an MFR2 (230°C/2.16 kg) measured according to ISO 1133 in the range of 75.0 to 500 g/10 min, preferably in the range of 79.0 to 400 g/ 10 min, more preferably in the range 80.0 to 350.0 g/10 min, as in the range 81.0 to 300 g/10 min.
    [021] Propylene homopolymer is especially characterized by its low emissions. In contrast to the propylene homopolymers known in the art the emissions are quite low at a specific molecular weight compared to known products. Thus, the homopolymer of propylene fulfills inequality (I), more preferably inequality (Ia),VOC < (MFR x 0.08) + 201.0 (I)VOC <■ (MFR x 0.08) + 170, 0 (Ia)VOC < (MFR x 0.08) + 150.0 (Ib)VOC < (MFR x 0.08) + 135.0 (Ia) where VOC is the amount of volatile organic compounds (VOC) [in ppm] measured in accordance with VDA 278:2002 of propylene homopolymer, preferably propylene homopolymer in the form of granules; eMFR is the melt index MFR2 (230°C/2.16 kg) measured according to ISO 113 of the homopolymer of propylene.
    [022] Preferably, the amount of volatile organic compounds (VOC) measured according to VDA 278:2002 of the homopolymer of propylene is equal to or less than 215 ppm, more preferably equal to or less than 180 ppm, such as equal to or less than 160 ppm.
    [023] VOC values are measured in granules as defined in detail below. However, also the VOC values measured on plates are reduced vis-à-vis the state of the art (see examples).
    [024] In addition or alternatively to the VOC value, the propylene homopolymer according to the present invention preferably meets inequality (II), more preferably inequality (IIa), even more preferably inequality (IIb),FOG £ (MFR x 1 .26) + 350.0 (II)FOG (MFR x 1.26) + 330.0 (lia)FOG (MFR x 1.26) + 320.0 (IIb) where FOG is the amount of fogging compounds (FOG ) [in ppm] measured according to VDA 278:2002 of the homopolymer of propylene, preferably of the homopolymer of propylene in the form of granules; eMFR is the melt index MFR2 (230°C/2.16 kg) measured according to ISO 113 of the homopolymer of propylene.
    Preferably, the amount of fogging compounds (FOG) measured according to VDA 278:2002 of the homopolymer of propylene is not more than 590 ppm, more preferably not more than 580 ppm.
    [026] FOG values are measured in granules as defined in detail below. However, also the FOG values measured on plates are reduced vis-à-vis the state of the art (see examples).
    [027] The propylene homopolymer is also defined by its microstructure.
    [028] Preferably, the homopolymer of propylene is isotactic. Therefore, it is preferable that the homopolymer of propylene has a rather high concentration in pentad (mmmm%) determined by 13 C-NMR spectroscopy, i.e. more than 93.0%, more preferably more than 93.5%, such as more than 93.5 to 97.5%, even more preferably at least 95.0%, as in the range of 95.0 to 97.5%.
    [029] Another characteristic of the propylene homopolymer is the low amount of failure of propylene inserts in the polymer chain, which indicates that the propylene homopolymer is produced in the presence of a Ziegler-Natta catalyst, preferably in the presence of a Ziegler-Natta catalyst (ZN-C) as defined in more detail below. Therefore, the propylene homopolymer is preferably characterized by a low amount of 2,1-erythro regio-defects, i.e. equal to or less than 0.4 mol%, more preferably equal to or less than 0 .2% by mol, such as not more than 0.1% by mol, determined by C-NMR spectroscopy. In an especially preferred embodiment, 2.1 erythro regiodefects are not detectable.
    [030] It is preferred that the propylene homopolymer according to the present invention is characterized by the rather high content of solubles in cold xylene (XCS), that is, by solubles in cold xylene (XCS) of at least 1.8% in weight, such as at least 2.0% by weight. Therefore, the propylene homopolymer preferably has a content of cold xylene solubles (XCS) in the range of 1.8 to 5.5% by weight, more preferably in the range of 2.0 to 5.0% by weight, further more preferably in the range of 2.2 to 5.0% by weight.
    [031] The amount of solubles in cold xylene (XCS) further indicates that the propylene homopolymer is preferably free of any elastomeric polymer component, such as an ethylene-propylene rubber. In other words, the propylene homopolymer must not be a heterophasic polypropylene, that is, a system consisting of a polypropylene matrix in which an elastomeric phase is dispersed. Such systems are characterized by a very high content of cold soluble xylene.
    [032] The amount of cold solubles in xylene (XCS) further indicates that the propylene homopolymer preferably does not contain elastomeric (co)polymers that form inclusions as a second phase to improve mechanical properties. A polymer containing elastomeric (co)polymers as second phase inserts could, on the other hand, be called heterophasic and preferably does not form part of the present invention. The presence of so-called second phases or inclusions are, for example, visible by high-resolution microscopy, such as electron microscopy or atomic force microscopy, or by dynamic-mechanical thermal analysis (DMTA). Specifically in DMTA the presence of a multiphase structure can be identified by the presence of at least two distinct glass transition temperatures.
    [033] Therefore, it is preferable that the propylene homopolymer according to this invention does not have the glass transition temperature below -30, preferably below -25°C, more preferably below -20°C.
    [034] On the other hand, in a preferred embodiment, the propylene homopolymer according to the present invention has a glass transition temperature in the range of -12 to 5°C, more preferably in the range of -10 to 4°C.
    [035] Furthermore, the homopolymer of propylene is preferably a crystalline. The term "crystalline" indicates that the homopolymer of propylene has a very high melting temperature. Thus throughout the invention, propylene homopolymer is considered to be crystalline unless otherwise indicated. Therefore, the homopolymer of propylene preferably has a melting temperature measured by differential scanning calorimetry (DSC) of equal to or greater than 160°C, i.e. equal to or greater than 160 to 168°C, plus preferably at least 161°C, i.e. in the range of 161 to 166°C.
    [036] Furthermore, it is preferred that the homopolymer of propylene has a crystallization temperature measured by differential scanning calorimetry (DSC) of equal to or greater than 114°C, more preferably in the range of 114 to 128°C, more preferably in the range of 118 to 126°C.
    [037] The propylene homopolymer is further characterized by a high rigidity. Therefore, the homopolymer of propylene has a very high tensile modulus. Therefore, it is preferred that the propylene homopolymer has a tensile modulus measured at 23°C in accordance with ISO 527-1 (pull speed 1 mm/min.) of at least 1400 MPa, more preferably in the range of 1400 to 2000 MPa, even more preferably in the range 1500 to 1800 MPa.
    [038] Preferably, the propylene homopolymer according to the present invention does not contain a 1, 3, 5 triazine derivatives of formula (I)
    where R' and R" are independently selected from the group, NHZ', NZ'Z", Cl to C10 alkyl, phenyl and benzyl Z' and Z" are independently selected from the group H, methyl, ethyl, n-propyl , iso-propyl, n-butyl, tert-butyl, and n-pentyl.
    [039] Preferably, the propylene homopolymer according to the present invention does not contain a hydrophobic aluminum silicate molecular sieve having a mole ratio of Si/Al in the crystal lattice above 35, a pore diameter of at least 5 .5 A (5.5 x 10”8 cm) and a water sorption capacity at 250°C and 4.6 torr (6132 Pa) of less than 10% by weight. Even more preferably, the propylene homopolymer according to the present invention does not contain a (hydrophobic) aluminum silicate.
    [040] Preferably, the homopolymer of propylene is obtained by polymerization of propylene in the presence of a Ziegler-Natta catalyst as defined in more detail below. Even more preferably, the propylene homopolymer according to the present invention is obtained by a process as defined in detail below, using the Ziegler-Natta catalyst as defined herein.
    [041] The invention is also directed to an article comprising the homopolymer of propylene. Preferably, the article comprises based on the total amount of the article, at least 50% by weight, such as 50 to 99.9% by weight, more preferably at least 60% by weight, such as 60 to 99% by weight, further more preferably 70% by weight, such as 70 to 99.9% by weight of the homopolymer of propylene.
    [042] Preferably, the article is an extruded article, such as a film, or an injection molded article. In one embodiment the article can also be a blow molded article, such as a blow molded and an injection molded article.
    [043] The propylene homopolymer according to the present invention (as described below) may comprise, more preferably, may consist of two fractions, i.e. a first fraction of propylene homopolymer (H-PP1) and a second fraction of propylene homopolymer (H-PP2) . Preferably, the weight ratio between the first fraction of propylene homopolymer (H-PP1) and the second fraction of propylene homopolymer (H-PP2) [(H-PP1):(H-PP2)] is 70: 30 to 40:60, more preferably 65:35 to 45:55.
    [044] The first fraction of propylene homopolymer (H-PP1) and the second fraction of propylene homopolymer (H-PP2) may differ in melt index. However, it is preferred that the melt index MFR2 (230°C) of the first propylene homopolymer fraction (H-PP1) and the second propylene homopolymer fraction (H-PP2) are closely identical, i.e., do not differ more than 15% as calculated from the smaller of the two values, preferably do not differ by more than 10%, as do not differ by more than 7%.
    [045] The propylene homopolymer as defined in the present invention may contain up to 5.0% by weight of additives (except the triazine derivatives as mentioned above), such as antioxidants, slip agents and anti-blocking agents. Preferably, the additive content is less than 3.0% by weight, such as below 1.0% by weight.
    [046] In case the propylene homopolymer comprises an a-nucleating agent, it is preferred that it be free of p-nucleating agents. The α-nucleating agent is preferably selected from the group consisting of (i) salts of monocarboxylic acids and polycarboxylic acids, e.g. sodium benzoate or aluminum tert-butylbenzoate, and(ii) dibenzylidenesorbitol (eg 1,3:2,4 dibenzylidenesorbitol) and C1 -Cg -alkyl substituted dibenzylidenesorbitol derivatives such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (by example, 1,3:2,4 di(methylbenzylidene)sorbitol), or substituted nonitol derivatives such as 1,2,3-trideoxy-4,6:5,7-bis-O-[(4propylphenyl)methylene] -nonitol, and (iii) salts of phosphoric acid diesters, for example 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate sodium or aluminum-hydroxy-bis[2,2'-methylene -bis(4,6-di-t-butylphenyl)phosphate], and(iv) vinylcycloalkane polymer and vinylalkane polymer (as discussed in more detail below), and(v) mixtures thereof.
    [047] Such additives are generally commercially available and are described, for example, in "Plastic Additives Handbook", pages 871-873, 5th edition, 2001 by Hans Zweifel.
    [048] Preferably, the propylene homopolymer contains up to 3% by weight of the α-nucleating agent. In a preferred embodiment, the propylene homopolymer does not contain more than 2000 ppm, more preferably from 5 to 1500 ppm, more preferably from 50 to 1000 ppm of an α-nucleating agent, in particular selected from the group consisting of dibenzylidenesorbitol (eg 1.3:2.4 dibenzylidene sorbitol), dibenzylidene sorbitol derivative, preferably dimethyldibenzylidene sorbitol (eg 1,3:2.4 di(methylbenzylidene) sorbitol), or substituted nonitol derivatives such as 1 sodium ,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonitol, 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, vinylcycloalkane polymer, vinylalkane polymer, and mixtures thereof.
    [049] In the following the manufacture of the homopolymer of propylene is described in more detail.
    [050] The propylene homopolymer according to the present invention is preferably produced in the presence of (a) a Ziegler-Natta (ZN-C) catalyst comprising the compounds (TC) of a transition metal from Group 4 to 6 of IUPAC, a Group 2 metal compound (MC) and an internal donor (ID), wherein said internal donor (ID) is a non-phthalic compound, preferably is a non-phthalic acid ester; (b) optionally a co-catalyst of (co), and (c) optionally an external donor (ED).
    [051] More preferably, the propylene homopolymer is produced in a sequential polymerization process comprising at least two reactors (R1) and (R2), in the first reactor (R1) the first fraction of propylene homopolymer (H-PP1) is produced and subsequently transferred to the second reactor (R2), in the second reactor (R2) the second fraction of homopolymer of propylene (H-PP2) is produced in the presence of the first fraction of homopolymer of propylene (H-PP1).
    [052] The term "sequential polymerization system" indicates that propylene homopolymer is produced in at least two reactors connected in series. Therefore, the present polymerization system comprises at least a first polymerization reactor (R1) and a second polymerization reactor (R2), and optionally a third polymerization reactor (R3). The term "polymerization reactor" will indicate that the main polymerization takes place. Thus, in case the process consists of two polymerization reactors, this definition does not exclude the option that the overall system comprises, for example, a prepolymerization step in a prepolymerization reactor. The term "consists of" is only an approximate formulation taking into account the main polymerization reactors.
    [053] Preferably, at least one of the two polymerization reactors (R1) and (R2) is a gas phase reactor (GPR). Even more preferably, the second polymerization reactor (R2) and the optional third polymerization reactor (R3) are gas phase reactors (GPRs), i.e. a first gas phase reactor (GPR1) and a second gas phase reactor (GPR2). A gas phase reactor (GPR) in accordance with the present invention is preferably a fluid bed reactor, a fast fluid bed reactor or a fixed bed reactor or any combination thereof.
    [054] Therefore, the first polymerization reactor (Rl) is preferably a suspension reactor (SR) and can be any simple or continuous stirred batch tank reactor or recirculation reactor in volume or suspension. Volume means a polymerization in a reaction medium comprising at least 60% (w/w) of monomer. According to the present invention, the suspension reactor (SR) is preferably a recirculation (volume) reactor (LR). Thus, the average concentration of the first fraction (Ia F) of the propylene homopolymer (i.e. the first fraction of the propylene homopolymer (H-PP1)) in the polymer suspension within the recirculating reactor (LR) is typically 15% by weight to 55% by weight, based on the total weight of the polymer suspension within the loop reactor (LR). In a preferred embodiment of the present invention, the average concentration of the first fraction of propylene homopolymer (H-PP1) in the polymer suspension within the recirculating reactor (LR) is from 20% by weight to 55% by weight and more preferably from 25% by weight to 52% by weight, based on the total weight of the polymer suspension within the loop reactor (LR).
    [055] Preferably, the propylene homopolymer of the first polymerization reactor (R1), that is, the first fraction of propylene homopolymer (H-PP1), more preferably, the polymer suspension of the recirculation reactor (LR) containing the first fraction of propylene homopolymer (H-PP1) is directly introduced into the second polymerization reactor (R2), that is, into the (first) gas phase reactor (GPR1), without a quick step between stages. This type of direct feed is described in EP 887379 A, EP 887380 A, EP 887381 A and EP 991684 A. By "direct feed" is meant a process in which the content of the first polymerization reactor (R1), i.e. from the recirculation reactor (LR), the polymer suspension comprising the first fraction of propylene homopolymer (H-PP1) is taken directly to the gas phase reactor in the next stage.
    [056] Alternatively, the propylene homopolymer of the first polymerization reactor (R1), i.e. the first fraction of propylene homopolymer (H-PP1), more preferably the polymer slurry of the recirculating reactor (LR) containing the first propylene homopolymer fraction (H-PP1), can also be directed to a fast step or through an additional concentration step before being fed to the second polymerization reactor (R2), i.e., into the in-phase reactor gaseous (GPR) . Therefore, this "indirect feeding" refers to a process in which the contents of the first polymerization reactor (R1), the recirculation reactor (LR), i.e. the polymer slurry, is fed into the second polymerization reactor (R2), to the (first) gas phase reactor (GPR1), through a reaction medium separation unit and the reaction medium as a separation unit gas.
    [057] More specifically, the second polymerization reactor (R2), and any subsequent reactor, for example, the third polymerization reactor (R3) are preferably gas phase reactors (GPRs). Such gas phase reactors (GPR) can be any fluid bed or mechanically mixed reactors.
    [058] Preferably, gas phase reactors (GPRS) comprise a mechanically stirred fluidized bed reactor with gas velocities of at least 0.2 m/s. Thus, the gas phase reactor is considered to be a fluidized bed type reactor preferably with a mechanical stirrer.
    [059] Thus, in a preferred embodiment, the first polymerization reactor (Rl) is a suspension reactor (SR), as a recirculation reactor (LR), while the second polymerization reactor (R2) and any subsequent optional reactor , like the third polymerization reactor (R3), are gas phase reactors (GPRs). Therefore for the present process, at least two, preferably two polymerization reactors (R1) and (R2) or three polymerization reactors (R1) (R2) and (R3), i.e. one slurry reactor (SR) , as a recirculation reactor (LR) and a (first) gas-phase reactor (GPR1) and optionally a second gas-phase reactor (GPR2), connected in series are used. If necessary before the suspension reactor (SR) a pre-polymerization reactor is placed.
    [060] The Ziegler-Natta catalyst (ZN-C) is introduced in the first polymerization reactor (Rl) and is transferred with the polymer (suspension) obtained in the first polymerization reactor (Rl) in the subsequent reactors. If the process also comprises a prepolymerization step, it is preferable that all the Ziegler-Natta (ZN-C) catalyst is fed into the prepolymerization reactor. Subsequently, the prepolymerization product containing the Ziegler-Natta catalyst (ZN-C) is transferred to the first polymerization reactor (Rl).
    [061] A preferred multistage process is a process in "gas phase-recirculation", as developed by Borealis AIS, Denmark (known as BORSTAR® technology) described, for example, in the patent literature, such as in EP 0887379, WO 92/12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
    [062] Another suitable gas-phase suspension process is the Spheripol® process from Basell.
    [063] Especially good results are obtained if the temperature in the reactors is carefully chosen.
    [064] Therefore, it is preferable that the operating temperature in the first polymerization reactor (R1) is in the range of 62 to 85°C, more preferably in the range of 65 to 82°C, even more preferably in the range of 67 to 80°C.
    [065] Alternatively or in addition to the previous paragraph, it is preferable that the operating temperature in the second polymerization reactor (R2) and optional in the third reactor (R3) is in the range of 75 to 95°C, more preferably in the range of 78 to 92°C.
    [066] Preferably, the operating temperature in the second polymerization reactor (R2) is equal to or greater than the operating temperature in the first polymerization reactor (R1). Therefore, it is preferable that the operating temperature (d) in the first polymerization reactor (R1) is in the range 62 to 85°C, more preferably in the range 65 to 85°C, even more preferably in the range 67 to 82°C, such as 70 to 80°C; (e) in the second polymerization reactor (R2) is in the range of 75 to 95°C, more preferably in the range of 78 to 92°C, even more preferably in the range of 78 at 88°C, with the proviso that the operating temperature in the second polymerization reactor (R2) is equal to or greater than the operating temperature of the first polymerization reactor (R1).
    [067] Typically, the pressure in the first polymerization reactor (R1), preferably in the recirculation reactor (LR), is in the range of 20 to 80 bar (2 to 8 MPa), preferably from 30 to 70 bar (3 to 7 MPa), as well as from 35 to 65 bar (3.5 to 6.5 MPa), while the pressure in the second polymerization reactor (R2), that is, in the (first) gas phase reactor (GPR1), and, optionally, in any subsequent reactor, as in the third polymerization reactor (R3), for example, in the second gas phase reactor (GPR2), it is in the range of 5 to 50 bar (0.5 to 5 MPa), of preferably 15 to 40 bar (1.5 to 4 MPa).
    [068] Preferably hydrogen is added in each of the polymerization reactors in order to control the molecular weight, ie the MFR2 melt index.
    [069] Preferably, the average residence time is quite long in the polymerization reactors (Rl) and (R2). In general, mean residence time (R) is defined as the ratio of the reaction volume (VR) to the reactor volumetric flow rate (Qo) (ie, VR/QO) , ie, i = VR /QO [tau = VR/QO] In the case of a recirculation reactor, the reaction volume (VR) is equal to the reactor volume.
    [070] Therefore, the average residence time (T) in the first polymerization reactor (R1) is preferably at least 15 minutes, more preferably in the range of 15 to 80 minutes, even more preferably in the range of 20 to 60 minutes, such as in the range of 24 to 50 minutes, and/or the average residence time (T) in the second polymerization reactor (R 2) is preferably at least 70 minutes, more preferably in the range of 70 to 220 minutes, even more preferably in the range of 80 to 210 minutes, even more preferably in the range of 90 to 200 minutes, such as in the range of 90 to 190 minutes. Preferably, the average residence time (i) in the third polymerization reactor (R3) - if present - is preferably at least 30 minutes, more preferably in the range of 30 to 120 minutes, even more preferably in the range of 40 to 100 minutes, as in the 50 to 90 minute range.
    [071] As mentioned above, the present process may comprise in addition the (main) polymerization of the homopolymer of propylene at least in the two polymerization reactors (R1, R2 and R3 optional) before the same a prepolymerization in a pre reactor. -polymerization (PR) upstream of the first polymerization reactor (Rl).
    [072] In the prepolymerization reactor (PR) a polypropylene (Pre-PP) is produced. The prepolymerization is carried out in the presence of Ziegler-Natta (ZN-C) catalyst. According to this modality of the Ziegler-Natta (ZN-C) catalyst, the co-catalyst (Co), and the external donor (ED) are introduced in the pre-polymerization step. However, this does not exclude the option that at a later stage, for example, more of the co-catalyst (Co) and/or external donor (ED) is added in the polymerization process, for example, in the first reactor (Rl) . In one embodiment the Ziegler-Natta catalyst (ZN-C), the co-catalyst (Co), and the external donor (ED) are only added to the prepolymerization reactor (PR) if a prepolymerization is applied. .
    [073] The prepolymerization reaction is typically carried out at a temperature from 0 to 60°C, preferably from 15 to 50°C, and more preferably from 20 to 45°C.
    [074] The pressure in the prepolymerization reactor is not critical, but it must be high enough to keep the reaction mixture in liquid phase. Thus, the pressure can be from 20 to 100 bar (2 s 10 MPa), for example 30 to 70 bar (3 to 7MPa).
    [075] In a preferred embodiment, the prepolymerization is carried out as volume suspension polymerization in liquid propylene, that is, the liquid phase mainly comprises propylene, with optionally inert components dissolved therein. Furthermore, according to the present invention, an ethylene feed is employed during prepolymerization as mentioned above.
    [076] It is possible to add other components also for the pre-polymerization phase. In this way, hydrogen can be added at the prepolymerization stage to control the molecular weight of polypropylene (Pre-PP) as is known in the art. In addition, the antistatic additive can be used to prevent the particles from adhering to each other or to the reactor walls.
    [077] Precise control of pre-polymerization conditions and reaction parameters are within the state of the art.
    [078] Due to the process conditions defined above in the pre-polymerization, a mixture (MI) of the Ziegler-Natta catalyst (ZN-C) and the polypropylene (Pre-PP) produced in the pre-reactor is preferably obtained. polymerization (PR) . Preferably the Ziegler-Natta (ZN-C) catalyst is (finely) dispersed in the polypropylene (Pre-PP). In other words, Ziegler-Natta (Zn-C) catalyst particles introduced into the prepolymerization reactor (PR) separate into smaller fragments, which are evenly distributed inside the growing polypropylene (Pre-PP). The particle sizes of introduced Ziegler-Natta catalyst (ZN-C) as well as the fragments obtained are not of essential importance to the present invention and within the skill of the art.
    [079] As mentioned above, if a pre-polymerization is used, subsequent to said pre-polymerization, the mixture (MI) of the Ziegler-Natta catalyst (ZN-C) and the polypropylene (Pre-PP) produced in the reactor of prepolymerization (PR) is transferred to the first reactor (Rl). Typically, the total amount of polypropylene (Pre-PP) in the final propylene copolymer (R-PP) is quite low and typically not more than 5.0% by weight, more preferably not more than 4.0% by weight , even more preferably in the range of 0.5 to 4.0% by weight, such as in the range of 1.0 to 3.0% by weight.
    [080] In the case that the prepolymerization is not used propylene and the other ingredients, such as the Ziegler-Natta catalyst (ZN-C) are directly introduced in the first polymerization reactor (Rl).
    [081] Therefore, the process according to the invention comprises the following steps under the conditions set out above (f) in the first polymerization reactor (Rl), that is, in a recirculation reactor (LR), the propylene is polymerized obtaining a first fraction of propylene homopolymer (H-PP1) of the propylene homopolymer (H-PP),(g) transferring said first fraction of propylene homopolymer (H-PP1) to a second polymerization reactor (R2),(h) ) in the second polymerization reactor (R2) propylene is polymerized in the presence of the first fraction of homopolymer of propylene (H-PP1) obtaining a second fraction of homopolymer of propylene (H-PP2) of the homopolymer of propylene, said first fraction of homopolymer of propylene (H-PP1) and said second fraction of propylene homopolymer (H-PP2) form the propylene homopolymer.
    [082] The pre-polymerization as described above can be carried out before step (a). The Ziegler-Natta catalyst (ZN-C), the external donor (ED) and the co-catalyst (Co)
    [083] As noted above, in the specific process for the preparation of the propylene copolymer (R-PP) as defined above a Ziegler-Natta (ZN-C) catalyst must be used. Therefore, the Ziegler-Natta catalyst (ZN-C) catalyst will now be described in more detail.
    [084] The catalyst used in the present invention is a solid Ziegler-Natta catalyst, which comprises the compounds (TC) of a IUPAC Group 4 to 6 transition metal, such as titanium, a Group 2 metal compound (MC) as a magnesium and an internal donor (ID) being a non-phthalic compound, preferably a non-phthalic acid ester, even more preferably being a non-phthalic dicarboxylic acid diester, as described in more detail below. Thus, the catalyst is totally free from unwanted phthalic compounds. Furthermore, the solid catalyst is free of any external support material, such as silica or MgCl2, but the catalyst is self-supporting.
    [085] The Ziegler-Natta (ZN-C) catalyst can be further defined by the way it is obtained. Therefore, the Ziegler-Natta (ZN-C) catalyst is preferably obtained by a process comprising steps a) to l) providing a solution of at least one Group 2 metal alkoxy (Ax) compound being the product of reaction of a group 2 metal compound (MC) and an alcohol (A) comprising, in addition to the hydroxyl moiety, at least an ether portion, optionally, in an organic liquid reaction medium; or a2) a solution of at least a Group 2 metal alkoxy compound (Ax') being the reaction product of a Group 2 metal compound (MC) and a mixture of alcohol of alcohol (A) and a monohydric alcohol (B) with the formula ROH, optionally in an organic liquid reaction medium; or a3) provide a solution of a mixture of a Group 2 alkoxy compound (Ax) and a Group 2 metal alkoxy compound (Bx) being the reaction product of a Group 2 metal compound ( MC) and the monohydric alcohol (B), optionally in an organic liquid reaction medium; and b) adding said solution from step a) to at least one compound (TC) of a Group 4 to 6 transition metal and c) obtaining the particles of the solid catalyst component, and adding a non-phthalic internal electron donor (ID) at any step before step c).
    [086] The internal donor (ID) or a precursor thereof is preferably added to the solution of step a).
    [087] According to the above procedure the Ziegler-Natta (ZN-C) catalyst can be obtained through the precipitation method or through emulsion (liquid/liquid two-phase system) - solidification method, depending on the conditions especially the temperature used in steps b) and c).
    [088] In both methods (precipitation or emulsion-solidification) the catalyst chemistry is the same.
    [089] In the precipitation method combining the solution of step a) with at least one transition metal compound (TC) in step b) is performed and the entire reaction mixture is kept at least at 50°C, plus preferably in the temperature range of 55 to 110°C, more preferably in the range of 70 to 10°C, to ensure complete precipitation of the catalyst component as solid particles (step c).
    [090] In the emulsion-solidification method in step b) the solution from step a) is typically added to at least one transition metal (TC) compound at a lower temperature such as -10 to below 50° C, preferably from -5 to 30°C. During stirring of the emulsion the temperature is typically maintained at -10 to below 40°C, preferably -5 to 30°C. Droplets from the dispersed phase of the emulsion form the composition of the active catalyst. The solidification (step c) of the droplets is suitably carried out by heating the emulsion to a temperature of 70 to 150°C, preferably 80 to 110°C.
    [091] The catalyst prepared by emulsion - solidification method is preferably used in the present invention.
    [092] In a preferred embodiment, in step a) the solution of a2) or a3) are used, that is, a solution of (Ax') or a solution of a mixture of (Ax) and (Bx).
    [093] Preferably the Group 2 metal (MC) is magnesium.
    [094] Magnesium alkoxy compounds (AX), (AX') and (Bx) can be prepared in situ in the first step of the catalyst preparation process, step a), by reacting the magnesium compound with the alcohol( s) as described above, either said magnesium alkoxy compounds can be separately prepared magnesium alkoxy compounds or they can be further commercially available as ready magnesium alkoxy compounds and used as such in the process of preparing the catalyst of the invention.
    [095] Illustrative examples of alcohols (A) are dihydric alcohol monoethers (glycol monoethers). Preferred alcohols (A) are C2 to C4 glycol monoethers, wherein the ether moieties comprise from 2 to 18 carbon atoms, preferably from 4 to 12 carbon atoms. Preferred examples are 2-(2-ethylhexyloxy)ethanol, 2-butyloxy ethanol, 2-hexyloxy ethanol and 1,3-propylene glycol-monobutyl ether, 3-butoxy-2-propanol, with 2-(2-ethylhexyloxy) ethanol and 1,3-propylene glycol-monobutyl ether, 3-butoxy-2-propanol being particularly preferred.
    [096] Illustrative monohydric alcohols (B) are of the formula ROH, where R being straight or branched chain C6-C10 alkyl residue. The most preferred monohydric alcohol is 2-ethyl-1-hexanol or octanol.
    [097] Preferably, a mixture of alkoxy compounds of Mg (Ax) and (Bx) or mixture of alcohols (A) and (B), respectively, are used and employed in a mole ratio of Bx:Ax or B :A from 8:1 to 2:1, more preferably 5:1 to 3:1.
    [098] Magnesium alkoxy compound can be a reaction product of alcohol(ols), as defined above, and a magnesium compound selected from dialkyl magnesiums, alkyl magnesium alkoxides, magnesium dialkoxides, magnesium alkoxy halides and alkyl magnesium halides. Alkyl groups can be similar or different to C 1 -C 20 alkyl, preferably C 2 -C 10 alkyl. Typical alkoxy-alkyl magnesium compounds, when used, are ethyl magnesium butoxide, butyl magnesium pentoxide, octyl magnesium butoxide and octyl magnesium octoxide. Preferably, dialkyl magnesiums are used. Most preferred dialkyl magnesiums are octyl butyl magnesium or ethyl butyl magnesium.
    [099] It is also possible that the magnesium compound can react in addition to alcohol (A) and alcohol (B), also with a polyhydric alcohol (C) with the formula R"(OH)m to obtain said compounds of magnesium alkoxide Preferred polyhydric alcohols, if used, are the alcohols, where R" is a straight chain C2 to C10 cyclic or branched hydrocarbon residue and m is an integer from 2 to 6.
    [100] The magnesium alkoxy compounds of step a) are thus selected from the group consisting of magnesium dialkoxides, diaryloxy magnesiums, alkyloxy magnesium halides, aryloxy magnesium halides, alkyl magnesium alkoxides, magnesium alkoxides of aryl and alkyl magnesium aryloxides. In addition a mixture of magnesium dihalide and a magnesium dialkoxide can be used.
    [101] The solvents to be used for the preparation of the catalyst of the present invention may be selected from cyclic and branched, linear aliphatic and aromatic hydrocarbons having 5 to 20 carbon atoms, more preferably 5 to 12 carbon atoms, or its mixtures. Suitable solvents include benzene, toluene, cumene, xylene, pentane, hexane, heptane, octane and nonane. Hexanes and pentanes are particularly preferred.
    [102] Compound Mg is typically provided as a 10 to 50% by weight solution in a solvent as indicated above. Typical commercially available Mg compounds, especially dialkyl magnesium solutions are 20 to 40% by weight solutions in toluene or heptanes.
    [103] The reaction for the preparation of the magnesium alkoxy compound can be carried out at a temperature of 40° to 70°C. The most suitable temperature is selected depending on the compound of Mg and alcohol(o) used.
    [104] The group 4 to 6 transition metal compound is preferably a titanium compound, more preferably a titanium halide such as TiCl4.
    [105] The internal donor (ID) used in preparing the catalyst used in the present invention is preferably selected from (di)esters of non-phthalic (di)carboxylic acids, 1,3-diethers, derivatives and mixtures thereof. Especially preferred donors are diesters of monounsaturated dicarboxylic acids, in particular esters belonging to a group comprising malonates, maleates, succinates, citraconates, glutarates, cyclohexene-1,2-dicarboxylate and benzoates, and any of their derivatives and /or its mixtures. Preferred examples are, for example, substituted maleates and citraconates, more preferably citraconates.
    [106] In the emulsion method, the liquid-liquid two-phase system can be formed by simple stirring and optionally the addition of (more) solvent(s) and additives such as the turbulence-minimizing agent (TMA) and /or emulsifying agents and/or emulsion stabilizers, such as surfactants, which are used in a manner known in the art to facilitate the formation of and/or stabilize the emulsion. Preferably, the surfactants are acrylic or methacrylic polymers. Particularly preferred are unbranched C12 to C20 (meth)acrylates such as poly(hexadecyl)methacrylate and poly(octadecyl)methacrylate and mixtures thereof. Turbulence Minimizing Agent (TMA), if used, is preferably selected from polymers of α-olefin monomers having 6 to 20 carbon atoms, such as polyoctene, polynonene, polydecene, polyundecene or polydodecene or mixtures thereof. Most preferable is polydecene.
    [107] The solid particulate product obtained by precipitation or emulsion - solidification method may be washed at least once, preferably at least twice, more preferably at least three times with aliphatic and/or aromatic hydrocarbons, preferably with toluene, heptane or pentane. The catalyst can be further dried, such as by evaporation or washing with nitrogen, or it can be mixed with an oily liquid without any drying step.
    [108] The finely obtained Ziegler-Natta catalyst is desirably in the form of particles generally having an average particle size range of 5 to 200 µm, preferably 10 to 100. The particles are compact with low porosity and have a surface area less than 20 g/m2, more preferably less than 10 g/m2. Typically, the amount of Ti is from 1 to 6% by weight, Mg from 10 to 20% by weight and donor from 10 to 40% by weight of the catalyst composition.
    [109] Detailed description of the preparation of catalysts is disclosed in WO 2012/007430, EP 2610271, EP 261027 and EP 2610272 which are incorporated herein by reference.
    [110] The Ziegler-Natta (ZN-C) catalyst is preferably used in association with an alkyl-aluminum co-catalyst and optionally external donors.
    [111] As an additional component in the present polymerization process an external donor (ED) is preferably present. Suitable external donors (ED) include certain silanes, ethers, esters, amines, ketones, heterocyclic compounds and mixtures thereof. It is especially preferred to use a silane. It is more preferred to use silanes of the general formulaRapRbqSi(0Rc)(4-pq)wherein Ra, Rb and Rc represent a hydrocarbon radical, in particular an alkyl group or cycloalkyl group, and which p and q are numbers ranging from 0 to 3, with a their sum p + q being equal to or less than 3. Ra, Rb and Rc can be chosen independently of each other and can be the same or different. Specific examples of such silanes are (tert-butyl) 2Si (OCH3) 2, (cyclohexyl) (methyl) Si (OCH3)2, (phenyl) 2Si (OCH3) 2 θ(cyclopentyl) 2Si (OCH3) 2, or of general formula Si(OCH2CH3)3(NR3R4)wherein R3 and R4 may be the same or different and represent a hydrocarbon group having 1 to 12 carbon atoms.
    [112] R3 and R4 are independently selected from the group consisting of linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms, and cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. carbon. It is particularly preferred that R3 and R4 are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso-pentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
    [113] More preferably both R1 and R2 are the same, even more preferably both R3 and R4 are an ethyl group.
    [114] Especially preferred external donors (ED) are the pentyl dimethoxy silane donor (Donor D) or the cyclohexylmethyl dimethoxy silane donor (Donor C), the latter being especially preferred.
    [115] In addition to the Ziegler-Natta catalyst (ZN-C) and the optional external donor (ED) a cocatalyst can be used. The cocatalyst is preferably a compound from group 13 of the Periodic Table (IUPAC), for example organoaluminium, such as an aluminum compound such as aluminum alkyl, aluminum halide or an aluminum alkyl halide compound. Thus, in a specific embodiment, the co-catalyst (Co) is a trialkylaluminum, such as triethylaluminum (TEAL), dialkyl aluminum chloride or alkyl aluminum dichloride or mixtures thereof. In a specific embodiment, the co-catalyst (Co) is triethylaluminum (TEAL).
    [116] Advantageously, aluminum triethyl (TEAL) has a hydride content, expressed as AIH3, of less than 1.0% by weight relative to aluminum triethyl (TEAL). More preferably, the hydride content is less than 0.5% by weight, and more preferably, the hydride content is less than 0.1% by weight.
    [117] Preferably, the ratio of co-catalyst (Co) to external donor (ED) [Co/ED] and/or the ratio of co-catalyst (Co) to transition metal (TM) [ Co/TM] must be carefully chosen.
    [118] Consequently (a) the mol ratio of co-catalyst (Co) to external donor (ED) [Co/ED] should be in the range of 5 to 45, preferably is in the range of 5 to 35, more preferably is in the range of 5 to 25; and optionally (b) the mol ratio of co-catalyst (Co) to titanium compound (TC) [Co/TC] should be in the range of above 80 to 500, preferably is in the range of 100 to 350, even more preferably it is in the range of 120 to 300.
    [119] The present invention is further illustrated below by means of examples.EXAMPLE. measurement methods
    [120] The following definitions of terms and methods of determination apply to the foregoing general description of the present invention including the claims as well as the examples below, unless otherwise defined. Microstructure quantification by NMR spectroscopy
    [121] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity and regioregularity of propylene homopolymers.
    [122] Quantitative 13C{1H] NMR spectra were recorded in the solution state using an Advance III 400 Bruker NMR spectrometer operating at 400.15 and 100.62 MHz for He C, respectively. All spectra were recorded using a 10mm extended temperature probe head optimized with 13C to 125°C using nitrogen gas for all tyres.
    [123] For propylene homopolymers approximately 200 mg of the material was dissolved in 1,2-tetrachloroethane-ck (TCE-d ). To ensure a homogeneous solution, after initial sample preparation in a heating block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion of the magnet, the tube was centrifuged at 10 Hz. This configuration was chosen mainly for the high resolution required for the quantification of tactical distribution (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) ) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromoecules 30 (1997) 6251). Standard single pulse excitation was employed using the NOE and bi-level WALTZ16 dissociation scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag, Reson 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 8192 (8k) transients were acquired per spectrum.
    [124] Quantitative 13C{XH} NMR spectra were processed, integrated, and quantitative relevant properties determined from the integrals using proprietary computer programs.
    [125] For all propylene homopolymers chemical shifts are internally referenced to the isotactic methyl pentad (mmmm) at 21.85 ppm
    [126] Characteristic signs corresponding to region defects (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253; Wng, WJ., Zhu, S. ., macromolecules 33 (2000), 1157; Cheng, HN, Macromolecules 17 (1984), 1950) or comonomer have been observed.
    [127] Tacticity distribution was quantified by integrating the methyl region between 23.6-19.7 ppm correcting for sites unrelated to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym Sci 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 30 (1997) 6251).
    [128] Specifically, the influence of region-defects and comonomer on the quantification of tacticity distribution was corrected by subtraction of region-defect and comonomer integrals representative of the specific integral regions of the stereo sequences.
    [129] Isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad sequences (mmmm) with respect to all pentad sequences: [mmmm]% = 100 * (mmmm/sum of all pentads).
    [130] The presence of 2.1-erythro regio-defects was indicated by the presence of two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites. Characteristic signs corresponding to other types of regio-defects were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).
    [131] The amount of 2.1-erythro regio-defects was quantified using the integral mean of the two characteristic methyl sites at 17.7 and 17.2 ppm: 21e = (Ie6 + lea)/2
    [132] The amount of primary 1,2-propene inserted 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: 12 = IcH3 + P12e
    [133] The total amount of propene was quantified as the sum of inserted primary propene and all other region defects present: Ptotal = P12 + 21e
    [134] The percentage in mol of 2.1-erythro region-defects was quantified in relation to all propenes: [21e] % in mol = 100* (P2ie/Ptotal)
    [135] MFR2 (230°C/2.16 kg) is measured in accordance with ISO 1133 (230°C, 2.16 kg load).
    [136] Fraction soluble in xylene at room temperature (XS, % by weight): The amount of polymer soluble in xylene at 25°C is determined in accordance with ISO 16152; first edition; 2005-07-01.
    [137] DSC analyses, melting temperature (Tm) and heat of melting (Hf), temperature of crystallization (Tc) and heat of crystallization (Hc): measured with a differential scanning calorimetry (DSC) TA Instrument Q200 in 5 to 7 mg samples. DSC is performed according to ISO 11357/part 3/method C2 in a heat/cold/heat cycle with a scan rate of 10°C/min in the temperature range from -30 to crystallization (Hc) are determined from from the cooling step, while the melting temperature and heat of melting (Hf) are determined from the second heating step p. -and
    [138] The glass transition temperature Tg is determined by dynamic mechanical analysis in accordance with ISO 6721-7. Measurements are made in the torsional mode in compression of molded samples (40x10xlmm3 between -100°C and +150°C, with a heating rate of 2°C/min and a frequency of 1 Hz.
    [139] Charpy Impact Test: Notched Charpy Impact Strength (NIS) was measured in accordance with ISO 179 leA at +23°C using 80xl0x4mm3 injection molded bar test samples prepared in accordance with ISO 294- 1:1996.
    [140] Tensile test: The modulus of tension was measured at 23°C in accordance with ISO 527-1 (pull speed 1 mm/min) using injection molded samples molded at 180°C or 200°C in accordance with ISO 527-2 (1B), produced in accordance with EN ISO 1873-2 (dog bone shape 10, thickness 4 mm).Total volatilesVOC
    [141] VOC was determined according to VDA 278:2002 from granules or plates 60x60x2mm3 prepared by injection molding according to ISO 294-1:1996.
    [142] VOC according to VDA 278 is the sum of all high and medium volatiles. It is calculated as toluene equivalent (TE). VOC according to VDA 278 represents all organic compounds at boiling point and elution range up to C2o (n-eicosane).FOG
    [143] FOG was determined according to VDA 278:2002 from granules or plates 60x60x2mm3 prepared by injection molding according to ISO 294-1:1996.
    [144] 4] FOG according to VDA 278 is the sum of all low volatility organic compounds that have an elution time greater than or equal to that of n-hexadecane. FOG is calculated as hexadecane equivalent (HE). FOG according to VDA 278 represents organic compounds in the boiling point range of C16 to C32 n-alkanes.
    [145] VDA standards are issued by "Verband der Automobilindustrie". The VDA standards used here are available from "Dokumentation Kraftfahrwesen (DKF); ülrichstrasse 14, D-74321 Bietigheim-Bissingen", Germany or can be downloaded from their website (www.dkf-ev.de).8. Examples
    [146] The catalyst used in the polymerization process of the propylene homopolymers of the examples of the invention (IE1 to IE3) was prepared as follows: Chemicals used: 20% solution in butyl ethyl magnesium toluene (Mg (Bu)( Et),BEM), supplied by Chemtura2-ethyl-hexanol, supplied by Amphochem3-Butoxy-2-propanol - (DOWANOL™ PNB), supplied by Dow bis(2-ethylhexyl)citraconate, supplied by SynphaBase TICI4, supplied by Millenium Chemicals Toluene, supplied by AspokemVISCOPLEX® 1-254, supplied by EvonikHeptano, supplied by Chevron Preparation of an alkoxy compound. of Mg
    [147] Magnesium alkoxide solution was prepared by adding, with stirring (70 rpm), 11 kg of a 20% by weight solution in butyl ethyl magnesium toluene (Mg(Bu)(Et)), a mixture. of 4.7 kg of 2-ethylhexanol and 1.2 kg of butoxypropanol in a 20 L stainless steel reactor. During the addition the reactor contents were kept below 45°C. After the addition was complete, mixing (70 rpm) of the reaction mixture was continued at 60°C for 30 minutes. After cooling to room temperature 2.3 kg g of bis(2-ethylhexyl)citraconate donor was added and the temperature of the Mg-alkoxide solution keeping the temperature below 25°C. Mixing was continued for 15 minutes under stirring (70 rpm). Preparation of solid catalyst component
    [148] 20.3 kg of TiCl4 and 1.1 kg of toluene were added to a 20 L stainless steel reactor. Under mixing at 350 rpm and keeping the temperature at 0°C, 14.5 kg of the alkoxy compound of Mg prepared in Example 1 was added over 1.5 hours. 1.7 L of Viscoplex® 1-254 and 7.5 kg of heptane were added and after 1 hour of mixing at 0°C the temperature of the formed emulsion was raised to 90°C within 1 hour. After 30 minutes, the mixture was stopped, catalyst drops were solidified and the formed catalyst particles were allowed to settle. After decanting (1 hour), the supernatant liquid was sucked out. Then, the catalyst particles were washed with 45 kg of toluene at 90°C for 20 minutes, followed by two washes with heptane (30 kg, 15 min). During the first wash with heptane the temperature was lowered to 50°C and during the second wash at room temperature.
    [149] The catalyst thus obtained was used together with triethyl aluminum (TEAL) as co-catalyst and dicyclopentyl dimethoxy silane (Donor D) or cyclohexylmethyl dimethoxy silane (Donor C) as donor.
    [150] The catalyst used in the polymerization processes of Comparative Examples (CEI and CE2) was the Avant ZN M1 catalyst together with triethyl aluminum (TEAL) as co-catalyst and cyclohexylmethyl dimethoxy silane (Donor C) as donor.
    [151] The aluminum to donor ratio, the aluminum to titanium ratio, and the polymerization conditions are shown in Table 1. Table 1: Preparation of Examples


    [152] CE2 is the commercial polypropylene homopolymer HK060AE available from Borealis AG.Table 2: Properties of Examples

    权利要求:
    Claims (12)
    [0001]
    1. Propylene homopolymer, characterized in that it has: (a) MFR2 melt index (230°C/2.16 kg) measured in accordance with ISO 1133 in the range of 75.0 to 500 g/10 min; and(b) a pentate isotacticity (mmmm) of more than 90.0%, determined by 13C-NMR spectroscopy, yet(c) the homopolymer of propylene fulfills the inequality (DVOC <■ (MFR x 0.08) + 201 .0where VOC is the amount of volatile organic compounds (VOC) [in ppm] measured according to VDA 278:2002 of the homopolymer of propylene; MFR is the melt index MFR2 (230°C/2.16 kg) measured accordingly with ISO 1133 of the homopolymer of propylene, and (d) the homopolymer of propylene has a melting temperature Tm of equal to or greater than 160°C.
    [0002]
    2. Propylene homopolymer according to claim 1, characterized in that it has an amount of volatile organic compounds (VOC) measured in accordance with VDA 278:2002 equal to or below 210 ppm.
    [0003]
    3. Propylene homopolymer according to claim 1 or 2, characterized in that it has a crystallization temperature of equal to or greater than 114 °C.
    [0004]
    4. Propylene homopolymer according to any one of the preceding claims, characterized in that it has a cold soluble xylene (XCS) content determined in accordance with ISO 16152 (25°C) of at least 1.8% by weight .
    [0005]
    5. Propylene homopolymer, according to any one of the preceding claims, characterized in that it has 2.1 erythro regio-defects equal to or below 0.4% in mol determined by 13C-NMR spectroscopy.
    [0006]
    6. Propylene homopolymer, according to any one of the preceding claims, characterized in that it has a pentate isotacticity (mramm) of more than 93.0%.
    [0007]
    7. Propylene homopolymer according to any of the preceding claims, characterized in that it meets the inequality (II)FOG < (MFR x 1.26) + 350.0 where FOG is the amount of erratic compounds (FOG) [in ppm] measured in accordance with VDA 278:2002 for propylene homopolymer; MFR is the melt index MFR2 (230°C/2.16 kg) measured in accordance with ISO 1133 for propylene homopolymer.
    [0008]
    8. Propylene homopolymer according to any one of the preceding claims, characterized in that the amount of fogging compounds (FOG) measured in accordance with. VDA 278:2002 of no more dc than 580 ppm.
    [0009]
    9. Propylene homopolymer according to any one of the preceding claims, characterized in that it has a modulus of tension measured at 23°C according to ISO 527-1 (pull speed of 1 mm/min) of at least 1500 MPa.
    [0010]
    10. Article, characterized in that it comprises propylene homopolymer as defined in any one of the preceding claims.
    [0011]
    11. Process for the production of a homopolymer of propylene, as defined in any one of the preceding claims, characterized in that the propylene was polymerized in the presence of (a) a Ziegler-Natta (ZN-C) catalyst comprising the compounds (TC) of an IUPAC Group 4 to 6 transition metal, a Group 2 metal compound (MC) and an internal donor (ID), wherein said internal donor (ID) is a non-phthalic compound selected from optionally substituted glutarates and citraconate; (b) optionally a co-catalyst (Co), (c) optionally an external donor (ED), and (d) the mole ratio of co-catalyst (Co) to external donor (ED) [Co/ED] is 5 to 45.
    [0012]
    12. Process according to claim 11, characterized in that the homopolymer of propylene is produced in a sequential polymerization process that comprises at least two reactors (Rl) and (R2), in the first reactor (Rl) a fraction of first homopolymer of propylene (H-PP1) is produced and subsequently transferred to the second reactor (R2), in the second reactor (R2) a second fraction of homopolymer of propylene (H-PP2) is produced in the presence of the first fraction of homopolymer of propylene (H-PP1).
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112016009549B1|2021-07-27|LOW EMISSION PROPYLENE HOMOPOLYMER WITH HIGH FLUIDITY INDEX
    US10100185B2|2018-10-16|Soft copolymers with high impact strength
    US9828698B2|2017-11-28|Phthalate-free PP homopolymers for meltblown fibers
    US9896524B2|2018-02-20|Low emission propylene homopolymer
    AU2014270633B2|2016-06-02|Polypropylene for film applications
    US10138335B2|2018-11-27|Injection molded article based on propylene homopolymer
    US10280285B2|2019-05-07|Propylene copolymer composition with improved long-term mechanical properties
    WO2016135108A1|2016-09-01|Propylene copolymer composition with improved long-term mechanical properties
    US10919993B2|2021-02-16|Injection molded article based on propylene homopolymer
    同族专利:
    公开号 | 公开日
    ZA201601229B|2017-05-31|
    EA201600372A1|2016-08-31|
    EP3071606B1|2017-08-16|
    MX2016005723A|2016-12-16|
    WO2015075088A1|2015-05-28|
    KR20160066551A|2016-06-10|
    CN105722872A|2016-06-29|
    JP2016537462A|2016-12-01|
    MX368147B|2019-09-20|
    EP3071606A1|2016-09-28|
    CN105722872B|2017-10-13|
    EA031527B1|2019-01-31|
    BR112016009549A2|2017-08-01|
    US20160272740A1|2016-09-22|
    ES2644829T3|2017-11-30|
    CA2927448A1|2015-05-28|
    CA2927448C|2017-01-17|
    US9751962B2|2017-09-05|
    KR101682342B1|2016-12-05|
    JP6106342B2|2017-03-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4107414A|1971-06-25|1978-08-15|Montecatini Edison S.P.A.|Process for the stereoregular polymerization of alpha olefins|
    US4226963A|1971-06-25|1980-10-07|Montedison S.P.A.|Process for the stereoregular polymerization of alpha-olephins|
    US4186107A|1978-04-14|1980-01-29|Hercules Incorporated|Solid catalyst component for olefin polymerization|
    US4347160A|1980-06-27|1982-08-31|Stauffer Chemical Company|Titanium halide catalyst system|
    IT1209255B|1980-08-13|1989-07-16|Montedison Spa|CATALYSTS FOR THE POLYMERIZATION OF OLEFINE.|
    JPS57153005A|1981-03-19|1982-09-21|Ube Ind Ltd|Polymerization of alpha-olefin|
    US4530912A|1981-06-04|1985-07-23|Chemplex Company|Polymerization catalyst and method|
    EP0072129B2|1981-08-07|1990-02-28|Imperial Chemical Industries Plc|Supported transition metal composition|
    US4382019A|1981-09-10|1983-05-03|Stauffer Chemical Company|Purified catalyst support|
    IT1190682B|1982-02-12|1988-02-24|Montedison Spa|CATALYSTS FOR THE POLYMERIZATION OF OLEFINE|
    IT1190683B|1982-02-12|1988-02-24|Montedison Spa|COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE|
    IT1190681B|1982-02-12|1988-02-24|Montedison Spa|COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE|
    US4532313A|1982-10-13|1985-07-30|Himont Incorporated|Method for preparing an improved catalyst support, Ziegler-Natta catalyst utilizing said support and polymerization of 1-olefins utilizing said catalyst|
    US4560671A|1983-07-01|1985-12-24|Union Carbide Corporation|Olefin polymerization catalysts adapted for gas phase processes|
    US4657882A|1984-11-26|1987-04-14|Amoco Corporation|Supported olefin polymerization catalyst produced from a magnesium alkyl/organophosphoryl complex|
    US4581342A|1984-11-26|1986-04-08|Standard Oil Company |Supported olefin polymerization catalyst|
    US4665208A|1985-07-11|1987-05-12|Exxon Chemical Patents Inc.|Process for the preparation of alumoxanes|
    FI80055C|1986-06-09|1990-04-10|Neste Oy|Process for preparing catalytic components for polymerization of olefins|
    US5077255A|1986-09-09|1991-12-31|Exxon Chemical Patents Inc.|New supported polymerization catalyst|
    EP0287666B1|1986-09-24|1993-05-26|Mitsui Petrochemical Industries, Ltd.|Process for polymerizing olefins|
    JPH0780933B2|1986-11-20|1995-08-30|三井石油化学工業株式会社|Olefin Polymerization Method|
    JPH0742301B2|1987-02-14|1995-05-10|三井石油化学工業株式会社|Particulate aluminoxane, its manufacturing method and its use|
    JP2538588B2|1987-04-03|1996-09-25|三井石油化学工業株式会社|Method for producing solid catalyst for olefin polymerization|
    US5206199A|1987-04-20|1993-04-27|Mitsui Petrochemical Industries, Ltd.|Catalyst for polymerizing an olefin and process for polymerizing an olefin|
    US5091352A|1988-09-14|1992-02-25|Mitsui Petrochemical Industries, Ltd.|Olefin polymerization catalyst component, olefin polymerization catalyst and process for the polymerization of olefins|
    IT1227260B|1988-09-30|1991-03-28|Himont Inc|DIETTERS THAT CAN BE USED IN THE PREPARATION OF ZIEGLER-NATTA CATALYSTS|
    US4908463A|1988-12-05|1990-03-13|Ethyl Corporation|Aluminoxane process|
    US5103031A|1989-02-21|1992-04-07|Ethyl Corporation|Falling film aluminoxane process|
    US4968827A|1989-06-06|1990-11-06|Ethyl Corporation|Alkylaluminoxane process|
    US4924018A|1989-06-26|1990-05-08|Ethyl Corporation|Alkylaluminoxane process|
    US5504169A|1989-09-13|1996-04-02|Exxon Chemical Patents Inc.|Process for producing amorphous poly-α-olefins with a monocyclopentadienyl transition metal catalyst system|
    US5036034A|1989-10-10|1991-07-30|Fina Technology, Inc.|Catalyst for producing hemiisotactic polypropylene|
    JPH0813826B2|1990-11-29|1996-02-14|信越化学工業株式会社|Thexyltrialkoxysilane|
    FI86866C|1990-12-19|1992-10-26|Neste Oy|FOERFARANDE FOER MODIFIERING AV CATALYSTATOR AVSEDDA FOER POLYMERISATION AV OLEFINER|
    FI86867C|1990-12-28|1992-10-26|Neste Oy|FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN|
    SE467825B|1991-01-22|1992-09-21|Neste Oy|SETTING OUT OF PLASTIC MATERIALS ELIMINATE SMELLING / TASTEING OBJECTS|
    FI88048C|1991-05-09|1993-03-25|Neste Oy|Coarse-grained polyolefin, its method of preparation and a catalyst used in the method|
    FI88049C|1991-05-09|1993-03-25|Neste Oy|Large pore polyolefin, process for its preparation and a catalyst used in the process|
    FI88047C|1991-05-09|1993-03-25|Neste Oy|Catalyst-based catalyst for polymerization of olivines|
    FI90247C|1991-05-31|1994-01-10|Borealis As|Process for the preparation of active and uniform carrier particles for polymerization catalysts|
    US5308815A|1991-07-26|1994-05-03|Ethyl Corporation|Heterogeneous methylaluminoxane catalyst system|
    US5157137A|1991-07-26|1992-10-20|Ethyl Corporation|Method of making gel free alkylaluminoxane solutions|
    US5416228A|1991-10-07|1995-05-16|Fina Technology, Inc.|Process and catalyst for producing isotactic polyolefins|
    FI90248C|1991-11-29|1994-01-10|Borealis As|A process for preparing a particulate support for an olefin polymerization catalyst|
    FI91967C|1991-11-29|1994-09-12|Borealis Polymers Oy|Process for the preparation of olefin polymerization catalysts|
    US5329032A|1992-03-18|1994-07-12|Akzo Chemicals Inc.|Polymethylaluminoxane of enhanced solution stability|
    US5235081A|1992-03-18|1993-08-10|Ethyl Corporation|Method of removing gel forming materials from methylaluminoxanes|
    FI95715C|1992-03-24|1996-03-11|Neste Oy|Preparation of polymerization catalyst support prepared by spray crystallization|
    US5248801A|1992-08-27|1993-09-28|Ethyl Corporation|Preparation of methylaluminoxanes|
    US5939346A|1992-11-02|1999-08-17|Akzo Nobel N.V.|Catalyst system comprising an aryloxyaluminoxane containing an electron withdrawing group|
    US5391793A|1992-11-02|1995-02-21|Akzo Nobel N.V.|Aryloxyaluminoxanes|
    US5332706A|1992-12-28|1994-07-26|Mobil Oil Corporation|Process and a catalyst for preventing reactor fouling|
    US5391529A|1993-02-01|1995-02-21|Albemarle Corporation|Siloxy-aluminoxane compositions, and catalysts which include such compositions with a metallocene|
    US5529850A|1994-07-05|1996-06-25|Montell North America Inc.|Fibers produced from crystalline propylene polymers having high melt flow rate values and a narrow molecular weight distribution|
    CA2121721C|1993-04-29|2004-11-23|Giampiero Morini|Crystalline propylene polymers having high melt flow rate values and a narrow molecular weight distribution|
    DE69431222T2|1993-06-07|2003-04-17|Mitsui Chemicals Inc|Transition metal compound, and polymerization catalyst containing the same|
    DE4337251A1|1993-09-27|1995-03-30|Hoechst Ag|Biaxially oriented polypropylene film with improved properties in terms of mechanics and barrier|
    FI96866C|1993-11-05|1996-09-10|Borealis As|Support olefin polymerization catalyst, its preparation and use|
    FI96214C|1994-05-31|1996-05-27|Borealis As|Stereospecific catalyst system for the polymerization of olefins|
    US6322883B1|1994-07-15|2001-11-27|Exxonmobil Oil Corporation|Uniaxially shrinkable biaxially oriented polypropylene film with HDPE skin|
    US5691043A|1994-07-15|1997-11-25|Mobil Oil Corporation|Uniaxially shrinkable biaxially oriented polypropylene film and its method of preparation|
    IL117114A|1995-02-21|2000-02-17|Montell North America Inc|Components and catalysts for the polymerization ofolefins|
    US5731253A|1995-07-27|1998-03-24|Albemarle Corporation|Hydrocarbylsilloxy - aluminoxane compositions|
    US6403772B1|1995-09-11|2002-06-11|Montell Technology Company, Bv|Open-pentadienyl metallocenes, precursors thereof and polymerization catalysts therefrom|
    US5922631A|1995-10-19|1999-07-13|Albemarle Corporation|Liquid clathrate aluminoxane compositions as co-catalysts with transition metal catalyst compounds|
    US5670682A|1995-10-19|1997-09-23|Albemarle Corporation|Liquid clathrate aluminoxane compositions|
    US5693838A|1995-11-13|1997-12-02|Albemarle Corporation|Aluminoxane process and product|
    FI104826B|1996-01-30|2000-04-14|Borealis As|Heteroatom-substituted metallose compounds for catalytic systems in olefin polymerization and process for their preparation|
    FI102070B1|1996-03-29|1998-10-15|Borealis As|New complex compound, its preparation and use|
    US5731451A|1996-07-12|1998-03-24|Akzo Nobel Nv|Modified polyalkylauminoxane composition formed using reagent containing aluminum trialkyl siloxide|
    FI963707A0|1996-09-19|1996-09-19|Borealis Polymers Oy|Free polymerization of an alpha-olefin, by polymerization with an optional catalyst and further preparation of a polymer|
    JP2001504401A|1996-10-14|2001-04-03|ディーエスエムエヌ．ブイ．|Rod-shaped pellets|
    US5744656A|1996-10-25|1998-04-28|Boulder Scientific Company|Conversion of hexafluorobenzene to bromopentafluorobenzene|
    BR9808827B1|1997-03-07|2009-12-01|process for the preparation of indanones, and use of an indanone.|
    FI971565A|1997-04-14|1998-10-15|Borealis As|Substituted metallocene compounds for catalyst systems intended for polymerization of olefins, intermediates and processes for their preparation|
    GB9708487D0|1997-04-25|1997-06-18|Bp Chem Int Ltd|Novel catalysts for olefin polymerisation|
    WO1998056831A1|1997-06-10|1998-12-17|Peroxid-Chemie Gmbh & Co. Kg.|New catalyst systems for polymerization reactions, metallocene amide halogenides, the production and use thereof|
    FI111847B|1997-06-24|2003-09-30|Borealis Tech Oy|A process for the preparation of copolymers of propylene|
    FI104824B|1997-06-24|2000-04-14|Borealis As|Process for producing propylene polymers|
    FI111846B|1997-06-24|2003-09-30|Borealis Tech Oy|Process and apparatus for preparing mixtures of polypropylene|
    FI111848B|1997-06-24|2003-09-30|Borealis Tech Oy|Process and equipment for the preparation of homopolymers and copolymers of propylene|
    FI111845B|1997-06-24|2003-09-30|Borealis Tech Oy|Process for producing propylene homopolymers and polymers with modified impact strength|
    CN1140554C|1997-06-24|2004-03-03|波里阿利斯有限公司|Process for preparing propylene copolymers|
    FI973451A0|1997-08-22|1997-08-22|Borealis As|New organometallic processes and methods For the polymerization of olefins with the aid of a catalytic composition with an organic compound|
    ID24448A|1997-09-05|2000-07-20|Bp Chemical Ltd|POLYMERIZATION CATALYSTS|
    FI980342A0|1997-11-07|1998-02-13|Borealis As|Polymerroer och -roerkopplingar|
    GB9721559D0|1997-10-11|1997-12-10|Bp Chem Int Ltd|Novel polymerisation catalysts|
    FI974175A|1997-11-07|1999-05-08|Borealis As|Process for producing polypropylene|
    JP2001527136A|1997-12-23|2001-12-25|ボレアリステクノロジーオイ|Catalyst component containing magnesium, titanium, halogen and electron donor, method of making and using the same|
    WO1999041290A1|1998-02-12|1999-08-19|University Of Delaware|Catalyst compounds with beta-diiminate anionic ligands and processes for polymerizing olefins|
    GB9826874D0|1998-12-07|1999-01-27|Borealis As|Process|
    FI991057A0|1999-05-07|1999-05-07|Borealis As|High stiffness propylene polymers and process for their preparation|
    BRPI0016723B1|1999-12-23|2018-02-27|Basell Polyolefine Gmbh.|METALOCENE, CATALYST SYSTEM, AND PROCESS FOR THE COPOLIMERIZATION OF PROPYLENE WITH ETHYLENE|
    US6384142B1|2000-02-08|2002-05-07|Exxonmobil Chemical Patents Inc.|Propylene impact copolymers|
    GB0007002D0|2000-03-22|2000-05-10|Borealis Polymers Oy|Catalysts|
    EP1313746B1|2000-06-30|2005-07-27|ExxonMobil Chemical Patents Inc.|Metallocenes with a bridged 4-phenyl-indenyl-ligand for olefin polymerisation|
    US6642317B1|2000-11-15|2003-11-04|Polypropylene Belgium Naamlose Vennootschap|Composition based on propylene polymers and process for obtaining same|
    US6586528B1|2000-11-15|2003-07-01|Polypropylene Belgium |Composition based on propylene polymers and process for obtaining same|
    TWI238169B|2000-12-22|2005-08-21|Basell Technology Co Bv|Bioriented polypropylene films|
    CA2406611A1|2000-12-22|2002-07-04|Basell Poliolefine Italia S.P.A.|Polyolefin sheets for thermoforming|
    ES2265376T3|2001-06-20|2007-02-16|Borealis Technology Oy|PREPARATION OF CATALYST COMPONENT FOR POLYMERIZATION OF OLEFINS.|
    AT328912T|2001-06-20|2006-06-15|Borealis Tech Oy|Preparation of a catalyst component for olefin polymerisation|
    EP1359171B1|2001-06-27|2005-10-26|Borealis Technology Oy|Propylene polymer resin with improved properties|
    DE60211012T2|2001-11-27|2007-05-03|Basell Poliolefine Italia S.R.L.|Transparent and flexible polypropylene compositions|
    TWI268939B|2001-12-12|2006-12-21|Basell Poliolefine Spa|Process for the polymerization of olefins|
    EP1323747A1|2001-12-19|2003-07-02|Borealis Technology Oy|Production of olefin polymerisation catalysts|
    ES2236371T5|2002-02-04|2011-08-01|Borealis Technology Oy|LAMINARY MATERIAL WITH HIGH IMPACT RESISTANCE.|
    WO2003082879A1|2002-03-28|2003-10-09|Albemarle Corporation|Ionic aluminoxanate compositions and their use in catalysis|
    BR0215768A|2002-06-25|2005-03-15|Borealis Tech Oy|Process for the preparation of a biomodal rubber polypropylene polymer composition, polymer product, use of polymer, and molded article|
    AT396472T|2002-06-26|2008-06-15|Avery Dennison Corp|LENGTH-ORIENTED POLYMER FILMS|
    AU2003250201B2|2002-08-01|2008-12-11|Basell Poliolefine Italia S.P.A.|Highly stereoregular polypropylene with improved properties|
    US7807769B2|2002-09-20|2010-10-05|Exxonmobil Chemical Patents Inc.|Isotactic polypropylene produced from supercritical polymerization process|
    AU2003270780A1|2002-09-20|2004-04-08|Exxonmobil Chemical Patents Inc.|Polymer production at supercritical conditions|
    EP1403292B1|2002-09-30|2016-04-13|Borealis Polymers Oy|Process for preparing an olefin polymerisation catalyst component with improved high temperature activity|
    AT364436T|2002-11-22|2007-07-15|Basell Polyolefine Gmbh|SECURE REMOVAL OF VOLATILE, OXIDIZABLE COMPOUNDS FROM PARTICLES, ESPECIALLY FROM POLYMER PARTICLES|
    EP1452630A1|2003-02-26|2004-09-01|Borealis Technology OY|Polypropylene fibres|
    EP1484343A1|2003-06-06|2004-12-08|Universiteit Twente|Process for the catalytic polymerization of olefins, a reactor system and its use in the same process|
    GB0317012D0|2003-07-21|2003-08-27|Borealis Tech Oy|Injection moulding polymer|
    DE10359366A1|2003-12-18|2005-07-21|Nordenia Deutschland Gronau Gmbh|Labeling film laminate|
    EP1697445A1|2003-12-24|2006-09-06|Petroquimica Cuyo S.A.I.C.|Sealing layer resin compositions|
    US20050187367A1|2004-02-19|2005-08-25|Sumitomo Chemical Company, Limited|Biaxially oriented polypropylene film|
    US20050200046A1|2004-03-10|2005-09-15|Breese D. R.|Machine-direction oriented multilayer films|
    US7285608B2|2004-04-21|2007-10-23|Novolen Technology Holdings C.V.|Metallocene ligands, metallocene compounds and metallocene catalysts, their synthesis and their use for the polymerization of olefins|
    ES2399823T3|2004-09-02|2013-04-03|Borealis Technology Oy|A polymer pipe without pressure, a composition for it, and a process for its preparation|
    US8222175B2|2004-12-31|2012-07-17|Borealis Technology Oy|Process for the preparation of an olefin polymerisation catalyst|
    CN100363417C|2005-01-28|2008-01-23|中国石油化工股份有限公司|Polypropylene composition and the biaxial stretching film prepared thereof|
    US20060177641A1|2005-02-09|2006-08-10|Breese D R|Multilayer polyethylene thin films|
    US20060211801A1|2005-03-16|2006-09-21|Fina Technology, Inc.|Polyolefin film and production thereof|
    ES2316050T3|2005-03-18|2009-04-01|Basell Polyolefine Gmbh|METALOCENE COMPOUNDS.|
    EP1726602A1|2005-05-27|2006-11-29|Borealis Technology Oy|Propylene polymer with high crystallinity|
    EP1741725B1|2005-07-08|2014-04-09|Borealis Technology Oy|Propylene polymer composition|
    EP1788023A1|2005-11-21|2007-05-23|Borealis Technology Oy|Multimodal polypropylene polymer composition|
    US7514509B2|2005-12-16|2009-04-07|Fina Technology, Inc.|Catalyst compositions and methods of forming isotactic polyproyplene|
    ES2588577T3|2005-12-30|2016-11-03|Borealis Technology Oy|Catalyst particles|
    EP1996600B1|2006-03-17|2011-09-28|Basell Polyolefine GmbH|Metallocene compounds|
    US20070235896A1|2006-04-06|2007-10-11|Fina Technology, Inc.|High shrink high modulus biaxially oriented films|
    EP2004664B1|2006-04-12|2016-12-14|Basell Polyolefine GmbH|Metallocene compounds|
    US7772338B2|2006-04-24|2010-08-10|Total Petrochemicals Research Feluy|Use of a Ziegler-Natta catalyst to make a polypropylene homopolymer or random copolymer having a high melt flow rate|
    ES2594859T3|2006-05-31|2016-12-23|Borealis Technology Oy|Catalyst with Al-alkoxy component|
    AT421760T|2006-07-10|2009-02-15|Borealis Tech Oy|ELECTRIC INSULATION FILM|
    US7977435B2|2006-07-12|2011-07-12|Lin Chon-Yie|Propylene polymer compositions and processes for making the same|
    EP1892264A1|2006-08-25|2008-02-27|Borealis Technology Oy|Extrusion coated substrate|
    EP1902837A1|2006-09-22|2008-03-26|Borealis Technology OY|Multilayer film|
    EP1923200A1|2006-11-20|2008-05-21|Borealis Technology Oy|Article|
    AT432165T|2006-12-18|2009-06-15|Borealis Tech Oy|TERPOLYMER WITH HIGH MELTING POINT|
    WO2008074713A1|2006-12-20|2008-06-26|Basell Poliolefine Italia S.R.L.|Filled polyolefin compositions|
    DE602006009412D1|2006-12-21|2009-11-05|Borealis Tech Oy|Movie|
    EP1947143A1|2007-01-19|2008-07-23|Borealis Technology Oy|Polypropylene-based resin composition and molded article thereof|
    EP1950233A1|2007-01-25|2008-07-30|Borealis Technology Oy|polymer|
    EP1950241A1|2007-01-25|2008-07-30|Borealis Technology Oy|Multimodal medium density polyethylene polymer composition|
    KR101497726B1|2007-04-27|2015-03-02|바셀 폴리올레핀 이탈리아 에스.알.엘|Butene-1 terpolymers and process for their preparation|
    AT438666T|2007-05-08|2009-08-15|Borealis Tech Oy|FOIL FOR ELECTRICAL INSULATION|
    EP2014714A1|2007-07-11|2009-01-14|Borealis Technology Oy|Heterophasic polyolefin composition|
    RU2458734C2|2007-08-03|2012-08-20|Базелль Полиолефин Италия С.Р.Л.|Method of producing propylene terpolymers|
    RU2487897C2|2008-08-21|2013-07-20|ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи|High melt flow rate, impact-resistant propylene copolymer and method for production thereof|
    CN101815727B|2007-08-27|2013-05-15|保瑞利斯科技公司|Catalysts|
    WO2009054832A1|2007-10-25|2009-04-30|Novolen Technology Holdings, C.V.|Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo-and copolymers|
    CN101855289A|2007-11-13|2010-10-06|普瑞曼聚合物株式会社|Propylene resin composition for stretched sheet, and stretched sheet and thermally molded article each comprising the composition|
    EP2062936A1|2007-11-20|2009-05-27|Borealis Technology OY|Improved glass fiber reinforced polypropylene|
    AT539815T|2007-11-30|2012-01-15|Borealis Tech Oy|PROCESS FOR THE PREPARATION OF RANDOM PROPYLENE COPOLYMERS|
    EP2363433B1|2007-12-17|2018-02-07|Borealis Technology OY|Heterophasic polypropylene with high flowability and excellent low temperature impact properties|
    CN101903424A|2007-12-18|2010-12-01|巴塞尔聚烯烃意大利有限责任公司|Copolymers of propylene with hexene-1 and blown films obtained from them|
    EP2350145B1|2008-11-04|2018-08-15|ExxonMobil Chemical Patents Inc.|Homogeneous propylene polymerization in supercritical state and polypropylenes made therefrom|
    AT513013T|2008-01-25|2011-07-15|Borealis Ag|WEAKKEY ADDITIVE COMPOSITION FOR APPLICATIONS IN MOTOR VEHICLE INTERIORS|
    EP2147939A1|2008-07-22|2010-01-27|Borealis AG|Polypropylene composition with improved optics for film and moulding applications|
    US20100081760A1|2008-10-01|2010-04-01|Sunoco, Inc. |Film comprising a random copolymer with enhanced ethylene content|
    WO2010039715A1|2008-10-01|2010-04-08|Sunoco Chemicals, Inc.|Random copolymer with enhanced ethylene content|
    EP2174980B2|2008-10-07|2018-10-24|Borealis AG|High flowable heterophasic polypropylene|
    ES2619729T3|2008-11-07|2017-06-26|Borealis Ag|Solid catalyst composition|
    EP2361267B1|2008-11-07|2015-03-04|Borealis AG|Process to prepare a solid catalyst composition|
    EP2417195B1|2009-04-09|2013-03-20|Borealis AG|Thermoplastic polyolefin composition|
    EP2251361B1|2009-05-04|2013-10-02|Borealis AG|Preparation of precipitated ZN PP catalysts with internal pore structure using nanoparticles|
    EP2275476A1|2009-06-09|2011-01-19|Borealis AG|Automotive material with excellent flow, high stiffness, excellent ductility and low CLTE|
    US8389660B1|2009-06-10|2013-03-05|The Florida State University Research Foundation|Polyolefins having reduced crystallinity|
    US20110031645A1|2009-08-07|2011-02-10|Dow Global Technologies Inc.|Polypropylene for use in bopp applications|
    EP2530116B1|2009-08-28|2017-10-11|Borealis AG|Polypropylene-talc composite with reduced malodour|
    EP2305723A1|2009-10-01|2011-04-06|Total Petrochemicals Research Feluy|Propylene polymer with improved processability in thermoforming.|
    SI2308923T1|2009-10-09|2012-08-31|Borealis Ag|Glass fibre composite of improved processability|
    EP2325248B1|2009-11-16|2012-05-16|Borealis AG|Melt blown fibers of polypropylene compositions|
    EP2553016B1|2010-03-26|2019-05-29|Basell Poliolefine Italia S.r.l.|Heterophasic polyolefin composition|
    ES2710606T3|2010-04-20|2019-04-26|Borealis Ag|Polypropylene bottles|
    ES2392240T3|2010-04-20|2012-12-07|Borealis Ag|Car interior compound|
    EP2386603B1|2010-04-21|2012-04-04|Borealis AG|Propylene/1-hexene copolymer composition with broad sealing window|
    BR112012026909B1|2010-04-21|2020-03-10|Borealis Ag|COMPOSITION OF PROPYLENE / 1-HEXEN COPOLYMER WITH LOW SEALING TEMPERATURE, ITS PREPARATION PROCESS, FILM, AND EXTRUSION COATED SUBSTRATE|
    JP5785609B2|2010-04-28|2015-09-30|ボレアリス エージー|catalyst|
    CN103025767B|2010-04-28|2015-01-14|博瑞立斯有限公司|Solid particulate catalysts comprising bridged metallocenes|
    EP2386583A1|2010-05-07|2011-11-16|Borealis AG|Process for the preparation of a solid metallocene catalyst system and its use in polymerisation of olefins|
    ES2564189T3|2010-05-07|2016-03-18|Borealis Ag|Preparation of a solid catalyst system|
    KR20150027234A|2010-05-12|2015-03-11|보레알리스 아게|Polypropylene with specific calcium stearate content for special capacitors|
    EP2571932B1|2010-05-21|2017-07-05|Borealis AG|Composition|
    BR112012033011B1|2010-06-24|2020-05-26|Basell Poliolefine Italia S.R.L.|CATALYST SYSTEM AND PROCESS FOR POLYMERIZING OLEFINS USING SUCH SYSTEM|
    EP2402353B1|2010-07-01|2018-04-25|Borealis AG|Group 4 metallocenes useful as catalysts for the polymerization of olefins|
    ES2525554T3|2010-07-13|2014-12-26|Borealis Ag|Catalyst component|
    EP2410007B1|2010-07-22|2014-06-11|Borealis AG|Polypropylene/talc composition with improved impact behavior|
    ES2455694T3|2010-08-06|2014-04-16|Borealis Ag|Multilayer film|
    EP2415831A1|2010-08-06|2012-02-08|Borealis AG|Heterophasic propylene copolymer with excellent impact/stiffness balance|
    ES2397547T3|2010-08-27|2013-03-07|Borealis Ag|Rigid polypropylene composition with excellent break elongation|
    US9062232B2|2011-01-03|2015-06-23|Borealis Ag|Sealing material of polypropylene with improved optical performance|
    EP2479025B1|2011-01-25|2019-03-06|Mondi Gronau GmbH|Sticker film|
    EP2487203B2|2011-02-14|2020-11-25|Borealis AG|Sealing propylene copolymer|
    EP2532687A3|2011-06-10|2013-04-10|Borealis AG|Bridged Metallocene Catalysts|
    US9969820B2|2011-07-01|2018-05-15|Basell Poliolefine Italia S.R.L.|Polypropylene films and sheets|
    ES2643158T3|2011-07-08|2017-11-21|Borealis Ag|Catalysts|
    ES2552779T3|2011-07-15|2015-12-02|Borealis Ag|Composition of high fluid polyolefin with low shrinkage and CLTE|
    ES2628836T3|2011-07-15|2017-08-04|Borealis Ag|Non-oriented film|
    ES2626661T3|2011-07-27|2017-07-25|Borealis Ag|Lightweight polypropylene resin with superior surface characteristics for use in automotive interior applications|
    EP2565221B2|2011-08-30|2018-08-08|Borealis AG|Process for the manufacture of a capacitor film|
    EP3181637B1|2011-09-21|2017-11-29|Borealis AG|Moulding composition|
    EP2578395A1|2011-10-04|2013-04-10|Rkw Se|Multilayer label film construction for pressure sensitive labels|
    EP2592112A1|2011-11-11|2013-05-15|Basell Poliolefine Italia S.r.l.|Polymer composition for bumpers and interiors and polyethylene-based resin precursor|
    CN103890081B|2011-12-23|2016-09-07|博里利斯股份公司|For the method preparing heterophasic propylene copolymer|
    BR112014014840B1|2011-12-23|2020-12-01|Borealis Ag|propylene copolymer for blow molded articles|
    PL2794689T3|2011-12-23|2016-10-31|Propylene copolymer for injection molded articles or films|
    EP2610270B1|2011-12-30|2015-10-07|Borealis AG|Catalyst component|
    EP2610271B1|2011-12-30|2019-03-20|Borealis AG|Preparation of phthalate free ZN PP catalysts|
    EP2610273B1|2011-12-30|2018-02-07|Borealis AG|Catalyst component|
    EP2610272B1|2011-12-30|2017-05-10|Borealis AG|Catalyst component|
    EP2820053B1|2012-02-27|2016-12-21|Borealis AG|Process for the preparation of polypropylene with low ash content|
    EP2666818B1|2012-05-21|2016-10-26|Borealis AG|High flow polypropylene with excellent mechanical properties|
    BR112015001309A2|2012-08-07|2017-07-04|Borealis Ag|process for preparing improved productivity polypropylene|
    CA2878998C|2012-08-07|2016-09-27|Borealis Ag|Process for the preparation of polypropylene with improved productivity|
    EP3033389B1|2013-08-14|2017-10-11|Borealis AG|Propylene composition with improved impact resistance at low temperature|
    WO2015024887A1|2013-08-21|2015-02-26|Borealis Ag|High flow polyolefin composition with high stiffness and toughness|
    KR101805396B1|2013-08-21|2017-12-06|보레알리스 아게|High flow polyolefin composition with high stiffness and toughness|
    PL2853563T3|2013-09-27|2016-12-30|Films suitable for BOPP processing from polymers with high XS and high Tm|
    ES2568615T3|2013-10-11|2016-05-03|Borealis Ag|Label film oriented in the machine direction|
    ES2574428T3|2013-10-24|2016-06-17|Borealis Ag|Blow molded article based on bimodal random copolymer|
    WO2015059229A1|2013-10-24|2015-04-30|Borealis Ag|Low melting pp homopolymer with high content of regioerrors and high molecular weight|
    US9670293B2|2013-10-29|2017-06-06|Borealis Ag|Solid single site catalysts with high polymerisation activity|
    CN105722872B|2013-11-22|2017-10-13|博里利斯股份公司|Low emission Noblen with high melt flows|
    US9828698B2|2013-12-04|2017-11-28|Borealis Ag|Phthalate-free PP homopolymers for meltblown fibers|
    WO2015091829A1|2013-12-18|2015-06-25|Borealis Ag|Bopp film having low shrinkage|
    MX2016007438A|2013-12-18|2016-10-03|Borealis Ag|Bopp film with improved stiffness/toughness balance.|
    EP2886600B1|2013-12-19|2018-05-30|Abu Dhabi Polymers Co. Ltd LLC.|Multimodal polypropylene with respect to comonomer content|
    US20160312018A1|2013-12-31|2016-10-27|Borealis Ag|Process for producing propylene terpolymer|
    CN105829364B|2014-01-17|2017-11-10|博里利斯股份公司|Method for preparing the butylene copolymer of propylene/1|
    ES2571587T3|2014-01-29|2016-05-26|Borealis Ag|High fluid polyolefin composition with high rigidity and puncture resistance|
    JP6474417B2|2014-02-06|2019-02-27|ボレアリス エージー|Soft and transparent impact copolymers|
    JP2017508032A|2014-02-06|2017-03-23|ボレアリス エージー|Soft copolymer with high impact strength|
    EP2947118B1|2014-05-20|2017-11-29|Borealis AG|Polypropylene composition for automotive interior applications|EP3033389B1|2013-08-14|2017-10-11|Borealis AG|Propylene composition with improved impact resistance at low temperature|
    WO2015024887A1|2013-08-21|2015-02-26|Borealis Ag|High flow polyolefin composition with high stiffness and toughness|
    KR101805396B1|2013-08-21|2017-12-06|보레알리스 아게|High flow polyolefin composition with high stiffness and toughness|
    PL2853563T3|2013-09-27|2016-12-30|Films suitable for BOPP processing from polymers with high XS and high Tm|
    ES2568615T3|2013-10-11|2016-05-03|Borealis Ag|Label film oriented in the machine direction|
    WO2015059229A1|2013-10-24|2015-04-30|Borealis Ag|Low melting pp homopolymer with high content of regioerrors and high molecular weight|
    ES2574428T3|2013-10-24|2016-06-17|Borealis Ag|Blow molded article based on bimodal random copolymer|
    US9670293B2|2013-10-29|2017-06-06|Borealis Ag|Solid single site catalysts with high polymerisation activity|
    CN105722872B|2013-11-22|2017-10-13|博里利斯股份公司|Low emission Noblen with high melt flows|
    US9828698B2|2013-12-04|2017-11-28|Borealis Ag|Phthalate-free PP homopolymers for meltblown fibers|
    MX2016007438A|2013-12-18|2016-10-03|Borealis Ag|Bopp film with improved stiffness/toughness balance.|
    CN105829364B|2014-01-17|2017-11-10|博里利斯股份公司|Method for preparing the butylene copolymer of propylene/1|
    JP2017508032A|2014-02-06|2017-03-23|ボレアリス エージー|Soft copolymer with high impact strength|
    JP6474417B2|2014-02-06|2019-02-27|ボレアリス エージー|Soft and transparent impact copolymers|
    EP2907841A1|2014-02-14|2015-08-19|Borealis AG|Polypropylene composite|
    EP2947118B1|2014-05-20|2017-11-29|Borealis AG|Polypropylene composition for automotive interior applications|
    CN107075207B|2014-11-19|2018-07-27|博里利斯股份公司|Injection molded article based on Noblen|
    EP3237466A1|2014-12-22|2017-11-01|Borealis AG|Process for producing polypropylene|
    EP3184587B1|2015-12-21|2020-03-18|Borealis AG|Extruded articles with improved optical properties|
    ES2765401T3|2015-12-21|2020-06-09|Borealis Ag|Items with improved optical properties|
    US10919993B2|2016-04-13|2021-02-16|Borealis Ag|Injection molded article based on propylene homopolymer|
    EP3526261A1|2016-10-12|2019-08-21|Borealis AG|Beta-nucleated propylene terpolymer composition with good toughness|
    EP3476888A1|2017-10-25|2019-05-01|Borealis AG|Filled polypropylene composition with improved thermo-mechanical properties|
    KR20210016122A|2019-07-31|2021-02-15|삼성디스플레이 주식회사|Dipoles aligning apparatus, method of aligning dipoles and method of fabricating display device|
    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-03-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/11/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13194123.9|2013-11-22|
    EP13194123|2013-11-22|
    PCT/EP2014/075054|WO2015075088A1|2013-11-22|2014-11-19|Low emission propylene homopolymer with high melt flow|
    [返回顶部]