Asymmetric
The present disclosure relates to asymmetric ansa-metallocene catalyst compounds that include at least one indenyl ligand substituted at the 3-position with a C 3 -C 40 α-branched alkyl, such as 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-ethylbutyl, 1,3-dimethylbutyl, 1-methyl-1-ethylbutyl, 1,1-diethylbutyl, 1-propylpentyl, and the like. Catalyst systems prepared with the catalyst compounds, polymerization methods using such catalyst systems, and polyolefins made using the polymerization methods are also described.
1. A catalyst compound represented by Formula (I):
where M is a group 4 metal,
R 3 is a C 3 -C 40 branched alkyl, wherein the branched alkyl group is branched at the α-position,
R 3′ is hydrogen, methyl, ethyl, or a group containing three or more carbon atoms having the formula CH 2 R′, where R′ is an alkyl, aryl, or silyl group;
each of R 2 , R 4 , R 5 , R 6 , R 7 , R 2′ , R 4′ , R 5′ , R 6′ , and R 7′ is independently hydrogen, a C 1 -C 40 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, alkoxyl, halogen, or siloxyl, or one or more of R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 4′ and R 5′ , R 5′ and R 6′ , and R 6′ and R 7′ are joined to form a completely saturated, partially saturated, or aromatic ring,
T is a bridging group, and
each X is independently a halide or C 1 -C 50 substituted or unsubstituted hydrocarbyl, hydride, amide, alkoxide, sulfide, phosphide, halide, or a combination thereof, or two of X are joined together to form a metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene.
2. The catalyst compound of claim 1 , wherein R 3 is a C 3 -C 40 branched alkyl represented by Formula (II):
where each R z and R x is, independently, a C 1 to C 20 alkyl group and R y is hydrogen or a C 1 to C 4 alkyl group, preferably a C 1 to C 2 alkyl group.
3. The catalyst compound of claim 1 , wherein T is represented by the formula R 8 2 J or (R 8 )J 2 , where each J is independently selected from C, Si, or Ge, and each R 8 is independently hydrogen, halogen, a C 1 to C 40 hydrocarbyl or a C 1 to C 40 substituted hydrocarbyl group, and two R 8 optionally form a cyclic structure including completely saturated, partially saturated, aromatic, or fused ring systems.
4. The catalyst compound of claim 2 , wherein R y is hydrogen.
5. The catalyst compound of claim 2 , wherein each R x , R y , and R z is different from any other R x , R y , and R z such that the catalyst compound has a chiral center on the α-carbon of R 3 .
6. The catalyst compound of claim 4 , wherein R z is n-propyl and R x is methyl.
7. The catalyst compound of claim 1 , wherein one or more of R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 4′ and R 5′ , R 5′ and R 6′ , and R 6′ and R 7′ are joined to form a completely saturated, partially saturated, or aromatic ring.
8. The catalyst compound of claim 7 , wherein R 5 and R 6 are joined to form a partially saturated 5-membered ring.
9. The catalyst compound of claim 1 , wherein R 3′ is methyl.
10. The catalyst compound of claim 1 , wherein each of R 2 , R 4 , R 5 , R 6 , R 7 , R 2′ , R 4′ , R 5′ , R 6′ , and R 7′ is hydrogen.
11. The catalyst compound of claim 10 , wherein R 3′ is methyl.
12. The catalyst compound of claim 1 , wherein J is Si and R 8 is a C 1 to C 40 hydrocarbyl or a C 1 to C 40 substituted hydrocarbyl group.
13. The catalyst compound of claim 1 , wherein each R 8 is a methyl group.
14. The catalyst compound of claim 1 , wherein M is Zr.
15. The catalyst compound of claim 1 , wherein each X is a halide.
16. The catalyst compound of claim 1 , wherein each X is chloride.
17. The catalyst compound of claim 1 , wherein the catalyst compound represented by Formula (I) corresponds to any one of the following structures:
18. A catalyst system comprising an activator and the catalyst compound of claim 1 .
19. A catalyst system according to claim 18 , wherein the catalyst system utilizes a single catalyst compound.
20. The catalyst system of claim 18 , wherein the catalyst system comprises a support material.
21. The catalyst system of claim 20 , wherein said support material is silica.
22. The catalyst system of claim 18 , wherein the activator comprises one or more of alumoxanes, aluminum alkyls, and ionizing activators.
23. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising:
contacting at least one olefin with the catalyst system of claim 18 ; and
obtaining a polyolefin.
24. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising:
contacting two or more different olefins with the catalyst system of claim 18 ; and
obtaining a polyolefin.
25. The method of claim 23 , wherein said at least one olefin is ethylene.
26. The method of claim 24 , wherein said two or more olefins are ethylene and 1-hexene.
27. The method of claim 23 , wherein said polyolefin has an Mw/Mn of about 3.0 to about 13.0.
28. The method according to claim 27 , wherein said polyolefin has an Mw/Mn of about 4.0 to about 13.0.
29. The method according to claim 28 , wherein said polyolefin has an Mw/Mn of about 6.0 to about 13.0.
30. The method of claim 23 , wherein said polyolefin is linear low density polyethylene.
31. The method of claim 23 , wherein said polyolefin has total unsaturation/1000 C greater than 0.25.
32. The method of claim 23 , wherein said polyolefin has g′ vis of about 0.9 to about 1.10.
33. The method of claim 23 , wherein said polyolefin has g′vis of from about 0.98 to 1.0.
34. The method of claim 23 , wherein said method is carried out in a gas phase or slurry process.
35. A catalyst system comprising an activator and the catalyst compound of claim 2 .
36. A catalyst system comprising an activator and the catalyst compound of claim 17 .
37. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising:
contacting at least one olefin with the catalyst system of claim 35 ; and
obtaining a polyolefin.
38. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising:
contacting at least one olefin with the catalyst system of claim 36 ; and
obtaining a polyolefin.
39. The catalyst system of claim 35 , wherein the catalyst system comprises a support material.
40. The catalyst system of claim 36 , claim 17 , wherein the catalyst system comprises a support material.
41. The method of claim 30 , wherein the is linear low density polyethylene is formed into a biaxially oriented film.
42. The method of claim 23 , wherein said polyolefin is formed into a biaxially oriented polyethylene film wherein said polyolefin is linear low density polyethylene.
43. The method of claim 23 , wherein the polyolefin produced herein has a multimodal composition distribution.