CATALYST SYSTEM

Abstract

New, improved silica supported catalyst system, which comprises a specific class of metallocene complexes in combination with a boron containing cocatalyst and an aluminoxane cocatalyst, its use for producing propylene homopolymers, propylene copolymers, especially with ethylene, as well as heterophasic propylene copolymers, preferably in a multistep process including a gas phase polymerization step.

Claims

1. A supported catalyst system comprising: (i) a metallocene complex; (ii) a cocatalyst system comprising a boron containing cocatalyst and a methylaluminoxane cocatalyst; and (iii) an inorganic porous support; wherein the metallocene complex is of formula (I): ##STR00026## wherein each X independently is a sigma-donor ligand; L is R.sub.2Si, ethylene, or methylene, and each R is independently a C.sub.1-C.sub.20-hydrocarbyl group; each Ar independently is an aryl or heteroaryl group having 3 to 20 carbon atoms; each R.sup.1 is bonded to a carbon and independently is hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20-arylalkyl group, a C.sub.7-20-alkylaryl group, a C.sub.6-20-aryl group, or an OY group, wherein Y is a C.sub.1-10-hydrocarbyl group, or wherein two adjacent R.sup.1 groups taken together with the carbons to which they are bonded form a ring; each R.sup.2 independently is a CHR.sup.8R.sup.8 group, with R.sup.8 being H, a linear or branched C.sub.1-6-alkyl group, a C.sub.3-8-cycloalkyl group, a C.sub.6-10-aryl group, or a heteroaryl group having 3 to 20 carbon atoms optionally substituted by one to three groups R.sup.11, and R.sub.8 is H or a C.sub.1-6 alkyl; R.sup.3 is a linear or branched C.sub.1-C.sub.6-alkyl group, a .sub.C7-20-arylalkyl group, a C.sub.7-20-alkylaryl group, or C.sub.6-C.sub.20-aryl group; R.sup.4 is a C(R.sup.9).sub.3 group, with each R.sup.9 independently being a linear or branched C.sub.1-C.sub.6-alkyl group; R.sup.5 and R.sup.6 are each independently hydrogen, an aliphatic C.sub.1-C.sub.20-hydrocarbyl group, or R.sup.5 and R.sup.6 taken together form a 5 membered saturated carbon ring which is optionally substituted by n groups R.sup.10, n being from 0 to 4, and each R.sup.10 independently is a C.sub.1-C.sub.20-hydrocarbyl group, or a C.sub.1-C.sub.20-hydrocarbyl radical; R.sup.7 is H, a linear or branched C.sub.1-C.sub.6-alkyl group, or an aryl or heteroaryl group having 3 to 20 carbon atoms optionally substituted by one to three groups R.sup.11; and each R.sup.11 independently is hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20-arylalkyl group, a C.sub.7-20-alkylaryl group, a C.sub.6-20-aryl group, or an OY group, wherein Y is a C.sub.1-10-hydrocarbyl group; wherein the boron containing cocatalyst is either of formula (B) or a borate containing an anion of formula (C): ##STR00027## wherein each Y independently is a hydrogen atom, an alkyl group of from 1 to about 20 carbon atoms, an aryl group of from 6 to about 15 carbon atoms, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6-20 carbon atoms in the aryl radical or fluorine; or Z is an optionally substituted phenyl derivative, said substituent being a halo-C1-6-alkyl or halo group, and as counterions protonated amine or aniline derivatives.

2. The supported catalyst system of claim 1, wherein the metallocene complex is of formula (II): ##STR00028## wherein each X independently is a sigma-donor ligand; L is R.sub.2Si, ethylene, or methylene, and each R is independently a C.sub.1-C.sub.20-hydrocarbyl group; each R.sup.1 is bonded to a phenyl carbon and independently is hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20 arylalkyl group, a C.sub.7-20 alkylaryl group, a C.sub.6-20 aryl group, or an OY group, wherein Y is a C.sub.1-10 hydrocarbyl group, or wherein two adjacent R.sup.1 groups taken together with the phenyl carbons to which they are bonded form a ring; each R.sup.2 independently is a CH.sub.2-R.sup.8 group, with R.sup.8 being H, a linear or branched C.sub.1-6-alkyl group, a C.sub.3-8 cycloalkyl group, or a C.sub.6-10 aryl group; R.sup.3 is a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20 arylalkyl group, a C.sub.7-20 alkylaryl group, or a C.sub.6-C.sub.20-aryl group; R.sup.4 is a C(R.sup.9).sub.3 group, with each R.sup.3 independently being a linear or branched C.sub.1-C.sub.6 alkyl group; R.sup.5 and R.sup.6 are each independently hydrogen or an aliphatic C.sub.1-C.sub.20 hydrocarbyl group, or R.sup.5 and R.sup.6 taken together form a 5 membered saturated carbon ring which is optionally substituted by n groups R.sup.10, n being from 0 to 4, and each R.sup.10 independently is a C.sub.1-C.sub.20 hydrocarbyl group, or a C.sub.1-C.sub.20 hydrocarbyl radical; R.sup.7 is H, a linear or branched C.sub.1-C.sub.6-alkyl group, or an aryl or heteroaryl group having 6 to 20 carbon atoms optionally substituted by one to 3 groups R.sup.11; and each R.sup.11 independently is hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20 arylalkyl group, a C.sub.7-20 alkylaryl group, a C.sub.6-20 aryl group, or an OY group, wherein Y is a C.sub.1-10 hydrocarbyl group.

3. The supported catalyst system according to claim 1, wherein in the formula (I) of the metallocene complex (i): each X independently is a hydrogen atom, a halogen atom, a linear, branched, or cyclic C.sub.1-20-alkyl or-alkoxy group, a C.sub.6-20-aryl group, a C.sub.7-20-alkylaryl group, or a C.sub.7-20-arylalkyl group; each R.sup.1 is independently hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group; both R.sup.2 are the same and are a CH.sub.2-R.sup.8 group, with R.sup.8 being H or linear or branched C.sub.1-C.sub.4-alkyl group; R.sup.3 is a linear or branched C.sub.1-C.sub.6-alkyl group or C.sub.6-20-aryl group; R.sup.4 is a C(R.sup.9)3 group, with each R.sup.9 independently being a linear or branched C.sub.1-C.sub.4-alkyl group; R.sup.5 and R.sup.6 are each independently hydrogen or an aliphatic C.sub.1-C.sub.20-hydrocarbyl group, or R.sup.5 and R.sup.6 taken together form a 5 membered saturated carbon ring which is optionally substituted by n groups R.sup.10, n being from 0 to 4, and each R.sup.10 independently is a C.sub.1-C.sub.20-hydrocarbyl group, or a C.sub.1-C.sup.20-hydrocarbyl radical; R.sup.7 is H or an aryl group having 6 to 10 carbon atoms optionally substituted by 1 to 3 groups R.sup.11; and each R.sup.11 independently being hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.6-20-aryl group, or an OY-group, wherein Y is a is a C.sub.1-4-hydrocarbyl group.

4. The supported catalyst system according to claim 1, wherein in the formula (I) of the metallocene complex: R.sup.7 is a linear or branched C1-C6-alkyl group or an aryl or heteroaryl group having 3 to 20 carbon atoms optionally substituted by one to three groups R.sup.11, wherein each R.sup.11 is independently a phenyl ring or a 5 or 6 membered heteroaryl ring.

5. The supported catalyst system according to claim 1, wherein in formula (I) of the metallocene complex: L is R.sub.2Si, wherein each R is independently a C.sub.1-C.sub.6-alkyl, C.sub.5-6-cycloalkyl, or C.sub.6-aryl group; each Ar independently is a phenyl ring or a 5 or 6 membered heteroaryl ring; each R.sup.1 is independently hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group; each R.sup.2 independently is a CHR.sup.8R.sup.8 group, with R.sup.8 being H or a linear or branched C.sub.1-6-alkyl group, and R.sup.8 is H or a C.sub.1-6 alkyl; R.sup.5 and R.sup.6 are both hydrogen, or R.sup.5 and R.sup.6 taken together form a 5 membered saturated carbon ring; R.sup.7 is a linear or branched C.sub.1-C.sub.6-alkyl group or an aryl or heteroaryl group having 3 to 20 carbon atoms optionally substituted by one to three groups R.sup.11; and each R.sup.11 independently is hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group.

6. The supported catalyst system according to claim 1, wherein in formula (I) of the metallocene complex: L is R.sub.2Si, wherein each R is independently a C.sub.1-C.sub.6-alkyl, C.sub.5-6-cycloalkyl, or C.sub.6-aryl group; each Ar independently is a phenyl ring or a 5 or 6 membered heteroaryl ring; each R.sup.1 is independently hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group; each R.sup.2 independently is a CHR.sup.8-R.sup.8 group, with R.sup.8 being H or a linear or branched C.sub.1-6-alkyl group, and R.sup.8 is H or a C.sub.1-6 alkyl; R.sup.3 is a linear or branched C.sub.1-C.sub.6-alkyl group; R.sup.5 and R.sup.6 taken together form a 5 membered saturated carbon ring; R.sup.7 is a phenyl ring or a 5 or 6 membered heteroaryl ring optionally substituted by one to three groups R.sup.11; and each R.sup.11 independently is hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group.

7. The supported catalyst system according to claim 2, wherein in formula (II) of the metallocene complex: each X independently is a halogen atom, a linear or branched C.sub.1-4-alkyl group, a linear or branched C.sub.1-4-alkoxy group, a phenyl group, or a benzyl group, L is or R.sub.2Si, wherein each R is independently a C.sub.1-C.sub.6-alkyl, C.sub.5-6-cycloalkyl or C.sub.6-aryl group; each R.sup.1 independently is hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group; each R.sup.2 independently is a CH.sub.2-R.sup.8 group, with R.sup.8 being H or a linear or branched C.sub.1-6-alkyl group; R.sup.3 is a linear or branched C.sub.1-C.sub.6-alkyl group; R.sup.5 and R.sup.6 are each hydrogen, or R.sup.5 and R.sup.6 taken together form a 5 membered saturated carbon ring; R.sup.7 is a phenyl group optionally substituted by one to 3 groups R.sup.11; and each R.sup.11 independently is hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group.

8. The supported catalyst system according to claim 2, wherein in formula (II) of the metallocene complex: each X independently a halogen atom, a linear or branched C.sub.1-4-alkyl group, a linear or branched C.sub.1-4-alkoxy group, a phenyl group, or a benzyl group; L is R.sub.2Si, wherein each R is independently a C.sub.1-C.sub.6-alkyl, C.sub.5-6-cycloalkyl, or C6-aryl group; each R.sup.1 independently is hydrogen, or a linear or branched C.sub.1-C.sup.6-alkyl group; each R.sup.2 is methyl; R.sup.3 is a linear or branched C.sub.1-C.sub.6-alkyl group; R.sup.5 and R.sup.6 are each hydrogen, or R.sup.5 and R.sup.6 taken together form a 5 membered saturated carbon ring; R.sup.7 is a phenyl group optionally substituted by one to 3 groups R.sup.11; and each R.sup.11 independently is hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group.

9. The supported catalyst system according to claim 1, wherein the metallocene complex is of formula (X): ##STR00029## wherein each X independently is a halogen atom, a linear or branched C.sub.1-4-alkyl group, a linear or branched C.sub.1-4-alkoxy group, a phenyl group, or benzyl group; L is R.sub.2Si, wherein each R is independently a C.sub.1-C.sub.6-alkyl, C.sub.5-6-cycloalkyl, or C6-aryl group; each R.sup.1 independently is hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group; each R.sup.2 independently is a CH.sub.2-R.sup.8 group, with R.sup.8 being H or a linear or branched C.sub.1-6-alkyl group; R.sup.3 is a linear or branched C.sub.1-C.sub.6-alkyl group; R.sub.4 is a C(R.sup.9)3 group, with each R9 independently being a linear or branched C.sub.1-C.sub.6 alkyl group; R.sup.7 is a phenyl group optionally substituted by one to 3 groups R.sup.11; and each R.sup.11 independently is hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group.

10. The supported catalyst system according to claim 1, wherein the metallocene complex is of formula (XI): ##STR00030## wherein each X independently is a halogen atom, a linear or branched C.sub.1-4-alkyl group, a linear or branched C.sub.1-4-alkoxy group, a phenyl group, or benzyl group; L is R.sub.2Si, wherein each R is independently a C.sub.1-C.sub.6-alkyl, C.sub.5-6-cycloalkyl, or C.sub.6-aryl group; each R.sup.1 independently is hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group; R.sup.3 is a linear or branched C.sub.1-C.sub.6-alkyl group; R.sup.4 is a C(R.sup.9)3 group, with each R.sup.9 independently being a linear or branched C.sub.1-C.sub.6 alkyl group; R7 is a phenyl group optionally substituted by one to 3 groups R.sup.11; and each R11 independently is hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group.

11. The supported catalyst system according to claim 10, wherein in formula (XI) of the metallocene complex L is Me.sub.2Si.

12. The supported catalyst system according to claim 1, wherein the metallocene complex (i) is selected from the group consisting of: rac-anti-dimethylsilanediyl[2-methyl-4-(4-tert.-butylphenyl)-inden-1-yl][2-methyl-4-(4-tert.-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(4-tert.-butylphenyl)-inden-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediy[2-methyl-4-(3,5-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediy|[2-methyl-4,8-bis-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl [2-methyl-4,8-bis-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, and rac-anti-dimethylsilanediyl [2-methyl-4,8-bis-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl] [2-methyl-4-(3,5-ditert-butyl-phenyl)-5- methoxy-6-tert-butylinden-1-yl]zirconium dichloride.

13. The supported catalyst system according to claim 1, wherein R.sup.7 is H.

14. The supported catalyst system according to claim 1, wherein R.sup.5 and R.sup.6 are taken together form a 5 membered saturated carbon ring which is optionally substituted by n groups R.sup.10, n being from 0 to 4, and each R.sup.10 independently is a C.sub.1-C.sub.20-hydrocarbyl group, or a C.sub.1-C.sub.20-hydrocarbyl radical.

15. The supported catalyst system according to claim 1, wherein the boron containing cocatalyst is: triphenylcarbeniumtetrakis (pentafluorophenyl) borate, N,N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, N,N-dimethylcyclohexylammoniumtetrakis (pentafluorophenyl) borate, or N,N-dimethylbenzylammoniumtetrakis (pentafluorophenyl) borate.

16. The supported catalyst system according to claim 1, wherein the metallocene complex, the boron containing cocatalyst, and the methylaluminoxane cocatalyst are each provided in an amount such that the molar ratio of boron in the boron containing cocatalyst to the Zirconium in the complex of formula (I) is in the range of 0.1:1 to 10:1 mol/mol, and the molar ratio of aluminum in the methylaluminoxane cocatalyst to the zirconium in the complex of formula (I) is in the range of 1:1 to 2000:1 mol/mol.

17. The supported catalyst system according to claim 1, wherein the inorganic porous support has an average particle size of from 10 to 100 m, an average pore size of from 10 to 100 nm, a pore volume of from 1 to 3 mL/g, or a combination thereof.

18. The supported catalyst system according to claim 1, wherein the catalyst system can contain from 10 to 100 umol of zirconium per gram of the inorganic porous support and from 5 to 10 mmol of Al per gram of the inorganic porous support.

19. A process for preparing the supported catalyst system according to claim 1, the process comprising the steps of: a) reacting the inorganic porous support with a first portion of the methylaluminoxane cocatalyst in a first suitable hydrocarbon solvent, with optional subsequent drying, to obtain a methylaluminoxane cocatalyst treated support, b) reacting the metallocene complex with a second portion of the methylaluminoxane cocatalyst in a second suitable hydrocarbon solvent, c) adding the boron containing cocatalyst to the solution obtained in step b) to obtain a solution of the metallocene complex, boron containing cocatalyst, and methylaluminoxane cocatalyst, whereby the boron containing cocatalyst is added in an amount such that a boron/zirconium molar ratio is in the range of 0.1:1 to 10:1, d) adding the solution obtained in step c) to the methylaluminoxane cocatalyst treated support obtained in step a) wherein the first portion of the methylaluminoxane cocatalyst added in step a) is 75.0 to 97.0 wt % of the total amount of the methylaluminoxane cocatalyst, and the second portion of the methylaluminoxane cocatalyst added in step b) is 3.0 to 25.0 wt % of the total amount of methylaluminoxane cocatalyst; and e) after step d), drying the supported catalyst system.

20. A process for the preparation of a heterophasic polypropylene copolymer, the process comprising: (I) polymerizing propylene in bulk in the presence of the supported catalyst system as claimed in claim 1 to form a polypropylene homopolymer matrix; and (II) in the presence of said polypropylene homopolymer matrix and said supported catalyst system, polymerizing propylene and ethylene in the gas phase to form a heterophasic polypropylene copolymer comprising a homopolymer matrix and an ethylene propylene rubber.

21. A process for the preparation of a heterophasic polypropylene copolymer, the process comprising: (I) polymerizing propylene in bulk in the presence of the supported catalyst system as claimed in claim 1 to form a polypropylene homopolymer; (II) in the presence of said polypropylene homopolymer and said supported catalyst system, polymerizing propylene in the gas phase to form a polypropylene homopolymer matrix; and (III) in the presence said polypropylene homopolymer matrix and said supported catalyst system, polymerizing propylene and ethylene in the gas phase to form a heterophasic polypropylene copolymer comprising a homopolymer matrix and an ethylene propylene rubber (EPR).

Description

BRIEF DESCRIPTION OF FIGURES

[0345] FIG. 1a is a schematic representation of the CRYSTEX QC instrument is shown in FIG. 1a. FIG. 1b shows an elution diagram of an exemplary ethylene-propylene copolymer sample and obtained soluble and crystalline fractions in the TREF column (column filled with inert material e.g. glass beads).

[0346] FIG. 2 plots the XCS of the iV fraction vs productivity in the gas phase for examples herein.

[0347] FIG. 3 plots the ethylene content of the XCS fraction vs the iV of the XCS fraction for examples of the invention.

[0348] FIG. 4 plots the ethylene content of the XCS fraction vs the iV of the XCS fraction for examples of the invention.

[0349] FIG. 5 plots the ethylene content of the polymer vs the productivity for examples of the invention.

[0350] FIG. 6 plots the ethylene content of the polymer vs the delta productivity for examples of the invention.

[0351] FIG. 7 plots the ethylene content of the polymer vs the MFR for examples of the invention.

MEASUREMENT METHODS

[0352] (a) Melt Flow Rate (MFR)

[0353] The melt flow rate is measured as the MFR2 in accordance with ISO 1133 15 (230 C., 2.16 kg load) for polypropylene. The MFR is an indication of the flowability, and hence the processability, of the polymer, but is also a measure of the polymer Mw. The higher the melt flow rate, the lower the viscosity of the polymer, hence its molecular weight. [0354] (b) Number Average Molecular Weight (Mn), Weight Average Molecular Weight (Mw) and Polydispersity (Mw/Mn)

[0355] Molecular weight averages (Mz, Mw and 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 16014-1:2003, ISO 16014-2:2003, ISO 16014- 4:2003 and ASTM D 6474-12 using the following formulas:

[00003]$\begin{array}{cc}{M}_n=\frac{{.Math.}_{i=1}^N{A}_i}{{.Math.}_{i=1}^N\left(A_i/M_i\right)}& \left(1\right)\end{array}$$\begin{array}{cc}{M}_w=\frac{{.Math.}_{i=1}^N\left(A_i{M}_i\right)}{{.Math.}_{i=1}^N{A}_i}& \left(2\right)\end{array}$$\begin{array}{cc}{M}_z=\frac{{.Math.}_{i=1}^N\left(A_i{M}_i^2\right)}{{.Math.}_{i=1}^N\left(A_i{M}_i\right)}& \left(3\right)\end{array}$

[0356] For a constant elution volume interval AVi, where Ai, and Mi are the chromatographic peak slice area and polyolefin molecular weight (MW), respectively associated with the elution volume, Vi, where N is equal to the number of data points obtained from the chromatogram between the integration limits.

[0357] A high temperature GPC instrument, equipped with either infrared (IR) detector (IR4 or IR5 from PolymerChar (Valencia, Spain), equipped with 3x Agilent-PLgel Olexis and 1x Agilent-PLgel Olexis Guard columns was used. As the solvent and mobile phase 1,2,4-trichlorobenzene (TCB) stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) was used. The chromatographic system was operated at 160 C. and at a constant flow rate of 1 mL/min. 200 uL of sample solution was injected per analysis. Data collection was performed using either Agilent Cirrus software version 3.3 or PolymerChar GPC-IR control software. The column set was calibrated using universal calibration (according to ISO 16014-2:2003) with 19 narrow MWD polystyrene (PS) standards in the range of 0,5 kg/mol to 11 500 kg/mol. The PS standards were dissolved at room temperature over several hours. The conversion of the polystyrene peak molecular weight to polyolefin molecular weights is accomplished by using the Mark Houwink equation and the following Mark Houwink constants:

[00004]$K_{\mathrm{PS}}=19{10}^{-3}\mathrm{mL}/g,{}_{\mathrm{PS}}=0.655$$K_{\mathrm{PE}}=39{10}^{-3}\mathrm{mL}/g,{}_{\mathrm{PE}}=0.725$$K_{\mathrm{PP}}=19{10}^{-3}\mathrm{mL}/g,{}_{\mathrm{PP}}=0.725$

[0358] A third order polynomial fit was used to fit the calibration data.

[0359] All samples were prepared in the concentration range of 0.5-1 mg/ml and dissolved at 160 C. for 2.5 hours for PP or 3 hours for PE under continuous gentle shaking.

(c) DSC Analysis, Peak Melting Temperature (T.SUB.m.), Heat of Melting (Hm), and Peak Crystallization Temperature (T.SUB.c.)

[0360] DSC analysis was measured with a Mettler TA Instrument Q2000 differential scanning calorimetry (DSC) on 5 to 7 mg samples. DSC is run according to ISO 11357/part 3/method C2 in a heat/cool/heat cycle with a scan rate of 10 C./min in the temperature range of 30to +225 C. Crystallization temperature (Tc) is determined from the cooling step, while peak melting temperature (Tm) and heat of melting (H.sub.m) are determined from the second heating step.

(d) Intrinsic Viscosity

[0361] Intrinsic viscosity (IV) has been measured according to DIN ISO 1628/1, October 1999 (in Decaline at 135 C.).

(e) Xylene Cold Soluble Fraction

[0362] The xylene cold solubles (XCS, wt %) were determined at 25 C. according to ISO 16152; 2005.

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

[0363] The elementary analysis of a catalyst was performed by taking a solid sample of mass, M, cooling over dry ice. Samples were diluted up to a known volume, V, by dissolving in nitric acid (HNO3, 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.

[0364] The analysis was run at room temperature using a Thermo Elemental iCAP 6300 Inductively Coupled PlasmaOptical Emmision Spectrometer (ICP-OES) which was calibrated using a blank (a solution of 5% HNO3, 3% HF in DI water), and 6 standards of 0.5 ppm, 1 ppm, 10ppm, 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.

[0365] Immediately before analysis the calibration is resloped using the blank and 100 ppm Al, 50ppm Hf, Zr standard, a quality control sample (20 ppm Al, 5 ppm Hf, Zr in a solution of 5%

[0366] 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.

[0367] 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.

[0368] 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.

(g) Crystex Analysis

Crystalline and Soluble Fractions Method

[0369] The crystalline (CF) and soluble fractions (SF) of the polypropylene (PP) compositions as well as the comonomer content and intrinsic viscosities of the respective fractions were analyzed by the CRYSTEX QC, Polymer Char (Valencia, Spain).

[0370] A schematic representation of the CRYSTEX QC instrument is shown in FIG. 1a. The crystalline and amorphous fractions are separated through temperature cycles of dissolution at 160 C., crystallization at 40 C. and re-dissolution in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160 C. as shown in FIG. 1b. Quantification of SF and CF and determination of ethylene content (C2) are achieved by means of an infrared detector (IR4) and an online 2-capillary viscometer which is used for the determination of the intrinsic viscosity (IV).

[0371] The IR4 detector is a multiple wavelength detector detecting IR absorbance at two different bands (CH3 and CH2) for the determination of the concentration and the Ethylene content in Ethylene-Propylene copolymers. IR4 detector is calibrated with series of 8 EP copolymers with known Ethylene content in the range of 2 wt % to 69 wt % (determined by 13C-NMR) and various concentration between 2 and 13 mg/ml for each used EP copolymer used for calibration.

[0372] The amount of Soluble fraction (SF) and Crystalline Fraction (CF) are correlated through the XCS calibration to the Xylene Cold Soluble (XCS) quantity and respectively Xylene Cold Insoluble (XCI) fractions, determined according to standard gravimetric method as per ISO16152. XCS calibration is achieved by testing various EP copolymers with XCS content in the range 2-31 wt %.

[0373] The intrinsic viscosity (IV) of the parent EP copolymer and its soluble and crystalline fractions are determined with a use of an online 2-capillary viscometer and are correlated to corresponding IV's determined by standard method in decalin according to ISO 1628. Calibration is achieved with various EP PP copolymers with IV =2-4 dL/g.

[0374] A sample of the PP composition to be analyzed is weighed out in concentrations of 10 mg/ml to 20 mg/ml. After automated filling of the vial with 1,2,4-TCB containing 250 mg/l 2,6-tert-butyl-4-methylphenol (BHT) as antioxidant, the sample is dissolved at 160 C. until complete dissolution is achieved, usually for 60 min, with constant stirring of 800 rpm. As shown in a FIGS. 1a and b, a defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part is taking place. This process is repeated two times.

[0375] During the first injection the whole sample is measured at high temperature, determining the IV[dl/g] and the C2[wt %] of the PP composition. During the second injection the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) with the crystallization cycle are measured (Wt % SF, Wt % C2, IV).

EP Means Ethylene Propylene Copolymer

PP Means Polypropylene

[0376] FIG. 1a shows a schematic diagram of the CRYSTEX QC instrument.

[0377] FIG. 1b shows an elution diagram of an exemplary ethylene-propylene copolymer sample and obtained soluble and crystalline fractions in the TREF column (column filled with inert material e.g. glass beads) (see Del Hierro, P.; Ortin, A.; Monrabal, B.; Soluble Fraction Analysis in polypropylene, The Column Advanstar Publications, February 2014. Pages 18-23). [0378] (h) Quantification of Microstructure by NMR Spectroscopy

[0379] Quantitative nuclear-magnetic resonance (NMR) spectroscopy was further used to quantify the comonomer content and comonomer sequence distribution of the polymers. Quantitative .sup.13C {.sup.1H} NMR spectra were recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1H and .sup.13C respectively. All spectra were recorded using a 13C optimised 10 mm extended temperature probehead at 125 C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d2 (TCE-d.sub.2) along with chromium-(III)-acetylacetonate (Cr (acac) 3) resulting in a 65 mM solution of relaxation agent in solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatary oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128). A total of 6144 (6k) transients were acquired per spectra.

[0380] Quantitative .sup.13C {.sup.1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present. Characteristic signals corresponding to the incorporation of ethylene were observed Cheng, H. N., Macromolecules 17 (1984), 1950).

[0381] With characteristic signals corresponding to 2,1 erythro regio defects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, H. N., Macromolecules 1984, 17, 1950, and in W-J. Wang and S. Zhu, Macromolecules 2000, 33 1157) the correction for the influence of the regio defects on determined properties was required. Characteristic signals corresponding to other types of regio defects were not observed.

[0382] The comonomer fraction was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) through integration of multiple signals across the whole spectral region in the .sup.13C {1H} spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.

[0383] For systems where only isolated ethylene in PPEPP sequences was observed the method of Wang et. al. was modified to reduce the influence of non-zero integrals of sites that are known to not be present. This approach reduced the overestimation of ethylene content for such systems and was achieved by reduction of the number of sites used to determine the absolute ethylene content to:

[00005]$E=0.5\left(S+S+S+0.5\left(S+S\right)\right)$

[0384] Through the use of this set of sites the corresponding integral equation becomes:

[00006]$E=0\text{.5}\left(I_H+I_G+0\text{.5}\left(I_C+I_D\right)\right)$

using the same notation used in the article of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157). Equations used for absolute propylene content were not modified.

[0385] The mole percent comonomer incorporation was calculated from the mole fraction:

[00007]$E=\left[\mathrm{mol}\%\right]=100\mathrm{fE}$

[0386] The weight percent comonomer incorporation was calculated from the mole fraction:

[00008]$E\left[\mathrm{wt}\%\right]=100\left(\mathrm{fE}28.06\right)/\left(\left(\mathrm{fE}28.06\right)+\left(\left(1-\mathrm{fE}\right)42.08\right)\right)$

Comonomer Content by IR Spectroscopy

[0387] Quantitative infrared (IR) spectroscopy was used to quantify the ethylene content of the copolymers through calibration to a primary method.

[0388] Calibration was facilitated through the use of a set of in-house non-commercial calibration standards of known ethylene contents determined by quantitative .sup.13C solution-state nuclear magnetic resonance (NMR) spectroscopy. The calibration procedure was undertaken in the conventional manner well documented in the literature. The calibration set consisted of 38 calibration standards with ethylene contents ranging 0.2-75.0 wt % produced at either pilot or full scale under a variety of conditions. The calibration set was selected to reflect the typical variety of copolymers encountered by the final quantitative IR spectroscopy method. Quantitative IR spectra were recorded in the solid-state using a Bruker Vertex 70 FTIR spectrometer. Spectra were recorded on 25x25 mm square films of 300 um thickness prepared by compression moulding at 180-210 C. and 4-6 mPa. For samples with very high ethylene contents (>50 mol %) 100 um thick films were used. Standard transmission FTIR spectroscopy was employed using a spectral range of 5000-500 cm.sup.1, an aperture of 6 mm, a spectral resolution of 2 cm.sup.1, 16 background scans, 16 spectrum scans, an interferogram zero filling factor of 64 and Blackmann-Harris 3-term apodisation. Quantitative analysis was undertaken using the total area of the CH.sub.2 rocking deformations at 730 and 720 cm.sup.1 (A.sub.Q) corresponding to (CH.sub.2).sub.>2 structural units (integration method G, limits 762 and 694 cm 1). The quantitative band was normalised to the area of the CH band at 4323 cm-1 (AR) corresponding to CH structural units (integration method G, limits 4650, 4007 cm-1). The ethylene content in units of weight percent was then predicted from the normalised absorption (AQ/AR) using a quadratic calibration curve. The calibration curve having previously been constructed by ordinary least squares (OLS) regression of the normalised absorptions and primary comonomer contents measured on the calibration set.

[0389] The present invention will now be illustrated by way of examples.

[0390] The following complex C1 as shown below was used in preparing catalysts for the Comparative Examples (CE1-CE4) and the Inventive Examples (IE1-IE4)

##STR00020##

[0391] C1 (rac-anti-dimethylsilanediyl (2-methyl-4-(3402 ,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl) (2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl inden-1-yl) zirconium dichloride) was synthesized according to the procedure as described in WO2019/007655, pp 49ff.

Preparation of MAO-Silica Support

[0392] A glass reactor equipped with a mechanical stirrer was charged with silica grade DM-L-303 from AGC Si-Tech Co, pre-calcined at 600 C. (10.0 g). Then dry toluene (50 mL) was added. The mixture was then heated to 35 C. and stirred at 35 C. (40 rpm) for 15 min. Next 30 wt % solution of MAO in toluene (25 mL) from Lanxess was added via cannula over the course of 25 minutes and then stirred for 2 more hours at 35 C. The solid was allowed to settle and the mother liquor was siphoned off and discarded. Toluene (50 mL) was added and the mixture was heated to 80 C. and stirred at this temperature for 1 hour. The solids were allowed to settle, and the liquid was siphoned off and discarded. The toluene wash was repeated two more times, followed by a heptane (50 mL) wash at 60 C. Then the cake was dried under vacuum at 60 C. over for hours to yield 13.7 g of support as white powder.

ICS 1 (Inventive Catalyst System 1): Catalyst Preparation

[0393] In a nitrogen filled glovebox, a solution of MAO 0.5 mL (30% wt in toluene, AXION 1330 CA Lanxess) in dry toluene (2 mL) was added to an aliquot of metallocene C1 (63.0 mg, 78 umol).

[0394] After 60 minutes stirring at room temperature, 72.0 mg of trityl tetrakis (pentafluorophenyl) borate was added. The mixture was stirred for 60 minutes at room temperature. Next, 2.0 g of MAO treated silica prepared as described above, was placed in a glass vial. The solution of metallocene, MAO and borate in toluene was then slowly added to the support over the course of 10 minutes with gentle mixing. The resulting mixture was shaken well and allowed to stay overnight. Then dry toluene (10 mL) was added, and the slurry was mixed well at 60 C. for 30 minutes. The solid was allowed to settle, and liquid was siphoned off and discarded. The wash was repeated twice with 10 mL toluene and once with 10 mL heptane at room temperature. The resulting cake was dried in Ar flow for 3 hours at 60 C. to yield 2.3 g of the catalyst as pink free flowing powder.

ICS 2 (Inventive Catalyst System 2): Catalyst Preparation

[0395] In a nitrogen filled glovebox, a solution of MAO 0.5 mL (30% wt in toluene, AXION 1330 CA Lanxess) in dry toluene (2 mL) was added to an aliquot of metallocene C1 (63.0 mg, 78 umol). After 60 minutes stirring at room temperature, 36.0 mg of trityl tetrakis (pentafluorophenyl) borate was added. The mixture was stirred for 60 minutes at room temperature. Next, 2.0 g of MAO treated silica prepared as described above (Support B), was placed in a glass vial. The solution of metallocene, MAO and borate in toluene was then slowly added to the support over the course of 10 minutes with gentle mixing. The resulting mixture was shaken well and allowed to stay overnight. Then dry toluene (10 mL) was added, and the slurry was mixed well at 60 C. for 30 minutes. The solid was allowed to settle, and liquid was siphoned off and discarded. The wash was repeated twice with 10 mL toluene and once with 10 mL heptane at room temperature. The resulting cake was dried in Ar flow for 3 hours at 60 C. to yield 2.2 g of the catalyst as pink free flowing powder.

CCS 1 (Comparative Catalyst System 1): Catalyst Preparation

[0396] In a nitrogen filled glovebox, a solution of MAO 0.25 mL (30% wt in toluene, AXION 1330 CA Lanxess) in dry toluene (1 mL) was added to an aliquot of metallocene C1 (31.5 mg, 38 umol). The mixture was stirred for 60 minutes at room temperature. Next, 1.0 g of MAO treated silica prepared as described above (support B), was placed in a glass vial. The solution of metallocene and MAO in toluene was then slowly added to the support over the course of 5 minutes with gentle mixing. The resulting mixture was shaken well and allowed to stay overnight. Then dry toluene (5 mL) was added, and the slurry was mixed well at 60 C. for 30minutes. The solid was allowed to settle, and liquid was siphoned off and discarded. The wash was repeated twice with 5 mL toluene and once with 5 mL heptane at room temperature. The resulting cake was dried in Ar flow for 3 hours at 60 C. to yield 1.0 g of the catalyst as pink free flowing powder.

CCS 2 (Comparative Catalyst System 2): Catalyst Preparation

[0397] Inside the glovebox, 86.8 mg of dry and degassed surfactant S2 were mixed with 2 mL of MAO in a septum bottle and left to react overnight. The following day, 41.1 mg of C1 (0.051mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another septum bottle and left to stir inside the glovebox.

[0398] 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 (perfluoro-1.3-dimethylcyclohexane) 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 600 rpm until the transfer is completed, then the speed was reduced to 300 rpm. After 15 minutes stirring, the oil bath was removed and the stirrer turned off. The catalyst was left to settle up on top of the PFC and after 35 minutes the solvent was siphoned off. The remaining 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. (Al 36.9 wt %, Zr 0.26 wt % Al/Zr (molar) 480) S2: 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.

[0399] The pre-polymerization step for the catalyst (off-line prepolymerization) 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 cm3) and the desired amount of the catalyst to be pre-polymerized 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 polymerization was reached. The reaction was stopped by flashing the volatile components. Inside glove box, the reactor was opened and the content poured into a glass vessel. The perfluoro-1,3-dimethylcyclohexane was evaporated until a constant weight was obtained to yield the pre-polymerized catalyst.

CC3 (Comparative Catalyst System 3): Catalyst Preparation

[0400] The same catalyst complex as for CC2 was used, but in addition to MAO also a borate cocatalyst was added.

[0401] Inside the glovebox, 234.3 mg of dry and degassed surfactant S2 (in 0.2 mL toluene) were added dropwise to 5 mL of MAO. The solution was left under stirring for 30 minutes. Then, 95.6 mg of C1 were added to the MAO/surfactant solution. After 60 minutes stirring, 104.9 mg of trityl tetrakis (pentafluorophenyl) borate were added.

[0402] After 60 minutes stirring, 5 mL of the surfactant-MAO-metallocene-borate solution was 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). A red emulsion formed immediately and was stirred during 15 minutes at-10 C./600 rpm. Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hot PFC at 90 C., and stirred at 600 rpm until the transfer is completed, then the speed was reduced to 300 rpm. After 15 minutes stirring, the oil bath was removed and the stirrer turned off. The catalyst was left to settle up on top of the PFC and after 35 minutes the solvent was siphoned off. The 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. under argon flow. 0.70 g of a red free flowing powder was obtained. (Al 31.9 wt %, Zr 0.56 wt % Al/Zr (molar) 193; B/Zr (molar) 0.98) The catalyst was prepolymerized as described above for CC2.

TABLE-US-00001 TABLE 1 Catalysts .sup.(*.sup.) MC content Degree of pre- based on Zr Catalyst polymerization Al Zr Al/Zr B/Zr wt % system g(PP)/g(cat) wt % wt % molar molar wt % CCS2 3.2 36.9 0.26 480 0 2.83 CCS3 5.5 31.9 0.56 193 1 6.77 ICS1 n.a. 12.30 0.13 320 1 1.16 ICS2 n.a. 12.00 0.15 280 0.5 1.30 .sup.(*.sup.) analytical data refer to the pure (non-prepolymerized) catalysts n.a. not applicable

Polymerizations

2-step bulk (C3 homo)+gas phase (C2/C3) polymerization

Step 1: Prepolymerization and Bulk Homopolymerization

[0403] The autoclave containing 0.4 barg propylene was filled with 4400 g propylene. Triethylaluminum (0.80 ml of a 0.62 mol/l solution in heptane) was injected into the reactor by additional x g propylene. The solution was stirred at 20 C. and 250 rpm for at least 20 min. The catalyst system as prepared above was injected as described in the following. The desired amount of solid catalyst was loaded into a 5 ml stainless steel vial inside a glovebox, then a second 5 ml vial containing 4 ml n-heptane and pressurized with 7 bars of nitrogen was added on top of it. This dual feeder system was mounted on a port on the lid of the autoclave. Directly follows the dosing of the desired H2 amount via mass flow controller. Afterwards 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 x g propylene. The prepolymerization was run for 10 min. At the end of the prepolymerization step, the temperature was raised to 75 C. and was held constant throughout the polymerization. The polymerization time was measured starting, when the internal reactor temperature reached 2 C. below the set polymerization temperature.

Step 2: Gas Phase C3C2 Copolymerization

[0404] After the bulk step was completed, the stirrer speed was reduced to 50 rpm and the pressure was reduced 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 the set value by feeding a defined C3/C2 gas mixture (see tables). Pressure and temperature were held constant by feeding via mass flow controller, a C3/C2 gas mixture, of composition, corresponding to the target polymer composition and by thermostat, until the set time for this step had expired.

[0405] 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 was 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.

TABLE-US-00002 TABLE 2 Polymerization procedures Transition to gas phase EP H2 fed Liquid Slurry step Feed before H2 fed Pressure Time C2 fed in C3 fed in C2/C3 Catalyst catalyst after T flashed transition transition transition during Catalyst amount feed ramp T time down to to GP2 (MFC) (MFC) transition Example System mg NL NL C. min barg min g g wt/wt IE1 ICS1 31.0 0.31 Prepoly 1.7 75 40 0.3 15 238 344 0.692 IE2 ICS1 37.0 2.00 at 20 C. 0.0 75 40 0.3 15 182 262 0.695 IE3 ICS2 35.0 2.01 for 10 min 0.0 75 40 0.3 14 237 333 0.712 IE4 ICS2 63.0 2.01 0.0 75 40 0.3 15 181 261 0.693 CE1 CCS1 90.0 2.01 0.0 75 40 0.3 16 234 339 0.690 CE2 CCS2 38.6 0.00 2.0 80 40 0.3 19 213 378 0.563 CE3 CCS3 15.3 2.01 0.0 75 40 0.3 17 236 337 0.700 CE4 CCS3 13.6 2.01 0.0 75 40 0.3 15 184 267 0.689 Gas phase Ptotal Added H2 C2 fed in GP2 C3 fed in GP2 Feed av. in GP Temperature time (MFC) (MFC) C2/C3 Example barg NL C. min g g wt/wt IE1 20 0 70 90 196 599 0.3 IE2 16 0 70 90 113 347 0.3 IE3 20 0 70 90 188 570 0.3 IE4 16 0 70 90 82 250 0.3 CE1 20 0 70 90 80 250 0.3 CE2 20 0 70 90 47 187 0.3 CE3 20 0 70 90 256 775 0.3 CE4 16 104 316 0.3 MFC mass flow controller

[0406] Table 3a)+3b) show the results of the polymerization

TABLE-US-00003 TABLE 3a) Whole polymer Overall Total Overall metallocene MFR.sub.2 SF Catalyst yield productivity productivity powder XCS Crystex Tm Ex. system g kg/g cat kg/gMC g/10 min wt % wt % C. IE1 ICS1 1406 23 1987 0.6 53 51 155 IE2 ICS1 1582 24 2036 1.1 29 30 157 IE3 ICS2 1953 30 2311 0.6 39 41 157 IE4 ICS2 1430 23 1746 1.4 24 23 157 CE1 CCS1 1273 14 n.d. 0.6 25 25 153 CE2 CCS2 866 22 732 13.6 n.d. 29 151 CE3 CCS3 2020 132 1852 1.1 51 53 157 CE4 CCS3 1335 98 1377 1.8 34 33 157

TABLE-US-00004 TABLE 3 b) Soluble Fraction iV (SF) C2(XCS) from Catalyst (Crystex) IR(XCS) Mw Example system dl/g % g/mol Mw/Mn IE1 ICS1 2.7 25.3 250500 3.0 IE2 ICS1 2.3 24.3 249000 2.6 IE3 ICS2 2.9 25.4 n.d. n.d. IE4 ICS2 2.5 24.5 n.d. n.d. CE1 CCS1 3.6 22.5 401500 2.6 CE2 CCS2 2.3 22.1 263000 2.9 CE3 CCS3 2.3 25.6 251500 3.2 CE4 CCS3 2.1 24.7 228000 2.8

[0407] From FIGS. 2 to 4 it can be clearly seen that by adding a borate to a silica/MAO/metallocene catalyst, catalyst systems with higher gas phase activity are obtained (FIG. 2), which furthermore yield heterophasic propylene copolymers having a higher molecular weight than heterophasic propylene copolymers produced with self-supported catalysts (produced according to Borealis Sirius catalyst technology) (FIGS. 3 and 4).

[0408] The following complex C2 as shown below was used in preparing catalysts for the Comparative Examples (CE5-CE9) and the Inventive Examples (IE5-IE9)

##STR00021##

4,8-Di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene

##STR00022##

[0409] To a mixture of 2.0 g (2.56 mmol) of NiCl.sub.2 (PPh3) IPr and 36.3 g (100.8 mmol) of 4,8-dibromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene 500 ml (250 mmol, 2.5 equiv) of 0.5 M 3,5-dimethylphenylmagnesium bromide in THF was added at a such rate to maintain a gentle reflux (for ca. 15 min). The resulting solution was refluxed additionally for 1 h, then cooled to room temperature, and 1200 ml of 0.5 M HCl and 500 ml of dichloromethane were added. The organic layer was separated, dried over K.sub.2CO.sub.3, passed through a short pad of silica gel 60 (40-63 m, ca. 30 ml) and then evaporated to dryness to give the crude mixture of the diastereoisomers of 4,8-di (3,5-dimethylphenyl)-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene as a brownish oil. Further on, 315 mg of TsOH was added to a solution of the crude product in 420 ml of toluene, and the resulting mixture was refluxed using Dean-Stark head for 10 min. Then, one more portion of 220 mg of TsOH was added, and the obtained mixture was refluxed for 10 min. Finally, the last operation was repeated with 50 mg of TsOH. After cooling to room temperature the reaction mixture was washed with 200 ml of 10% K2CO.sub.3. The organic layer was separated, and the aqueous layer was additionally extracted with 200 ml of dichloromethane. The combined organic extract was dried over anhydrous K.sub.2CO.sub.3 (the organic layer became crimson at this stage), passed through a short pad of silica gel 60 (40-63 m, 30 ml), and the resulting light-yellow solution was evaporated to ca. 30 ml to give a solution with a significant amount of a white precipitate. To this mixture 300 ml of n-hexane was added. The precipitated solid was filtered off (G3), washed with n-hexane, and dried in vacuum. This procedure gave 29.33 g (77.48 mmol, 76.9%) of 4,8-di (3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene as a white fine-crystalline solid. The mother liquor was evaporated to dryness to give a yellowish solid mass. This mass was triturated with 40 ml of warm n-hexane, cooled to room temperature, and filtered off (G3). The obtained solid was washed with n-hexane and dried in vacuum. This procedure gave additionally 4.55 g (12.02 mmol, 11.9%) of 4,8-di (3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene as a white powder. Thus, the total yield the title product was 33.88 g (89.5 mmol, 88.8%).

[0410] 1H NMR (CDCl3): 7.04 (s, 2H), 7.03 (s, 2H), 6.98 (s, 2H), 6.43 (m, 1H), 3.23 (s, 2H), 2.89 (t, J=7.3 Hz, 2H), 2.83 (t, J =7.3 Hz, 2H), 2.38 (s, 6H), 2.37 (s, 6H), 2.04 (s, 3H), 1.99 (quint, J =7.3 Hz, 2H). 13C {1H} NMR (CDCl.sub.3): 145.38, 142.84, 140.85, 140.43, 140.21, 139.80, 138.37, 137.55, 137.39, 133.44, 129.64, 128.39, 128.19, 127.31, 126.61, 126.34, 42.49, 32.76, 32.51, 26.08, 21.43, 16.81

[4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane

##STR00023##

[0411] 2.43 MTo a suspension of 11.96 g (31.59 mmol) of 4,8-di (3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in a mixture of 250 ml of ether and 40 ml of THF, cooled to 2.43 M-30 C., 13.0 ml (31.59 mmol) of BuLi in hexanes was added in one portion. The resulting mixture was stirred overnight at room temperature, then thus obtained light-orange solution with a large amount of orange precipitate was cooled to-50 C., and 19.0 ml (20.33 g, 157.5 mmol, 4.99 eqv.) 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 filter cake were rinsed with 50 ml of toluene. The filtrate was evaporated to dryness to give 14.9 g (100%) of the title compound as a white solid mass which was further used without an additional purification.

[0412] .sup.1H NMR (CDCl.sub.3): 0 7.09 (s, 2H), 7.02-6.94 (m, 4H), 6.51 (m, 1H), 4.07 (s, 1H), 3.26-3.14 (m, 1H), 2.95-2.79 (m, 2H), 2.60 (ddd, J=12.4 Hz, J=8.4 Hz, J =4.1 Hz, 1H), 2.38 and 2.37 (2s, sum 12H), 2.24 (s, 3H), 2.12-1.99 (m, 1H), 1.95-1.80 (m, 1H),-0.16 (s, 3H),-0.20 (s, 3H). .sup.13C {1H} NMR (CDCIl.sub.3): 146.19, 143.17, 140.68, 140.29, 139.94, 139.92, 138.37, 137.59, 137.42, 132.60, 129.86, 128.52, 128.24, 127.85, 127.28, 126.32, 49.67, 33.33, 32.73, 26.15, 21.45, 21.42, 18.10, 3.92,-1.45.

[4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl] [6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-1H-inden-1-yl]dimethylsilane

##STR00024##

[0413] To a solution of 10.13 g (31.59 mmol) of 5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-2-methyl-1 H-indene (produced as described above for MC-1) in 250 ml of ether, cooled to 30 C., 13.0 ml (31.59 mmol) of 2.43 M BuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then the resulting light-orange solution with a small amount of precipitate was cooled to 45 C., and 200 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at-25 C., then a solution of 14.9 g (31.59 mmol) of [4,8-bis (3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane (prepared above) in 200 ml of THF was added in one portion. This mixture was stirred overnight at room temperature, then filtered through a pad of silica gel 60 (40-63 m), which was additionally washed by 250 ml of dichloromethane. The combined organic elute was evaporated to dryness, and the residue was dried in vacuum at elevated temperature to give 24.0 g (ca. 100% of ca. 90% purity) of the title product (ca. 55:45 mixture of the stereoisomers) as a slightly yellowish solid foam which was further used without an additional purification. 1H NMR (CDCl3): 0 7.27 and 7.25 (2 s, sum 2H), 7.04 (s, 4H), 6.98, 6.95 and 6.93 (3s, sum 3H), 6.90 and 6.85 (2s, sum 1H), 6.46 (s, 1H), 6.23 and 6.20 (2 s, sum 1H), 4.41 and 4.16 (2s, sum 1H), 3.30-2.62 (m, 1H), 3.22 and 3.20 (2s, sum 3H), 3.04-2.79 (m, 2H), 2.68-2.56 (m, 1H), 2.39 (s, 6H), 2.35 (s, 9H), 2.32 (s, 3H), 2.18-1.80 (6 s and 2 m, sum 9H), 1.44 and 1.38 (2 s, sum 9H),-0.52,-0.58,-0.62 and-0.73 (4s, sum 6H).

[0414] Anti-dimethylsilanediyl [2-methyl-4,8-di (3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride

##STR00025##

[0415] To a slightly cloudy yellowish solution of 23.06 g (30.54 mmol) of [4,8-bis(3,5-methylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5-methyl-phenyl)-5-methoxy-2-methyl-1 H-inden-1-yl]dimethylsilane in 250 ml of ether, cooled to-30 C., 25.1 ml (60.99 mmol) of 2.43 M BuLi in hexanes was added in one portion. This mixture was stirred for 5.5 h at room temperature, then, the resulting red solution was cooled to 50 C., and 7.12 g (30.55 mmol) of ZrCl4 was added. The reaction mixture was stirred for 24 h at room temperature to give dark-red solution with precipitate of LiCl. On the evidence of NMR spectroscopy, this solution included a ca. 85/15 mixture of anti-and syn-zirconocene dichlorides contaminated with some other impurities. This mixture was evaporated to dryness (to the state of red foam), and the residue was treated with 100 ml of warm toluene. The obtained suspension was filtered through glass frit (G4), the filter cake was washed with 250 ml of warm toluene. The filtrate was evaporated to dryness, and the residue was dissolved in 70 ml of hot n-hexane. The light-orange precipitate fallen from this solution overnight at room temperature was collected and dried in vacuum. This procedure gave 7.8 g of anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, containing ca. 1.0 mol of n-hexane per mol of the complex, so the adjusted net weight of the isolated anti-complex was 7.13 g (26%). The mother liquor was evaporated to ca. 60 ml. Light-orange powder precipitated from this solution overnight at-25 C. was collected and dried in vacuum. This procedure gave 8.6 g of anti-dimethylsilanediyl[2-methyl-4,8-di (3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1 -yl]zirconium dichloride, containing ca. 0.75 mol of n-hexane per mol of the complex (or 0.57 g of n-hexane in 8.6 g of the product), so the adjusted net weight of the isolated anti-complex was 8.03 g (29%). anti-dimethylsilanediyl[2-methyl-4,8-di (3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride x 1.0 hexane.

[0416] Anal. calc. for C.sub.54H.sub.60Cl.sub.2OSiZr x C.sub.6H.sub.14: C, 71.96; H, 7.45. Found: C, 72.30; H, 7.69.

[0417] 1H NMR (CDCl.sub.3): 0 7.55-6.90 (very br.s., 4H), 7.39 (s, 1H), 7.10 (s, 1H), 7.03 (s, 1H), 6.98 (s, 1H), 6.95 (s, 1H), 6.94 (s, 1H), 6.81 (s, 1H), 6.58 (s, 1H), 3.41 (s, 3H), 3.15-3.01 (m, 2H), 2.93 (ddd, J=16.0 Hz, 8.1 Hz, 3.3 Hz, 1H), 2.51-2.41 (m, 1H), 2.39 (s, 3H), 2.36 (s, 3H), 2.34 (s, 12H), 2.30 (s, 3H), 2.04 (s, 3H), 2.07-1.95 (m, 1H), 1.85-1.68 (m, 1H), 1.35 (s, 9H), 1.14 (s, 3H), 0.13 (s, 3H). 13C {1H} NMR (CDCl.sub.3): 159.87, 144.73, 144.10, 143.25, 141.39, 138.39, 138.08, 137.81, 137.47, 136.90, 134.61, 134.39, 134.26, 132.05, 131.96, 131.74, 131.11, 128.96, 128.91, 128.82, 128.74, 127.74, 127.44, 127.01 (br.s), 126.76, 123.42, 123.12, 121.60, 121.08, 82.55, 81.91, 62.67, 35.68, 33.87, 32.39, 30.39, 26.04, 21.53, 21.47, 21.41, 21.24, 19.78, 18.60, 3.62, 1.70.

Preparation of MAO-Silica Support

[0418] A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set to 20 C. Next silica grade DM-L-303 from AGC Si-Tech Co, pre-calcined at 600 C. (5.0 kg) was added from a feeding drum followed by careful pressuring and depressurising with nitrogen using manual valves. Then toluene (22 kg) was added. The mixture was stirred for 15 min. Next 30 wt % solution of MAO in toluene (9.0 kg) from Lanxess was added via feed line on the top of the reactor within 70 min. The reaction mixture was then heated up to 90 C. and stirred at 90 C. for additional two hours. The slurry was allowed to settle and the mother liquor was filtered off. The catalyst was washed twice with toluene (22 kg) at 90 C., following by settling and filtration. The reactor was cooled off to 60 C. and the solid was washed with heptane (22.2 kg). Finally MAO treated SiO2 was dried at 60 under nitrogen flow for 2 hours and then for 5 hours under vacuum (0.5 barg) with stirring. MAO treated support was collected as a free-flowing white powder found to contain 12.2% Al by weight.

Inventive Catalyst System 3 (ICS3) Catalyst Preparation

[0419] 30 wt % MAO in toluene (0.7 kg) was added into a steel nitrogen blanked reactor via a burette at 20 C. Toluene (5.4 kg) was then added under stirring. Metallocene C2 (93 g) was added from a metal cylinder followed by flushing with 1 kg toluene. The mixture was stirred for 60 minutes at 20 C. Trityl tetrakis (pentafluorophenyl) borate (91 g) was then added from a metal cylinder followed by a flush with 1 kg of toluene. The mixture was stirred for 1 h at room temperature. The resulting silution was added to a a stirred cake of MAO-silica support prepared as described above over 1 hour. The cake was allowed to stay for 12 hours, folled by drying under N2 flow at 60 C. for 2 h and additionaly for 5 h under vacuum (-0.5 barg) under stirring stirring.

[0420] Dried catalyst was sampled in the form of pink free flowing powder containing 13.9% Al and 0.11% Zr.

Comparative Catalyst System 4 (CCS4)

[0421] 30 wt % MAO in toluene (0.7 kg) was added into a steel nitrogen blanked reactor via a burette at 20 C. Toluene (6.4 kg) was then added under stirring.Metallocene C2 (93 g) was added from a metal cylinder followed by flushing with 1 kg toluene. The mixture was stirred for 60 minutes at 20 C. The resulting silution was added to a a stirred cake of MAO-silica support prepared as described above over 1 hour. The cake was allowed to stay for 12 hours, folled by drying under N2 flow at 60 C. for 2 h and additionaly for 5 h under vacuum (0.5 barg) under stirring stirring.

[0422] Dried catalyst was sampled in the form of pink free flowing powder containing 12.8% Al and 0.084% Zr

Polymerizations

Prepolymerization and Bulk Polymerization

[0423] A 21.2 L autoclave 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 desired H2 amount is fed into the reactor via mass flow controller. The catalyst was injected as described in the following. The desired amount of solid catalyst was loaded into a 5 ml stainless steel vial inside a glovebox, then a second 5 ml vial containing 4 ml n-heptane and pressurized with 7 bars of nitrogen was added on top of it. This dual feeder system was mounted on a port on the lid of the autoclave. Afterwards 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 prepolymerization was run for 10 min. At the end of the prepolymerization step, the temperature was raised to 75 C. and was held constant throughout the polymerization. In case of ethylene-propylene copolymerization experiments, ethylene was added starting at 55 C. Amounts and feeding rate can be found in the table 4. The polymerization time was measured starting when the internal reactor temperature reached 2 C. below the set polymerization temperature. When the desired polymerization time had lapsed, 5 ml ETOH was fed into the reactor to stop the polymerization. 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 was 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.

[0424] The exact amounts of catalyst, H2 and C2 can be seen in table 4:

TABLE-US-00005 TABLE 4 MC Time content of transition temperature temp. catalyst unprepped MC Pro- Hydro- from prepoly ethylene of ethylene av. amount catalyst amount pylene gen to bulk ethylene feed rate addition bulk time Example Catalyst mg wt % mg g NL min g g/min C. C. min IE5 ICS3 48.0 1.10 0.53 4463 2.01 prepoly- 17 75 40 IE6 ICS3 24.0 1.10 0.26 4460 2.01 merisation 18 20 5 55 75 40 IE7 ICS3 19.0 1.10 0.21 4460 2.01 at 20 C. 18 50 10 55 75 40 IE8 ICS3 20.0 1.10 0.22 4479 2.00 for 10 min 18 109 25 55 75 40 IE9 ICS3 18.0 1.10 0.20 4460 2.01 17 168 35 56 75 40 CE5 CCS4 50.0 0.86 0.43 4455 2.00 16 75 40 CE6 CCS4 34.0 0.86 0.29 4463 2.00 17 20 5 55 75 40 CE7 CCS4 31.0 0.86 0.27 4463 2.00 17 50 10 55 75 40 CE8 CCS4 28.0 0.86 0.24 4480 2.00 17 109 25 55 75 40 CE9 CCS4 24.0 0.86 0.21 4480 2.00 17 168 35 55 75 40

[0425] Table 5 shows the results of the polymerization

TABLE-US-00006 TABLE 5 catalyst metallocene MFR2 Ethylene in productivity productivity powder T.sub.m M.sub.w polymer (NMR) Example Catalyst kg/g cat kg/gMC g/10 min C. g/mol M.sub.w/M.sub.n wt % IE5 ICS3 24.7 2242 4.7 156 278000 3.1 0.00 IE6 ICS3 32.5 2955 6.0 152 247000 3.0 0.3 IE7 ICS3 44.7 4062 5.7 146 246000 3.1 0.9 IE8 ICS3 52.5 4768 3.4 137 286500 2.9 2.2 IE9 ICS3 65.9 5995 1.2 127 344000 2.9 3.5 CE5 CCS4 13.7 1593 5.0 151 254000 3.2 0.0 CE6 CCS4 16.8 1949 7.0 148 254500 3.1 0.4 CE7 CCS4 18.3 2131 8.3 143 252000 3.1 0.9 CE8 CCS4 15.4 1786 5.0 135 284500 3.1 2.4 CE9 CCS4 11.9 1386 2.2 125 315500 3.4 3.6

[0426] From FIGS. 5 and 6 one can easily see that the more ethylene is added the bigger is the difference in productivity using the catalyst system according to the invention compared to catalyst systems without the boron containing cocatalyst.

[0427] The silica-MAO catalyst containing the tritylborate co-activator has also a slightly better MFR control (lower MFR at same H2 concentration) at any given C2 content compared to the non-borate catalyst. This effect is seen in FIG. 7.