Catalysts

Abstract

A complex of formula (I): (I′) M is Hf; each X is a sigma ligand; L is a bridge of formula -(ER.sup.8.sub.2).sub.y—; y is 1 or 2; E is C or Si; each R.sup.8 is independently a C.sub.1-C.sub.20-hydrocarbyl, tri(C.sub.1-C.sub.20-alkyl)silyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-arylalkyl or C.sub.7-C.sub.20-alkylaryl or L is an alkylene group such as methylene or ethylene; Ar and Ar′ are each independently an aryl or heteroaryl group optionally substituted by 1 to 3 groups R.sup.1 or R.sup.1′ respectively; R.sup.1 and R.sup.1′ are each independently the same or can be different and are a linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group or C.sub.6-20 aryl group with the proviso that if there are four or more R.sup.1 and R.sup.1′ groups present in total, one or more of R.sup.1 and R.sup.1′ is other than tert butyl; R.sup.2 and R.sup.2′ are the same or are different and are a CH.sub.2—R.sup.9 group, with R.sup.9 being H or linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.3-8 cycloalkyl group, C.sub.6-10 aryl group; each R is a —CH.sub.2—, —CHRx- or C(Rx).sub.2- group wherein Rx is C.sub.1-4 alkyl and where m is 2-6; R.sup.5 is a linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group or C.sub.6-C.sub.20-aryl group; R.sup.6 is a C(R.sup.10).sub.3 group, with R.sup.10 being a linear or branched C.sub.1-C.sub.6 alkyl group; and R.sup.6 and R.sup.7′ are the same or are different and are H or a linear or branched C.sub.1-C.sub.6-alkyl group. Invention relates also to a catalyst in solid form comprising (i) a complex of formula (I) and (ii) a cocatalyst of an aluminium compound and (iii) a cocatalyst of a boron compound. ##STR00001##

Claims

1. A process for the preparation of a propylene polymer, the process comprising: polymerizing propylene optionally with ethylene and/or a C4-10 alpha olefin in the presence of a catalyst; wherein the catalyst comprises: (i) a complex; (ii) a cocatalyst of an aluminum compound; and (iii) a cocatalyst of a boron compound; wherein the complex is of formula (I): ##STR00043## wherein: M is Hf each X is a sigma ligand; L is an alkylene group or a bridge of formula -(ER.sup.8.sub.2).sub.y—; y is 1 or 2; E is C or Si; and each R.sup.8 is independently a C.sub.1-C.sub.20-hydrocarbyl, tri(C.sub.1-C.sub.20-alkyl)silyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-arylalkyl, or C.sub.7-C.sub.20-alkylaryl; Ar and Ar′ are each independently an aryl or heteroaryl group optionally substituted by 1 to 3 R.sup.1 or R.sup.1′ groups respectively; R.sup.1 and R.sup.1′ are each independently a linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.7-20 arylalkyl group, C.sub.7-20 alkylaryl group, or C.sub.6-20 aryl group, with the proviso that when there are four or more R.sup.1 and R.sup.1′ groups present in total, then one or more of R.sup.1 and/or R.sup.1′ is other than tert butyl; R.sup.2 and R.sup.2′ are each independently a CH.sub.2—R.sup.9 group, with R.sup.9 being H, linear or branched C.sub.1-6-alkyl group, C.sub.3-8 cycloalkyl group, or C.sub.6-10 aryl group; each R.sup.3 is a —CH.sub.2—, —CHRx-, or C(Rx).sub.2- group wherein Rx is C1-4 alkyl; m is 2-6; R.sup.5 is a linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group, or C.sub.6-C.sub.20-aryl group; R.sup.6 is a C(R.sup.10).sub.3 group, with R.sup.10 being a linear or branched C.sub.1-C.sub.6 alkyl group; and R.sup.7 and R.sup.7′ are each independently H or a linear or branched C.sub.1-C.sub.6-alkyl group.

2. The process of claim 1, wherein the complex is of formula (Ia): ##STR00044## wherein: M is Hf; each X is a sigma ligand; L is an alkylene group or a bridge of formula -(ER.sup.8.sub.2).sub.y—; y is 1 or 2; E is C or Si; and each R.sup.8 is independently a C.sub.1-C.sub.20-hydrocarbyl, tri(C.sub.1-C.sub.20-alkyl)silyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-arylalkyl, or C.sub.7-C.sub.20-alkylaryl; each n is independently 0, 1, 2 or 3; R.sup.1 and R.sup.1′ are each independently a linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.7-20 arylalkyl group, C.sub.7-20 alkylaryl group, or C.sub.6-20 aryl group, with the proviso that when there are four or more R.sup.1 and R.sup.1′ groups present in total, then one or more of R.sup.1 and/or R.sup.1′ is other than tert butyl; R.sup.2 and R.sup.2′ are each independently a CH.sub.2—R.sup.9 group, with R.sup.9 being H, linear or branched C.sub.1-6-alkyl group, C.sub.3-8 cycloalkyl group, or C.sub.6-10 aryl group; each R.sup.3 is a —CH.sub.2—, —CHRx-, or C(Rx).sub.2- wherein Rx is C.sub.1-4 alkyl; m is 2-6; R.sup.5 is a linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group, or C.sub.6-C.sub.20-aryl group; R.sup.6 is a C(R.sup.10).sub.3 group, with R.sup.10 being a linear or branched C.sub.1-C.sub.6 alkyl group; and R.sup.7 and R.sup.7′ are each independently H or a linear or branched C.sub.1-C.sub.6-alkyl group.

3. The process of claim 2, wherein L is of formula —SiR.sup.8.sub.2—, wherein each R.sup.8 is independently a C.sub.1-C.sub.20-hydrocarbyl, tri(C.sub.1-C.sub.20-alkyl)silyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-arylalkyl, or C.sub.7-C.sub.20-alkylaryl.

4. The process of claim 1, wherein the complex is of formula (Ib): ##STR00045## wherein M is Hf; each X is a sigma ligand; L is an alkylene bridge or a bridge of the formula —SiR.sup.8.sub.2—, wherein each R.sup.8 is independently a C.sub.1-C.sub.20-hydrocarbyl, tri(C.sub.1-C.sub.20-alkyl)silyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-arylalkyl, or C.sub.7-C.sub.20-alkylaryl; each n is independently 0, 1, 2 or 3; R.sup.1 and R.sup.1′ are each independently a linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group, or C.sub.6-20 aryl group, with the proviso that when there are four or more R.sup.1 and R.sup.1′ groups present in total, then one or more of R.sup.1 and R.sup.1′ is other than tert butyl; R.sup.2 and R.sup.2′ are each independently a CH.sub.2—R.sup.9 group, with R.sup.9 being H, linear or branched C.sub.1-6-alkyl group, C.sub.3-8 cycloalkyl group, or C.sub.6-10 aryl group; R.sup.5 is a linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.7-20 arylalkyl group, C.sub.7-20 alkylaryl group, or C.sub.6-C.sub.20-aryl group; R.sup.6 is a C(R.sup.10).sub.3 group, with R.sup.10 being a linear or branched C.sub.1-C.sub.6 alkyl group; and R.sup.7 and R.sup.7′ are each independently H or a linear or branched C.sub.1-C.sub.6-alkyl group.

5. The process of claim 4, wherein each n is 1 or 2.

6. The process of claim 1, wherein the complex is of formula (II): ##STR00046## wherein M is Hf; X is a sigma ligand; L is an alkylene bridge or a bridge of the formula wherein each R.sup.8 is independently C.sub.1-C.sub.6-alkyl, C.sub.3-8 cycloalkyl, or C.sub.6-aryl group; each n is independently 1 or 2; R.sup.1 and R.sup.1′ are each independently a linear or branched C.sub.1-C.sub.6-alkyl group, with the proviso that when there are four R.sup.1 and R.sup.1′ groups present, then one or more of R.sup.1 and/or R.sup.1′ is not tert butyl; R.sup.2 and R.sup.2′ are each independently a CH.sub.2—R.sup.9 group, with R.sup.9 being H or linear or branched C.sub.1-6-alkyl group; R.sup.5 is a linear or branched C.sub.1-C.sub.6-alkyl group; and R.sup.6 is a C(R.sup.10).sub.3 group, with R.sup.10 being a linear or branched C.sub.1-C.sub.6 alkyl group.

7. The process of claim 1, wherein the complex is of formula (III): ##STR00047## wherein M is Hf; each X is a sigma ligand; L is —SiR.sup.8.sub.2—, wherein each R.sup.8 is C.sub.1-6 alkyl or C.sub.3-8 cycloalkyl; each n is independently 1 or 2; R.sup.1 and R.sup.1′ are each independently a linear or branched C.sub.1-C.sub.6-alkyl group, with the proviso that when there are four R.sup.1 and R.sup.1′ groups present, then one or more of R.sup.1 and/or R.sup.1′ is not tert butyl; R.sup.5 is a linear or branched C.sub.1-C.sub.6-alkyl group; and R.sup.6 is a C(R.sup.10).sub.3 group, with R.sup.10 being a linear or branched C.sub.1-C.sub.6 alkyl group.

8. The process of claim 1, wherein the complex is of formula (IV): ##STR00048## wherein M is Hf; each X is a hydrogen atom, a halogen atom, C.sub.1-6 alkoxy group, C.sub.1-6 alkyl, phenyl, or benzyl group; L is —SiR.sup.8.sub.2—, wherein each R.sup.8 is C.sub.1-4 alkyl or C.sub.5-6 cycloalkyl; each n is independently 1 or 2; R.sup.1 and R.sup.1′ are each independently a linear or branched C.sub.1-C.sub.6-alkyl group, with the proviso that when there are four R.sup.1 and R.sup.1′ groups present, then one or more of R.sup.1 and/or R.sup.1′ is not tert butyl; R.sup.5 is a linear or branched C.sub.1-C.sub.6-alkyl group; and R.sup.6 is a C(R.sup.10).sub.3 group, with R.sup.10 being a linear or branched C.sub.1-C.sub.6 alkyl group.

9. The process of claim 1, wherein the complex is of formula (V): ##STR00049## wherein M is Hf; X is a hydrogen atom, a halogen atom, C.sub.1-6 alkoxy group, C.sub.1-6 alkyl, phenyl, or benzyl group; L is —SiMe.sub.2; each n is independently 1 or 2; R.sup.1 and R.sup.1′ are each independently a linear or branched C.sub.1-C.sub.6-alkyl group, with the proviso that when there are four R.sup.1 and R.sup.1′ groups present, then one or more of R.sup.1 and/or R.sup.1′ is not tert butyl, R.sup.5 is a linear or branched C.sub.1-C.sub.4-alkyl group; and R.sup.6 is a C(R.sup.10).sub.3 group, with R.sup.10 being a linear or branched C.sub.1-C.sub.4 alkyl group.

10. The process of claim 1, wherein the complex is of formula (VI): ##STR00050## wherein M is Hf; X is a hydrogen atom, a halogen atom, C.sub.1-6 alkoxy group, C.sub.1-6 alkyl, phenyl, or benzyl group; L is —SiMe.sub.2; each n is independently 1 or 2; R.sup.1 and R.sup.1′ are each independently a linear or branched C.sub.1-C.sub.6-alkyl group, with the proviso that when there are four R.sup.1 and R.sup.1′ groups present, then one or more of R.sup.1 and/or R.sup.1′ is not tert butyl; R.sup.5 is a linear C.sub.1-C.sub.4-alkyl group; and R.sup.6 is tert butyl.

11. The process of claim 1, wherein the complex is of formula (VII): ##STR00051## wherein M is Hf; X is a hydrogen atom, a halogen atom, C.sub.1-6 alkoxy group, C.sub.1-6 alkyl, phenyl, or benzyl group; L is —SiMe.sub.2; each n is independently 1 or 2; R.sup.1 and R.sup.1′ are each independently a linear or branched C.sub.1-C.sub.4-alkyl group, with the proviso that when there are four R.sup.1 and R.sup.1′ groups present, then one or more of R.sup.1 and/or R.sup.1′ is not tert butyl; R.sup.5 is methyl; and R.sup.6 is tert butyl.

12. The process of claim 1, wherein the complex is of formula (VIII): ##STR00052## wherein M is Hf; X is Cl; L is —SiMe.sub.2; each n is independently 1 or 2; R.sup.1 and R.sup.1′ are each independently methyl or tert butyl, with the proviso that when there are four R.sup.1 and R.sup.1′ groups present, then one or more of R.sup.1 and/or R.sup.1′ is not tert butyl, R.sup.5 is methyl; and R.sup.6 is tert butyl.

13. The process of claim 1, wherein at least one of the C(4) or C(4′) phenyl rings is 3,5-dimethyl phenyl.

14. The process of claim 1, wherein at least one of the C(4) or C(4′) phenyl rings is 4-(tert-butyl)-phenyl.

15. The process of claim 1, wherein R.sup.1, R.sup.1′, and each value of n are selected such that the C(4) or C(4′) phenyl rings are 3,5-dimethyl phenyl, 3,5-ditertbutylphenyl, and/or 4-(tert-butyl)-phenyl.

16. The process of claim 1, wherein the catalyst is in solid form.

17. The process of claim 1, wherein the catalyst is supported on an external carrier or is in solid particulate form free from an external carrier.

18. A process for the manufacture of the catalyst of claim 1, said process comprising: contacting complex (i), cocatalyst (ii), and cocatalyst (iii) to provide a catalyst solution; forming a liquid/liquid emulsion system by dispersing the catalyst solution in a solvent in the form of dispersed droplets; and solidifying said dispersed droplets to form solid particles of said catalyst.

19. The process of claim 1, wherein the cocatalyst (ii) of an aluminum compound is an aluminoxane; wherein the cocatalyst (iii) of a boron compound is a borate; or a combination thereof.

20. The process of claim 1, wherein each X is independently a hydrogen atom, halogen atom, C.sub.1-6 alkoxy group, C.sub.1-6 alkyl, phenyl, or benzyl group.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 illustrates polypropylene homopolymer melting temperatures for samples produced with the comparative and inventive catalysts CE1, CE2 and IE1; and CE4, CE5 and IE2. Inventive catalysts provide propylene homopolymer with at least roughly 4 degrees higher melting temperature than polymers produced using comparative catalysts.

(2) FIG. 2 illustrates MFR.sub.21 results for the propylene homopolymer samples produced with the comparative and inventive catalysts CE1, CE2 and IE1; and CE4, CE5 and IE2. MFR values are clearly lower, indicating a higher molecular weight, for the polymers produced with the inventive catalysts than with the comparative catalysts.

(3) FIG. 3 illustrates activity of the catalysts in producing propylene homopolymer with the comparative and inventive catalysts CE1, CE2 and IE1; and CE4, CE5 and IE2. With inventive catalysts activity is higher than with related comparative examples.

ANALYTICAL TESTS

(4) Measurement Methods:

(5) Al, Zr and Hf Determination (ICP-Method)

(6) 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.

(7) The analysis was run at room temperature using a Thermo Elemental iCAP 6300 Inductively Coupled Plasma-Optical Emission 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.

(8) 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.

(9) 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.

(10) 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.

(11) In the case of analysing the elemental composition of off-line prepolymerised catalysts, the polymeric portion is digested by ashing in such a way that the elements can be freely dissolved by the acids. The total content is calculated to correspond to the weight-% for the prepolymerised catalyst. In the examples as disclosed below no off-line prepolymerisation step was used.

(12) DSC Analysis for Propylene Homopolymerisation Examples

(13) Melting temperature T.sub.m was measured on approx. 5 mg samples with a Mettler-Toledo 822e differential scanning calorimeter (DSC), according to ISO11357-3 in a heat/cool/heat cycle with a scan rate of 10° C./min in the temperature range of +23 to +225° C. under a nitrogen flow rate of 50 ml min.sup.−1. Melting temperature was taken as the endotherm peak, respectively in the second heating step. Calibration of the instrument was performed with H.sub.2O, Lead, Tin, Indium, according to ISO 11357-1.

(14) DSC Analysis, Main Melting Temperature (T.sub.m), Heat of Melting (H.sub.m), and Crystallization Temperature (T.sub.c) for Heterophasic Propylene Copolymer Examples

(15) DSC analysis was measured with a Mettler 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 (Tc) is determined from the cooling step, while main melting temperature (Tm) and heat of melting (H.sub.m) are determined from the second heating step.
Melt Flow Rate

(16) 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).

(17) Intrinsic Viscosity

(18) Intrinsic viscosity (iV) has been measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135° C.).

(19) Xylene Cold Soluble Fraction

(20) The xylene cold solubles (XCS, wt %) were determined at 25° C. according to ISO 16152; 2005.

(21) Crystex Analysis

(22) Crystalline and Soluble Fractions Method

(23) The crystalline (CF) and soluble fractions (SF) of the polypropylene (PP) compositions as well as the comonomer content and intrinsic viscosities of the respective fractions were analyzed by the CRYSTEX QC, Polymer Char (Valencia, Spain).

(24) The crystalline and amorphous fractions are separated through temperature cycles of dissolution at 160° C., crystallization at 40° C. and re-dissolution in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160° C. Quantification of SF and CF and determination of ethylene content (C2) are achieved by means of an infrared detector (IR4) and an online 2-capillary viscometer which is used for the determination of the intrinsic viscosity (IV).

(25) The IR4 detector is a multiple wavelength detector detecting IR absorbance at two different bands (CH3 and CH2) for the determination of the concentration and the Ethylene content in Ethylene-Propylene copolymers. IR4 detector is calibrated with series of 8 EP copolymers with known Ethylene content in the range of 2 wt % to 69 wt % (determined by 13C-NMR) and various concentration between 2 and 13 mg/ml for each used EP copolymer used for calibration.

(26) The amount of Soluble fraction (SF) and Crystalline Fraction (CF) are correlated through the XS calibration to the “Xylene Cold Soluble” (XCS) quantity and respectively Xylene Cold Insoluble (XCI) fractions, determined according to standard gravimetric method as per ISO 16152. XS calibration is achieved by testing various EP copolymers with XS content in the range 2-31 wt %.

(27) The intrinsic viscosity (IV) of the parent EP copolymer and its soluble and crystalline fractions are determined with a use of an online 2-capillary viscometer and are correlated to corresponding IV's determined by standard method in decalin according to ISO 1628. Calibration is achieved with various EP PP copolymers with IV=2-4 dL/g.

(28) A sample of the PP composition to be analyzed is weighed out in concentrations of 10 mg/ml to 20 mg/ml. After automated filling of the vial with 1,2,4-TCB containing 250 mg/l 2,6-tert-butyl-4-methylphenol (BHT) as antioxidant, the sample is dissolved at 160° C. until complete dissolution is achieved, usually for 60 min, with constant stirring of 800 rpm.

(29) A defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part is taking place. This process is repeated two times. During the first injection the whole sample is measured at high temperature, determining the IV[dl/g] and the C2[wt %] of the PP composition. During the second injection the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) with the crystallization cycle are measured (Wt % SF, Wt % C2, IV). (EP means ethylene propylene copolymer. PP means polypropylene.)

(30) The Crystex test is further described in WO2019/002345. We cross reference FIGS. 1a and b thereof.

(31) Flexural Modulus

(32) Flexural Modulus is determined according to ISO 178 at 23° C. on injection moulded test specimens as described in EN ISO 1873-2 (80×10×4 mm).

(33) Charpy Notched Impact

(34) Charpy notched impact strength (NIS) was determined according to ISO 179/1 eA at injection moulded test specimens as described in EN ISO 1873-2 (80×10×4 mm).

(35) Dynamic Mechanical Thermal Analysis (DMTA)

(36) Dynamic mechanical, thermal analysis (DMTA) were done according to ISO 6721-7. The measurements are done in torsion mode on compression moulded samples (40×10×1 mm.sup.3) between −130° C. and +150° C. with, a heating rate of 2° C./min and a frequency of 1 Hz. The storage modulus at 23° C. (G′) and glass transition temperature of EPR phase (tg1) and matrix (Tg2) are reported.

Examples

(37) Metallocene Synthesis

(38) Reagents

(39) 2,6-Dimethylaniline (Acros), 1-bromo-3,5-dimethylbenzene (Acros), 1-bromo-3,5-di-tert-butylbenzene (Acros), bis(2,6-diisopropylphenyl)imidazolium chloride (Aldrich), triphenylphosphine (Acros), NiCl.sub.2(DME) (Aldrich), dichlorodimethylsilane (Merck), ZrCl.sub.4 (Merck), HfCl.sub.4, <1% Zr (Strem Chemicals), trimethylborate (Acros), Pd(OAc).sub.2 (Aldrich), NaBH.sub.4 (Acros), 2.5 M nBuLi in hexanes (Chemetal), CuCN (Merck), magnesium turnings (Acros), silica gel 60, 40-63 μm (Merck), bromine (Merck), 96% sulfuric acid (Reachim), sodium nitrite (Merck), copper powder (Alfa), potassium hydroxide (Merck), K.sub.2CO.sub.3 (Merck), 12 M HCl (Reachim), TsOH (Aldrich), MgSO.sub.4 (Merck), Na.sub.2CO.sub.3 (Merck), Na.sub.2SO.sub.4 (Akzo Nobel), methanol (Merck), diethyl ether (Merck), 1,2-dimethoxyethane (DME, Aldrich), 95% ethanol (Merck), dichloromethane (Merck), hexane (Merck), THF (Merck), and toluene (Merck) were used as received. Hexane, toluene and dichloromethane for organometallic synthesis were dried over molecular sieves 4 A (Merck). Diethyl ether, THF, and 1,2-dimethoxyethane for organometallic synthesis were distilled over sodium benzophenoneketyl. CDCl.sub.3 (Deutero GmbH) and CD.sub.2Cl.sub.2 (Deutero GmbH) were dried over molecular sieves 4 A. 4-Bromo-6-tert-butyl-5-methoxy-2-methylindan-1-one was obtained as described in WO2013/007650.

Synthesis of MC CE1 (Comparative)

4-(4-tert-Butylphenyl)-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene

(40) ##STR00018##

(41) The precursor 4-bromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene was made according to the procedure described in WO2015/158790 A2 (pp 26-29).

(42) To a mixture of 1.5 g (1.92 mmol, 0.6 mol. %) of NiCl.sub.2(PPh.sub.3)IPr and 89.5 g (318.3 mmol) of 4-bromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene, 500 ml (500 mmol, 1.57 equiv) of 1.0 M 4-tert-butyl phenyl magnesium bromide in THF was added. The resulting solution was refluxed for 3 h, then cooled to room temperature, and 1000 ml of 0.5 M HCl was added. Further on, this mixture was extracted with 1000 ml of dichloromethane, the organic layer was separated, and the aqueous layer was extracted with 250 ml of dichloromethane. The combined organic extract was evaporated to dryness to give a greenish oil. The title product was isolated by flash-chromatography on silica gel 60 (40-63 μm; eluent: hexanes-dichloromethane=3:1, vol., then 1:3, vol.). This procedure gave 107 g (ca. 100%) of 1-methoxy-2-methyl-4-(4-tert-butylphenyl)-1,2,3,5,6,7-hexahydro-s-indacene as a white solid mass.

(43) Anal. calc, for C.sub.24H.sub.30O: C, 86.18; H, 9.04. Found: C, 85.99; H, 9.18.

(44) .sup.1H NMR (CDCl.sub.3), syn-isomer: δ 7.42-7.37 (m, 2H), 7.25-7.20 (m, 3H), 4.48 (d, J=5.5 Hz, 1H), 3.44 (s, 3H), 2.99-2.47 (m, 7H), 2.09-1.94 (m, 2H), 1.35 (s, 9H), 1.07 (d, J=6.9 Hz, 3H); Anti-isomer: δ 7.42-7.37 (m, 2H), 7.25-7.19 (m, 3H), 4.39 (d, J=3.9 Hz, 1H), 3.49 (s, 3H), 3.09 (dd, J=15.9 Hz, J=7.5 Hz, 1H), 2.94 (t, J=7.3 Hz, 2H), 2.78 (tm, J=7.3 Hz, 2H), 2.51-2.39 (m, 1H), 2.29 (dd, J=15.9 Hz, J=5.0 Hz, 1H), 2.01 (quin, J=7.3 Hz, 2H), 1.36 (s, 9H), 1.11 (d, J=7.1 Hz, 3H). .sup.13C{.sup.1H} NMR(CDCl.sub.3), syn-isomer: δ 149.31, 142.71, 142.58, 141.46, 140.03, 136.71, 135.07, 128.55, 124.77, 120.02, 86.23, 56.74, 39.41, 37.65, 34.49, 33.06, 32.45, 31.38, 25.95, 13.68; Anti-isomer: δ 149.34, 143.21, 142.90, 140.86, 139.31, 136.69, 135.11, 128.49, 124.82, 119.98, 91.53, 56.50, 40.12, 37.76, 34.50, 33.04, 32.40, 31.38, 25.97, 19.35.

4-(4-tert-Butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene

(45) ##STR00019##

(46) To a solution of 107 g 1-methoxy-2-methyl-4-(4-tert-butylphenyl)-1,2,3,5,6,7-hexahydro-s-indacene (prepared above) in 700 ml of toluene, 600 mg of TsOH was added, and the resulting solution was refluxed using Dean-Stark head for 10 min. After cooling to room temperature the reaction mixture was washed with 200 ml of 10% NaHCO.sub.3. The organic layer was separated, and the aqueous layer was additionally extracted with 2×100 ml of dichloromethane. The combined organic extract was evaporated to dryness to give a red oil. The product was purified by flash-chromatography on silica gel 60 (40-63 μm; eluent: hexanes, then hexanes-dichloromethane=5:1, vol.) followed by vacuum distillation, b.p. 210-216° C./5-6 mm Hg. This procedure gave 77.1 g (80%) of 4-(4-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene as a yellowish glassy material.

(47) Anal. calc, for C.sub.23H.sub.26: C, 91.34; H, 8.66. Found: C, 91.47; H, 8.50.

(48) .sup.1H NMR (CDCl.sub.3): δ 7.44-7.37 (m, 2H), 7.33-7.26 (m, 2H), 7.10 (s, 1H), 6.45 (br.s, 1H), 3.17 (s, 2H), 2.95 (t, J=7.3 Hz, 2H), 2.78 (t, J=7.3 Hz, 2H), 2.07 (s, 3H), 2.02 (quin, J=7.3 Hz, 2H), 1.37 (s, 9H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 149.37, 145.54, 144.79, 142.91, 139.92, 138.05, 137.15, 134.06, 128.36, 127.02, 124.96, 114.84, 42.11, 34.53, 33.25, 32.16, 31.41, 25.96, 16.77.

2-methyl-[4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl](chloro)dimethylsilane

(49) ##STR00020##

(50) To a solution of 22.3 g (73.73 mmol) of 4-(4-tert-butyl phenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in 300 ml of ether, cooled to −50° C., 30.4 ml (73.87 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. The resulting mixture was stirred overnight at room temperature, then the resulting suspension with a large amount of precipitate was cooled to −78° C. (wherein the precipitate was substantially dissolved to form an orange solution), and 47.6 g (369 mmol, 5 equiv.) of dichlorodimethylsilane was added in one portion. The obtained solution was stirred overnight at room temperature and then filtered through a glass frit (G4). The filtrate was evaporated to dryness to give 28.49 g (98%) of 2-methyl-[4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl](chloro) dimethylsilane as a colorless glass which was used without further purification.

(51) .sup.1H NMR (CDCl.sub.3): δ 7-50-7.45 (m, 2H), 7.36 (s, 1H), 7.35-7.32 (m, 2H), 6.60 (s, 1H), 3.60 (s, 1H), 3.10-2.82 (m, 4H), 2.24 (s, 3H), 2.08 (quin, J=7.3 Hz, 2H), 1.42 (s, 9H), 0.48 (s, 3H), 0.22 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 149.27, 144.41, 142.15, 141.41, 139.94, 139.83, 136.85, 130.19, 129.07, 126.88, 124.86, 118.67, 49.76, 34.55, 33.27, 32.32, 31.44, 26.00, 17.6

2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butyl-indan-1-one

(52) ##STR00021##

(53) A mixture of 31.1 g (100 mmol) of 2-methyl-4-bromo-5-methoxy-6-tert-butyl-indan-1-one, 25.0 g (140 mmol) of 4-tert-butylphenylboronic acid, 29.4 g (280 mmol) of Na.sub.2CO.sub.3, 1.35 g (6.00 mmol, 6 mol. %) of Pd(OAc).sub.2, and 3.15 g (12.0 mmol, 12 mol. %) of PPh.sub.3 in 130 ml of water and 380 ml of DME was refluxed for 6 h in argon atmosphere. The formed mixture was evaporated to dryness. To the residue 500 ml of dichloromethane and 500 ml of water were added. The organic layer was separated, the aqueous layer was additionally extracted with 100 ml of dichloromethane. The combined organic extract was dried over Na.sub.2SO.sub.4, evaporated to dryness, and the crude product was isolated using flash chromatography on silica gel 60 (40-63 μm; eluent: hexanes-dichloromethane=2:1, vol.). This crude product was recrystallized from n-hexane to give 29.1 g (81%) of a white solid.

(54) Anal. calc, for C.sub.25H.sub.32O.sub.2: C, 82.37; H, 8.85. Found: C, 82.26; H, 8.81.

(55) .sup.1H NMR (CDCl.sub.3): δ 7.74 (s, 1H, 7-H in indenyl), 7.48 (d, J=8.0 Hz, 2H, 2,6-H in C.sub.6H.sub.4.sup.tBu), 7.33 (d, J=8.0 Hz, 2H, 3,5-H in C.sub.6H.sub.4.sup.tBu), 3.27 (s, 3H, OMe), 3.15 (dd, J=17.3 Hz, J=7.7 Hz, 1H, 3-H in indan-1-on), 2.67-2.59 (m, 1H, 2-H in indan-1-on), 2.48 (dd, J=17.3 Hz, J=3.7 Hz, 3′-H in indan-1-on), 1.42 (s, 9H, feu in C.sub.6H.sub.4.sup.tBu), 1.38 (s, 9H, 6-feu in indan-1-on), 1.25 (d, J=7.3 Hz, 3H, 2-Me in indan-1-one).

2-methyl-5-tert-butyl-6-methoxy-7-(4-tert-butylphenyl)-1H-indene

(56) ##STR00022##

(57) To a solution of 28.9 g (79.2 mmol) of 2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butyl-indan-1-one in 400 ml of THF cooled to 5° C. 5.00 g (132 mmol) of NaBH.sub.4 was added. Further on, 100 ml of methanol was added dropwise to this mixture by vigorous stirring for ca. 7 h at 5° C. The resulting mixture was evaporated to dryness, and the residue wad partitioned between 500 ml of dichloromethane and 1000 ml of 0.5 M HCl. The organic layer was separated, the aqueous layer was additionally extracted with 100 ml of dichloromethane. The combined organic extract was evaporated to dryness to give a colorless oil. To a solution of this oil in 500 ml of toluene 1.0 g of TsOH was added. The formed mixture was refluxed with Dean-Stark head for 15 min and then cooled to room temperature using water bath. The resulting reddish solution was washed by 10% aqueous Na.sub.2CO.sub.3, the organic layer was separated, the aqueous layer was extracted with 2×100 ml of dichloromethane. The combined organic extract was dried over K.sub.2CO.sub.3 and then passed through short pad of silica gel 60 (40-63 μm). The silica gel pad was additionally washed with 50 ml of dichloromethane. The combined organic elute was evaporated to dryness to give a yellowish crystalline mass. The product was isolated by re-crystallization of this mass from 150 ml of hot n-hexane. Crystals precipitated at 5° C. were collected dried in vacuum. This procedure gave 23.8 g of white macrocrystalline 2-methyl-5-tert-butyl-6-methoxy-7-(4-tert-butylphenyl)-1H-indene. The mother liquor was evaporated to dryness and the residue was recrystallized from 20 ml of hot n-hexane in the same way. This procedure gave additional 2.28 g of the product. Thus, the total yield of the title product was 26.1 g (95%).

(58) Anal. calc, for C.sub.25H.sub.32O: C, 86.15; H, 9.25. Found: C, 86.24; H, 9.40.

(59) .sup.1H NMR (CDCl.sub.3): δ 7.44 (d, J=8.5 Hz, 2H, 2,6-H in C.sub.6H.sub.4.sup.tBu), 7.40 (d, J=8.5 Hz, 2H, 3,5-H in C.sub.6H/BU), 7.21 (s, 1H, 4-H in indenyl), 6.43 (m, 1H, 3-H in indenyl), 3.20 (s, 3H, OMe), 3.15 (s, 2H, 1-H in indenyl), 2.05 (s, 3H, 2-Me in indenyl), 1.43 (s, 9H, 5-.sup.tBu in indenyl), 1.37 (s, 9H, .sup.tBu in C.sub.6H.sub.4.sup.tBu).

[2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane

(60) ##STR00023##

(61) To a solution of 8.38 g (24.04 mmol) of 2-methyl-5-tert-butyl-7-(4-tert-butylphenyl)-6-methoxy-1H-indene in 150 ml of ether 9.9 ml (24.06 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion at −50° C. This mixture was stirred overnight at room temperature, then the resulting yellow solution with yellow precipitate was cooled to −50° C., and 150 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at −25° C., then a solution of 9.5 g (24.05 mmol) of 2-methyl-[4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl](chloro)dimethylsilane in 150 ml of ether was added in one portion. This mixture was stirred overnight at room temperature, then filtered through a pad of silica gel 60 (40-63 μm), which was additionally washed by 2×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure, and the residue was dried in vacuum at elevated temperature. This procedure gave 17.2 g (ca. 100%) of [2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (ca. 95% purity by NMR spectroscopy, approx. 1:1 mixture of stereoisomers) as yellowish glassy solid which was used in the next step without additional purification.

(62) .sup.1H NMR (CDCl.sub.3): δ 7.50 (s, 0.5H), 7.48-7.41 (m, 6H), 7.37-7.33 (m, 2.5H), 7.26 (s, 0.5H), 7.22 (s, 0.5H), 6.57 and 6.50 (2s, sum 2H), 3.71, 3.69, 3.67 and 3.65 (4s, sum 2H), 3.23 and 3.22 (2s, sum 3H), 3.03-2.80 (m, 4H), 2.20, 2.16 and 2.14 (3s, sum 6H), 2.08-1.99 (m, 2H), 1.43 and 1.41 (2s, sum 9H), 1.39 (s, 18H), −0.19, −0.20, −0.21 and −0.23 (4s, sum 6H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 155.49, 155.46, 149.41, 149.14, 149.11, 147.48, 147.44, 146.01, 145.77, 143.95, 143.91, 143.76, 143.71, 142.14, 142.10, 139.52, 139.42, 139.34, 139.29, 139.20, 139.16, 137.10, 137.05, 137.03, 135.20, 130.05, 130.03, 129.73, 129.11, 127.25, 127.22, 126.20, 126.13, 125.98, 125.94, 125.05, 124.82, 120.59, 120.52, 118.51, 118.26, 60.51, 60.48, 47.31, 46.89, 46.72, 35.14, 34.55, 33.34, 33.28, 32.30, 31.47, 31.45, 31.24, 31.19, 26.02, 25.99, 17.95, 17.86.

Anti-dimethylsilanediyl[2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride

(63) ##STR00024##

(64) To a solution of 17.2 g (ca. 24.04 mol) of [2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(4-tert-butyl phenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (prepared above) in 250 ml of ether, cooled to −50° C., 19.8 ml (48.11 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. This mixture was stirred for 4 h at room temperature, then the resulting cherry-red solution was cooled to −60° C., and 5.7 g (24.46 mmol) of ZrCl.sub.4 was added. The reaction mixture was stirred for 24 h at room temperature to give red solution with orange precipitate. This mixture was evaporated to dryness. The residue was heated with 200 ml of toluene, and the formed suspension was filtered through glass frit (G4). The filtrate was evaporated to 90 ml. Yellow powder precipitated from this solution overnight at room temperature was collected, washed with 10 ml of cold toluene, and dried in vacuum. This procedure gave 4.6 g (22%) of a ca. 4 to 1 mixture of anti- and syn-zirconocenes. The mother liquor was evaporated to ca. 40 ml, and 20 ml of n-hexane was added. Orange powder precipitated from this solution overnight at room temperature was collected and dried in vacuum. This procedure gave 6.2 g (30%) of a ca. 1 to 1 mixture of anti- and syn-zirconocenes. Thus, the total yield of anti- and syn-zirconocenes isolated in this synthesis was 10.8 g (52%). Pure anti-zirconocene was obtained after crystallization of the above-described 4.6 g sample of a ca. 4 to 1 mixture of anti- and syn-zirconocenes from 20 ml of toluene. This procedure gave 1.2 g of pure anti-zirconocene.

(65) Anti-dimethylsilanediyl[2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride:

(66) Anal. calc, for C.sub.50H.sub.60Cl.sub.2OSiZr: C, 69.25; H, 6.97. Found: C, 69.43; H, 7.15.

(67) .sup.1H NMR (CDCl.sub.3): δ 7.59-7.38 (group of m, 10H), 6.74 (s, 1H), 6.61 (s, 1H), 3.37 (s, 3H), 3.08-2.90 (m, 3H), 2.86-2.78 (m, 1H), 2.20 (s, 3H), 2.19 (s, 3H), 2.10-1.92 (m, 2H), 1.38 (s, 9H), 1.33 (s, 18H), 1.30 (s, 3H), 1.29 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 159.94, 150.05, 149.86, 144.79, 144.01, 143.20, 135.50, 135.41, 133.87, 133.73, 133.62, 132.82, 132.29, 129.23, 128.74, 126.95, 126.87, 125.36, 125.12, 122.93, 121.68, 121.32, 120.84, 117.90, 81.65, 81.11, 62.57, 35.74, 34.58, 33.23, 32.17, 31.37, 31.36, 30.32, 26.60, 18.39, 18.30, 2.65, 2.57.sup.1. .sup.1 Resonance originated from one carbon atom was not found because of overlapping with some other signal.

Synthesis of MC-CE2 (Comparative)

4-Bromo-2,6-dimethylaniline

(68) ##STR00025##

(69) 159.8 g (1.0 mol) of bromine was slowly (over 2 h) added to a stirred solution of 121.2 g (1.0 mol) of 2,6-dimethylaniline in 500 ml of methanol. The resulting dark-red solution was stirred overnight at room temperature, then poured into a cold solution of 140 g (2.5 mol) of potassium hydroxide in 1100 ml of water.

(70) The organic layer was separated, and the aqueous one was extracted with 500 ml of diethyl ether. The combined organic extract was washed with 1000 ml of water, dried over K.sub.2CO.sub.3, and evaporated in vacuum to give 202.1 g of 4-bromo-2,6-dimethylaniline (purity ca. 90%) as dark-red oil which crystallized upon standing at room temperature. This material was further used without additional purification.

(71) .sup.1H NMR (CDCl.sub.3): δ 7.04 (s, 2H), 3.53 (br.s, 2H), 2.13 (s, 6H).

1-Bromo-3,5-dimethylbenzene

(72) ##STR00026##

(73) 97 ml (1.82 mol) of 96% sulfuric acid was added dropwise to a solution of 134.7 g (ca. 673 mmol) of 4-bromo-2,6-dimethylaniline (prepared above, purity ca. 90%) in 1400 ml of 95% ethanol cooled to −10° C., at a such a rate to maintain the reaction temperature below 7° C. After the addition was complete, the solution was stirred at room temperature for 1 h. Then, the reaction mixture was cooled in an ice-bath, and a solution of 72.5 g (1.05 mol) of sodium nitrite in 150 ml of water was added dropwise over ca. 1 h. The formed solution was stirred at the same temperature for 30 min. Then the cooling bath was removed, and 18 g of copper powder was added. Upon completion of the rapid evolution of nitrogen additional portions (ca. 5 g each, ca. 50 g in total) of copper powder were added with 10 min intervals until gas evolution ceased completely. The reaction mixture was stirred at room temperature overnight, then filtered through a glass frit (G3), diluted with two-fold volume of water, and the crude product was extracted with 4×150 ml of dichloromethane. The combined extract was dried over K.sub.2CO.sub.3, evaporated to dryness, and then distilled in vacuum (b.p. 60-63° C./5 mm Hg) to give a yellowish liquid. This product was additionally purified by flash-chromatography on silica gel 60 (40-63 μm; eluent: hexane) and distilled once again (b.p. 51-52° C./3 mm Hg) to give 63.5 g (51%) of 1-bromo-3,5-dimethylbenzene as a colorless liquid.

(74) .sup.1H NMR (CDCl.sub.3): δ 7.12 (s, 2H), 6.89 (s, 1H), 2.27 (s, 6H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 139.81, 129.03, 128.61, 122.04, 20.99.

(3,5-Dimethylphenyl)boronic acid

(75) ##STR00027##

(76) A solution of 3,5-dimethylphenylmagnesium bromide obtained from a solution of 190.3 g (1.03 mol) of 1-bromo-3,5-dimethylbenzene in 1000 ml of THF and 32 g (1.32 mol, 28% excess) of magnesium turnings was cooled to −78° C., and 104 g (1.0 mol) of trimethylborate was added in one portion. The resulting heterogeneous mixture was stirred overnight at room temperature. The boronic ester was hydrolyzed by careful addition of 1200 ml of 2 M HCl. 500 ml of diethyl ether was added, the organic layer was separated, and the aqueous layer was additionally extracted with 2×500 ml of diethyl ether. The combined organic extract was dried over Na.sub.2SO.sub.4 and then evaporated to dryness to give white mass. The latter was triturated with 200 ml of n-hexane, filtered through glass frit (G3), and the precipitate was dried in vacuo. This procedure gave 114.6 g (74%) of (3,5-dimethylphenyl)boronic acid.

(77) Anal. calc, for C.sub.8H.sub.11BO.sub.2: C, 64.06; H, 7.39. Found: C, 64.38; H, 7.72.

(78) .sup.1H NMR (DMSO-d.sub.6): δ 7.38 (s, 2H), 7.00 (s, 1H), 3.44 (very br.s, 2H), 2.24 (s, 6H).

2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-indan-1-one

(79) ##STR00028##

(80) A mixture of 49.14 g (157.9 mmol) of 2-methyl-4-bromo-5-methoxy-6-tert-butylindan-1-one, 29.6 g (197.4 mmol, 1.25 eq.) of (3,5-dimethylphenyl)boronic acid, 45.2 g (427 mmol) of Na.sub.2CO.sub.3, 1.87 g (8.3 mmol, 5 mol. %) of Pd(OAc).sub.2, 4.36 g (16.6 mmol, 10 mol. %) of PPh.sub.3, 200 ml of water, and 500 ml of 1,2-dimethoxyethane was refluxed for 6.5 h. DME was evaporated on a rotary evaporator, 600 ml of water and 700 ml of dichloromethane were added to the residue. The organic layer was separated, and the aqueous one was additionally extracted with 200 ml of dichloromethane. The combined extract was dried over K.sub.2CO.sub.3 and then evaporated to dryness to give a black oil. The crude product was purified by flash chromatography on silica gel 60 (40-63 μm, hexane-dichloromethane=1:1, vol., then, 1:3, vol.) to give 48.43 g (91%) of 2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindan-1-one as a brownish oil.

(81) Anal. calc, for C.sub.23H.sub.28O.sub.2: C, 82.10; H, 8.39. Found: C, 82.39; H, 8.52.

(82) .sup.1H NMR (CDCl.sub.3): δ 7.73 (s, 1H), 7.02 (s, 3H), 7.01 (s, 3H), 3.32 (s, 3H), 3.13 (dd, J=17.5 Hz, J=7.8 Hz, 1H), 2.68-2.57 (m, 1H), 2.44 (dd, J=17.5 Hz, J=3.9 Hz), 2.36 (s, 6H), 1.42 (s, 9H), 1.25 (d, J=7.5 Hz, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 208.90, 163.50, 152.90, 143.32, 138.08, 136.26, 132.68, 130.84, 129.08, 127.18, 121.30, 60.52, 42.17, 35.37, 34.34, 30.52, 21.38, 16.40.

2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

(83) ##STR00029##

(84) 8.2 g (217 mmol) of NaBH.sub.4 was added to a solution of 48.43 g (143.9 mmol) of 2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindan-1-one in 300 ml of THF cooled to 5° C. Then, 150 ml of methanol was added dropwise to this mixture by vigorous stirring for ca. 7 h at 5° C. The resulting mixture was evaporated to dryness, and the residue was partitioned between 500 ml of dichloromethane and 500 ml of 2 M HCl. The organic layer was separated, the aqueous layer was additionally extracted with 100 ml of dichloromethane. The combined organic extract was evaporated to dryness to give a slightly yellowish oil. To a solution of this oil in 600 ml of toluene 400 mg of TsOH was added, this mixture was refluxed with Dean-Stark head for 10 min and then cooled to room temperature using a water bath. The formed solution was washed by 10% Na.sub.2CO.sub.3, the organic layer was separated, the aqueous layer was extracted with 150 ml of dichloromethane. The combined organic extract was dried over K.sub.2CO.sub.3 and then passed through a short layer of silica gel 60 (40-63 μm). The silica gel layer was additionally washed by 100 ml of dichloromethane. The combined organic elute was evaporated to dryness, and the resulting oil was dried in vacuum at elevated temperature. This procedure gave 45.34 g (98%) of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene which was used without additional purification.

(85) Anal. calc, for C.sub.23H.sub.28O: C, 86.20; H, 8.81. Found: C, 86.29; H, 9.07.

(86) .sup.1H NMR (CDCl.sub.3): δ 7.20 (s, 1H), 7.08 (br.s, 1H), 6.98 (br.s, 1H), 6.42 (m, 1H), 3.25 (s, 3H), 3.11 (s, 2H), 2.36 (s, 6H), 2.06 (s, 3H), 1.43 (s, 9H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 154.20, 145.22, 141.78, 140.82, 140.64, 138.30, 137.64, 131.80, 128.44, 127.18, 126.85, 116.98, 60.65, 42.80, 35.12, 31.01, 21.41, 16.65.

[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-Butyl-1H-inden-1-yl](chloro)dimethylsilane

(87) ##STR00030##

(88) To a solution of 9.0 g (28.08 mmol) of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-di methyl phenyl)-1H-indene in 150 ml of ether, cooled to −50° C., 11.6 ml (28.19 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. The resulting mixture was stirred for 6 h at room temperature, then the obtained yellow suspension was cooled to −60° C., and 18.1 g (140.3 mmol, 5 equiv.) of dichlorodimethylsilane was added in one portion. The obtained solution was stirred overnight at room temperature and then filtered through a glass frit (G3). The filtrate was evaporated to dryness to give [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-Butyl-1H-inden-1-yl](chloro)dimethylsilane as a slightly yellowish oil which was further used without an additional purification.

(89) .sup.1H NMR (CDCl.sub.3): δ 7.38 (s, 1H), 7.08 (s, 2H), 6.98 (s, 1H), 6.43 (s, 1H), 3.53 (s, 1H), 3.25 (s, 3H), 2.37 (s, 6H), 2.19 (s, 3H), 1.43 (s, 9H), 0.43 (s, 3H), 0.17 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 155.78, 145.88, 143.73, 137.98, 137.56, 137.49, 136.74, 128.32, 127.86, 127.55, 126.64, 120.86, 60.46, 49.99, 35.15, 31.16, 21.41, 17.55, 1.11, −0.58.

1-methoxy-2-methyl-4-(3,5-Dimethylphenyl)-1,2,3,5,6,7-hexahydro-s-indacene

(90) ##STR00031##

(91) To a mixture of 2.0 g (2.56 mmol, 1.8 mol. %) of NiCl.sub.2(PPh.sub.3)IPr and 40.0 g (142.3 mmol) of 4-bromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene, 200 ml (200 mmol, 1.4 eq) of 3,5-dimethylphenylmagnesium bromide 1.0 M in THF was added. The resulting solution was refluxed for 3 h, then cooled to room temperature, and 400 ml of water followed by 500 ml of 1.0 M HCl solution were added. Further on, this mixture was extracted with 600 ml of dichloromethane, the organic layer was separated, and the aqueous layer was extracted with 2×100 ml of dichloromethane. The combined organic extract was evaporated to dryness to give a slightly greenish oil. The product was isolated by flash-chromatography on silica gel 60 (40-63 μm; eluent: hexanes-dichloromethane=2:1, vol., then 1:2, vol.). This procedure gave 43.02 g (99%) of 1-methoxy-2-methyl-4-(3,5-dimethylphenyl)-1,2,3,5,6,7-hexahydro-s-indacene as a colorless thick oil as a mixture of two diastereoisomers.

(92) Anal. calc, for C.sub.22H.sub.26O: C, 86.23; H, 8.55. Found: C, 86.07; H, 8.82.

(93) .sup.1H NMR (CDCl.sub.3), Syn-isomer: δ 7.21 (s, 1H), 6.94 (br.s, 1H), 6.90 (br.s, 2H), 4.48 (d, J=5.5 Hz, 1H), 3.43 (s, 3H), 2.94 (t, J=7.5 Hz, 2H), 2.87-2.65 (m, 3H), 2.63-2.48 (m, 2H), 2.33 (s, 6H), 2.02 (quin, J=7.5 Hz, 2H), 1.07 (d, J=6.7 Hz, 3H); Anti-isomer: δ 7.22 (s, 1H), 6.94 (br.s, 1H), 6.89 (br.s, 2H), 4.38 (d, J=4.0 Hz, 1H), 3.48 (s, 3H), 3.06 (dd, J=16.0 Hz, J=7.5 Hz, 1H), 2.93 (t, J=7.3 Hz, 2H), 2.75 (td, J=7.3 Hz, J=3.2 Hz, 2H), 2.51-2.40 (m, 1H), 2.34 (s, 6H), 2.25 (dd, J=16.0 Hz, J=5.0 Hz, 1H), 2.01 (quin, J=7.3 Hz, 2H), 1.11 (d, J=7.1 Hz, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3), Syn-isomer: δ 142.69, 142.49, 141.43, 139.97, 139.80, 137.40, 135.46, 128.34, 126.73, 120.09, 86.29, 56.76, 39.43, 37.59, 33.11, 32.37, 25.92, 21.41, 13.73; Anti-isomer: δ 143.11, 142.72, 140.76, 139.72, 139.16, 137.37, 135.43, 128.29, 126.60, 119.98, 91.53, 56.45, 40.06, 37.65, 33.03, 32.24, 25.88, 21.36, 19.36.

4-(3,5-Dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene

(94) ##STR00032##

(95) To the solution of 43.02 g (140.4 mmol) 1-methoxy-2-methyl-4-(3,5-dimethylphenyl)-1,2,3,5,6,7-hexahydro-s-indacene in 600 ml of toluene, 200 mg of TsOH was added, and the resulting solution was refluxed using Dean-Stark head for 15 min. After cooling to room temperature the reaction mixture was washed with 200 ml of 10% NaHCO.sub.3. The organic layer was separated, and the aqueous layer was additionally extracted with 300 ml of dichloromethane. The combined organic extract was evaporated to dryness to give light orange oil. The product was isolated by flash-chromatography on silica gel 60 (40-63 μm; eluent: hexanes, then hexanes-dichloromethane=10:1, vol.). This procedure gave 35.66 g (93%) of 4-(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene as a slightly yellowish oil which spontaneously solidified to form a white mass.

(96) Anal. calc, for C.sub.21H.sub.22: C, 91.92; H, 8.08. Found: C, 91.78; H, 8.25.

(97) .sup.1H NMR (CDCl.sub.3): δ 7.09 (s, 1H), 6.98 (br.s, 2H), 6.96 (br.s, 1H), 6.44 (m, 1H), 3.14 (s, 2H), 2.95 (t, J=7.3 Hz, 2H), 2.76 (t, J=7.3 Hz, 2H), 2.35 (s, 6H), 2.07 (s, 3H), 2.02 (quin, J=7.3 Hz, 2H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 145.46, 144.71, 142.81, 140.17, 139.80, 137.81, 137.50, 134.33, 128.35, 127.03, 126.48, 114.83, 42.00, 33.23, 32.00, 25.87, 21.38, 16.74.

[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-Butyl-1H-inden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane

(98) ##STR00033##

(99) To a solution of 7.71 g (28.1 mmol) of 4-(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in a mixture of 150 ml of ether and 20 ml of THF 11.6 ml (28.19 mmol) of 2.43 M.sup.nBuLi in hexanes was added in one portion at −50° C. This mixture was stirred for 6 h at room temperature, then the resulting orange solution was cooled to −50° C., and 150 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at −25° C., then a solution of [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl](chloro)dimethylsilane (prepared above, ca. 28.08 mmol) in 150 ml of ether was added in one portion. This mixture was stirred overnight at room temperature, then filtered through a pad of silica gel 60 (40-63 μm), which was additionally washed by 2×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure to give a yellow oil. The product was isolated by flash-chromatography on silica gel 60 (40-63 μm; eluent: hexanes-dichloromethane=10:1, vol., then 5:1, vol.). This procedure gave 11.95 g (65%) of [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-Butyl-1H-inden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (as ca. 1:1 mixture of stereoisomers) as a yellowish glassy solid.

(100) Anal. calc, for C.sub.46H.sub.54OSi: C, 84.87; H, 8.36. Found: C, 85.12; H, 8.59.

(101) .sup.1H NMR (CDCl.sub.3): δ 7.48 and 7.33 (2s, sum 1H), 7.26-7.18 (m, 1H), 7.16-7.07 (m, 2H), 7.04-6.95 (m, 4H), 6.51 and 6.45 (2s, sum 2H), 3.69 and 3.65 (2s, sum 2H), 3.28 and 3.26 (2s, sum 3H), 3.01-2.74 (m, 4H), 2.38 ad 2.37 (2s, sum 12H), 2.20 and 2.15 (2s, sum 6H), 2.09-1.97 (m, 2H), 1.43 and 1.42 (2s, sum 9H), −0.17, −0.18, −0.19 and −0.24 (4s, sum 6H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 155.29, 147.45, 147.39, 145.99, 145.75, 143.93, 143.90, 143.72, 143.69, 142.06, 142.01, 140.08, 140.06, 139.46, 139.37, 139.26, 139.03, 139.00, 138.24, 137.50, 137.34, 137.07, 136.99, 130.39, 128.23, 128.14, 127.92, 127.50, 127.46, 127.26, 126.12, 126.05, 125.99, 125.94, 120.55, 120.51, 118.46, 118.27, 60.49, 47.33, 46.86, 46.76, 35.14, 33.33, 33.28, 32.18, 31.26, 31.21, 25.95, 25.91, 21.44, 17.96, 17.88, −5.27, −5.39, −5.50, −5.82.

Anti-dimethylsilanediyl[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride

(102) ##STR00034##

(103) To a solution of 11.95 g (18.36 mol) of [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (prepared above) in 200 ml of ether, cooled to −50° C., 15.1 ml (35.7 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. This mixture was stirred for 3 h at room temperature, then the resulting red solution was cooled to −78° C., and 4.28 g (18.37 mmol) of ZrCl.sub.4 was added. The reaction mixture was stirred for 24 h at room temperature to give light red solution with orange precipitate. This mixture was evaporated to dryness. The residue was treated with 250 ml of hot toluene, and the formed suspension was filtered through glass frit (G4). The filtrate was evaporated to 40 ml. Red powder precipitated from this solution overnight at room temperature was collected, washed with 10 ml of cold toluene, and dried in vacuum. This procedure gave 0.6 g of syn-zirconocene. The mother liquor was evaporated to ca. 35 ml, and 15 ml of n-hexane was added to the warm solution. The red powder precipitated from this solution overnight at room temperature was collected and dried in vacuum. This procedure gave 3.49 g syn-zirconocene. The mother liquor was evaporated to ca. 20 ml, and 30 ml of n-hexane was added to the warm solution. The yellow powder precipitated from this solution overnight at room temperature was collected and dried in vacuum. This procedure gave 4.76 g anti-zirconocene as a solvate with toluene (×0.6 toluene) contaminated with ca. 2% of syn-isomer. Thus, the total yield of syn- and anti-zirconocenes isolated in this synthesis was 8.85 g (59%).

Anti-dimethylsilanediyl[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride

(104) Anal. calc, for C.sub.46H.sub.52Cl.sub.2OSiZr×0.6C.sub.7H.sub.8: C, 69.59; H, 6.61. Found: C, 69.74; H, 6.68.

(105) .sup.1H NMR (CDCl.sub.3): δ 1.41 (s, 1H), 7.40 (s, 1H), 7.37-7.03 (m, 4H), 6.95 (s, 2H), 6.71 (s, 1H), 6.55 (s, 1H), 3.43 (s, 3H), 3.03-2.96 (m, 2H), 2.96-2.87 (m, 1H), 2.87-2.76 (m, 1H), 2.34 and 2.33 (2s, sum 12H), 2.19 and 2.18 (2s, sum 6H), 2.06-1.94 (m, 2H), 1.38 (s, 9H), 1.28 (s, 3H), 1.27 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 159.73, 144.59, 143.99, 143.00, 138.26, 137.84, 137.59, 136.80, 135.35, 133.85, 133.63, 132.95, 132.52, 128.90, 128.80, 127.40, 126.95, 126.87, 126.65, 122.89, 121.61, 121.53, 120.82, 117.98, 81.77, 81.31, 62.62, 35.73, 33.20, 32.12, 30.37, 26.49, 21.47, 21.38, 18.40, 18.26, 2.64, 2.54.

Syn-dimethylsilanediyl[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride

(106) Anal. calc, for C.sub.46H.sub.52Cl.sub.2OSiZr: C, 68.11; H, 6.46. Found: C, 68.37; H, 6.65.

(107) .sup.1H NMR (CDCl.sub.3): δ 7.51 (s, 1H), 7.39 (s, 1H), 7.36-6.99 (m, 4H), 6.95 (s, 2H), 6.60 (s, 1H), 6.44 (s, 1H), 3.27 (s, 3H), 2.91-2.75 (m, 4H), 2.38 and 2.34 (2s, sum 18H), 1.99-1.87 (m, 1H), 1.87-1.74 (m, 1H), 1.42 (s, 3H), 1.36 (s, 9H), 1.19 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 158.74, 143.41, 142.84, 142.31, 138.30, 137.77, 137.55, 136.85, 135.87, 135.73, 134.99, 134.75, 131.64, 128.83, 128.76, 127.97, 127.32, 126.82, 126.22, 123.91, 121.35, 121.02, 120.85, 118.56, 83.47, 83.08, 62.32, 35.53, 33.33, 31.96, 30.33, 26.53, 21.45 (two resonances), 18.56, 18.43, 2.93, 2.65.

Synthesis of metallocene MC-IE1 (Inventive) 2-methyl-[4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane

(108) ##STR00035##

(109) BuLi in hexanes (2.43 M, 30.4 ml, 73.87 mmol) was added in one portion to a solution of 22.3 g (73.73 mmol) of 4-(4-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in 300 ml of ether, cooled to −50° C. The resulting mixture was stirred overnight at room temperature, then the resulting suspension with a large amount of precipitate was cooled to −78° C. (wherein the precipitate was substantially dissolved to form an orange solution) and 47.6 g (369 mmol, 5 equiv.) of dichlorodimethylsilane was added in one portion. The obtained solution was stirred overnight at room temperature and then filtered through a glass frit (G4). The filtrate was evaporated to dryness to give 28.49 g (98%) of 2-methyl-[4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethyl silane as a colorless glass which was used without further purification.

(110) .sup.1H NMR (CDCl.sub.3): δ 7-50-7.45 (m, 2H), 7.36 (s, 1H), 7.35-7.32 (m, 2H), 6.60 (s, 1H), 3.60 (s, 1H), 3.10-2.82 (m, 4H), 2.24 (s, 3H), 2.08 (quin, J=7.3 Hz, 2H), 1.42 (s, 9H), 0.48 (s, 3H), 0.22 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 149.27, 144.41, 142.15, 141.41, 139.94, 139.83, 136.85, 130.19, 129.07, 126.88, 124.86, 118.67, 49.76, 34.55, 33.27, 32.32, 31.44, 26.00, 17.6

[2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane

(111) ##STR00036##

(112) .sup.nBuLi in hexanes (2.43 M, 9.6 ml, 23.33 mmol) was added in one portion to a solution of 8.12 g (23.3 mmol) of 2-methyl-5-tert-butyl-7-(4-tert-buty 1 phenyl)-6-methoxy-1H-indene in 150 ml of ether at −50° C. This mixture was stirred overnight at room temperature, then the resulting yellow suspension was cooled to −50° C., and 150 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at −25° C., then a solution of 9.2 g (23.29 mmol) of [2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane in a mixture of 100 ml of ether and ml of THF was added in one portion. This mixture was stirred overnight at room temperature, then filtered through a pad of silica gel 60 (40-63 μm). The precipitate was additionally washed with 2×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure, and the residue was dried under vacuum at elevated temperature. This procedure gave 16.6 g (ca. 100%) of [2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (ca. 95% purity by NMR, approx. 1:1 mixture of stereoisomers) as yellowish glass which was further used without an additional purification.

(113) .sup.1H NMR (CDCl.sub.3): δ 7.50 (s, 0.5H), 7.48-7.41 (m, 6H), 7.37-7.33 (m, 2.5H), 7.26 (s, 0.5H), 7.22 (s, 0.5H), 6.57 and 6.50 (2s, sum 2H), 3.71, 3.69, 3.67 and 3.65 (4s, sum 2H), 3.23 and 3.22 (2s, sum 3H), 3.03-2.80 (m, 4H), 2.20, 2.16 and 2.14 (3s, sum 6H), 2.08-1.99 (m, 2H), 1.43 and 1.41 (2s, sum 9H), 1.39 (s, 18H), −0.19, −0.20, −0.21 and −0.23 (4s, sum 6H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 155.49, 155.46, 149.41, 149.14, 149.11, 147.48, 147.44, 146.01, 145.77, 143.95, 143.91, 143.76, 143.71, 142.14, 142.10, 139.52, 139.42, 139.34, 139.29, 139.20, 139.16, 137.10, 137.05, 137.03, 135.20, 130.05, 130.03, 129.73, 129.11, 127.25, 127.22, 126.20, 126.13, 125.98, 125.94, 125.05, 124.82, 120.59, 120.52, 118.51, 118.26, 60.51, 60.48, 47.31, 46.89, 46.72, 35.14, 34.55, 33.34, 33.28, 32.30, 31.47, 31.45, 31.24, 31.19, 26.02, 25.99, 17.95, 17.86.

Anti-dimethylsilanediyl[2-methyl-4-(4-tert-butyl phenyl)-5-methoxy-6-tert-butyl-inden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]hafnium dichloride

(114) ##STR00037##

(115) BuLi in hexanes (2.43 M, 19.2 ml, 46.7 mmol) was added in one portion to a solution of 16.6 g (23.3 mol) of [2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (prepared above) in 250 ml of ether, cooled to −50° C. This mixture was stirred overnight at room temperature, then the resulting cherry red solution was cooled to −60° C., and 7.46 g (23.29 mmol) of HfCl.sub.4 was added. The reaction mixture was stirred for 24 h at room temperature to give an orange suspension. This suspension was filtered through glass frit (G4), and the precipitate was washed with 30 ml of ether. On the evidence of NMR spectroscopy, this precipitate was pure anti-hafnocene dichloride (and LiCl), while the filtrate included a mixture of syn- and anti-hafnocene dichlorides in a ca. 77/23 ratio (in favor to syn-) contaminated with some other impurities. The precipitate was dissolved in 100 ml of hot toluene, and the formed suspension was filtered from LiCl through glass frit (G4). The filtrate was evaporated to ca. 20 ml, and 40 ml of n-hexane was added. Yellow solid precipitated at room temperature was filtered off (G3), washed with 15 ml of cold n-hexane, and then dried in vacuum. This procedure gave 4.70 g (21%) of pure anti-complex. The mother liquor was evaporated to ca. 15 ml, and 40 ml of n-hexane was added. Yellow precipitate formed was filtered off (G3) and then dried under vacuum. This procedure gave 3.60 g (16%) of a ca. 4/1 mixture of syn- and anti-hafnocenes (in favor of syn-). Thus, the total yield of anti- and syn-hafnocenes isolated in this synthesis was 8.3 g (37%).

Anti-dimethylsilanediyl[2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butyl-inden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]hafnium dichloride

(116) Anal. calc, for C.sub.50H.sub.60Cl.sub.2HfOSi: C, 62.92; H, 6.34. Found: C, 63.11; H, 6.58.

(117) .sup.1H NMR (CDCl.sub.3): δ 7.59-7.36 (m, 10H), 6.65 (s, 1H), 6.52 (s, 1H), 3.35 (s, 3H), 3.15-2.91 (m, 3H), 2.91-2.79 (m, 1H), 2.27 (s, 6H), 2.10-1.88 (m, 2H), 1.38 (s, 9H), 1.33 (s, 18H), 1.28 (2s, 6H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 159.75, 150.01, 149.82, 144.36, 143.58, 143.04, 135.53, 133.86, 133.07, 132.80, 132.26, 131.87, 131.20, 129.23, 128.74, 126.52, 125.34, 125.10, 121.31, 120.85, 119.82, 119.47, 117.81, 82.78, 82.20, 62.56, 35.68, 34.58, 33.13, 32.12, 31.37, 30.36, 26.67, 18.26, 18.15, 2.63, 2.55.

Synthesis of metallocene MC-IE2 (Inventive)

[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl]chlorodimethylsilane

(118) ##STR00038##

(119) .sup.nBuLi in hexanes (2.43 M, 25.2 ml, 61.24 mmol) was added in one portion to a solution of 19.66 g (61.35 mmol) of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene in 300 ml of ether cooled to −50° C. The resulting mixture was stirred for 4 h at room temperature, then the resulting yellow suspension was cooled to −60° C., and 40.0 ml (42.8 g, 331.6 mmol, 5.4 eqv.) of dichlorodimethylsilane was added in one portion. The obtained solution was stirred overnight at room temperature and then filtered through a glass frit (G3). The filtrate was evaporated to dryness to give [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl]chlorodimethylsilane as a slightly yellowish oil which was further used without an additional purification.

(120) .sup.1H NMR (CDCl.sub.3): δ 7.38 (s, 1H), 7.08 (s, 2H), 6.98 (s, 1H), 6.43 (s, 1H), 3.53 (s, 1H), 3.25 (s, 3H), 2.37 (s, 6H), 2.19 (s, 3H), 1.43 (s, 9H), 0.43 (s, 3H), 0.17 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 155.78, 145.88, 143.73, 137.98, 137.56, 137.49, 136.74, 128.32, 127.86, 127.55, 126.64, 120.86, 60.46, 49.99, 35.15, 31.16, 21.41, 17.55, 1.11, −0.58.

[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-inden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane

(121) ##STR00039##

(122) .sup.nBuLi in hexanes (2.43 M, 25.2 ml, 61.24 mmol) was added in one portion to a solution of 16.83 g (61.33 mmol) of 4-(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in a mixture of 300 ml of ether and 40 ml of THF, cooled to −50° C. This mixture was stirred overnight at room temperature, then the resulting reddish solution was cooled to −50° C., and 300 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at −25° C., then a solution of [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl]chlorodimethylsilane (prepared above, ca. 61.24 mmol) in 150 ml of ether was added in one portion. This mixture was stirred overnight at room temperature, then filtered through a pad of silica gel 60 (40-63 μm), which was additionally washed with 2×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure, and the residue was dried in vacuum at elevated temperature. This procedure gave 39.22 g (98%) of [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (a ca. 3:2 mixture of stereoisomers) as a reddish glass.

(123) .sup.1H NMR (CDCl.sub.3): δ 7.48 and 7.33 (2s, sum 1H), 7.26-7.18 (m, 1H), 7.16-7.07 (m, 2H), 7.04-6.95 (m, 4H), 6.51 and 6.45 (2s, sum 2H), 3.69 and 3.65 (2s, sum 2H), 3.28 and 3.26 (2s, sum 3H), 3.01-2.74 (m, 4H), 2.38 ad 2.37 (2s, sum 12H), 2.20 and 2.15 (2s, sum 6H), 2.09-1.97 (m, 2H), 1.43 and 1.42 (2s, sum 9H), −0.17, −0.18, −0.19 and −0.24 (4s, sum 6H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 155.29, 147.45, 147.39, 145.99, 145.75, 143.93, 143.90, 143.72, 143.69, 142.06, 142.01, 140.08, 140.06, 139.46, 139.37, 139.26, 139.03, 139.00, 138.24, 137.50, 137.34, 137.07, 136.99, 130.39, 128.23, 128.14, 127.92, 127.50, 127.46, 127.26, 126.12, 126.05, 125.99, 125.94, 120.55, 120.51, 118.46, 118.27, 60.49, 47.33, 46.86, 46.76, 35.14, 33.33, 33.28, 32.18, 31.26, 31.21, 25.95, 25.91, 21.44, 17.96, 17.88, −5.27, −5.39, −5.50, −5.82.

Anti-dimethylsilanediyl[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-inden-1-yl][2-methyl-4-(3,5-di methyl phenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]hafnium dichloride

(124) ##STR00040##

(125) .sup.nBuLi in hexanes (2.43 M, 49.6 ml, 120.5 mmol) was added in one portion to a solution of 39.22 g (60.25 mmol) of [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (prepared above) in 400 ml of ether, cooled to −50° C. This mixture was stirred overnight at room temperature. The resulting red solution was then cooled to −78° C., and 19.3 g (60.26 mmol) of HfCl.sub.4 was added. The reaction mixture was stirred for 24 h at room temperature to give an orange suspension. The precipitate was filtered off (G4), then washed with 30 ml of cold ether. On the evidence of NMR spectroscopy, this precipitate was pure syn-hafnocene dichloride (with LiCl), while the filtrate included a ca. 4/1 mixture of anti- and syn-hafnocene dichlorides (in favor to anti-) contaminated with some other impurities. The precipitate was dissolved in 150 ml of hot toluene, and the formed suspension was filtered to remove LiCl through glass frit (G4). The filtrate was evaporated to ca. 45 ml. Orange sold material precipitated overnight at room temperature was filtered off (G3) and then dried in vacuum. This procedure gave 8.1 g (15%) of pure syn-complex. The mother liquor was evaporated almost to dryness, and the residue was triturated with 20 ml of n-hexane to give 2.6 g (4.8%) of syn-hafnocene dichloride as an orange powder. The ether mother liquor was evaporated to ca. 60 ml, the precipitated yellow powder was filtered off (G4), washed with 20 ml of cold (0° C.) ether, and then dried under vacuum. This procedure gave 10.2 g (19%) of pure anti-hafnocene dichloride. Thus, the total yield of anti- and syn-hafnocene dichlorides isolated in this synthesis was 20.9 g (39%).

Anti-dimethylsilanediyl[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-inden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]hafnium dichloride

(126) Anal. calc, for C.sub.46H.sub.52Cl.sub.2OSiHf: C, 61.50; H, 5.83. Found: C, 61.38; H, 6.15.

(127) .sup.1H NMR (CDCl.sub.3): δ 7.51 (s, 1H), 7.43 (s, 1H), 7.34-7.02 (br.m, 4H), 6.94 (s, 2H), 6.61 (s, 1H), 6.46 (s, 1H), 3.42 (s, 3H), 3.11-2.79 (m, 4H), 2.33 (s, 6H), 2.32 (s, 6H), 2.27 (s, 6H), 2.07-1.92 (m, 2H), 1.38 (s, 9H), 1.27 (s, 3H), 1.26 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 159.55, 144.17, 143.58, 142.84, 138.38, 137.82, 137.57, 136.94, 133.09, 132.67, 132.40, 132.11, 131.23, 128.84, 128.76, 127.40, 126.88, 126.53, 124.97, 121.28, 120.84, 119.76, 119.71, 117.90, 82.92, 82.40, 62.62, 35.68, 33.11, 32.07, 30.43, 26.56, 21.46, 21.38, 18.26, 18.12, 2.63, 2.53.

Syn-dimethylsilanediyl[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-inden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]hafnium dichloride

(128) Anal. calc, for C.sub.46H.sub.52Cl.sub.2OSiHf: C, 61.50; H, 5.83. Found: C, 61.59; H, 6.06.

(129) .sup.1H NMR (CDCl.sub.3): δ 7.53 (s, 1H), 7.41 (s, 1H), 7.29-7.06 (m, 4H), 6.94 (s, 2H), 6.50 (s, 1H), 6.35 (s, 1H), 3.26 (s, 3H), 2.95-2.77 (m, 4H), 2.49 (s, 3H), 2.46 (s, 3H), 2.33 (2s, sum 12H), 1.99-1.86 (m, 1H), 1.86-1.73 (m, 1H), 1.40 (s, 3H), 1.37 (s, 9H), 1.18 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 158.61, 143.03, 142.46, 142.16, 138.42, 137.73, 137.52, 136.98, 135.33, 134.60, 133.69, 132.53, 131.19, 128.79, 128.71, 127.34, 126.85, 126.00, 125.76, 121.95, 121.45, 119.12, 118.91, 118.55, 84.66, 84.26, 62.31, 35.48, 33.25, 31.94, 30.40, 26.60, 21.44, 18.44, 18.31, 2.93, 2.61

(130) Summary of Metallocene Examples Used in the Examples

(131) ##STR00041## ##STR00042##
Catalyst Preparation Examples
Materials

(132) Inventive metallocenes MC-IE1 and MC-IE2; and comparative metallocenes MC-CE1 and MC-CE2 as described above were used in preparing catalysts.

(133) MAO was used as a 30 wt-% solution in toluene. Trityl tetrakis(pentafluorophenyl)borate (Boulder Chemicals) was used as purchased. As surfactants were used perfluoroalkylethyl acrylate esters (CAS number 65605-70-1) purchased from the Cytonix corporation, dried over activated molecular sieves (2 times) and degassed by argon bubbling prior to use (SI) or 1H,1H-Perfluoro(2-methyl-3-oxahexan-1-ol) (CAS 26537-88-2) purchased from Unimatec, dried over activated molecular sieves (2 times) and degassed by argon bubbling prior to use (S2). Hexadecafluoro-1,3-dimethylyclohexane (PFC) (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. Propylene is provided by Borealis and adequately purified before use. Triethylaluminum was purchased from Crompton and used in pure form. Hydrogen is provided by AGA and purified before use.

(134) 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.

Catalyst Example CE1 (Comparative)

(135) Inside the glovebox, 85.9 mg of dry and degassed surfactant S2 was mixed with 2 mL of MAO in a septum bottle and left to react overnight. The following day, 43.9 mg MC-CE1 (0,076 mmol, 1 equivalent) was dissolved with 4 mL of the MAO solution in another septum bottle and left to stir inside the glovebox.

(136) After 60 minutes, 4 mL of the MAO-metallocene solution and 1 mL of the surfactant solution were successively added into a 50 mL emulsification glass reactor containing 40 mL of PFC at −10° C. and equipped with an overhead stirrer (stirring speed=600 rpm). Total amount of MAO is 5 mL (450 equivalents). A red emulsion formed immediately and 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 PFC at 90° C., and stirred at 600 rpm until the transfer is completed, then 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 PFC and after 45 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 of a red free flowing powder was obtained.

Catalyst Example CE2 (Comparative)

(137) Inside the glovebox, surfactant S2 solution (28.8 mg of dry and degassed S2 dilute in 0.2 mL toluene) was added dropwise to 5 mL of 30 wt.-% Chemtura MAO. The solutions were left under stirring for 10 minutes. Then, 98.7 mg of metallocene MC-CE1 was added to MAO/surfactant. After 60 minutes stirring, 104.9 mg of trityl tetrakis(pentafluorophenyl) borate was added.

(138) After 60 minutes stirring, the surfactant-MAO-metallocene-borate solution were added into a 50 mL emulsification glass reactor containing 40 mL of PFC at −10° C. and equipped with an overhead stirrer (stirring speed=600 rpm). A red emulsion formed immediately and stirred during 15 minutes at −10° C./600 rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot PFC at 90° C. and stirred at 600 rpm until the transfer is completed. Then 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 PFC and after 35 minutes the solvent was siphoned off. The remaining catalyst was dried during 2 hours at 50° C. over an argon flow. 0.90 g of a red free flowing powder was obtained.

Catalyst Example CE3 (Comparative, No B-Cocatalyst)

(139) Inside the glovebox, surfactant S2 solution (28.8 mg of dry and degassed S2 dilute in 0.2 mL toluene) was added dropwise to 5 mL of 30 wt.-% Chemtura MAO. The solutions were left under stirring for 10 minutes. Then, 48.3 mg of metallocene MC-IE1 was added to MAO/surfactant.

(140) After 60 minutes stirring, the surfactant-MAO-metallocene solution were added into a 50 mL emulsification glass reactor containing 40 mL of PFC at −10° C. and equipped with an overhead stirrer (stirring speed=600 rpm). A yellow emulsion formed immediately and stirred during 15 minutes at −10° C./600 rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot PFC at 90° C. and stirred at 600 rpm until the transfer is completed. Then 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 PFC and after 35 minutes the solvent was siphoned off. The remaining catalyst was dried during 2 hours at 50° C. over an argon flow. 0.80 g of a yellow free flowing powder was obtained.

Catalyst Example IE1 (Inventive)

(141) Inside the glovebox, surfactant S2 solution (28.8 mg of dry and degassed S2 dilute in 0.2 mL toluene) was added dropwise to 5 mL of 30 wt.-% Chemtura MAO. The solutions were left under stirring for 10 minutes. Then, 108.7 mg of metallocene MC-IE1 was added to MAO/surfactant. After 60 minutes, 106.0 mg of trityl tetrakis(pentafluorophenyl)borate was added. The mixture was left to react at room temperature inside the glovebox for 60 min.

(142) Then, the surfactant-MAO-metallocene-borate solution were added into a 50 mL emulsification glass reactor containing 40 mL of PFC at −10° C. and equipped with an overhead stirrer (stirring speed=600 rpm). A yellow emulsion formed immediately and stirred during 15 minutes at −10° C./600 rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot PFC at 90° C. and stirred at 600 rpm until the transfer is completed. Then 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 PFC and after 35 minutes the solvent was siphoned off. The remaining catalyst was dried during 2 hours at 50° C. over an argon flow. 0.75 g of a yellow free flowing powder was obtained.

Catalyst Example CE4 (Comparative)

(143) Inside the glovebox, 86.8 mg of dry and degassed S2 were mixed with 2 mL of 30 wt.-% Chemtura MAO in a septum bottle and left to react overnight. The following day, 41.1 mg of Metalloene MC-CE2 (0,051 mmol, 1 equivalent) were dissolved with 4 mL of the 30 wt.-% Chemtura MAO solution in another septum bottle and left to stir inside the glovebox.

(144) After 60 minutes, 1 mL of the surfactant solution and the 4 mL of the MAO-metallocene solution were successively added into a 50 mL emulsification glass reactor containing 40 mL of PFC 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 stirred during 15 minutes at −10° C./600 rpm. Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hot PFC at 90° C., and stirred at 600 rpm until the transfer is completed, and then 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 PFC and after 35 minutes the solvent was siphoned off. The remaining catalyst was dried during 2 hours at 50° C. over an argon flow. 0.54 g of a red free flowing powder was obtained.

Catalyst Example CE5 (Comparative)

(145) Inside the glovebox, surfactant S2 solution (28.8 mg of dry and degassed S2 dilute in 0.2 mL toluene) was added dropwise to 5 mL of 30 wt.-% Chemtura MAO. The solutions were left under stirring for 10 minutes. Then, 92.3 mg of metallocene MC-CE2 was added to MAO/surfactant. After 60 minutes stirring, 106 mg of trityl tetrakis(pentafluorophenyl)borate was added.

(146) After 60 minutes stirring, the surfactant-MAO-metallocene-borate solution were added into a 50 mL emulsification glass reactor containing 40 mL of PFC at −10° C. and equipped with an overhead stirrer (stirring speed=600 rpm). A red emulsion formed immediately and stirred during 15 minutes at −10° C./600 rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot PFC at 90° C. and stirred at 600 rpm until the transfer is completed. Then 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 PFC and after 35 minutes the solvent was siphoned off. The remaining catalyst was dried during 2 hours at 50° C. over an argon flow. 0.6 g of a red free flowing powder was obtained.

Catalyst Example IE2 (Inventive)

(147) Inside the glovebox, surfactant S2 solution (28.8 mg of dry and degassed S2 dilute in 0.2 mL toluene) was added dropwise to 5 mL of 30 wt.-% Chemtura MAO. The solutions were left under stirring for 10 minutes. Then, 102.23 mg of metallocene MC-IE2 was added to MAO/surfactant. After 60 minutes, 104.9 mg of trityl tetrakis(pentafluorophenyl)borate was added. The mixture was left to react at room temperature inside the glovebox for 60 min.

(148) Then, the surfactant-MAO-metallocene-borate solution were added into a 50 mL emulsification glass reactor containing 40 mL of PFC at −10° C. and equipped with an overhead stirrer (stirring speed=600 rpm). A yellow emulsion formed immediately and stirred during 15 minutes at −10° C./600 rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot PFC at 90° C. and stirred at 600 rpm until the transfer is completed. Then 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 PFC and after 35 minutes the solvent was siphoned off. The remaining catalyst was dried during 2 hours at 50° C. over an argon flow. 0.67 g of a yellow free flowing powder was obtained.

(149) Catalyst results are disclosed in Table 1

(150) TABLE-US-00001 TABLE 1 ICP Al ICP Hf ICP Zr Al/M* Catalyst MC (wt.- %) (wt.- %) (wt.- %) (mol/mol) Cat-CE1 MC-CE1 37.0 0.26 481 Cat-CE2 MC-CE1 30.2 0.55 185 Cat-CE3 MC-IE1 30.6 0.53 382 Cat-IE1 MC-IE1 29.4 1.07 182 Cat-CE4 MC-CE2 37.0 0.26 486 Cat-CE5 MC-CE2 31.9 0.56 192 Cat-IE2 MC-IE2 31.4 1.19 174 *M is Zr or Hf
Off-Line Pre-Polymerisation of Catalysts of Examples CE4, CE5 and IE2

(151) The catalysts of examples CE4, CE5 and IE2 were pre-polymerised according to the following procedure: Off-line pre-polymerisation experiment was 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 catalyst to be pre-polymerised were loaded into the reactor inside a glove box and the reactor was sealed. The reactor was then taken out from the glove box and placed inside a water cooled bath kept at 25° C. The overhead stirrer and the feeding lines were connected and stirring speed set to 450 rpm. The experiment was started by opening the propylene feed into the reactor. The total pressure in the reactor was raised to about 5 barg and held constant by propylene feed via mass flow controller until the target degree of polymerisation was reached. The reaction was stopped by flashing the volatile components. Inside glove box, the reactor was opened and the content poured into a glass vessel. The perfluoro-1,3-dimethylcyclohexane was evaporated until a constant weight was obtained to yield the off-line pre-polymerised catalyst.

(152) The off-line pre-polymerised catalysts are marked as pCE4, pCE5 and pIE2 and pre-polymerisation degrees (DP) thereof are disclosed in Table 2.

(153) The pre-polymerisation degree (DP) is defined as weight of polymer matrix/weight of solid catalyst before the off-line pre-polymerisation step.

(154) The composition of the catalysts (before off-line pre-polymerisation) can determined by ICP. The metallocene (MC) content of the off-line pre-polymerised catalysts can be calculated from the ICP data as follows:

(155) $\begin{array}{cc}\frac{\mathrm{Al}}{\mathrm{Zr}}\left(\mathrm{mol}/\mathrm{mol}\right)=\frac{\mathrm{Al}\left(\mathrm{wt}\%,\mathrm{ICP}\right)/26,98}{\mathrm{Zr}\left(\mathrm{wt}\%,\mathrm{ICP}\right)/91,22}& \mathrm{Equation}1\end{array}$$\begin{array}{cc}\mathrm{Zr}\left(\mathrm{mol}\%\right)=\frac{100}{\frac{\mathrm{Al}}{\mathrm{Zr}}\left(\mathrm{mol}/\mathrm{mol}\right)+1}& \mathrm{Equation}2\end{array}$$\begin{array}{cc}\mathrm{MC}\left(\mathrm{wt}\%,\mathrm{before}\mathrm{off}-\mathrm{line}\mathrm{prepol}\mathrm{cat}\right)=\frac{100\times \left(\mathrm{Zr},\mathrm{mol}\%\times \mathrm{MwMC}\right)}{\mathrm{Zr},\mathrm{mol}\%\times \mathrm{MwMC}+\left(100-\mathrm{Zr},\mathrm{mol}\%\right)\times \mathrm{MwMAO}}& \mathrm{Equation}3\end{array}$$\begin{array}{cc}\mathrm{MC}\left(\mathrm{wt}\%,\mathrm{off}-\mathrm{line}\mathrm{prepolym}\mathrm{cat}\right)=\frac{\mathrm{MC}\left(\mathrm{wt}\%,\mathrm{before}\mathrm{off}-\mathrm{line}\mathrm{prepol}\mathrm{cat}\right)}{DP+1}& \mathrm{Equation}4\end{array}$

(156) TABLE-US-00002 TABLE 2 Off-line prepolymerised catalyst pCE4 pCE5 pIE2 Pre-polymerisation degree, g/g 3.15 5.47 3.62 Metallocene content, wt % in off- 0.68 1.05 1.76 line prepolymerised catalyst

Polymerisation Examples

(157) Homopolymerisation of Propylene

(158) The polymerisations were performed in a 5 L reactor. 200 μl of triethylaluminum (TEA) was fed as a scavenger in 5 mL of dry and degassed pentane. The desired amount of hydrogen was then loaded (1 mmol) and 1100 g of liquid propylene was fed into the reactor. The temperature was set to 20° C. The desired amount of catalyst in 5 mL of PFC is flushed into the reactor with a nitrogen overpressure. After 5 minutes prepolymerisation, the temperature is raised to 70° C. over a period of 15 minutes. The polymerisation is stopped after 60 minutes by venting the reactor and flushing with nitrogen before the polymer is collected.

(159) The catalyst activities were calculated on the basis of the 60 minute (homopolymerisation of propylene) period according to the following formula:

(160) $\mathrm{Catalyst}\mathrm{Activity}\left(\mathrm{kg}-\mathrm{PP}/g-\mathrm{Cat}/h\right)=\frac{\mathrm{amount}\mathrm{of}\mathrm{polymer}\mathrm{produced}\left(\mathrm{kg}\right)}{\mathrm{catalyst}\mathrm{loading}\left(g\right)\times \mathrm{polymerisation}\mathrm{time}\left(h\right)}$

(161) Polymerisation results are disclosed in table 3. Polymerisation examples are marked as P-CEn/P-IEn.

(162) TABLE-US-00003 TABLE 3 Homopolymerisation results and polymer analysis Homo- polymer- Cata- Poly- Activity MFR.sub.21 isation lyst mer (kg-PP/ (g/10 T.sub.m T.sub.c Example Catalyst (mg) (g) g-cat/h) min) (° C.) (° C.) P-CE1 Cat-CE1 11.1 144.4 13.0 3.61  152.1 108.0 P-CE2 Cat-CE2  5.9 179.9 30.5 5.5  155.1 109.8 P-CE3 Cat-CE3 26.3  87.7  3.3 0.55  155.4 109.2 P-IE1 Cat-IE1  8.7 307.4 35.3 2.26  158.8 112.1 P-CE4 Cat-CE4 10.9 136.9 12.6 2.06  150.1 108.3 P-CE5 Cat-CE5  5.8  98.3 16.9 5.99  156.3 112.1 P-IE2 Cat-IE2 10.9 236.6 21.7 0.703 160.3 112.1

(163) As can be seen from the homopolymerisation results the inventive catalysts have clearly higher Tm compared to the comparative examples with similar ligand structure of the metallocene complex, but with Zr as the metal; or with Hf, but not using boron cocatalyst. Further, activity is on a higher level in inventive examples.

(164) Copolymerisation of Propylene with Ethylene

(165) Step 1: Prepolymerisation and Bulk Homopolymerisation

(166) A 21.2 L stainless-steel reactor containing 0.4 barg propylene was filled with 3950 g propylene. Triethylaluminum was injected into the reactor by additional 240 g propylene. The solution was stirred at 20° C. and 250 rpm for at least 20 min. The catalyst was injected as described in the following: The desired amount of solid, off-line prepolymerised catalyst was loaded into a 5 ml stainless steel vial inside a glovebox and a second 5 ml vial containing 4 ml n-heptane pressurized with 10 bars of nitrogen was added on top of the first vial. This catalyst feeder system was mounted on a port on top of the autoclave. In experiments P-pCE5 and P-pIE2-2, immediately afterwards 2 NL of H2 was dosed via mass flow controller in one minute. The valve between the two vials was opened and the solid catalyst was contacted with heptane under nitrogen pressure for 2 s, then flushed into the reactor with 240 g propylene. The prepolymerisation was run for 10 min. At the end of the prepolymerisation step the temperature was raised to 80° C. When the internal reactor temperature has reached 71° C. 1.5 NL (procedures 1 and 2) or 2.0 NL of H2 (procedure 3) was added via mass flow controller in three minutes. The reactor temperature was held constant at 80° C. throughout the polymerisation. The polymerisation time was measured starting when the internal reactor temperature reached 2° C. below the set polymerisation temperature.

(167) Step 2: Gas Phase Homopolymerisation

(168) After the bulk step was completed, the stirrer speed was reduced to 50 rpm and the pressure was reduced to 23 bar-g by venting the monomer. Afterwards the stirrer speed was set to 180 rpm, the reactor temperature to 80° C. and the pressure to 24 bar-g. 2.0 NL of hydrogen was added via flow controller in 4 minutes. During the gas phase homopolymerisation, both pressure and temperature have been held constant via mass flow controller (feeding propylene) and thermostat for 40 minutes.

(169) Step 3: Gas Phase Ethylene-Propylene Copolymerisation

(170) After the gas phase homopolymerisation step (Step 2) was completed, the stirrer speed was reduced to 50 rpm and the pressure was reduced down to 0.3 bar-g by venting the monomers. Then triethylaluminum (0.80 ml of a 0.62 mol/1 solution in heptane) was injected into the reactor by additional 250 g propylene through a steel vial, except in experiment P-pIE2-2 in which no TEA was added in this step. The pressure was then again reduced down to 0.3 bar-g by venting the monomers. The stirrer speed was set to 180 rpm and the reactor temperature was set to 70° C. (85° C. in experiment P-pIE2-2). Then the reactor pressure was increased to 20 bar-g by feeding a C3/C2 gas mixture (C2/C3=0.56 wt/wt). The temperature was held constant by thermostat and the pressure was held constant by feeding via mass flow controller a C3/C2 gas mixture of composition corresponding to the target polymer composition, until the set time for this step had expired.

(171) Then the reactor was cooled down to about 30° C. and the volatile components vented out. After purging the reactor 3 times with N2 and one vacuum/N2 cycle, the product was taken out and dried overnight in a fume hood. 100 g of the polymer is additivated with 0.5 wt % Irganox B225 (solution in acetone) and dried overnight in a hood followed by one hour in a vacuum drying oven at 60° C.

(172) The copolymerisation conditions are shown in Table 4 and copolymerisation results in Table 5.

(173) TABLE-US-00004 TABLE 4 Copolymerisation conditions Catalyst bulk GP1 GP2 Copolymerisation amount* T H2 Time P T Time H2 P T Time example Catalyst mg ° C. NL min barg ° C. Min NL barg ° C. min P-pCE4 pCE4 162 80 2.0 40 24 80 40 2.0 20 70  90 P-pCE5 pCE5  87 80 1.5 40 24 80 40 2.0 20 70 120 P-pIE2-1 pIE2  82 80 2.0 40 24 80 40 2.0 20 70 120 P-pIE2-2 pIE2 143 80 2.0 40 24 80 40 2.0 20 85 120 *Amount of Off-line prepolymerised catalyst

(174) TABLE-US-00005 TABLE 5 Copolymerisation results P-pCE4 P-pCE5 P-pIE2-1 P-pIE2-2 iV.sub.whole/dL/g 1.9 2.6 2.5 2.6 iV.sub.Matrix/dL/g 1.8 2.7 2.3 2.6 T.sub.m matrix/° C. 149 156 157 158 Overall productivity/ 22 129 32 75 kg/g.sub.cat* Overall productivity/ 790 1980 390 920 kg/g.sub.metallocene GP2 EPR activity/ 4 10.1 6.4 4.0 kg/g.sub.cat* Soluble 29 15 14 7 fraction.sub.(Crystex)/wt % C2(XS).sub.Crystex/wt % 20.3 20.8 17.8 17.2 iV.sub.EPR/dL/g 2.29 1.94 3.12 2.21 *catalyst amount before the off-line prepolymerisation

(175) Table 5 shows that the catalyst pIE2 produces heterophasic copolymers with higher T.sub.m and having the rubber phase with a higher molecular weight (indicated by iV.sub.EPR/dL/g) compared to the Zr analogues. In addition, high iV(EPR) can be obtained also at a polymerisation temperature as high as 85° C.

(176) The materials from P-pIE2-1 and P-pCE5 were compounded with 1500 ppm of B225 and 500 ppm of calcium stearate on TSE 16 respectively, with melt temperature of 210° C. and throughput of 2 kg/h. The products after compounding were named as IE1-prod (for P-pIE2-1 base) and CE2-prod (for P-pCE5 base). The properties are listed in Table 6.

(177) As can be seen, IE1 gives higher flexural modulus and impact strength at 0 and −20° C.

(178) TABLE-US-00006 TABLE 6 Stiffness/impact balance of IE-prod and CE-prod. IE1-prod CE2-prod Flexural modulus MPa 1109 1002 NIS/0° C. kj/m2 4.97 4.14 NIS/−20° C. kj/m2 2.11 1.35 Tg1 ° C. −36.3 −39.7 Tg2 ° C. 1.4 0.6 G′ MPa 615 572