Catalysts
A metallocene complex of formula (I): each X is a sigma-ligand; in the group R 2 Si— at least one R is methyl or ethyl, and the other R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, pentyl, hexyl, cyclohexyl and phenyl; each R 1 independently is the same or can be different and are a CH 2 —R 7 group, with R 7 being H or linear or branched C 1-6 -alkyl group, C 3-8 cycloalkyl group, or C 6-10 aryl group; each R 2 is independently a —CH═, —CY═, —CH 2 —, —CHY— or —CY 2 — group, wherein Y is a C 1-6 hydrocarbyl group and where n is 2-6; each R 3 and R 4 are independently the same or can be different and are hydrogen, a linear or branched C 1-6 -alkyl group, a C 7-20 arylalkyl, C 7-20 alkylaryl group, C 6-20 aryl group, or an —OY group, wherein Y is a is a C 1-6 hydrocarbyl group; R 5 is a linear or branched C 1-6 -alkyl group, C 7-20 arylalkyl, C 7-20 alkylaryl group or C 6-20 -aryl group; and R 6 is a C(R 8 ) 3 group, with R 8 being a linear or branched C 1-6 alkyl group; (A) wherein at least one R 3 per phenyl group and at least one R 4 is not hydrogen, and wherein at least one R 3 per phenyl group and at least one R 4 is hydrogen; or (B) wherein one R 3 is an —OY group, wherein Y is a is a C 1-6 hydrocarbyl group, in 4 position of each phenyl group and the two other R 3 groups are tert-butyl groups; and/or (C) wherein one R 4 is an —OY group, wherein Y is a is a C 1-6 hydrocarbyl group, in 4-position of the phenyl ring and the two other R 4 groups are tert-butyl groups.
1. A metallocene complex of formula (I):
wherein
each X is a sigma-ligand;
in the group R 2 Si— at least one R is methyl or ethyl, and the other R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, pentyl, hexyl, cyclohexyl and phenyl;
each R 1 independently is a CH 2 —R 7 group, with R 7 being H or linear or branched C 1-6 -alkyl group, C 3-8 cycloalkyl group, or C 6-10 aryl group;
each R 2 is independently a —CH═, —CY═, —CH 2 —, —CHY— or —CY 2 — group, wherein Y is a C 1-6 hydrocarbyl group and where n is 2-6;
each R 3 and R 4 independently is hydrogen, a linear or branched C 1-6 -alkyl group, a C 7-20 arylalkyl, C 7-20 alkylaryl group, C 6-20 aryl group, or an —OY group, wherein Y is a is a C 1-6 hydrocarbyl group;
R 5 is a linear or branched C 1-6 -alkyl group, C 7-20 arylalkyl, C 7-20 alkylaryl group or C 6-20 -aryl group; and
R 6 is a C(R 8 ) 3 group, with each R 8 being independently a linear or branched C 1-6 alkyl group;
(A) wherein at least one R 3 per phenyl group and at least one R 4 is not hydrogen, and wherein at least one R 3 per phenyl group and at least one R 4 is hydrogen; or
(B) wherein one R 3 is an —OY group, wherein Y is a is a C 1-6 hydrocarbyl group, in 4 position of each phenyl group and the two other R 3 groups are tert-butyl groups; and/or
(C) wherein one R 4 is an —OY group, wherein Y is a is a C 1-6 hydrocarbyl group, in 4-position of the phenyl ring and the two other R 4 groups are tert-butyl groups.
2. The metallocene complex according to claim 1 , wherein:
each X is independently a hydrogen atom, halide, C 1-6 alkoxy group, or an R′ group, where R′ is a C 1-6 alkyl, phenyl or benzyl group;
R 2 Si— is Me 2 Si—, Et 2 Si— or (cyclohexyl)Me-Si—;
each R 1 independently is a CH 2 —R 7 group, with R 7 being H, linear or branched C 1-6 -alkyl group, or C 6-10 aryl group;
each R 2 is independently a —CH═, —CY═, —CH 2 —, —CHY— or —CY 2 — group, wherein Y is a C 1-4 hydrocarbyl group and where n is 3-4,
each R 3 and R 4 independently is hydrogen, a linear or branched C 1 -C 6 -alkyl group or C 6-20 aryl group, wherein at least one R 3 per phenyl group and at least one R 4 is not hydrogen and wherein at least one R 3 per phenyl group and at least one R 4 is hydrogen,
R 5 is a linear or branched C 1 -C 6 alkyl group or C 6-20 aryl group and
R 6 is a C(R 8 ) 3 group, with each R 8 being independently a linear or branched C 1 -C 4 alkyl group.
3. The metallocene complex according to claim 1 , wherein:
each X is independently a chloride, benzyl or a methyl group,
both R 1 groups are the same and are a CH 2 —R 7 group, with R 7 being H or linear or branched C 1 -C 3 -alkyl group,
each R 2 is a —CH 2 — group where n is 3-4,
each R 3 and R 4 independently is hydrogen, a linear or branched C 1 -C 6 -alkyl group, or C 6-20 aryl group, wherein at least one R 3 per phenyl group and at least one R 4 is not hydrogen and wherein at least one R 3 per phenyl group and at least one R 4 is hydrogen,
R 5 is a linear or branched C 1 -C 6 alkyl group or C 6-20 aryl group and
R 6 is a C(R 8 ) 3 group, R 8 being the same and being a C 1 -C 2 -alkyl group.
4. The metallocene complex as claimed in claim 1 , wherein the metallocene complex is of formula (II)
wherein
each X is a sigma-ligand selected from chloride, benzyl, and C 1-6 -alkyl;
R 2 Si— is Me 2 Si or Et 2 Si—;
each R 3 and R 4 independently is hydrogen, a linear or branched C 1-6 -alkyl group, or —OY group where Y is a C 1-6 alkyl group; and wherein:
(A) at least one R 3 per phenyl group and at least one R 4 is not hydrogen, and at least one R 3 per phenyl group and at least one R 4 is hydrogen; or
(B) at least one R 3 is an —OY group, wherein Y is a is a C 1-6 hydrocarbyl group, in the 4 position of each phenyl ring and the two other R 3 groups are tert-butyl groups; and/or
(C) at least one R 4 is an —OY group, wherein Y is a is a C 1-6 hydrocarbyl group in the 4-position of the phenyl ring and the two other R 4 groups are tert-butyl groups;
R 5 is a linear or branched C 1-6 -alkyl group; and
R 6 is a —C(R 8 ) 3 group, with R 8 being a linear or branched C 1 or C 2 alkyl group.
5. The metallocene complex as claimed in claim 1 , wherein the metallocene complex is of formula (III)
wherein
each X is the same and is a sigma-ligand selected from chloro chloride, benzyl and C 1-6 alkyl;
R 2 Si— is Me 2 Si or Et 2 Si—;
each non-hydrogen R 3 is the same and each non-hydrogen R 4 is the same;
R 3 is hydrogen, a linear or branched C 1-6 -alkyl group;
R 4 is hydrogen, a linear or branched C 1-6 -alkyl group;
wherein at least one R 3 per phenyl group and at least one R 4 is not hydrogen, and wherein at least one R 3 per phenyl group and at least one R 4 is hydrogen,
R 5 is a linear or branched C 1-4 -alkyl group; and
R 6 is a —C(R 8 ) 3 group, with R 8 being a linear or branched C 1 or C 2 alkyl group.
6. The metallocene complex as claimed in claim 1 , wherein the metallocene complex is of formula (IVa) to (IVd)
wherein
each X is the same and is chloride, benzyl, or C 1-6 -alkyl;
each R 3 and R 4 independently is a linear or branched C 1-6 -alkyl group.
7. The metallocene complex according to claim 1 , wherein the complex is:
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] Hafnium dichloride (MC-1);
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] Hafnium dichloride (MC-2);
rac-anti-dimethylsilanediyl [2-methyl-4,8-bis-(4′-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(4′-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl] Hafnium dichloride (MC-3);
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′-di-tert-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl] Hafnium dichloride (MC-4); or
rac-anti-dimethylsilanediyl [2-methyl-4,8-bis-(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl] [2-methyl-4-(4′-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl] Hafnium dichloride (MC-5).
8. A catalyst system comprising:
(i) the metallocene complex according to claim 1 ; and
(ii) a cocatalyst comprising a compound of a group 13 element.
9. The catalyst system according to claim 8 , wherein cocatalyst (ii) comprises alumoxane, combinations of alumoxane with Al-alkyls, boron or borate cocatalysts, or combinations of alumoxanes with boron-based cocatalysts.
10. The catalyst system as claimed in claim 8 , wherein the catalyst system is in solid form, being supported on an external carrier.
11. The catalyst system as claimed in claim 10 , wherein the catalyst system is supported on silica.
12. A process for the polymerization of propylene comprising reacting propylene and optional comonomers with the catalyst system as claimed in claim 8 .
13. The process as claimed in claim 12 , wherein the process is for the preparation of a heterophasic propylene ethylene or heterophasic propylene ethylene 1-butene copolymer, the process comprising:
(I) polymerising propylene and optionally ethylene and/or 1-butene in the presence of the catalyst system so as to form:
a1) a crystalline fraction (CF) comprising a propylene homopolymer or propylene copolymer matrix having up to 2 wt % comonomer as said matrix component; and
(II) subsequently polymerising additional propylene and ethylene and optionally 1-butene in the presence of the matrix component of step (I) so as to form:
a2) a propylene ethylene or propylene ethylene 1-butene copolymer soluble fraction (SF) having a comonomer content of 12 to 85 wt %;
wherein the crystalline fraction (CF) constitutes 30.0 to 95.0 wt % and the soluble fraction (SF) constitutes 5.0 to 70.0 wt % of the heterophasic propylene ethylene or heterophasic propylene ethylene 1-butene copolymer, wherein the amount of crystalline fraction (CF) and the amount soluble fraction (SF) are determined in 1,2,4-trichlorobenzene at 40° C.; and
wherein the soluble fraction (SF) of the heterophasic propylene ethylene or propylene ethylene 1-butene copolymer has an intrinsic viscosity IV(SF) in decalin at 135° C. of 1.5 to 10 dl/g.