Propylene copolymer for thin-wall packaging

Abstract

Propylene copolymer having a comonomer content in the range of 2.0 to 11.0 mol.-% and a melt flow rate MFR.sub.2 (230° C.) in the range of 25.0 to 100 g/10 min, wherein said propylene copolymer is featured by good toughness.

Claims

1. Propylene copolymer (R-PP) having: (a) a comonomer content in the range of 2.0 to 11.0 mol. %; (b) a melt flow rate MFR2 (230° C.) measured according to ISO 1133 in the range of 25.0 to 100 g/10 min; and (c) a relative content of isolated to block ethylene sequences (I(E)) in the range of 55.0 to 70.0%, wherein the I(E) content is defined by equation (I): $\begin{array}{cc}I\left(E\right)=\frac{\mathrm{fPEP}}{\left(\mathrm{fEEE}+\mathrm{fPEE}+\mathrm{fPEP}\right)}\times 100& \left(I\right)\end{array}$ 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 .sup.13C-NMR data.

2. Propylene copolymer (R-PP) according to claim 1, wherein said propylene copolymer (R-PP) has a xylene cold soluble fraction (XCS) in the range of 4.0 to 25.0 wt. %.

3. Propylene copolymer (R-PP) according to claim 1, wherein said propylene copolymer (R-PP) has: (a) a glass transition temperature in the range of −12 to +2° C.; and/or (b) no glass transition temperature below −20° C.

4. Propylene copolymer (R-PP) according to claim 1, wherein said propylene copolymer (R-PP) has: (a) a main melting temperature in the range of 133 to 155° C.; and/or (b) a crystallization temperature in the range of 110 to 128° C.

5. Propylene copolymer (R-PP) according to claim 1, wherein said propylene copolymer (R-PP) has: (a) has 2,1 regio-defects of at most 0.4% determined by .sup.13C-NMR spectroscopy; and/or (b) is monophasic.

6. Propylene copolymer (R-PP) according to claim 1, wherein the comonomer is selected from ethylene, C.sub.4 to C.sub.12 α-olefin, or mixtures thereof.

7. Propylene copolymer (R-PP) according to claim 1, wherein said propylene copolymer (R-PP) comprises two fractions, a first propylene copolymer fraction (R-PP1) and a second propylene copolymer fraction (R-PP2), said first propylene copolymer fraction (R-PP1) differs from said second propylene copolymer fraction (R-PP2) in the comonomer content.

8. Propylene copolymer (R-PP) according to claim 7, wherein: (a) the weight ratio between the first propylene copolymer fraction (R-PP1) and the second propylene copolymer fraction (R-PP2) [(R-PP1):(R-PP2)] is 70:30 to 30:70; and/or (b) the comonomers for the first propylene copolymer fraction (R-PP1) and the second propylene copolymer fraction (R-PP2) are the same and are selected from ethylene, C.sub.4 to C.sub.12 α-olefin, or mixtures thereof.

9. Propylene copolymer (R-PP) according to claim 7, wherein: the first propylene copolymer fraction (R-PP1) is the comonomer lean fraction and the second propylene copolymer fraction (R-PP2) is the comonomer rich fraction.

10. Propylene copolymer (R-PP) according to claim 7, wherein: (a) the first propylene copolymer fraction (R-PP1) has a comonomer content in the range of 1.0 to 6.0 mol-% based on the first propylene copolymer fraction (R-PP1); and/or, (b) the second propylene copolymer fraction (R-PP2) has a comonomer content in the range of more than 6.0 to 14.0 mol % based on the second propylene copolymer fraction (R-PP2).

11. Propylene copolymer (R-PP) according to claim 7, wherein: (a) the first propylene copolymer fraction (R-PP1) and the second propylene copolymer fraction (R-PP2) fulfill together the inequality (IV): $\begin{array}{cc}\frac{\mathrm{Co}\left(R-\mathrm{PP}2\right)}{\mathrm{Co}\left(R-\mathrm{PP}1\right)}\ge 1.0;& \left(\mathrm{IV}\right)\end{array}$ wherein: Co(R-PP1) is the comonomer content [mol. %] of the first propylene copolymer fraction (R-PP1), Co(R-PP2) is the comonomer content [mol. %] of the second propylene copolymer fraction (R-PP2), and/or, (b) the first propylene copolymer fraction (R-PP1) and the propylene copolymer fraction (R-PP) fulfill together the inequality (V): $\begin{array}{cc}\frac{\mathrm{Co}\left(R-\mathrm{PP}\right)}{\mathrm{Co}\left(R-\mathrm{PP}1\right)}\ge 1.0& \left(V\right)\end{array}$ wherein: Co(R-PP1) is the comonomer content [mol. %] of the first propylene copolymer fraction (R-PP1), Co(R-PP) is the comonomer content [mol. %] of the propylene copolymer (R-PP).

12. Injection molded article comprising a propylene copolymer according to claim 1.

13. Thin wall packaging made by injection molding, comprising a propylene copolymer according to claim 1.

14. Process for producing a propylene copolymer (R-PP) according to claim 1, wherein the process comprises polymerizing propylene in the presence of: (a) a Ziegler-Natta catalyst (ZN-C) comprises a titanium compound (TC), a magnesium compound (MC) and an internal donor (ID), wherein said internal donor (ID) is a non-phthalic acid ester, (b) optionally a co-catalyst (Co), and (c) optionally an external donor (ED).

15. Process according to claim 14, wherein: (a) the internal donor (ID) is selected from optionally substituted malonates, maleates, succinates, glutarates, cyclohexene-1,2-dicarboxylates, benzoates and derivatives or mixtures thereof; (b) the molar-ratio of co-catalyst (Co) to external donor (ED) [Co/ED] is 5 to 45.

16. Process according to claim 14, wherein the process comprises polymerizing propylene in a sequential polymerization process comprising at least two reactors (R1) and (R2), in the first reactor (R1) the first propylene copolymer fraction (R-PP1) is produced and subsequently transferred into the second reactor (R2), in the second reactor (R2) the second propylene copolymer fraction (R-PP2) is produced in the presence of the first propylene copolymer fraction (R-PP1).

Description

EXAMPLES

(1) 1. Measuring Methods

(2) 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.

(3) Calculation of comonomer content of the second propylene copolymer fraction (R-PP2):

(4) $\begin{array}{cc}\frac{C\left(\mathrm{PP}\right)-w\left(\mathrm{PP}1\right)\times C\left(\mathrm{PP}1\right)}{w\left(\mathrm{PP}2\right)}=C\left(\mathrm{PP}2\right)& \left(I\right)\end{array}$
wherein w(PP1) is the weight fraction [in wt.-%] of the first propylene copolymer fraction (R-PP1), w(PP2) is the weight fraction [in wt.-%] of second propylene copolymer fraction (R-PP2), C(PP1) is the comonomer content [in mol-%] of the first random propylene copolymer fraction (R-PP1), C(PP) is the comonomer content [in mol-%] of the random propylene copolymer (R-PP), C(PP2) is the calculated comonomer content [in mol-%] of the second random propylene copolymer fraction (R-PP2).

(5) Calculation of melt flow rate MFR.sub.2 (230° C.) of the second propylene copolymer fraction (R-PP2):

(6) $\begin{array}{cc}\mathrm{MFR}\left(\mathrm{PP}2\right)={10}^{\left[\frac{\log \left(\mathrm{MFR}\left(\mathrm{PP}\right)\right)-w\left(\mathrm{PP}1\right)\times \log \left(\mathrm{MFR}\left(\mathrm{PP}1\right)\right)}{w\left(\mathrm{PP}2\right)}\right]}& \left(\mathrm{III}\right)\end{array}$
wherein w(PP1) is the weight fraction [in wt.-%] of the first propylene copolymer fraction (R-PP1), w(PP2) is the weight fraction [in wt.-%] of second propylene copolymer fraction (R-PP2), MFR(PP1) is the melt flow rate MFR.sub.2 (230° C.) [in g/10 min] of the first propylene copolymer fraction (R-PP1), MFR(PP) is the melt flow rate MFR.sub.2 (230° C.) [in g/10 min] of the propylene copolymer (R-PP), MFR(PP2) is the calculated melt flow rate MFR.sub.2 (230° C.) [in g/10 min] of the second propylene copolymer fraction (R-PP2).

(7) MFR.sub.2 (230° C.) is measured according to ISO 1133 (230° C., 2.16 kg load).

(8) Quantification of Microstructure by NMR Spectroscopy

(9) Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content and comonomer sequence distribution of the polymers. Quantitative .sup.13C{.sup.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 .sup.1H and .sup.13C respectively. All spectra were recorded using a .sup.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-d.sub.2 (TCE-d.sub.2) along with chromium-(III)-acetylacetonate (Cr(acac).sub.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 .sup.13C{.sup.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).

(10) 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.

(11) 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 .sup.13C {.sup.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.

(12) 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))

(13) Through the use of this set of sites the corresponding integral equation becomes:
E=0.5(I.sub.H+I.sub.G+0.5(I.sub.C+I.sub.D))
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.

(14) The mole percent comonomer incorporation was calculated from the mole fraction:
E [mol %]=100*fE

(15) The weight percent comonomer incorporation was calculated from the mole fraction:
E [wt %]=100*(fE*28.06)/((fE*28.06)+((1−fE)*42.08))

(16) 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.

(17) The relative content of isolated to block ethylene incorporation was calculated from the triad sequence distribution using the following relationship (equation (I)):

(18) $\begin{array}{cc}I\left(E\right)=\frac{f\mathrm{PEP}}{\left(f\mathrm{EEE}+f\mathrm{PEE}+f\mathrm{PEP}\right)}\times 100& \left(I\right)\end{array}$
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 Bulk density, BD, is measured according ASTM D 1895
Particle Size Distribution, PSD

(19) Coulter Counter LS 200 at room temperature with heptane as medium.

(20) The xylene solubles (XCS, wt.-%): Content of xylene cold solubles (XCS) is determined at 25° C. according ISO 16152; first edition; 2005-07-01

(21) The hexane extractable fraction is determined according to FDA method (federal registration, title 21, Chapter 1, part 177, section 1520, s. Annex B) on cast films of 100 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 extraction was performed at a temperature of 50° C. and an extraction time of 30 min.

(22) Number average molecular weight (M.sub.n), weight average molecular weight (M.sub.w) and polydispersity (Mw/Mn)

(23) are determined by Gel Permeation Chromatography (GPC) according to the following method:

(24) The weight average molecular weight Mw and the polydispersity (Mw/Mn), wherein Mn is the number average molecular weight and Mw is the weight average molecular weight) is measured by a method based on ISO 16014-1:2003 and ISO 16014-4:2003. A Waters Alliance GPCV 2000 instrument, equipped with refractive index detector and online viscosimeter was used with 3×TSK-gel columns (GMHXL-HT) from TosoHaas and 1,2,4-trichlorobenzene (TCB, stabilized with 200 mg/L 2,6-Di tert butyl-4-methyl-phenol) as solvent at 145° C. and at a constant flow rate of 1 mL/min. 216.5 μL of sample solution were injected per analysis. The column set was calibrated using relative calibration with 19 narrow MWD polystyrene (PS) standards in the range of 0.5 kg/mol to 11 500 kg/mol and a set of well characterized broad polypropylene standards. All samples were prepared by dissolving 5-10 mg of polymer in 10 mL (at 160° C.) of stabilized TCB (same as mobile phase) and keeping for 3 hours with continuous shaking prior sampling in into the GPC instrument.

(25) DSC analysis, melting temperature (T.sub.m) and heat of fusion (H.sub.f), crystallization temperature (T.sub.c) and heat of crystallization (H.sub.c): measured with a TA Instrument Q2000 differential scanning calorimetry (DSC) on 5 to 7 mg samples. DSC is run according to ISO 11357/part 3/method C2 in a heat/cool/heat cycle with a scan rate of 10° C./min in the temperature range of −30 to +225° C. Crystallization temperature and heat of crystallization (H.sub.c) are determined from the cooling step, while melting temperature and heat of fusion (H.sub.f) are determined from the second heating step.

(26) The glass transition temperature Tg is determined by dynamic mechanical analysis according to ISO 6721-7. The measurements are done in torsion mode on compression moulded samples (40×10×1 mm.sup.3) between −100° C. and +150° C. with a heating rate of 2° C./min and a frequency of 1 Hz.

(27) Flexural Modulus: The flexural modulus was determined in 3-point-bending at 23° C. according to ISO 178 on 80×10×4 mm.sub.3 test bars injection moulded in line with EN ISO 1873-2.

(28) Charpy impact test: The Charpy notched impact strength (NIS) was measured according to ISO 179 1eA at +23° C., using injection molded bar test specimens of 80×10×4 mm.sup.3 prepared in accordance with ISO 294-1:1996

(29) Puncture energy was determined in the instrumental falling weight (IFW) test according to ISO 6603-2 using injection moulded plaques of 60×60×2 mm 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.

(30) The Top load test was performed by compression between two plates attached to a universal testing machine with a test speed of 10 mm/min according to an internal procedure in general agreement with ASTM D642. For testing, the cup is placed upside down (i.e. with the bottom facing the moving plate) into the test setup and compressed to the point of collapse which is noticed by a force drop on the force-deformation curve, for which the maximum force is noted. At least 8 cups are tested to determine an average result.

(31) Transparency, Clarity, and Haze Measurement on Cups

(32) Instrument: Haze-gard plus from BYK-Gardner

(33) Testing: according to ASTM D1003 (as for injection molded plates)

(34) Method: The measurement is done on the outer wall of the cups as produced below. The top and bottom of the cups are cut off. The resulting round wall is then split in two, horizontally. Then from this wall six equal samples of app. 60×60 mm are cut from close to the middle. The specimens are placed into the instrument with their convex side facing the haze port. Then the transparency, haze and clarity are measured for each of the six samples and the haze value is reported as the average of these six parallels.

(35) Preparation of 840 ml Cups

(36) With the polymers as defined below cups are produced by injection molding using an Engel speed 180 machine with a 35 mm barrier screw (supplied by Engel Austria GmbH). The melt temperature was adjusted to 245° C. and the mould temperature to 10° C.; an injection speed of 770 cm.sup.3/s with an injection time of 0.08 s was used, followed by a holding pressure time of 0.1 s with 1300 bar (decreasing to 800 bar) and a cooling time of 1.5 s, giving a standard cycle time of 3.8 s. The dimensions of the cup are as follows: Height 100 mm, diameter top 115 mm, diameter bottom 95 mm, bottom wall thickness 0.44 mm, side-wall thickness 0.40 mm. For the cycle time optimization the machine was run with standard injection parameters first. The machine was run in full automatic mode, reducing the cooling time after a stabilization time of 5 minutes from 1.5 to 0.3 sec. Depending on the material behaviour the cups were then either deformed or could not get de-moulded. Then the cooling time was increased in steps of 0.1 s until the part quality was found to be optically and mechanically satisfactory. The cycle time resulting from this experiment can be found in table 2.

(37) 2. Examples

(38) The catalyst used in the polymerization process for the propylene copolymer of the inventive examples (IE1) and (IE2) was produced as follows:

(39) Used Chemicals:

(40) 20% solution in toluene of butyl ethyl magnesium (Mg(Bu)(Et), BEM), provided by Chemtura 2-ethylhexanol, provided by Amphochem 3-Butoxy-2-propanol—(DOWANOL™ PnB), provided by Dow bis(2-ethylhexyl)citraconate, provided by SynphaBase TiCl.sub.4, provided by Millenium Chemicals Toluene, provided by Aspokem Viscoplex® 1-254, provided by Evonik Heptane, provided by Chevron
Preparation of a Mg Complex

(41) First a magnesium alkoxide solution was prepared by adding, with stirring (70 rpm), into 11 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)

(42) Preparation of Solid Catalyst Component

(43) 20.3 kg of TiCl.sub.4 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.

(44) 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.

(45) The solid catalyst component was used along with triethyl-aluminium (TEAL) as co-catalyst and dicyclo pentyl dimethoxy silane (D-donor) as donor.

(46) 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.

(47) The aluminium to donor ratio, the aluminium to titanium ratio and the polymerization conditions are indicated in table 1.

(48) TABLE-US-00001 TABLE 1 Preparation of the Examples IE1 IE2 CE1 TEAL/Ti [mol/mol] 171 145 150 TEAL/Donor [mol/mol] 6.1 6.1 4.0 Loop (R-PP1) Time [h] 0.74 0.76 0.50 Temperature [° C.] 70 70 75 MFR.sub.2 [g/10 min] 33.0 43.0 45.0 XCS [wt.-%] 8.2 7.5 5.5 C2 content [mol-%] 4.6 4.0 4.1 H.sub.2/C3 ratio [mol/kmol] 4.77 5.46 6.55 C2/C3 ratio [mol/kmol] 7.96 8.11 9.01 amount [wt.-%] 52 47 45 1 GPR (R-PP2) Time [h] 2.07 2.12 2.00 Temperature [° C.] 83 86 80 MFR.sub.2 [g/10 min] 37.0 38.0 45.0 C2 content [mol-%] 6.1 6.3 6.2 H.sub.2/C3 ratio [mol/kmol] 49.8 56.9 60.8 C2/C3 ratio [mol/kmol] 22.7 22.1 25.0 amount [wt.-%] 48 53 55 Final MFR.sub.2 [g/10 min] 35.0 40.0 45.0 C2 content [mol-%] 5.3 5.2 5.3 XCS [wt.-%] 8.1 8.1 5.6 Mw [kg/mol] 152 160 147 Mw/Mn [—] 4.4 4.3 4.2 2,1 [%] n.d. n.d. n.d. n.d. not detectable

(49) 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 0.1 wt.-% calcium stearate. The materials of the inventive examples IE1 and IE2 were nucleated with 2 wt.-% of a propylene homopolymer having an MFR.sub.2 of 20 g/10 min and 200 ppm of vinylcycloalkane polymer (pVCH) to give inventive examples IE3 and IE4, respectively. In the same way, the material of comparative example CE1 was nucleated with 2 wt.-% of a propylene homopolymer having an MFR.sub.2 of 20 g/10 min and 200 ppm of vinylcycloalkane polymer (pVCH) to give comparative example CE2.

(50) TABLE-US-00002 TABLE 2 Properties of the Examples Example IE3 IE4 CE2 MFR [g/10 min] 33 40 44 Tm, 1 [° C.] 135 136 135 Hm, 1 [J/g] 66.4 64.0 59.6 Tm, 2 [° C.] 149 149 151 Hm, 2 [J/g] 26.1 27.7 26.7 Tc [° C.] 120 121 121 Tg [° C.] −4.7 −4.7 −4.5 C2 [mol-%] 5.3 5.2 5.3 XCS [wt.-%] 8.1 8.1 5.6 Hexane solubles [wt.-%] 3.5 3.6 2.9 Flexural Modulus [MPa] 991 988 1107 Charpy NIS +23° C. [kJ/m.sup.2] 4.5 4.5 3.6 Puncture Energy [J] 3.6 3.1 0.4 Average drop height [m] 0.72 0.63 0.5 Top load/Force Max [N] 250 252 258 Haze [%] 9.5 9.3 10.6 Clarity [%] 99 99 98.4 Transparency [%] 93.6 93.4 94

(51) TABLE-US-00003 TABLE 3 Relative content of isolated to block ethylene sequences (I(E)) Example 1E3 1E4 CE2 n-PEP.sup.1) [%] 65.4 65.3 72.1 EEE [mol-%] 0.61 0.61 0.42 EEP [mol-%] 0.98 1.38 1.11 PEP [mol-%] 3.01 3.75 3.95 PPP [mol-%] 88.7 85.88 86.28 EPP [mol-%] 6.70 8.10 8.02 EPE [mol-%] 0.00 0.28 0.21 .sup.1)0$I\left(E\right)=\frac{\mathrm{fPEP}}{\left(\mathrm{fEEE}+\mathrm{fPEE}+\mathrm{fPEP}\right)}\times 100\left(I\right)$