Metallocene compounds having appended Lewis acids and polymerization therewith
This invention relates to metallocene compounds represented by the formula: catalyst systems comprising said metallocene compound and an activator or a reaction product of the metallocene compound with the at least one activator, and polymerization processes using such metallocene compounds and activators, where Cp a and Cp b are optionally-substituted cyclopentadienyl rings; A is bridging group; q is zero or 1; Q is O, O(CR 3 R 4 ) m , (CR 3 R 4 ) m O, or (CR 3 R 4 ) m ; m is 0 to 18; Z is (CR 3 R 4 ) 2 ; LA is a Lewis acid; M is a transition metal; X 1 and X 2 are independently R 5 or OR 5 ; R 1 and R 2 are independently selected from optionally-substituted hydrocarbyl groups; R 3 and R 4 are independently selected from the group consisting of H, halogen, and an optionally-substituted hydrocarbyl group; and R 5 is alkyl, aryl, perfluoroalkyl, or perfluoroaryl.
1. A metallocene compound represented by the formula:
wherein:
Cp a and Cp b are optionally-substituted cyclopentadienyl rings;
A is an optional bridging group linking Cp a to Cp b ;
q is zero or 1;
Q is O, O(CR 3 R 4 ) m , (CR 3 R 4 ) m O, or (CR 3 R 4 ) m , and m is an integer ranging from 0 to about 18;
Z is (CR 3 R 4 ) 2 ;
LA is a Lewis acid;
M is a transition metal haptically bonded to Cp a and Cp b ;
X 1 and X 2 are independently R 5 or OR 5 ;
wherein R 1 and R 2 are independently selected from a first optionally-substituted hydrocarbyl group having 1 to about 20 carbon atoms, the first optionally-substituted hydrocarbyl group being linear, branched, saturated, unsaturated, aliphatic, aromatic, cyclic, or acyclic;
wherein R 3 and R 4 are independently selected from the group consisting of H, halogen, and second optionally-substituted hydrocarbyl group having 1 to about 20 carbon atoms, the second optionally-substituted hydrocarbyl group being linear, branched, saturated, unsaturated, aliphatic, aromatic, cyclic, or acyclic; and
wherein when X 1 or X 2 is R 5 , then R 5 is alkyl, perfluoroalkyl, or perfluoroaryl, and when X 1 or X 2 is OR 5 , then R 5 in the OR 5 is alkyl, aryl, perfluoroalkyl, or perfluoroaryl.
2. The composition of claim 1 , wherein M is Zr or Hf, and LA is Al or B.
3. The composition of claim 2 , wherein q is 1, and A is an alkylene or a silylene group.
4. The composition of claim 3 , wherein X 1 and X 2 are pentafluorophenoxy.
5. The composition of claim 1 , wherein q is 1 and A is SiR 6 R 7 ; wherein R 6 and R 7 are independently a third optionally-substituted hydrocarbyl group having 1 to about 20 carbon atoms, the third optionally-substituted hydrocarbyl group being linear, branched, saturated, unsaturated, aliphatic, aromatic, cyclic, acyclic.
6. The composition of claim 5 , wherein X 1 and X 2 are pentafluorophenoxy.
7. The composition of claim 5 , wherein Q is (CH 2 ) m and Z is (CH 2 ) 2 , and m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
8. The composition of claim 7 , wherein m ranges from 0, 1, 2, 3, or 4.
9. The composition of claim 8 , wherein M is Hf.
10. The composition of claim 2 , wherein Q is (CH 2 ) m and Z is (CH 2 ) 2 , and m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
11. The composition of claim 10 , wherein m is 0, 1, 2, 3 or 4.
12. The composition of claim 10 , wherein X 1 and X 2 are pentafluorophenoxy.
13. The composition of claim 10 , wherein M is Hf.
14. A catalyst composition comprising: at least one activator; and a metallocene compound represented by the formula:
or a reaction product of the metallocene compound with the at least one activator;
wherein:
Cp a and Cp b are optionally-substituted cyclopentadienyl rings;
q is zero or 1;
A is an optional bridging group linking Cp a to Cp b ;
Q is O, O(CR 3 R 4 ) m , (CR 3 R 4 ) m O, or (CR 3 R 4 ) m , and m is an integer ranging from 0 to about 18;
Z is (CR 3 R 4 ) 2 ;
LA is a Lewis acid;
M is a transition metal haptically bonded to Cp a and Cp b ;
X 1 and X 2 are independently R 5 or OR 5 ;
wherein R 1 and R 2 are independently selected from a first optionally-substituted hydrocarbyl group having 1 to about 20 carbon atoms, the first optionally-substituted hydrocarbyl group being linear, branched, saturated, unsaturated, aliphatic, aromatic, cyclic, or acyclic;
wherein R 3 and R 4 are independently selected from the group consisting of H, halogen, and a second optionally-substituted hydrocarbyl group having 1 to about 20 carbon atoms, the second optionally-substituted hydrocarbyl group being linear, branched, saturated, unsaturated, aliphatic, aromatic, cyclic, or acyclic; and
wherein when X 1 or X 2 is R 5 , then R 5 is alkyl, perfluoroalkyl, or perfluoroaryl, and when X 1 or X 2 is OR 5 , then R 5 in the OR 5 is alkyl, aryl, perfluoroalkyl, or perfluoroaryl.
15. The catalyst composition of claim 14 , wherein the at least one activator comprises an alumoxane.
16. The catalyst composition of claim 14 , wherein the at least one activator comprises methylalumoxane.
17. The catalyst composition of claim 14 , wherein the catalyst composition is disposed on a solid support.
18. The catalyst composition of claim 15 , wherein M is Zr or Hf, and LA is Al or B.
19. The catalyst composition of claim 18 , wherein q is 1 and is an alkylene or a silylene group.
20. The catalyst composition of claim 19 , wherein X 1 and X 2 are pentafluorophenoxy.
21. The catalyst composition of claim 14 , wherein q is 1 and A is SiR 6 R 7 ; wherein R 6 and R 7 are independently third optionally-substituted hydrocarbyl group having 1 to about 20 carbon atoms, the third optionally-substituted hydrocarbyl group being linear, branched, saturated, unsaturated, aliphatic, aromatic, cyclic, or acyclic.
22. The catalyst composition of claim 21 , wherein X 1 and X 2 are pentafluorophenoxy.
23. The catalyst composition of claim 21 , wherein Q is (CH 2 ) m and Z is (CH 2 ) 2 , and m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
24. The catalyst composition of claim 23 , wherein m is 0, 1, 2, 3, or 4.
25. The catalyst composition of claim 21 , wherein M is Hf.
26. The catalyst composition of claim 15 , wherein Q is (CH 2 ) m and Z is (CH 2 ) 2 , and m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
27. The catalyst composition of claim 26 , wherein m is 0, 1, 2, 3, or 4.
28. The catalyst composition of claim 26 , wherein X 1 and X 2 are pentafluorophenoxy.
29. The catalyst composition of claim 26 , wherein M is Hf.
30. A method comprising: providing an olefinic feed; and contacting the catalyst composition of claim 14 with the olefinic feed under polymerization reaction conditions.
31. The method of claim 30 , wherein the polymerization reaction conditions include hydrogen gas.
32. The method of claim 30 , wherein the catalyst composition is disposed upon a solid support.
33. The catalyst composition of claim 15 , wherein the catalyst composition is disposed on a solid support.
34. The method of claim 30 , wherein: the at least one activator comprises an alumoxane; the catalyst composition is disposed on a solid support; M is Zr or Hf, LA is Al or B.
35. The method of claim 34 wherein X 1 and X 2 are pentafluorophenoxy.
36. The method of claim 34 wherein q is 1, A is an alkylene or a silylene group and Q is (CH 2 ) m and Z is (CH 2 ) 2 , and m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
37. The method of claim 34 , wherein q is 1 and A is SiR 6 R 7 ; wherein R 6 and R 7 are independently a third optionally-substituted hydrocarbyl group having 1 to about 20 carbon atoms, the third optionally-substituted hydrocarbyl group being linear, branched, saturated, unsaturated, aliphatic, aromatic, cyclic, or acyclic.
38. A metallocene compound represented by Formulas 6, 7, 8 and 9, wherein M=Zr or Hf, LA is Al or B; and R 1 and R 2 are independently selected from an optionally-substituted hydrocarbyl group having 1 to about 20 carbon atoms, the optionally-substituted hydrocarbyl group being linear, branched, saturated, unsaturated, aliphatic, aromatic, cyclic, or acyclic:
39. The metallocene of claim 38 , wherein M is Hf, LA is Al, and R 1 and R 2 are isobutyl.
40. The metallocene of claim 38 , where in M is Hf, LA is B, and R 1 and R 2 are pentafluorophenyl.