propylene copolymer, injection molded article, thin packaging and copolymer production process

专利摘要:
The present invention relates to propylene copolymer having a comonomer content in the range of 2.0 to 11.0% by mol and a melt rate MFR2 (230°C) in the range of 25.0 to 100 g/10 min, wherein said propylene copolymer is characterized by good toughness.
公开号:BR112015028319B1
申请号:R112015028319-5
申请日:2014-05-12
公开日:2021-05-18
发明作者:Markus Gahleitner；Jingbo Wang；Johanna LILJA
申请人:Borealis Ag；
IPC主号:

专利说明:

[001] The present invention relates to a new propylene copolymer, its manufacture as well as packaging with small thickness comprising said new propylene copolymer.
[002] In the field of packaging with small thickness, it is of great importance to have a material with good flowability with good mechanical properties, that is, a high modulus of elasticity and good impact resistance. Good fluidity is necessary to obtain good processability in various article manufacturing methods, eg injection molding processes, thus allowing for the high production speed required in this mass production market. Mechanical properties are also critical in view of thin articles. Particularly in the field of containers, there is a need to maintain the content such as food contained in them as well as having sufficient rigidity to be stacked. Finally, the materials must also withstand damage from mechanical impact, which is often caused, for example, by falling articles.
[003] Still additionally, also mist must be acceptable. In particular, a good balance between stiffness and fog is desirable.
[004] However, at least some of these goals can only be achieved at the expense of others of these goals. For example, with increasing pour rate, stiffness can be improved, however, impact properties drop significantly. Thus, the impact and fluidity behavior of a polymer behaves in a conflicting manner.
[005] Furthermore, a high degree of crystallinity of polypropylene makes the material quite rigid, however it also increases haze. Crystallinity is influenced by the amount of comonomer contained in the polymer and by the insertion of the comonomer into the polymer chain.
[006] Therefore, it is an object of the present invention to provide a polypropylene that allows a person skilled in the art to produce packaging with small thickness in an economical way. Consequently, it is in particular an object of the present invention to provide a polypropylene with high fluidity and at the same time maintain the impact properties and optical properties at a high level.
[007] The discovery of the present invention is to provide a propylene copolymer with very high flow rate and being single-phase, while having a moderate to low randomness.
[008] Consequently, the present invention is directed to a copolymer of propylene (R-PP) having: (a) a comonomer content in the range of 2.0 to 11.0% by mol; (b) an MFR2 flow rate (230°C) measured in accordance with ISO 1133 in the range of 25.0 to 100 g/10min; and (c) a relative content of isolated and block ethylene sequences (I(E)) in the range of 45.0 to 70.0%, where the content of I(E) is defined by equation (I)
where: I(E) is the relative content of isolated and block ethylene sequences [in%]; fPEP is the fraction in mol of the propylene/ethylene/propylene sequences fPEE is the fraction (PEP) in the mol sample; of propylene/ethylene/ethylene (PEE) and ethylene/ethylene/propylene (EEP) sequences in the sample; fEEE is the mole fraction of ethylene/ethylene/ethylene (EEE) sequences in the sample; where all sequence concentrations are based on a triad statistical analysis of 13C-NMR data.
[009] Preferably, the propylene copolymer (R-PP) is monophasic. Alternatively or additionally, the propylene copolymer (R-PP) preferably has no glass transition temperature below -20°C.
[0010] Surprisingly, the propylene copolymer (R-PP) according to the invention has high impact and good optical properties even though the melt rate MFR2 (230°C) is relatively high.
[0011] Therefore in a specific embodiment, the present invention is directed to an injection molded article, such as a packaging element with small thickness, comprising the propylene copolymer (R-PP) of the present invention. More preferably, the present invention is directed to a packaging element with small thickness, selected from the group consisting of cups, boxes, trays, buckets, buckets, bowls, lids, flaps, covers, CD covers and DVD covers, in that said small thickness packaging element comprises the propylene copolymer (R-PP) of the present invention.
[0012] In the following, propylene copolymer (R-PP) is defined in more detail.
[0013] As mentioned above, the propylene copolymer (R-PP) according to this invention is preferably monophasic. Consequently, it is preferred that the propylene copolymer (R-PP) does not contain elastomeric (co)polymers forming inclusions as a second phase to improve the mechanical properties. A polymer containing elastomeric (co)polymers as second phase inserts would instead be called heterophasic and preferably is not part of the present invention. The presence of second phases or so-called inclusions is, 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.
[0014] Consequently, it is preferred that the propylene copolymer (R-PP) according to this invention has no glass transition temperature below -30, preferably below -25°C, more preferably below -20°C.
[0015] On the other hand, in a preferred embodiment, the propylene copolymer (R-PP) according to this invention has a glass transition temperature in the range of -12 to +2°C,
[0016] The propylene copolymer (R-PP) according to this invention has a melt rate MFR2 (230°C) measured according to ISO 1133 in the range of 25.0 to 100 g/10min, more preferably in the range from 28.0 to 90 g/10min, even more preferably in the range from 30.0 to 80g/10min.
[0017] The copolymer of propylene (R-PP) comprises, except for propylene, also comonomers.
[0018] Preferably, the propylene copolymer (R-PP) comprises except for propylene ethylene and/or C4 to C12 α-olefins. Accordingly, the term "propylene copolymer" according to this invention is preferably understood as a polypropylene comprising, preferably consisting of units derivable from: a) propylene; and b) ethylene and/or C4 to C12 α-olefins.
[0019] Thus, the propylene copolymer (R-PP) according to this invention preferably comprises monomers copolymerizable with propylene, for example, comonomers such as ethylene and/or C4 to C12 α-olefins, in particular ethylene and/or C4 to C8 α-olefins, for example 1-butene and/or 1-hexene. Preferably, the propylene copolymer (R-PP) according to this invention comprises, especially consists of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the propylene copolymer (R-PP) of this invention comprises - except for propylene - derivable units of ethylene and/or 1-butene. In a preferred embodiment, the propylene copolymer (R-PP) according to this invention comprises derivable units of ethylene and propylene only.
[0020] Additionally, it is appreciated that the propylene copolymer (R-PP) preferably has a comonomer content in a very specific range which contributes to impact strength and good optical properties. Thus, it is necessary that the comonomer content of the propylene copolymer (R-PP) is in the range of 2.0 to below 11.0% by mol, preferably in the range of 2.5 to below 10.0% in mol, more preferably in the range of 3.0 to below 9.5% by mol, even more preferably in the range of 3.5 to 9.0% by mol, even more preferably in the range of 4.0 to 8, 5% by mol.
[0021] Additionally, the propylene copolymer is characterized by its relative content of isolated ethylene sequences in block I(E). The content of I(E) [%] is defined by equation (I)
where: I(E) is the relative content of isolated and block ethylene sequences [in%]; fPEP is the mole fraction of propylene/ethylene/propylene (PEP) sequences in the sample; fPEE is the fraction in moles of propylene/ethylene/ethylene (PEE) and ethylene/ethylene/propylene (EEP) sequences in the sample; fEEE is the mole fraction of ethylene/ethylene/ethylene (EEE) sequences in the sample where all sequence concentrations are based on a statistical triad analysis of 13C-NMR data.
Accordingly, it is preferred that the propylene copolymer (R-PP) has a normalized PEP value (nPEP) in the range 45.0 to 70.0%, more preferably in the range 50.0 to 70.0% even more preferably in the range of 55.0 to 70.0%, even more preferably in the range of 58.0 to 69.0%.
[0023] Additionally, the propylene copolymer (R-PP) has a main melting temperature, i.e. a melting temperature representing more than 50% of the melting enthalpy, of at least 130°C, more preferably in the range from 133 to 155°C, even more preferably in the range from 134 to 152°C.
[0024] Additionally, it is preferred that the propylene copolymer (R-PP) has a crystallization temperature of at least 110°C, more preferably in the range of 110 to 128°C, even more preferably in the range of 112 to 126° C, as in the 114 to 124°C range.
[0025] Preferably, the propylene copolymer (R-PP) has a cold soluble xylene fraction (XCS) in the range of 4.0 to 25.0% by weight, preferably in the range of 4.5 to 20.0% by weight, more preferably in the range of 5.0 to 15.0% by weight.
[0026] Additionally it is preferred that the propylene copolymer (R-PP) has a hexane soluble content of below 6.0% by weight, more preferably in the range of above 1.0 to below 6.0% in weight, even more preferably in the range of 2.0 to 5.0% by weight.
[0027] Preferably, the propylene copolymer (R-PP) has a molecular weight distribution (Mw/Mn) of at least 3.0, more preferably in the range from 3.0 to 6.0, even more preferably in the range from 3.5 to 5.5, as in the range from 3.7 to 5.3.
[0028] In addition or alternatively to the molecular weight distribution (Mw/Mn), as defined in the previous paragraph, the propylene copolymer (R-PP) preferably has a weight average molecular weight Mw in the range of 90 to 500 kg/mol, plus preferably in the range of 90 to 250 kg/mol, such as in the range of 100 to 220 kg/mol.
[0029] Preferably, the propylene copolymer according to this invention was produced in the presence of a Ziegler-Natta catalyst. The catalyst influences in particular the microstructure of the polymer. In particular, polypropylenes prepared using a metallocene catalyst provide a different microstructure compared to polypropylenes prepared using Ziegler-Natta (ZN) catalysts. The most significant difference is the presence of regiodefects in polypropylenes made from metallocene which is not the case for polypropylenes made by Ziegler-Natta (ZN). The regiodefects can be of three different types, namely 2.1-erythro (2.1e), 2.1-threo (2, 1t) and 3.1 defects. A detailed description of the structure and mechanism of regiodefect formation in polypropylene can be found in Chemical Reviews 2000.100(4), pages 1316-1327.
[0030] The term "2.1 regiodefects" as used in the present invention defines the sum of 2.1 erythro regiodefects and 2.1 threo regiodefects.
[0031] Consequently, it is preferred that the propylene copolymer (R-PP) according to this invention has 2.1 regiodefects, such as 2.1 erythro regiodefects, of at most 0.4%, more preferably of at most 0, 3%, even more preferably at most 0.2%, determined by 13 C-NMR spectroscopy. In a specific embodiment, no 2.1 regiodefects, such as 2.1 erythro regiodefects, are detectable for the propylene copolymer (R-PP).
[0032] The propylene copolymer (R-PP) preferably comprises at least two polymer fractions, such as two or three polymer fractions, all of which are propylene copolymers. Preferably, the random propylene copolymer (R-PP) comprises at least two different propylene copolymer fractions, such as two different propylene copolymer fractions, wherein the other two propylene copolymer fractions preferably differ in comonomer content.
[0033] Preferably, a fraction of the two polymeric copolymer fractions of the propylene copolymer (R-PP) is the fraction weak in comonomer and the other fraction is the fraction rich in comonomer, more preferably the weak fraction and the rich fraction together satisfy inequality (II), more preferably inequality (IIa), even more preferably inequality (IIb), even more preferably inequality (IIIc),
where: Co (poor) is the comonomer content [% in mol] of the fraction of propylene copolymer with the lowest comonomer content; Co (rich) is the comonomer content [% by mol] of the fraction of propylene copolymer with the highest comonomer content.
[0034] In addition or alternatively to inequality (III), one fraction of the two polymer copolymer fractions of the propylene copolymer (R-PP) is the low flow rate fraction MFR2(230°C) and the other fraction is the high flow rate fraction MFR2 (230°C), wherein more preferably the low flow fraction and the high flow fraction together satisfy inequality (III), more preferably inequality (IIIa), even more preferably inequality ( IIIb),
where: MFR (high) is the melt rate MFR2 (230°C) [g/10min] of the propylene copolymer fraction with the highest melt rate MFR2 (230°C); MFR (low) is the melt rate MFR2 (230°C) [g/10min] of the propylene copolymer fraction with a lower melt rate MFR2 (230°C).
[0035] Even more preferred, the propylene copolymer (R-PP) comprises, preferably consists of a first fraction of propylene copolymer (R-PP1) and a second fraction of propylene copolymer (R-PP2), wherein additionally the first fraction of propylene copolymer (R-PP1) and the second fraction of propylene copolymer (R-PP2) differ in comonomer content and/or melt rate MFR2 (230°C). In one embodiment, they differ in comonomer content and MFR2 flow rate (230°C).
[0036] So in one embodiment, the first random fraction of propylene copolymer (R-PP1) has a higher comonomer content and melt rate MFR2 (230°C) than the second random fraction of propylene copolymer (R- PP2). [1st option]
[0037] In another embodiment, the first random fraction of propylene copolymer (R-PP1) has a higher comonomer content, but a lower melt rate MFR2 (230°C) than the second random fraction of propylene copolymer ( R-PP2). [2nd option]
[0038] In yet another modality, the first random fraction of propylene copolymer (R-PP1) has a higher comonomer content than the second random fraction of propylene copolymer (R-PP2) and the melt rate MFR2 (230 °C) of the first random fraction of propylene copolymer (R-PP1) and the second random fraction of propylene copolymer (R-PP2) are essentially the same, eg they differ by no more than 8 g/10 min, more preferably in no more than 6 g/10 min, even more preferably in no more than 5 g/10 min. [3rd option]
[0039] In yet another embodiment, the second random fraction of propylene copolymer (R-PP2) has a higher comonomer content, but a lower melt rate MFR2 (230°C) than the first random fraction of propylene copolymer (R-PP1). [4th option]
[0040] Still in modality, the second random fraction of propylene copolymer (R-PP2) has a higher comonomer content and melt rate MFR2 (230°C) than the first random fraction of propylene copolymer (R-PP1 ). This modality is especially preferred. [5th option]
[0041] The 1st, 2nd and 3rd options are especially preferred.
[0042] Consequently, it is preferred that the first random fraction of propylene copolymer (R-PP1) and the second random fraction of propylene copolymer (R-PP2) together satisfy inequality (IV), more preferably inequality (IVa) , even more preferably the inequality (IVb), even more preferably the inequality (IVc),
where: Co (R-PP1) is the comonomer content [% by mol] of the first fraction of propylene copolymer (R-PP1); Co (R-PP2) is the comonomer content [% by mol] of the second fraction of propylene copolymer (R-PP2).
[0043] It is especially preferred that the propylene copolymer (R-PP) has a higher comonomer content than the first random fraction propylene copolymer (R-PP1). Consequently, the random propylene copolymer (R-PP) comprises, preferably consists of the first random fraction of propylene copolymer (R-PP1) and the second random fraction of propylene copolymer (R-PP2), wherein additionally the copolymer of random propylene (R-PP) satisfies: (a) the inequality (V), more preferably the inequality (Va), even more preferably the inequality (Vb), even more preferably the inequality (Vc),
where: Co (R-PP1) is the comonomer content [% by mol] of the first random fraction of propylene copolymer (R-PP1); Co (R-PP) is the comonomer content [% by mol] of the propylene copolymer (R-PP).
[0044] It is further preferred that the melt rate MFR2 (230°C) of the first random fraction of propylene copolymer (R-PP1) to the melt rate MFR2 (230°C) of the propylene copolymer (R-PP) in not more than 8g/10min, more preferably in not more than 6g/10min, even more preferably in no more than 4g/10min.
[0045] Thus, it is preferred that the first random fraction of propylene copolymer (R-PP1) has a comonomer content equal to or below 8.0 mol%, more preferably equal to or below 7.0 mol%, even more preferably at or below 6.0 mol%, even more preferably in the range 1.0 to 7.0 mol%, even more preferably in the range 1.0 to 6.0 mol%, as in the range 2 0.0 to 5.5% by mol.
[0046] Preferably, the first random fraction of propylene copolymer (R-PP1) preferably has a flow rate MFR2 (230°C) in the range of in the range 20.0 to 120 g/10min, more preferably in the range 25 0.0 to 100 g/10min, even more preferably in the range of 25.0 to 80g/10min.
[0047] On the other hand, the second random fraction of propylene copolymer (R-PP2) preferably has a comonomer content of at least 4.0% by mol, more preferably of at least 5.0% by weight, even more preferably from more than 6.0% by mol, even more preferably in the range from 5.0 to 14.0% by mol, even more preferably in the range from more than 6.0 to 14.0% by mol, further more preferably in the range 6.1 to 12.0 mol%.
[0048] Preferably, the second random fraction of propylene copolymer (R-PP2) preferably has a flow rate MFR2 (230°C) in the range of 20.0 to 120 g/10min, more preferably in the range of 25.0 to 100g/10min, even more preferably in the range of 25.0 to 80g/10min.
[0049] The comonomers of the first fraction of propylene copolymer (R-PP1) and random fraction of propylene copolymer (R-PP2), respectively, copolymerizable with propylene are ethylene and/or C4 to C12 α-olefins, in particular ethylene and/or C4 to C8 α-olefins, for example 1-butene and/or 1-hexene. Preferably, the first fraction of propylene copolymer (R-PP1) and second fraction of propylene copolymer (R-PP2), respectively, comprise, especially consist of monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1 -hexene. More specifically, the first fraction of propylene copolymer (R-PP1) and second fraction of propylene copolymer (R-PP2), respectively, comprise - except for propylene - derivable units of ethylene and/or 1-butene. In a preferred embodiment, the first propylene copolymer fraction (R-PP1) and the second propylene copolymer fraction (R-PP2) comprise the same comonomers, i.e., ethylene only.
[0050] Preferably, the weight ratio between the first fraction of propylene copolymer (R-PP1) and the second fraction of propylene copolymer (R-PP2) is 20/80 to 80/20, more preferably 30/70 to 70/30, such as 35/65 to 65/35.
[0051] The propylene copolymer (R-PP) as defined in the present invention may contain up to 5.0% by weight of additives such as α-nucleating agents and antioxidants, as well as slip agents and anti-blocking agents. Preferably, the additive content (without α-nucleating agents) is below 3.0% by weight, such as below 1.0% by weight.
[0052] Preferably, the propylene copolymer (R-PP) comprises a nucleating agent α. Even more preferred, the present invention is free of β-nucleating agents. The nucleating agent α is preferably selected from the group consisting of salts of: (i) salts of monocarboxylic acids and polycarboxylic acids, for example sodium benzoate or aluminum tert-butyl benzoate and; (ii) dibenzylidenesorbitol (eg 1.3:2.4 dibenzylidenesorbitol) and C1-C8-alkyl-substituted dibenzylidenesorbitol derivatives such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (eg 1,3:2,4 di(methylbenzylidene) sorbitol), or substituted nonitol derivatives such as 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol and; (iii) salts of phosphoric acid diesters, for example 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; and (v) mixtures thereof.
[0053] Such additives are generally commercially available and are described, for example, in "Plastic Additives Handbook", 5th edition, 2001 by Hans Zweifel.
[0054] Preferably, the propylene copolymer (R-PP) contains up to 2.0% by weight of the nucleating agent α. In a preferred embodiment, the propylene copolymer (R-PP) contains not more than 3000 ppm, more preferably 1 to 3000 ppm, more preferably 5 to 2000 ppm of a nucleating agent α, in particular selected from the group consisting of in dibenzylidenesorbitol (for example 1.3 : 2.4 dibenzylidene sorbitol), dibenzylidene sorbitol derivative, preferably dimethyldibenzylidene sorbitol (for example 1.3 : 2.4 di(methylbenzylidene) sorbitol) or substituted nonitol derivatives such as 1,2, 3,-trideoxy-4,6:5,7-bis-0-[(4-propylphenyl)methylene]-nonitol, vinylcycloalkane polymer, vinylalkane polymer and mixtures thereof.
[0055] The present invention is also directed to injection molded articles comprising at least 70% by weight, more preferably at least 90% by weight, even more preferably at least 95% by weight, even more preferably consisting of a copolymer of propylene (R-PP) as defined herein.
[0056] Additionally, the present invention is also directed to packaging elements with small thickness, such as packaging elements with small thickness produced by injection molding, comprising at least 70% by weight, more preferably at least 90% by weight, further more preferably at least 95% by weight, even more preferably consisting of a copolymer of propylene (R-PP) as defined herein.
[0057] Small thickness packaging elements, such as small thickness packaging elements produced by injection molding, preferably have a thickness equal to or below 2 mm, preferably in the range of 0.2 to 2.0 mm. Said packaging elements with small thickness are preferably produced by injection molding. Furthermore, the thin thickness packaging elements are preferably selected from the group consisting of cups, boxes, trays, buckets, buckets, bowls, lids, flaps, lids, CD covers, DVD covers and the like.
[0058] The propylene copolymer (R-PP) according to this invention is preferably produced in a sequential polymerization process in the presence of a Ziegler-Natta catalyst as defined below.
[0059] Consequently, it is preferred that the propylene copolymer (R-PP) is produced in the presence of: (a) a Ziegler-Natta (ZN-C) catalyst comprises a titanium compound (TC), a magnesium compound ( MC) and an inner donor (ID), wherein said inner donor (ID) is a non-phthalic acid ester; (b) optionally a co-catalyst (Co); and (c) optionally an external donor (ED).
[0060] Preferably, the propylene copolymer (R-PP) 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 copolymer (R -PP1) is produced and subsequently transferred into the second reactor (R2), in the second reactor (R2), the second propylene copolymer fraction (R-PP2) is produced in the presence of the first propylene copolymer fraction (R- PP1).
[0061] The term "sequential polymerization system" indicates that propylene copolymer (R-PP) is produced in at least two reactors connected in series. Accordingly, 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" should 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 total system comprises, for example, a prepolymerization step in a prepolymerization reactor. The term "consists of" is just a closure formulation in view of the main polymerization reactors.
[0062] 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 this invention is preferably a fluid bed reactor, a fast fluid bed reactor or a set bed reactor or any combination thereof.
[0063] Consequently, the first polymerization reactor (R1) is preferably a slurry reactor (SR) and may be continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry. Mass means a polymerization in a reaction medium comprising at least 60% (w/w) of monomer. According to the present invention, the slurry reactor (SR) is preferably a loop (bulk) reactor (LR). Consequently, the average concentration of propylene copolymer (R-PP), ie the first fraction (1a F) of the propylene copolymer (R-PP) (ie the first fraction of propylene copolymer (R-PP1) ), in the polymer slurry within the loop reactor (LR) is typically from 15% by weight to 55% by weight, based on the total weight of the polymer slurry within the loop reactor (LR). In a preferred embodiment of the present invention, the average concentration of the first fraction of propylene copolymer (R-PP1) in the polymer slurry within the loop 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 polymer slurry within the loop reactor (LR).
[0064] Preferably, the propylene copolymer of the first polymerization reactor (R1), i.e., of the first fraction of propylene copolymer (R-PP1), more preferably the polymer slurry of the loop reactor (LR) containing the first Propylene copolymer fraction (R-PP1) is directly fed into the second polymerization reactor (R2), that is, into the (first) gas phase reactor (GPR1), without a flash 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 loop reactor (LR), the polymer slurry comprising the first fraction of propylene copolymer (R-PP1) is taken directly to the next stage gas phase reactor.
[0065] Alternatively, the propylene copolymer from the first polymerization reactor (R1), i.e. the first fraction of the propylene copolymer (R-PP1), more preferably loop reactor polymer slurry (LR) containing the first fraction of propylene copolymer (R-PP1) can also be directed to a flash step or through a concentration step before feeding into the second polymerization reactor (R2), i.e., into the gas phase reactor (GPR). Consequently, this "indirect feed" refers to a process in which the content of the first polymerization reactor (R1), loop reactor (LR), i.e., polymer slurry is fed into the second polymerization reactor (R2) , in the (first) gas-phase reactor (GPR1), by means of a reaction medium separation unit and the reaction medium as a separation unit gas.
[0066] 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 mechanically mixed or fluid bed reactors.
[0067] Preferably, gas phase reactors (GPRs) comprise mechanically stirred fluid bed reactor with gas velocities of at least 0.2 m/s. thus, it is appreciated that the gas phase reactor is a fluidized bed type reactor preferably with a mechanical stirrer.
[0068] Thus, in a preferred embodiment, the first polymerization reactor (R1) is a slurry reactor (SR), like loop reactor (LR), while the second polymerization reactor (R2) and any subsequent optional reactor like the third polymerization reactor (R3) are gas phase reactors (GPRs). Consequently, for the present process at least two, preferably two polymerization reactors (R1) and (R2) or three polymerization reactors (R1), (R2) and (R3), viz. a slurry reactor (SR) , as loop 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 slurry reactor (SR) a polymerization pre-reactor is placed.
[0069] The Ziegler-Natta catalyst (ZN-C) is fed into the first polymerization reactor (R1) and is transferred with the polymer (slurry) obtained in the first polymerization reactor (R1) into the subsequent reactors. If the process also covers a prepolymerization step it is preferred that all the Ziegler-Natta (ZN-C) catalyst is fed into the prepolymerization reactor.
[0070] Subsequently, the prepolymerization product containing the Ziegler-Natta catalyst (ZN-C) is transferred into the first polymerization reactor (R1).
[0071] A preferred multistage process is a "gas-loop-phase" process as developed by Borealis A/S, Denmark (known as BORSTAR® technology) described, for example, in the patent literature as in EP 0 887 379 , WO 92/12182 WO 2004/000899 , WO 2004/111095 , WO 99/24478 , WO 99/24479 or in WO 00/68315 .
[0072] An additional suitable gas-phase slurry process is the Spheripol® process from Basell.
[0073] Especially good results are achieved if the temperature in the reactors is chosen carefully.
[0074] Consequently, it is preferred 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° Ç.
[0075] Alternatively or in addition to the previous paragraph, it is preferred 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.
[0076] 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). Consequently, it is preferred that the operating temperature: (a) in the first polymerization reactor (R1) is in the range 62 to 85°C, more preferably in the range 65 to 82°C, even more preferably in the range 67 to 80 °C, such as 67 to 75 °C, for example 70 °C; and (b) 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 to 88°C, with the proviso that the operating temperature in the second polymerization reactor (R2) is equal to or greater than the operating temperature in the first polymerization reactor (R1).
[0077] Even more preferably, the operating temperature of the third polymerization reactor (R3) - if present - is greater than the operating temperature of the first polymerization reactor (R1). In a specific embodiment, the operating temperature of the third polymerization reactor (R3) - if present - is greater than the operating temperature in the first polymerization reactor (R1) and in the second polymerization reactor (R2). Consequently, it is preferred that the operating temperature: (a) in the first polymerization reactor (R1) is in the range 62 to 85°C, more preferably in the range 65 to 82°C, even more preferably in the range 67 to 80 °C, such as 67 to 75 °C, for example 70 °C; (b) 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 to 88°C and; (c) in the third polymerization reactor (R3) - if present - is in the range from 75 to 95°C, more preferably in the range from 78 to 92°C, even more preferably in the range from 85 to 92°C, as in 87 to 92°C range; with the proviso that the operating temperature in the second polymerization reactor (R2) is equal to or greater than the operating temperature in the first polymerization reactor (R1); and with the proviso that the third polymerization reactor (R3) is greater than the operating temperature in the first polymerization reactor (R1), preferably it is greater than the operating temperature in the first polymerization reactor (R1) and in the second reactor of polymerization (R2).
[0078] Typically, the pressure in the first polymerization reactor (R1), preferably in the loop reactor (LR), is in the range of 20 to 80 bar (2 to 8 MPa), preferably 30 to 70 bar (3 to 7 MPa) , as 35 to 65 bar (3.5 to 6.5 MPa), while the pressure in the second polymerization reactor (R2), ie in the (first) gas phase reactor (GPR1) and optionally in any reactor subsequent, as in the third polymerization reactor (R3), for example in the second gas phase reactor (GPR2), is in the range of 5 to 50 bar (0.5 to 5 MPa), preferably 15 to 40 bar (1, 5 to 4 MPa).
[0079] Preferably, hydrogen is added in each polymerization reactor in order to control the molecular weight, i.e. the MFR2 flow rate.
[0080] Preferably, the average residence time is quite long in the polymerization reactors (R1) and (R2). In general, the mean residence time (T) is defined as the ratio of the reaction volume (VR) to the reactor volumetric flow rate (Q0) (ie, VR/Q0), ie, t = VR/ Q0 [tau = VR/QO]. In the case of a loop reactor, the reaction volume (VR) is equal to the reactor volume.
[0081] Consequently, the average residence time (t) in the first polymerization reactor (R1) is preferably at least 20 min, more preferably in the range of 20 to 80 min, even more preferably in the range of 25 to 60 min, as in the range of 28 to 50 min, and/or the average residence time (t) in the second polymerization reactor (R2) is preferably at least 90 min, more preferably in the range of 90 to 220 min, even more preferably in the range of 100 to 210 min, even more preferably in the range 105 to 200 min, as in the range 105 to 190 min. Preferably, the average residence time (T) in the third polymerization reactor (R3) - if present - is preferably at least 30 min, more preferably in the range of 30 to 120 min, even more preferably in the range of 40 to 100 min, as in the range of 50 to 90 min.
[0082] Additionally it is preferred that the average residence time (t) in the sequential total polymerization system, more preferably than the average residence time (t) in the first (R1) and second polymerization reactors (R2) and third reactor of optional polymerization (R3) together is at least 140 min, more preferably at least 160 min, even more preferably in the range 140 to 260 min, more preferably in the range 160 to 240 min, even more preferably in the range 160 to 220 min , even more preferably in the range of 160 to 220 min.
[0083] As mentioned above, the present process may comprise in addition to the (main) polymerization of propylene copolymer (R-PP) in the at least two polymerization reactors (R1, R3 and optional R3) before a pre-polymerization in a prepolymerization reactor (PR) upstream of the first polymerization reactor (R1).
[0084] In the prepolymerization reactor (PR), a polypropylene (Pre-PP) is produced. Prepolymerization is carried out in the presence of Ziegler-Natta (ZN-C) catalyst. According to this modality, the Ziegler-Natta (ZN-C) catalyst, the co-catalyst (Co) and the external donor (ED) are all introduced in the pre-polymerization step. However, this should not exclude the option that at a later stage, for example, another co-catalyst (Co) and/or external donor (ED) is added in the polymerization process, for example, in the first reactor (R1). In one embodiment, Ziegler-Natta catalyst (ZN-C), cocatalyst (Co) and external donor (ED) are only added to the prepolymerization reactor (PR) if a prepolymerization is applied.
[0085] The prepolymerization reaction is typically conducted at a temperature from 0 to 60°C, preferably from 15 to 50°C, and more preferably from 20 to 45°C.
[0086] The pressure in the prepolymerization reactor is not critical, but it should be high enough to keep the reaction mixture in the liquid phase. Thus, the pressure can be from 20 to 100 bar (2 to 10 MPa), for example 30 to 70 bar (3 to 7 MPa).
[0087] In a preferred embodiment, the prepolymerization is conducted as bulk slurry polymerization in liquid propylene, i.e. the liquid phase mainly comprises propylene, with optionally inert components dissolved therein. Furthermore, in accordance with the present invention, an ethylene feed is employed during prepolymerization as mentioned above.
[0088] It is possible to add other components also in the pre-polymerization stage. Thus, hydrogen can be added at the prepolymerization stage to control the molecular weight of polypropylene (Pre-PP) as is known in the art. Additionally, the antistatic additive can be used to prevent the particles from adhering to each other or to the reactor walls.
[0089] Precise control of prepolymerization conditions and reaction parameters is within the skill of the art.
[0090] Due to the process conditions defined above in the pre-polymerization, preferably a mixture (MI) of the Ziegler-Natta catalyst (ZN-C) and the polypropylene (Pre-PP) produced in the pre-polymerization reactor (PR) is obtained. 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) split into smaller fragments that are evenly distributed within the growing polypropylene (Pre-PP). The sizes of the introduced Ziegler-Natta (ZN-C) catalyst particles as well as the fragments obtained are not of essential relevance to the present invention and within the knowledge in the art.
[0091] 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 pre-reactor -polymerization (PR) is transferred to the first reactor (R1). 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.
[0092] In the case where prepolymerization is not used, propylene and other ingredients such as introduced into the first polymerization reactor (R1).
[0093] Consequently, the process according to the present invention comprises the following steps under the conditions determined above: (a) in the first polymerization reactor (R1), that is, in a loop reactor (LR), propylene and a comonomer being ethylene and/or a C4 to C12 α-olefin, preferably propylene and ethylene, are polymerized obtaining a first propylene copolymer (R-PP1) fraction of the propylene copolymer (R-PP); (b) transferring said first fraction of propylene copolymer (R-PP1) to a second polymerization reactor (R2); (c) in the second polymerization reactor (R2) propylene and a comonomer being ethylene and/or a C4 to C12 α-olefin, preferably propylene and ethylene, are polymerized in the presence of the first fraction of propylene copolymer (R-PP1) obtaining a second propylene copolymer fraction (R-PP2) of the propylene copolymer (R-PP), said first propylene copolymer fraction (R-PP1) and said second propylene copolymer fraction (R-PP2) form the copolymer of propylene (R-PP).
[0094] A prepolymerization 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)
[0095] 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. Consequently, the Ziegler-Natta (ZN-C) catalyst will now be described in more detail.
[0096] The catalyst used in the present invention is a solid Ziegler-Natta catalyst (ZN-C), which comprises a titanium compound (TC), a magnesium compound (MC) and an internal donor (ID), wherein the said internal donor (ID) is a non-phthalic acid ester, more preferably a non-phthalic dicarboxylic acid diester as described in more detail below. Thus, the catalyst used in the present invention is totally free from unwanted phthalic compounds.
[0097] The Ziegler-Natta (ZN-C) catalyst can be further defined by the way it is obtained.
[0098] Consequently, the Ziegler-Natta (ZN-C) catalyst is preferably obtained by a process comprising the steps of: a) Provision of a solution of at least one complex (A) being a complex of a magnesium compound (MC ) and an alcohol comprising in addition to the hydroxyl moiety at least another oxygen-bearing moiety (A1) being different from a hydroxyl group and optionally at least one complex (B) being a complex of said magnesium compound (MC) and an alcohol not comprising any other portion carrying oxygen (B1); b) combining said solution with a titanium compound (TC) and producing a dispersed phase emulsion which contains more than 50% mol of magnesium; c) stirring the emulsion in order to keep the droplets of said dispersed phase preferably within an average size range of 5 to 200 µm; d) solidifying said droplets of the dispersed phase; e) recovering solidified particles from the olefin polymerization catalyst component and wherein an internal donor (ID) is added at any step before step c) and said internal donor (ID) is non-phthalic acid ester, preferably the said internal donor (ID) is a diester of non-phthalic dicarboxylic acids as described in more detail below.
[0099] The detailed description showing how such a Ziegler-Natta (ZN-C) catalyst can be obtained is disclosed in WO 2012/007430.
[00100] In a preferred embodiment in step a), the magnesium compound (MC) complex solution is a mixture of magnesium compound (MC) complexes (complexes (A) and (B)).
[00101] The magnesium compound (MC) complexes (complexes (A) and (B)) can be prepared in situ in the first step of the catalyst preparation process by reacting said magnesium compound (MC) with the(s) ) alcohol(s) as described above and in more detail below or said complexes can be separately prepared complexes or they can be further commercially available as ready-made complexes and used as such in the process of preparing the catalyst of the invention. In case the mixture of magnesium compound (MC) complexes (complexes (A) and (B)) are prepared in situ in the first stage of the catalyst preparation process, they are preferably prepared by the reaction of said magnesium compound (MC) ) with the mixture of alcohols (A1) and (B1).
[00102] Preferably, the alcohol (A1) comprising in addition to the hydroxyl portion at least one additional oxygen-bearing group other than a hydroxyl group to be employed in accordance with the present invention is an ether-bearing alcohol.
[00103] Illustrative examples of such preferred alcohols (A1) comprising in addition to the hydroxyl moiety at least one additional oxygen-bearing group to be employed according to the present invention are glycol monoethers, in particular C2 to C4 glycol monoethers, such as ethylene or propylene glycol monoethers wherein the ether moieties comprise from 2 to 18 carbon atoms, preferably from 4 to 12 carbon atoms. Preferred monoethers are C2 to C4 glycol monoethers and derivatives thereof. Illustrative and 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.
[00104] In case a mixture of complexes (A) and (B) (or alcohols (A1) and (B1) respectively) are used, the different complexes or alcohols are generally employed in a mole ratio of A:B, or A1:B1 from 1.0:10 to 1.0:0.5, preferably this mol ratio is from 1.0:8.0 to 1.0:1.0, more preferably 1.0:6.0 to 1.0:2.0, even more preferably 1.0:5.0 to 1.0:3.0. As indicated in the above reasons, it is more preferred that the amount of alcohol A1, preferably alcohol with ether moiety, is greater than alcohol B1 i.e. alcohol without any other moiety bearing oxygen other than hydroxyl.
[00105] The internal donor (ID) used in the preparation of the Ziegler-Natta (ZN-C) catalyst is preferably selected from (di)esters of non-phthalic (di)carboxylic acids and derivatives and mixtures thereof. The ester moieties, i.e. the moieties derived from an alcohol (i.e. the alkoxy group of the ester), may be identical or different, preferably these ester moieties are identical. Typically, the ester moieties are aliphatic or aromatic hydrocarbon groups. Preferred examples thereof are linear or branched aliphatic groups having 1 to 20 carbon atoms, preferably 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms, or aromatic groups having 6 to 12 carbon atoms, optionally containing heteroatoms from Groups 14 to 17 of the IUPAC Periodic Table, especially N, O, S and/or P. the acid portion of the di- or monoacid(di)ester, preferably of the diacid diester, preferably comprises 1 to 30 atoms of carbon, more preferably 2 to 20 carbon atoms, even more preferably 2 to 16 carbon atoms, optionally being substituted by cyclic or aliphatic aromatic or saturated or unsaturated hydrocarbyls having 1 to 20 C, preferably 1 to 10 carbon atoms and optionally containing heteroatoms from Groups 14 to 17 of the IUPAC Periodic Table, especially N, O, S and/or P. Especially preferred esters are diesters of monounsaturated dicarboxylic acids.
[00106] In particular preferred esters are esters belonging to a group comprising malonates, maleates, succinates, glutarates, cyclohexene-1,2-dicarboxylates and benzoates, optionally being substituted as defined below and any derivatives and/or mixtures thereof . Preferred examples are, for example, substituted maleates and citraconates, more preferably citraconates.
[00107] The internal donor (ID) or precursor thereof, as further defined below, is preferably added in step a) in said solution.
[00108] Esters used as internal donors (ID) can be prepared as is well known in the art. As an example, dicarboxylic acid diesters can be formed by simply reacting a dicarboxylic acid anhydride with a C1-C20 alkanol and/or diol.
[00109] The titanium compound (TC) is preferably a titanium halide such as TiCl4.
[00110] The complexes of magnesium compounds may be magnesium alkoxy complexes, preferably selected from the group consisting of magnesium dialkoxides and complexes of a magnesium dihalide and a magnesium dialkoxide. It can be a reaction product of an alcohol and a magnesium compound selected from the group consisting of dialkyl magnesiums, alkyl magnesium alkoxides and alkyl magnesium halides, preferably dialkyl magnesium. It can be further selected from the group consisting of dialkyloxy magnesiums, diaryloxy magnesiums, alkyloxy magnesium halides, aryloxy magnesium halides, alkyl magnesium alkoxides, aryl magnesium alkoxides and alkyl magnesium aryloxides.
[00111] Magnesium dialkoxide can be the reaction product of a magnesium dialkyl of the formula R2Mg, wherein each of the two "R" is a similar or different C1-C20 alkyl, preferably a similar or different C2-C10 alkyl with alcohols as defined in this application. Typical magnesium alkyls are ethylbutyl magnesium, dibutyl magnesium, dipropyl magnesium, propylbutyl magnesium, dipentyl magnesium, butylpentyl magnesium, butyloctyl magnesium and dioctyl magnesium. More preferably, one R of the formula R2Mg is a butyl group and the other R is an octyl or ethyl group, i.e. the dialkyl magnesium compound is butyl octyl magnesium or butyl ethyl magnesium.
[00112] Typical RMgOR alkyl alkoxy magnesium compounds, when used, are ethyl magnesium butoxide, butyl magnesium pentoxide, octyl magnesium butoxide and octyl magnesium octoxide.
[00113] The dialkyl magnesium or alkyl magnesium alkoxide can react in addition to alcohol containing in addition to the hydroxyl group at least one additional portion bearing oxygen being different from the hydroxyl portion, which is defined above in this application with a monohydric alcohol R 'OH or a mixture thereof with a polyhydric alcohol R'(OH)m.
Preferred monohydric alcohols are alcohols of the formula Rb(OH), wherein Rb is a C1-C20 alkyl residue, preferably a C4-C12 and more preferably a C6-C10 straight or branched chain or an aryl residue C6-C12. Preferred monohydric alcohols include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-amyl alcohol, iso-amyl alcohol, sec-amyl alcohol, tert-amyl alcohol, diethyl carbinol, sec-isoamyl alcohol, tert-butyl carbinol, 1-hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, 1-heptanol, 2-heptanol, 4-heptanol, 2,4-dimethyl-3-pentanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 5-nonanol, diisobutyl carbinol, 1-decanol and 2,7-dimethyl-2 -octanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol and phenol or benzyl alcohol. Aliphatic monohydric alcohols can be optionally unsaturated as they do not act as catalyst poisons. The most preferred monohydric alcohol is 2-ethyl-1-hexanol.
[00115] Preferred polyhydric alcohols are alcohols of the formula Ra(OH)m, wherein Ra is a straight, cyclic or branched chain C2 to C6 hydrocarbon residue, (OH) denotes hydroxyl portions of the hydrocarbon residue and is a number integer from 2 to 6, preferably 3 to 5. Especially preferred polyhydric alcohols include ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2, 3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, pinacol, diethylene glycol, triethylene glycol, 1,2-catechol, 1,3-catechol and 1,4-catechol, and triols such as glycerol and pentaerythritol.
[00116] The solvents to be used for the preparation of the Ziegler-Natta catalyst (ZN-C) can be selected from aromatic and aliphatic solvents or mixtures thereof. Preferably, the solvents are aromatic and/or aliphatic hydrocarbons having 5 to 20 carbon atoms, preferably 5 to 16, more preferably 5 to 12 carbon atoms, examples of which include benzene, toluene, cumene, xylol and the like, with toluene being preferred, as are pentane, hexane, heptane, octane and nonane including straight chain, branched and cyclic compounds and the like, with hexanes and heptanes being particularly preferred.
[00117] The Mg compound (MC) is typically provided as a 10 to 50% by weight solution in a solvent as indicated above. Typical commercially available MC solutions are solutions in toluene or heptanes with 20 - 40% by weight.
[00118] The reaction for the preparation of the magnesium compound (MC) complex can be carried out at a temperature of 40° to 70°C.
[00119] In step b), the solution from step a) is typically added to the titanium compound (TC), such as titanium tetrachloride. This addition is preferably carried out at a low temperature, such as -10 to 40°C, preferably -5 to 20°C, such as about -5°C to 15°C.
[00120] The temperature for steps b) and c) is typically -10 to 50°C, preferably -5 to 30°C, while solidification typically requires heating as described in further detail below.
[00121] The emulsion, i.e., the liquid-liquid two-phase system, can be formed in all embodiments of the present invention by simple stirring and optionally (additional) addition of solvent(s) and additives, such as the minimizing agent. turbulence (TMA) and/or the emulsifying agents described further below.
[00122] The preparation of Ziegler-Natta (ZN-C) catalyst used in the present invention is based on a liquid/liquid two-phase system where no separate external carrier material such as silica or MgCl2 is needed in order to achieve solid catalyst particles.
[00123] The present Ziegler-Natta (ZN-C) catalyst particles are spherical and they preferably have an average particle size of 5 to 500 µm, such as from 5 to 300 µm and in modalities from 5 to 200 µm, or even from 10 to 100 µm. These ranges also apply to the dispersed phase droplets of the emulsion, as described here, as the droplet size may change (decrease) during the solidification step.
[00124] The process of preparing the Ziegler-Natta catalyst (ZN-C) as an intermediate stage yields to an emulsion of a titanium compound (TC)/insoluble in denser toluene, dispersed phase in oil typically having a mole ratio of titanium compound (TC)/magnesium from 0.1 to 10 and an oil dispersed phase having a titanium compound (TC)/magnesium mole ratio of from 10 to 100. The titanium compound (TC) is preferably TiCl4 . This emulsion is then typically stirred, optionally in the presence of an emulsion stabilizer and/or a turbulence-minimizing agent, in order to keep the droplets of said dispersed phase, typically within an average size range of 5 to 200 µm. Catalyst particles are obtained after solidification of said dispersed phase particles, for example, by heating.
[00125] In effect, therefore, virtually all of the reaction product of the Mg complex with the titanium compound (TC) - which is the precursor of the final catalyst component - becomes the dispersed phase and proceeds through the additional processing steps to the final particulate form. The dispersed phase, still containing a useful amount of titanium compound (TC) can be reprocessed to recover that metal.
[00126] Furthermore, emulsifying agents/emulsion stabilizers can be additionally used in a manner known in the art to facilitate the formation and/or stability of the emulsion. For said purposes, eg surfactants, eg a grade based on acrylic or methacrylic polymers can be used. Preferably, said emulsion stabilizers are acrylic or methacrylic polymers, in particular those with medium sized ester side chains having more than 10, preferably more than 12 carbon atoms and preferably less than 30, and preferably 12 to 20 carbon atoms in the ester side chain. Particularly preferred are C12 to C20 unbranched (meth)acrylates such as poly(hexadecyl)methacrylate and poly(octadecyl)methacrylate.
[00127] In addition, in some embodiments, a turbulence minimization agent (TMA) can be added to the reaction mixture in order to improve the formation of the emulsion and maintain the structure of the emulsion. Said TMA agent has to be inert and soluble in the reaction mixture under the reaction conditions, which means that polymers without polar groups are preferred, as polymers having aliphatic linear or branched carbon backbone chains. Said TMA is in particular preferably selected from α-olefin polymers and α-olefin monomers with 6 to 20 carbon atoms, such as polyoctene, polynonene, polydecene, polyundecene or polydodecene or mixtures thereof. Most preferable is polydecene.
[00128] TMA may be added to the emulsion in an amount of, for example, 1 to 1000 ppm, preferably 5 to 100 ppm and more preferable 5 to 50 ppm, based on the total weight of the reaction mixture.
[00129] It has been found that the best results are obtained when the mol ratio of titanium compound (TC)/Mg of the dispersed phase (denser oil) is 1 to 5, preferably 2 to 4 and that of the dispersed phase oil is 55 to 65. Generally, the ratio of mole ratio of titanium compound (TC)/Mg in dispersed phase oil to that in denser oil is at least 10.
[00130] The solidification of the dispersed phase droplets by heating is suitably carried out at a temperature of 70 to 150°C, generally at 80 to 110°C, preferably at 90 to 110°C. Warming up can be done faster or slower. Special slow heating here means heating with a heating rate of about 5°C/min or less and special rapid heating, for example 10°C/min or more. Often slower heating rates are preferable to obtain good catalyst component morphology.
The solidified particulate product can be washed at least once, preferably at least twice, more preferably at least three times with a hydrocarbon, which is preferably selected from aromatic and aliphatic hydrocarbons, preferably with toluene, heptane or pentane. Washes can be done with hot (eg 90°C) or cold (room temperature) hydrocarbons or combinations thereof.
[00132] Finally, the washed Ziegler-Natta (ZN-C) catalyst is recovered. It can be further dried, such as by evaporation or nitrogen purging, or it can be fluidized to an oily liquid without any drying step.
[00133] The finally obtained Ziegler-Natta (ZN-C) catalyst is desirably in the form of particles generally having an average size range of 5 to 200 µm, preferably 10 to 100, still an average size range of 20 to 60 µm it's possible.
The Ziegler-Natta (ZN-C) catalyst is preferably used in association with an alkyl aluminum cocatalyst and optionally external donors.
[00135] 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 formula RapRbqSi(ORc)(4-pq) where Ra, Rb and Rc denote a hydrocarbon radical, in particular an alkyl or cycloalkyl group and where p and q are numbers ranging from 0 to 3 with 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 and (cyclopentyl)2Si(OCH3)2 or of the general formula: Si(OCH2CH3)3(NR3R4) wherein R3 and R4 may be the same or different to represent a hydrocarbon group having 1 to 12 carbon atoms.
[00136] 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. 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.
[00137] More preferably both R1 and R2 are the same, even more preferably both R3 and R4 are an ethyl group.
[00138] In addition to the Ziegler-Natta catalyst (ZN-C) and the optional external donor (ED), a co-catalyst can be used. The cocatalyst is preferably a periodic table group 13 compound (IUPAC), for example organoaluminium, such as an aluminum compound such as aluminum alkyl, aluminum halide or aluminum alkyl halide compound. Accordingly, in a specific embodiment, the cocatalyst (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).
[00139] Advantageously, triethyl aluminum (TEAL) has a hydride content, expressed as AlH3, less than 1.0% by weight with respect to triethyl aluminum (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.
[00140] 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.
[00141] Consequently: (a) The mole ratio of co-catalyst (Co) to external donor (ED) [Co/ED] should be in the range of 5 to 45, preferably it is in the range of 5 to 35, more preferably is in the range of 5 to 25, even more preferably is in the range of 5 to 20; and optionally (b) the mol ratio of co-catalyst (Co) to titanium compound (TC) [Co/TC] should be in the range above 80 to 500, preferably it is in the range 120 to 300, even more preferably it's in the range of 140 to 200.
[00142] Below, the present invention is further illustrated by means of examples. EXAMPLES 1. Measurement Methods
[00143] The following definitions of terms and methods of determination apply in the above general description of the invention as well as the examples below unless otherwise defined.
[00144] Calculation of comonomer content of the second fraction of propylene copolymer (R-PP2):
where: w(PP1) is the fraction by weight [in% by weight] of the first fraction of propylene copolymer (R-PP1), w(PP2) is the fraction by weight [in% by weight] of the second fraction of propylene copolymer (R-PP2), C(PP1) is the comonomer content [in mol%] of the first random fraction of propylene copolymer (R-PP1), C(PP) is the comonomer content [in% in mol] of random propylene copolymer (R-PP), C(PP2) is the calculated comonomer content [in mol%] of the second random fraction of propylene copolymer (R-PP2).
[00145] Calculation of the flow rate MFR2 (230°C) of the second fraction of propylene copolymer (R-PP2):
where: w(PP1) is the fraction by weight [in% by weight] of the first fraction of propylene copolymer (R-PP1), w(PP2) is the fraction by weight [in% by weight] of the second fraction of propylene copolymer (R-PP2), MFR(PP1) is the melt rate MFR2 (230°C) [in g/10 min] of the first fraction of propylene copolymer (R-PP1), MFR(PP) is the pour rate MFR2 (230°C) [in g/10 min] of the propylene copolymer (R-PP), MFR(PP2) is the calculated pour rate MFR2 (230°C) [in g/10 min] of second fraction of propylene copolymer (R-PP2); MFR2 (230°C) is measured in accordance with ISO 1133 (230°C, 2.16 kg load). Microstructure quantification by WALTZ16 two-level dissociation spectroscopy (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. 28, 1128). A total of 6144 (6k) transients were acquired by spectra. Quantitative NMR spectra were processed, integrated and the relevant quantitative properties determined from the integral numbers using proprietary computer programs. All chemical changes were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the solvent chemical change. This approach allowed comparable referencing even when this structural unit was not present. The characteristic signs corresponding to ethylene incorporation were observed in Cheng, HN, Macromolecules 17 (1984), (1950).
[00146] Quantitative Nuclear Magnetic Resonance (NMR) spectroscopy was used to quantify the comonomer content and comonomer sequence distribution of the polymers. Quantitative 13C{1H} NMR spectra were recorded in the solution state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1H and *13C, respectively. All spectra were recorded using a 10mm optimized 13C amplified temperature probe head at 125°C using nitrogen gas for all tires. Approximately 200 mg of material was dissolved in 3 ml 1,2-tetrachloroethane-d2 (TCE-d2) with chromium-(III)-acetylacetonate (Cr(acac)3) resulting in a 65 mM relaxing agent solution in solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogeneous solution, after initial sample preparation on a heating block, the NMR tube was further heated in a rotary oven for at least 1 hour. Upon insertion into the magnet, the tube was rotated at 10 Hz. This configuration was chosen primarily for the high resolution and quantitatively necessary for accurate quantification of the ethylene content. Standard single pulse excitation was employed without NOE, using an optimized tip angle, 1 s recycle delay, and a
With characteristic signs corresponding to 2.1 erythro regiodefects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, HN, Macromolecules 1984, 17, 1950 and in WJ. Wang and S. Zhu, Macromolecules 2000, 33 1157) the correction for the influence of regiodefects on the determined properties was required. The characteristic signs that correspond to other types of regiodefects were not observed.
[00148] The comonomer fraction was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) by integrating multiple signals across the entire spectral region in the 13C{1H} spectra. This method was chosen for its robust nature and ability to account for the presence of region defects when needed. The integral regions were slightly adjusted to increase applicability across the entire range of comonomer contents found.
[00149] For systems where only ethylene isolated in PPEPP sequences was observed, the method of Wang et. al. It has been modified to reduce the influence of non-zero integral numbers from places that are known not to be present. This approach reduced the overestimate of the ethylene content for such systems and was obtained by reducing the number of sites used to determine the absolute ethylene content to: E = 0.5(Sββ + Sβy + 8βδ + 0.5(Sαβ + Say ))
[00150] Through the use of this set of locations, the corresponding integral equation becomes: E = 0.5(IH +IG + 0.5(IC + ID))
[00151] Using the same notation used in the article by Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157). The equations used for the absolute propylene content have not been modified.
[00152] The incorporation of the comonomer in percentage in mol was calculated from the fraction in mol: E [mol%] = 100 * fE
[00153] Comonomer incorporation in mole percent was calculated from the mole fraction: E [% by weight] = 100 * (fE * 28.06) / ((fE * 28.06) + ((1- fE) * 42.08))
The comonomer sequence distribution at the triad level was determined using the analysis method of Kakugo et al. (Kakugo, M., Naito, I., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150). This method was chosen for its robust nature and lightly adjusted integration regions to increase applicability for a wider range of comonomer contents.
[00155] The relative content of isolated and bulk ethylene incorporation was calculated from the triad sequence distribution using the following relationship (equation (I)):
where: I(E) is the relative content of isolated and block ethylene sequences [in%]; fPEP is the mole fraction of propylene/ethylene/propylene (PEP) sequences in the sample; fPEE is the mole fraction of propylene/ethylene/ethylene (PEE) and ethylene/ethylene/propylene (EEP) sequences in the sample; fEEE is the mole fraction of ethylene/ethylene/ethylene (EEE) sequences in the sample.
[00156] Bulk density, BD, is measured in accordance with ASTM D 1895.
[00157] Particle size distribution, PSD Coulter Counter LS 200 at room temperature with heptane as the medium.
[00158] Solubles in xylene (XCS, % by weight): Content of cold solubles in xylene (XCS) is determined at 25°C according to ISO 16152; first edition; 2005-07-01.
[00159] The extractable fraction in hexane is determined according to the FDA method (Federal registration, title 21, chapter 1, part 177, section 1520, n. Annex B) on cast films of 100 μm thickness produced in a line of monolayer cast film having a melting temperature of 220°C and a cooling roll temperature of 20°C. The extraction was carried out at a temperature of 50°C and an extraction time of 30 min.
[00160] Number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (Mw/Mn) are determined by Gel Permeation Chromatography (GPC) according to the following method.
[00161] The weight average molecular weight Mw and polydispersity (Mw/Mn), where Mn is the number average molecular weight and Mw is the weight average molecular weight are measured by a method based on ISO 16014-1:2003 and ISO 16014-4:2003. A Waters Alliance GPCV 2000 instrument equipped with refractive index detector and online viscometer was used with 3 x TSK (GMHXL-HT) gel columns from TosoHaas and 1,2,4-trichlorobenzene (TCB, stabilized with 200 mg/L of 2,6-di-tert-butyl-4-methyl-phenol) as solvent at 145 °C and at a constant flow rate of 1 mL/min. 216.5 μL of sample solution was injected per analysis. The column set was calibrated using relative calibration with 19 MWD narrow polystyrene (PS) standards in the range of 0.5 kg/mol to 11,500 kg/mol and a well-characterized broad polypropylene standard set. All samples were prepared by dissolving 5 - 10 mg of polymer in 10 mL (at 160°C) of stabilized TCB (same as in mobile phase) and holding for 3 hours with continuous agitation before sampling on the GPC instrument.
[00162] Analysis of DSC, melting temperature (Tm) and heat of melting (Hf), temperature of crystallization (Tc) and heat of crystallization (Hc): measured with a TA Instrument Q2000 differential scanning calorimetry (DSC) instrument in samples with 5 to 7 mg. DSC is performed according to ISO 11357 / part 3 / method C2 in a heat / cold / heat cycle with a scan rate of 10°C/min in the temperature range of -30 to +225°C. The crystallization temperature and heat of crystallization (Hc) are determined from the cooling step, while the melting temperature and melting heat (Hf) are determined from the heating step.
[00163] The glass transition temperature Tg is determined by dynamic mechanical analysis according to ISO 6721-7. Measurements are made in torsional mode on compression molded samples (40x10x1 mm3) between -100°C and +150°C with a heating rate of 2°C/min and a frequency of 1 Hz.
[00164] Flexural Modulus: The flexural modulus was determined at 3-point inclination at 23°C according to ISO 178 on 80x10x4 mm3 injection molded test bars in line with EN ISO 1873-2.
[00165] Charpy impact test: Charpy notched impact strength (NIS) was measured in accordance with ISO 179 1eA at +23°C, using 80x10x4 mm3 injection molded test bar specimens prepared in accordance with ISO 294 -1 : 1996
[00166] Puncture energy was determined in the Instrumental Weight Drop Test (IFW) according to ISO 66032 using injection molded plates of 60x60x2 mm and a test speed of 2.2 m/s. Puncture energy reported results from an integral speech energy curve measured at +23°C.
[00167] The top load test was performed by compression between two plates fixed on a universal testing machine with a test speed of 10 mm/min according to an internal procedure in general consensus with ASTM D642. For testing, the cup is placed upside down (ie with the bottom facing the moving plate) in the test configuration and compressed at the point of collapse which is noted by a drop in force on the deformation curve. force, for which the maximum force is noted. At least 8 glasses are tested to determine an average result. Measurement of Transparency, Clarity and Fog in Glasses
[00168] Instrument: BYK-Gardner Haze-gard plus
[00169] Test: according to ASTM D1003 (as for injection molded plates).
[00170] Method: The measurement is taken on the outer wall of the cups as produced below. The top and bottom of the cups are cut off. The resulting rounded wall is then split in two, horizontally. Then, from this wall, six equal samples of approximately 60x60 mm are cut from the closure to the middle. The specimens are placed in the instrument with their convex side facing the mist hole. Next, transparency, haze and clarity are measured for each of the six samples and the haze value is reported as the average of these six parallels. Preparation of 840 ml cups
[00171] With the polymers as defined below, cups are produced by injection molding using an Engel speed 180 machine with a 35 mm barrier screw (supplied by Engel Austria GmbH). The melting temperature was set at 245°C and the mold temperature at 10°C; an injection speed of 770 cm3/s with an injection time of 0.08 s was used, followed by a pressure hold time of 0.1 s with 1300 bar (130 MPa) (down to 800 bar (80 MPa) )) and a cool-down time of 1.5 s, giving a default cycle time of 3.8 s. The dimensions of the cup are as follows: height 100 mm, top diameter 115 mm, bottom diameter 95 mm, bottom wall thickness 0.44 mm, side wall thickness 0.40 mm. For cycle time optimization, the machine was run with standard injection parameters first. The machine was run in full automatic mode, reducing the cool-down time after a 5-minute settling time from 1.5 to 0.3 s. Depending on the behavior of the material, the cups were then deformed or could not be demoulded. Then, the cooling time was increased in steps of 0.1 s until the quality of the part was verified as optically and mechanically satisfactory. The cycle time resulting from this experiment can be seen in table 2. 2. Examples
[00172] The catalyst used in the polymerization process for the propylene copolymer of the examples of the invention (IE1) and (IE2) was produced as follows: Chemicals used:
[00173] 20% toluene solution of butyl ethyl magnesium (Mg(Bu)(Et), BEM), provided by Chemtura.
[00174] 2-ethylhexanol, provided by Amphochem.
3-Butoxy-2-propanol-(DOWANOL™ PnB), provided by Dow.
[00176] bis(2-ethylhexyl)citraconate, provided by SynphaBase.
[00177] TiCl4, provided by Millenium Chemicals.
[00178] Toluene, provided by Aspokem.
[00179] Viscoplex® 1-254, provided by Evonik.
[00180] Heptane, provided by Chevron. Preparation of a Mg complex
[00181] First a solution of magnesium alkoxide was prepared by adding, with stirring (70 rpm), in 11 kg of a toluene solution of butyl ethyl magnesium (Mg(Bu)(Et), BEM) at 20% by weight , 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, 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 to the Mg alkoxide solution keeping the temperature below 25°C. mixing continued for 15 minutes under agitation (70 rpm). Solid Catalyst Component Preparation
[00182] 20.3 kg of TiCl4 and 1.1 kg of toluene are 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 Mg complex 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 of mixing was stopped, the catalyst drops were solidified and the formed catalyst particles were allowed to settle. After settling (1 hour), the supernatant liquid was sucked out.
Next, 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.
[00184] Solid catalyst component as used with triethyl aluminum (TEAL) as co-catalyst and dicyclopentyl dimethoxy silane (D donor) as donor.
[00185] The catalyst used in the polymerization processes of the comparative example (CE1) was the catalyst of the example section of the document WO 2010009827 Al (see pages 30 and 31) with aluminum triethyl (TEAL) as co-catalyst and dicyclopentyl dimethoxy silane (donor D) as a donor.
[00186] The aluminum to donor ratio, the aluminum to titanium ratio and the polymerization conditions are given in table 1. TABLE 1: PREPARATION OF EXAMPLES


*nd not detectable
[00187] All polymer powders were compounded in a Coperion ZSK 57 co-rotating twin screw extruder at 220°C with 0.2% by weight of Irganox B225 (1:1 - mixture of Irganox 1010 (Pentaerythryl-tetrakis(3-( 3',5'-di-tert.butyl-4-hydroxytoluyl)-propionate and tris(2,4-di-t-butylphenyl)phosphate)phosphite) from BASF AG, Germany) and 0.1% by weight of stearate of calcium. The materials of invention examples IE1 and IE2 were seeded with 2% by weight of a propylene homopolymer having an MFR2 of 20g/10min and 200ppm vinylcycloalkane polymer (pVCH) to give invention examples IE3 and IE4, respectively. Similarly, the material of comparative example CE1 was seeded with 2% by weight of a homopolymer of propylene having an MFR2 of 20g/10min and 200ppm of vinylcycloalkane polymer (pVCH) to give comparative example CE2. TABLE 2: PROPERTIES OF EXAMPLES

TABLE 3 : RELATIVE CONTENT OF BLOCK ETHYLENE SEQUENCES (I(E))

权利要求:
Claims (16)
[0001]
1. Propylene copolymer (R-PP), characterized by the fact that it has: (a) a comonomer content in the range of 2.0 to 11.0% in mol; (b) an MFR2 flow rate (230°C) measured in accordance with ISO 1133 in the range of 25.0 to 100 g/10min and; (c) a relative content of isolated and block ethylene sequences (I(E)) in the range of 55.0 to 70.0%, where the content of I(E) content is defined by equation (I):
[0002]
2. Propylene copolymer (R-PP) according to claim 1, characterized in that said propylene copolymer (R-PP) has a cold soluble xylene fraction (XCS) in the range from 4.0 to 25.0% by weight.
[0003]
3. Propylene copolymer (R-PP) according to claim 1 or 2, characterized in that said propylene copolymer (R-PP) has: (a) a glass transition temperature in the range of -12 at +2°C; and/or (b) no glass transition temperature below -20°C.
[0004]
4. Propylene copolymer (R-PP), according to any one of the preceding claims, characterized in that said propylene copolymer (R-PP) has: (a) a main melting temperature in the range of 133 to 155°C; and/or (b) a crystallization temperature in the range of 110 to 128°C.
[0005]
5. Propylene copolymer (R-PP), according to any one of the preceding claims, characterized in that said propylene copolymer (R-PP): (a) has region defects 2.1 of at most 0.4 % determined by 3C-NMR spectroscopy; and/or (b) is single-phase.
[0006]
6. Propylene copolymer (R-PP), according to any one of the preceding claims, characterized in that the comonomer is selected from ethylene, C4 to C12 α-olefin and mixtures thereof, preferably the comonomer is ethylene.
[0007]
7. Propylene copolymer (R-PP), according to any one of the preceding claims, characterized in that said propylene copolymer (R-PP) comprises two fractions, a first fraction of propylene copolymer (R-PP1 ) and a second fraction of propylene copolymer (R-PP2), said first fraction of propylene copolymer (R-PP1) differs from said second fraction of propylene copolymer (R-PP2) in comonomer content.
[0008]
8. Propylene copolymer (R-PP), according to claim 7, characterized in that: (a) the weight ratio between the first fraction of propylene copolymer (R-PP1) and the second fraction of copolymer of propylene (R-PP2) [(R-PP1):(R-PP2)] is 70:30 to 30:70; and/or (b) the comonomers for the first propylene copolymer fraction (R-PP1) and the second propylene copolymer fraction (R-PP2) are selected from ethylene, C4 to C12 α-olefin and mixtures thereof, preferably the comonomers for the first propylene copolymer fraction (R-PP1) and the second propylene copolymer fraction (R-PP2) are the same and are selected from ethylene, C4 to C12 α-olefin and mixtures thereof.
[0009]
9. Propylene copolymer (R-PP), according to claim 7 or 8, characterized in that: (a) the first fraction of propylene copolymer (R-PP1) is the weak fraction in comonomer and the second propylene copolymer fraction (R-PP2) is the fraction rich in comonomer; and/or (b) the first fraction of propylene copolymer (R-PP1) has a lower comonomer content than the propylene copolymer (R-PP).
[0010]
10. Propylene copolymer (R-PP) according to any one of claims 7 to 9, characterized in that: (a) the first fraction of propylene copolymer (R-PP1) has a comonomer content in the range 1.0 to 6.0% by mol based on the first fraction of propylene copolymer (R-PP1); and/or, preferably and, (b) the second fraction of propylene copolymer (R-PP2)
[0011]
11. Propylene copolymer (R-PP), according to any one of claims 7 to 10, characterized in that: (a) the first random fraction of propylene copolymer (R-PP1) and the second random fraction of propylene copolymer (R-PP2) together satisfy inequality (IV):
[0012]
12. Injection molded article, characterized in that it comprises a copolymer of propylene defined in any one of the preceding claims 1 to 11.
[0013]
13. Small thickness packaging, preferably a small thickness packaging made by injection molding, characterized in that it comprises a propylene copolymer defined in any one of the preceding claims 1 to 11.
[0014]
14. Process for the production of a propylene copolymer (R-PP) defined in any one of the preceding claims 1 to 11, characterized in that the propylene copolymer (R-PP) was produced in the presence of: (a) a Ziegler-Natta (ZN-C) catalyst comprises a titanium compound (TC), a magnesium compound (MC) and an internal donor (ID), wherein said internal donor (ID) is a non-phthalic acid ester ; (b) optionally a co-catalyst (Co); and (c) optionally an external donor (ED).
[0015]
15. Process according to claim 14, characterized in that: (a) the internal donor (ID) is selected from malonates, maleates, succinates, glutarates, cyclohexane-1,2-dicarboxylates, optionally substituted benzoates and derivatives and/or mixtures thereof, preferably the internal donor (ID) is a citraconate; (b) the molar ratio of co-catalyst (Co) to external donor (ED) [Co/ED] is 5 to 45.
[0016]
16. Process according to claim 14 or 15, characterized in that the propylene copolymer (R-PP) 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 copolymer (R-PP1) is produced and subsequently transferred into the second reactor (R2), in the second reactor (R2), the second fraction of propylene copolymer (R- PP2) is produced in the presence of the first fraction of propylene copolymer (R-PP1).

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-12-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-03-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-05-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/05/2014, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-06-29| B09W| Correction of the decision to grant [chapter 9.1.4 patent gazette]|Free format text: REFERENCIA: RPI 2617 DE 02.03.2021 - CODIGO 9.1 |

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2021-07-06| B16C| Correction of notification of the grant [chapter 16.3 patent gazette]|Free format text: REFERENTE AO DESPACHO 16.1 PUBLICADO NA RPI 2628 DE 18.05.2021, QUANTO AS REIVINDICACOES |

优先权:

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申请号 | 申请日 | 专利标题

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EP13168763|2013-05-22|

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EP13168763.4|2013-05-22|

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PCT/EP2014/059601|WO2014187687A1|2013-05-22|2014-05-12|Propylene copolymer for thin-wall packaging|

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