Cyclopentadienyl-substituted salan catalysts
A cyclopentadienyl-substituted Salan catalyst, a catalyst system comprising an activator and the cyclopentadienyl-substituted Salan catalyst, a process comprising contacting one or more olefins with the catalyst system, and polymers produced by the process are disclosed herein.
1. A catalyst compound represented by the formula:
wherein each solid line represents a covalent bond and each arrow represents a bond having a varying degree of covalency and a varying degree of coordination;
wherein M is a Group 3, 4, 5 or 6 transition metal;
N 1 and N 2 are nitrogen;
O is oxygen;
each of X 1 and X 2 is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure, provided however when M is trivalent X 2 is not present;
wherein each of R* 1 and R* 2 independently comprises a bulky functional group, an electron withdrawing group, or a combination thereof, and wherein at least one of R* 1 and R* 2 independently comprises a cyclopentadienyl radical having the structure:
wherein C* indicates an attachment carbon of the radical;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof;
R 7 is a C 1 -C 40 hydrocarbyl radical or a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements; and
Y is a divalent C 1 to C 20 hydrocarbyl radical.
2. The catalyst compound of claim 1 , wherein each of R* 1 and R* 2 independently comprises a substituted or unsubstituted cyclopentadienyl radical, and wherein one of R* 1 and R* 2 independently comprises a substituted or unsubstituted cyclopentadienyl radical represented by the formula:
wherein C* indicates an attachment carbon of the radical;
wherein each of R 18 , R 19 , R 20 , R 21 , and R 22 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 19 , R 20 , R 21 , and R 22 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof.
3. The catalyst compound of claim 2 , wherein each of R 7 and R 18 is a C 1 -C 12 aliphatic radical or a phenyl radical.
4. The catalyst compound of claim 1 , wherein at least one of R* 1 and R* 2 independently comprises a substituted or unsubstituted C 4 -C 20 aliphatic radical or a C 4 -C 20 alicyclic radical.
5. The catalyst compound of claim 1 , wherein at least one of R* 1 and R* 2 independently comprises an electron withdrawing functional group comprising —NO 2 , —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —CN, —SO 3 H, —COOH, —CHO, —F, —Cl, —Br, —I, —COOR α , —COR α , —NR α 3 + , or a combination thereof, wherein each R α is independently hydrogen or a C 1 -C 20 alkyl radical.
6. The catalyst compound of claim 1 , wherein Y is a divalent cyclic, branched or linear C 1 to C 12 aliphatic radical.
7. The catalyst compound of claim 1 , wherein Y is selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene, undecylene, dodecylene, cyclohexylene, phenylene, and isomers thereof.
8. The catalyst compound of claim 1 , wherein Y is ethylene (—CH 2 CH 2 —), 1,2-cyclohexylene, 1,2-phenylene, or 2-benzylene.
9. The catalyst compound of claim 1 , wherein M is Hf, Ti, or Zr.
10. The catalyst compound of claim 1 , wherein each of X 1 and X 2 is, independently, a halogen or a C 1 to C 7 hydrocarbyl radical, provided however when M is trivalent, X 2 is not present.
11. The catalyst compound of claim 1 , wherein each of X 1 and X 2 is a benzyl radical, provided however when M is trivalent, X 2 is not present.
12. The catalyst compound of claim 1 , wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a halogen, or a C 1 to C 30 hydrocarbyl radical.
13. The catalyst compound of claim 1 , wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a halogen, or a C 1 to C 10 hydrocarbyl radical.
14. The catalyst compound of claim 1 , wherein at least one of R* 1 and R* 2 independently comprises a 6-membered aromatic ring.
15. The catalyst compound of claim 1 , wherein at least one of R* 1 and R* 2 independently comprises an indenyl ring system or a fluorenyl ring system.
16. The catalyst compound of claim 1 , wherein R 1 and R 12 are independently selected from the group consisting of methyl, trifluoromethyl and 2,2,2-trifluoroethyl, wherein at least one of R 1 and R 12 is trifluoromethyl or 2,2,2-trifluoroethyl.
17. The catalyst compound of claim 1 , represented by the formula:
wherein each R 39 and R 40 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, R 39 and R 40 join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof.
18. The catalyst compound of claim 1 , represented by the formula:
and wherein each of R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , and R 54 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , and R 54 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof.
19. A catalyst compound represented by the formula:
wherein each solid line represents a covalent bond and each arrow represents a bond having a varying degree of covalency and a varying degree of coordination;
wherein M is a Group 3, 4, 5 or 6 transition metal;
N 1 and N 2 are nitrogen;
O is oxygen;
each of X 1 and X 2 is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure, provided however when M is trivalent X 2 is not present;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 19 , R 20 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , and R 30 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 19 , R 20 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , and R 30 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof;
each R 7 and R 18 is, independently, a C 1 -C 40 hydrocarbyl radical or a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements; and
Y is a divalent C 1 to C 20 hydrocarbyl radical.
20. A catalyst compound represented by the formula:
wherein each solid line represents a covalent bond and each arrow represents a bond having a varying degree of covalency and a varying degree of coordination;
wherein M is a Group 3, 4, 5 or 6 transition metal;
N 1 and N 2 are nitrogen;
O is oxygen;
each of X 1 and X 2 is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure, provided however when M is trivalent X 2 is not present;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , and R 38 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , and R 38 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof;
each R 7 and R 18 is, independently, a C 1 -C 40 hydrocarbyl radical or a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements; and
Y is a divalent C 1 to C 20 hydrocarbyl radical.
21. The catalyst compound of claim 20 , wherein:
M is Zr or Hf;
X 1 and X 2 are benzyl radicals;
R 1 , R 5 , R 7 , R 12 , R 16 , and R 18 are methyl radicals;
R 2 , R 3 , R 4 , R 6 , R 13 , R 14 , R 15 , R 17 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , and R 38 are hydrogen; and
Y is ethylene (—CH 2 CH 2 —).
22. A catalyst system comprising:
an activator and a catalyst compound represented by the formula:
wherein each solid line represents a covalent bond and each arrow represents a bond having a varying degree of covalency and a varying degree of coordination;
wherein M is a Group 3, 4, 5 or 6 transition metal;
N 1 and N 2 are nitrogen;
O is oxygen;
each of X 1 and X 2 is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure, provided however when M is trivalent X 2 is not present;
wherein each of R* 1 and R* 2 independently comprises a bulky functional group, an electron withdrawing group, or a combination thereof, and wherein at least one of R* 1 and R* 2 independently comprises a cyclopentadienyl radical having the structure:
wherein C* indicates an attachment carbon of the radical;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 12 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof;
R 7 is a C 1 -C 40 hydrocarbyl radical or a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements; and
Y is a divalent C 1 to C 20 hydrocarbyl radical.
23. A process comprising:
contacting one or more olefins with a catalyst system at a temperature, a pressure, and for a period of time sufficient to produce a polyolefin;
the catalyst system comprising an activator and a catalyst compound represented by the formula:
wherein each solid line represents a covalent bond and each arrow represents a bond having a varying degree of covalency and a varying degree of coordination;
wherein M is a Group 3, 4, 5 or 6 transition metal;
N 1 and N 2 are nitrogen;
O is oxygen;
each of X 1 and X 2 is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure, provided however when M is trivalent X 2 is not present;
wherein each of R* 1 and R* 2 independently comprises a bulky functional group, an electron withdrawing group, or a combination thereof, and wherein at least one of R* 1 and R* 2 independently comprises a cyclopentadienyl radical having the structure:
wherein C* indicates an attachment carbon of the radical;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof;
R 7 is a C 1 -C 40 hydrocarbyl radical or a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements; and
Y is a divalent C 1 to C 20 hydrocarbyl radical.
24. The process of claim 23 , wherein the catalyst compound is according to one of formula I, formula II, or formula III,
formula I comprising:
wherein each of R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , and R 54 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , and R 54 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof;
formula II comprising:
wherein each R 7 and R 18 is, independently, a C 1 -C 40 hydrocarbyl radical or a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements; and
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 19 , R 20 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , and R 30 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 19 , R 20 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , and R 30 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof;
formula (III) comprising:
wherein each R 7 and R 18 is, independently, a C 1 -C 40 hydrocarbyl radical or a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements; and
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , and R 38 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , and R 38 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof.
25. The process of claim 23 , wherein the catalyst compound is disposed on a support.
26. The process of claim 23 wherein the polyolefin produced comprises an ethylene polymer having an Mw of at least 500,000 g/mol.
27. The process of claim 23 wherein the polyolefin produced comprises a propylene polymer having an isotacticity of at least 90%.
28. The process of claim 27 , wherein the propylene polymer has an Mw of at least 500,000 g/mol.