Patent Application
20180037717
The present invention relates to new propylene-ethylene random copolymers with improved long-term mechanical properties, especially improved impact strength retention, to their manufacture as well as their use, e.g. for the production of moulded articles, particularly injection moulded articles, such as thin-walled plastic containers for packaging.
Polypropylene derives its mechanical and optical performance from the amount and nature of crystalline phases being present in the final product. Apart from designing the polymer itself, like selecting the average molecular weight, the molecular weight distribution, the type and relative amount of comonomer(s) and the comonomer distribution, the crystalline phase will also be influenced by the presence of crystal nucleating agents. It is well known that different types of crystal nucleating agents will affect the crystal structure of the polymer differently, enhancing the presence and relative amounts of specific crystal modifications of polypropylene, like the monoclinic α-modification, the hexagonal β-modification and the orthorhombic γ-modification. While the polymer structure will affect the degree of expression of a specific nucleation, the type of crystal formed will be determined by the nucleating agent.
A class of polypropylenes especially requiring modification by nucleating agents comprises polypropylene random copolymers being characterized by a homogeneous structure without phase separation and by a low to moderate comonomer content. Commonly used comonomers for said random copolymers are ethylene and/or higher α-olefins with 4 to 8 carbon atoms. Such random copolymers will exhibit a decrease of the spherulitic growth speed and a reduced overall crystallinity upon processing, resulting in better optical properties but at the same time reduced mechanical strength and impaired long-term stability.
Additionally it has to be taken into consideration that the application properties and the lifespan of polymers are decisively influenced by property changes after conversion into the final shape. In case of polypropylene, a semicrystalline polymer that is mostly applied above its glass transition temperature, a combination of physical aging and post-crystallization occurs.
Physical ageing is a very important process characteristic of all glassy materials. Final products of glassy polymers are made by shaping them in the molten state, followed by rapid cooling to below the glass-transition temperature. During the cooling the material solidifies and stiffens, but this process can't to be completed, because the period time is too short: the molecular motions become too sluggish and freeze. Solidification and stiffening continue very slowly during the life of the product: thus many material properties change with time.
In particular, the modulus and toughness undergo steady changes even after long times.
The temperature level of the ageing process plays a decisive role in determining the effects. Apart from that, the nature of the polymer and the type and conditions of conversion are also important. The cumulative effects of crystallization behavior of the polymer and cooling history determine the crystallinity and superstructure of the formed article, which in turn determines the ageing behavior.
The phenomenon of ageing and annealing processes for homo- and copolymers has for example been analysed and described by Gahleitner et al. (J. Macromol. Sci. Phys., B41 (2002) 833-49). Storage of a polypropylene random copolymer at standard conditions (+23±1° C., 50% relative humidity) has been found to result in increased modulus and reduced toughness over a period of more than 5000 h in case of injection-moulded specimens (
It is therefore an object of the present invention to provide propylene-ethylene random copolymers which have improved long-term mechanical properties, especially improved impact strength retention, thus avoiding the negative influence of physical ageing and post-crystallization
The finding of the present invention is to provide propylene-ethylene random copolymers which are nucleated with a special combination of alpha-nucleating agents and have a special polymer design.
Accordingly the present invention is directed to propylene-ethylene random copolymers having
(i) a melt flow rate MFR2 (according to ISO 1133, 230° C., 2.16 kg) in the range of 30 to 70 g/10 min,
(ii) a total ethylene comonomer content of 2.0 to 5.0 mol %
(iii) a content of the orthorhombic gamma-crystal phase 100.Kγ of 20% to less than 40% as determined by wide-angle X-ray diffraction (WAXS) on a 60×60×2 mm3 injection moulded test specimens as described in the experimental part and comprising
a) a blend of
a-1) 1.0 to 10.0 wt %, based on the total weight of the propylene-ethylene random copolymer, of a masterbatch comprising a propylene homopolymer as carrier polymer and 10 to 2000 ppm, based on the masterbatch, of a polymeric α-nucleating agent (pNA), and
a-2) 0.02 to 1.0 wt %, based on the total weight of the propylene-ethylene random copolymer, of a soluble α-nucleating agent (sNA).
The propylene-ethylene random copolymers as defined above are furthermore characterized by comprising two propylene copolymer fractions
b) a first propylene copolymer fraction and
c) a second propylene copolymer fraction having an ethylene comonomer content of at most 6.5 mol %,
said first propylene copolymer fraction having a higher MFR2 and/or a lower ethylene comonomer content than said second propylene copolymer fraction.
In another aspect of the present invention, the propylene-ethylene random copolymers have been polymerized in the presence of a) a Ziegler-Natta catalyst (ZN-C) comprising compounds (TC) of a transition metal of Group 4 to 6 of IUPAC, a Group 2 metal compound (MC) and an internal donor (ID), wherein said internal donor (ID) is preferably a non-phthalic compound, more preferably a non-phthalic acid ester; b) optionally a co-catalyst (Co), and c) optionally an external donor (ED). It is most preferred that a) the internal donor (ID) is selected from optionally substituted malonates, maleates, succinates, glutarates, cyclohexene-1,2-dicarboxylates, 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.
In yet another embodiment of the present invention, the propylene-ethylene random copolymers are produced in at least one reactor (R1) or in a sequential polymerization process comprising at least two reactors (R1) and (R2), whereby in the first reactor (R1) a propylene copolymer fraction (PP-COPO-1) is produced, which is subsequently transferred into the second reactor (R2), and wherein in the second reactor (R2) a second propylene copolymer fraction (PP-COPO-2) is produced in the presence of the first propylene copolymer fraction (PP-COPO-1).
The propylene-ethylene random copolymers as defined above are highly suitable for the use in the production of moulded articles, particularly injection moulded articles, such as thin-walled plastic containers for packaging, which is a further aspect of the present invention.
Moulded articles, especially injection moulded articles prepared form the propylene-ethylene random copolymers of the present invention are characterized by a high tensile modulus (measured according to ISO 527) measured after 96 hours of storage at +23±1° C. and 50% relative humidity (=standard conditions)
and even higher high tensile modulus (measured according to ISO 527) measured after 1344 hours of storage at standard conditions.
Simultaneously the puncture energy (measured according to ISO 6603-2; 60×60×2 mm3 specimens) is at a high level measured after 96 hours of storage at standard conditions and stays approximately on that level when measured after 1344 hours of storage at standard conditions.
As Comparative Examples show, this effect is really surprising.
In the following the invention is described in more detail.
The propylene-ethylene copolymers according to this invention have a melt flow rate MFR2 (230° C.) measured according to ISO 1133 in the range of 30.0 to 70.0 g/10 min, preferably in the range of 35.0 to 65.0 g/10 min and more preferably in the range of 40.0 to 55.0 g/10 min.
It is appreciated that the propylene-ethylene copolymers preferably have an ethylene comonomer content in a very specific range. Thus it is required that the ethylene comonomer content of the propylene-ethylene copolymers is in the range of 2.0 to 5.0 mol %, preferably in the range of 2.5 to 5.0 mol % and more preferably in the range of 3.0 to 5.0 mol %.
Furthermore the propylene-ethylene copolymers according to this invention are characterized by a content of the orthorhombic gamma-crystal phase 100.Kγ of less than 40%, preferably of less than 37%, as determined by wide-angle X-ray scattering (WAXS on injection moulded plaque samples of 60×60×2 mm3, as described in the experimental part).
A lower limit of the content of the orthorhombic gamma-crystal phase 100.Kγ is 20% and more preferably 25%.
Surprisingly the inventors of the present invention have found that a low content of the orthorhombic gamma-crystal phase (i.e. 100.Kγ of less than 40%) decreases post-crystallization processes in the final articles made of the inventive propylene-ethylene copolymers and thus improves the long-term mechanical properties, especially improves the impact strength retention.
Further the propylene-ethylene copolymers are preferably featured by their relative content of isolated to block ethylene sequences (I(E). The I(E) content [%] is defined by equation (I)
I(E)=fPEP/(fEEE+fPEE+fPEP)×100 (I)
wherein
I(E) is the relative content of isolated to block ethylene sequences [in %];
fPEP is the mol fraction of propylene/ethylene/propylene sequences (PEP) in the sample;
fPEE is the mol fraction of propylene/ethylene/ethylene sequences (PEE) and of ethylene/ethylene/propylene sequences (EEP) in the sample;
fEEE is the mol fraction of ethylene/ethylene/ethylene sequences (EEE) in the sample wherein all sequence concentrations being based on a statistical triad analysis of 13C-NMR data.
Accordingly it is preferred that the propylene-ethylene copolymers have a normalized PEP value (nPEP) in the range 45.0 to 70.0%, more preferably in the range of 50.0 to 70.0%, still more preferably in the range of 55.0 to 70.0%, yet more preferably in the range of 58.0 to 69.0%.
Further the propylene-ethylene copolymers have 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 of 133 to 155° C., still more preferably in the range of 134 to 152° C.
Further it is preferred that the propylene-ethylene copolymers have a crystallization temperature of at least 110° C., more preferably in the range of 110 to 128° C., still more preferably in the range of 112 to 126° C., like in the range of 114 to 124° C.
Preferably, the propylene-ethylene copolymers have a xylene cold soluble fraction (XCS) in the range of 4.0 to 20.0 wt %, preferably in the range of 4.5 to 150.0 wt %, more preferably in the range of 5.0 to 10.0 wt %.
Preferably the propylene-ethylene copolymers according to this invention have been produced in the presence of a Ziegler-Natta catalyst, which will be described in detail below.
The propylene-ethylene copolymers preferably comprise at least two polymer fractions, like two or three polymer fraction, all of them being propylene copolymers. Preferably the random propylene-ethylene copolymers comprise at least two different propylene copolymer fractions, like two different propylene copolymer fractions, wherein further the two propylene copolymer fractions preferably differ in the comonomer content.
Even more preferred the propylene-ethylene copolymers comprise, preferably consists of, a first propylene copolymer fraction (PP-COPO-1) and a second propylene copolymer fraction (PP-COPO-2), wherein further the first propylene copolymer fraction (PP-COPO-1) and the second propylene copolymer fraction (PP-COPO-2) differ in the comonomer content and/or in the melt flow rate MFR2 (230° C.). In one embodiment they differ in the comonomer content and in the melt flow rate MFR2 (230° C.).
In still another embodiment the first random propylene copolymer fraction (PP-COPO-1) has a lower ethylene comonomer content but a higher melt flow rate MFR2 (230° C.) than the second random propylene copolymer fraction (PP-COPO-2).
Thus it is preferred that the second random propylene copolymer fraction (PP-COPO-2) has an ethylene comonomer content of at most 6.5 mol % and more preferably of at most 6.0 mol %. Preferably the second random propylene copolymer fraction (PP-COPO-2) has a comonomer content of at least 2.0 mol %, preferably of at least 3.0 mol %.
The first random propylene copolymer fraction (PP-COPO-1) preferably has an ethylene comonomer content below that of the second random propylene copolymer fraction (PP-COPO-2).
Thus it is preferred that the first random propylene copolymer fraction (PP-COPO-1) has an ethylene comonomer content in the range of 0.5 mol % to at most 5.0 mol %, preferably in the range of 1.0 mol % to at most 4.5 mol %.
Preferably the first random propylene copolymer fraction (PP-COPO-1) preferably has a melt flow rate MFR2 (230° C.) in the range of in the range of 20.0 to 120 g/10 min, more preferably in the range 25.0 to 100 g/10 min, still more preferably in the range of 25.0 to 80 g/10 min.
Preferably the second random propylene copolymer fraction (PP-COPO-2) has a melt flow rate MFR2 (230° C.) in the range of 20.0 to 120 g/10 min, more preferably in the range of 25.0 to 100 g/10 min, still more preferably in the range of 25.0 to 80 g/10 min, whereby the MFR2 of the second random propylene copolymer fraction (PP-COPO-2) is preferably lower than the MFR2 of the first random propylene copolymer fraction (PP-COPO-1). It is further preferred that the second random propylene copolymer fraction (PP-COPO-2) has an ethylene comonomer content which is higher than the ethylene comonomer content of the first random propylene copolymer fraction (PP-COPO-1).
Preferably the weight ratio between the first propylene copolymer fraction (PP-COPO-1) and the second propylene copolymer fraction (PP-COPO-2) is 30/70 to 70/30, more preferably 40/60 to 60/40, like 43/57 to 57/43.
The propylene-ethylene copolymers as defined above comprise a blend of two α-nucleating agents, i.e. a polymeric α-nucleating agent (pNA) and a soluble α-nucleating agent (sNA).
The polymeric α-nucleating agent (pNA) is added in form of a masterbatch together with a carrier polymer, where an already nucleated propylene homopolymer, i.e. the carrier polymer, containing the polymeric nucleating agent (masterbatch) is blended with the propylene homopolymer.
Preferably the polymeric α-nucleating agent (pNA) is a polymerized vinyl compound of formula (I)
wherein R1 and R2 together form a 5 or 6 membered saturated or unsaturated or aromatic ring or they stand independently for a lower alkyl comprising 1 to 4 carbon atoms.
Preferably the polymeric α-nucleating agent (pNA) is a polymerized vinyl compound selected from the group consisting of vinyl cycloalkanes, in particular vinyl cyclohexane (VCH), vinyl cyclopentane, vinyl-2-methyl cyclohexane and vinyl norbornane, 3-methyl-Ibutene, 3-ethyl 1-hexene or mixtures thereof. It is especially preferred that the polymeric α-nucleating agent (pNA) is a polymerized a vinyl cycloalkane, especially polymerized vinyl cyclohexane (pVCH).
The polymeric α-nucleating agent (pNA) is added in the form of a masterbatch (MB), whereby the masterbatch (MB) contains the polymeric α-nucleating agent, most preferably a vinylcycloalkane, like vinylcyclohexane (VCH), polymer and/or vinylalkane polymer, preferably vinylcyclohexane (VCH) polymer, as defined above, in an amount of not more than 2000 ppm, preferably in an amount of 10 to 2000 ppm, more preferably of 20 to 1000 ppm, and still more preferably in an amount of 50 to 500 ppm, based on the weight of the masterbatch (MB) (100 wt. %).
Said masterbatch (MB) is present in an amount of 1.0 to 10.0 wt %, preferably 1.5 wt % to 5.0 wt %, based on the total amount of the propylene-ethylene copolymer. The masterbatch (MB) furthermore comprises, preferably consists of a homopolymer of propylene which has been nucleated according to BNT-technology as described below.
Such a masterbatch is preferably prepared by polymerizing propylene in a sequential polymerization process.
The term “sequential polymerization system” indicates that the propylene homopolymer 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” shall 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 instance a pre-polymerization step in a prepolymerization reactor. The term “consist of” is only a closing formulation in view of the main polymerization reactors.
Preferably, at least one of the two polymerization reactors (R1) and (R2) is a gas phase reactor (GPR). Still 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) according to this invention is preferably a fluidized bed reactor, a fast fluidized bed reactor or a settled bed reactor or any combination thereof.
Accordingly, the first polymerization reactor (R1) is preferably a slurry reactor (SR) and can be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry. Bulk means a polymerization in a reaction medium that comprises of at least 60% (w/w) monomer. According to the present invention the slurry reactor (SR) is preferably a (bulk) loop reactor (LR). Accordingly the average concentration of the first fraction (1st F) of the propylene homopolymer (i.e. the first propylene homopolymer fraction (H-PP1)), in the polymer slurry within the loop reactor (LR) is typically from 15 wt % to 55 wt %, based on the total weight of the polymer slurry within the loop reactor (LR). In one preferred embodiment of the present invention the average concentration of the first propylene homopolymer fraction (H-PP1) in the polymer slurry within the loop reactor (LR) is from 20 wt % to 55 wt % and more preferably from 25 wt % to 52 wt %, based on the total weight of the polymer slurry within the loop reactor (LR).
Preferably the propylene homopolymer of the first polymerization reactor (R1), i.e. the first propylene homopolymer fraction (H-PP1), more preferably the polymer slurry of the loop reactor (LR) containing the first propylene homopolymer fraction (H-PP1), is directly fed into the second polymerization reactor (R2), i.e. into the (first) gas phase reactor (GPR1), without a flash step between the stages. This kind 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 wherein the content of the first polymerization reactor (R1), i.e. of the loop reactor (LR), the polymer slurry comprising the first propylene homopolymer fraction (H-PP1), is led directly to the next stage gas phase reactor.
Alternatively, the propylene homopolymer of the first polymerization reactor (R1), i.e. the first propylene homopolymer fraction (H-PP1), more preferably polymer slurry of the loop reactor (LR) containing the first propylene homopolymer fraction (H-PP1), may be also directed into a flash step or through a further concentration step before fed into the second polymerization reactor (R2), i.e. into the gas phase reactor (GPR). Accordingly, this “indirect feed” refers to a process wherein the content of the first polymerization reactor (R1), of the loop reactor (LR), i.e. the polymer slurry, is fed into the second polymerization reactor (R2), into the (first) gas phase reactor (GPR1), via a reaction medium separation unit and the reaction medium as a gas from the separation unit.
More specifically, the second polymerization reactor (R2), and any subsequent reactor, for instance 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. Preferably the gas phase reactors (GPRs) comprise a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec. Thus it is appreciated that the gas phase reactor is a fluidized bed type reactor preferably with a mechanical stirrer.
Thus, in a preferred embodiment the first polymerization reactor (R1) is a slurry reactor (SR), like loop reactor (LR), whereas the second polymerization reactor (R2) and any optional subsequent reactor, like the third polymerization reactor (R3), are gas phase reactors (GPRs). Accordingly for the instant process at least two, preferably two polymerization reactors (R1) and (R2) or three polymerization reactors (R1), (R2) and (R3), namely a slurry reactor (SR), like loop reactor (LR) and a (first) gas phase reactor (GPR1) and optionally a second gas phase reactor (GPR2), connected in series are used.
Furthermore the process comprises a prepolymerization step in which the above defined polymeric nucleating agent, preferably the vinyl compound according to formula (I) as defined above, even more preferably vinyl cyclohexane (VCH), is first polymerized in the presence of a catalyst system, comprising a solid Ziegler Natta catalyst component, a cocatalyst and optional external donor, according to the BNT-technology.
The so obtained reaction mixture of the polymer of the vinyl compound according to formula (I) as defined above, even more preferably vinyl cyclohexane (VCH) polymer and the catalyst system is then introduced in the first polymerization reactor (R1).
With regard to the BNT-technology reference is made to the international applications WO 99/24478, WO 99/24479 and particularly WO 00/68315. According to this technology a catalyst system, preferably a Ziegler-Natta procatalyst, is modified by polymerizing the vinyl compound, as described above, in the presence of the catalyst system, comprising a Ziegler-Natta procatalyst, an external donor and a cocatalyst.
The weight ratio of vinyl compound to solid catalyst component in the modification step of the catalyst is preferably of up to 5 (5:1), preferably up to 3 (3:1) most preferably from 0.5 (1:2) to 2 (2:1). The most preferred vinyl compound is vinylcyclohexane (VCH).
Such masterbatches, comprising a polypropylene homopolymer and the polymeric α-nucleating agent, are furthermore commercially available from Borealis.
As second nucleating agent a soluble α-nucleating agent (sNA) is present.
The term “soluble” in connection with the soluble α-nucleating agent (NA) indicates that the soluble α-nucleating agent (sNA) particles are dissolved in the melt of the propylene-ethylene copolymers during melt-mixing and will recrystallize from said melt upon solidification. In other words, the propylene-ethylene copolymers and the soluble α-nucleating agent (sNA) particles do not form a mixture of separate particles (dry blends) but a microscale dispersion of recrystallized fibrils of the nucleating agent, said fibrils having a diameter of less than 0.25 μm, preferably less than 0.1 μm, measured according by transmission electron microscopy (TEM) or scanning (atomic) force microscopy (AFM). Examples for such determinations can be found in the literature, e.g. by Shepard et al., J. Polym. Sci. B: Polym. Phys. 35, p. 2617-2628 (1997) and by Lipp et al., Langmuir, 22, p. 6398-640 (2006).
Preferred soluble α-nucleating agent (sNA)s are those which are soluble in the propylene-ethylene copolymer. Soluble α-nucleating agents (sNA) are characterized by demonstrating a sequence of dissolution in heating and recrystallization in cooling to improve the degree of dispersion. Methods for determining said dissolution and recrystallization are described for example by Kristiansen et al. in Macromolecules 38 (2005) pages 10461-10465 and by Balzano et al. in Macromolecules 41 (2008) pages 5350-5355. In detail, the dissolution and recrystallization can be monitored by means of melt rheology in dynamic mode as defined by ISO 6271-10:1999.
Accordingly, it is preferred that the soluble α-nucleating agent (sNA) is selected from the group consisting of sorbitol derivatives, nonitol derivatives, benzene-trisamides, and mixtures thereof.
Suitable sorbitol derivatives are diacetals of sorbitol or xylitol, for example di(alkylbenzylidene)sorbitols, like 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (CAS-no. 135861-56-2, e.g. Millad 3988, supplier Milliken)
A suitable nonitol based nucleating agent is for instance 1,2,3-trideoxy-4,6:5,7-bis-O-((4-propylphenyl) methylene) nonitol (CAS-no. 882073-43-0, e.g. Millad NX8000, supplier Milliken).
The soluble α-nucleating agent (sNA) is present in an amount of 0.02 to 1.0 wt %, preferably in an amount of 0.05 to 0.8 wt % and more preferably in an amount of 0.1 to 0.5 wt %, based on the total weight of the propylene-ethylene copolymer.
The two nucleating agents can be added separately or can be first mixed together.
The propylene-ethylene copolymers as defined in the instant invention may further contain up to 5.0 wt % additives, like antioxidants, as well as slip agents and antiblocking agents. Preferably the additive content (without α-nucleating agents) is below 3.0 wt %, like below 1.0 wt %.
The propylene-ethylene copolymers according to this invention are preferably produced in a sequential polymerization process in the presence of a Ziegler-Natta catalyst as defined below.
Accordingly it is preferred that the propylene-ethylene copolymers are produced in the presence of
Preferably the propylene-ethylene copolymers are produced in a sequential polymerization process comprising at least two reactors (R1) and (R2). In the first reactor (R1) the first propylene copolymer fraction (PP-COPO-1) is produced and subsequently transferred into the second reactor (R2), whereby in the second reactor (R2) the second propylene copolymer fraction (PP-COPO-2) is produced in the presence of the first propylene copolymer fraction (PP-COPO-1).
The term “sequential polymerization system” again indicates that the 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” shall 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 instance a pre-polymerization step in a pre-polymerization reactor. The term “consist of” is only a closing formulation in view of the main polymerization reactors.
Preferably at least one of the two polymerization reactors (R1) and (R2) is a gas phase reactor (GPR). Still 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) according to this invention is preferably a fluidized bed reactor, a fast fluidized bed reactor or a settled bed reactor or any combination thereof.
Accordingly, the first polymerization reactor (R1) is preferably a slurry reactor (SR) and can be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry. Bulk means a polymerization in a reaction medium that comprises of at least 60% (w/w) monomer. According to the present invention the slurry reactor (SR) is preferably a (bulk) loop reactor (LR). Accordingly the average concentration of propylene-ethylene copolymer, i.e. the first fraction of the propylene copolymer (i.e. the first propylene copolymer fraction (PP-COPO-11)), in the polymer slurry within the loop reactor (LR) is typically from 15 wt % to 55 wt %, based on the total weight of the polymer slurry within the loop reactor (LR). In one preferred embodiment of the present invention the average concentration of the first propylene copolymer fraction (PP-COPO-1), in the polymer slurry within the loop reactor (LR) is from 20 wt % to 55 wt % and more preferably from 25 wt % to 52 wt %, based on the total weight of the polymer slurry within the loop reactor (LR).
Preferably the propylene copolymer of the first polymerization reactor (R1), i.e. the first propylene copolymer fraction (PP-COPO-1), more preferably the polymer slurry of the loop reactor (LR) containing the first propylene copolymer fraction (PP-COPO-1), is directly fed into the second polymerization reactor (R2), i.e. into the (first) gas phase reactor (GPR1), without a flash step between the stages. This kind 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 wherein the content of the first polymerization reactor (R1), i.e. of the loop reactor (LR), the polymer slurry comprising the first propylene copolymer fraction (PP-COPO-1), is led directly to the next stage gas phase reactor.
Alternatively, the propylene copolymer of the first polymerization reactor (R1), i.e. the first propylene copolymer fraction (PP-COPO-1), more preferably polymer slurry of the loop reactor (LR) containing the first propylene copolymer fraction (PP-COPO-1), may be also directed into a flash step or through a further concentration step before fed into the second polymerization reactor (R2), i.e. into the gas phase reactor (GPR). Accordingly, this “indirect feed” refers to a process wherein the content of the first polymerization reactor (R1), of the loop reactor (LR), i.e. the polymer slurry, is fed into the second polymerization reactor (R2), into the (first) gas phase reactor (GPR1), via a reaction medium separation unit and the reaction medium as a gas from the separation unit.
More specifically, the second polymerization reactor (R2), and any subsequent reactor, for instance 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. Preferably the gas phase reactors (GPRs) comprise a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec. Thus it is appreciated that the gas phase reactor is a fluidized bed type reactor preferably with a mechanical stirrer.
Thus in a preferred embodiment the first polymerization reactor (R1) is a slurry reactor (SR), like loop reactor (LR), whereas the second polymerization reactor (R2) and any optional subsequent reactor, like the third polymerization reactor (R3), are gas phase reactors (GPRs). Accordingly for the instant process at least two, preferably two polymerization reactors (R1) and (R2) or three polymerization reactors (R1), (R2) and (R3), namely a slurry reactor (SR), like loop reactor (LR) and a (first) gas phase reactor (GPR1) and optionally a second gas phase reactor (GPR2), connected in series are used. If needed prior to the slurry reactor (SR) a pre-polymerization reactor is placed.
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 covers also a pre-polymerization step it is preferred that all of the Ziegler-Natta catalyst (ZN-C) is fed in the pre-polymerization reactor. Subsequently the pre-polymerization product containing the Ziegler-Natta catalyst (ZN-C) is transferred into the first polymerization reactor (R1).
A preferred multistage process is a “loop-gas phase”-process, such as developed by Borealis A/S, Denmark (known as BORSTAR® technology) described e.g. in patent literature, such as in EP 0 887 379, WO 92/12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
A further suitable slurry-gas phase process is the Spheripol® process of Basell.
Especially good results are achieved in case the temperature in the reactors is carefully chosen.
Accordingly 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., still more preferably in the range of 67 to 80° C.
Alternatively or additionally 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.
Preferably the operating temperature in the second polymerization reactor (R2) is equal or higher to the operating temperature in the first polymerization reactor (R1). Accordingly it is preferred that the operating temperature
(a) 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., still more preferably in the range of 67 to 80° C., like 67 to 75° C., e.g. 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., still more preferably in the range of 78 to 88° C., with the proviso that the operating temperature in the in the second polymerization reactor (R2) is equal or higher to the operating temperature in the first polymerization reactor (R1).
Still more preferably the operating temperature of the third polymerization reactor (R3)—if present—is higher than the operating temperature in the first polymerization reactor (R1). In one specific embodiment the operating temperature of the third polymerization reactor (R3)—if present—is higher than the operating temperature in the first polymerization reactor (R1) and in the second polymerization reactor (R2). Accordingly it is preferred that the operating temperature
(a) 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., still more preferably in the range of 67 to 80° C., like 67 to 75° C., e.g. 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., still more preferably in the range of 78 to 88° C., and
(c) in the third polymerization reactor (R3)—if present—is in the range of 75 to 95° C., more preferably in the range of 78 to 92° C., still more preferably in the range of 85 to 92° C., like in the range of 87 to 92° C., with the proviso that the operating temperature in the in the second polymerization reactor (R2) is equal or higher to the operating temperature in the first polymerization reactor (R1) and with the proviso that the third polymerization reactor (R3) is higher than the operating temperature in the first polymerization reactor (R1), preferably is higher than the operating temperature in the first polymerization reactor (R1) and in the second polymerization reactor (R2).
Typically the pressure in the first polymerization reactor (R1), preferably in the loop reactor (LR), is in the range of from 20 to 80 bar, preferably 30 to 70 bar, like 35 to 65 bar, whereas the pressure in the second polymerization reactor (R2), i.e. in the (first) gas phase reactor (GPR1), and optionally in any subsequent reactor, like in the third polymerization reactor (R3), e.g. in the second gas phase reactor (GPR2), is in the range of from 5 to 50 bar, preferably 15 to 40 bar.
Preferably hydrogen is added in each polymerization reactor in order to control the molecular weight, i.e. the melt flow rate MFR2.
Preferably the average residence time is rather long in the polymerization reactors (R1) and (R2). In general, the average residence time (τ) is defined as the ratio of the reaction volume (VR) to the volumetric outflow rate from the reactor (Qo) (i.e. VR/Qo), i.e. T=VR/Qo [tau=VR/Qo]. In case of a loop reactor the reaction volume (VR) equals to the reactor volume.
Accordingly the average residence time (τ) in the first polymerization reactor (R1) is preferably at least 20 min, more preferably in the range of 20 to 80 min, still more preferably in the range of 25 to 60 min, like in the range of 28 to 50 min, and/or the average residence time (τ) in the second polymerization reactor (R2) is preferably at least 90 min, more preferably in the range of 90 to 220 min, still more preferably in the range of 100 to 210 min, yet more preferably in the range of 105 to 200 min, like in the range of 105 to 190 min. Preferably the average residence time (τ) in the third polymerization reactor (R3)—if present—is preferably at least 30 min, more preferably in the range of 30 to 120 min, still more preferably in the range of 40 to 100 min, like in the range of 50 to 90 min.
Further it is preferred that the average residence time (τ) in the total sequential polymerization system, more preferably that the average residence time (τ) in the first (R1) second polymerization reactors (R2) and optional third polymerization reactor (R3) together, is at least 140 min, more preferably at least 160 min, still more preferably in the range of 140 to 260 min, more preferably in the range of 160 to 240 min, still more preferably in the range of 160 to 220 min, yet more preferably in the range of 160 to 220 min.
As mentioned above the instant process can comprises in addition to the (main) polymerization of the propylene-ethylene copolymer in the at least two polymerization reactors (R1, R2 and optional R3) prior thereto a pre-polymerization in a pre-polymerization reactor (PR) upstream to the first polymerization reactor (R1).
In the pre-polymerization reactor (PR) a polypropylene (Pre-PP) is produced. The pre-polymerization is conducted in the presence of the Ziegler-Natta catalyst (ZN-C). According to this embodiment the Ziegler-Natta catalyst (ZN-C), the co-catalyst (Co), and the external donor (ED) are all introduced to the pre-polymerization step. However, this shall not exclude the option that at a later stage for instance further co-catalyst (Co) and/or external donor (ED) is added in the polymerization process, for instance in the first reactor (R1). In one embodiment the Ziegler-Natta catalyst (ZN-C), the co-catalyst (Co), and the external donor (ED) are only added in the pre-polymerization reactor (PR), if a pre-polymerization is applied.
The pre-polymerization reaction is typically conducted at a temperature of 0 to 60° C., preferably from 15 to 50° C., and more preferably from 20 to 45° C.
The pressure in the pre-polymerization reactor is not critical but must be sufficiently high to maintain the reaction mixture in liquid phase. Thus, the pressure may be from 20 to 100 bar, for example 30 to 70 bar.
In a preferred embodiment, the pre-polymerization is conducted as bulk slurry polymerization in liquid propylene, i.e. the liquid phase mainly comprises propylene, with optionally inert components dissolved therein. Furthermore, according to the present invention, an ethylene feed is employed during pre-polymerization as mentioned above.
It is possible to add other components also to the pre-polymerization stage. Thus, hydrogen may be added into the pre-polymerization stage to control the molecular weight of the polypropylene (Pre-PP) as is known in the art. Further, antistatic additive may be used to prevent the particles from adhering to each other or to the walls of the reactor.
The precise control of the pre-polymerization conditions and reaction parameters is within the skill of the art.
Due to the above defined process conditions 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 catalyst (ZN-C) is (finely) dispersed in the polypropylene (Pre-PP). In other words, the Ziegler-Natta catalyst (ZN-C) particles introduced in the pre-polymerization reactor (PR) split into smaller fragments which are evenly distributed within the growing polypropylene (Pre-PP). The sizes of the introduced Ziegler-Natta catalyst (ZN-C) particles as well as of the obtained fragments are not of essential relevance for the instant invention and within the skilled knowledge.
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-polymerization reactor (PR) is transferred to the first reactor (R1). Typically the total amount of the polypropylene (Pre-PP) in the final propylene copolymer (R-PP) is rather low and typically not more than 5.0 wt %, more preferably not more than 4.0 wt %, still more preferably in the range of 0.5 to 4.0 wt %, like in the range 1.0 of to 3.0 wt %.
In case that pre-polymerization is not used propylene and the other ingredients such as the Ziegler-Natta catalyst (ZN-C) are directly introduced into the first polymerization reactor (R1).
Accordingly the process according the instant invention comprises the following steps under the conditions set out above
(a) in the first polymerization reactor (R1), i.e. in a loop reactor (LR), propylene and a ethylene are polymerized obtaining a first propylene copolymer fraction (PP-COPO-1) of the propylene-ethylene copolymer,
(b) transferring said first propylene copolymer fraction (PP-COPO-1) to a second polymerization reactor (R2),
(c) in the second polymerization reactor (R2) propylene and ethylene are polymerized in the presence of the first propylene copolymer fraction (PP-COPO-1) obtaining a second propylene copolymer fraction (PP-COPO-2) of the propylene-ethylene copolymer, said first propylene copolymer fraction (PP-COPO-1) and said second propylene copolymer fraction (PP-COPO-2) form the propylene-ethylene copolymer.
A pre-polymerization as described above can be accomplished prior to step (a).
As pointed out above in the specific process for the preparation of the propylene-ethylene copolymer as defined above a Ziegler-Natta catalyst (ZN-C) is preferably used. Accordingly the Ziegler-Natta catalyst (ZN-C) will be now described in more detail.
The catalyst used in the present invention is a solid Ziegler-Natta catalyst, which comprises compounds of a transition metal of Group 4 to 6 of IUPAC, like titanium, a Group 2 metal compound, like magnesium, and an internal donor being preferably a non-phthalic compound, more preferably a non-phthalic acid ester, still more preferably being a diester of non-phthalic dicarboxylic acids as described in more detail below. Thus, the catalyst is fully free of undesired phthalic compounds.
Further, the solid catalyst is free of any external support material, like silica or MgCl2, but the catalyst is self-supported.
The Ziegler-Natta catalyst (ZN-C) can be further defined by the way as obtained.
Accordingly, the Ziegler-Natta catalyst (ZN-C) is preferably obtained by a process comprising the steps of
a)
a1) providing a solution of at least a Group 2 metal alkoxy compound (Ax) being the reaction product of a Group 2 metal compound and a monohydric alcohol (A) comprising in addition to the hydroxyl moiety at least one ether moiety 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 and an alcohol mixture of the monohydric alcohol (A) and a monohydric alcohol (B) of formula ROH, optionally in an organic liquid reaction medium; or
a3) providing a solution of a mixture of the Group 2 alkoxy compound (Ax) and a Group 2 metal alkoxy compound (Bx) being the reaction product of a Group 2 metal compound and the monohydric alcohol (B), optionally in an organic liquid reaction medium; or
a4) providing a solution of Group 2 alkoxide of formula M(OR1)n(OR2)mX2-n-m or mixture of Group 2 alkoxides M(OR1)n′X2-n′ and M(OR2)m′X2-m′, where M is Group 2 metal, X is halogen, R1 and R2 are different alkyl groups of C2 to C16 carbon atoms, and 0<n<2, 0<m<2 and n+m+(2-n-m)=2, provided that both n and m≠0, 0<n′<2 and 0<m′<2; and
b) adding said solution from step a) to at least one compound of a transition metal of Group 4 to 6 and
c) obtaining the solid catalyst component particles,
and adding an internal electron donor, preferably a non-phthalic internal donor, at any step prior to step c).
The internal donor or precursor thereof is added preferably to the solution of step a).
Detailed description as to how such a Ziegler-Natta catalyst (ZN-C) can be obtained is disclosed in WO 2012/007430.
According to the procedure above the Ziegler-Natta catalyst can be obtained via precipitation method or via emulsion (liquid/liquid two-phase system)—solidification method depending on the physical conditions, especially temperature used in steps b) and c).
In both methods (precipitation or emulsion-solidification) the catalyst chemistry is the same.
In precipitation method combination of the solution of step a) with at least one transition metal compound in step b) is carried out and the whole reaction mixture is kept at least at 50° C., more preferably in the temperature range of 55° C. to 110° C., more preferably in the range of 70° C. to 100° C., to secure full precipitation of the catalyst component in form of a solid particles (step c).
In emulsion-solidification method in step b) the solution of step a) is typically added to the at least one transition metal compound at a lower temperature, such as from −10 to below 50° C., preferably from −5 to 30° C. During agitation of the emulsion the temperature is typically kept at −10 to below 40° C., preferably from −5 to 30° C. Droplets of the dispersed phase of the emulsion form the active catalyst composition. Solidification (step c) of the droplets is suitably carried out by heating the emulsion to a temperature of 70 to 150° C., preferably to 80 to 110° C.
The catalyst prepared by emulsion-solidification method is preferably used in the present invention.
In a preferred embodiment in step a) the solution of a2) or a3) are used, i.e. a solution of (Ax′) or a solution of a mixture of (Ax) and (Bx).
Preferably the Group 2 metal is magnesium.
The 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, or said magnesium alkoxy compounds can be separately prepared magnesium alkoxy compounds or they can be even commercially available as ready magnesium alkoxy compounds and used as such in the catalyst preparation process of the invention.
Illustrative examples of alcohols (A) are monoethers of dihydric alcohols (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-glycolmonobutyl ether, 3-butoxy-2-propanol, with 2-(2-ethylhexyloxy)ethanol and 1,3-propyleneglycol-monobutyl ether, 3-butoxy-2-propanol being particularly preferred.
Illustrative monohydric alcohols (B) are of formula ROH, with R being straight-chain or branched C6-C10 alkyl residue. The most preferred monohydric alcohol is 2-ethyl-1-hexanol or octanol.
Preferably a mixture of Mg alkoxy compounds (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.
Magnesium alkoxy compound may be a reaction product of alcohol(s), as defined above, and a magnesium compound selected from dialkyl magnesiums, alkyl magnesium alkoxides, magnesium dialkoxides, alkoxy magnesium halides and alkyl magnesium halides. Alkyl groups can be a similar or different C1-C20 alkyl, preferably C2-C10 alkyl. Typical alkyl-alkoxy magnesium compounds, when used, are ethyl magnesium butoxide, butyl magnesium pentoxide, octyl magnesium butoxide and octyl magnesium octoxide. Preferably the dialkyl magnesiums are used. Most preferred dialkyl magnesiums are butyl octyl magnesium or butyl ethyl magnesium.
It is also possible that magnesium compound can react in addition to the alcohol (A) and alcohol (B) also with a polyhydric alcohol (C) of formula R″(OH)m to obtain said magnesium alkoxide compounds. Preferred polyhydric alcohols, if used, are alcohols, wherein R″ is a straight-chain, cyclic or branched C2 to C10 hydrocarbon residue, and m is an integer of 2 to 6.
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, aryl magnesium alkoxides and alkyl magnesium aryloxides. In addition a mixture of magnesium dihalide and a magnesium dialkoxide can be used.
The solvents to be employed for the preparation of the present catalyst may be selected among aromatic and aliphatic straight chain, branched and cyclic hydrocarbons with 5 to 20 carbon atoms, more preferably 5 to 12 carbon atoms, or mixtures thereof. Suitable solvents include benzene, toluene, cumene, xylol, pentane, hexane, heptane, octane and nonane. Hexanes and pentanes are particular preferred.
Mg compound is typically provided as a 10 to 50 wt % solution in a solvent as indicated above. Typical commercially available Mg compound, especially dialkyl magnesium solutions are 20-40 wt % solutions in toluene or heptanes.
The reaction for the preparation of the magnesium alkoxy compound may be carried out at a temperature of 40° to 70° C. Most suitable temperature is selected depending on the Mg compound and alcohol(s) used.
The transition metal compound of Group 4 to 6 is preferably a titanium compound, most preferably a titanium halide, like TiCl4.
The non-phthalic internal donor used in the preparation of the catalyst used in the present invention is preferably selected from (di)esters of non-phthalic carboxylic (di)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-dicarboxylates and benzoates, and any derivatives and/or mixtures thereof. Preferred examples are e.g. substituted maleates and citraconates, most preferably citraconates.
In emulsion method, the two phase liquid-liquid system may be formed by simple stirring and optionally adding (further) solvent(s) and additives, such as the turbulence minimizing agent (TMA) and/or the emulsifying agents and/or emulsion stabilizers, like surfactants, which are used in a manner known in the art for facilitating the formation of and/or stabilize the emulsion. Preferably, surfactants are acrylic or methacrylic polymers. Particular 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 α-olefin polymers of α-olefin monomers with 6 to 20 carbon 20 atoms, like polyoctene, polynonene, polydecene, polyundecene or polydodecene or mixtures thereof. Most preferable it is polydecene.
Solidification of the dispersed phase droplets by heating is suitably carried out at a temperature of 70 to 150° C., usually at 80 to 110° C., preferably at 90 to 110° C. The heating may be done faster or slower. As especial slow heating is understood here heating with a heating rate of about 5° C./min or less, and especial fast heating e.g. 10° C./min or more. Often slower heating rates are preferable for obtaining good morphology of the catalyst component.
The solid particulate product obtained by precipitation or emulsion-solidification method may be washed at least once, preferably at least twice, most preferably at least three times with an aromatic and/or aliphatic hydrocarbons, preferably with toluene, heptane or pentane. The catalyst can further be dried, as by evaporation or flushing with nitrogen, or it can be slurried to an oily liquid without any drying step.
The finally obtained Ziegler-Natta catalyst is desirably in the form of particles having generally an average particle size range of 5 to 200 μm, preferably 10 to 100. Particles are compact with low porosity and have surface area below 20 g/m2, more preferably below 10 g/m2.
Typically the amount of Ti is 1 to 6 wt %, Mg 10 to 20 wt % and donor 10 to 40 wt % of the catalyst composition.
Detailed description of preparation of catalysts is disclosed in WO 2012/007430, EP 2610271, EP 261027 and EP2610272 which are incorporated here by reference.
The Ziegler-Natta catalyst is preferably used in association with an alkyl aluminum cocatalyst and optionally external donors.
As further component in the instant polymerization process an external donor is preferably present. Suitable external donors include certain silanes, ethers, esters, amines, ketones, heterocyclic compounds and blends of these. It is especially preferred to use a silane. It is most preferred to use silanes of the general formula
RapRbqSi(ORc)(4-p-q)
wherein Ra, Rb and Rc denote a hydrocarbon radical, in particular an alkyl or cycloalkyl group, and wherein 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 from one another 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 general formula
Si(OCH2CH3)3(NR3R4)
wherein R3 and R4 can be the same or different a represent a hydrocarbon group having 1 to 12 carbon atoms.
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 in particular 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.
More preferably both R3 and R4 are the same, yet more preferably both R3 and R4 are an ethyl group.
Especially preferred external donors are the dicyclopentyl dimethoxy silane donor (D-donor) or the cyclohexylmethyl dimethoxy silane donor (C-Donor).
In addition to the Ziegler-Natta catalyst and the optional external donor a co-catalyst can be used. The co-catalyst is preferably a compound of group 13 of the periodic table (IUPAC), e.g. organo aluminum, such as an aluminum compound, like aluminum alkyl, aluminium halide or aluminum alkyl halide compound. Accordingly, in one specific embodiment the cocatalyst is a trialkylaluminium, like triethylaluminium (TEAL), dialkyl aluminium chloride or alkyl aluminium dichloride or mixtures thereof. In one specific embodiment the co-catalyst is triethylaluminium (TEAL).
Preferably the ratio between the co-catalyst (Co) and the external donor (ED) [Co/ED] and/or the ratio between the co-catalyst (Co) and the transition metal (TM) [Co/TM] should be carefully chosen.
Accordingly,
(a) the mol-ratio of co-catalyst (Co) to external donor (ED) [Co/ED] must 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] must be in the range of above 80 to 500, preferably is in the range of 100 to 350, still more preferably is in the range of 120 to 300.
The propylene-ethylene copolymers obtained by the above described process using the above described catalyst system are subsequently alpha nucleated with the blend of the two alpha nucleating agents as described above.
The α-nucleating agents and optionally further additives are added to the propylene-ethylene copolymers, which are collected from the final reactor of the series of reactors.
Preferably, these additives are mixed into the copolymers prior to or during the extrusion process in a one-step compounding process.
For mixing, a conventional compounding or blending apparatus, e.g. a Banbury mixer, a 2-roll rubber mill, Buss-co-kneader or a twin screw extruder may be used. The twin screw extruder may be co-rotating or counter-rotating, preferably co-rotating. Preferably, the final polymer (i.e. propylene-ethylene copolymer and additives including the two alpha nucleating agents) will be prepared by blending the additives together with the propylene-ethylene copolymer derived from the final reactor at a temperature, which is sufficiently high to soften and plasticize the polymer. The temperatures and pressures used in the operation of the extruder are known in the art.
Typically the temperature may be selected from the range of 150 to 350° C. The pressure used for extrusion preferably is 50 to 500 bar. The polymer materials recovered from the extruder are usually in the form of pellets. These pellets are then preferably further processed, e.g. by injection moulding to generate articles and products of the inventive compositions.
The present invention is also directed to injection moulded articles comprising at least 70 wt %, more preferably at least 90 wt %, yet more preferably at least 95 wt %, still more preferably consisting of, a propylene-ethylene copolymer as defined above.
Further present invention is also directed to the use of the propylene-ethylene copolymers according to the present invention in the production of moulded articles, particularly injection moulded articles, such as thin-walled plastic containers for packaging.
Thin-walled plastic containers for packaging produced by injection moulding, comprising at least 70 wt %, more preferably at least 90 wt %, yet more preferably at least 95 wt %, still more preferably consisting of, a propylene-ethylene copolymer as defined above.
The thin-walled plastic containers for packaging preferably have a thickness of equal or below 2 mm, preferably in the range of 0.2 to 2.0 mm. Said thin-walled plastic containers for packaging are preferably produced by injection moulding.
Further the thin-walled plastic containers for packaging are preferably selected from the group consisting of cups, boxes, trays, pails, buckets, bowls, lids, flaps, caps, CD covers, DVD covers and the like.
Moulded articles, especially injection moulded articles prepared form the propylene-ethylene random copolymers of the present invention are characterized by a high tensile modulus (measured according to ISO 527) measured after 96 hours of storage at +23±1° C. and 50% relative humidity (standard conditions) and even higher high tensile modulus (measured according to ISO 527) measured after 1344 hours of storage at +23±1° C. and 50% relative humidity (standard conditions).
Thus the articles have a tensile modulus (measured according to ISO 527) measured after 96 hours of storage of at least 1000 MPa, preferably of at least 1050 MPa; and measured after 1344 hours of storage of at least 1100 MPa, preferably of at least 1150 MPa.
Simultaneously the puncture energy (measured according to ISO 6603-2; 60×60×2 mm3 specimens) is at a high level measured after 96 hours of storage at +23±1° C. and 50% relative humidity (standard conditions) and stays approximately on that level when measured after 1344 hours of storage at +23±1° C. and 50% relative humidity (standard conditions). Thus the articles have a puncture energy (measured according to ISO 6603-2; 60×60×2 mm3 specimens) measured after 96 hours of storage of at least 19 J, preferably at least 21 J and measured after 1344 hours of storage again of at least 19 J, preferably at least 21 J.
The following definitions of terms and determination methods apply for the above general description of the invention as well as to the below examples unless otherwise defined.
Calculation of comonomer content of the second propylene copolymer fraction (PP-COPO-2):
wherein
Calculation of melt flow rate MFR2 (230° C.) of the second propylene copolymer fraction (PP-COPO-2):
wherein
MFR2 (230° C.) is measured according to ISO 1133 (230° C., 2.16 kg load).
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 13C optimised 10 mm extended temperature probehead at 125° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d2) along with chromium-(III)-acetylacetonate (Cr(acac)3) resulting in a 65 mM solution of relaxation agent in solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatary oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling 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, 1128). A total of 6144 (6 k) transients were acquired per spectra.
Quantitative 13C{1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present. Characteristic signals corresponding to the incorporation of ethylene were observed Cheng, H. N., Macromolecules 17 (1984), 1950).
With characteristic signals corresponding to 2,1 erythro regio defects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, H. N., Macromolecules 1984, 17, 1950, and in W-J. Wang and S. Zhu, Macromolecules 2000, 33 1157) the correction for the influence of the regio defects on determined properties was required. Characteristic signals corresponding to other types of regio defects were not observed.
The comonomer fraction was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) through integration of multiple signals across the whole spectral region in the 13C{1H} spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.
For systems where only isolated ethylene in PPEPP sequences was observed the method of Wang et. al. was modified to reduce the influence of non-zero integrals of sites that are known to not be present. This approach reduced the overestimation of ethylene content for such systems and was achieved by reduction of the number of sites used to determine the absolute ethylene content to:
E=0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ))
Through the use of this set of sites the corresponding integral equation becomes:
E=0.5(IH+IG+0.5(IC+ID))
using the same notation used in the article of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157). Equations used for absolute propylene content were not modified.
The mole percent comonomer incorporation was calculated from the mole fraction:
E [mol %]=100*fE
The weight percent comonomer incorporation was calculated from the mole fraction:
E [wt %]=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, Y., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150). This method was chosen for its robust nature and integration regions slightly adjusted to increase applicability to a wider range of comonomer contents. The relative content of isolated to block ethylene incorporation was calculated from the triad sequence distribution using the following relationship (equation (I)):
wherein
I(E) is the relative content of isolated to block ethylene sequences [in %];
fPEP is the mol fraction of propylene/ethylene/propylene sequences (PEP) in the sample;
fPEE is the mol fraction of propylene/ethylene/ethylene sequences (PEE) and of ethylene/ethylene/propylene sequences (EEP) in the sample;
fEEE is the mol fraction of ethylene/ethylene/ethylene sequences (EEE) in the sample
Content of xylene cold solubles (XCS) is determined at 25° C. according ISO 16152; first edition; 2005-07-01
The tensile modulus was measured at 23° C. according to ISO 527-1 (cross head speed 1 mm/min) using injection moulded specimens moulded at 180° C. or 200° C. according to ISO 527-2(1B), produced according to EN ISO 1873-2 (dog 10 bone shape, 4 mm thickness).
The tensile modulus for the examples was measured after 96 h and 1344 hours of storage.
Puncture energy was determined in the instrumental falling weight (IFW) test according to ISO 6603-2 using injection moulded plaques of 60×60×2 mm3 and a test speed of 2.2 m/s. Puncture energy reported results from an integral of the failure energy curve measured at +23° C.
The puncture energy for the examples was measured after 96 h and 1344 hours of storage
Samples prepared for WAXS were prepared in the same way as for the puncture energy measurement.
The determination of crystallinity and of polymorphic composition was performed in reflection geometry using a Bruker D8 Discover with GADDS x-ray diffractometer operating with the following settings: x-ray generator: 30 kV and 20 mA; θ1=6° & θ2=13°; sample-detector distance: 20 cm; beam size (collimator): 500 μm; and duration/scan: 300 seconds. 3 measurements have been performed on each sample. Intensity vs. 2θ curves between 2θ=10° and 2θ=32.5° were obtained by integrating the 2-dimensional spectra. The quantification of intensity vs. 2θ curves were then performed as follows:
Intensity vs. 2θ curve was acquired with the same measurement settings on an amorphous iPP sample, which was prepared by solvent extraction. An amorphous halo was obtained by smoothing the intensity vs. 2θ curve. The amorphous halo has been subtracted from each intensity vs. 2θ curve obtained on actual samples and this results in the crystalline curve.
The crystallinity index Xc is defined with the area under the crystalline curve and the original curve using the method proposed by Challa et al. (Makromol. Chem. vol. 56 (1962), pages 169-178) as:
In a two-phase crystalline system (containing α- and β-modifications), the amount of β-modification within the crystalline phase B was calculated using the method proposed by Turner-Jones et al. (Makromol. Chem. Vol. 75 (1964), pages 134-158) as:
where, Iβ(300) is the intensity of β(300) peak, Iα (110) is the intensity of α(110) peak, Iα(040) is the intensity of α(040) peak and Iα(130) is the intensity of α(130) peak obtained after subtracting the amorphous halo.
In a two-phase crystalline system (containing α- and γ-modifications), the amount of γ-modification within the crystalline phase G (=Kγ) was calculated using the method developed by Pae (J. Polym. Sci., Part A2, vol. 6 (1968), pages 657-663) as:
where, Iα(130) is the intensity of α(130) peak and Iγ(117) is the intensity of γ(117) peak obtained after subtracting a base line joining the base of these peaks.
20% solution in toluene of butyl ethyl magnesium (Mg(Bu)(Et), BEM), provided by Chemtura 2-ethylhexanol, provided by Amphochem
3-Butoxy-2-propanol—(DOWANGL™ PnB), provided by Dow
bis(2-ethylhexyl)citraconate, provided by SynphaBase
TiCl4, provided by Millenium Chemicals
Toluene, provided by Aspokem
Viscoplex® 1-254, provided by Evonik
Heptane, provided by Chevron
First a magnesium alkoxide solution was prepared by adding, with stirring (70 rpm), into 1 1 kg of a 20 wt-% solution in toluene of butyl ethyl magnesium (Mg(Bu)(Et), BEM), 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 maintained below 45° C. After addition was completed, 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 the donor bis(2-ethylhexyl)citraconate was added to the Mg-alkoxide solution keeping temperature below 25° C. Mixing was continued for 15 minutes under stirring (70 rpm)
20.3 kg of TiCl4 and 1.1 kg of toluene were added into a 20 l stainless steel reactor. Under 350 rpm mixing and keeping the temperature at 0° C., 14.5 kg of the Mg complex prepared in example 1 was added during 1.5 hours. 1.7 l of Viscoplex® 1-254 and 7.5 kg of heptane were added and after 1 hour mixing at 0° C. the temperature of the formed emulsion was raised to 90° C. within 1 hour. After 30 minutes mixing was stopped catalyst droplets were solidified and the formed catalyst particles were allowed to settle. After settling (1 hour), the supernatant liquid was siphoned away.
Then the catalyst particles were washed with 45 kg of toluene at 90° C. for 20 minutes followed by two heptane washes (30 kg, 15 min). During the first heptane wash the temperature was decreased to 50° C. and during the second wash to room temperature.
The solid catalyst component was used along with triethyl-aluminium (TEAL) as co-catalyst and dicyclo pentyl dimethoxy silane (D-donor) as donor.
The catalyst used in the polymerization processes of the comparative example (CE1) was the catalyst of the example section of WO 2010009827 A1 (see pages 30 and 31) along with triethyl-aluminium (TEAL) as co-catalyst and dicyclo pentyl dimethoxy silane (D-donor) as donor.
The catalyst used in the polymerization processes of the comparative example (CE2) was prepared as described now:
First, 0.1 mol of MgCl2×3 EtOH was suspended under inert conditions in 250 ml of decane in a reactor at atmospheric pressure. The solution was cooled to the temperature of −15° C. and 300 ml of cold TiCl4 was added while maintaining the temperature at said level. Then, the temperature of the slurry was increased slowly to 20° C. At this temperature, 0.02 mol of dioctylphthalate (DOP) was added to the slurry. After the addition of the phthalate, the temperature was raised to 135° C. during 90 minutes and the slurry was allowed to stand for 60 minutes. Then, another 300 ml of TiCl4 was added and the temperature was kept at 135° C. for 120 minutes. After this, the catalyst was filtered from the liquid and washed six times with 300 ml heptane at 80° C. Then, the solid catalyst component was filtered and dried. Catalyst and its preparation concept is described in general e.g. in patent publications EP491566, EP591224 and EP586390.
The catalyst was used along with triethyl-aluminium (TEAL) as co-catalyst and cyclohexylmethyl dimethoxy silane (C-donor) as donor.
The polymerization was done in a Borstar pilot plant with a prepolymerization reactor, a loop reactor and a gas phase reactor (1st GPR) for IE1 and CE1 and for CE2 a Spheripol pilot plant with a prepolymerization reactor and two loop reactors were used.
The polymerization conditions are indicated in table 1.
All polymer powders were compounded in a co-rotating twin-screw extruder Coperion ZSK 57 at 220° C. with 0.2 wt.-% of Irganox B225 (1:1-blend of Irganox 1010 (Pentaerythrityl-tetrakis(3-(3′,5′-di-tert.butyl-4-hydroxytoluyl)-propionate and tris (2,4-di-t-butylphenyl) phosphate) phosphite) of BASF AG, Germany) and 0.05 wt.-% calcium stearate and the below described nucleating agents.
The material of the inventive example IE1 as well as the materials of comparative examples CE1 and CE2 were nucleated with a) 2 wt % of a masterbatch of a propylene homopolymer having an MFR2 of 20 g/10 min and 200 ppm of vinylcycloalkane polymer (pVCH), based on the total weight of the propylene-ethylene copolymers and
b) 0.2 wt % of the sorbitol M3988, commercially available from Milled, based on the total weight of the propylene-ethylene copolymers.
A catalyst prepared as described above for the Inventive Examples was modified with vinylcyclohexane (VCH).
41 liters of mineral oil (Paraffinum Liquidum PL68) were added to the prepolymerization reactor of a Borstar pilot plant followed by 1.79 kg of triethyl aluminium (TEAL) and 0.79 kg of dicyclopentyl dimethoxy silane (donor D) under inert conditions at room temperature. Afterwards 5.5 kg of the catalyst prepared as described above for the inventive Examples was added, followed by 5.55 kg of vinylcyclohexane (VCH).
Propylene homopolymer was prepared in the Borstar pilot plant comprising the Prepolymerization reactor (CSTR), one loop reactor and one gas phase reactor.
The polymer was stabilized by melt mixing a co-rotating twin-screw extruder at 200-230° C. with 0.2 wt.-% of Irganox B225 (1:1-blend of Irganox 1010 (Pentaerythrityl-tetrakis(3-(3′,5′-di-tert.butyl-4-hydroxytoluyl)-propionate and tris (2,4-di-t-butylphenyl) phosphate) phosphite) of BASF AG, Germany) and 0.1 wt.-% calcium stearate.
As Comparative Example 3 (CE3), Inventive Example 4 (IE4) of WO 2014187687 was added.
The polymers according to this patent application were produced with the same catalyst and the same process as IE1 of the instant invention.
The polymers differ in the C2 total amount and in the C2 amount of the second propylene fraction (PP-COPO-2).
The polymers of WO 2014187687 were nucleated only with 2 wt % of a masterbatch of a propylene homopolymer having an MFR2 of 20 g/10 min and 200 ppm of vinylcycloalkane polymer (pVCH) (prepared as described above), based on the total weight of the propylene-ethylene copolymers. No soluble alpha nucleating agent was added.
The properties of the nucleated copolymers are shown in Table 2:
From Table 1 it can be seen that the inventive propylene-ethylene copolymer has clearly higher puncture energy after 96 h than the polymer of CE4.
From
From
| Number | Date | Country | Kind |
|---|---|---|---|
| 15156438.2 | Feb 2015 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2016/053697 | 2/23/2016 | WO | 00 |
