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 of formula (I): ##STR00024## wherein each X independently is a sigma-donor ligand, L is a carbon, silicon or germanium based divalent bridge in which one or two backbone atoms link the ligands; each Ar is an aryl or heteroaryl group having 3 to 20 carbon atoms, such as a phenyl ring or a 5 or 6 membered heteroaryl ring; each R.sup.1 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20-arylalkyl, C.sub.7-20-alkylaryl group or C.sub.6-20-aryl group or an OY group, wherein Y is a C.sub.1-10-hydrocarbyl group, and optionally two adjacent R.sup.1 groups can be part of a ring including the carbons to which they are bonded, each R.sup.2 independently are the same or can be different and are a CHR.sup.8—R.sup.8 group, with R.sup.8 being H or linear or branched C.sub.1-6-alkyl group, C.sub.3-8-cycloalkyl group, 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.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, C.sub.7-20-arylalkyl, 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 R.sup.9 being a linear or branched C.sub.1-C.sub.6-alkyl group; R.sup.5 is hydrogen or an aliphatic C.sub.1-C.sub.20-hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements; R.sup.6 is hydrogen or an aliphatic C.sub.1-C.sub.20-hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements; or R.sup.5 and R.sup.6 can be taken together to form a 5 membered saturated carbon ring which is optionally substituted by n groups R.sup.10, n being from 0 to 4; each R.sup.10 is same or different and may be a C.sub.1-C.sub.20-hydrocarbyl group, or a C.sub.1-C.sub.20-hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16 of the periodic table of elements; R.sup.7 is H or 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 such as a phenyl ring or a 5 or 6 membered heteroaryl ring each R.sup.11 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20-arylalkyl, C.sub.7-20-alkylaryl group or C.sub.6-20-aryl group or an OY group, wherein Y is a C.sub.1-10-hydrocarbyl group; (ii) a cocatalyst system comprising a boron containing cocatalyst and an aluminoxane cocatalyst, (iii) an inorganic porous support, such as silica support.

2. A supported catalyst system wherein the metallocene complex is a metallocene complex of formula (II): ##STR00025## wherein each X independently is a sigma-donor ligand, L is a divalent bridge selected from —R′.sub.2C—, —R′.sub.2C—CR′.sub.2—, —R′.sub.2Si—, —R′.sub.2Si—SiR′.sub.2—, —R′.sub.2Ge—, wherein each R′ is independently a hydrogen atom or a C.sub.1-C.sub.20-hydrocarbyl group optionally containing one or more heteroatoms of Group 14-16 of the periodic table or fluorine atoms, or optionally two R′ groups taken together can form a ring, each R.sup.1 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group or C.sub.6-20 aryl group or an OY group, wherein Y is a C.sub.1-10 hydrocarbyl group, and optionally two adjacent R.sup.1 groups can be part of a ring including the phenyl carbons to which they are bonded, each R.sup.2 independently are the same or can be different and are a CH.sub.2—R.sup.8 group, with R.sup.8 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.3 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.4 is a C(R.sup.9)3 group, with R.sup.9 being a linear or branched C.sub.1-C.sub.6 alkyl group, R.sup.5 is hydrogen or an aliphatic C.sub.1-C.sub.20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements; R.sup.6 is hydrogen or an aliphatic C.sub.1-C.sub.20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements; or R.sup.5 and R.sup.6 can be taken together to form a 5 membered saturated carbon ring which is optionally substituted by n groups R.sup.10, n being from 0 to 4; each R.sup.10 is same or different and may be a C.sub.1-C.sub.20 hydrocarbyl group, or a C.sub.1-C.sub.20 hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16 of the periodic table of elements; R.sup.7 is H or 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, each R.sup.11 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group or C.sub.6-20 aryl group or an OY group, wherein Y is a C.sub.1-10 hydrocarbyl group,

3. A supported catalyst system according to claim 1 or 2, wherein in the formula (I) of the metallocene complex (i) each X may be the same or different, and is preferably a hydrogen atom, a halogen atom, a linear or branched, cyclic or acyclic 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; optionally containing one or more heteroatoms of Group 14-16 of the periodic table, more preferably, each X is independently a hydrogen atom, a halogen atom, a linear or branched C.sub.1-6-alkyl or C.sub.1-6-alkoxy group, a phenyl or benzyl group; L is preferably —R′.sub.2Si—, ethylene or methylene, whereby in the formula —R′.sub.2Si—, each R′ is preferably independently a C.sub.1-C.sub.20-hydrocarbyl group; each R.sup.1 are preferably independently the same or can be different and are hydrogen, or a linear or branched C.sub.1-C.sub.6-alkyl group, like methyl or tert.-butyl; preferably 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, more preferably, 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.3-alkyl group; R.sup.3 is preferably a linear or branched C.sub.1-C.sub.6-alkyl group or C.sub.6-20-aryl group, more preferably a linear C.sub.1-C.sub.4-alkyl group; R.sup.4 is a C(R.sup.9)3 group, with each R.sup.9 being the same or different whereby R.sup.9 is a linear or branched C.sub.1-C.sub.4-alkyl group, preferably with R.sup.9 being the same and being a C.sub.1-C.sub.2-alkyl group; R.sup.5 and R.sup.6 are either independently the same or can be different and are hydrogen or an aliphatic C.sub.1-C.sub.20-hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements, like an alkoxy group, e.g. a C.sub.1-C.sub.10-alkoxy group or R.sup.5 and R.sup.6 can be taken together to form a 5 membered saturated carbon ring which is optionally substituted by n groups R.sup.10, n being from 0 to 4, preferably 0 or 2 and more preferably 0; whereby each R.sup.10 can be the same or different and may be a C.sub.1-C.sub.20-hydrocarbyl group, or a C.sub.1-C.sub.20-hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16 of the periodic table of elements; preferably a linear or branched C.sub.1-C.sub.6-alkyl group; 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, more preferably R.sup.7 is H or a phenyl group optionally substituted by 1 to 3 groups R.sup.11, with each R.sup.11 being independently the same or different and being hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group or C.sub.6-20-aryl groups or an OY-group, wherein Y is a is a C.sub.1-4-hydrocarbyl group.

4. A supported catalyst system according to claim 1 wherein the metallocene complex is of formula (III) ##STR00026## each X independently is a sigma-donor ligand, L is a carbon, silicon or germanium based divalent bridge in which one or two backbone atoms link the ligands; each Ar is an aryl or heteroaryl group having 3 to 20 carbon atoms, such as a phenyl ring or a 5 or 6 membered heteroaryl ring; each R.sup.1 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20-arylalkyl, C.sub.7-20-alkylaryl group or C.sub.6-20-aryl group or an OY group, wherein Y is a C.sub.1-10-hydrocarbyl group, and optionally two adjacent R.sup.1 groups can be part of a ring including the phenyl carbons to which they are bonded, each R.sup.2 independently are the same or can be different and are a CHR.sup.8—R.sup.8 group, with R.sup.8 being H or linear or branched C.sub.1-6-alkyl group, C.sub.3-8-cycloalkyl group, 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.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, C.sub.7-20-arylalkyl, 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 R.sup.9 being a linear or branched C.sub.1-C.sub.6-alkyl group; R.sup.5 is hydrogen or an aliphatic C.sub.1-C.sub.20-hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements; R.sup.6 is hydrogen or an aliphatic C.sub.1-C.sub.20-hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements; or R.sup.5 and R.sup.6 can be taken together to form a 5 membered saturated carbon ring which is optionally substituted by n groups R.sup.10, n being from 0 to 4; each R.sup.10 is same or different and may be a C.sub.1-C.sub.20-hydrocarbyl group, or a C.sub.1-C.sub.20-hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16 of the periodic table of elements; 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, such as a phenyl ring or a 5 or 6 membered heteroaryl ring each R.sup.11 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20-arylalkyl, C.sub.7-20-alkylaryl group or C.sub.6-20-aryl group or an OY group, wherein Y is a C.sub.1-10-hydrocarbyl group.

5. A supported catalyst system according to claim 1 wherein the metallocene complex is of formula (VI) ##STR00027## each X independently is a sigma-donor ligand, L is a divalent bridge selected from —R′.sub.2C—, or —R′.sub.2Si—; wherein each R′ is independently a C.sub.1-C.sub.6-alkyl, C.sub.5-6-cycloalkyl, C.sub.1-10-alkyl-O—C.sub.1-10 alkyl or C.sub.6-aryl group; each Ar is a phenyl ring or a 5 or 6 membered heteroaryl ring; each R.sup.1 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, each R.sup.2 independently are the same or can be different and are a CHR.sup.8—R.sup.8 group, with R.sup.8 being H or 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, C.sub.7-20-arylalkyl, 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 R.sup.9 being a linear or branched C.sub.1-C.sub.6-alkyl group; R.sup.5 is hydrogen; R.sup.6 is hydrogen; or R.sup.5 and R.sup.6 can be taken together to 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, such as 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 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group.

6. A supported catalyst system according to claim 1 wherein the metallocene complex is of formula (VII) ##STR00028## each X independently is a sigma-donor ligand, L is a divalent bridge selected from —R′.sub.2C—, or —R′.sub.2Si—; wherein each R′ is independently a C.sub.1-C.sub.6-alkyl, C.sub.5-6-cycloalkyl, C.sub.1-10-alkyl-O—C.sub.1-10 alkyl or C.sub.6-aryl group; each Ar is a phenyl ring or a 5 or 6 membered heteroaryl ring; each R.sup.1 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, each R.sup.2 independently are the same or can be different and are a CHR.sup.8—R.sup.8 group, with R.sup.8 being H or 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.4 is a C(R.sup.9).sub.3 group, with R.sup.9 being a linear or branched C.sub.1-C.sub.6-alkyl group; R.sup.5 and R.sup.6 can be taken together to 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 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group.

7. A supported catalyst system according to claim 1 wherein the metallocene complex is of formula (VIII) ##STR00029## each X independently is a sigma-donor ligand such as a halogen atom, a linear or branched C.sub.1-4-alkyl or C.sub.1-4-alkoxy group, a phenyl or benzyl group, L is a divalent bridge selected from —R′.sub.2C—, or —R′.sub.2Si—; wherein each R′ is independently a C.sub.1-C.sub.6-alkyl, C.sub.5-6-cycloalkyl, C.sub.1-10-alkyl-O—C.sub.1-10 alkyl or C.sub.6-aryl group; each R.sup.1 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group; each R.sup.2 independently are the same or can be different and are a CH.sub.2—R.sup.8 group, with R.sup.8 being H or 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.4 is a C(R.sup.9)3 group, with R.sup.9 being a linear or branched C.sub.1-C.sub.6 alkyl group, R.sup.5 is hydrogen; R.sup.6 is hydrogen; or R.sup.5 and R.sup.6 can be taken together to form a 5 membered saturated carbon ring; R.sup.7 is a phenyl group optionally substituted by one to 3 groups R.sup.11, each R.sup.11 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group.

8. A supported catalyst system according to claim 1 wherein the metallocene complex is of formula (IX) ##STR00030## each X independently is a sigma-donor ligand such as a halogen atom, a linear or branched C.sub.1-4-alkyl or C.sub.1-4-alkoxy group, a phenyl 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, 10 alkyl or C.sub.6-aryl group; each R.sup.1 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.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.4 is a C(R.sup.9)3 group, with R.sup.9 being a linear or branched C.sub.1-C.sub.6 alkyl group, R.sup.5 is hydrogen; R.sup.6 is hydrogen; or R.sup.5 and R.sup.6 can be taken together to form a 5 membered saturated carbon ring; R.sup.7 is a phenyl group optionally substituted by one to 3 groups R.sup.11, each R.sup.11 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group.

9. A supported catalyst system according to claim 1 wherein the metallocene complex is of formula (X) ##STR00031## each X independently is a sigma-donor ligand such as a halogen atom, a linear or branched C.sub.1-4-alkyl or C.sub.1-4-alkoxy group, a phenyl or benzyl group, L is a —R′.sub.2Si—; wherein each R′ is independently a C.sub.1-C.sub.6-alkyl, C.sub.5-6_cycloalkyl, C.sub.1-10-alkyl-O—C.sub.1-10 alkyl or C.sub.6-aryl group; each R.sup.1 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group; each R.sup.2 independently are the same or can be different and are a CH.sub.2—R.sup.8 group, with R.sup.8 being H or 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.4 is a C(R.sup.9)3 group, with R.sup.9 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, each R.sup.11 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group.

10. A supported catalyst system according to claim 1 wherein the metallocene complex is of formula (XI) ##STR00032## each X independently is a sigma-donor ligand such as a halogen atom, a linear or branched C.sub.1-4-alkyl or C.sub.1-4-alkoxy group, a phenyl 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, C.sub.1-10-alkyl-O—C.sub.1-10 alkyl or C.sub.6-aryl group; each R.sup.1 are independently the same or can be different and are hydrogen, 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 R.sup.9 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, each R.sup.11 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group.

11. A supported catalyst system according to claim 1 wherein the metallocene complex is of formula (XII) ##STR00033## each X independently is a sigma-donor ligand such as a halogen atom, a linear or branched C.sub.1-4-alkyl or C.sub.1-4-alkoxy group, a phenyl or benzyl group, L is -Me.sub.2Si—, each R.sup.1 are independently the same or can be different and are hydrogen, 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 R.sup.9 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, each R.sup.11 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group.

12. A supported catalyst system according to claim 1 wherein the metallocene (i) is selected from rac-dimethylsilanediyl-bis[2-methyl-4-(3′5′-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-(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-dimethylsilanediyl[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-dimethylsilanediyl[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 or 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. A supported catalyst system according to any of the preceding claims wherein the aluminoxane cocatalyst is one of formula (A) ##STR00034## where n is from 6 to 20 and R can be C.sub.1-C.sub.10-alkyl, preferably C.sub.1-C.sub.5-alkyl, or C.sub.3-C.sub.10-cycloalkyl, C.sub.7-C.sub.12-arylalkyl or -alkylaryl and/or phenyl or naphthyl, preferably MAO.

14. A supported catalyst system according to any of the preceding claims wherein the boron containing cocatalyst is either one of formula (B)
BY.sub.3  (B) wherein Y independently is the same or can be different and 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 a borate containing an anion of formula:
(Z).sub.4B—  (C) where 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 such as methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylanilinium or p-nitro-N,N-dimethylanilinium or triphenylcarbenium ion.

15. A supported catalyst system according to any of the preceding claims, 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, more preferably triphenylcarbeniumtetrakis(pentafluorophenyl) borate.

16. A supported catalyst system according to any of the preceding claims, wherein the molar ratio of feed amounts 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, preferably 0.3:1 to 7:1, especially 0.3:1 to 5:1 mol/mol and the molar ratio of aluminium in the aluminoxane cocatalyst to the zirconium in the complex of formula (I) is in the range of 1:1 to 2000:1 mol/mol, preferably 10:1 to 1000:1, and more preferably 50:1 to 600:1 mol/mol.

17. A supported catalyst system according to any of the preceding, wherein the average particle size of the support such as silica support is from 10 to 100 μm, preferably 15 to 80 μm.

18. A supported catalyst system according to any of the preceding claims, wherein the average pore size of the support such as silica support can be in the range 10 to 100 nm, the pore volume can be from 1 to 3 mL/g.

19. A supported catalyst system according to any of the preceding claims, wherein the catalyst system can contain from 10 to 100 μmol of zirconium per gram support such as silica support and 5 to 10 mmol of Al per gram of support such as silica support.

20. A supported catalyst system according to any of the preceeding claims, wherein the catalyst system comprises metallocene (i), MAO and borate cocatalysts and support such as silica support and shows a higher productivity in the polymerization of propylene and ethylene as the same catalyst system without borate cocatalyst according to inequation
Δproductivity [kgPP/gcat]>10×C2 [wt %], in which Δproductivity is the difference between the productivity of the metallocene-MAO-borate catalyst and the productivity of the metallocene-MAO catalyst at a given ethylene concentration in the monomer feed in propylene-ethylene copolymerizations.

21. Preparation of a supported catalyst system according to any of the preceding claims, the process comprising the steps of a) reacting the support such as silica support with aluminoxane cocatalyst in a suitable hydrocarbon solvent, such as toluene with optional subsequent drying, to obtain aluminoxane cocatalyst treated support, b) reacting metallocene complex as defined in claims 1 to 12 with aluminoxane cocatalyst in a suitable hydrocarbon solvent, such as toluene, c) adding borate cocatalyst to the solution obtained in step b) to obtain a solution of metallocene complex of formula (I), borate cocatalyst and aluminoxane cocatalyst whereby the borate cocatalyst is added in an amount that a boron/zirconium molar ratio of feed amounts in the range of 0.1:1 to 10:1 is reached, d) adding the solution obtained in step c) to the aluminoxane cocatalyst treated support obtained in step a) wherein the amount of aluminoxane cocatalyst added in step a) is 75.0 to 97.0 wt % of the total amount of aluminoxane cocatalyst and the amount of aluminoxane cocatalyst added in step b) is 3.0 to 25.0 wt % of the total amount of aluminoxane cocatalyst; and e) drying the so obtained supported catalyst system.

22. Use of the supported catalyst system according to any of the preceding claims 1 to 20 for the preparation of propylene homopolymers, propylene random copolymers and heterophasic propylene copolymers.

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

25. A metallocene complex of formula (III) ##STR00035## each X independently is a sigma-donor ligand, L is a carbon, silicon or germanium based divalent bridge in which one or two backbone atoms link the ligands; each Ar is an aryl or heteroaryl group having 3 to 20 carbon atoms, such as a phenyl ring or a 5 or 6 membered heteroaryl ring; each R.sup.1 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20-arylalkyl, C.sub.7-20-alkylaryl group or C.sub.6-20-aryl group or an OY group, wherein Y is a C.sub.1-10-hydrocarbyl group, and optionally two adjacent R.sup.1 groups can be part of a ring including the carbons to which they are bonded, each R.sup.2 independently are the same or can be different and are a CR.sup.8—R.sup.8 group, with R.sup.8 being H or linear or branched C.sub.1-6-alkyl group, C.sub.3-8-cycloalkyl group, 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.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, C.sub.7-20-arylalkyl, 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 R.sup.9 being a linear or branched C.sub.1-C.sub.6-alkyl group; R.sup.5 is hydrogen or an aliphatic C.sub.1-C.sub.20-hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements; R.sup.6 is hydrogen or an aliphatic C.sub.1-C.sub.20-hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements; or R.sup.5 and R.sup.6 can be taken together to form a 5 membered saturated carbon ring which is optionally substituted by n groups R.sup.10, n being from 0 to 4; each R.sup.10 is same or different and may be a C.sub.1-C.sub.20-hydrocarbyl group, or a C.sub.1-C.sub.20-hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16 of the periodic table of elements; 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, such as a phenyl ring or a 5 or 6 membered heteroaryl ring each R.sup.11 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, a C.sub.7-20-arylalkyl, C.sub.7-20-alkylaryl group or C.sub.6-20-aryl group or an OY group, wherein Y is a C.sub.1-10-hydrocarbyl group.

26. A metallocene complex as defined on claim 25 having the general formula (VI) to (XII) as defined in claims 4 to 12.

Description

[0359] The invention will now be illustrated by reference to the following non-limiting Examples and figures.

[0360] 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).

[0361] FIG. 2 plots the XCS of the iV fraction vs productivity in the gas phase for examples herein.

[0362] FIG. 3 plots the ethylene content of the XCS fraction vs the iV of the XCS fraction for examples of the invention.

[0363] FIG. 4 plots the ethylene content of the XCS fraction vs the iV of the XCS fraction for examples of the invention.

[0364] FIG. 5 plots the ethylene content of the polymer vs the productivity for examples of the invention.

[0365] FIG. 6 plots the ethylene content of the polymer vs the delta productivity for examples of the invention.

[0366] FIG. 7 plots the ethylene content of the polymer vs the MFR for examples of the invention.

MEASUREMENT METHODS

[0367] (a) Melt Flow Rate (MFR)

[0368] The melt flow rate is measured as the MFR.sub.2 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.

[0369] (b) Number Average Molecular Weight (Mn), Weight Average Molecular Weight (Mw) and Polydispersity (Mw/Mn)

[0370] 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]$\begin{array}{cc}{M}_n=\frac{{\Sigma }_{i=1}^N{A}_i}{{\Sigma }_{i=1}^N\left(A_i/M_i\right)}& \left(1\right)\\ M_w=\frac{{\Sigma }_{i=1}^N\left(A_{i}x{M}_i\right)}{{\Sigma }_{i=1}^N{A}_i}& \left(2\right)\\ M_z=\frac{{\Sigma }_{i=1}^N\left(A_{i}x{M}_i^2\right)}{{\Sigma }_{i=1}^N\left(A_{i}x{M}_i\right)}& \left(3\right)\end{array}$

[0371] For a constant elution volume interval ΔV.sub.i, where A.sub.i, and M.sub.i are the chromatographic peak slice area and polyolefin molecular weight (MW), respectively associated with the elution volume, V.sub.i, where N is equal to the number of data points obtained from the chromatogram between the integration limits.

[0372] A high temperature GPC instrument, equipped with either infrared (IR) detector (IR4 or IR5 from PolymerChar (Valencia, Spain), equipped with 3× Agilent-PLgel Olexis and 1× 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 μL 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.

[0373] 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\times {10}^{-3}\mathrm{mL}\text{/}g,{\alpha }_{PS}=0.655$$K_{\mathrm{PE}}=39\times {10}^{-3}\mathrm{mL}\text{/}g,{\alpha }_{PE}=0.725$$K_{\mathrm{PP}}=19\times {10}^{-3}\mathrm{mL}\text{/}g,{\alpha }_{PP}=0.725$

[0374] A third order polynomial fit was used to fit the calibration data.

[0375] 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.

[0376] (c) DSC Analysis, Peak Melting Temperature (T.sub.m), Heat of Melting (H.sub.m), and Peak Crystallization Temperature (T.sub.a)

[0377] DSC analysis was measured with a Mettler TA Instrument Q2000 differential scanning calorimetry (DSC) on 5 to 7 mg samples. DSC is run according to ISO 11357/part 3/method C2 in a heat/cool/heat cycle with a scan rate of 10° C./min in the temperature range of −30 to +225° C. Crystallization temperature (Tc) is determined from the cooling step, while peak melting temperature (Tm) and heat of melting (H.sub.m) are determined from the second heating step.

[0378] (d) Intrinsic Viscosity

[0379] Intrinsic viscosity (iV) has been measured according to DIN ISO 1628/1, October 1999 (in Decaline at 135° C.).

[0380] (e) Xylene Cold Soluble Fraction

[0381] The xylene cold solubles (XCS, wt %) were determined at 25° C. according to ISO 16152; 2005.

[0382] (f) Al and Zr Determination (ICP-Method)

[0383] 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.

[0384] The analysis was run at room temperature using a Thermo Elemental iCAP 6300 Inductively Coupled Plasma—Optical Emmision Spectrometer (ICP-OES) which was calibrated using a blank (a solution of 5% HNO3, 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.

[0385] 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.

[0386] 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.

[0387] 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.

[0388] (g) Crystex Analysis

[0389] Crystalline and Soluble Fractions Method

[0390] 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).

[0391] 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 (C.sub.2) 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).

[0392] 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.

[0393] 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 %.

[0394] 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.

[0395] 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/I 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.

[0396] 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. 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).

[0397] EP means ethylene propylene copolymer.

[0398] PP means polypropylene.

[0399] FIG. 1a shows a schematic diagram of the CRYSTEX QC instrument.

[0400] 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).

[0401] (h) Quantification of Microstructure by NMR Spectroscopy

[0402] 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 .sup.1H and .sup.13C respectively. All spectra were recorded using a .sup.13C optimised 10 mm extended temperature probehead at 125° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d.sub.2 (TCE-d.sub.2) along 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). 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 (6 k) transients were acquired per spectra.

[0403] 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).

[0404] 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.

[0405] 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{.sup.1H} spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.

[0406] 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]$E=0.5\left(S\beta \beta +S\mathrm{\beta \gamma }+S\mathrm{\beta \delta }+0.5\left(S\mathrm{\alpha \beta }+S\mathrm{\alpha \gamma }\right)\right)$

[0407] Through the use of this set of sites the corresponding integral equation becomes:

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

[0408] 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.

[0409] The mole percent comonomer incorporation was calculated from the mole fraction:

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

[0410] The weight percent comonomer incorporation was calculated from the mole fraction:

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

[0411] Comonomer Content by IR Spectroscopy

[0412] Quantitative infrared (IR) spectroscopy was used to quantify the ethylene content of the copolymers through calibration to a primary method.

[0413] 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 25×25 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 urn 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.sup.−1). The quantitative band was normalised to the area of the CH band at 4323 cm.sup.−1 (A.sub.R) corresponding to CH structural units (integration method G, limits 4650, 4007 cm.sup.−1). The ethylene content in units of weight percent was then predicted from the normalised absorption (A.sub.Q/A.sub.R) 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.

[0414] The present invention will now be illustrated by way of examples.

[0415] The following complex C1 as shown below was used in preparing catalysts for the Comparative Examples (CE1-CE4) and the Inventive Examples (IE1-IE4)

##STR00018##

[0416] C1 (rac-anti-dimethylsilanediyl(2-methyl-4-(3′,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.

[0417] Preparation of MAO-Silica Support

[0418] 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.

[0419] ICS 1 (Inventive Catalyst System 1): Catalyst Preparation

[0420] 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 μmol). 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.

[0421] ICS 2 (Inventive Catalyst System 2): Catalyst Preparation

[0422] 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 μmol). 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.

[0423] CCS 1 (Comparative Catalyst System 1): Catalyst Preparation

[0424] 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 μmol). 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 30 minutes. 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.

[0425] CCS 2 (Comparative Catalyst System 2): Catalyst Preparation

[0426] 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 (0,051 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another septum bottle and left to stir inside the glovebox.

[0427] 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./600 rpm. Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hot PFC at 90° C., and stirred at 600 rpm until the transfer is completed, then the speed was reduced to 300 rpm. After 15 minutes stirring, the oil bath was removed and the stirrer turned off. The catalyst was left to settle up on top of the PFC and after 35 minutes the solvent was siphoned off. The remaining 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)

[0428] 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.

[0429] 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.

[0430] CC3 (Comparative Catalyst System 3): Catalyst Preparation

[0431] The same catalyst complex as for CC2 was used, but in addition to MAO also a borate cocatalyst was added.

[0432] 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.

[0433] 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)

[0434] 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

[0435] Polymerizations:

[0436] 2-Step Bulk (C3 Homo)+Gas Phase (C2/C3) Polymerization

[0437] Step 1: Prepolymerization and Bulk Homopolymerization

[0438] 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.

[0439] Step 2: Gas Phase C3C2 Copolymerization

[0440] 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.

[0441] Then the reactor was cooled down (to about 30° C.) and the volatile components flashed out. After purging the reactor 3 times with N.sub.2 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 Time C2 fed in C3 fed in feed before H2 fed Pressure transition transition transition C2/C3 Catalyst catalyst after T flashed to GP2 (MEC) (MEC) during Catalyst amount feed T time transition Example system mg NL NL ° C. min barg min g g wt/wt IE1 ICS1 61.0 0.31 Prepoly 1.7 75 40 0.3 15 238 344 0.692 IE2 ICS1 67.0 2.00 at 20° C. 0.0 75 40 0.3 15 182 262 0.695 IE3 ICS2 65.0 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 C2 fed in GP2 C3 fed in GP2 Ptotal added H2 (MEC) (MFC) feed av. in GP Temperature time 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 0 70 90 104 316 0.3 MFC mass flow controller indicates data missing or illegible when filed

[0442] 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

[0443] 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).

[0444] The following complex C2 as shown below was used in preparing catalysts for the Comparative Examples (CE5-CE9) and the Inventive Examples (IE5-IE9)

##STR00019##

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

[0445] ##STR00020##

[0446] To a mixture of 2.0 g (2.56 mmol) of NiCl.sub.2(PPh.sub.3)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 μm, 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% K.sub.2CO.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 μm, 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%).

[0447] .sup.1H NMR (CDCl.sub.3): δ 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). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 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

[0448] ##STR00021##

[0449] To 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 −30° C., 13.0 ml (31.59 mmol) of 2.43 M .sup.nBuLi 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.

[0450] .sup.1H NMR (CDCl.sub.3): δ 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{.sup.1H} NMR (CDCl.sub.3): δ 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

[0451] ##STR00022##

[0452] To a solution of 10.13 g (31.59 mmol) of 5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-2-methyl-1H-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 nBuLi 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 μm), which was additionally washed by 2×50 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.

[0453] .sup.1H NMR (CDCl.sub.3): δ 7.27 and 7.25 (2s, 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 (2s, 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 (6s and 2m, sum 9H), 1.44 and 1.38 (2s, sum 9H), -0.52, -0.58, -0.62 and -0.73 (4s, sum 6H).

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

[0454] ##STR00023##

[0455] To a slightly cloudy yellowish solution of 23.06 g (30.54 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5-dimethyl-phenyl)-5-methoxy-2-methyl-1H-inden-1-yl]dimethylsilane in 250 ml of ether, cooled to −30° C., 25.1 ml (60.99 mmol) of 2.43 M .sup.nBuLi 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 ZrCl.sub.4 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 2×50 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×1.0 .SUP.n.hexane

[0456] Anal. calc. for C54H.sub.60Cl.sub.2OSiZr×C.sub.6H.sub.14: C, 71.96; H, 7.45. Found: C, 72.30; H, 7.69.

[0457] .sup.1H NMR (CDCl.sub.3): δ 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). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 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.

[0458] Preparation of MAO-Silica Support

[0459] 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 SiO.sub.2 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.

[0460] Inventive Catalyst System 3 (ICS3) Catalyst Preparation

[0461] 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 solution was added to a stirred cake of MAO-silica support prepared as described above over 1 hour. The cake was allowed to stay for 12 hours, foiled by drying under N.sub.2 flow at 60° C. for 2 h and additionally for 5 h under vacuum (−0.5 barg) under stirring.

[0462] Dried catalyst was sampled in the form of pink free flowing powder containing 13.9% Al and 0.11% Zr.

[0463] Comparative Catalyst System 4 (CCS4)

[0464] 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 solution was added to a stirred cake of MAO-silica support prepared as described above over 1 hour. The cake was allowed to stay for 12 hours, foiled by drying under N.sub.2 flow at 60° C. for 2 h and additionally for 5 h under vacuum (−0.5 barg) under stirring.

[0465] Dried catalyst was sampled in the form of pink free flowing powder containing 12.8% Al and 0.084% Zr

[0466] Polymerizations:

Prepolymerization and Bulk Polymerization

[0467] 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.

[0468] Then the reactor was cooled down to about 30° C. and the volatile components flashed out. After purging the reactor 3 times with N.sub.2 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.

[0469] 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

[0470] 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

[0471] 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.

[0472] 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.