Metallocene catalyst compositions and polymerization process therewith
This invention relates bisindenyl metallocene catalyst compounds having long (at least 4 carbon atoms) linear alkyl groups substituted at the two position and substituted or unsubstituted aryl groups at the four position and process using such catalyst compounds, particularly in the solution process at higher temperatures.
1. A metallocene catalyst compound represented by the formula:
wherein:
R 2 and R 8 are, independently, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl,
R 4 is a phenyl group substituted at the 2′ position with an alkyl or aryl group,
R 10 is an aryl group substituted at the 3′ and 5′ positions with C 1 to a C 10 alkyl groups or aryl groups or combinations thereof and,
the 4′ position is H or optionally, substituted with a group selected from (XR′ n ) − , wherein X is a Group 14-17 heteroatom having an atomic weight of 13 to 79 and R′ is one of a hydrogen atom, halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group and n is 0, 1, 2, or 3,
M is a group transition 2, 3 or 4 metal,
T is a bridging group represented by the formula R 2 a J, where J is Si, and each R a is, independently, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl;
each X is an anionic leaving group, and
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, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents 1 wherein one of R 5 and R 6 or R 11 and R 12 join together to form a ring structure.
2. The metallocene catalyst compound of claim 1 , wherein M is Hf, Ti and/or Zr.
3. The metallocene catalyst compound of claim 1 , wherein the rac/meso ratio is 10:1 or greater.
4. The metallocene catalyst compound of claim 1 , wherein
R 10 is a phenyl group substituted at the 3′ and 5′ positions with C 1 to a C 10 alkyl groups or aryl groups or combinations thereof and optionally, the 4′ position is substituted with a group selected from (XR′ n ) − , wherein X is a Group 14-17 heteroatom having an atomic weight of 13 to 79 and R′ is one of a hydrogen atom, halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group and n is 0, 1, 2, or 3; and
M is Hf, Ti and/or Zr.
5. The metallocene catalyst compound of claim 4 , wherein the rac/meso ratio of the catalyst compound is 10:1 or greater.
6. A metallocene catalyst compound represented by:
7. A catalyst system comprising an activator and the metallocene compound of claim 1 , and optional a support.
8. The catalyst system of claim 1 , wherein the activator comprises alumoxane, non-coordinating anion activator, or alumoxane and a non-coordinating anion activator.
9. A catalyst system comprising activator, the metallocene compound claim of 4 , and an optional support.
10. A catalyst system comprising activator, the metallocene compound of claim 1 , and optional support; wherein
R 10 is a phenyl group substituted at the 3′ and 5′ positions with C 1 to a C 10 alkyl groups or aryl groups or combinations thereof and, optionally, the 4′ position is substituted with a group selected from (XR′ n ) − , wherein X is a Group 14-17 heteroatom having an atomic weight of 13 to 79 and R′ is one of a hydrogen atom, halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group and n is 0, 1, 2, or 3;
M is Hf, Ti and/or Zr.
11. A process to polymerize olefins comprising contacting one or more olefins with the catalyst system of claim 7 .
12. A process to polymerize olefins comprising contacting one or more olefins with the catalyst system of claim 9 .
13. A process to polymerize olefins comprising contacting one or more olefins with the catalyst system of claim 10 .