Heterophasic copolymers

Abstract

A heterophasic polypropylene resin comprising a polypropylene homopolymer matrix phase (A) and an ethylene-propylene copolymer phase (B) dispersed within the matrix, wherein the xylene soluble fraction of the heterophasic polypropylene resin is in the range 20 to less than 50 wt %; the heterophasic polypropylene resin has an MFR2 of 0.01 to 50 g/10 min; the ethylene content of the xylene soluble fraction of the heterophasic polypropylene resin is in the range of at least 20 wt % to less than 50 wt %; the heterophasic polypropylene resin has a notched charpy impact strength at 20 C of at least 25 kJ/m.sup.2, preferably at least 50 kJ/m.sup.2; and wherein the MFR.sub.2 (Matrix)/MFR.sub.2(XS)5, preferably 10.

Claims

1. A heterophasic polypropylene resin comprising an asymmetrical metallocene-produced polypropylene homopolymer phase (A) and an asymmetrical metallocene-produced ethylene-propylene copolymer phase (B) dispersed within the phase (A), wherein the same asymmetrical metallocene catalyst is used to produce the phase (A) and the phase (B), and wherein the xylene soluble (XS) fraction of the heterophasic polypropylene resin is in the range 20 to less than 50 wt %; the heterophasic polypropylene resin has an MFR.sub.2 of 0.05 to 2 g/10 min; the ethylene content of the xylene soluble fraction of the heterophasic polypropylene resin is in the range of at least 20 wt % to less than 50 wt %; the MFR.sub.2 (xylene insoluble) is 0.2 g/10 min or less; the MFR.sub.2 (XS)/MFR.sub.2 (xylene insoluble) 350; and wherein the heterophasic polypropylene resin has a notched Charpy impact strength at 20 C. that is at least 75 kJ/m.sup.2.

2. The heterophasic polypropylene resin of claim 1, wherein the MFR.sub.2 (XS)/MFR.sub.2(xylene insoluble)500.

3. The heterophasic polypropylene resin of claim 1, wherein the brittle-to-ductile transition temperature BDTT is less than 25 C.

4. The heterophasic polypropylene resin of claim 1, wherein the notched Charpy impact strength at 20 C. is at least 90 kJ/m.sup.2.

5. The heterophasic polypropylene resin of claim 1, wherein the heterophasic polypropylene resin comprises 25 to 45 wt % XS content.

6. The heterophasic polypropylene resin of claim 1, having a tensile modulus of 50 to 800 MPa.

7. An article comprising the heterophasic polypropylene resin of claim 1.

8. A polymer blend comprising the heterophasic polypropylene copolymer as claimed in claim 1 and a second different polyolefin.

Description

(1) The invention will now be illustrated by reference to the following non-limiting examples and figures. The scope of the invention includes heterophasic polypropylene resins as hereinbefore defined, e.g. in the claims, except those recited in examples 1 to 3 below. The scope of the invention includes heterophasic polypropylene resins as hereinbefore defined, e.g. in the claims, including those recited in examples 1 to 3 below. The invention also provides the examples below as specific embodiments of the invention.

(2) FIG. 1 shows brittle-to-ductile transition curves for SSC-based inventive and comparative examples.

ANALYTICAL TESTS

(3) Measurement Methods:

(4) Al and Zr Determination (ICP-Method)

(5) The elementary analysis of a catalyst was performed by taking a solid sample of mass, M, cooling over dry ice. Samples were diluted up to a known volume, V, by dissolving in nitric acid (HNO.sub.3, 65%, 5% of V) and freshly deionised (DI) water (5% of V). The solution was then added to hydrofluoric acid (HF, 40%, 3% of V), diluted with DI water up to the final volume, V, and left to stabilise for two hours.

(6) The analysis was run at room temperature using a Thermo Elemental iCAP 6300 Inductively Coupled Plasma-Optical Emmision Spectrometer (ICP-OES) which was calibrated using a blank (a solution of 5% HNO.sub.3, 3% HF in DI water), and 6 standards of 0.5 ppm, 1 ppm, 10 ppm, 50 ppm, 100 ppm and 300 ppm of Al, with 0.5 ppm, 1 ppm, 5 ppm, 20 ppm, 50 ppm and 100 ppm of Hf and Zr in solutions of 5% HNO3, 3% HF in DI water.

(7) Immediately before analysis the calibration is resloped using the blank and 100 ppm Al, 50 ppm Hf, Zr standard, a quality control sample (20 ppm Al, 5 ppm Hf, Zr in a solution of 5% HNO3, 3% HF in DI water) is run to confirm the reslope. The QC sample is also run after every 5th sample and at the end of a scheduled analysis set.

(8) The content of hafnium was monitored using the 282.022 nm and 339.980 nm lines and the content for zirconium using 339.198 nm line. The content of aluminium was monitored via the 167.079 nm line, when Al concentration in ICP sample was between 0-10 ppm (calibrated only to 100 ppm) and via the 396.152 nm line for Al concentrations above 10 ppm.

(9) The reported values are an average of three successive aliquots taken from the same sample and are related back to the original catalyst by inputting the original mass of sample and the dilution volume into the software.

(10) DSC Analysis

(11) The melting point (T.sub.m) and crystallization temperature (T.sub.c) were determined on a DSC200 TA instrument, by placing a 5-7 mg polymer sample, into a closed DSC aluminum pan, heating the sample from 10 C. to 210 C. at 10 C./min, holding for 5 min at 210 C., cooling from 210 C. to 10 C., holding for 5 min at 10 C., heating from 10 C. to 210 C. at 10 C./min. The reported T.sub.m is the maximum of the curve from the second heating scan and T.sub.c is the maximum of the curve of the cooling scan.

(12) Melt Flow Rate

(13) The melt flow rate (MFR) is determined according to ISO 1133 and is indicated in g/10 min. The MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR is determined at 230 C. and may be determined at different loadings such as 2.16 kg (MFR.sub.2) or 21.6 kg (MFR.sub.21).

(14) The MFR of the XS fraction can also be calculated from the intrinsic viscosity (IV) of said fraction using the correlations defined in C. Grein, M. Gahleitner, B. Knogler & S. Nestelberger, Melt viscosity effects in Ethylene-Propylene Copolymers, Rheol. Acta, 46 (2007) 1083-1089. From the MFR of the total polymer and the MFR of the XS fraction, the MFR of the matrix component of an impact copolymer can be calculated using a logarithmic mixing rule, i.e. assuming the validity of the following equation:
MFR(Total)=10.sup.(1-w(EPR))log 10(MFR(Matrix))+w(EPR)log 10(MFR(XCS)
with w(EPR) being the weight fraction of the elastomeric phase, approximated by the weight fraction of the XS.

(15) Intrinsic viscosity is measured according to DIN ISO 1628/1 and /3, October 1999 (in Decalin at 135 C.). The intrinsic viscosity (IV) value increases with the molecular weight of a polymer.

(16) Glass Transition Temperature

(17) 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.

(18) GPC:

(19) Molecular weight averages, molecular weight distribution, and polydispersity index (M.sub.n, M.sub.w, M.sub.w/M.sub.n)

(20) Molecular weight averages (Mw, Mn), Molecular weight distribution (MWD) and its broadness, described by polydispersity index, PDI=Mw/Mn (wherein Mn is the number average molecular weight and Mw is the weight average molecular weight) were determined by Gel Permeation Chromatography (GPC) according to ISO 16014-4:2003 and ASTM D 6474-99. A Waters GPCV2000 instrument, equipped with differential refractive index detector and online viscosimeter was used with 2GMHXL-HT and 1G7000HXL-HT TSK-gel columns from Tosoh Bioscience and 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) as solvent at 140 C. and at a constant flow rate of 1 mL/min. 209.5 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 1 kg/mol to 12 000 kg/mol. Mark Houwink constants for PS, PE and PP used are as per ASTM D 6474-99. All samples were prepared by dissolving 0.5-4.0 mg of polymer in 4 mL (at 140 C.) of stabilized TCB (same as mobile phase) and keeping for max. 3 hours at max. 160 C. with continuous gentle shaking prior sampling into the GPC instrument.

(21) Determination of Xylene Soluble Fraction (XS):

(22) The xylene soluble fraction (XS) as defined and described in the present invention is determined as follows: 2.0 g of the polymer were dissolved in 250 ml p-xylene at 135 C. under agitation. After 30 minutes, the solution was allowed to cool for 15 minutes at ambient temperature and then allowed to settle for 30 minutes at 250.5 C. The solution was filtered with filter paper into two 100 ml flasks. The solution from the first 100 ml vessel was evaporated in nitrogen flow and the residue dried under vacuum at 90 C. until constant weight is reached. The xylene soluble fraction (percent) can then be determined as follows:
XS %=(100m1v0)/(m0v1),
wherein m0 designates the initial polymer amount (grams), m1 defines the weight of residue (grams), v0 defines the initial volume (milliliter) and v1 defines the volume of the analysed sample (milliliter).
Ethylene Content (FTIR C.sub.2)

(23) Ethylene content was measured with Fourier transform infrared spectroscopy (FTIR) calibrated to results obtained by .sup.13C NMR spectroscopy using a method which accounts for regio-irregular propene insertion. When measuring the ethylene content in polypropylene, a thin film of the sample (thickness about 0.220 to 0.250 mm) was prepared by hotpressing at 230 C. (preheat 5 min., press 1 min., cooling (cold water) 5 min.) using a Graseby Specac press. The FTIR spectra of the sample was recorded immediately with Nicolet Protg 460 spectrometer from 4000 to 400 cm.sup.1, resolution 4 cm.sup.1, scans 64. The area of absorption peak at 733 cm.sup.1 (baseline from 700 cm.sup.1 to 760 cm.sup.1) and height of reference peak at 809 cm.sup.1 (baseline from 780 cm.sup.1 to 880 cm.sup.1) were evaluated. The result was calculated using the following formula
E.sub.tot=aA/R+b where A=area of absorption peak at 733 cm.sup.1 R=height of reference peak at 809 cm.sup.1 E.sub.tot=C2 content (wt.-%) a, b are calibration constants determined by correlation of multiple calibration standards of know ethylene content as determined by .sup.13C NMR spectroscopy to A/R.

(24) The result was reported as an average of two measurements.

(25) DMTA

(26) The dynamic-mechanical analysis (DMTA) data are obtained according to ISO 6721-1 (General principles) & 6721-7 (Torsional vibration-Non-resonance method)

(27) Experimental Setup:

(28) A Rheometric scientific ARES rheometer, equipped with a liquid nitrogen unit and an oven (convection and radiation heating), a standard torsion rectangular tool and a software orchestrator V6.5.8, or Anton Paar MCR301 rheometer with a TC30 temperature control unit combined with a liquid nitrogen unit and an CTD600 oven (convection and radiation heating) a standard torsion rectangular tool and a software RHEOPLUS/32 v3.40 are used.

(29) Sample Preparation

(30) Stabilized dry pellets are compression molded at 210 C. (gel time 5 min, pressure time 25 bar/3 min, cooling rate 25 bar/15K/min, de-molding temperature 40 C.) in a 100*100*1 mm mould. Only from homogeneous, bubble free plates are punched to 50101 mm stripes and are conditioned at least 96 hours at room temperature.

(31) Conducting the Experiment:

(32) The device is cooled with the clamped sample to the initial temperature (standard 130 C.). After 5 min delay time the experiment is started with a test frequency of 1 Hz, a heating rate of 2K/min and a strain of 0.1%. The measurements are carried out under inert atmosphere (nitrogen) and a tension (vertically) force of 50 g (+/20 g).

(33) Temperature dependence of storage modulus G, loss modulus G, and loss angle tangent tan() are used for evaluations.

(34) Determinations of transition sections (e.g. glass transition temperature, T.sub.g) is based on the loss tangent tan() vs. temperature curve (peak of the curve).

(35) Number of specimen: 1. Precision: +/5%, temperature values: +/1.5K

(36) Charpy Notched Impact Strength

(37) Charpy impact strength was determined according to ISO 179-1eA:2000 on V-notched samples of 80104 mm.sup.3 at 23 C. (Charpy impact strength (23 C.)) and 20 C. (Charpy impact strength (20 C.)). A standard impact velocity of 2.9 m/s was used.

(38) The test specimens having a dimension of 80104 mm.sup.3 were cut from the central part of ISO multibar specimens prepared by injection moulding in line with ISO 1872-2.

(39) Brittle-to-Ductile Transition Temperature

(40) The determination of the brittle-to-ductile transition temperature (BDTT) is based on the a(cN) values as determined from Charpy instrumented impact strength according to ISO 179-2:2000 on V-notched specimen with a geometry of 80104 mm3 as required in ISO 179-1eA.

(41) The a(cN) values are determined in intervals of 3 C. from 40 C. to +41 C. with an impact velocity of 1.5 m/s and plotted over temperature, calculating the BDTT as the average value of the step increase. For a detailed description of the determination of the BDTT reference is made to Grein, C. et al, Impact Modified Isotactic Polypropylene with Controlled Rubber Intrinsic Viscosities: Some New Aspects About Morphology and Fracture, J Appl Polymer Sci, 87 (2003), 1702-1712.

(42) Tensile Modulus and Strain at Break

(43) Tensile properties were determined according to ISO 527-2 (cross head speed=50 mm/min; 23 C.) using injection moulded specimens as described in EN ISO 1873-2 (dog bone shape, 4 mm thickness).

EXAMPLES

Chemicals

(44) All the chemicals and chemical reactions were handled under an inert gas atmosphere using Schlenk and glovebox techniques, with oven-dried glassware, syringes, needles or cannulas.

(45) MAO was purchased from Albermarle and used as a 30 wt-% solution in toluene. Perfluoroalkylethyl acrylate ester mixture (CAS number 65605-70-1) was purchased from the Cytonix corporation, dried over activated molecular sieves (2 times) and degassed by argon bubbling prior to use. Hexadecafluoro-1,3-dimethylcyclohexane (CAS number 335-27-3) was obtained from commercial sources and dried over activated molecular sieves (2 times) and degassed by argon bubbling prior to use. Triethylaluminum was purchased from Crompton and used in pure form. Hydrogen is provided by AGA and purified before use. Propylene is provided by Borealis and adequately purified before use.

(46) 1-tert-Butyl-2-methoxybenzene was synthesized via alkylation of 2-tert-butylphenol (Acros) by dimethylsulfate (Merck) in the presence of aqueous NaOH (Reachim, Russia) as described in [Stork, G.; White, W. N. J. Am. Chem. Soc. 1956, 78, 4604.]. 2-Methyl-4-bromo-6-tert-butylindanone-1 was obtained as described in the literature [Resconi, L.; Nifant'ev, I. E.; Ivchenko, P. V.; Bagrov, V.; Focante, F.; Moscardi, G. Int. Pat. Appl. WO2007/107448 A1].

(47) 7-Bromo-5-tert-butyl-2-methyl-1H-indene was obtained from 2-methyl-4-bromo-6-tert-butylindanone-1 as described in [Voskoboynikov, A. Z.; Asachenko, A. F.; Kononovich, D. S.; Nikulin M. V.; Tsarev, A. A.; Maaranen, J.; Vanne, T.; Kauhanen, J.; Mansner, E.; Kokko, E.; Saarinen, L. Int. Pat. Appl. WO2009/027075].

(48) Bis(2,6-diisopropylphenyl)imidazolium chloride, i.e. IPr(HCl), and (IPr)NiCl.sub.2(PPh.sub.3) were synthesized as described in [Hintermann, L. Beilstein J. Org. Chem. 2007, 3, 1.] and [Matsubara, K.; Ueno, K.; Shibata, Y. Organometallics 2006, 25, 3422.], respectively.

(49) 4/7-Bromo-2-methyl-3/1/H-indene was obtained as described in [Izmer, V. V.; Lebedev, A. Y.; Nikulin, M. V.; Ryabov, A. N.; Asachenko, A. F.; Lygin, A. V.; Sorokin, D. F.; Voskoboynikov, A. Z. Organometallics 2006, 25, 1217.].

(50) Anisole (Acros), 3-methylanisole (Acros), tert-Butyltoluene (Aldrich), 1-Bromo-4-tert-butylbenzene (Acros), P.sub.4O.sub.10 (Reachim), Pd(P.sup.tBu.sub.3).sub.2 (Strem), 1.0 M ZnCl.sub.2 in THF (Aldrich), 1.0 M 3,5-di-tert-butylphenylmagnesium bromide in THF (Aldrich), hexanes (Reachim, Russia), N-bromosuccinimide (Acros), diethyl methylmalonate (Aldrich), methyl iodide (Acros), acetone (Reachim, Russia), tetraethylammonium iodide (Acros), triphenylphosphine (Acros), CuCN (Merck), methanesulfonic acid (Aldrich), sodium tetraphenylborate (Aldrich), palladium acetate (Aldrich), copper cyanide (Merck), magnesium turnings (Acros), lithium aluminiumhydride (Aldrich), bromobenzene (Acros), 2.5 M .sup.nBuLi in hexanes (Chemetall), ZrCl.sub.4(THF).sub.2 (Aldrich), NaBH.sub.4 (Aldrich), Ni(OAc).sub.2 (Aldrich), silica gel 60 (40-63 um, Merck), AlCl.sub.3 (Merck), bromine (Merck), benzoyl peroxide (Aldrich), iodine (Merck), NaHCO.sub.3 (Merck), Na.sub.2CO.sub.3 (Merck), K.sub.2CO.sub.3 (Merck), Na.sub.2SO.sub.4 (Merck), Na.sub.2SO.sub.3 (Merck), sodium metal (Merck), thionyl chloride (Merck), sodium acetate, trihydrate (Merck), tetraethylammonium iodide (Acros), triphenylphosphine (Acros), KOH (Merck), Na.sub.2SO.sub.4 (Akzo Nobel), TsOH (Aldrich), 12 M HCl (Reachim, Russia), methanol (Merck), anhydrous ethanol (Merck), CDCl.sub.3 and DMSO-d.sub.6 (Deutero GmbH) as well as hexanes (Merck), carbon tetrachloride (Merck), ether (Merck), ethyl acetate (Merck), toluene (Merck) and CH.sub.2Cl.sub.2 (Merck) for extractions were used as received.

(51) Tetrahydrofurane (Merck), ether (Merck), and dimethoxyethane (Acros) freshly distilled from benzophenone ketyl were used. Dichloromethane (Merck) for organometallic synthesis as well as CD.sub.2Cl.sub.2 (Deutero GmbH) for NMR experiments were dried and kept over CaH.sub.2. Toluene (Merck), n-octane (Merck), and hexanes (Merck) for organometallic synthesis were kept and distilled over Na/K alloy. Dichlorodimethylsilane (Merck) and methacrylic acid (Acros) were distilled before use.

Rac-methyl(cyclohexyl)silanediylbis[2-methyl-4-(4-tert-butylphenyl)indenyl]zirconium dichloride (C1)

(52) ##STR00020##

(53) was purchased from a commercial source.

Rac-dimethylsilanediylbis(2-methyl-4-phenyl-5-methoxy-6-tert-butylindenyl) zirconium dichloride (C2)

(54) ##STR00021##

(55) was synthesized as described in WO 2007/116034.

Preparation of Example Metallocene Complexes

Synthesis of anti-Dimethylsilylene(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-phenyl-6-tert-butyl-indenyl)zirconium dichloride

Metallocene E1

6-tert-Butyl-5-methoxy-2-methylindan-1-one

(56) ##STR00022##

(57) To an Eaton's reagent obtained from 110 g of P.sub.4O.sub.10 and 560 ml of methanesulfonic acid a mixture of 65.6 g (0.399 mol) of 1-tert-butyl-2-methoxybenzene and 43.0 g (0.50 mol) of methacrylic acid was added for ca. 1 h at 50-55 C. The resulting mixture was stirred for 1 h at this temperature, then cooled to room temperature, and poured on a mixture of 1 liter of cold water and 1 kg of ice. The crude product was extracted with 3500 ml of dichloromethane. The combined organic extract was washed by aqueous K.sub.2CO.sub.3 and then evaporated to dryness. Fractional rectification of the residue gave 64.9 g of yellowish oil which crystallizes at room temperature. On the evidence of NMR spectroscopy, this product includes ca. 90% of the target material. Further on, this product was dissolved in 180 ml of hot hexanes. Crystals precipitated from this solution at room temperature were collected, washed by 100 ml of cold hexanes, and dried in vacuum. This procedure gave 39.6 g (43%) of the analytically pure substituted indanone.

(58) Anal. calc. for C.sub.15H.sub.20O.sub.2: C, 77.55; H, 8.68. Found: C, 77.48; H, 8.79.

(59) .sup.1H NMR (CDCl.sub.3): 7.68 (s, 1H, 7-H in indanone), 6.87 (s, 1H, 4-H in indanone), 3.93 (s, 3H, OMe), 3.32 (m, 1H, 3-H in indanone), 2.69 (m, 1H, 2-H in indanone), 2.64 (m, 1H, 3-H in indanone), 1.37 (s, 9H, .sup.tBu), 1.29 (d, J=7.3 Hz, 3H, 2-Me in indanone). .sup.13C {.sup.1H} NMR (CDCl.sub.3): 208.1, 164.6, 154.4, 138.8, 128.7, 122.1, 107.8, 55.2, 42.1, 35.0, 34.7, 29.6, 16.6.

6-tert-Butyl-5-methoxy-2-methylindan-1-one (second experiment)

(60) To Eaton's reagent obtained from 118 g of P.sub.4O.sub.10 and 600 ml of methanesulfonic acid a mixture of 70.3 g (0.428 mol) of 1-tert-butyl-2-methoxybenzene and 295.0 g (3.43 mol, 8 eqv.) of methacrylic acid was added for ca. 1 h at 50-55 C. The resulting mixture was stirred for 0.5 h at this temperature, then cooled to room temperature, and poured on a mixture of 1.5 liter of cold water and 2 kg of ice. After the ice melts, the precipitated crude 6-tert-butyl-5-methoxy-2-methylindan-1-one was filtered off and then washed with 2100 ml of cold water. The crude product was dissolved in 500 ml of dichloromethane, and this solution was washed by aqueous K.sub.2CO.sub.3, dried over anhydrous K.sub.2CO.sub.3, and then evaporated on Rotavap. The residue was distilled in vacuum to give 70.6 g of crude 6-tert-butyl-5-methoxy-2-methylindan-1-one, b.p. 155-165 C./5 mm Hg. This product was dissolved in 200 ml of hot hexanes. Crystals precipitated from this solution at 5 C. were collected, washed by 50 ml of cold hexanes, and dried in vacuum. This procedure gave 64.1 g (65%) of the analytically pure substituted indanone.

4-Bromo-6-tert-butyl-5-methoxy-2-methylindan-1-one

(61) ##STR00023##

(62) To a mixture of 60.0 g (0.258 mol) of 6-tert-butyl-5-methoxy-2-methylindan-1-one, 130 g of NaOAc(H.sub.2O).sub.3, 1.5 g of Et.sub.4NI, 220 ml of dichloromethane, and 450 ml of water cooled to 5 C. 45.0 g (0.282 mol) of bromine was added for ca. 5 min by vigorous stirring. This mixture was stirred for 1 h at 5 C., and then a solution of 60.0 g of NaOAc(H.sub.2O).sub.3 in 200 ml of water was added. To the resulting mixture 23.5 (0.147 mmol) of bromine was added at 5 C. The resulting solution was stirred for 30 min and then Na.sub.2SO.sub.3 was added by small portions to remove an excess of bromine. The CH.sub.2Cl.sub.2-layer was separated from the top aqueous one and the latter was extracted with 2300 ml of dichloromethane. The combined organic extract was dried over K.sub.2CO.sub.3, passed through a short layer of silica gel 60 (40-63 um) and then evaporated to dryness. The residue was dried in vacuum to give 79.9 g (99%) of the title compound which was further used without an additional purification.

(63) Anal. calc. for C.sub.15H.sub.19BrO.sub.2: C, 57.89; H, 6.15. Found: C, 57.70; H, 6.08.

(64) .sup.1H NMR (CDCl.sub.3): 7.70 (s, 1H, 7-H in indanone), 4.03 (s, 3H, OMe), 3.31 (dd, J=17.4 Hz, J=7.8 Hz, 1H, 3-H in indanone), 2.72 (m, 1H, 2-H in indanone), 2.62 (dd, J=17.4 Hz, J=3.8 Hz, 1H, 3-H in indanone), 1.40 (s, 9H, .sup.tBu), 1.32 (d, J=7.6 Hz, 3H, 2-Me in indanone). .sup.13C {.sup.1H} NMR (CDCl.sub.3): 208.0, 162.8, 154.0, 145.5, 132.7, 121.5, 116.7, 61.7, 42.2, 36.1, 35.7, 30.6, 16.4.

6-tert-Butyl-5-methoxy-2-methyl-4-phenylindan-1-one

(65) ##STR00024##

(66) To a mixture of 46.7 g (0.150 mol) of 4-bromo-6-tert-butyl-5-methoxy-2-methylindan-1-one, 44.0 g (0.415 mol) of Na.sub.2CO.sub.3, 25.7 g (0.075 mol) of NaBPh.sub.4, 600 ml of DME, and 240 ml of water 1.01 g (4.50 mmol) of Pd(OAc).sub.2 and 2.36 g (9.00 mmol) of PPh.sub.3 were added. The resulting mixture was refluxed for 12 h, cooled to room temperature, and then evaporated to dryness. To the residue 1 liter of cold water was added, and the crude product was extracted with 3300 ml of dichloromethane. The combined organic extract was dried over K.sub.2CO.sub.3 and then evaporated to dryness. The product was isolated by flash chromatography on silica gel 60 (40-63 um; eluent: hexanes-dichloromethane-ether=20:10:1, vol.). Yield 46.0 g (99%) of yellowish crystalline solid.

(67) Anal. calc. for C.sub.21H.sub.24O.sub.2: C, 81.78; H, 7.84. Found: C, 81.90; H, 7.93.

(68) .sup.1H NMR (CDCl.sub.3): 7.76 (s, 1H, 7-H in indanone), 7.47 (m, 2H, 3,5-H in Ph), 7.42 (m, 2H, 2,6-H in Ph), 7.39 (m, 1H, 4-H in Ph), 3.29 (s, 3H, OMe), 3.13 (dd, J=17.4 Hz, J=7.8 Hz, 1H, 3-H in indanone), 2.63 (m, 1H, 2-H in indanone), 2.47 (dd, J=17.4 Hz, J=3.8 Hz, 1H, 3-H in indanone), 1.43 (s, 9H, .sup.tBu), 1.25 (d, J=7.3 Hz, 3H, 2-Me in indanone). .sup.13C {.sup.1H} NMR (CDCl.sub.3): 208.7, 163.5, 152.7, 143.5, 136.4, 132.5, 131.0, 129.5, 128.7, 127.5, 121.6, 60.5, 42.2, 35.4, 34.3, 30.5, 16.4.

6-tert-Butyl-5-methoxy-2-methyl-4-phenylindan-1-one (second experiment)

(69) To a mixture of 46.7 g (0.150 mol) of 4-bromo-6-tert-butyl-5-methoxy-2-methylindan-1-one, 44.5 g (0.420 mol) of Na.sub.2CO.sub.3, 22.0 g (0.180 mol) of PhB(OH).sub.2, 570 ml of DME, and 195 ml of water 0.674 g (3.0 mmol) of Pd(OAc).sub.2 and 1.58 g (6.00 mmol) of PPh.sub.3 were added. The resulting mixture was refluxed for 12 h, cooled to room temperature, and then DME was evaporated on Rotavap. To the residue 1 liter of cold water was added, and the crude product was extracted with 3300 ml of dichloromethane. The combined organic extract was dried over K.sub.2CO.sub.3 and then evaporated to dryness. The residue after evaporation was extracted with hot hexane (500 ml, then 3250 ml) and this extracts while hot were passed through a short pad of silicagel, evaporated on Rotavap to yield 45.1 g (98%) of 6-tert-butyl-5-methoxy-2-methyl-4-phenylindan-1-one as a slightly yellowish crystalline solid which was further used without an additional purification.

5-tert-Butyl-6-methoxy-2-methyl-7-phenyl-1H-indene

(70) ##STR00025##

(71) To a solution of 45.9 g (0.149 mmol) of 6-tert-butyl-5-methoxy-2-methyl-4-phenylindan-1-one in 300 ml of THF cooled to 5 C. 8.51 g (0.225 mol) of NaBH.sub.4 was added. Further on, 150 ml of methanol was added dropwise to this mixture by vigorous stirring for ca. 7 h at 5 C. The resulting mixture was stirred overnight at room temperature, and then 1 liter of cold water and 12 M HCl to pH1 were added. The crude product was extracted with 3200 ml of dichloromethane, the combined organic extract was dried over K.sub.2CO.sub.3 and then evaporated to dryness. To a solution of the residue in 800 ml of toluene 1.0 g of TsOH was added, this mixture was refluxed with Dean-Stark head for 10 min and then cooled to room temperature using water bath. The resulting solution was washed by 10% aqueous Na.sub.2CO.sub.3, the organic layer was separated, the aqueous layer was extracted with 250 ml of dichloromethane. The combined organic solution was dried over K.sub.2CO.sub.3 and then passed through short layer of silica gel 60 (40-63 um). The silica gel layer was additionally washed by 100 ml of dichloromethane. The combined organic elute was evaporated to dryness. This procedure gave 43.1 g (99%) of yellowish oil which was further used without an additional purification.

(72) Anal. calc. for C.sub.21H.sub.24O: C, 86.26; H, 8.27. Found: C, 86.39; H, 8.37.

(73) .sup.1H NMR (CDCl.sub.3): 7.47-7.49 (m, 2H, 2,6-H in Ph), 7.43 (m, 2H, 3,5-H in Ph), 7.34 (m, 1H, 4-H in Ph), 7.22 (s, 1H, 4-H in indene), 6.44 (m, 1H, 3-H in indene), 3.22 (s, 3H, OMe), 3.12 (s, 2H, 1,1-H in indene), 2.06 (s, 3H, 2-Me in indene), 1.44 (s, 9H, .sup.tBu). .sup.13C{.sup.1H} NMR (CDCl.sub.3): 154.3, 145.3, 141.7, 141.0, 138.5, 131.6, 129.5, 128.3, 126.9, 126.8, 117.2, 60.7, 42.8, 35.2, 31.0, 16.6.

5-tert-Butyl-6-methoxy-2-methyl-7-phenyl-1H-indene (second experiment)

(74) To a solution of 44.3 g (0.144 mmol) of 6-tert-butyl-5-methoxy-2-methyl-4-phenylindan-1-one in 150 ml of THF cooled to 5 C. 2.72 g (71.9 mmol) of NaBH.sub.4 was added. Further on, 75 ml of methanol was added dropwise to this mixture by vigorous stirring for 1 h at 5 C. The resulting mixture was stirred additionally 1 h at 5 C., then 0.5 h at room temperature, and then added to 1 liter of cold water and 30 ml of 12 M HCl in separating funnel. The crude product was extracted consequentially with 250, 100 and 50 ml of dichloromethane, and the combined organic extract was evaporated to dryness. To a solution of the residue in 500 ml of toluene 1.0 g of TsOH was added, this mixture was refluxed with Dean-Stark head for 10 min and then cooled to room temperature using water bath. The resulting solution was washed by aqueous K.sub.2CO.sub.3 (20 g K.sub.2CO.sub.3 in 200 ml of H.sub.2O), the organic layer was separated, the aqueous layer was extracted with 250 ml of dichloromethane. The combined organic solution was dried over K.sub.2CO.sub.3 and then passed through short layer of silica gel 60 (40-63 um, ca. 10 g). The silica gel layer was additionally washed by 50 ml of dichloromethane. The combined organic elute was evaporated to dryness. This procedure gave 42.0 g (100%) of yellowish oil which was further used without an additional purification.

(6-tert-Butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)(chloro)dimethylsilane

(75) ##STR00026##

(76) To a solution of 16.2 g (55.4 mmol) of 5-tert-butyl-6-methoxy-2-methyl-7-phenyl-1H-indene in 300 ml of toluene, 22.2 ml (55.5 mmol) of 2.5 M .sup.nBuLi in hexanes was added at room temperature. The resulting viscous solution was stirred for 2 h, and then 15 ml of THF was added. The formed suspension was stirred for 12 h at room temperature, ca. 2 h at 60 C., then cooled to 20 C., and 35.8 g (277 mmol) of dichlorodimethylsilane was added in one portion. The resulting solution was warmed to 60 C. and stirred for 1 h at this temperature. The resulting mixture was evaporated to ca. of its volume, then filtered through glass frit (G3). The precipitate was additionally washed by 20 ml of toluene. The combined filtrate was evaporated to dryness to give 21.2 g (99%) of viscous yellowish oil.

(77) Anal. calc. for C.sub.23H.sub.29ClOSi: C, 71.75; H, 7.59. Found: C, 71.92; H, 7.80.

(78) .sup.1H NMR (CDCl.sub.3): 7.52-7.54 (m, 2H, 2,6-H in Ph), 7.48 (m, 2H, 3,5-H in Ph), 7.45 (s, 1H, 7-H in indenyl), 7.38 (m, 1H, 4-H in Ph), 6.49 (m, 1H, 3-H in indenyl), 3.59 (m, 1H, 1-H in indenyl), 3.27 (s, 3H, OMe), 2.23 (m, 3H, 2-Me in indenyl), 1.48 (s, 9H, .sup.tBu), 0.47 (s, 3H, SiMeMe), 0.22 (s, 3H, SiMeMe). .sup.13C {.sup.1H} NMR (CDCl.sub.3): 155.8, 146.2, 143.7, 138.2, 137.6, 137.0, 130.2, 128.3, 127.4, 126.7, 126.5, 121.1, 60.5, 50.1, 35.2, 31.2, 17.6, 1.1, 0.6.

5-tert-Butyl-2-methyl-7-phenyl-1H-indene

(79) ##STR00027##

(80) To a solution of PhMgBr obtained from 89.0 g (567 mmol) of bromobenzene, 15.8 g (650 mmol) of magnesium turnings and 450 ml of THF, 1.60 g (3.76 mmol) of bis(2,6-diisopropylphenyl)imidazolium chloride, i.e. IPr(HCl) and 0.66 g (3.76 mmol) of Ni(OAc).sub.2 were added. Further on, a solution of 50.0 g (189 mmol) of 7-bromo-5-tert-butyl-2-methyl-1H-indene in 50 ml of THF was added. The resulting mixture was stirred for 2 h at room temperature, refluxed for 1 h, cooled to ambient temperature, and then 200 ml of water was added dropwise. Finally, 100 ml of 12 M HCl was added dropwise. The product was extracted with 300 ml of ether. The organic layer was separated, and the aqueous layer was additionally extracted with 2150 ml of dichloromethane. The combined organic extract was dried over K.sub.2CO.sub.3, passed through a short layer of silica gel 60 (40-63 um), and then evaporated to dryness. Fractional rectification of the residue gave 34.7 g (70%) of viscous yellow oil, b.p. 180-210 C./5 mm Hg. The product is a ca. 1 to 1 mixture of 6-tert-butyl-2-methyl-4-phenyl-1H-indene and 5-tert-butyl-2-methyl-7-phenyl-1H-indene.

(81) Anal. calc. for C.sub.20H.sub.22: C, 91.55; H, 8.45. Found: C, 91.61; H, 8.50.

(82) .sup.1H NMR (CDCl.sub.3): 7.52 (m, 4H), 7.40-7.43 (m, 6H), 7.29-7.33 (m, 3H), 7.17 (m, 1H), 6.62 (m, 1H), 6.50 (m, 1H), 3.32 (s, 4H), 2.10 (s, 6H), 1.37 (s, 9H), 1.36 (s, 9H).

(6-tert-Butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)-(6-tert-butyl-2-methyl-4-phenyl-1H-inden-1-yl)dimethylsilane

(83) ##STR00028##

(84) To a solution of 14.5 g (55.4 mmol) of 5-tert-butyl-2-methyl-7-phenyl-1H-indene in 400 ml of ether cooled to 78 C., 22.2 ml (55.5 mmol) of 2.5 M .sup.nBuLi in hexanes was added. This mixture was stirred overnight at room temperature, then cooled to 78 C., and 200 mg (2.23 mmol) of CuCN was added. The resulting mixture was stirred for 30 min at 20 C., then cooled to 78 C., and a solution of 21.2 g (55.4 mmol) of (6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)(chloro)dimethylsilane in 200 ml of ether was added. This mixture was stirred overnight at room temperature, then 1 ml of water was added. The obtained mixture was passed through a short layer of silica gel 60 (40-63 um), the elute was evaporated to dryness. The product was isolated by flash-chromatography on silica gel 60 (40-63 um; eluent: hexanes-dichloromethane=10:1, vol., then 3:1, vol.). This procedure gave 24.5 g (72%) of yellowish glassy solid.

(85) Anal. calc. for C.sub.43H.sub.50OSi: C, 84.54; H, 8.25. Found: C, 84.69; H, 8.34.

(86) .sup.1H NMR (CDCl.sub.3): 7.35-7.62 (m), 6.81 (s), 6.75 (s), 6.63 (s), 6.45 (s), 3.73 (s), 3.71 (s), 3.70 (s), 3.30 (s), 2.23 (s), 2.22 (s), 2.15 (s), 2.08 (s), 1.50 (s), 1.49 (s), 1.43 (s), 1.42 (s), 0.06 (s), 0.06 (s), 0.07 (s), 0.08 (s), 0.12 (s).

Anti-Dimethylsilylene(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-phenyl-6-tert-butyl-indenyl)zirconium dichloride (metallocene E1)

(87) ##STR00029##

(88) To a solution of 7.64 g (12.5 mmol) of (6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1-inden-1-yl)(6-tert-butyl-2-methyl-4-phenyl-1H-inden-1-yl) dimethylsilane in 200 ml of ether cooled to 78 C., 10.0 ml (25.0 mmol) of 2.5 M .sup.nBuLi in hexanes was added. The resulting mixture was stirred overnight at room temperature, then cooled to 78 C., and 4.72 g (12.5 mmol) of ZrCl.sub.4(THF).sub.2 was added. This mixture was stirred for 24 h at room temperature. On the evidence of NMR spectroscopy, this mixture included anti and syn zirconocenes in ratio equal to ca. 70:30. This mixture was filtered through glass frit (G4), the filtrate was evaporated to dryness. The residue was dissolved in a mixture of 60 ml of n-octane and 15 ml of toluene at reflux. Crystals precipitated from this solution at 30 C. were collected, washed by 210 ml of cold hexanes, and dried in vacuum. This procedure gave 1.97 g (20%) of pure racemic-anti zirconocene. Additional amount of this product was obtained in similar manner from the mother liquid. Thus, the combined yield of the product was 3.54 g (37%) as yellowish-orange crystalline solid.

(89) Anal. calc. for C.sub.43H.sub.48Cl.sub.2OSiZr: C, 66.98; H, 6.27. Found: C, 67.09; H, 6.33.

(90) .sup.1H NMR (CDCl.sub.3): 7.28-7.70 (m, 13H, 7-H and 5,7-H in indenyls and Ph), 6.94 (s, 1H, 3-H in indenyl), 6.60 (s, 1H, 3-H in indenyl), 3.41 (s, 3H, OMe), 2.26 (s, 3H, 2-Me in indenyl), 2.23 (s, 3H, 2-Me in indenyl), 1.42 (s, 9H, .sup.tBu), 1.36 (s, 3H, SiMeMe), 1.35 (s, 9H, .sup.tBu), 1.34 (s, 3H, SiMeMe).

Synthesis of anti-dimethylsilylene(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butyl-phenyl)indenyl)zirconium dichloride

Metallocene E2

4/7-(4-tert-Butylphenyl)-2-methyl-3/1H-indene

(91) ##STR00030##

(92) To a solution of 4-tert-butylphenylmagnesium bromide obtained from 110 g (0.518 mol) of 1-bromo-4-tert-butylbenzene and 12.6 g (0.518 mol) of magnesium turnings in 500 ml of THF, 0.65 g (0.83 mmol) (IPr)NiCl.sub.2PPh.sub.3 and a solution of 77.6 g (0.371 mol) of 4/7-bromo-2-methyl-3/1H-indene in 50 ml of THF were added. This mixture was stirred at reflux for 30 min, and then for 20 min at room temperature. Finally, 150 ml of water and then 70 ml of 4 M HCl were added. The product was extracted with 200 ml of ether and then 2100 ml of dichloromethane. The combined organic extract was dried over K.sub.2CO.sub.3, passed through a short column with Silica Gel 60, and evaporated to dryness. Rectification of the residue, b.p. 163-171 C./5 mm Hg, gave 93.8 g (96%) of a mixture of the title isomeric indenes as yellowish viscous oil which is slowly crystallized.

(93) Anal. calc. for C.sub.20H.sub.22: C, 91.55; H, 8.45. Found: C, 91.62; H, 8.52.

(94) .sup.1H NMR (CDCl.sub.3): 7.62 (m, C.sub.6H.sub.4 of both isomers), 7.46 (m, 5- and 6-H in 4- and 7-arylindenes), 7.40 (m, 7- and 4-H in 4- and 7-arylindenes), 7.31 (m, 6- and 5-H in 4- and 7-arylindenes), 6.88 (m, 3-H in 4/7-arylindene), 6.68 (m, 3-H in 7/4-arylindene), 3.55 (m, 1-CH.sub.2 in 7/4-arylindene), 3.49 (m, 1-CH.sub.2 in 4/7-arylindene), 2.28 (2-Me in 4/7-arylindene), 2.27 (2-Me in 7/4-arylindene), 1.54 (s, .sup.tBu in 4- and 7-arylindenes).

(6-tert-Butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)[4-(4-tert-butylphenyl)-2-methyl-1H-inden-1-yl]dimethylsilane

(95) ##STR00031##

(96) To a solution of 11.5 g (43.8 mmol) of 7-(4-tert-butylphenyl)-2-methyl-1H-indene in 300 ml of ether, 17.0 ml (42.5 mmol) of 2.5 M .sup.nBuLi in hexanes was added in one portion at 78 C. This mixture was stirred overnight at room temperature, then cooled to 60 C., and 150 mg of CuCN was added. The resulting mixture was stirred for 1 h at 20 C., then cooled to 70 C., and 16.2 g of (6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)(chloro)-dimethylsilane (42.08 mmol) in 150 ml of ether was added. Further on, this mixture was stirred overnight at ambient temperature, then 0.5 ml of water was added. This solution was filtered through a pad of silica gel 60 (40-63 um) which was additionally washed by dichloromethane. The combined organic elute was evaporated to dryness, and the obtained yellowish oil was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-dichloromethane, from 10:1 to 3:1, vol.). This procedure gave 23.4 g (91%) of the title compound as yellowish glass.

(97) Anal. Calcd. for C.sub.43H.sub.50OSi: C, 84.54; H, 8.25%. Found: C, 84.70; H, 8.33%.

(98) .sup.1H NMR (CDCl.sub.3): 7.59-7.18 (m), 6.89 (m), 6.83 (m), 6.51 (m), 6.48 (m), 3.77 (m), 3.73 (m), 3.68-3.70 (m), 3.31 (s), 3.29 (s), 2.25 (s), 2.23 (s), 2.16 (s), 2.10 (s), 1.50 (s), 1.48 (s), 1.45 (s), 1.44 (s), 0.00 (s), 0.09 (s), 0.11 (s), 0.12 (s).

Anti- and syn-dimethylsilylene(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butyl-phenyl)indenyl)zirconium dichloride

(99) ##STR00032##

(100) To a solution of 15.3 g (25.0 mmol) of (6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)[4-(4-tert-butylphenyl)-2-methyl-1H-inden-1-yl]dimethylsilane in 300 ml of ether cooled to 78 C., 20.0 ml (50.0 mmol) of 2.5 M .sup.nBuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then cooled to 60 C., and 9.43 g (25.0 mmol) of ZrCl.sub.4(THF).sub.2 was added. The resulting mixture was stirred for 24 h (a light orange solution with a significant amount of precipitate was formed), then evaporated to dryness, and 350 ml of toluene was added. The resulting solution warmed to 80 C. was filtered through glass frit (G4) to form on the evidence of NMR spectroscopy a ca. 1 to 1 mixture of anti- and syn-zirconocenes. Crystals precipitated overnight from this solution at room temperature were collected, washed by 210 ml of cold toluene, and dried in vacuum. This procedure gave 3.50 g of pure syn-zirconocene as a light-orange microcrystalline powder. The mother liquor was evaporated to ca. 100 ml. Crystals precipitated overnight from this solution at room temperature were collected, washed with 10 ml of cold toluene, and dried in vacuum. This procedure gave additional amount (4.10 g) of pure syn-zirconocene. Thus, the combined yield of pure syn-zirconocene was 7.60 g (39%) as a light-orange microcrystalline powder. Crystals precipitated after 3 days at room temperature were collected, washed by 10 ml of cold toluene, and dried in vacuum. This procedure gave 2.95 g of pure anti-zirconocene as a slightly orange microcrystalline powder. Additional amount of this product was obtained in a similar manner from mother liquor evaporated to ca. 35 ml. Thus, the combined yield of anti-zirconocene was 5.65 g (29%).

(101) Anti-E2

(102) Anal. Calcd. for C.sub.43H.sub.48Cl.sub.2OSiZr: C, 66.98; H, 6.27%. Found: C, 67.00; H, 6.31%.

(103) .sup.1H NMR (CDCl.sub.3): 7.61-7.63 (m, 3H, 2,6-H in C.sub.6H.sub.4 and 5-H in indenyl of I), 7.54 (s, 1H, 7-H in indenyl of II), 7.46-7.48 (m, 2H, 3,5-H in C.sub.6H.sub.4 of I), 7.42 (m, 2H, 3,5-H in Ph of II), 7.37 (d, J=7.1 Hz, 1H, 7-H in indenyl of I), 7.32 (m, 1H, 4-H in Ph of II), 7.09 (dd, J=8.6 Hz, J=7.1 Hz, 1H, 6-H in indenyl of I), 7.02 (s, 1H, 3-H in indenyl of II), 6.57 (s, 1H, 3-H in indenyl of I), 3.39 (s, 3H, OMe), 2.25 (s, 3H, 2-Me in I), 2.17 (s, 3H, 2-Me in II), 1.39 (s, 9H, 6-.sup.tBu in II), 1.33 (s, 9H, 4-.sup.tBu in I), 1.31 (s, 6H, SiMe.sub.2); where I is 4-(4-tert-butylphenyl)-2-methyl-1H-inden-1-yl, II6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl.

(104) Syn-E2

(105) Anal. Found: C, 66.12; H, 6.35%.

(106) .sup.1H NMR (CDCl.sub.3): 7.64 (m, 1H, 5-H in indenyl of I), 7.56-7.58 (m, 2H, 2,6-H in C.sub.6H.sub.4 of I), 7.54 (s, 1H, 7-H in indenyl of II), 7.44-7.46 (m, 2H, 3,5-H in C.sub.6H.sub.4 of I), 7.41 (m, 2H, 3,5-H in Ph of II), 7.30 (m, 1H, 4-H in Ph of II), 7.15 (d, J=7.1 Hz, 1H, 7-H in indenyl of I), 6.91 (s, 1H, 3-H in indenyl of II), 6.87 (dd, J=8.6 Hz, J=7.1 Hz, 1H, 6-H in indenyl of I), 6.47 (s, 1H, 3-H in indenyl of I), 3.20 (s, 3H, OMe), 2.44 (s, 3H, 2-Me in I), 2.37 (s, 3H, 2-Me in II), 1.44 (s, 3H, SiMeMe), 1.34 (s, 9H, 6-.sup.tBu in II), 1.33 (s, 9H, 4-.sup.tBu in I), 1.22 (s, 3H, SiMeMe); where I is 4-(4-tert-butylphenyl)-2-methyl-1H-inden-1-yl, II6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl.

Synthesis of anti-dimethylsilylene(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(3,5-di-tert-butyl-phenyl)-6-tert-butyl-indenyl)zirconium dichloride

Metallocene E3

4/7-Bromo-2-methyl-6/5-tert-butyl-1H-indene

(107) ##STR00033##

(108) To 81.0 ml (47.0 mmol) of 0.58 M 3,5-di-tert-butylphenylmagnesium bromide in THF, 51.0 ml (51.0 mmol) of 1.0 M ZnCl.sub.2 in THF was added. Further on, a solution of 11.4 g (43.0 mmol) of 7-bromo-2-methyl-5-tert-butyl-1H-indene and 438 mg of Pd(P.sup.tBu.sub.3).sub.2 in 100 ml of THF was added. The resulting mixture was stirred overnight at 65 C., then cooled to room temperature and, finally, poured into 200 ml of water. The organic layer was separated, and the aqueous layer was extracted with 3100 ml of ethyl acetate. The combined organic extract was washed with 2100 ml of cold water, dried over Na.sub.2SO.sub.4, and evaporated to dryness. The residue was distilled in vacuum using Kugelrohr apparatus. This procedure gave 12.0 g (74%) of white crystalline solid.

(109) Anal. Calcd. for C.sub.28H.sub.38: C, 89.78; H, 10.22%. Found: C, 89.69; H, 10.29%.

(110) .sup.1H NMR (CDCl.sub.3): 7.42 (m), 7.38 (m), 7.35 (m), 7.30-7.32 (m), 7.19 (m), 6.59 (m, 3-H in indenyl), 6.62 (m, 3-H in indenyl), 3.36 (m, 1,1-H in indenyl), 3.33 (m, 1,1-H in indenyl), 2.13 (s, 2-Me in indenyl), 1.38-1.39 (s, 27H, .sup.tBu).

[6-tert-Butyl-4-(3,5-di-tert-butylphenyl)-2-methyl-1H-inden-1-yl]-(6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)dimethylsilane

(111) ##STR00034##

(112) To a solution of 11.1 g (29.6 mmol) of 4/7-bromo-2-methyl-6/5-tert-butyl-1H-indene in 250 ml of ether, 11.9 ml (29.8 mmol) of 2.5 M .sup.nBuLi in hexanes was added in one portion at 78 C. This mixture was stirred overnight at room temperature, then cooled to 60 C., and 150 mg of CuCN was added. The resulting mixture was stirred for 1 h at 20 C., and then a solution of 11.4 g (29.6 mmol) of (6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)(chloro)-dimethylsilane in 200 ml of ether was quickly added at 70 C. The reaction mixture was allowed to warm to room temperature and stirred overnight, then treated with 0.5 ml of water, filtered through a short pad of silica gel 60 (40-63 um). The silica gel layer was additionally washed by 100 ml of dichloromethane. The combined elute was evaporated to dryness giving a yellowish oil which was purified by flash chromatography on silica gel 60 (4-63 m; eluent: hexanes-dichloromethane from 10:1 to 3:1, vol.). This procedure gave 15.2 g (71%) of the title product as yellowish glassy solid.

(113) Anal. Calcd. for C.sub.51H.sub.66OSi: C, 84.70; H, 9.20%. Found: C, 84.92; H, 9.34%.

(114) .sup.1H NMR (CDCl.sub.3): 7.42-7.70 (m), 6.85 (s), 6.57 (s), 6.53 (s), 3.84 (m), 3.80 (m), 3.77 (m), 3.34 (s), 1.54 (s), 1.53 (s), 1.51 (s), 1.50 (s), 1.49 (s), 1.48 (s), 0.04 (s), 0.06 (s), 0.10 (s), 0.11 (s).

Complexes anti- and syn-dimethylsilanediyl[2-methyl-4-(3,5-di-tert-butylphenyl)-6-tert-butyl-inden-1-yl](2-methyl-4-phenyl-5-methoxy-6-tert-butyl-1H-inden-1-yl)zirconium dichloride

(115) ##STR00035##

(116) To a solution of 15.0 g (20.7 mmol) of [6-tert-butyl-4-(3,5-di-tert-butylphenyl)-2-methyl-1H-inden-1-yl] (6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)dimethylsilane in 200 ml of ether cooled to 78 C., 16.5 ml (41.3 mmol) of 2.5 M .sup.nBuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then cooled to 78 C., and 7.80 g (20.7 mmol) of ZrCl.sub.4(THF).sub.2 was added. The resulting mixture was stirred for 24 h (a light orange solution with a significant amount of precipitate was formed), then evaporated to dryness, and 350 ml of toluene was added. The resulting mixture warmed to 80 C. was filtered through glass frit (G4). On the evidence of NMR spectroscopy, this mixture contained anti- and syn-zirconocenes in a ratio of ca. 70:30. The filtrate was evaporated to 100 ml, warmed to 80 C., and 25 ml of n-octane was added. Crystals precipitated after 24 h at 30 C. were collected, washed by 210 ml of a ca. 1 to 1 (vol.) mixture of toluene and n-hexane, and dried in vacuum. This procedure gave 6.62 g (36%) of pure anti-zirconocene as a light-orange crystalline powder. The mother liquor was evaporated to 50 ml, diluted with 100 ml of n-hexane, and crystallized overnight at 30 C. The formed precipitate was filtered through glass frit (G3) and then dried in vacuum. This procedure gave 6.40 g of a mixture of anti- and syn-zirconocene in the ratio of 3:2. The mother liquor was evaporated to dryness, and the residue was dissolved in 20 ml of hot n-octane. Crystals precipitated at 30 C. were collected, washed by 25 ml of cold n-hexane, and dried in vacuum. This procedure gave additional amount (450 mg) of pure anti-zirconocene. A precipitate formed after keeping a mother liquor at room temperature for 3 days was filtered off (G3), and then dried in vacuum. This procedure gave 210 mg of pure syn-zirconocene.

(117) Anti-E3

(118) Anal. Calcd. for C.sub.51H.sub.64Cl.sub.2OSiZr: C, 69.35; H, 7.30%. Found: C, 69.43; H, 7.41%.

(119) .sup.1H NMR (CDCl.sub.3): 7.15-7.60 (m, 11H, 5,7-H in indenyl and 2,4,6-H in aryl of I as well as 7-H in indenyl and Ph in II), 6.87 (s, 1H, 3-H in indenyl of I), 6.53 (s, 1H, 3-H in indenyl of II), 3.40 (s, 3H, OMe), 2.22 (s, 3H, 2-Me in indenyl), 2.20 (s, 3H, 2-Me in indenyl), 1.40 (s, 9H, 6-.sup.tBu in indenyl of I), 1.36 (s, 18H, 3,5-.sup.tBu in aryl), 1.33 (s, 9H, 6-.sup.tBu in indenyl of II), 1.32 (s, 3H, SiMeMe), 1.30 (s, 3H, SiMeMe), where I is 6-tert-butyl-4-(3,5-di-tert-butylphenyl)-2-methyl-1H-inden-1-yl, II6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl.

(120) Syn-E3

(121) Anal. Found: C, 69.47; H, 7.40%.

(122) .sup.1H NMR (CDCl.sub.3): 7.16-7.54 (m, 11H, 5,7-H in indenyl and 2,4,6-H in aryl of I as well as 7-H in indenyl and Ph in II), 6.88 (s, 1H, 3-H in indenyl of I), 6.53 (s, 1H, 3-H in indenyl of II), 3.17 (s, 3H, OMe), 2.45 (s, 3H, 2-Me in indenyl), 2.40 (s, 3H, 2-Me in indenyl), 1.45 (s, 3H, SiMeMe), 1.38 (s, 18H, 3,5-.sup.tBu in aryl), 1.35 (s, 9H, 6-.sup.tBu in indenyl of I), 1.31 (s, 9H, 6-.sup.tBu in indenyl of II), 1.21 (s, 3H, SiMeMe), where I is 6-tert-butyl-4-(3,5-di-tert-butylphenyl)-2-methyl-1H-inden-1-yl, II6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl.

(123) Preparation of the Solid Catalysts

(124) Catalyst E1:

(125) Inside the glovebox, 80 L of a dry and degassed mixture of perfluoroalkylethyl acrylate ester were mixed in a septum vial with 2 mL of a 30 wt-% solution of MAO in toluene and left to react overnight. The following day, 58.9 mg of the metallocene E1 of the invention (rac-anti-Me.sub.2Si(2-Me-4-Ph-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl.sub.2) (0.076 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another septum bottle and left to stir inside the glovebox. After 60 minutes, the 4 mL of the MAO-metallocene solution and 1 mL of the perfluoroalkylethyl acrylate ester mixture in MAO solution were successively added into a 50 mL emulsification glass reactor containing 40 mL of hexadecafluoro-1,3-dimethylcyclohexane kept at 10 C. and equipped with an overhead stirrer (stirring speed=600 rpm). Total amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and was stirred during 15 minutes at 0 C./600 rpm. Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hot hexadecafluoro-1,3-dimethylcyclohexane heated to 90 C., and stirred at 600 rpm until the transfer is completed. The speed was reduced to 300 rpm. After 15 minutes stirring, the oil bath was removed and the stirrer turned off. The catalyst was left to settle up on top of the hexadecafluoro-1,3-dimethylcyclohexane and after 35 minutes the solvent was siphoned off. The remaining red catalyst was dried during 2 hours at 50 C. over an argon flow. 0.62 g (catalyst E1) of a red free flowing powder was obtained.

(126) Catalyst E2:

(127) Inside the glovebox, 80 L of a dry and degassed mixture of perfluoroalkylethyl acrylate ester were mixed in a septum vial with 2 mL of a 30 wt-% solution of MAO in toluene and left to react overnight. The following day, 58.7 mg of the metallocene E2 of the invention (rac-anti-Me.sub.2Si(2-Me-4-(p-tBuPh)-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl.sub.2) (0.076 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another septum bottle and left to stir inside the glovebox. After 60 minutes, the 4 mL of the MAO-metallocene solution and 1 mL of the perfluoroalkylethyl acrylate ester mixture in MAO solution were successively added into a 50 mL emulsification glass reactor containing 40 mL of hexadecafluoro-1,3-dimethylcyclohexane kept at 10 C. and equipped with an overhead stirrer (stirring speed=600 rpm). Total amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and was stirred during 15 minutes at 0 C./600 rpm. Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hot hexadecafluoro-1,3-dimethylcyclohexane heated to 90 C., and stirred at 600 rpm until the transfer is completed. The speed was reduced to 300 rpm. After 15 minutes stirring, the oil bath was removed and the stirrer turned off. The catalyst was left to settle up on top of the hexadecafluoro-1,3-dimethylcyclohexane and after 35 minutes the solvent was siphoned off. The remaining red catalyst was dried during 2 hours at 50 C. over an argon flow. 0.52 g (catalyst E2) of a red free flowing powder was obtained.

(128) Catalyst E3:

(129) Inside the glovebox, 80 L of a dry and degassed mixture of perfluoroalkylethyl acrylate ester were mixed in a septum vial with 2 mL of a 30 wt-% solution of MAO in toluene and left to react overnight. The following day, 67.1 mg of the metallocene E3 of the invention (rac-anti-Me.sub.2Si(2-Me-4-(3,5-di-tBuPh)-6-tBu-Ind)(2-Me-4-Ph-5-OMe-6-tBu-Ind)ZrCl.sub.2) (0.076 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another septum bottle and left to stir inside the glovebox. After 60 minutes, the 4 mL of the MAO-metallocene solution and 1 mL of the perfluoroalkylethyl acrylate ester mixture in MAO solution were successively added into a 50 mL emulsification glass reactor containing 40 mL of hexadecafluoro-1,3-dimethylcyclohexane kept at 10 C. and equipped with an overhead stirrer (stirring speed=600 rpm). Total amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and was stirred during 15 minutes at 0 C./600 rpm. Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hot hexadecafluoro-1,3-dimethylcyclohexane heated to 90 C., and stirred at 600 rpm until the transfer is completed. The speed was reduced to 300 rpm. After 15 minutes stirring, the oil bath was removed and the stirrer turned off. The catalyst was left to settle up on top of the hexadecafluoro-1,3-dimethylcyclohexane and after 35 minutes the solvent was siphoned off. The remaining red catalyst was dried during 2 hours at 50 C. over an argon flow. 0.67 g (catalyst E3) of a red free flowing powder was obtained.

Comparative Catalyst C1

(130) Comparative example catalyst C1 was synthesized according to the above described recipe with 78.2 mg of rac-methyl(cyclohexyl)silanediylbis[2-methyl-4-(4-tert-butylphenyl)indenyl]zirconium dichloride as the metallocene.

Comparative Example C2

(131) Comparative example catalyst C2 was prepared according to the example E1 of WO2012/001052 using rac-1,1-dimethylsilylene-bis[2-isobutyl-4-(4-tert-butylphenyl)-5,6,7-trihydro-s-indacen-1-yl]zirconium dichloride as the metallocene.

Comparative Example C3

(132) C-3a is the commercial product Borsoft SA233CF commercially available from Borealis AG, a random-heterophasic copolymer having an MFR (230 C./2.16 kg) of 0.8 g/10 min. C-3b is the commercial product BEC5012 commercially available from Borealis AG, a heterophasic copolymer for non-pressure pipes having an MFR (230 C./2.16 kg) of 0.3 g/10 min.

(133) TABLE-US-00002 TABLE 1 Catalyst composition as determined by ICP Al Zr Al/Zr Cat. (%) (%) (molar) E1 26.20 0.31 285 E2 18.90 0.24 266 E3 26.10 0.32 276 C1 31.00 0.37 283
E1P, E2P, E3P and C1P: Off-Line Prepolymerization of Catalysts E1, E2, E3 and C1

(134) The catalysts of the invention E1, E2 and E3 as well comparative catalyst C1 were pre-polymerised according to the following procedure: off-line pre-polymerisation experiments were done in a 125 mL pressure reactor equipped with gas-feeding lines and an overhead stirrer. Dry and degassed hexadecafluoro-1,3-dimethylcyclohexane (15 mL) and the desired amount of the red catalyst to be pre-polymerised were loaded into the reactor inside a glovebox and the reactor was sealed. The reactor was then taken out from the glovebox and placed inside a water cooled bath. The overhead stirrer and the feeding lines were then connected. The feeding line was pressurized with hydrogen, and the experiment was started by opening the valve between the H.sub.2 feed line and the reactor. At the same time propylene feed was started through the same H.sub.2 feeding line in order to ensure that all the hydrogen would be fed into the reactor. The propylene feed was left open, and the monomer consumption was compensated by keeping the total pressure in the reactor constant (about 5 barg). The experiment was continued until a polymerisation time sufficient to provide the desired degree of polymerisation. The reactor was then taken back inside the glovebox before opening and the content was poured into a glass vessel. The hexadecafluoro-1,3-dimethylcyclohexane was evaporated until a constant weight was obtained to yield a pre-polymerised pink catalyst. The degree of polymerisation was determined gravimetrically and/or by analysis of the ash and/or aluminium content of the catalyst to be 3.5 for E1P, 4.6 for E2P, 2.9 for E3P and 3.1 for C1P.

(135) C2P: Off-Line Prepolymerization of Catalyst C2

(136) The solid catalyst C2 was further prepolymerised according to the following procedure. The catalyst was off-line prepolymerised according to the following procedure: off-line pre-polymerisation experiments were done in a 125 mL pressure reactor equipped with gas-feeding lines and an overhead stirrer. Dry and degassed perfluoro-1,3-dimethylcyclohexane (15 cm.sup.3) and the desired amount of the red catalyst to be pre-polymerised were loaded into the reactor inside a glovebox and the reactor was sealed. The reactor was then taken out from the glovebox and placed inside a water cooled bath. The overhead stirrer and the feeding lines were then connected. The feeding line was pressurized with hydrogen, and the experiment was started by opening the valve between the hydrogen feed line and the reactor. At the same time propylene feed was started through the same hydrogen feeding line in order to ensure that all the hydrogen would be fed into the reactor. The propylene feed was left open, and the monomer consumption was compensated by keeping the total pressure in the reactor constant (about 5 barg). The experiment was continued until a polymerisation time sufficient to provide the desired degree of polymerisation. The reactor was then taken back inside the glovebox before opening and the content was poured into a glass vessel. The perfluoro-1,3-dimethylcyclohexane was evaporated until a constant weight was obtained to yield a pre-polymerised pink catalyst. The prepolymerisation degree (weight of polymer matrix/weight of solid catalyst before prepolymerisation step) was determined gravimetrically and/or by analysis of the ash and/or aluminium content of the catalyst.

(137) Polymerisations:

(138) Heterophasic Ethylene-Propylene Copolymerization with Catalyst E1P.

(139) Heterophasic copolymer was prepared with catalyst E1P in a sequential bulk/gas phase process as follows: A 21.2 L autoclave with double helix stirrer containing 0.4 barg propylene was filled with additional 5.18 kg propylene. After adding 0.2 NL H.sub.2 and 0.97 mmol triethylaluminium (1 molar solution in hexane) using a stream of 248 g propylene, the solution was stirred at 250 rpm. After 20 min the reactor temperature was increased to 40 C. and 298 mg of the solid, pre-polymerized catalyst E1P was contacted with 5 ml perfluoro-1,3-dimethylcyclohexane under N.sub.2 pressure (0.003 mol at 10 barg) in a stainless-steel vial connected to the autoclave for 60 sec and flushed into the reactor with 494 g propylene. After that the stirring speed was increased to 350 rpm and the temperature in the reactor increased to 70 C. over 13 min. This temperature was held for 30 min after achieving 68 C. After that the pressure was decreased to 1 bar-a via flashing. To achieve target conditions for gas phase of 15 bar-g at 60 C., ethylene and propylene are dosed in a ratio of C3/C2=1.26 g/g into the reactor until a total amount of 429 g over 8 min. 60 C. (temperature decreased during flashing because of vaporization enthalpy) was achieved 16 min after start of pressure increase and the total pressure was constantly held at 15 bar-g via dosing ethylene and propylene in a ratio of C3/C2=1.83 g/g. The polymerisation was stopped 67 min after start of pressure increase to 15 barg via flashing and cooling. The residence time used for calculation of catalyst activity in gas phase was 55.5 min (start after achieving of polymerisation temperature of 58 C. in gas phase).

(140) After 3 times spilling the reactor with N.sub.2 and one vacuum/N.sub.2 cycle the product was taken out and dried overnight in a hood and additionally 2 hours in a vacuum drying oven at 60 C.

(141) Heterophasic Ethylene-Propylene Copolymerization with Catalyst E2P

(142) Heterophasic copolymer was prepared with catalyst E2P in a sequential bulk/gas phase process as follows: A 21.2 L autoclave with double helix stirrer containing 0.5 barg propylene was filled with additional 3.97 kg propylene. After adding 0.2 NL hydrogen and 0.73 mmol triethylaluminium (1 molar solution in hexane) using a stream of 246 g propylene the solution was stirred at 250 rpm. After 20 min the reactor temperature was increased to 40 C. and 253 mg of the solid, pre-polymerized catalyst E2P (degree of polymerisation 4.6) was contacted with 5 ml perfluoro-1,3-dimethylcyclohexane under nitrogen-pressure (0.003 mol at 10 bar-g) for 60 sec and spilled into the reactor with 243 g propylene. After that the stirring speed was increased to 350 rpm and the temperature in the reactor increased to 70 C. over 17 min. This temperature was held for 30 mins after achieving 68 C. After that the pressure was decreased to 1.1 barg via flashing. To achieve target conditions for gas phase of 15 barg at 60 C., ethylene and propylene are dosed in a ratio of C3/C2=1.23 g/g into the reactor until a total amount of 406 g over 8 min. 60 C. (temperature decreased during flashing because of vaporization enthalpy) was achieved 14 min after start of pressure increase and the total pressure was constantly held at 15 barg via dosing ethylene and propylene in a ratio of C3/C2=1.83 g/g. The polymerisation was stopped 41.5 min after start of pressure increase to 15 barg via flashing and cooling. The residence time used for calculation of catalyst activity in gas phase was 27.5 min (start after achieving of polymerisation temperature of 58 C. in gas phase).

(143) After 3 times spilling the reactor with nitrogen and one vacuum/nitrogen cycle the product is taken out and dried overnight in a hood and additionally 2 hours in a vacuum drying oven at 60 C.

(144) This polymerisation was repeated using different amount of catalyst and C3/C2 feeds.

(145) Heterophasic Ethylene-Propylene Copolymerization with Catalyst E3P.

(146) Heterophasic copolymer was prepared with catalyst E3P in a sequential bulk/gas phase process as follows: A 21.2 L autoclave with double helix stirrer containing 0.5 barg propylene was filled with additional 3.96 kg propylene. After adding 0.2 NL hydrogen and 0.73 mmol triethylaluminium (1 molar solution in hexane) using a stream of 247 g propylene the solution was stirred at 250 rpm. After 20 min the reactor temperature was increased to 40 C. and 212 mg of the solid, pre-polymerized catalyst E3P (degree of polymerisation 2.9) was contacted with 5 ml perfluoro-1,3-dimethylcyclohexane under nitrogen-pressure (0.003 mol at 10 bar-g) for 60 sec and spilled into the reactor with 242 g propylene. After that the stirring speed was increased to 350 rpm and the temperature in the reactor increased to 70 C. over 15 min. This temperature was held for 30 mins after achieving 68 C. After that the pressure was decreased to 0.9 bara via flashing. To achieve target conditions for gas phase of 15 barg at 60 C., ethylene and propylene are dosed in a ratio of C3/C2=0.4 g/g into the reactor until a total amount of 351 g over 8 min. 60 C. (temperature decreased during flashing because of vaporization enthalpy) was achieved 18 min after start of pressure increase and the total pressure was constantly held at 15 barg via dosing ethylene and propylene in a ratio of C3/C2=1 g/g. The polymerisation was stopped 93 min after start of pressure increase to 15 barg via flashing and cooling. The residence time used for calculation of catalyst activity in gas phase was 82 min (start after achieving of polymerisation temperature of 58 C. in gas phase).

(147) After 3 times spilling the reactor with nitrogen and one vacuum/nitrogen cycle the product is taken out and dried overnight in a hood and additionally 2 hours in a vacuum drying oven at 60 C.

(148) Heterophasic Ethylene-Propylene Copolymerisation with C1P (Comparative)

(149) Batch production of a heterophasic ethylene copolymer with pre-polymerized comparison catalyst C1P in bulk/gas phase process: A stirred autoclave (double helix stirrer) with a volume of 21.2 dm.sup.3 containing 0.5 barg propylene was filled with additional 5.18 kg propylene. After adding 0.2 In hydrogen and 0.97 mmol triethylaluminium (1 molar solution in hexane) using a stream of 244 g propylene the solution was stirred at 250 rpm. After 20 min the reactor temperature was increased to 40 C. and 494 mg of the solid, pre-polymerized catalyst C1P was contacted with 5 ml perfluoro-1,3-dimethylcyclohexane under nitrogen pressure (0.003 mol at 10 barg) for 60 sec and spilled into the reactor with 491 g propylene. After that the stirring speed was increased to 350 rpm and the temperature in the reactor increased to 70 C. over 17 min. This temperature was held for 30 min after achieving 68 C. After that the pressure is decreased to 1.1 barg via flashing. To achieve target conditions for gas phase of 15 barg at 60 C. ethylene and propylene are dosed in a ratio of C3/C2=1.23 g/g into the reactor until a total amount of 401 g over 8 min. 60 C. (temperature decreased during flashing because of vaporization enthalpy) was achieved 19 min after start of pressure increase and the total pressure was constantly held at 15 barg via dosing ethylene and propylene in a ratio of C3/C2=1.83 g/g. The polymerisation was stopped 103 min after start of pressure increase to 15 barg via flashing and cooling. The residence time used for calculation of catalyst activity in gas phase was 90 min (start after achieving of polymerisation temperature of 58 C. in gas phase).

(150) After 3 times spilling the reactor with nitrogen and one vacuum/nitrogen cycle the product was taken out and dried over night in a hood and additionally 2 hours in a vacuum drying oven at 60 C.

(151) Catalyst activity for E1P and E2P and E3P was determined according to:
Activity kg/g(cat)/h={amount of polymer produced in kg/[(prepolymerized catalyst loading in grams)polymerization time in hours]}(1+prepolymerization degree).
Heterophasic Ethylene-Propylene Copolymerisation with C2P (Ex A) (Comparative)

(152) A stirred autoclave (double helix stirrer) with a volume of 21.2 dm.sup.3 containing 0.4 barg propylene was filled with additional 3.97 kg propylene. After adding 0.4 NL hydrogen and 1.83 mmol triethylaluminium (1 molar solution in hexane) using a stream of 245 g propylene the solution was stirred at 250 rpm. After 20 min the reactor temperature was increased to 40 C. and 65 mg of the solid, pre-polymerized catalyst C2P (degree of polymerisation 3.9) was contacted with 5 ml perfluoro-1,3-dimethylcyclohexane under nitrogen-pressure (0.003 mol at 10 barg) for 60 sec and spilled into the reactor with 244 g propylene. After that the stirring speed is increased to 350 rpm and the temperature in the reactor held at 40 C. for 15 min (pre-polymerisation). Then the temperature is increased to 70 C. over 16 min and 1.17 NL hydrogen added during this period. This temperature is held for 30 min after achieving 68 C. After that the pressure was decreased to 1.3 barg via flashing. To achieve target conditions for gas phase of 15 barg at 60 C., ethylene and propylene were dosed in a ratio of C3/C2=1.22 [g/g] into the reactor until a total amount of 421 g over 7.5 min. Achieving 60 C. (temperature decreased during flashing because of vaporization enthalpy) 16 min after start of pressure increase the total pressure was constantly held at 15 barg via dosing ethylene and propylene in a ratio of C3/C2=1.83 [g/g]. The polymerisation has been stopped 149 min after pressure increase to 15 barg via flashing and cooling.

(153) After 3 times spilling the reactor with nitrogen and one vacuum/nitrogen cycle the product was taken out and dried over night in a hood and additionally 2 hours in a vacuum drying oven at 60 C.

(154) Heterophasic Ethylene-Propylene Copolymerisation with C2P (Ex B) (Comparative)

(155) A stirred autoclave (double helix stirrer) with a volume of 21.2 dm.sup.3 containing 0.4 barg propylene was filled with additional 3.97 kg propylene. After adding 0.4 NL H.sub.2 and 0.73 mmol triethylaluminium (1 molar solution in hexane) using a stream of 244 g propylene the solution was stirred at 250 rpm. After 20 min 64 mg of the solid, pre-polymerized catalyst C2P (degree of polymerisation 3.9) was contacted with 5 ml perfluoro-1,3-dimethylcyclohexane under nitrogen-pressure (0.003 mol at 10 barg) for 60 sec and spilled into the reactor with 242 g propylene at a stirring speed of 350 rpm. The temperature in the reactor was held at 20 C. for 10 min (pre-polymerisation). Then the temperature was increased to 70 C. over 23 min and 0.6 NL H.sub.2 are added during this period. This temperature was held for 30 min after achieving 68 C. After that the pressure was decreased to 1.2 barg via flashing. To achieve target conditions for gas phase of 25 barg at 80 C., ethylene and propylene were dosed in a ratio of C3/C2=1.86 [g/g] into the reactor until a total amount of 799 g was present over 7.2 min. Achieving 80 C. (temperature decreased during flashing because of vaporization enthalpy) 14 min after start of pressure increase the total pressure was constantly held at 25 barg via dosing ethylene and propylene in a ratio of C3/C2=2.48 g/g. The polymerisation was stopped 138 min after pressure increase to 25 barg via flashing and cooling.

(156) After 3 times spilling the reactor with nitrogen and one vacuum/N.sub.2 cycle the product was taken out and dried over night in a hood and additionally 2 hours in a vacuum drying oven at 60 C.

(157) Results of heterophasic polymerisations are summarised in Tables 1 to 4.

(158) TABLE-US-00003 TABLE 1 Heterophasic ethylene-propylene copolymerisations Polym C3/C2 in C3/C2 Polym Prepoly'd Total Yield feed in feed Residence Yield Activity Catalyst polymer in Activity (transition (gas time in gas in.sup.(1) gas amount yield bulk in bulk gas phase) phase) (gas phase) phase) phase Ex Cat. (mg) (g) (g) kg.sub.PP/g.sub.cat/h (g/g) (g/g) (min) (g) kg/g.sub.cat/h c-1 C1P 494 915 601 10.0 1.23 1.83 90 314 1.74 1 E1P 298 1301 787 23.8 1.26 1.83 55.5 514 8.39 2 E2P 257 680 483 21.0 0.40 1.00 22.5 197 11.45 3 E2P 253 692 428 18.9 1.23 1.83 27.5 264 12.75 4 E3P 212 1100 762 28.0 0.4 1.00 82 338 4.6 .sup.(1)Activity in kg of polymer per gram of catalyst per hour (MFR(XS) calculated from iV(XS) & C2(XS) based on Grein et al. Rheol.Acta 2007, MFR(Matrix) from logarithmic mixing rule);

(159) TABLE-US-00004 TABLE 2 Heterophasic ethylene-propylene copolymerisationspolymer properties M.sub.w at the max of MWD curve of the C2C3 M.sub.w MFR.sub.2 C2 in XS XS IV (XS) G23 C. Tg copolymer (XS) Ex Cat. (g/10 min) (IR) wt % wt-% dL/g MPa (EPR) kg/mol kg/mol c-1 C1P 2.43 23.3 34.3 0.58 228 38.6 47 41 1 E1P 0.47 23 38 1.15 185 38 94 94 2 E2P 0.07 43.3 28.6 1.26 311 54 140 101 3 E2P 0.15 22.3 35 1.24 222 36 129 111 4 E3P 0.35 39.9 35.2 1.55 271 52 146 125 C-2Pa C-2P 7.7 20.7 23.7 2.12 350 C-2Pb C-2P 0.5 18.5 31.4 3.67 306 C-3a ZN 0.8 30.5 28.7 2.34 277 C-3b ZN 0.3 63.2 12.0 2.8 552

(160) TABLE-US-00005 TABLE 3 MFR Tg(EPR) MFR(XS) (Matrix) MFR(XS)/ Ex C. g/10 min g/10 min MFR (Matrix) c-1 38.6 110 0.32 331 1 38 65 0.023 2837 2 54 57 0.005 11932 3 36 48 0.007 7146 4 52 35 0.029 1220 C-2Pa 34 1.2 13.7 0.087 C-2Pb 33 0.08 1.16 0.069 C-3a 54 0.8 0.8 1 C-3b 65 0.6 0.27 2.20

(161) For examples 1 and 4, an extended mechanical characterization has been done demonstrating an extremely low brittle-to-ductile transition temperature (BDTT) based on Charpy notched impact values (see FIG. 1).

(162) The inventive examples show an extremely advantageous mechanical profile despite the low molecular weight of the EPR phase which is normally considered to be detrimental for impact strength. An additional comparison with two commercial copolymer grades based on Ziegler Natta catalysts (C-3a and C-3b) is summarized in Table 4 showing clearly the improved performance at 20 C.

(163) TABLE-US-00006 TABLE 4 MFR(XS)/ MFR MFR IV MFR C2 Charpy NIS Tensile Strain @ (Matrix) (Total) (XS) XS (Matrix) (XS) BDTT 20 C. 23 C. Mod. break Catalyst g/10 min g/10 min dl/g wt % wt % C. kJ/m.sup.2 kJ/M.sup.2 MPa % C-2a 13.7 7.7 2.12 23.7 0.087 20.7 7 4.9 49.0 882 345 C-2b 1.17 0.5 3.67 31.4 0.069 18.5 19 64.8 77.1 709 360 1 0.023 0.5 1.15 38.0 2837 23.5 33 107.6 NB 222 112 4 0.029 0.4 1.55 35.2 7146 39.9 34 112.3 NB 558 108 C-3a 0.8 0.8 2.34 28.7 1.0 30.5 n.d. 5.0 83.0 470 460 C-3b 0.26 0.3 2.80 12.0 2.2 63.2 n.d. 5.0 70.0 1295 450