Supported metallocene catalyst systems for polymerization

1. An olefin polymerization catalyst system comprising:

i) a metallocene catalyst compound represented by the formula:

wherein R 2 and R 8 are different and, independently, a C 1 to C 20 linear alkyl group, provided that at least one of R 2 and R 8 has at least 4 carbon atoms;

R 4 and R 10 are substituted or unsubstituted aryl groups;

M is a transition metal selected from Group 2, 3, or 4 of the Periodic Table;

T is a bridging group;

each X is an anionic leaving group;

each R 1 , R 3 , R 5 , R 6 , R 7 , R 9 , R 11 , R 12 , R 13 , and R 14 is, independently, hydrogen, a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;

wherein either or both of R 5 and R 6 or R 11 and R 12 optionally join together to form a ring structure; and

ii) a support having an average surface area of from about 400 m 2 /g to 800 m 2 /g, an average pore diameter of from 60 Angstroms to 200 Angstroms; and at least 20% of the incremental pore volume comprises pores having a pore diameter larger than 100 Angstroms;

and

iii) an aluminoxane having an aluminoxane loading of greater than about 7 mmol Al/g support.

2. The catalyst system of claim 1 , wherein the support has:

an average pore diameter of from 60 Angstroms to 180 Angstroms;

at least 20% of the incremental pore volume comprises pores having a pore diameter larger than 215 Angstroms; and

an aluminoxane loading of greater than about 9.0 mmol Al/g support.

3. The catalyst system of claim 1 , wherein the support has:

an average surface area of from about 550 m 2 /g to 650 m 2 /g support;

an average pore diameter of from about 80 Angstroms to 130 Angstroms;

an average pore volume of from about 0.5 ml/g to 2.5 ml/g support; and

an average particle size of from about 20 micrometers to 200 micrometers.

4. The catalyst system of claim 1 , wherein the support comprises agglomerates of a plurality of primary particles.

5. The catalyst system of claim 1 , wherein R 2 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl.

6. The catalyst system of claim 1 , wherein R 8 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl.

7. The catalyst system of claim 1 , wherein at least one of R 4 and R 10 is a phenyl group substituted at the 3′ and 5′ positions with C 1 to C 10 alkyl groups, aryl groups, or combinations thereof.

8. The catalyst system of claim 1 , wherein R 4 and R 10 are independently a phenyl group substituted at the 3′ and 5′ positions with C 1 to C 10 alkyl groups, aryl groups, or combinations thereof and, optionally, the 4′ position is substituted with a group selected from (XR′n) − , wherein X is a heteroatom selected from Groups 14 to 17 of the Periodic Table having an atomic weight of 13 to 79, and R′ is one of a hydrogen atom, a halogen atom, a C 1 to C 10 alkyl group or a C 6 to C 10 aryl group, and n is 0, 1, 2, or 3.

9. The catalyst system of claim 1 , wherein at least one of R 4 and R 10 is a phenyl group substituted at the 2′ position with an alkyl or aryl group.

10. The catalyst system of claim 1 , wherein one of R 5 and R 6 or R 11 and R 12 join together to form a ring structure.

11. The catalyst system of claim 1 , wherein each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof and two X optionally form a part of a fused ring or a ring system.

12. The catalyst system of claim 1 , wherein T is represented by the formula R a 2 J, where J is C, Si, or Ge, each R a is, independently, a hydrogen atom, a halogen atom, a C 1 to C 20 hydrocarbyl or a C 1 to C 20 substituted hydrocarbyl, and two R a optionally form a cyclic structure including an aromatic, a partially saturated, or a saturated cyclic or fused ring system.

13. The catalyst system of claim 1 , wherein T is CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , SiMe 2 , SiPh 2 , SiMePh, Si(CH 2 ) 3 , Si(CH 2 ) 4 , Si(Me 3 SiPh) 2 , or Si(CH 2 ) 5 .

14. An olefin polymerization catalyst system comprising:

i) a metallocene catalyst compound is represented by one or more of the following compounds:

and

ii) a support having an average surface area of from about 400 m 2 /g to 800 m 2 /g support; and

iii) an aluminoxane.

15. The catalyst system of claim 1 , wherein the aluminoxane is present at a molar ratio of aluminum to metallocene catalyst compound transition metal of 100:1 or more.

16. The catalyst system of claim 1 , wherein a rac-isomer to meso-isomer ratio is 10:1 or greater.

17. The catalyst system of claim 1 , further comprising an aluminum alkyl.

18. A process to polymerize olefins comprising contacting one or more olefins with the catalyst system of claim 1 in a reactor and recovering a polymer.

19. The process of claim 18 , wherein molecular hydrogen is not added to the reactor.

20. A process to produce isotactic polypropylene, the process comprising contacting the catalyst system of claim 1 , with propylene and obtaining isotactic polypropylene.

21. The process of claim 20 , further comprising contacting the catalyst system with propylene at a first hydrogen concentration in the reactor, adjusting to a second hydrogen concentration, and recovering isotactic polypropylene having a bimodal molecular weight distribution.

22. The process of claim 21 , further comprising contacting the isotactic polypropylene with ethylene and optional comonomer to produce an impact copolymer.

23. The process of claim 21 , wherein the isotactic polypropylene has a melt flow rate (MFR, ASTM D-1238, 2.16 kg and 230° C.) of less than about 0.3 dg/min.

24. The process of claim 20 , wherein the catalyst system has a catalyst activity of at least 3000 g polymer/g catalyst hr and the weight average molecular weight of the isotactic polypropylene is at least 600 kg/mol.

25. The process of claim 20 , wherein the catalyst system has a catalyst activity of at least 4000 g polymer/g catalyst hr and the weight average molecular weight of the isotactic polypropylene is at least 1400 kg/mol.

26. The process of claim 20 , wherein the isotactic polypropylene has a melting temperature, Tm, DSC peak second melt, of at least 151° C.

27. The catalyst system of claim 1 , wherein:

a) the support has:

i) an average pore diameter of from 60 Angstroms to 300 Angstroms;

ii) at least 20% of the incremental pore volume comprises pores having a pore diameter larger than 100 Angstroms; and

iii) an aluminoxane loading of greater than about 7 mmol Al/g support;

b) the support comprises agglomerates of a plurality of primary particles;

c) R 2 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl;

d) R 8 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl; and

e) at least one of R 4 and R 10 is a phenyl group substituted at the 3′ and 5′ positions with C 1 to C 10 alkyl groups, aryl groups, or combinations thereof.

28. The catalyst system of claim 1 , wherein:

a) the support has:

i) an average surface area of from about 550 m 2 /g to 650 m 2 /g support;

ii) an average pore diameter of from about 80 Angstroms to 130 Angstroms;

iii) an average pore volume of from about 0.5 ml/g to 2.5 ml/g support;

iv) an average particle size of from about 20 micrometers to 200 micrometers;

b) the support comprises agglomerates of a plurality of primary particles;

c) R 2 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl;

d) R 8 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl; and

e) R 4 and R 10 are independently a phenyl group substituted at the 3′ and 5′ positions with C 1 to C 10 alkyl groups, aryl groups, or combinations thereof and, optionally, the 4′ position is substituted with a group selected from (XR′n) − , wherein X is a heteroatom selected from Groups 14 to 17 of the Periodic Table having an atomic weight of 13 to 79, and R′ is one of a hydrogen atom, a halogen atom, a C 1 to C 10 alkyl group or a C 6 to C 10 aryl group, and n is 0, 1, 2, or 3.

29. The catalyst system of claim 27 , wherein each X is, independently, selected from the group consisting of: hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof; and two X optionally form a part of a fused ring or a ring system; and T is represented by the formula R a 2 J, where J is C, Si, or Ge, each R a is, independently, a hydrogen atom, a halogen atom, a C 1 to C 20 hydrocarbyl or a C 1 to C 20 substituted hydrocarbyl, and two R a optionally form a cyclic structure including an aromatic, a partially saturated, or a saturated cyclic or fused ring system.

30. A process to polymerize olefins comprising contacting one or more olefins with the catalyst system of claim 27 in a reactor and recovering a polymer.

31. A process to produce isotactic polypropylene, the process comprising contacting the catalyst system of claim 28 with propylene and obtaining isotactic polypropylene.

32. A process to produce isotactic polypropylene, the process comprising contacting the catalyst system of claim 29 with propylene and obtaining isotactic polypropylene.

33. The catalyst system of claim 1 , wherein R 2 is methyl, ethyl, n-propyl, n-butyl, and R 8 is n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl.

34. The catalyst system of claim 1 , wherein R 2 is methyl, ethyl, n-propyl, and R 8 is n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl.

35. The catalyst system of claim 1 , wherein the support has an aluminoxane loading of greater than about 10 mmol Al/g support.

36. The catalyst system of claim 1 , wherein the support has an aluminoxane loading of 10 mmol Al/g support to 20 mmol Al/g support.

37. The catalyst system of claim 1 , wherein the support has an aluminoxane loading of 10 mmol Al/g support to 20 mmol Al/g support.

38. An olefin polymerization catalyst system comprising:

i) a metallocene catalyst compound represented by the formula:

wherein R 2 and R 8 are, independently, a C 1 to C 20 linear alkyl group, provided that at least one of R 2 and R 8 has at least 4 carbon atoms;

R 4 and R 10 are substituted or unsubstituted aryl groups;

M is a transition metal selected from Group 2, 3, or 4 of the Periodic Table;

T is a bridging group;

each X is an anionic leaving group;

each R1, R3, R5, R6, R7, R9, R11, R12, R13, and R 14 is, independently, hydrogen, a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;

wherein either or both of R 5 and R 6 and R 11 and R 12 optionally join together to form a ring structure; and

ii) a support having an average surface area of from about 400 to 800 m 2 /g support, an average pore diameter of from 60 to 200 Angstrom; and at least 20% of an incremental pore volume comprising pores having a pore diameter larger than 100 Angstrom;

and

iii) an aluminoxane having an aluminoxane loading of greater than about 7 mmol Al/g support;

wherein the catalyst system has an activity of at least 3,000 g polymer/g catalyst·hr when polymerizing propylene at 70° C. without adding H 2 .

39. An olefin polymerization catalyst system comprising:

i) a metallocene catalyst compound represented by the formula:

wherein R 2 and R 8 are both a C4 linear alkyl group;

R 4 and R 10 are substituted or unsubstituted aryl groups;

M is a transition metal selected from Group 2, 3, or 4 of the Periodic Table;

T is a bridging group;

each X is an anionic leaving group;

each R1, R3, R5, R6, R7, R9, R11, R12, R13, and R 14 is, independently, hydrogen, a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;

wherein either or both of R 5 and R 6 and R 11 and R 12 optionally join together to form a ring structure; and

ii) a support having an average surface area of from about 400 to 800 m 2 /g, an average pore diameter of from 60 to 200 Angstrom; and at least 20% of an incremental pore volume comprising pores having a pore diameter larger than 100 Angstrom;

and

iii) an aluminoxane having an aluminoxane loading of greater than about 7 mmol Al/g support.

40. The catalyst system of claim 14 , wherein the support has an aluminoxane loading of greater than about 7 mmol Al/g support.