Patent Application
20250197619
The present invention relates to a polypropylene composition derived from single site catalysts.
Packaging films based on polyolefins are well known in the literature. Food packaging in particular places several high demands on the material used. First, the packaging must be sufficiently tight in order to sufficiently protect the packaged or sealed-material, and to make the handling of the sealed products, in particular during transport, sufficiently safe. Thus, good sealing behaviour is desired. Ideally, the films are heat-sealable at as a low temperature as possible to minimise energy input during the sealing process. Another important consideration is mechanical properties. Polymers with higher stiffness may allow for the use of lower film thicknesses, leading to both material and energy savings. Good impact behaviour is also essential so the contents of the packaging remain safely contained, even if dropped. Sterilisation behaviour must also be considered since materials used in food packaging application are now typically subjected to sterilisation before use. The most common sterilisation procedures are the use of heat (steam), radiation (beta radiation, electrons, or gamma radiation) or chemicals (usually ethylene oxide). Steam sterilisation is usually carried out in a temperature range of about 120 to 130° C. Thus, the material should have a sufficient thermal stability. In addition to that, haze, particularly haze when made into a film should be as low as possible since this yields better acceptance by the consumers.
Single site derived propylene butene copolymers and film made therefrom are generally known from Macromolecules 2020, 53, 11, 4407-4421.
WO2020099563A1 concerns a multimodal propylene butene random copolymer having a melt flow rate (MFR2) of 1.0 to 20.0 g/10 min and a butene content of 5.0 to 20.0 wt.-%, wherein said copolymer is prepared using a single site catalyst as well as films made therefrom. Film haze values as low as 0.34% have been reported when having a total 1-butene content of 6.6 wt.-% and a xylene soluble fraction of 0.86 wt.-% at a moderately high melting temperature of 138° C. and low stiffness of 1015 MPa. Thus, there remains the need for a propylene copolymer having even better balance of properties, particularly good haze properties, even better temperature resistance as well as good seal strength as well as film stiffness.
The present invention insofar provides a polypropylene composition having
It is especially preferred that said one melting temperature Tm measured by differential scanning calorimetry (DSC) according to ISO 11357-3 is ranging between 150 to 160° C. It is more preferred that the melting temperature Tm measured by differential scanning calorimetry (DSC) according to ISO 11357-3 is ranging between 152 to 156° C.
The amount of 2.1 erythro regio-defects specifies the microstructure of the polypropylene composition. It is well known in the art that Ziegler Natta catalyst derived polypropylene copolymers do not have such microstructure, i.e. the 2.1 erythro regio-defects are essentially zero for Ziegler Natta catalyst derived polypropylene copolymers.
The polypropylene composition according to the present invention is further characterized by an exceptionally high melting temperature for a given 1-butene content. This exceptionally high melting temperature exists for unnucleated and nucleated compositions. Since the nucleating agent and its amount also play a minor role, two different equations apply. The exceptionally high melting temperature indicates high crystallinity. It goes without saying, when the polypropylene composition is composed of two polymers, a propylene homopolymer and a propylene 1-butene copolymer, the melting temperature may be further improved. However, it should be understood that a high melting temperature cannot be achieved by extremes, i.e. using a propylene homopolymer and simultaneously a very high 1-butene copolymer, such as more than 15.0 wt.-% 1-butene, because the 1-butene copolymer containing high amounts of 1-butene would result in a high amount of xylene soluble fraction which is excluded for the present invention.
In a preferred aspect, the polypropylene composition according to the present invention preferably has a haze (measured according to ASTM D1003-00 on a test specimen of 1 mm thickness which is prepared in accordance with ISO 294-1:2017) of below 35%, more preferably below 25% and most preferably below 20%.
It is likewise preferred that polypropylene composition according to the present invention has a film haze (measured on a 50 μm cast film, according to ASTM D1003-00) of below 2.0%, more preferably of below 1.0%.
A higher content of 1-butene supports lower haze but simultaneously deteriorates melting point.
It is preferred that the polypropylene composition according to the present invention has a content of units derived from 1-butene of 1.5 to 4.0 wt.-% as determined by FT-IR spectroscopy calibrated by quantitative 13C-NMR spectroscopy.
In yet a further preferred aspect, the polypropylene composition as described herein has a flexural modulus determined in 3-point-bending according to ISO 178 on injection molded specimens of 80×10×4 mm3 prepared in accordance with ISO 294-1:2017 of 1100 to 1600 MPa, and particularly from 1250 to 1550 MPa.
Independently therefrom the polypropylene composition is preferably characterized by a sealing initiation temperature (SIT) (as determined by a method described in the experimental part on a 50 μm cast film) of below 127° C. Said sealing initiation temperature (SIT) will normally be higher than 90° C.
In yet a further preferred aspect, the polypropylene composition includes
The polypropylene composition according to present invention further preferably has a melt flow rate (ISO1133, 230° C., 2.16 kg) of 2.0 to 7.0 g/10 min.
In another preferred aspect, the polypropylene composition according to the present invention has a tensile modulus in machine direction (TM-MD) measured according to ISO 527 ranging between 670 to 790 MPa, more preferably between 700 to 770 MPa.
In another preferred aspect, the polypropylene composition according to the present invention has a tensile modulus in transverse direction (TM-TD) measured according to ISO 527 ranging between 650 to 780 MPa, more preferably between 700 to 760 MPa.
In another preferred aspect, the polypropylene composition according to the present invention has seal strength at 135° C. measured according to the method described in description ranging between 9.5 to 16 N, more preferably between 13 to 15 N.
The present invention further concerns a film made from the polypropylene composition as described herein. All aspects as disclosed for the polypropylene composition shall also hold for the film. The film according to the present invention is preferably a cast film.
The polypropylene composition according to the present invention is made by a multistage process.
For the preparation of the polypropylene composition according to the present invention specific catalyst systems should be used. Such catalyst systems are obtainable by a metallocene catalyst complex and a cocatalyst as described in the following.
Preferred complexes of the metallocene catalyst include: rac-dimethylsilanediylbis[2-methyl-4-(3′,5′-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(4′-tert-butylphenyl)-inden-1-yl][2-methyl-4-(4′-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(4′-tert-butylphenyl)-inden-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(3′,5′-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4′-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s indacen-1-yl][2-methyl-4-(3′,5′-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-ditert-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride.
Especially preferred is rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s indacen-1-yl][2-methyl-4-(3′,5′-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride.
To form an active catalytic species it is necessary to employ a cocatalyst as is well known in the art. According to the present invention a cocatalyst system comprising a boron containing cocatalyst and an aluminoxane cocatalyst is used in combination with the above defined metallocene catalyst complex.
The aluminoxane cocatalyst can be one of formula (I):
Aluminoxanes are formed on partial hydrolysis of organoaluminum compounds, for example those of the formula AIR3, AIR2Y and AI2R3Y3 where R can be, for example, C1-C10-alkyl, preferably C1-C5-alkyl, or C3-C10-cycloalkyl, C7-C12-arylalkyl or -alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C10-alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (I).
The preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used according to the invention as cocatalysts are not, owing to their mode of preparation, pure compounds, the molarity of aluminoxane solutions hereinafter is based on their aluminium content. Also a boron containing cocatalyst is used in combination with the aluminoxane cocatalyst.
The catalyst complex ideally comprises a co-catalyst, certain boron containing cocatalysts are preferred. Especially preferred borates of use in the invention therefore comprise the trityl, i.e. triphenylcarbenium, ion. Thus the use of Ph3CB(PhF5)4 and analogues therefore are especially favoured.
The catalyst system of the invention is used in supported form. The particulate support material used is silica or a mixed oxide such as silica-alumina, in particular silica. The use of a silica support is preferred. The skilled man is aware of the procedures required to support a metallocene catalyst. In a preferred embodiment, the catalyst system corresponds to the ICS3 of WO 2020/239602 A1.
The polypropylene composition according to the present invention is made by a multistage process. It is highly recommendable to use a combination of loop reactor(s) and gas phase reactor(s). Usually the first reactor will be a loop reactor. It is preferred to use a loop-gas phase reactor 1-gas phase reactor 2 combination. In a preferred embodiment a polypropylene homopolymer is produced in a first loop and a first gas phase reactor. The homopolymer obtained is then transferred from gas phase reactor 1 to the gas phase reactor 2 and further polymerized in the presence of 1-butene. It is particularly preferential to use a C4/C3 ratio of 150 mol/kmol in said gas phase reactor 2.
Generally, the quantity of catalyst used will depend upon the nature of the catalyst, the reactor types and conditions and the properties desired for the polymer product. As is well known in the art hydrogen can be used for controlling the molecular weight of the polymer.
The composition according to the present invention preferably includes at least one nucleating agent, more preferably an α-nucleating agent. Even more preferred the polypropylene composition according to the present invention is free of β-nucleating agents. Accordingly, the nucleating agent is preferably selected from the group consisting of
Preferably, the α-nucleating agent is a nucleating agent selected from 1,2-cyclohexane dicarboxylic acid, hydroxybis(2,4,8,10-tetra-tert.butyl-6-hydroxy-12H-dibenzo(d,g)(1,3,2)dioxaphosphocin 6-oxidato)aluminium and mixtures thereof. For example, commercially available α-nucleating agents, which can be used for the composition of the invention are, for example, Irgaclear XT 386 from Ciba Specialty Chemicals, Hyperform HPN-68L and Hyperform HPN-20E from Milliken & Company and/or ADK STAB NA-21 nucleating agent.
Hyperform HPN-20E from Milliken & Company has the highest overall preference.
In the following specifically preferred embodiments shall be described.
A first particularly preferred embodiment is a
All preferred ranges as given above also hold for this embodiment as far as appropriate. This holds particularly for haze, SIT, melting temperature and melt flow rate.
A second particularly preferred embodiment is a film, preferably a cast film, made from a
This film is further characterized by the fact that the composition has a haze measured according to ASTM D1003-00 on a test specimen of 1 mm thickness which is prepared in accordance with ISO 294-1:2017 as below 35%, more preferably below 25% and most preferably below 20%, and that the film has a haze of below 2.0%, more preferably of below 1.0% measured on a thickness of 50 μm, according to ASTM D1003-00.
The melt flow rate (MFR2) was determined according to ISO 1133 and is indicated in g/10 min. The MFR2 of heterophasic propylene copolymer is determined at a temperature of 230° C. and under a load of 2.16 kg.
Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the polypropylene copolymer.
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 1,2-tetrachloroethane-d2 (TCE-d2). To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatory 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 needed for tacticity distribution quantification (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251). Standard single-pulse excitation was employed utilising the NOE and 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, 11289). A total of 8192 (8k) transients were acquired per spectrum.
Quantitative 13C{1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs.
For propylene homopolymers all chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.
Characteristic signals corresponding to regio defects (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253; Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157; Cheng, H. N., Macromolecules 17 (1984), 1950) or comonomer were observed.
The presence of 2,1 erythro regio-defects was indicated by the presence of the two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites. Characteristic signals corresponding to other types of regio-defects were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).
The amount of 2,1 erythro regio-defects was quantified using the average integral of the two characteristic methyl sites at 17.7 and 17.2 ppm:
The amount of 1,2 primary inserted propene was quantified based on the methyl region with correction undertaken for sites included in this region not related to primary insertion and for primary insertion sites excluded from this region:
The total amount of propene was quantified as the sum of primary inserted propene and all other present regio-defects:
The mole percent of 2,1 erythro regio-defects was quantified with respect to all propene:
“Xylene Cold Soluble” (XCS) fraction and “Xylene Cold Insoluble” (XCI) fraction, respectively, is determined according to standard gravimetric method as per ISO 16152.
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Quantitative 13C{1H} NMR spectra recorded in the molten-state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for 1H and 13C respectively. All spectra were recorded using a 13C optimised 7 mm magic-angle spinning (MAS) probehead at 180° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was packed into a 7 mm outer diameter zirconia MAS rotor and spun at 4 kHz. This setup was chosen primarily for the high sensitivity needed for rapid identification and accurate quantification. (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382, Parkinson, M., Klimke, K., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128, Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373). Standard single-pulse excitation was employed utilising the NOE at short recycle delays of 3 s (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382., Pollard, M., Klimke, K., Graf, R., Spiess, H. W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37:813.). and the RS-HEPT decoupling scheme (Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239, Griffin, J. M., Tripon, C., Samoson, A., Filip, C., and Brown, S. P., Mag. Res. in Chem. 2007 45, S1, S198). A total of 16384 (16k) transients were acquired per spectra.
Quantitative 13C{1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.
Basic Comonomer Content Method Spectral Analysis Method Characteristic signals corresponding to the incorporation of 1-butene were observed and the comonomer content quantified in the following way.
The amount 1-butene incorporated in PPBPP isolated sequences was quantified using the integral of the αB2 sites at 43.6 ppm accounting for the number of reporting sites per comonomer:
The amount of 1-butene incorporated in PPBBPP double consecutively sequences was quantified using the integral of the ααB2B2 site at 40.5 ppm accounting for the number of reporting sites per comonomer:
When double consecutive incorporation was observed the amount of 1-butene incorporated in PPBPP isolated sequences needed to be compensated due to the overlap of the signals αB2 and αB2B2 at 43.9 ppm:
The total 1-butene content was calculated based on the sum of isolated and consecutively incorporated 1-butene:
The amount of propene was quantified based on the main Sαα methylene sites at 46.7 ppm and compensating for the relative amount of αB2 and αB2B2 methylene unit of propene not accounted for (note B and BB count number of butane monomers per sequence not the number of sequences):
The total mole fraction of 1-butene in the polymer was then calculated as:
The full integral equation for the mole fraction of 1-butene in the polymer was:
This simplifies to:
The total comonomer incorporation of 1-butene in mole percent was calculated from the mole fraction in the usual manner:
The total comonomer incorporation of 1-butene in weight percent was calculated from the mole fraction in the standard manner:
Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content 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 rotatory 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 (6k) 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:
The mole percent comonomer incorporation was calculated from the mole fraction:
The weight percent comonomer incorporation was calculated from the mole fraction:
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.
af) Melting Temperature Tm and Crystallization Temperature Tc
The melting temperature Tm was determined by differential scanning calorimetry (DSC) according to ISO 11357-3 with a TA-Instruments 2920 Dual-Cell with RSC refrigeration apparatus and data station. A heating and cooling rate of 10° C./min was applied in a heat/cool/heat cycle between +23 and +210° C. The crystallization temperature (Tc) was determined from the cooling step, while melting temperature (Tm) and melting enthalpy (Hm) are being determined in the second heating step.
The flexural modulus was determined in 3-point-bending at 23° C. according to ISO 178 on 80×10×4 mm3 test bars injection molded in line with ISO 294-1:2017.
Tensile modulus was measured according to ISO 527 at a temperature of 23° C. on 10 mm wide strips cut in machine direction (MD) and in transverse direction (TD) from cast films of 50 μm thickness produced on a monolayer cast film line with a melt temperature of 220° C. and a chill roll temperature of 20° C.
Haze on plaques is determined according to ASTM D1003-00 on 60×60×1 mm3 plaques injection molded in line with ISO 294-1:2017.
Haze on film is determined according to ASTM D1003-00 on cast films of 50 μm thickness produced on a monolayer cast film line with a melt temperature of 220° C. and a chill roll temperature of 20° C.
The Charpy notched impact strength (NIS) was measured according to ISO 179 1 eA at −20° C., 0° C. and +23° C., using injection molded bar test specimens of 80×10×4 mm3 prepared in accordance with ISO 294-1:2017.
The method determines the sealing temperature range (sealing range) of polypropylene films, in particular blown films or cast films according to ASTM F1921-12. Seal pressure, cool time and peel speed are modified as stated below. The sealing temperature range is the temperature range, in which the films can be sealed according to conditions given below.
The lower limit (heat sealing initiation temperature (SIT)) is the sealing temperature at which a sealing strength of >5 N is achieved. The upper limit (sealing end temperature (SET)) is reached, when the films stick to the sealing device.
The sealing range is determined on a J&B Universal Sealing Machine Type 3000 with a blown film of 50 μm thickness with the following further parameters:
specimen is sealed A to A at each sealbar temperature and seal strength (force) is determined at each step.
The temperature is determined at which the seal strength reaches 5 N.
The heat-seal experiments were performed on at least 3 film specimens of 85 mm wide by 200 mm length cut in the machine direction. The 5 mm×150 mm Teflon coated steel heating bars were set to a temperature of 110° C. Two films were sealed by positioning, one on top of the other using a 0.5 s sealing time and 0.67 N/mm2 pressure. The resulting sealed area was 85 mm×5 mm. The specimens were then conditioned for 7 days (±24 h) at 23° C. (±2° C.)/50% RH (±10%). 10 specimens of 15 mm width were cut and tested in tensile mode at 23° C. (±2° C.)/50% RH (±10%) on a Universal Testing Machine (Zwick Z005). The clamping distance used was 100 mm, and a test speed of 200 mm/min. The yielding force and maximum force were measured for each test specimen.
The metallocene (MC) used was Anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-
methoxy-6-tert-butylinden-1-yl] zirconium dichloride as disclosed in WO2020/239602.
Preparation of MAO-silica support (as described in WO2020/239602 at page 57) A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set to 20° C. Next silica grade DM-L-303 from AGC Si-Tech Co, pre-calcined at 600° C. (5.0 kg) was added from a feeding drum followed by careful pressuring and depressurising with nitrogen using manual valves. Then toluene (22 kg) was added. The mixture was stirred for 15 min. Next 30 wt % solution of MAO in toluene (9.0 kg) from Lanxess was added via feed line on the top of the reactor within 70 min. The reaction mixture was then heated up to 90° C. and stirred at 90° C. for additional two hours. The slurry was allowed to settle and the mother liquor was filtered off. The catalyst was washed twice with toluene (22 kg) at 90° C., following by settling and filtration.
The reactor was cooled off to 60° C. and the solid was washed with heptane (22.2 kg). Finally MAO treated SiO2 was dried at 60° under nitrogen flow for 2 hours and then for 5 hours under vacuum (−0.5 barg) with stirring. MAO treated support was collected as a free-flowing white powder found to contain 12.2% Al by weight.
Catalyst preparation (as described in WO2020/239602 as ICS3) 30 wt % MAO in toluene (0.7 kg) was added into a steel nitrogen blanked reactor via a burette at 20° C. Toluene (5.4 kg) was then added under stirring. The MC as cited above (93 g) was added from a metal cylinder followed by flushing with 1 kg toluene. The mixture 5 was stirred for 60 minutes at 20° C. Trityl tetrakis(pentafluorophenyl) borate (91 g) was then added from a metal cylinder followed by a flush with 1 kg of toluene. The mixture was stirred for 1 h at room temperature. The resulting solution was added to a stirred cake of MAO-silica support prepared as described above over 1 hour. The cake was allowed to stay for 12 hours, followed by drying under N2 flow at 60° C. for 2 h and additionally for 5 h 10 under vacuum (−0.5 barg) under stirring. Dried catalyst was sampled in the form of pink free flowing powder containing 13.9% Al by weight and 0.11% Zr by weight.
The product from the final reactor was compounded and pelletized in the presence of a conventional additive package including antioxidant (Irganox B215, BASF AG, Germany; 0.15 wt.-%) and acid scavenger (synthetic hydrotalcite, CAS-No. 11097-59-9, available from Kisuma Chemicals under the trade name DHT-4A). In the case of IE2, Calcium cis-1,2-cyclohexanedicarboxylate (CAS-No. 491589-22-1, commercially available as Hyperform® HPN-20E as available from Milliken) was added as α-nucleating agent to the polymer of inventive example IE1
Results are shown in Table 2.
Films were produced on a Collin 30 lab scale cast film line with a melt temperature of 220° C. and chill roll temperature of 20° C. Throughput was 8 kg/h. The film thickness was 50 μm.
It can be seen that example IE1 and IE2 had significantly higher stiffness, higher melting temperature, at still acceptable haze and acceptable SIT increase. Seal strength was also good, while XCS remained at a low level.
| Number | Date | Country | Kind |
|---|---|---|---|
| 22164143.4 | Mar 2022 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2023/057306 | 3/22/2023 | WO |
