CATALYSTS

Abstract

Claimed are metallocene-complexes of formula (I) [formula (I′)] wherein M is Hf or Zr, L is a bridge comprising 1-2 C- or Si-atoms, The other variables are as defined in the claims.

##STR00001##

Claims

1. A complex of formula (I): ##STR00067## M is Hf or Zr; 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.1-6-alkyl group, C.sub.3-8 cycloalkyl group, 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 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.7 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.

2. A complex as claimed in claim 1, wherein the complex is of formula (Ia) ##STR00068## M is Hf or Zr; 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; each n is independently 0, 1, 2 or 3; 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.1-6-alkyl group, C.sub.3-8 cycloalkyl group, 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 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.7 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.

3. A complex as claimed in claim 2 wherein L isof formula —SiR.sup.82-, 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. A complex as claimed in claim 1, wherein the complex isof formula (Ib): ##STR00069## wherein M is Hf or Zr; each X is a sigma ligand; L is an alkylene bridge or a bridge of the formula —SiR.sup.82-, 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 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 CH2-R.sup.9 group, with R.sup.9 being H or linear or branched C.sub.1-6-alkyl group, C.sub.3-8 cycloalkyl group, 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, C.sub.7-20 alkylaryl group or C.sub.6-C.sub.20-aryl group; R.sup.6 is a C(R.sup.10)3 group, with R′° being a linear or branched C.sub.1-C.sub.6 alkyl group, and R.sup.7 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.

5. A complex according to claim 4 in which each n is 1 or 2.

6. A complex according to any preceding claim of claim 1, wherein the complex isof formula (II) ##STR00070## wherein M is Hf or Zr; X is a sigma ligand, preferably each X is independently a hydrogen atom, a halogen atom, C-1-6 alkoxy group, C.sub.1 alkyl, phenyl or benzyl group; 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 the same or can be different and are a linear or branched C.sub.1-C.sub.6-alkyl group with the proviso that if there are four R.sup.1 and R.sup.1′ groups present, all 4 cannot simultaneously be tert butyl; R.sup.2 and R.sup.2′ are the same or are different and are a CH2-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)3 group, with R′° being a linear or branched C.sub.1-C.sub.6 alkyl group.

7. A complex according to any preceding claim of claim 1 wherein the complex isof formula (III) ##STR00071## wherein M is Hf or Zr; each X is a sigma ligand, preferably each X is independently a hydrogen atom, a halogen atom, C-1-6 alkoxy group, C.sub.4-4 alkyl, phenyl or benzyl group; L is -SiR.sup.82-, 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 the same or can be different and are a linear or branched C.sub.1-C.sub.6-alkyl group, group with the proviso that if there are four R.sup.1 and R.sup.1′ groups present, all 4 cannot simultaneously be 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)3 group, with R′° being a linear or branched C.sub.1-C.sub.6 alkyl group.

8. A complex according to any preceding claim of claim 1, wherein the complex isof formula (IV) ##STR00072## wherein M is Hf or Zr; 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.82-, 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 the same or can be different and are a linear or branched C.sub.1-C.sub.6-alkyl group with the proviso that if there are four R.sup.1 and R.sup.1′ groups present, all 4 cannot simultaneously be 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)3 group, with R′° being a linear or branched C.sub.1-C.sub.6 alkyl group.

9. A complex according to any preceding claim of claim 1, wherein the complex isof formula (V) ##STR00073## wherein M is Hf or Zr; 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 the same or can be different and are a linear or branched C.sub.1-C.sub.6-alkyl group, group with the proviso that if there are four R.sup.1 and R.sup.1′ groups present, all 4 cannot simultaneously be 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)3 group, with R′° being a linear or branched C.sub.1-C.sub.4 alkyl group.

10. A complex according to any preceding claim of claim 1, wherein the complex isof formula (VI) ##STR00074## wherein M is Hf or Zr; 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; T.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, group with the proviso that if there are four R.sup.1 and R.sup.1′ groups present, all 4 cannot simultaneously be tert butyl; R.sup.5 is a linear C.sub.1-C.sub.4-alkyl group such as methyl; and R.sup.6 is tert butyl.

11. A complex according to any preceding claim of claim 1, wherein the complex isof formula (VII) ##STR00075## wherein M is Hf or Zr; X is a hydrogen atom, a halogen atom, C.sub.1-6 alkoxy group, C.sub.1-6 alkyl, phenyl or benzyl group, especially chlorine; L is —SiMe.sub.2; each n is independently 1 or 2; 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.4-alkyl group with the proviso that if there are four R.sup.1 and R.sup.1′ groups present, all 4 cannot simultaneously be tert butyl; R.sup.5 is methyl; and R.sup.6 is tert butyl.

12. A complex according to claim 1, wherein the complex isof formula (VIII) ##STR00076## wherein M is Hf or Zr; 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 if there are four R.sup.1 and R.sup.1′ groups present, all 4 cannot simultaneously be tert butyl, R.sup.5 is methyl; and R.sup.6 is tert butyl.

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

14. A complex according to claim 1, wherein at least one of the C(4) or C(4′) phenyl rings is 4-(tert-butyl)-phenyl.

15. A complex according to 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. A catalyst system comprising: a complex according to claim 1; and (ii) a cocatalyst.

17. A catalyst system according to claim 16 comprising a boron containing cocatalyst, an A1 cocatalyst or both A1 and B cocatalysts.

18. A catalyst system as claimed in claim 16 in solid form.

19. A catalyst system as claimed in claim 18 supported on silica.

20. A process for the manufacture of a catalyst system as claimed in claim 16, said catalyst system comprising obtaining a complex (i) as claimed in any of claims 1 to 15 and a cocatalyst (ii); said process comprising forming a liquid/liquid emulsion system, which comprises a solution of catalyst components (i) and (ii) dispersed in a solvent in the form of dispersed droplets, and solidifying said dispersed droplets to form solid particles of said catalyst system.

21. A process as claimed in claim 20 further comprising off line prepolymerisation of the catalyst.

22. A process for the preparation of a polypropylene homopolymer, a propylene-ethylene copolymer, or a propylene C4-10 alpha olefin copolymer comprising polymerising propylene, propylene and ethylene or proplene and a C4-10 alpha olefin, in the presence of a catalyst system according to claim 16.

23. A process for the preparation of a heterophasic polypropylene copolymer comprising: (I) polymerising propylene in bulk in the presence of a catalyst as claimed in claim 16 to form a polypropylene homopolymer matrix; (II) in the presence of said matrix and said catalyst and in the gas phase, polymerising propylene and ethylene to form a heterophasic polypropylene copolymer comprising a homopolymer matrix and an ethylene propylene rubber.

24. A process for the preparation of a heterophasic polypropylene copolymer comprising: (I) polymerising propylene in bulk in the presence of a catalyst as claimed in claim 16 to form a polypropylene homopolymer; (II) in the presence of said homopolymer and said catalyst and in the gas phase, polymerising propylene to form a polypropylene homopolymer matrix; (III) in the presence said matrix and said catalyst and in the gas phase, polymerising propylene and ethylene to form a heterophasic polypropylene copolymer comprising a homopolymer matrix and an ethylene propylene rubber (EPR).

25. A process as claimed in claim 23 in which the EPR component is fully soluble in xylene at room temperature.

26. A process as claimed in claim 23 where the iV of the EPR is above 2.0 dL/g when measured in decaline.

27. A process as claimed in claim 23 wherein the Mw/Mn of the polypropylene homopolymer matrix component, as measured by GPC, is broader than 3.5.

28. A process as claimed in claim 23 wherein the Mw/Mn of the polypropylene homopolymer matrix component, as measured by GPC, is 4.0 to 8.0.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0334] FIG. 1 illustrates metal activities of the inventive examples and closest references (comparative examples) in bulk propylene homopolymerisation experiments. Both MC-E1 and MC-E2 demonstrate improved performance over the references, while MC-E3 has performance comparable to the 0-symmetric reference MC-CE1.

[0335] FIG. 2 illustrates polypropylene homopolymer melting temperatures for samples produced with the inventive examples and closest references (comparative examples). Inventive examples provide at least roughly 2 degrees higher melting temperature when compared to polymers produced using the known 0-symmetric metallocenes. . The C.sub.2-symmetric references provide comparable or higher melting temperature, however, with clearly lower activity.

[0336] FIG. 3 illustrates metal activities of the inventive examples and closest references (comparative examples) in ethylene-propylene random copolymerisation. All inventive examples provide clearly improved performance when compared to the references.

[0337] FIG. 4 illustrates Mw results for the propylene homopolymer samples produced with inventive examples and closest references (comparative examples) in bulk propylene homopolymerisation experiments. The Mw values are comparable to the results obtained with the Cl-symmetric references and improved over the result with the C.sub.2-symmetric references.

[0338] FIG. 5 illustrates that catalysts of the invention provide high Mw in ethylene-propylene random copolymerisation. Moreover, comparison of the results in FIG. 5 and FIG. 4 shows that ethylene has a strong positive effect on Mw with the catalysts of the invention, while with MC-CE1, MC-CE2 and MC-CE4 Mw results are comparable. With MC-CE3, ethylene has a strong negative effect on Mw.

[0339] FIG. 6 illustrates productivity-MFR correlation for silica catalysts (2-step experiments). Productivities are based on metallocene amounts.

[0340] FIG. 7 illustrates composition—molecular weight correlation of the rubber phase (xylene insoluble fraction) of heterophasic copolymers produced with silica catalysts (3-step experiments).

ANALYTICAL TESTS

Measurement Methods:

Al and Zr Determination (ICP-Method)

[0341] The elementary analysisof 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.

[0342] 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.

[0343] 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.

[0344] 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.

[0345] 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.

[0346] 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.

DSC Analysis

[0347] Melting temperature Tm was measured on approx. 5 mg samples with a Mettler-Toledo 822e differential scanning calorimeter (DSC), according to IS011357-3 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.20, Lead, Tin, Indium, according to ISO 11357-1.

Melt Flow Rate

[0348] 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).

Intrinsic Viscosity

[0349] Intrinsic viscosity (iV) has been measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135° C.).

[0350] GPC: Molecular weight averages, molecular weight distribution, and polydispersity index (M.sub.n, M.sub.w, M.sub.w/M.sub.n)

[0351] 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.

[0352] A PolymerChar GPC instrument, equipped with infrared (IR) detector was used with 3× Olexis and 1× Olexis Guard columns from Polymer Laboratories and 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) as solvent at 160° C. and at a constant flow rate of 1 mL/min. 200 μL of sample solution were injected per analysis. The column set was calibrated using universal calibration (according to ISO 16014-2:2003) with at least 15 narrow MWD polystyrene (PS) standards in the range of 0.5 kg/mol to 11 500 kg/mol. Mark Houwink constants for PS, PE and PP used are as described per ASTM D 6474-99. All samples were prepared by dissolving 5.0-9.0 mg of polymer in δ mL (at 160° C.) of stabilized TCB (same as mobile phase) for 2.5 hours for PP or 3 hours for PE at max. 160° C. under continuous gentle shaking in the autosampler of the GPC instrument

Quantification of Polypropylene Homopolymer Microstructure by NMR Spectroscopy

[0353] Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity and content of regio-defects of the polypropylene homopolymers. Quantitative .sup.13C{.sup.1H} NMR spectra recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for .sup.1H and .sup.13C respectively. All spectra were recorded using a.sup.l-3C optimised 10 mm selective excitation probehead at 125° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d.sub.2 (TCE-d.sub.2). This setup was chosen primarily for the high resolution needed for tacticity distribution quantification (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251). Standard single-pulse excitation was employed utilising the NOE and bi-level WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 6144 (6k) transients were acquired per spectra using a 3 s recycle delay. Quantitative .sup.13C{.sup.1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts are internally referenced to the methyl signal of the isotactic pentad mmmm at 21.85 ppm.

[0354] The tacticity distribution was quantified through integration of the methyl region between 23.6 and 19.7 ppm correcting for any sites not related to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251). The pentad isotacticity was determined through direct integration of the methyl region and reported as either the mole fraction or percentage of isotactic pentad mmmm with respect to all steric pentads i.e. [mmmm]=mmmm/sum of all steric pentads. When appropriate integrals were corrected for the presence of sites not directly associated with steric pentads.

[0355] Characteristic signals corresponding to regio irregular propene insertion were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253). The presence of secondary inserted propene in the form of 2.1 erythro regio defects was indicated by the presence of the two methyl signals at 17.7 and 17.2 ppm and confirmed by the presence of other characteristic signals. The amount of 2.1 erythro regio defects was quantified using the average integral (e) of the e6 and e δ sites observed at 17.7 and 17.2 ppm respectively, i.e. e=0.5 * (e6+e8). Characteristic signals corresponding to other types of regio irregularity were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253). The amount of primary inserted propene (p) was quantified based on the integral of all signals in the methyl region (CH3) from 23.6 to 19.7 ppm paying attention to correct for other species included in the integral not related to primary insertion and for primary insertion signals excluded from this region such that p=CH3+2*e. The relative content of a specific type of regio defect was reported as the mole fraction or percentage of said regio defect with respect all observed forms of propene insertion i.e. sum of all primary (1.2), secondary (2.1) and tertiary (3.1) inserted propene units, e.g. [21e]=e/(p+e+t+i). The total amount of secondary inserted propene in the form of 2,1-erythro or 2,1-threo regio defects was quantified as sum of all said regio irregular units, i.e. [21]=[21e]+[21t]. [0356] Quantification of Copolymer Microstructure by NMR Spectroscopy

[0357] Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content and comonomer distribution of the copolymers, specifically propene-co-ethylene copolymers. Quantitative .sup.13C NMR spectra recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for .sup.1H and .sup.13C respectively. All spectra were recorded using a .sup.13C optimised 10 mm selective excitation probehead at 125° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d.sub.2 (TCE-d.sub.2) with chromium-(III)-acetylacetonate (Cr(acac).sub.3) resulting in a 65 mM solution of relaxation agent in solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). This setup was chosen primarily for the high resolution and quantitative spectra needed for accurate ethylene content determination. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and bi-level WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 6144 (6k) transients were acquired per spectra. Quantitative .sup.13C{.sup.1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present.

[0358] Characteristic signals corresponding to regio irregular propene insertion were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).].

[0359] Characteristic signals corresponding to the incorporation of ethylene were observed (Cheng, H. N., Macromolecules 17, 1984, 1950). The comonomer content was calculated as the mole fraction or percent of incorporated ethylene with respect to all monomer in the copolymer using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33, 2000, 1157) through integration of multiple signals spanning the whole spectral .sup.13C spectra. This analyse method was chosen for its robust nature and ability to account for the presence of regio irregular propene insertion when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.

[0360] For systems where only isolated ethylene incorporation (PPEPP) was observed the method of Wang et. al. was modified to reduce the influence of non-zero integrals used to quantify higher order comonomer sequences. In such cases the term for the absolute ethylene content was determined based upon only E=0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ□)) or E=0.5(I.sub.h+I.sub.G+0.5(I.sub.C+I.sub.D)) using the same notation as Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33, 2000, 1157). The term used for absolute propylene content (P) was not modified and the mole fraction of ethylene calculated as [E]=E/(E+P). The comonomer content in weight percent was calculated from the mole fraction in the usual way i.e. [E wt %]=100 * ([E] * 28.06)/(([E] * 28.06)+((1-[E]) * 42.08)).

EXAMPLES

Metallocene Synthesis

Reagents

[0361] 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), trimethylborate (Acros), Pd(OAc).sub.2 (Aldrich), NaBH.sub.4 (Acros), 2.5 M .sup.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 4A (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 4A. 4-Bromo-6-tert-butyl-5-methoxy-2-methylindan-1-one was obtained as described in WO2013/007650.

Synthesisof MC IE1

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

[0362] ##STR00027##

[0363] 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).

[0364] 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-butylphenylmagnesium 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.

[0365] Anal. calc. for C.sub.24H.sub.30O: C, 86.18; H, 9.04. Found: C, 85.99; H, 9.18.

[0366] .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

[0367] ##STR00028##

[0368] 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.

[0369] Anal. calc. for C.sub.23H.sub.26: C, 91.34; H, 8.66. Found: C, 91.47; H, 8.50.

[0370] .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

[0371] ##STR00029##

[0372] 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., 30.4 ml (73.87 mmol) of 2.43 M “BuLi 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.

[0373] .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.sub.1.sup.1F11 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

[0374] ##STR00030##

[0375] 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)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.

[0376] Anal. calc. for C.sub.25H.sub.32O.sub.2: C, 82.37; H, 8.85. Found: C, 82.26; H, 8.81.

[0377] .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.6H4.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, .sup.tBu in C.sub.6H.sub.4.sup.tBu), 1.38 (s, 9H, 6-.sup.tBu 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

[0378] ##STR00031##

[0379] 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 thisoil 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%).

[0380] Anal. calc. for C.sub.25H.sub.32O: C, 86.15; H, 9.25. Found: C, 86.24; H, 9.40.

[0381] .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.sub.4.sup.tBu), 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

[0382] ##STR00032##

[0383] 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 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.

[0384] .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

[0385] ##STR00033##

[0386] 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-butylphenyl)-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.

[0387] 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:

[0388] Anal. calc. for C.sub.50H.sub.60Cl.sub.2OSiZr: C, 69.25; H, 6.97. Found: C, 69.43; H, 7.15.

[0389] .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.

Synthesisof MC-IE2

4-Bromo-2,6-dimethylaniline

[0390] ##STR00034##

[0391] 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. 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.

[0392] .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

[0393] ##STR00035##

[0394] 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. Afterthe 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.

[0395] .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

[0396] ##STR00036##

[0397] 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.

[0398] Anal. calc. for C.sub.8H.sub.11BO.sub.2: C, 64.06; H, 7.39. Found: C, 64.38; H, 7.72.

[0399] .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

[0400] ##STR00037##

[0401] 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.

[0402] Anal. calc. for C.sub.23H.sub.28O.sub.2: C, 82.10; H, 8.39. Found: C, 82.39; H, 8.52.

[0403] .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

[0404] ##STR00038##

[0405] 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 thisoil 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.

[0406] Anal. calc. for C.sub.23H.sub.28O: C, 86.20; H, 8.81. Found: C, 86.29; H, 9.07.

[0407] .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

[0408] ##STR00039##

[0409] To a solution of 9.0 g (28.08 mmol) of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-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.

[0410] .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

[0411] ##STR00040##

[0412] 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.

[0413] Anal. calc. for C.sub.22H.sub.26O: C, 86.23; H, 8.55. Found: C, 86.07; H, 8.82.

[0414] .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

[0415] ##STR00041##

[0416] 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.

[0417] Anal. calc. for C.sub.21H.sub.22: C, 91.92; H, 8.08. Found: C, 91.78; H, 8.25.

[0418] .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

[0419] ##STR00042##

[0420] 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.

[0421] Anal. calc. for C.sub.46H.sub.54OSi: C, 84.87; H, 8.36. Found: C, 85.12; H, 8.59.

[0422] .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

[0423] ##STR00043##

[0424] 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%).

[0425] 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:

[0426] 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.

[0427] .sup.1H NMR (CDCl.sub.3): δ 7.47 (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 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.

[0428] 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.

[0429] Anal. calc. for C.sub.46H.sub.52Cl.sub.2OSiZr: C, 68.11; H, 6.46. Found: C, 68.37; H, 6.65.

[0430] .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.

[0431] Alternative Synthesisof MC-IE2

[0432] 2-methyl-4-bromo-5-methoxy-6-tert-butyl-indan-1-one isobtained as described above.

One pot Synthesisof 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene from 2-methyl-4-bromo-5-methoxy-6-tert-butyl-indan-1-one

[0433] ##STR00044##

[0434] Step 1: 2 mol. % Pd(P.sup.tBu3)2, 2-MeTHF, 7 h at reflux

[0435] A mixture of 2-methyl-4-bromo-5-methoxy-6-tert-butyl-indan-1-one (15.75 g, 50.61 mmol), (3,5-dimethylphenyl)boronic acid (9.5 g, 63.34 mmol, 1.25 equiv.), Na.sub.2CO.sub.3 (14.5 g, 137 mmol), Pd(P.sup.tBu.sub.3)2 (0.51 g, 1 mmol), 66 ml of water and 165 ml of 2-methyltetrahydrofuran was refluxed for 7 h. After cooling to room temperature, the organic layer was separated, dried over K.sub.2CO.sub.3, and the resulting solution was used in the following step without additional purification.

[0436] .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

[0437] Step 2: a) NaBH.sub.4/2-MeTHF/MeOH; b) TsOH/toluene at reflux

[0438] NaBH.sub.4 (5.2 g, 138 mmol) was added to the above solution of 2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-indan-1-one in 165 ml of 2-methyltetrahydrofuran cooled to 5° C. Further on, 80 ml of methanol was added dropwise to this mixture for ca. 7 h at 5° C. The resulting mixture was evaporated to dryness, 300 ml of dichloromethane and 300 ml water were added to the residue, and thus obtained mixture was acidified with 2 M HCl to pH˜6.5. The organic layer was separated; the aqueous layer was additionally extracted with 100 ml of dichloromethane. The combined organic extract was passed through a pad (˜200 ml) of silica gel 60 (40-63 μm; eluent: dichloromethane). The obtained elute was evaporated to dryness to give a slightly brownish oil. 200 mg of TsOH was added to a solution of thisoil in 200 ml of toluene. 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 with 10% Na.sub.2CO.sub.3, the organic layer was separated, and the aqueous layer was extracted with 50 ml of dichloromethane. The combined organic extract was dried over K.sub.2CO.sub.3 and then evaporated to dryness. The residue was dissolved in 100 ml of n-hexane, and the obtained solution was passed through a short pad (˜20 ml) of silica gel 60 (40-63 μm; eluent: n-hexane). The silica gel layer was additionally washed by 40 ml of n-hexane. The combined organic elute was evaporated to dryness, and the resulting oil was dried in vacuum at elevated temperature to give 15.35 g (95%) of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene which was used in the following step without additional purification.

[0439] .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 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.

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

[0440] ##STR00045##

[0441] Step 3 to 6 according to patent literature (e.g. WO2015158790).

[0442] Step 7:

[0443] 200 ml (200 mmol, 1.4 eq) of 3,5-dimethylphenylmagnesium bromide 1.0 M in THF was added 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 1-methoxy-2-methyl-4-bromo-1,2,3,5,6,7-hexahydro-s-indacene. The resulting solution was refluxed for 3 h and then cooled to room temperature, and 400 ml of water followed by 500 ml of 1.0 M HCl solution were added. Then 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 um; 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.

[0444] .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.

[0445] Step 8:

[0446] TsOH (200 mg) was added to the solution of 43.02 g (140.4 mmol) of 1-methoxy-2-methyl-4-(3,5-dimethylphenyl)-1,2,3,5,6,7-hexahydro-s-indacene in 600 ml of toluene 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.

[0447] .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.sub.1.sup.11-11 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

[0448] Synthesisof MC-IE2

##STR00046##

[0449] Step 9: a) .sup.nBuLi in .sup.nBu.sub.2O, −5° C.; b) 5 equiv Me2SiCl.sub.2, THF, −30° C.

[0450] .sup.nBuLi in hexanes (2.43 M, 20.2 ml, 49.09 mmol) was added in one portion to a solution of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene (15.69 g, 48.96 mmol) in 250 ml of di-n-butyl ether cooled to −5° C. The resulting mixture was stirred overnight at room temperature, then the formed white suspension with a large amount of precipitate (which makes effective stirring difficult) was cooled to −30° C., and THF (8 ml, 7.11 g, i.e. ca. 2.01 ratio of THF to the starting indene was used) was added to give a clear orange solution. This solution was cooled to −30° C., and then dichlorodimethylsilane (31.6 g, 244.9 mmol, 5 equiv.) was added in one portion. The obtained mixture 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 (containing some hard-to-remove impurity of di-n-butyl ether) which was used in the following step without additional purification

[0451] Step 10: .sup.nBuLi in hexanes (2.43 M, 20.1 ml, 48.84 mmol) was added in one portion to a solution of 4-(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene (13.43 g, 48.94 mmol) in a mixture of di-n-butyl ether (200 mL) and THF (8 ml, 7.11 g, i.e. ca. 2.02 ratio of THF to the starting indene) at −10° C. This mixture was stirred overnight at room temperature, giving an orange suspension. To this suspension, a solution of [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl]chlorodimethylsilane (as prepared above, ca. 48.96 mmol) in 120 ml of di-n-butyl ether was added in one portion. This mixture was stirred overnight at room temperature.

[0452] Step 11:

[0453] .sup.nBuLi in hexanes (2.43 M, 11.6 ml, 28.19 mmol) was added in one portion to a solution of 9.16 g (14.07 mol) of [6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-1H-inden-1-yl][4-(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane in 190 ml of di-n-butyl ether cooled to −30° C. This mixture was stirred for 4 h at room temperature, then the resulting ruby solution was cooled to −30° C. (some yellow precipitate formed), and then ZrCl.sub.4 (3.28 g, 14.08 mmol) was added. The reaction mixture was stirred for 24 h at room temperature to give light red solution with orange precipitate. This precipitate was filtered off (G4) and then dried in vacuum to give 4.7 g of a mixture of syn-complex and LiCl (thus, the adjusted net weight of syn-complex was 3.51 g). The filtrate was evaporated until a viscous oil was obtained, which was then triturated with 40 ml of n-hexane. The obtained suspension was filtered through glass frit (G3), and the so obtained precipitate was dried under vacuum. This procedure gave 3.5 g of pure anti-zirconocene dichloride (D69) as a yellow powder. Yellow powder precipitated from the solution overnight at −25° C. was collected and dried under vacuum. This procedure gave 1.85 g of anti-zirconocene contaminated with 5% of its syn-isomer. Thus, the total yield of syn- and anti-zirconocenes isolated in this synthesis was 8.86 g (78%).

[0454] Synthesisof MC-IE3

[2-methyl-4-(3,5-dimethylphenyl)-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

[0455] ##STR00047##

[0456] To a solution of 7.87 g (24.56 mmol) of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene in 150 ml of ether, 10.1 ml (24.54 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 a large amount of yellow precipitate was cooled to −50° C. (wherein the precipitate disappeared completely), and 150 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at −25° C., then a solution of 9.70 g (24.55 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 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 16.2 g (97%) of [2-methyl-4-(3,5-dimethylphenyl)-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 (>95% purity by NMR, approx. 1:1 mixture of the stereoisomers) as a yellowish glassy solid which was further used without an additional purification.

[0457] .sup.1H NMR (CDCl.sub.3): δ 7.49 (s, 0.5H), 7.47-7.42 (m, 2H), 7.37-7.32 (m, 2.5H), 7.25 (s, 0.5H), 7.22 (s, 0.5H), 7.15-7.09 (m, 2H), 7.01-6.97 (m, 1H), 6.57, 6.56 and 6.45 (3s, sum 2H), 3.70, 3.69, 3.67 and 3.65 (4s, sum 2H), 3.28 and 3.27 (2s, sum 3H), 3.01-2.79 (m, 4H), 2.38 (s, 6H), 2.19, 2.16 and 2.13 (3s, sum 6H), 2.07-2.00 (m, 2H), 1.43 and 1.41 (2s, sum 9H), 1.38 (s, 9H), −0.18, −0.19, −0.20 and −0.23 (4s, sum 6H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): 155.30, 155.27, 149.14, 149.10, 147.45, 147.38, 146.01, 145.77, 143.98, 143.92, 143.73, 143.68, 142.13, 142.09, 139.51, 139.41, 139.26, 139.23, 139.19, 139.15, 138.22, 137.51, 137.08, 137.05, 136.98, 130.05, 130.01, 129.11, 128.22, 127.90, 127.48, 127.44, 126.18, 126.13, 125.97, 125.92, 124.82, 120.55, 120.49, 118.50, 118.27, 60.54, 60.50, 47.34, 47.33, 46.87, 46.72, 35.14, 34.54, 33.34, 33.28, 32.30, 31.44, 31.25, 31.20, 26.02, 26.01, 21.45, 17.95, 17.87.

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

[0458] ##STR00048##

[0459] To a solution of 16.2 g (23.86 mmol) of [2-methyl-4-(3,5-dimethylphenyl)-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., 19.7 ml (47.87 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 red solution was cooled to −50° C., and 5.57 g (23.9 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 treated with 150 ml of hot toluene, and the formed suspension was filtered through glass frit (G4). The filtrate was evaporated to 50 ml, and then 20 ml of n-hexane was added. The orange crystals precipitated from this solution overnight at room temperature were collected, washed with 10 ml of cold toluene, and dried in vacuum. This procedure gave 5.02 g (25%) of anti-zirconocene as a solvate with toluene (×0.75 toluene). The mother liquor was evaporated to ca. 30 ml, and 30 ml of n-hexane was added. The orange powder precipitated from this solution overnight at room temperature was collected and dried in vacuum. This procedure gave 6.89 g (34%) of a ca. 3 to 7 mixture of anti- and syn-zirconocenes. Thus, the total yield of rac-zirconocene isolated in this synthesis was 11.91 g (60%).

[0460] Anti-dimethylsilanediyl[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride.

[0461] Anal. calc. for C.sub.48H.sub.56Cl.sub.2OsiZr×0.75C.sub.7H.sub.8: C, 70.42; H, 6.88. Found: C, 70.51; H, 6.99.

[0462] .sup.1H NMR (CDCl.sub.3): δ 7.63-7.03 (very br.s, 2H), 7.59-7.51 (br.m, 2H), 7.51-7.42 (m, 4H), 6.98 (s, 1H), 6.78 (s, 1H), 6.60 (s, 1H), 3.46 (s, 3H), 3.11-3.04 (m, 1H), 3.04-2.93 (m, 2H), 2.88-2.81 (m, 1H), 2.36 (s, 6H), 2.22 (s, 3H), 2.21 (s, 3H), 2.12-1.94 (m, 2H), 1.41 (s, 9H), 1.36 (s, 9H), 1.32 (s, 3H), 1.31 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3,): 8159.78, 149.90, 144.67, 144.07, 143.07, 136.75, 135.44, 135.40, 133.97, 133.51, 132.90, 132.23, 128.84, 128.76, 127.34, 127.01, 126.73, 125.28, 125.17, 122.89, 121.68, 121.59, 120.84, 117.94, 81.60, 81.26, 62.61, 35.73, 34.60, 33.20, 32.17, 31.36, 30.34, 26.56, 21.40, 18.41, 18.26, 2.65, 2.54.

[0463] Synthesisof MC-IE4

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

[0464] ##STR00049##

[0465] .sup.nBuLi in hexanes (2.43 M, 16.9 ml, 41.07 mmol) was added in one portion to a solution of 12.43 g (41.1 mmol) of 4-(4-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in 200 ml of ether cooled to −50° C. The resulting mixture was stirred overnight at room temperature; the resulting yellow slurry (light orange solution with a large amount of yellow precipitate) was then cooled to −50° C., during the cooling the precipitate completely dissolved to form an orange solution, and 26.5 g (205 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 flask and the filter cake were rinsed with 50 ml of toluene. The filtrate was evaporated to dryness to give 16 g (99%) of chloro[2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane as slightly yellowish oil which was used without further purification.

[0466] .sup.1H NMR (CDCl.sub.3): δ 7.47-7.41 (m, 2H), 7.34-7.27 (m, 3H), 6.56 (s, 1H), 3.56 (s, 1H), 3.05-2.78 (m, 4H), 2.20 (s, 3H), 2.04 (quin, J=7.4 Hz, 2H), 1.38 (s, 9H), 0.44 (s, 3H), 0.18 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 149.27, 144.42, 142.14, 141.40, 139.94, 139.83, 136.84, 130.18, 129.07, 126.87, 124.86, 118.67, 49.76, 34.55, 33.26, 32.31, 31.43, 26.00, 17.60, 1.17, −0.60

[2-methyl-4-(3,5-di-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

[0467] ##STR00050##

[0468] .sup.nBuLi in hexanes (2.43 M, 13.8 ml, 33.53 mmol) was added in one portion to a solution of 13.55 g (33.49 mmol) of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-di-tert-butylphenyl)-1H-indene in 200 ml of ether at −50° C. This mixture was stirred for 5 h at room temperature; the resulting orange slurry with a large amount of yellow precipitate was then 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 13.23 g (33.49 mmol) of chloro[2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]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 with 2×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure, and the product was isolated by flash-chromatography on silica gel 60 (40-63 μm; eluent: hexanes-dichloromethane=10:1, then 3:1 vol). This procedure gave 18.4 g (72%) of [2-methyl-4-(3,5-di-tert-butylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][4-(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (>95% purity by NMR, approx. 1:1 mixture of stereoisomers) as yellowish glass which was used without further purification.

[0469] .sup.1H NMR (CDCl.sub.3): δ 7.52-7.40 (m, 3H), 7.40-7.30 (m, 4H), 7.27 (s, 1H), 7.22 (s, 1H), 6.57, 6.52 and 6.51 (3s, sum 2H), 3.71, 3.69 and 3.66 (3s, sum 2H), 3.20 and 3.19 (2s, sum 3H), 3.02-2.77 (m, 4H), 2.20, 2.18 and 2.16 (3s, sum 6H), 2.09-1.97 (m, 2H), 1.43 and 1.42 (2s, sum 9H), 1.38 and 1.37 (2s, sum 27H), −0.18, −0.19 and −0.23 (3s, sum 6H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 155.49, 150.23, 149.15, 149.11, 147.36, 147.29, 146.04, 145.83, 143.99, 143.70, 142.15, 142.10, 139.53, 139.42, 139.24, 139.18, 139.13, 137.21, 137.17, 137.10, 130.07, 130.02, 129.13, 128.06, 126.18, 124.82, 124.72, 120.46, 120.40, 119.84, 118.54, 118.31, 60.08, 47.29, 46.92, 46.80, 35.17, 34.86, 34.54, 33.31, 32.31, 31.57, 31.46, 31.23, 31.19, 26.01, 18.08, 18.04, 17.99, 17.88, −5.30, −5.57, −5.62, −5.84.

Anti-dimethylsilanediyl[2-methyl-4-(3,5-di-tert-butylphenyl)-5-methoxy-6-tert-butyl-inden-1-yl][2-methyl-4-(4-tert-butylphenyl)-5,6,7-trihydro-s-indacen-1-yl]zirconium dichloride MC-IE4

[0470] ##STR00051##

[0471] .sup.nBuLi in hexanes (2.43 M, 19.9 ml, 48.36 mmol) was added in one portion to a solution of 18.4 g (24.11 mmol) of [2-methyl-4-(3,5-di-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 (as prepared above) in 200 ml of ether cooled to −60° C. This mixture was stirred overnight at room temperature; the resulting orange slurry was then cooled to −60° C. and 5.62 g (24.12 mmol) of ZrCl.sub.4 was added. The reaction mixture was stirred for 24 h at room temperature to give a red solution with a small amount of precipitate. This mixture was evaporated to dryness. The residue was heated with 150 ml of toluene, and the formed suspension was filtered through glass frit (G4). The filtrate was evaporated to 80 ml, and then 20 ml of n-pentane was added. Orange powder precipitated from this solution overnight at room temperature was collected and dried in vacuum. This procedure gave 6.02 g (27%) of syn-zirconocene as a solvate with toluene (×1 PhMe) contaminated with ca. 2% of anti-isomer. The mother liquor was evaporated to ca. 30 ml, and 30 ml of n-hexane was added. Orange powder precipitated from this solution overnight at room temperature was collected and dried under vacuum. This procedure gave 1.38 g (6%) of syn-zirconocene as a solvate with toluene (×1 PhMe) contaminated with ca. 8% of anti-isomer. The mother liquor was evaporated to the oily state, and thisoil was dissolved in 50 ml of n-hexane. Yellow powder precipitated from this solution over 2 days at −30° C. was collected and dried in vacuum. This procedure gave 7.3 g (33%) of anti-zirconocene contaminated with ca. 3% of syn-isomer. Thus, the total yield of anti- and syn-zirconocenes isolated in this synthesis was 14.7 g (66%).

[0472] 7.3 g (33%) of anti-zirconocene contaminated with ca. 3% of syn-isomer was additionally recrystallized from a hot mixture of 15 ml of toluene and 30 ml of n-hexane. Light-orange crystals precipitated overnight at room temperature were collected and dried under vacuum. This procedure gave 4.6 g of pure anti-zirconocene as a solvate with toluene (×0.8 PhMe).

[0473] Anti-dimethylsilanediyl[2-methyl-4-(3,5-di-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(4-tert-butylphenyl)-5,6,7-trihydro-s-indacen-1-yl]zirconium dichloride

[0474] Anal. calc. for C.sub.54H.sub.68Cl.sub.2OSiZr×0.8C.sub.7H.sub.8: C, 71.80; H, 7.52. Found: C, 72.04; H, 7.75.

[0475] .sup.1H NMR (CDCl.sub.3): δ 7.60-7.30 (set of signals, sum 9H), 6.73 (s, 1H), 6.60 (s, 1H), 3.33 (s, 3H), 3.16-3.02 (m, 1H), 3.02-2.88 (m, 2H), 2.88-2.77 (m, 1H), 2.20 (s, 3H), 2.19 (s, 3H), 2.11-1.91 (m, 2H), 1.38 (s, 9H), 1.34 (s, 9H), 1.33 (s, 18H), 1.29 (s, 3H), 1.28 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3,): δ 160.02, 149.90, 144.69, 143.96, 143.05, 135.95, 135.51, 135.40, 133.99, 133.72, 132.85, 132.16, 128.80, 127.54, 126.97, 125.16, 124.25, 122.74, 121.76, 121.12, 120.68, 120.45, 117.96, 81.85, 81.23, 62.26, 35.77, 34.96, 34.61, 33.18, 32.14, 31.56, 31.38, 30.32, 26.53, 18.39 (two resonances), 2.66, 2.61.

[0476] Synthesis of MC-IE5

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

[0477] ##STR00052##

[0478] .sup.nBuLi in hexanes (2.43 M, 12.6 ml, 30.62 mmol) was added in one portion to a solution of 8.4 g (30.61 mmol) of 4-(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in a mixture of 150 ml of ether and 10 ml of THF cooled to −50° C. The resulting mixture was stirred overnight at room temperature; the obtained red solution was then cooled to −50° C., and 19.8 g (153.4 mmol, 5.01 equiv.) of dichlorodimethylsilane was added in one portion. This mixture was stirred overnight at room temperature and then filtered through a glass frit (G3), the flask and the filter cake were rinsed with 50 ml of toluene. The filtrate was evaporated to dryness to give 11.3 g (ca. 100%) of chloro[2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane as reddish oil which was used without further purification.

[0479] .sup.1H NMR (CDCl.sub.3): δ 7.29 (s, 1H), 6.97 (s, 3H), 6.50 (m, 1H), 3.55 (s, 1H), 3.06-2.72 (m, 4H), 2.37 (s, 6H), 2.20 (s, 3H), 2.04 (quin, J=7.4 Hz, 2H), 0.43 (s, 3H), 0.19 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 144.39, 142.06, 141.36, 139.81, 139.78, 137.40, 130.49, 128.24, 127.20, 126.80, 118.65, 49.74, 33.25, 32.20, 25.93, 21.43, 17.63, 1.16, −0.53

[2-methyl-4-(3,5-di-tert-butylphenyl)-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

[0480] ##STR00053##

[0481] .sup.nBuLi in hexanes (2.43 M, 12.6 ml, 30.62 mmol) was added in one portion to a solution of 12.39 g (30.62 mmol) of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-di-tert-butylphenyl)-1H-indene in 200 ml of ether at −50° C. This mixture was stirred overnight at room temperature; the resulting yellow slurry was then 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 11.3 g (30.61 mmol) of chloro[2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (as prepared above) in 150 ml of ether was added in one portion. This mixture was stirred for 20 h 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 22.34 g (99%) of [2-methyl-4-(3,5-di-tert-butylphenyl)-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 orange glass which was used without further purification.

Anti-dimethylsilanediyl[2-methyl-4-(3,5-di-tert-butylphenyl)-5-methoxy-6-tert-butyl-inden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5,6,7-trihydro-s-indacen-1-yl]zirconium dichloride MC-IE5

[0482] ##STR00054##

[0483] .sup.nBuLi in hexanes (2.43 M, 25 ml, 60.75 mmol) was added in one portion to a solution of 22.34 g (30.39 mmol) of [2-methyl-4-(3,5-di-tert-butylphenyl)-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 prepared above) in 250 ml of ether cooled to −50° C. This mixture was stirred overnight at room temperature, then the resulting dark-red solution was cooled to −60° C., and 7.09 g (30.43 mmol) of ZrCl.sub.4 was added. The reaction mixture was stirred for 24 h at room temperature to give orange slurry (red solution with yellow precipitate). This mixture was evaporated to dryness. The residue was heated with 150 ml of toluene, and the formed suspension was filtered through glass frit (G4). The filtrate was evaporated to 60 ml, and the obtained suspension was heated to get a clear solution. Yellow powder precipitated from this solution over 30 min at room temperature was collected and dried under vacuum. This procedure gave 3.7 g of pure anti-zirconocene. Yellow powder precipitated from the mother liquor overnight at room temperature was collected and dried under vacuum. This procedure gave 10.1 g of a ca. 40 to 60 mixture of anti- and syn-zirconocenes. The mother liquor was evaporated to dryness and triturated with 10 ml of n-hexane. This procedure gave 3.38 g of a ca. 40 to 60 mixture of anti- and syn-zirconocenes. Thus, the total yield of anti- and syn-zirconocenes isolated in this synthesis was 17.18 g (63%).

[0484] Anti-dimethylsilanediyl[2-methyl-4-(3,5-di-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5,6,7-trihydro-s-indacen-1-yl]zirconium dichloride

[0485] Anal. calc. for C.sub.52H.sub.64Cl.sub.2OSiZr: C, 69.76; H, 7.21. Found: C, 69.93; H, 7.49.

[0486] .sup.1H NMR (CDCl.sub.3): δ 7.75-7.01 (4 very br.s, sum 4H), 7.49 (s, 1H), 7.40 (s, 1H), 7.34 (t, J=1.8 Hz, 1H), 6.95 (m, 1H), 6.66 (s, 1H), 6.57 (s, 1H), 3.30 (s, 3H), 3.09-3.01 (m, 1H), 2.98-2.90 (m, 2H), 2.86-2.79 (m, 1H), 2.32 (s, 6H), 2.18 (s, 3H), 2.17 (s, 3H), 2.08-1.94 (m, 2H), 1.38 (s, 9H), 1.32 (s, 18H), 1.29 (s,3H), 1.28 (s, 3H). NMR (CDCl.sub.3,): δ 159.85, 150.41 (broad s), 144.69, 143.92, 142.96, 138.30, 137.59 (broad s), 135.87, 135.35, 134.02, 133.57, 132.73, 132.42, 128.79, 127.55, 127.10, 126.97 (broad s), 124.41 (broad s), 122.83, 122.14, 121.24, 120.65, 120.38, 117.94, 81.87, 81.03, 62.25, 35.77, 34.98, 33.18, 31.99, 31.49, 30.37, 26.43, 21.31, 18.44, 18.37, 2.66, 2.63.

[0487] Synthesisof MC-IE6

Chloro[2-methyl-4-(3,5-di-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane

[0488] ##STR00055##

[0489] .sup.nBuLi in hexanes (2.43 M, 15.0 ml, 36.45 mmol) was added in one portion to a solution of 13.07 g (36.45 mmol) of 4-(3,5-di-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in 200 ml of ether cooled to −50° C. The resulting mixture was stirred overnight at room temperature; the so obtained light-orange solution containing a large amount of white precipitate was then cooled to −60° C. and 23.5 g (182.1 mmol, 5 equiv.) of dichlorodimethylsilane was added in one portion. This mixture was stirred overnight at room temperature and then filtered through a glass frit (G3), the flask and the filter cake were rinsed with 50 ml of toluene. The filtrate was evaporated to dryness to give 16.6 g (ca. 100%) of chloro[2-methyl-4-(3,5-di-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane as yellowish oil which was used without further purification.

[0490] .sup.1H NMR (CDCl.sub.3): δ 7.36 (s, 1H), 7.30 (s, 1H), 7.23 (s, 2H), 6.58 (s, 1H), 3.57 (s, 1H), 3.05-2.93 (m, 2H), 2.93-2.83 (m, 2H), 2.21 (s, 3H), 2.10-2.01 (m, 2H), 1.36 (s, 18H), 0.45 (s, 3H), 0.20 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 150.02, 144.42, 142.12, 141.53, 139.93, 139.91, 138.77, 131.40, 127.00, 123.93, 120.15, 118.63, 49.77, 34.88, 33.31, 32.50, 31.56, 26.03, 17.71, 1.25, −0.53.

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

[0491] ##STR00056##

[0492] .sup.nBuLi in hexanes (2.43 M, 15.0 ml, 36.45 mmol) was added in one portion to a solution of 12.7 g (36.44 mmol) of 2-methyl-5-tert-butyl-6-methoxy-7-(4-tert-butylphenyl)-1H-indene in 200 ml of ether at −50° C. This mixture was stirred overnight at room temperature, then the resulting yellowish slurry with a large amount of precipitate was cooled to −40° C. and 100 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at −25° C., then a solution of 16.6 g (ca. 36.45 mmol) of chloro[2-methyl-4-(3,5-di-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]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 nm) 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 27.78 g (ca. 100%) of [2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(3,5-di-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 used without further purification.

[0493] .sup.1H NMR (CDCl.sub.3): δ 7.54-7.20 (set of signals, sum 9H), 6.59 (s, 1H), 6.51 (s, 1H), 3.74, 3.69, 3.68 and 3.67 (4s, sum 2H), 3.23 and 3.22 (2s, sum 3H), 3.05-2.83 (m, 4H), 2.22 and 2.16 (2s, sum 6H), 2.11-1.99 (m, 2H), 1.44 and 1.41 (2s, sum 9H), 1.39 and 1.37 (2s, sum 27H), -0.18,-0.19 and -0.22 (3s, sum 6H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 155.52, 149.97, 149.95, 149.43, 147.47, 146.01, 145.79, 144.10, 144.06, 143.79, 143.75, 142.15, 142.11, 139.65, 139.53, 139.40, 139.32, 139.18, 139.15, 139.04, 139.00, 137.14, 137.09, 135.26, 131.29, 129.77, 127.29, 127.27, 126.34, 126.27, 126.00, 125.05, 124.01, 120.62, 120.55, 120.04, 120.01, 118.49, 118.25, 60.52, 60.48, 47.42, 47.35, 46.92, 46.72, 35.17, 34.89, 34.57, 33.40, 33.35, 32.49, 31.58, 31.50, 31.28, 31.23, 26.04, 26.02, 18.09, 17.97.

Anti-dimethylsilanediyl[2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(3,5-di-tert-butylphenyl)-5,6,7-trihydro-s-in dacen-1-yl]zirconium dichloride MC-IE-6

[0494] ##STR00057##

[0495] .sup.nBuLi in hexanes (2.43 M, 30 ml, 72.9 mmol) was added in one portion to a solution of 27.78 g (36.4 mmol) of [2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(3,5-di-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (as prepared above) in 300 ml of ether cooled to −50° C. This mixture was stirred overnight at room temperature; the resulting red solution was then cooled to −50° C. and 8.49 g (36.43 mmol) of ZrCl.sub.4 was added. The reaction mixture was stirred for 24 h at room temperature to give an orange slurry (red solution with orange precipitate). This mixture was evaporated to dryness. The residue was heated with 150 ml of toluene, and the formed suspension was filtered through glass frit (G4). The filtrate was evaporated to 80 ml and heated to get a clear solution. Light-red crystals precipitated from this solution overnight at room temperature were collected and dried under vacuum. This procedure gave 8.3 g of syn-zirconocene as a solvate with toluene (×1 PhMe) contaminated with ca. 2% of anti-isomer. The mother liquor was evaporated to ca. 60 ml, 15 ml of n-hexane was added, and the resulting mixture was heated to get a clear solution. Yellow crystals precipitated from this solution overnight at room temperature were collected and dried in vacuum. This procedure gave 6.1 g of anti-zirconocene contaminated with ca. 2% of syn-isomer. The mother liquor was evaporated to ca. 30 ml, the resulting suspension was heated to ca. 100° C. and was filtered while hot via glass frit (G3). The obtained solid was dried under vacuum to give 2.4 g of anti-zirconocene contaminated with less than 1% of syn-isomer. The mother liquor was evaporated to dryness, and the obtained residue was recrystallized from a mixture of 20 ml of toluene and 5 ml of n-hexane to give 8.4 g of a ca. 28 to 72 mixture of anti- and syn-zirconocenes. Thus, the total yield of anti- and syn-zirconocenes isolated in this synthesis was 25.2 g (75%).

[0496] Anti-dimethylsilanediyl[2-methyl-4-(4-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(3,5-di-tert-butylphenyl)-5,6,7-trihydro-s-indacen-1-yl]zirconium dichloride:

[0497] Anal. calc. for C.sub.54H.sub.68Cl.sub.2OSiZr: C, 70.24; H, 7.42. Found: C, 70.52; H, 7.70.

[0498] .sup.1H NMR (CDCl.sub.3): δ 7.61-7.30 (set of signals, sum 9H), 6.71 (s, 1H), 6.56 (s, 1H), 3.38 (s, 3H), 3.12-3.01 (m, 1H), 3.01-2.88 (m, 2H), 2.88-2.76 (m, 1H), 2.19 (s, 3H), 2.17 (s, 3H), 2.12-1.88 (m, 2H), 1.38 (s, 9H), 1.34 (s, 27H), 1.29 (s, 3H), 1.28 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3,): δ 159.92, 150.25, 150.00, 144.60, 143.92, 143.11, 137.55, 135.17, 134.00, 133.83, 133.76, 133.39, 133.21, 129.29, 126.92, 126.77, 125.31, 123.68, 123.09, 121.36, 121.21, 120.82, 117.84, 81.87, 81.42, 62.71, 35.74, 35.00, 34.62, 33.27, 32.45, 31.58, 31.42, 30.42, 26.64, 18.46, 18.29, 2.73, 2.60.

[0499] Synthesisof Comparative Metallocene MC-CE1

##STR00058##

[0500] MC-CE1 (rac-anti-dimethylsilanediyl(2-methyl-4-(4-tert-butylphenyl) inden-1-yl)(2-methyl-4-(4′-tert-butylphenyl)-5-methoxy-6-tert-butyl inden-1-yl) zirconium dichloride) was synthetized according to the procedure as decribed in WO WO2013007650, E7.

[0501] Synthesisof comparative metallocene MC-CE2

##STR00059##

[0502] MC-CE2 (rac-anti-dimethylsilanediyl(2-methyl-4-(4′-tert-butylphenyl) inden-1-yl)(2-methyl-4-phenyl-5-methoxy-6-tert-butyl inden-1-yl) zirconium dichloride) was synthetized according to the procedure as decribed in WO WO2013007650, E2.

[0503] Synthesisof Comparative Metallocene MC-CE3

##STR00060##

[0504] MC-CE3 (rac-dimethylsilanediylbis[2-methyl-4-(4-tert-butylphenypindenyl] zirconium dichloride) was synthetized according to the procedure as described in WO98040331, example 65.

[0505] Synthesisof Comparative Metallocene MC-CE4

##STR00061##

[0506] MC-CE4 (rac-an ti-dimethylsilanediyl[2-methyl-4-(3′,5′-di-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-di-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride) was synthetized according to the procedure as described in WO2015158790, example C.sub.2—Zr.

[0507] Synthesisof Comparative Metallocene MC-CE5

##STR00062##

[0508] MC-CE5 (rac-μ-{bis-[η.sup.5-2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilanediyl}dichlorozirconium) was prepared as described in WO2006/097497A1. The 1H NMR spectrum of it corresponds to that reported in the mentioned patent application.

[0509] Comparative metallocene MC-CE6 and comparative metallocene MC-CE7 are made analogously.

Summary of Examples

[0510] ##STR00063## ##STR00064## ##STR00065## ##STR00066##

NON SUPPORTED CATALYST PREPARATION EXAMPLES

[0511] Materials

[0512] Inventive metallocenes MC-IE1, MC-IE2, MC-IE3, MC-IE4, MC-IE5 and MC-IE6 and comparative metallocenes MC-CE1, MC-CE2, MC-CE3, MC-CE4, MC-CES, MC-CE6 and MC-CE7 as described above were used in preparing catalysts. 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 (S1) 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.

[0513] 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 IE1

[0514] 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-IE1 (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.

[0515] 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 IE-2

[0516] Inside the glovebox, 86.2 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, 41.1 mg MC-IE2 (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.

[0517] 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. 0.54 g of a red free flowing powder was obtained.

Catalyst Example IE-3

[0518] Inside the glovebox, 85.3 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, 42.4 mg MC-IE-3 (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.

[0519] 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. 0.52 g of a red free flowing powder was obtained.

Catalyst Example IE-3.1b

[0520] Inside the glovebox, 234.3 mg of S2 surfactant solution (14 wt % in toluene) was added dropwise to 5 mL of 30 wt.-% MAO. The solutions were left under stirring for 30 min. Then, around 95.6 mg of metallocene MC-IE3 (0.114 mmol, 1 equivalent) was added to MAO/surfactant solution and the solution was stirred for 60 minutes. Then 104.9 mg of trityl tetrakis(pentafluorophenyl)borate was added. The mixture was left to react at room temperature inside the glovebox for 60 minutes.

[0521] Then, 5 mL of catalyst 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./600rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot PFC at 90° C. and stirred at 600rpm 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 red catalyst was dried during 2 hours at 50° C. over an argon flow. 0.70 g of a red free flowing powder was obtained.

Catalyst Example 1E4

[0522] Inside the glovebox, S2 surfactant solution (27.6 mg of dry and degassed S2 dilute in 0.2 mL toluene) was added dropwise to 5 mL of 30 wt.-% MAO. The solution was left under stirring for 10 min. Then, around 46.7 mg of metallocene was added to 5 ml MAO/surfactant solution and the solution was stirred for 60 minutes Then, the MAO/MC-IE-4/S2 solution (5.2 mL) was 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./600rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot PFC at 90° C. and stirred at 600rpm 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 on top of the PFC and after 35 minutes, the solvent was siphoned off. The remaining nice red catalyst was dried during 2 hours at 50° C. over an argon flow.

Comparative Catalyst example CE-1

[0523] Inside the glovebox, 80 μl of dry and degassed surfactant Slwas mixed with 2 mL of MAO in a septum bottle and left to react overnight. The following day, 66.3 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. 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 (300 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. 0.31 g of a red free flowing powder was obtained.

Comparative Catalyst example CE-1b (Same Metallocene as Comparative Example CE-1)

[0524] Inside the glovebox, 85.6 mg of dry and degassed S2 were mixed with 2 mL of MAO in a septum bottle and left to react overnight. The following day, 44.2 mg of MC-CE1 (0.051 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another septum bottle and left to stir inside the glovebox.

[0525] 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. 0.75 g of a red free flowing powder was obtained.

Comparative Catalyst Example CE-2

[0526] Inside the glovebox, 80 μl of dry and degassed surfactant Slwas mixed with 2 mL of MAO in a septum bottle and left to react overnight. The following day, 58.7 mg MC-CE2 (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.

[0527] 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 (300 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. 0.52 g of a red free flowing powder was obtained.

Comparative Catalyst Example CE-3

[0528] Inside the glovebox, 80 μl of dry and degassed surfactant Si was mixed with 2 mL of MAO in a septum bottle and left to react overnight. The following day, 56.2 mg MC-CE3 (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.

[0529] 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 (300 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. 0.56 g of a red free flowing powder was obtained.

Comparative Catalyst Example CE-4

[0530] Inside the glovebox, 80 μl of dry and degassed surfactant S1was mixed with 2 mL of MAO in a septum bottle and left to react overnight. The following day, 73.0 mg MC-CE4 (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.

[0531] 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 (300 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. under an argon flow. 0.50 g of a red free flowing powder was obtained.

Comparative Catalyst Example CE-5

[0532] Inside the glovebox, 85.7 mg of dry and degassed S2 were mixed with 2 mL of MAO in a septum bottle and left to react overnight. The following day, 38.0 mg of MC-CE5 (0.051 mmol, 1 equivalent) were dissolved with 4 mL of MAO in another septum bottle and left to stir inside the glovebox.

[0533] 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. 0.66 g of a red free flowing powder was obtained.

Comparative Catalyst Example CE-6

[0534] Inside the glovebox, 85.7 mg of dry and degassed S2 were mixed with 2 mL of MAO in a septum bottle and left to react overnight. The following day, 58.1 mg of MC-CE6 (0.051 mmol, 1 equivalent) were dissolved with 4 mL of MAO in another septum bottle and left to stir inside the glovebox.

[0535] 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. 0.60 g of a red free flowing powder was obtained.

Comparative Catalyst Example CE-7

[0536] Inside the glovebox, 72.0 mg of dry and degassed S2 were mixed with 2 mL MAO in a septum bottle and left to react overnight. The following day, 39.8 mg of MC-CE7 (0.051 mmol, 1 equivalent) were dissolved with 4 mL of MAO in another septum bottle and left to stir inside the glovebox.

[0537] 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. 0.72 g of a red free flowing powder was obtained.

TABLE-US-00003 TABLE 1 Catalyst synthesis summary and elemental analysis Cat ICP Zr Metallocene Ex (wt.-%) Al/Zr (mol/mol) MC-IE1 IE1 0.27 453 MC-IE2 IE2 0.26 479 MC-IE3 IE3 0.26 481 MC-IE3 IE3b 0.50 215 MC-IE4 IE4 0.26 479 MC-CE1 CE1 0.35 291 MC-CE1 CE1b 0.31 421 MC-CE2 CE2* 0.41 283 MC-CE3 CE3 0.40 294 MC-CE4 CE4 0.33 335 MC-CE5 CE5 0.28 474 MC-CE6 CE6 0.37 346 MC-CE7 CE7 0.28 423 *CE2 Zr content (ICP) was re-measured over WO2013/007650 (E2).

Silica Supported Catalyst Examples

[0538] The silica-MAO catalysts have been prepared on 30.sub.11 SUNSPERA DM-L-303 silica produced by AGC Si-Tech Co, previously calcined at 600° C. for 2 hours in an Electric Muffle Furnace under a flow of dry air.

[0539] Preparation of Silica Supported Metallocene Catalyst (Silica-IE1)

[0540] Step-1

[0541] Toluene was dried over molecular sieves and degassed by bubbling with argon for at least 30 minutes.

[0542] Inside the glovebox, 6.3 g of the calcined silica was charged into a round-bottom flask equipped with an overhead stirrer and a sealed septum, and then −30 mL of dry and degassed toluene was added into it. The resulting suspension was cooled down to 0° C. under mild stirring (200-300 rpm) and 16 mL of MAO solution added dropwise.

[0543] After around 20 minutes, the cooling bath was removed and stirring was continued for 2 hours. The silica-MAO slurry was allowed to settle and then the supernatant toluene solution was siphoned off via a 2/4 teflon tube. Then, around 20 mL of dried and degassed toluene was added and the slurry was stirred for 15 minutes at room temperature.

[0544] The flask was placed into the oil bath and warmed up to 80° C. and the slurry solution was stirred for additional 30 min. Then the silica-MAO slurry was again allowed to settle for 10 min. The hot toluene solution was siphoned off

[0545] This washing procedure was repeated one more time, and then an additional washing has been performed using toluene (20 ml pentane, stirring 15 min). The toluene layer was siphoned off, then the solid was dried under argon flow at room temperature for about 3 h. The white flowing MAO-silica powder was collected and used for supported catalyst preparation Silica-TEL

[0546] Step-2

[0547] Inside the glove box, 0.25 mL of MAO solution was added to MC-IE1 solution (30 mg of MC-IE1 in 1 ml of toluene) in a septum bottle.

[0548] 1 g of dry silica-MAO powder was placed into a 20 mL glass vial, and then −5 mL of dry and degassed toluene was added into it. Then the complex solution was added and the slurry solution was stirred for 60 minutes at room temperature and the resulting slurry was allowed to stand overnight in the glove box. Then 5 mL of dried and degassed toluene was added; the bath temperature was set to 40° C. and stirred for 60 minutes. The solid catalyst was allowed to settle, and then the toluene layer was removed. Then another 5 mL of dried and degassed toluene was added; the bath temperature was set to 60° C. and stirred for 2 hours minutes. The solid catalyst was allowed to settle, and then the toluene layer was removed. Then three additional washing step has been performed at room temperature using 5 ml of dry toluene and the toluene layer was siphoned off and then the solid was dried under argon flow at room temperature for 3 h. 0.967 g of a red silica supported flowing powder was collected.

Preparation of Silica Supported Metallocene Catalyst (Silica-IE2)

[0549] Step 1

[0550] Toluene was dried over molecular sieves and degassed by bubbling with argon for at least 30 minutes. Inside the glovebox, 10 g of the calcined silica was charged into a round-bottom flask equipped with an overhead stirrer and a sealed septum, then −50 mL of dry and degassed toluene was added into it. The resulting suspension was cooled down to 0° C. under mild stirring (200—300 rpm) by means of a cooling bath. 25 mL of a 30 wt-% MAO solution in toluene was slowly added with a dry and degassed syringe or by siphonation onto the silica suspension (dropwise, adding time˜1 h). Then the cooling bath was removed and stirring was continued for 2 hours. The silica-MAO slurry was allowed to settle and then the supernatant toluene solution was siphoned off with an oven-dried cannula.

[0551] ˜30 mL of dried and degassed toluene was added, the slurry was stirred for 15 minutes at room temperature, then the flask was placed into the oil bath and warmed up to 80° C. Stirring was continued for additional 15 min, then the slurry was again allowed to settle for 10 min. The hot toluene solution was siphoned off from the top of the settled silica-MAO layer. This washing procedure was repeated one more time, and then an additional washing has been performed using pentane (30 ml pentane, stirring 15 min, settling 10min). The pentane layer was siphoned off, then the solid was dried under argon flow at room temperature (20-25° C.) for about 3 h and finally the flask was placed in a water bath (+50° C.) and the last residues of solvent were removed under argon flow through silica-MAO solid layer. During the final drying steps the silica-MAO solid turned into an easily flowing powder.

[0552] This MAO-silica activated carrier was used to prepare catalyst Silica-IE2 (and to prepare Silica-CE1, and Silica-CE2).

[0553] Step 2

[0554] Preparation of complex solution. Inside a glove box, 0.25 mL of the toluene-MAO solution was added to a solution of 23 mg of rac-anti-dimethylsilanediyl[2-methyl-4-(3′5′-dimethyl phenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′5′-dimethylphenyl)-5-methoxy-6-tertbutylinden-1-yl]zirconiumdichloride metallocene (MC-IE2) in 1 ml of toluene in a septum bottle.

[0555] 1 g of the previously prepared silica-MAO dry powder was placed into a 20 mL glass vial, and the complex solution was added. The resulting slurry was allowed to stand overnight in the glove box. 5 mL of dried and degassed toluene was added; the bath temperature was set to 60° C. and stirred for 30 minutes. The solid catalyst was allowed to settle, and then the toluene layer was removed by syringe. The washing step was repeated twice more (2×5 mL toluene). The solid was allowed to cool down to room temperature and one final washing step was carried out by adding 5 ml of dry pentane, stirring the slurry gently for 30 min, allowing the catalyst to settle, and finally removing pentane by syringe and drying the solid under argon flow for 3 h.

[0556] Preparation of Silica Supported Metallocene Catalyst (Silica-CE2)

[0557] Preparation was carried out as for catalyst Silica-IE2 but using 32 mg of metallocene MC-CE2

[0558] Preparation of Silica Supported Metallocene Catalyst (Silica-CE1)

[0559] Preparation was carried out as for catalyst Silica-IE2 but using 30 mg of metallocene MC-CE1

[0560] The available composition data of the catalysts from ICP are listed in Table 1.

TABLE-US-00004 TABLE 1 Composition data of the catalysts used in this investigation Zr Al Al/Zr MC Catalyst MC (wt %) (wt %) (molar) (wt %) Silica-CE2 MC-CE2 0.20 14.8 250 1.69 Silica-CE1 MC-CE1 0.18 14.8 280 1.63 Silica-IE1 MC-IE1 0.27 17.7 220 2.57 Silica-IE2 MC-IE2 0.19 15.3 270 1.69

[0561] Polymerisation Examples

[0562] Homopolymerisation of Propylene with Unsupported Metallocenes

[0563] The polymerisations were performed in a 5 L reactor. 200 μl of triethylaluminum was fed as a scavenger in 5 mL of dry and degassed pentane. The desired amount of hydrogen was then loaded (measured in mmol) and 1100 g of liquid propylene was fed into the reactor. The temperature was set to 20° C. The desired amount of catalyst (5 to 15 mg) 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. Polymerisation conditions and results are disclosed in Table 2.

[0564] C.sub.3/C.sub.2 Random Copolymerisation with Unsupported Metallocenes

[0565] The polymerisations were performed in a 5 L reactor. 200 μl of triethylaluminum was fed as a scavenger in 5 mL of dry and degassed pentane. The desired amount of hydrogen (6 mmol) was then loaded and 1100 g of liquid propylene was fed into the reactor. Desired amount of ethylene was fed in to the reactor. The temperature was set to 30° C. The desired amount of catalyst (5 to 20 mg) in 5 mL of PFC is flushed into the reactor with a nitrogen overpressure. The temperature is then raised to 70° C. over a period of 15 minutes. The polymerisation is stopped after 30 minutes by venting the reactor and flushing with nitrogen before the polymer is collected.

[0566] The catalyst activities were calculated on the basisof the 60 minute (homopolymerisation of propylene) or 30 minute (C.sub.3/C.sub.2 random copolymerisation) period according to the following formula:

[00001]$\mathrm{Catalyst}\mathrm{Activity}\left(\text{kg-}\mathrm{PP}\text{/g-}\mathrm{Cat}\text{/h}\right)=\frac{\mathrm{amount}\mathrm{of}\mathrm{polymer}\mathrm{produced}\left(\mathrm{kg}\right)}{\mathrm{catalyst}\mathrm{loading}\left(g\right)⨯\mathrm{polymerisation}\mathrm{time}\left(h\right)}$

[0567] Polymerisation results of C.sub.3/C.sub.2 random copolymerisations are collected in Table 3.

[0568] Performance of the inventive examples with comparison to the closest references is summarised in FIGS. 1-5. The best overall performance isobtained with the new metallocenes of the invention: high activity in homopolymerisation and in C.sub.3/C.sub.2 random copolymerisation, good homopolymer melting temperature and good molecular weight capability. Most importantly, ethylene has a strong positive effect on Mw with the catalysts of the invention.

Polymer Analysis

[0569]

TABLE-US-00005 TABLE 2 Propylene homopolymerisation in liquid propylene. Polymerisation time 60 minutes. Tp = 70° C. Catalyst Amt H2 Yield Activity Metal activity Mw Tm 2, 1e Mmmm Run # (mg) (mmol) (g) (kg-PP/g-Cat/h) (kg-PP/g-Zr/h) (kg/mol) Mw/Mn (° C.) (%) (%) IE 1.1 9.1 6 372 40.8 15128 516 2.5 150.9 0.96 99.59 IE 2.1 9.1 6 322 39.7 15266 514 2.6 150.4 0.93 99.70 IE 3.1 7.7 6 250 32.5 12493 510 2.7 150.8 0.91 99.61 IE 3.1b 6.7 6 463 69.1 13926 521 2.5 156.4 — — CE 1.1 9.8 6 479 48.8 13956 472 2.2 149.4 1.09 99.77 CE 2.1 10.0 6 298 29.8 7268 486 2.3 146.9 n.d n.d. CE 3.1 10.0 6 269 26.9 6720 418 2.3 151.0 0.92 99.38 CE 4.1 8.7 6 213 24.4 7409 233 2.8 156.2 0.54 99.44

TABLE-US-00006 TABLE 3 Ethylene-propylene random copolymerisations (with hydrogen, 6 mmol). Polymerisation time 30 minutes. Tp = 70° C. Catalyst Amt C2 Yield Activity Metal activity Mw Tm NMR Ce Run # (mg) (mmol) (g) (kg-PP/g-Cat/h) (kg-PP/g-Zr/h) (kg/mol) Mw/Mn (° C.) (wt.-%) IE 1.2 7.5 50.0 247. 66.1 24464 702 2.6 119.4 4.22 IE 3.2 8.1 50.0 433. 107.0 41149 720 2.7 121.4 4.06 CE 1.2 7.6 49.9 199 52.4 14962 517 2.4 120.3 4.15 CE 2.2 15.0 49.9 236 31.4 7665 504 2.6 119.3 3.58 CE 3.2 8.7 50.0 85 19.6 4908 297 2.4 124.3 3.55 CE 4.2 9.1 50.5 176 38.6 11688 246 2.3 113.4 5.17

[0570] Polymerisation Examples with Offline Prepolymerised Catalyst.

[0571] Off-Line Prepolymerization (“Prepping”) Procedure

[0572] The CE5 catalyst was 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 (CE5, 398.7 mg) 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 1.8057 g of the pre-polymerised catalyst.

[0573] The catalysts listed in the table 4 below were prepolymerised as described in the above procedure.

TABLE-US-00007 TABLE 4 prepolymerisation of catalysts (pp = offline prepolymerised) Catalyst weighed Prep-degree (g- Catalyst-name amount (mg) Yield (g) Pol/g-Cat) ppCE5 398.7 1.8057 3.5 ppCE6 393.3 1.6514 3.2 ppCE1b 400.3 1.8622 3.7 ppCE7 399.5 1.7488 3.4 ppIE1 399.5 1.8154 3.5 ppIE3 408.6 1.8096 3.4 ppIE2 402.0 1.6670 3.2

[0574] The polymers have been produced in a 20-L reactor following three different procedures, as described in Table 5.

TABLE-US-00008 TABLE 5 Polymerisation procedures bulk GP1 GP2 T H2 Time P T Time H2 P T Time C2/C3 procedure steps ° C. NL min barg ° C. min NL barg ° C. min wt/wt 1 2 80 1.5 ~40 20 70 ~70 0.25 2 3 80 1.5 40 24 80 60 1.2 20 70 90 0.25 3 3 80 1.5 40 24 80 60 1.2 20 70 90-120 1.00

[0575] The details of the polymerisation procedures are described in the following:

[0576] Procedure 1: 2-Step Polymerisation

[0577] Step 1: Prepolymerisation and Bulk Homopolymerisation

[0578] A 21.2 L stainless-steel reactor containing 0.4 barg propylene was filled with 3950 g propylene. Triethylaluminum (0.80 ml of a 0.62 mol/l solution in heptane) 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, prepolymerised catalyst was loaded into a 5 ml stainless steel vial and a second 5 ml vial containing 4 ml n-heptane was added on top inside a glovebox. Then the vial on top was pressurized with 10 bars of nitrogen and attached to the autoclave. The valve between the two vials was opened and the solid catalyst was contacted with n-heptane under nitrogen pressure for 2 s, and 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 of H2 was added via mass flow controller in one minute. 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.

[0579] Jacket T constraints: during the transition between prepolymerisation and target reactor temperature, the jacket temperature is controlled with a cooling device (HB-Therm). The set temperature limits to prevent overheating of the reactor were:

[0580] dTSW: Defines the maximum temperature of the jacket liquid

[0581] Set=max10° C. >target temperature

[0582] dTIW: Defines the maximum temperature difference between jacket and reactor during heating .

[0583] Set=max35° C. >actual temperature

[0584] Step 2: Gas Phase C.sub.3C.sub.2 r-PP.Polymerisation

[0585] Afterthe bulk step 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/l solution in heptane) was injected into the reactor by additional 250 g propylene through a steel vial. 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. Then the reactor pressure was increased to 20 bar-g by feeding a C.sub.3/C.sub.2 gas mixture (C.sub.2/C.sub.3=0.74 wt/wt). Pressure and temperature were held constant by feeding via mass flow controller a C.sub.3/C.sub.2 gas mixture (of composition corresponding to the target polymer composition) and by thermostat, until the set time for this step had expired.

[0586] Then the reactor was cooled down (to about 30° C.) and the volatile components flashed out. After flushing 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 2 hours in a vacuum drying oven at 60° C.

[0587] Jacket T constraints. During the transition between bulk and gas phase temperature, the jacket temperature is controlled with a cooling device (HB-Therm). The set temperature limits to prevent overheating of the reactor were:

[0588] dTSW: Defines the maximum temperature of the jacket liquid

[0589] Set=max10° C. >target temperature

[0590] dTIW: Defines the maximum temperature difference between jacket and reactor during heating .

[0591] Set=max35° C. >actual temperature.

[0592] Procedure 2: 3-step polymerisation

[0593] Step 1: Prepolymerisation and Bulk Homopolymerisation

[0594] Step 1 was performed as described in procedure 1 above.

[0595] Step 2: Gas Phase Homopolymerisation

[0596] Afterthe 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. Hydrogen (1.2 NL) was added via flow controller in one minute. During the gas phase homopolymerisation, both pressure and temperature have been held constant via mass flow controller (feeding propylene) and thermostat for 60 minutes.

[0597] Step 3: Gas Phase Ethylene Propylene Copolymerisation

[0598] Step 3 was performed as step 2 of procedure 1 described above. Differences: Feeding a C.sub.2/C.sub.3 gas mixture of C.sub.2/C.sub.3=0.56(wt/wt) in the transition. Polymerisation in this step was run for 90 min.

[0599] Procedure 3: 3-Step Polymerisation

[0600] Step 1: Prepolymerisation and Bulk Homopolymerisation

[0601] The autoclave containing 0.4 barg propylene was filled with 3970 g propylene. Triethylaluminum (0.80 ml of a 0.62 mol/l solution in heptane) 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, prepolymerised catalyst was loaded into a 5 ml stainless steel vial and a second 5 ml vial containing 4 ml n-heptane was added on top inside a glovebox. Then the vial on top was pressurized with 10 bars of nitrogen and attached to the autoclave. The valve between the two vials was opened and the solid catalyst was contacted with n-heptane under nitrogen pressure for 2 s, and 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 of H2 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.

[0602] Jacket T constraints. During the transition between prepolymerisation and target reactor temperature, the jacket temperature is controlled with a cooling device (HB-Therm). The set temperature limits to prevent overheating of the reactor were:

[0603] dTSW: Defines the maximum temperature of the jacket liquid

[0604] Set=max10° C. >target temperature

[0605] dTIW: Defines the maximum temperature difference between jacket and reactor during heating .

[0606] Set=max35° C. >actual temperature

[0607] Step 2: Gas Phase Homopolymerisation

[0608] Afterthe bulkstep was completed, the stirrer speed was reduced to 50 rpm and the pressure was reduced to the desired gas phase pressure.(=target pressure-0.5) by venting the monomer. Afterwards the stirrer speed was set to 180 rpm, the reactor temperature to 80° C. and the pressure to 24barg. The desired amount of hydrogen was added via flow controller. During the gas phase homopolymerisation, both target pressure and temperature have been held constant via mass flow controller (feeding propylene) and thermostat until the runtime for this step was expired.

[0609] Step 3: Gas Phase C.sub.3C.sub.2 r-PP.Polymerisation

[0610] Afterthe first gasphase step was completed, the stirrer speed was reduced to 50 rpm and the pressure was reduced down to 0.3 barg by venting the monomers. Then triethylaluminum (0.80 ml of a 0.62 mol/l solution in heptane) was injected into the reactor by additional 250 g propylene through a steel vial. The pressure was then again reduced down to 0.3 barg by venting the monomers. The stirrer speed was set to 180 rpm and the reactor temperature was set to 70° C. Then the reactor pressure was increased to 20 bar-g by feeding a C.sub.3/C.sub.2 gas mixture (C.sub.2/C.sub.3=2.22 wt/wt). Pressure and temperature were held constant by feeding via mass flow controller a C.sub.3/C.sub.2 gas mixture (of composition corresponding to the target polymer composition) and by thermostat, until the set time for this step had expired.

[0611] Then the reactor was cooled down (to about 30° C.) and the volatile components flashed 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.

[0612] Jacket T constraints. During the transition between bulk and first gas phase and first and second gasphase, the jacket temperature is controlled with a cooling device (HB-Therm). The set temperature limits to prevent overheating of the reactor were:

[0613] dTSW: Defines the maximum temperature of the jacket liquid

[0614] Set=max10° C. >target temperature

[0615] dTIW: Defines the maximum temperature difference between jacket and reactor during heating .

[0616] Set=max35° C. >actual temperature.

[0617] Results are set out in tables 6 to 8.

TABLE-US-00009 TABLE 6 Two-step polymerisations (procedure 1), result summary Metallocene MC-CE1 MC-CE5 MC-CE6 MC-IE1 MC-IE2 Catalyst ppCE1b ppCE5 ppCE6 ppIE1 ppIE2 MFR whole material 9.4 5 16 4 2.5 XS.sub.gravim 57 64 52 63 54 C2(XS) 24.8 27.3 27.1 27.7 24.4 iV.sub.EPR 1.6 1.9 1.6 2.3 2.3

TABLE-US-00010 TABLE 7 Three-step polymerisations (procedure 2), result summary Metallocene MC-CE1 MC-CE7 MC-IE3 MC-IE2 Catalyst ppCE1b ppCE7 ppIE3 ppIE2 MFR whole material 9 14 9 6 Split bulk-GP1-GP2 50-35-15 43-32-25 39-32-29 38-36-26 (calc with MFC) XS.sub.gravim (XS.sub.Crystex) 19 (17) 31 (28) 31 (30) 27 (26) C2(XS) 21.4 20.9 21.6 20.8 iV.sub.EPR 1.6 1.9 2.3 2.4

TABLE-US-00011 TABLE 8 Three-step polymerisations (procedure 3), result summary Metallocene MC-CE1 MC-IE1 MC-IE3 MC-IE2 Catalyst ppCE1b ppIE1 ppIE3 ppIE2 MFR whole material 9.6 18.6 21.4 9.4 Split bulk-GP1-GP2 45-37-18 40-40-20 39-43-18 44-37-19 (calc with MFC) XS.sub.gravim (XS.sub.Crystex) 20 (20) 20 (20) 17 (18) 20 (20) C2(XS) 47.9 47.0 47.6 47.3 iV.sub.EPR 1.7 2.1 2.0 2.2

[0618] The results clearly indicate that the catalysts ppIE1, ppIE2, and ppIE3 produce heterophasic copolymers having a rubber phase with a higher molecular weight than the heterophasic copolymers produced under similar conditions with the comparison catalysts.

[0619] The Mw/Mn of the matrix produced in the three-step experiments ranges from 4.5 to 6.2.

[0620] The need for a cyclopentyl ring condensed on one of the indenes is shown by comparing the iV(EPR) of the heterophasic copolymer obtained with CE1 or CE7 to those obtained with the three inventive metallocenes (Tables 6-8).

[0621] Polymerisation Procedure for 1-Step Homopolymerisation hPP in Bulk (5 Litre Reactor) Using Unsupported Metallocene Catalyst 1E4

[0622] Polymerisation Procedure

[0623] The polymerisations were performed in a 5 L reactor. 200 μl of triethylaluminum was fed as a scavenger in 5 mL of dry and degassed pentane. The desired amount of hydrogen was then loaded (mmol, see Table 9) and 1100 g of liquid propylene was fed into the reactor. The temperature was set to 20° C. The desired amount of catalyst (5 to 15 mg) 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.

[0624] The catalyst activity was calculated based on the 60 minute period at 70° C. according to the following formula:

[00002]$\mathrm{Catalyst}\mathrm{Activity}\left(\text{kg-}\mathrm{PP}\text{/g-}\mathrm{Cat}\text{/h}\right)=\frac{\mathrm{amount}\mathrm{of}\mathrm{polymer}\mathrm{produced}\left(\mathrm{kg}\right)}{\mathrm{catalyst}\mathrm{loading}\left(g\right)⨯\mathrm{polymerisation}\mathrm{time}\left(h\right)}$

[0625] Polymerisation results are collected in Table 9.

TABLE-US-00012 TABLE 9 Results for homopolymerisation in liquid propylene experiments and for the polymer characterisation. Polymerisation time 60 minutes. Tp = 70 °C. Activity Catalyst H2 Yield (kg-PP/g- MFR21 Catalyst (mg) (mmol) (g) Cat/h) (g/10 min) Tm (° C.) IE4 13.7 1 244.4 17.8 4.64 155.4 IE4 9.0 6 329.5 36.6 72.1 156.7

[0626] Polymerisation Procedure for 2-Step hPP in Bulk+Gas Phase Experiments Using Silica Supported Metallocenes

[0627] Step 1: Prepolymerisation and Bulk Homopolymerisation

[0628] A 20.9 L stainless-steel reactor containing 0.4 bar-g propylene was filled with 3950 g propylene. Triethylaluminum (0.80 ml of a 0.62 mol/l solution in heptane) was placed into a stainless steel vial and injected into the reactor by means of a flow of 240 g propylene. 2.0 NL of H2 was added via mass flow controller in one minute. 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, 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 the lid of the reactor, the valve between the two vials was opened and the solid catalyst was contacted with heptane under nitrogen pressure for 2 s, and 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. The reactor temperature was held constant at 80° C. throughout the polymerisation. The liquid propylene polymerisation was run for 40 minutes. The polymerisation time was measured starting when the internal reactor temperature reached 2° C. below the set polymerisation temperature.

[0629] Step 2: Gas Phase Homopolymerisation

[0630] Afterthe bulk step was completed, the stirrer speed was reduced to 50 rpm and the pressure was reduced to 23.5 bar-g by venting the monomer. Afterwards the stirrer speed was set to 180 rpm, the reactor pressure was set at 24 bar-g while keeping the reactor temperature at 80° C., and 2.0 NL hydrogen were added via flow controller in 4 minutes. The gas phase homopolymerisation was run for 60 minutes, while keeping the pressure constant by feeding propylene via mass flow controller and the temperature constant at 80° C. by thermostat.

[0631] The 2-step hPP in bulk+ gas phase polymerisation results with the SiO2 supported catalysts and metallocenes CE1, CE2, 1E2 are listed in Table 10 and Table 11. FIG. 6 shows the results graphically.

TABLE-US-00013 TABLE 10 2-step homopolymerisation experiments: settings and results. Prepoly 10 min, all H2 fed before prepoly; Bulk step at 80° C., 40 min; Gas phase step at 80° C., 24 bar-g. Time MC from Time amount 20° C. from C3fed Powder Catalyst in to bulk to in GP Total Overall Bulk GP1 bulk amount catalyst 80° C. GP (MFC) yield productivity Split split MFR2 density Catalyst mg mg min min g g kg/g.sub.cat kg/g.sub.MC wt % wt % g/10 min g/cm.sup.3 Silica 113 1.91 18 11 195 2158 19 1130 77 23 1.9 0.49 CE2 Silica 79 1.29 18 15 364 1585 20 1231 77 23 2.6 0.47 CE1 Silica 55 0.93 22 5 302 1571 29 1690 81 19 2.8 0.46 IE2

TABLE-US-00014 TABLE 11 2-step homopolymers: analytics XS T.sub.m M.sub.n M.sub.w catalyst (wt %) (° C.) (g/mol) (g/mol) M.sub.w/M.sub.n Silica CE2 0.4 150 96200 335000 3.5 Silica CE1 0.2 151 89250 311500 3.5 Silica IE2 0.3 154 71000 304000 4.3

[0632] Polymerisation Procedure for 3-Step Heterophasic PP/EPR (Bulk+Gas Phase+Gas Phase) Experiments with Silica Supported Metallocenes

[0633] Step 1: Prepolymerisation and Bulk Homopolymerisation

[0634] A 20.9 L stainless-steel reactor containing 0.4 bar-g propylene was filled with 3950 g propylene. Triethylaluminum (0.80 ml of a 0.62 mol/l solution in heptane) was placed into a stainless steel vial and injected into the reactor by means of a flow of 240 g propylene. 2.0 NL of H2 was added via mass flow controller in one minute. 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, 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 the lid of the reactor, the valve between the two vials was opened and the solid catalyst was contacted with heptane under nitrogen pressure for 2 s, and 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. The reactor temperature was held constant at 80° C. throughout the polymerisation. The liquid propylene polymerisation was run for 30 minutes. The polymerisation time was measured starting when the internal reactor temperature reached 2° C. below the set polymerisation temperature.

[0635] Step 2: Gas Phase Homopolymerisation

[0636] Afterthe bulk step was completed, the stirrer speed was reduced to 50 rpm and the pressure was reduced to 23.5 bar-g by venting the monomer. Afterwards the stirrer speed was set to 180 rpm, the reactor pressure was set at 24 bar-g while keeping the reactor temperature at 80° C., and 2.0 NL hydrogen were added via flow controller in 4 minutes. The gas phase homopolymerisation was run for 40 minutes, while keeping the pressure constant by feeding propylene via mass flow controller and the temperature constant at 80° C. by thermostat.1

[0637] Step 3: Gas Phase Ethylene Propylene Copolymerisation

[0638] Afterthe gas phase homopolymerisation step 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/l solution in heptane) was injected into the reactor by additional 250 g propylene through a steel vial. 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. Then the reactor pressure was increased to 20 bar-g by feeding a C.sub.2/C.sub.3 gas mixture (C.sub.2/C.sub.3=0.56 wt/wt). The temperature was held constant by thermostat and the mposition C.sub.2/C.sub.3=0.25 wt/wt for a set time (values in table 6).

[0639] Then the reactor was cooled down to about 30° C. while the volatile components were flashed 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 was additivated with 0.5 wt % Irganox B225 (solution in acetone) and dried overnight in a hood followed by 2 hours in a pressure was held constant by feeding via mass flow controller a C.sub.3/C.sub.2 gas mixture of covacuum drying oven at 60° C.

[0640] The 3-step heterophasic copolymers have been produced in three polymerisation steps: hPP in bulk at 80° C., hPP in gas phase at 80° C., 24 bar-g, then a C.sub.2/C.sub.3 copolymerisation in gas phase at 70° C., 20 bar-g, without adding H2. The polymerisation results with the SiO2/MAO catalysts based on Asahi Sunspera DM-L-33-C.sub.1 silica and metallocenes MC-CE2, MC-CE2, MC-IE1 and MC-IE2 are listed in table 12 and Table 13.

TABLE-US-00015 TABLE 12 3-step heterophasic copolymerisation experiments: settings and results. Prepoly 10 min, all H2 fed before prepoly; Bulk step at 80° C., 30 min; Gas phase 1 step at 80° C., 40 min, 24 bar-g; Gas phase 2 step at 70° C., 20 bar-g, no added H2. Transition Transition Transition 20 to 80° C. bulk to GP1 GP1 GP1 to GP2 Time (C3) Time of Time of Pre- transition Bulk Propylene transition H2 Propylene transition Propylene Ethylene Catalyst polym. prepoly Total fed in bulk to in fed GP1 to fed in fed in Catalyst amount H2 H2 to bulk H2 transition GP1 GP in GP1 GP2 transition transition name mg NL NL min NL g min NL g min g g Silica- 118 2,018 0 17 2,018 170 11 2,01 452 7 372 208 CE2 Silica- 80 2,018 0 18 2,018 80 12 2,01 287 7 378 212 CE1 Silica 56 2,020 1,01 19 3,030 0 7 3,02 189 7 366 206 IE2 Silica 74 2,019 0 18 2,019 159 21 2,01 372 14 376 214 IE1 3-step heterophasic copolymerisation experiments: settings and results. Prepoly 10 min, all H2 fed before prepoly; Bulk step at 80° C., 30 min; Gas phase 1 step at 80° C., 40 min, 24 bar-g; Gas phase 2 step at 70° C., 20 bar-g, no added H2. GP2 (C2/C3) Feed Propylene Ethylene C2/C3 Duration fed in fed in in gas Catalyst GP2 GP2 GP2 phase 2 yield productivity min g g wt/wt g kg/g cat 90 686 172 0,25 3018 26 90 296 73 0,25 1831 23 120 178 45 0,25 1465 26 90 259 64 0,25 2295 31

TABLE-US-00016 TABLE 13 3-step heterophasic copolymers: analytics powder split split C2 bulk split gas gas soluble (FT-IR) MFR2, density bulk phase 1 phase 2 fraction T.sub.m2 iV(XS) (XS) Catalyst powder g/ml % % % wt % ° C. dl/g wt % Silica-CE2 2,31 0,45 56,6 15,0 28 27,5 150 2,1 19,9 Silica-CE1 0,89 0,45 64,2 15,7 20 16,7 151 2,4 18,5 Silica IE2 4,3 0,44 71,8 12,9 15 11.8 152 3,2 19,2 Silica IE1 5,64 0,44 69,7 16,2 14,1 13,3 153 3,4 20,1

[0641] FIG. 7 shows the correlation between ethylene content of the rubber phase (C.sub.2 wt % in xylene soluble fraction) and its molecular weight (intrinsic viscosity). It is apparent that the inventive examples give much higher molecular weight compared to the comparative examples at the same ethylene content in the rubber.