Catalyst systems comprising multiple non-coordinating anion activators and methods for polymerization therewith
This invention relates to a method to polymerize olefins comprising contacting olefins with a catalyst system comprising a transition metal catalyst compound and: 1) at least two NCA activators represented by the formula: Z d + (A d- ), where Z is a Bronsted acid or a reducible Lewis acid, A d- is a boron containing NCA, d is 1, 2, or 3, and where Z is a Bronsted acid and Z is a reducible Lewis acid in the first and second NCA activators, respectively; or 2) at least two NCA activators, one as described in Formula I and one not as described in Formula I; or 3) two NCA activators as described in Formula I except that the N in the second NCA in the ArNHal is at a different position in the nitrogen containing aromatic ring than the N in the first NCA.
1. A method to polymerize olefins comprising contacting one or more olefins with a catalyst system comprising a transition metal catalyst compound and at least two boron containing non-coordinating anion “NCA” activators represented by the formula:
(Z + ) d l (A d- )
where: Z is (L-H) or a reducible Lewis acid; L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A d- is a boron containing non-coordinating anion having the charge d−; and d is 1, 2, or 3;
where in the first NCA activator Z is a Bronsted acid and in the second NCA activator Z is a reducible Lewis acid.
2. The method of claim 1 , wherein a polymer having multimodal molecular weight distribution is produced.
3. The method of claim 1 , wherein the Mw of the polymer produced using two or more NCAs is at least 10,000 g/mol less than the Mw of both of the polymers produced under the same conditions using the NCAs alone.
4. The method of claim 1 , wherein the olefins comprise ethylene and/or propylene.
5. The method of claim 1 , wherein the olefins are one or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene dodecene, and isomers thereof.
6. The method of claim 1 , wherein the reducible Lewis acid is represented by the formula: (Ph 3 C + ), where Ph is phenyl or phenyl substituted with a heteroatom, a C 1 to C 40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl.
7. The method of claim 1 , wherein in the second NCA activator (Z + ) d is triphenylcarbonium.
8. The method of claim 1 , wherein in the first NCA activator (Z + ) d is represented by the formula: (L-H) d + , wherein L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3.
9. The method of claim 7 , wherein (L-H) d + is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.
10. The method of claim 1 , wherein the anion component A d- is represented by the formula [M k+ Q n ] d- wherein k is 3; n is 1, 2, 3, 4, 5, or 6; n−k=d; M is boron; and Q is independently selected from hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide.
11. The method of claim 1 , wherein the two NCAs are [Ph 3 C + ][B(C 6 F 5 ) 4 − ] and [Me 3 NH + ][B(C 6 F 5 ) 4 − ] where Ph is phenyl and Me is methyl.
12. The method of claim 1 , wherein the reducible Lewis acid is represented by the formula: (Ar 3 C + ), where Ar is aryl or aryl substituted with a heteroatom, a C 1 to C 40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl.
13. A catalyst system comprising a transition metal catalyst compound and at least two boron containing non-coordinating anion “NCA” activators represented by the formula:
(Z + ) d (A d- )
where: Z is (L-H) or a reducible Lewis acid; L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A d- is a boron containing non-coordinating anion having the charge d−; and d is 1, 2, or 3;
where in the first NCA activator Z is a Bronsted acid and in the second NCA activator Z is a reducible Lewis acid.
14. The catalyst system of claim 13 , wherein the reducible Lewis acid is represented by the formula: (Ar 3 C + ), where Ar is aryl or aryl substituted with a heteroatom, a C 1 to C 40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl.
15. The catalyst system of claim 13 , wherein the reducible Lewis acid is represented by the formula: (Ph 3 C + ), where Ph is phenyl or phenyl substituted with a heteroatom, a C 1 to C 40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl.
16. The catalyst system of claim 13 , wherein, for the second NCA activators, (Z + ) d is triphenylcarbonium.
17. A method to polymerize olefins comprising contacting one or more olefins with a catalyst system comprising a transition metal catalyst compound and at least two non-coordinating anion “NCA” activators, where at least one NCA activator comprises an anion as described in Formula I and at least one NCA activator does not comprise an anion as described in Formula I, where Formula I is:
R n M(ArNHal) 4-n (I)
where R is a monoanionic ligand; M is a Group 13 metal or metalloid; ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together; and n is 0, 1, 2, or 3.
18. The method of claim 17 , wherein a polymer having multimodal molecular weight distribution is produced.
19. The method of claim 17 , wherein the olefins comprise ethylene and or propylene.
20. The method of claim 17 , wherein the olefins are one or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene dodecene, and isomers thereof.
21. The method of claim 17 , wherein R is selected from the group consisting of substituted or unsubstituted C 1 to C 30 hydrocarbyl aliphatic or aromatic groups, where substituted means that at least one hydrogen on a carbon atom is replaced with a hydrocarbyl, halide, halocarbyl, hydrocarbyl or halocarbyl substituted organometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido, alkylphosphido or other anionic substituent; fluoride; bulky alkoxides, where bulky means C 4 to C 20 hydrocarbyl groups; —SR 1 ; —NR 2 2 , and —PR 3 2 , where each R 1 , R 2 , or R 3 is independently a substituted or unsubstituted hydrocarbyl as defined above; or a C 1 to C 30 hydrocarbyl substituted organometalloid.
22. The method of claim 17 , wherein M is B or Al.
23. The method of claim 17 , wherein ArNHal is one or more of tetrafluoropyridine, hexafluoroquinoline, or hexafluoroisoquinoline.
24. The method of claim 17 , wherein the NCA that does not comprise an anion represented by Formula I is represented by the formula:
(Z + ) d (A d- )
where: Z is (L-H) or a reducible Lewis acid; L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A d- is a boron containing non-coordinating anion having the charge d−; and d is 1, 2, or 3.
25. The method of claim 24 , wherein (Z + ) d is triphenylcarbonium.
26. A catalyst system comprising a transition metal catalyst compound and at least two non-coordinating anion “NCA” activators, where at least one NCA activator comprises an anion as described in Formula I and at least one NCA activator does not comprise an anion as described in Formula I, where Formula I is:
R n M(ArNHal) 4-n (I)
where R is a monoanionic ligand; M is a Group 13 metal or metalloid; ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together; and n is 0, 1, 2, or 3.
27. The catalyst system of claim 26 , wherein the NCA that does not comprise an anion represented by Formula I is represented by the formula:
(Z + ) d (A d- )
where:
Z is (L-H) or a reducible Lewis acid; L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A d- is a boron containing non-coordinating anion having the charge d−; and d is 1, 2, or 3.
28. The catalyst system of claim 26 , wherein (Z + ) d is triphenylcarbonium.
29. The catalyst system of claim 26 , wherein M is B or Al.
30. The catalyst system of claim 26 , wherein ArNHal is one or more of tetrafluoropyridine, hexafluoroquinoline, or hexafluoroisoquinoline.
31. A method to polymerize olefins comprising contacting one or more olefins with a catalyst system comprising a transition metal catalyst compound and at least two non-coordinating anion “NCA” activators, where the two NCA activators each comprise anions as described in Formula I except that the N in the second NCA in the ArNHal is at a different position in the nitrogen containing aromatic ring than the N in the ArNHal of the first NCA, where Formula I is:
R n M(ArNHal) 4-n (I)
where R is a monoanionic ligand; M is a Group 13 metal or metalloid; ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together; and n is 0, 1, 2, or 3.
32. The method of claim 31 , wherein a polymer having multimodal molecular weight distribution is produced.
33. The method of claim 31 , wherein the olefins comprise ethylene and/or propylene.
34. The method of claim 31 , wherein the olefins are one or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene dodecene, and isomers thereof.
35. The method of claim 31 , wherein R is selected from the group consisting of substituted or unsubstituted C 1 to C 30 hydrocarbyl aliphatic or aromatic groups, where substituted means that at least one hydrogen on a carbon atom is replaced with a hydrocarbyl, halide, halocarbyl, hydrocarbyl or halocarbyl substituted organometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido, alkylphosphido or other anionic substituent; fluoride; bulky alkoxides, where bulky means C 4 to C 20 hydrocarbyl groups; —SR 1 ; —NR 2 2 , and —PR 3 2 , where each R 1 , R 2 , or R 3 is independently a substituted or unsubstituted hydrocarbyl as defined above; or a C 1 to C 30 hydrocarbyl substituted organometalloid.
36. The method of claim 31 , wherein M is B or Al.
37. The method of claim 21 , wherein ArNHal is one or more of tetrafluoropyridine, hexafluoroquinoline, or hexafluoroisoquinoline.
38. A catalyst system comprising a transition metal catalyst compound and at least two non-coordinating anion “NCA” activators, where the two NCA activators each comprise anions as described in Formula I except that the N in the second NCA in the ArNHal is at a different position in the nitrogen containing aromatic ring than the N in the ArNHal of the first NCA, where Formula I is:
R n M(ArNHal) 4-n (I)
where R is a monoanionic ligand; M is a Group 13 metal or metalloid; ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together; and n is 0, 1, 2, or 3.
39. The catalyst system of claim 38 , wherein M is B or Al.
40. The catalyst system of claim 38 , wherein ArNHal is one or more of tetrafluoropyridine, hexafluoroquinoline, or hexafluoroisoquinoline.
41. The method of claim 17 , wherein the two NCAs are triphenyl carbonium tetrakis(pentafluorophenyl)borate and triphenyl carbonium 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, where Ph is phenyl and Me is methyl.
42. The method of claim 17 , wherein the two NCAs are [Ph 3 C + ][B(C 6 F 5 ) 4 − ] and 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium.
43. The method of claim 17 , wherein the NCA activator comprising an anion represented by Formula I is represented by the formula:
[Z d ] + [R n M(ArNHal) 4-n ] −
where R is a monoanionic ligand; M is a Group 13 metal or metalloid; ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together; n is 0, 1, 2, or 3; Z is (L-H) or a reducible Lewis acid; L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3.
44. The catalyst system of claim 13 , wherein the two NCAs are [Ph 3 C + ][B(C 6 F 5 ) 4 − ] and [Me 3 NH + ][B(C 6 F 5 ) 4 − ] where Ph is phenyl and Me is methyl.
45. The method of claim 31 , wherein the NCA activators comprising an anion represented by Formula I are each independently represented by the formula:
[Z d ] + [R n M(ArNHal) 4-n ] −
where R is a monoanionic ligand; M is a Group 13 metal or metalloid; ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together; n is 0, 1, 2, or 3; Z is (L-H) or a reducible Lewis acid; L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3.