Polypropylene with extreme broad molecular weight distribution

Abstract

Polypropylene having a melt flow rate MFR.sub.2 (230 C.) of at least 20 g/10 min; and a M.sub.w/M.sub.n ratio of at least 15.0.

Claims

1. Polypropylene having: (a) a melt flow rate MFR.sub.2 (230 C.) measured according to ISO 1133 of at least 20 g/10min; and (b) a complex viscosity ratio eta*(0.05 rad/sec)/eta*(300 rad/sec) of at least 20.0 measured by dynamic rheology according to ISO 6271-10 at 200 C.; wherein said polypropylene has a first polypropylene fraction (PP1), a second polypropylene fraction (PP2), and a third polypropylene fraction (PP3), said first polypropylene fraction(PP1) , second polypropylene fraction (PP2), and third polyproplene fraction (PP3)differ in the melt flow rate MFR.sub.2 (230 C. by at least 30 g/10min.

2. Polypropylene according to claim 1, wherein said polypropylene has: a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) [Mw/Mn] of at least 15.0 determined by Gel Permeation Chromatography (GPC).

3. Polypropylene according to claim 1, wherein said polypropylene has (a) a xylene cold soluble content (XCS) determined according ISO 16152 (25 C.) of at least 2.8 wt. %; and/or (b) a melting temperature Tm of more than 161 C.

4. Polypropylene according to claim 1, wherein said polypropylene has: (a) 2,1 erythro regio-defects of equal or below 0.4 mol.-% determined by .sup.13C-NMR spectroscopy; and/or (b) a pentad isotacticity (mmmm) of more than 95.0 mol. %.

5. Polypropylene according to claim 1, wherein said polypropylene has: (a) a ratio of z-average molecular weight (Mz) to weight average molecular weight (Mw) [Mz/Mw] of at least 9.0; and/or (b) a ratio of z-average molecular weight (Mz) to number average molecular weight (Mn) [Mz/Mn] of at least 150.

6. Polypropylene according to claim 1, wherein said polypropylene is -nucleated.

7. Polypropylene according to claim 1, wherein said polypropylene has: (a) a weight ratio of the crystalline fractions melting in the temperature range of above 160 to 180 C. to the crystalline fractions melting in the temperature range of 90 to 160 of at least 3.20, wherein said fractions are determined by the stepwise isothermal segregation technique (SIST); and/or (b) a crystallization temperature of at least 125 C.; and/or (c) a tensile modulus measured according to ISO 527-2 of at least 2250 MPa.

8. Polypropylene according to claim 1, wherein said polypropylene has a first polypropylene fraction (PP1), a second polypropylene fraction (PP2) and a third polypropylene fraction (PP3), and the amount: (a) of the first polypropylene fraction (PP1) is in the range of 40 to 60 wt. %, (b) of the second polypropylene fraction (PP2) is in the range of 20 to 59.0 wt. %, and (c) of the third polypropylene fraction (PP3) is in the range of 1.0 to 15.0 wt. %, based on the total amount of the polypropylene.

9. Polypropylene according to claim 1, wherein: (a) the melt flow rate MFR.sub.2 (230 C.) of the first polypropylene fraction (PP1) is at least 5 times higher than the melt flow rate MFR.sub.2 (230 C.) of the second polypropylene fraction (PP2); and/or (b) the melt flow rate MFR.sub.2 (230 C.) of the second polypropylene fraction (PP2) is at least 5,000 times higher than the melt flow rate MFR.sub.2 (230 C.) of the third polypropylene fraction (PP3).

10. Polypropylene according to claim 1, wherein: (a) the melt flow rate MFR.sub.2 (230 C.) of the first polypropylene fraction (PP1) is at least 200 g/10min; and/or (b) the melt flow rate MFR.sub.2 (230 C.) of the second polypropylene fraction (PP2) is in the range of 10 to below 200 g/10min; and/or (c) the melt flow rate MFR.sub.2 (230 C.) of the third polypropylene fraction (PP3) is below 0.1 g/10min.

11. Process for the manufacture of the polypropylene according to claim 1, in a sequential polymerization system comprising a pre-polymerization reactor (PR) and at least three polymerization reactors (R1), (R2) and (R3) connected in series, feeding propylene (C3) and optionally hydrogen (H2) to said pre-polymerization reactor (PR) in a H2/C3 feed ratio of 0.00 to 0.10 mol/kmol to form a pre-polypropylene (Pre-PP) and polymerizing the pre-polypropylene (Pre-PP) in the at least three polymerization reactors (R1), (R2), and (R3), wherein the polymerization in the at least three polymerization reactors (R1), (R2) and (R3) takes place in the presence of a Ziegler-Natta catalyst (ZN-C), said Ziegler-Natta catalyst (ZN-C) comprises (a) a pro-catalyst (PC) comprising a titanium compound (TC) having at least one titanium-halogen bond and an internal donor (ID), both supported on a magnesium halide; (b) a co-catalyst (Co); and (c) an external donor (ED); wherein: the internal donor (ID) comprises at least 80 wt.-% of a compound selected from the group consisting of succinate, citraconate, di-ketone, enaminoimine, and mixtures thereof; the mol-ratio of co-catalyst (Co) to external donor (ED) [Co/ED] of said Ziegler-Natta catalyst (ZN-C) is below 20.0; and said Ziegler-Natta catalyst (ZN-C) is present in the pre-polymerization reactor (PR).

12. Process according to claim 11, wherein: (a) the mol-ratio of co-catalyst (Co) to titanium compound (TC) (TC) [Co/TC] is at most 130; and/or (b) the mol-ratio of external donor (ED) to titanium compound (TC)) [Co/TC] is below 50.

13. Process according to claim 11, wherein: (a) the operating temperature in the pre-polymerization reactor (PR) is in the range of more than 20 C. to 80 C.; and/or (b) the average residance time of the Ziegler-Natta catalyst (ZN-C) in the pre-polymerization reactor (PR) is in the range of more than 3 to 20 min.

14. Process according to claim 11, wherein: (a) the average residence time in the first polymerization reactor (R1) is at least 20 min; and/or (b) the average residence time in the second polymerization reactor (R2) is at least 30 min; and/or (c) the average residence time in the third polymerization reactor (R3) is at least 80 min; and/or (d) the total residence time in the three polymerization reactors (R1), (R2), and (R3) together is at most 700 min.

15. Process according to claim 11, wherein: (a) the feed ratio of hydrogen (H.sub.2) to propylene (C.sub.3) [H.sub.2/C.sub.3] in the first polymerization reactor (R1) is in the range of 10 to 60 mol/kmol; and/or (b) the feed ratio of hydrogen (H.sub.2) to propylene (C.sub.3) [H.sub.2/C.sub.3] in the second polymerization reactor (R2) is in the range of 10 to 260 mol/kmol; and/or (c) the feed ratio of hydrogen (H.sub.2) to propylene (C.sub.3) [H.sub.2/C.sub.3] in the third polymerization reactor (R3) is in the range of 0 to 20 mol/kmol.

16. Polypropylene according to claim 1, wherein said polypropylene has a polydispersity index (PI) of at least 10.0.

Description

EXAMPLES

(1) A. Measuring Methods

(2) The following definitions of terms and determination methods apply for the above general description of the invention including the claims as well as to the below examples unless otherwise defined.

(3) Quantification of Microstructure by NMR Spectroscopy

(4) Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity and regio-regularity of the polypropylene homopolymers.

(5) 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.

(6) For polypropylene homopolymers approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d.sub.2 (TCE-d.sub.2). To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotataory 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 spectra.

(7) Quantitative .sup.13C{.sup.1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs.

(8) For polypropylene homopolymers all chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.

(9) 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 co-monomer were observed.

(10) The tacticity distribution was quantified through integration of the methyl region between 23.6-19.7 ppm correcting for any sites not related to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251).

(11) Specifically the influence of regio-defects and co-monomer on the quantification of the tacticity distribution was corrected for by subtraction of representative regio-defect and co-monomer integrals from the specific integral regions of the stereo sequences.

(12) The isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences with respect to all pentad sequences:
[mmmm]%=100*(mmmm/sum of all pentads)

(13) 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).

(14) 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:
P.sub.21e=(I.sub.e6+I.sub.e8)/2

(15) 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:
P.sub.12=I.sub.CH3+P.sub.12e

(16) The total amount of propene was quantified as the sum of primary inserted propene and all other present regio-defects:
P.sub.total=P.sub.12+P.sub.21e

(17) The mole percent of 2,1 erythro regio-defects was quantified with respect to all propene:
[21e] mol.-%=100*(P.sub.21e/P.sub.total)

(18) Characteristic signals corresponding to the incorporation of ethylene were observed (as described in Cheng, H. N., Macromolecules 1984, 17, 1950) and the co-monomer fraction calculated as the fraction of ethylene in the polymer with respect to all monomer in the polymer.

(19) The comonomer fraction was quantified using the method of W-J. Wang and S. Zhu, Macromolecules 2000, 33 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 co-monomer contents.

(20) The mole percent co-monomer incorporation was calculated from the mole fraction. The weight percent co-monomer incorporation was calculated from the mole fraction.

(21) Calculation of co-monomer content of the second propylene copolymer fraction (R-PP2):

(22) $\begin{array}{cc}\frac{C\left(\mathrm{PP}\right)-w\left(\mathrm{PP}1\right)C\left(\mathrm{PP}1\right)}{w\left(\mathrm{PP}2\right)}=C\left(\mathrm{PP}2\right)& \left(I\right)\end{array}$
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 the second propylene copolymer fraction (R-PP2), C(PP1) is the co-monomer content [in wt-%] of the first propylene copolymer fraction (R-PP1), C(PP) is the co-monomer content [in wt-%] of the polypropylene obtained after the second polymerization reactor (R2), i.e. of the mixture of the first polypropylene fraction (PP1) and second polypropylene fraction (PP2), C(PP2) is the calculated co-monomer content [in wt-%] of the second propylene copolymer fraction (R-PP2).

(23) Calculation of co-monomer content of the third propylene copolymer fraction (R-PP3):

(24) $\begin{array}{cc}\frac{C\left(\mathrm{PP}\right)-w\left(\mathrm{PP}1/2\right)C\left(\mathrm{PP}1/2\right)}{w\left(\mathrm{PP}3\right)}=C\left(\mathrm{PP}3\right)& \left(I\right)\end{array}$
wherein w(PP1/2) is the weight fraction [in wt.-%] of the mixture of first propylene copolymer fraction (R-PP1) and second propylene copolymer fraction (R-PP2), w(PP3) is the weight fraction [in wt.-%] of the third propylene copolymer fraction (R-PP3), C(PP1/2) is the co-monomer content [in mol-%] of the mixture of first propylene copolymer fraction (R-PP1) and second propylene copolymer fraction (R-PP2), C(PP) is the co-monomer content [in wt-%] of the propylene copolymer, C(PP3) is the calculated co-monomer content [in wt-%] of the third propylene copolymer fraction (R-PP3).

(25) Calculation of melt flow rate MFR.sub.2 (230 C.) of the second propylene homo-polymer fraction (PP2):

(26) $\begin{array}{cc}MFR\left(\mathrm{PP}2\right)={10}^{\left[\frac{\log \left(\mathrm{MFR}\left(\mathrm{PP}1/2\right)\right)-w\left(\mathrm{PP}1\right)\log \left(\mathrm{MFR}\left(\mathrm{PP}1\right)\right)}{w\left(\mathrm{PP}2\right)}\right]}& \left(I\right)\end{array}$
wherein w(PP1) is the weight fraction [in wt.-%] of the first polypropylene fraction (PP1), w(PP2) is the weight fraction [in wt-%] of the second polypropylene fraction (PP2), MFR(PP1) is the melt flow rate MFR.sub.2 (230 C.) [in g/10 min] of the first polypropylene fraction (PP1), MFR(PP1/2) is the melt flow rate MFR.sub.2 (230 C.) [in g/10 min] of the polypropylene obtained after the second polymerization reactor (R2), i.e. of the mixture of the first polypropylene fraction (PP1) and second polypropylene fraction (PP2), MFR(PP2) is the calculated melt flow rate MFR.sub.2 (230 C.) [in g/10 min] of the second polypropylene fraction (PP2).

(27) Calculation of melt flow rate MFR.sub.2 (230 C.) of the third polypropylene fraction (PP3):

(28) $\begin{array}{cc}MFR\left(\mathrm{PP}3\right)={10}^{\left[\frac{\log \left(\mathrm{MFR}(\mathrm{PP})\right)-w\left(\mathrm{PP}1/2\right)\log \left(\mathrm{MFR}\left(\mathrm{PP}1/2\right)\right)}{w\left(\mathrm{PP}3\right)}\right]}& \left(\mathrm{II}\right)\end{array}$
wherein w(PP1/2) is the weight fraction [in wt.-%] of the polypropylene obtained after the second polymerization reactor (R2), i.e. of the mixture of the first polypropylene fraction (PP1) and second polypropylene fraction (PP2), w(PP3) is the weight fraction [in wt.-%] of the third polypropylene fraction (PP3), MFR(PP1/2) is the melt flow rate MFR.sub.2 (230 C.) [in g/10 min] of the polypropylene obtained after the second polymerization reactor (R2), i.e. of the mixture of the first polypropylene fraction (PP1) and second polypropylene fraction (PP2), MFR(PP) is the melt flow rate MFR.sub.2 (230 C.) [in g/10 min] of the polypropylene, MFR(PP3) is the calculated melt flow rate MFR.sub.2 (230 C.) [in g/10 min] of the third polypropylene fraction (PP3). MFR.sub.2 (230 C.) is measured according to ISO 1133 (230 C., 2.16 kg load)
Number Average Molecular Weight (M.sub.n), Weight Average Molecular Weight (M.sub.w), z-Average Molecular Weight (M.sub.z)

(29) Molecular weight averages Mw, Mn and Mz were determined by Gel Permeation Chromatography (GPC) according to ISO 16014-4:2003 and ASTM D 6474-99. A PolymerChar GPC instrument, equipped with infrared (IR) detector was used with 3 Olexis and 1 Olexis Guard columns from Polymer Laboratories and 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) as solvent at 160 C. and at a constant flow rate of 1 mL/min. 200 L of sample solution were injected per analysis. The column set was calibrated using universal calibration (according to ISO 16014-2:2003) with at least 15 narrow MWD polystyrene (PS) standards in the range of 0.5 kg/mol to 11 500 kg/mol. Mark Houwink constants for PS, PE and PP used are as described per ASTM D 6474-99. All samples were prepared by dissolving 5.0-9.0 mg of polymer in 8 mL (at 160 C.) of stabilized TCB (same as mobile phase) for 2.5 hours for PP or 3 hours for PE at max. 160 C. under continuous gentley shaking in the autosampler of the GPC instrument.

(30) The Xylene Soluble Fraction at Room Temperature (XS, Wt.-%): The amount of the polymer soluble in xylene is determined at 25 C. according to ISO 16152; first edition; 2005-07-01.

(31) Rheology: Dynamic rheological measurements were carried out with Rheometrics RDA-II QC on compression moulded samples under nitrogen atmosphere at 230 C. using 25 mm-diameter plate and plate geometry. The oscillatory shear experiments were done within the linear viscoelastic range of strain at frequencies from 0.015 to 300 rad/s (ISO 6721-10). The values of storage modulus (G), loss modulus (G), complex modulus (G*) and complex viscosity (*) were obtained as a function of frequency ().

(32) The Zero shear viscosity (.sub.0) was calculated using complex fluidity defined as the reciprocal of complex viscosity. Its real and imaginary part are thus defined by
f()=()/[().sup.2+().sup.2] and
f()=()/[().sup.2+().sup.2]

(33) The complex viscosity ratio eta*(0.05 rad/sec)/eta*(300 rad/sec) is the ratio of the complex viscosity (*) at 0.05 rad/sec to the complex viscosity (*) at 300 rad/sec.

(34) The Polydispersity Index, PI,

(35) PI=10.sup.5/G.sub.c, is calculated from the cross-over point of G() and G(), for which G(.sub.c)=G(.sub.c)=G.sub.c holds.

(36) 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.

(37) 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 (40101 mm.sup.3) between 100 C. and +150 C. with a heating rate of 2 C./min and a frequency of 1 Hz.

(38) Tensile Test: The tensile test (modulus, strength and tensile strain at break) is measured at 23 C. according to ISO 527-1 (cross head speed 1 mm/min) using injection moulded specimens according to ISO 527-2(1B), produced according to EN ISO 1873-2 (dog 10 bone shape, 4 mm thickness, moulded at 180 C. or at 200 C.).

(39) Stepwise Isothermal Segregation Technique (SIST)

(40) The isothermal crystallisation for SIST analysis was performed in a Mettler TA820 DSC on 30.5 mg samples at decreasing temperatures between 200 C. and 105 C. (i) the samples were melted at 225 C. for 5 min., (ii) then cooled with 80 C./min to 145 C. (iii) held for 2 hours at 145 C., (iv) then cooled with 80 C./min to 135 C. (v) held for 2 hours at 135 C., (vi) then cooled with 80 C./min to 125 C. (vii) held for 2 hours at 125 C., (viii) then cooled with 80 C./min to 115 C. (ix) held for 2 hours at 115 C., (x) then cooled with 80 C./min to 105 C. (xi) held for 2 hours at 105 C.

(41) After the last step the sample was cooled down with 80 C./min to 10 C. and the melting curve was obtained by heating the cooled sample at a heating rate of 10 C./min up to 200 C. All measurements were performed in a nitrogen atmosphere. The melt enthalpy is recorded as function of temperature and evaluated through measuring the melt enthalpy of fractions melting within temperature intervals of 50 to 60 C.; 60 to 70 C.; 70 to 80 C.; 80 to 90 C.; 90 to 100 C.; 100 to 110 C.; 110 to 120 C.; 120 to 130 C.; 130 to 140 C.; 140 to 150 C.; 150 to 160 C.; 160 to 170 C.; 170 to 180 C.; 180 to 190 C.; 190 to 200 C.

(42) B. Examples

(43) The catalyst used in the polymerization process for the polypropylene of the inventive examples (IE1 to IE5) and the comparative example CE7 was the commercial Ziegler-Natta catalyst ZN168M catalyst (succinate as internal donor, 2.5 wt.-% Ti) from Lyondell-Basell prepolymerised with vinylcyclohexane (VCH; before used in the poylmerisation process) used along with triethyl-aluminium (TEAL) as co-catalyst and dicyclo pentyl dimethoxy silane (D-donor) and diethylaminotriethoxysilane (CH.sub.3CH.sub.2).sub.2NSi(OCH.sub.2CH.sub.3).sub.3 (referred to as U-donor), respectively, as external donor (see table 1). The catalyst used in the polymerization process for the polypropylene of the comparative examples (CE1 to CE6) was the commercial Ziegler-Natta catalyst ZN168M catalyst (succinate as internal donor, 2.5 wt.-% Ti) from Lyondell-Basell not prepolymerised with vinylcyclohexane (before used in the polymerisation process) used along with triethyl-aluminium (TEAL) as co-catalyst and dicyclopentyl dimethoxysilane (D-donor) as external donor (see table 1).

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

(45) TABLE-US-00001 TABLE 1 a: Preparation of inventive propylene homopolymers IE1 IE2 IE3 IE4 IE5 Donor D D D + U* D + U* D + U* TEAL/Ti [mol/mol] 50 50 50 50 50 TEAL/Donor [mol/mol] 2 2 2 2 2 Donor/Ti [mol/mol] 25 25 25 25 25 Pre-polymerization temp [ C.] 45 45 45 45 65 time [min] 6 6 6 6 8 H2/C3 ratio [mol/kmol] 0.009 0.009 0.010 0.010 0 LOOP time [min] 25 25 25 25 30 temp [ C.] 75 75 75 75 75 split [wt.-%] 52.2 54.4 53 52.9 57.9 MFR.sub.2 [g/10] 537 537 632 632 n.a. H2/C3 [mol/kmol] 37.0 36.9 37.5 37.3 35.9 pressure [bar] 32 32 32 32 32 activity [kg PP/g cat h] 58.5 59.7 54.3 51.8 51.0 GPR1 time [min] 70 74 47 51 61 temp [ C.] 80 80 80 80 80 split [wt.-%] 34.8 35.3 34.1 34.3 30.1 MFR.sub.2 [g/10] 85.4 85.4 42.4 60.0 n.a. H2/C3 mol/kmol 66.1 66.1 37.7 49.4 54.7 pressure [bar] 32 32 32 32 32 activity [kg PP/g cat h] 14.1 12.5 18.6 16.4 14.0 GPR2 time [min] 242 179 167 167 190 temp [ C.] 80 80 80 80 70 split [wt.-%] 13.0 10.3 12.9 12.8 12.0 MFR.sub.2 [g/10] 10.sup.4 21 11 8 59 n.a H2/C3 mol/kmol 1.91 1.90 0.85 1.03 1.17 pressure [bar] 32 32 32 32 32 activity [kg PP/g cat h] 1.5 1.5 2.0 2.0 1.7 b: Preparation of comparative propylene homopolymers CE1 CE2 CE3 CE4 CE5 CE6 CE7 Donor D D D D D D + U* D TEAL/Ti [mol/mol] 250 250 250 250 250 250 250 TEAL/Donor [mol/mol] 5 5 5 5 5 5 5 Donor/Ti [mol/mol] 50 50 50 50 50 50 50 Pre-polymerization temp [ C.] 20 20 20 20 20 20 20 time [min] 6 6 6 6 6 6 6 H2/C3 ratio [mol/kmol] 0.22 0.22 0.22 0.22 0.22 0.22 0.22 LOOP time [min] 25 25 25 25 25 25 25 temp [ C.] 80 80 80 80 80 75 75 split [wt.-%] 58.8 57.5 54.3 57.0 57.3 55.6 56.4 MFR.sub.2 [g/10] 1003 550 415 550 550 489 503 H2/C3 [mol/kmol] 38.3 26.4 22.3 26.4 25.7 23.1 29.5 pressure [bar] 49.8 44.4 42.5 44.5 44.0 32 32 activity [kg PP/g cat h] 76.4 81.1 84.6 79.5 74.5 71.6 58.5 GPR1 time [min] 154 121 106 115 111 161 157 temp [ C.] 80 80 80 80 80 80 80 split [wt.-%] 36.1 36.8 36.2 36.4 38.2 38.5 38 MFR.sub.2 [g/10] 213 79 60 79 79 57 60 H2/C3 mol % 10 6.1 5.6 6.2 6.2 36.5 79.0 pressure [bar] 32 32 32 32 32 32 32 activity [kg PP/g cat h] 8.1 10.9 13.3 12.0 11.5 8.4 6.3 GPR2 time [min] 161 173 136 140 243 215 265 temp [ C.] 80 80 80 80 80 80 80 split [wt.-%] 5.1 5.7 9.5 6.6 4.5 5.9 5.6 MFR.sub.2 [g/10] 10.sup.4 5.4 1.6 290 7 16.4 21 5 H2/C3 mol % 0.2 0.13 0.32 0.22 0.23 1.53 3.25 pressure [bar] 32 32 32 32 32 32 32 activity [kg PP/g cat h] 1.1 1.1 2.6 1.8 1.5 1.0 0.9 n.a. = not analyzed *molar ration of D/U is 3/7 n.d. = not detectable *molar ratio of D/U is 3/7

(46) TABLE-US-00002 TABLE 2 a: Properties of inventive propylene homopolymers (containing 0.15 wt.-% NA11 and 0.01 wt.-% pVCH) IE1 IE2 IE3 IE4 IE5 XCS [wt %] 4.0 4.4 4.4 4.7 4.5 MFR.sub.2 [g/10] 56 73 44 64 63 Mn [g/kmol] 10 10 11** 10** 10 Mw [g/kmol] 230 214 264** 232** 245 Mz [g/kmol] 2283 2112 3011** 2337** 2248 Mw/Mn [] 23.0 21.4 24** 23.** 24.5 Mz/Mw [] 9.9 9.9 11.4 10.1** 9.2 Mz/Mn [] 228.3 211.2 273.7** 233.7** 224.8 PI [Pa.sup.1] 31 24 33 36 31 eta*(0.05/300) [] 41.0 35.7 45.9 42.8 39.6 Tm [ C.] 165 164 164 163 164 Hc [J/g] 121 121 124 126 119 Tc [ C.] 132 132 131 132 132 2,1 e [%] n.d. n.d. n.d. n.d. n.d. mmmm [%] 96.3 96.3 95.8 95.7 96.1 Tg [ C.] 8 9.5 8 10 3 TM [MPa] 2460 2449 2683* 2631 2625 TSB [%] 2.27 2.13 2.85* 2.1 2.14 b: Properties of comparative propylene homopolymers (containing 0.15 wt-% NA11 and 0.01 wt.-% pVCH, CE7 does not contain pVCH) CE1 CE2 CE3 CE4 CE5 CE6 CE7 XCS [wt %] 4.4 3.9 3.7 3.9 4.0 3.9 3.2 MFR.sub.2 [g/10] 274 114 83 110 91 103 110 Mn [g/kmol] 6 8 8 7 12 12 12 Mw [g/kmol] 86 105 111 109 184 176 155 Mz [g/kmol] 825 829 753 931 1504 1735 1244 Mw/Mn [] 14.3 13.1 13.9 15.6 15.3 14.7 12.9 Mz/Mw [] 9.6 7.9 6.8 8.5 8.2 9.9 8.0 Mz/Mn [] 137.5 103.6 94.1 133 125.3 145 104 PI [Pa.sup.1] n.d. n.d. n.d. n.d. n.d. 10 n.d. *(0.05)/*(300) [] 7.6 9.8 9.7 11.7 12.8 11.8 9.7 Tm [ C.] 162 163 164 164 164 163 165 Tc [ C.] 134 134 134 134 132 130 127 2,1 e [%] n.d. n.d. n.d. n.d. n.d. n.d. n.d. mmmm [%] 96.2 96.0 96.5 96.3 96.7 95.4 96.9 Tg [ C.] 10 8 6 8 6 6 4 TM [MPa] 2318 2347 2299 2397 2391 2423 2336 TSB [%] 1.8 2.1 2.6 2.2 2.8 2.5 2.7 *moulding temp. 200 C. **measured on samples without nucleation with NA11 n.d. not detectable PI polydispersity index *(0.05)/*(300) complex viscosity ratio eta*(0.05 rad/sec)/eta*(300 rad/sec) TM tensile modulus TSB tensile strain at break NA11 2.2-methylenebis (4.6.-di-tert-butylphenyl) phosphate pVCH polyvinylcyclohexane

(47) TABLE-US-00003 TABLE 3a a: SIST data of the inventive propylene homopolymers homopolymers (containing 0.15 wt-% NA11 and 0.01 wt.-% pVCH) IE1 IE2 IE3 IE4 IE5 Temp. Range/ C. [wt %] [wt %] [wt %] [wt %] [wt %] 90-100 0 0 0 0 0 100-110 0.04 0.03 0.2 0.09 0.06 110-120 0.36 0.34 0.59 0.39 0.33 120-130 1.01 0.98 1.31 1.07 0.95 130-140 2.04 2.01 2.39 2.08 1.96 140-150 4.47 4.45 4.78 4.49 4.29 150-160 14.16 14.23 13.07 13.94 13.86 160-170 59.11 60.32 53.52 57.99 57.96 170-180 18.83 17.61 24.07 19.86 20.57 180- SIST ratio 3.53 3.54 3.47 3.53 3.66 b: SIST data of the comparative propylene homopolymers (containing 0.15 wt-% NA11 and 0.01 wt.-% pVCH, CE7 does not contain pVCH) CE1 CE2 CE3 CE4 CE5 CE6 CE7 Temp. Range/ C. [wt %] [wt %] [wt %] [wt %] [wt %] [wt %] [wt %] 90-100 0 0.04 0.15 0 n.d 0.19 0 100-110 0.03 0.09 0.21 0 n.d 0.27 0.02 110-120 0.39 0.42 0.54 0.27 n.d 0.56 0.28 120-130 1.12 1.11 1.19 0.95 n.d 1.18 0.88 130-140 2.32 2.20 2.24 1.99 n.d 2.04 1.81 140-150 4.89 4.60 4.64 4.41 n.d 4.3 3.94 150-160 15.09 14.06 14.30 14.03 n.d 13.33 12.37 160-170 65.54 57.09 56.88 58.97 n.d 57.29 56.04 170-180 10.62 20.39 19.81 19.38 n.d 20.76 24.64 180- 0.05 SIST ratio 3.19 3.44 3.29 3.62 n.d 4.18 3.56 SIST ratio: the weight ratio of the crystalline fractions melting in the temperature range of above 160 to 180 C. to the crystalline fractions melting in the temperature range of 90 to 160 [(>160-180)/(90-160)]