Catalyst systems and processes for poly alpha-olefin having high vinylidene content
A process for making a poly alpha-olefin (PAO) having a relatively high vinylidene content (or combined vinylidene and tri-substituted vinylene content) and a relatively low vinyl and/or di-substituted vinylene content, as well as a relatively low molecular weight. The process includes: contacting a feed containing a C 2 -C 32 alpha-olefin with a catalyst system comprising activator and a bis-cyclopentadienyl metallocene compound, typically a cyclopentadienyl-benzindenyl group 4 transition metal compound.
1. A process for making a poly alpha-olefin, PAO, the process comprising:
contacting a feed comprising a C 6 -C 32 alpha-olefin with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture comprising vinylidenes, tri-substituted vinylenes, optionally di-substituted vinylenes, and optionally vinyls; and
obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the unsaturated PAO product comprises vinylidenes, tri-substituted vinylenes, optionally di-substituted vinylenes, optionally vinyls,
wherein the conversion is about 10% or more and the polymerization reaction exhibits a selectivity toward greater than or equal to about 80 mol % vinylidenes, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes in the unsaturated PAO product,
wherein the metallocene compound is represented by formula (F-MC):
wherein:
R 2 is hydrogen and one of R 1 and R 3 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 6 hydrocarbyl group, and the other one of R 1 and R 3 is a hydrogen;
R 4 and R 5 taken together with the carbon atoms in the cyclopentadienyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annulated to the cyclopentadienyl ring;
R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a hydrogen, or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl, silylcarbyl, or germanyl group, and optionally at least three of R 12 , R 13 , R 14 , R 15 , and R 16 are not hydrogen;
M is a group 3, 4 or 5 transition metal having an integer coordination number of v; wherein v is 3, 4, or 5,
each X is independently a halogen, a hydride, an amide, an alkoxide, or a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties together form a fused ring or ring system; and
m is an integer equal to v−2.
2. The process of claim 1 wherein: the process comprises obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the polymerization reaction exhibits a selectivity toward greater than or equal to about 80 mol % vinylidenes, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes in the unsaturated PAO product; and
wherein the metallocene compound is represented by formula (I):
wherein:
R 6 , R 7 , R 17 , and R 18 are each independently hydrogen; a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl group; or R 6 and R 7 , R 7 and R 17 , or R 17 and R 18 , taken together with the carbon atoms in the indenyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annulated to the indenyl ring;
R 12 , R 13 , R 14 , and R 15 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;
R 16 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group or silylcarbyl group;
each X is independently a halogen, a hydride, an amide, an alkoxide, a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or ring system;
M is a group 3, 4 or 5 transition metal having an integer coordination number of v; and
m is an integer equal to v−2.
3. The process of claim 2 where in the conversion is 40% or more.
4. The process of claim 2 , wherein R 2 is hydrogen and at least one of R 1 and R 3 is not hydrogen.
5. The process of claim 1 , wherein:
one of R 1 and R 3 comprise an alpha carbon atom directly attached to the indenyl ring, a beta Group 14 atom attached to the alpha atom, and two or more, substituted or unsubstituted linear, branched, or cyclic C 1 -C 8 hydrocarbyl groups attached to the beta atom.
6. The process of claim 1 , wherein the metallocene compound is represented by formula (II):
wherein:
R 1 and R 2 are hydrogen;
R 23 and R 19 comprise carbon atoms;
R 20 , R 21 , and R 22 are independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group and at least two of R 20 , R 21 , and R 22 are independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;
R 6 , R 7 , R 17 , and R 18 are each independently hydrogen; a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl group; or R 6 and R 7 , R 7 and R 17 , or R 17 and R 18 , taken together with the carbon atoms in the indenyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annulated to the indenyl ring;
R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 8 hydrocarbyl group;
each X is independently a halogen, a hydride, an amide, an alkoxide, or a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or ring system;
M is a group 3, 4 or 5 transition metal having an integer coordination number of v; wherein v is 3, 4, or 5, and
m is an integer equal to v−2.
7. The process of claim 2 , wherein R 6 and R 7 , or R 7 and R 17 , or R 17 and R 18 , taken together with the respective carbon atoms in the indenyl ring to which they are directly connected, form a ring annulated to the indenyl ring.
8. The process of claim 7 wherein the ring annulated to the indenyl ring comprises one or more saturated carbon atoms.
9. The process of claim 1 wherein at least four of R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 8 hydrocarbyl group.
10. The process of claim 9 , wherein each of R 12 , R 13 , R 14 , R 15 and R 16 is independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 8 hydrocarbyl group.
11. The process of claim 2 , wherein:
i) at least three of R 12 , R 13 , R 14 , R 15 and R 16 are independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 8 hydrocarbyl group;
ii) two or more of R 12 , R 13 , R 14 , R 15 and R 16 when next to each other optionally form a fused ring or ring system;
iii) at least two of R 6 , R 7 , R 17 , and R 18 are hydrogen;
iv) each X is independently a halogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 6 hydrocarbyl group;
v) M comprises Zr or Hf;
or a combination thereof.
12. The process of claim 1 , wherein R 12 , R 13 , R 14 , R 15 and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 8 hydrocarbyl group.
13. The process of claim 1 , wherein the metallocene compound is represented by formula (I-B), (III-B), (IV-B), (VI), (VIII), (IX), (X), (XI), (XII), (XVIII), or (XIX):
wherein each X is independently a halogen, a hydride, an amide, an alkoxide, or a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or ring system;
M is Hf or Zr; and
m is 2.
14. The process of claim 13 wherein the metallocene is not represented by formula (I-B).
15. The process of claim 1 , wherein the polymerization reaction exhibits a selectivity toward a combination of greater than or equal to about 96.5 mol % vinylidenes, from 0.5 mol % to 3.5 mol % tri-substituted vinylenes, less than or equal to about 1.5 mol % di-substituted vinylenes, and less than or equal to about 1.5 mol % vinyls, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes in the unsaturated PAO product.
16. The process of claim 2 , wherein the polymerization reaction exhibits a selectivity toward a combination of vinylidenes of equal to or greater than 97.0 mol %; tri-substituted vinylenes of less than 2.1 mol %; di-substituted vinylenes of 0.5 mol % or less; and vinyls of 1.0 mol % or less, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes in the unsaturated PAO product.
17. The process of claim 1 , wherein the polymerization reaction exhibits a selectivity towards a combination of vinylidenes and tri-substituted vinylenes of collectively greater than 98.0 mol %, and a combination of di-substituted vinylenes and vinyls of collectively less than 2.0 mol %, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes in the unsaturated PAO product.
18. The process of claim 1 , wherein the polymerization reaction results in the unsaturated PAO product having a number average molecular weight (Mn) of 1500 g/mol or less, as measured by 1 H NMR.
19. The process of claim 1 , wherein the catalyst system further comprises a non-coordinating anion type activator, wherein the non-coordinating anion type activator comprises: N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbonium tetrakis(perfluorophenyl)borate, triphenylcarbonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)aluminate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)aluminate,
or combinations thereof.
20. The process of claim 1 , wherein:
the polymerization conditions comprise a reaction temperature from 40° C. to 150° C.;
an average activity level of at least 1200 g/s·mol;
the polymerization reaction mixture exhibits a yield of at least 10%;
or a combination thereof.
21. The process of claim 1 , further comprising:
a) contacting the unsaturated PAO product with hydrogen to convert at least a portion of the unsaturated PAO product to a hydrogenated PAO product;
b) contacting the unsaturated PAO product with a chemical reagent to convert at least a portion of the unsaturated PAO product to a functionalized PAO product;
or a combination thereof.
22. The process of claim 1 , further comprising any combination of C 2 -C 5 alpha-olefins in the alpha-olefin feed at no higher than 25 mol%, based on the total moles of the alpha-olefins supplied to the polymerization reactor.
23. The process of claim 1 wherein the unsaturated PAO product comprises dimer.
24. The process of claim 1 wherein the unsaturated PAO product is represented by the following formula (F-1):
where R 1 , R 2a , R 2b , R 3 , each of R 4 and R 5 , R 6 , and R 7 , the same or different at each occurrence, independently represents a hydrogen or a substituted or unsubstituted hydrocarbyl, and n is a non-negative integer corresponding to the degree of polymerization.
25. The process of claim 24 wherein where R 1 is not hydrogen, and both R 2a and R 2b are hydrogen and n is 0.
26. The process of claim 1 wherein the unsaturated PAO product is represented by the following formula (F-1):
where R 1 , R 2a , R 2b , R 3 , each of R 4 and R 5 , R 6 , and R 7 , the same or different at each occurrence, independently represents a hydrogen or a substituted or unsubstituted hydrocarbyl, and n is a non-negative integer corresponding to the degree of polymerization, where R 1 is not hydrogen, and both R 2a and R 2b are hydrogen and n is 0.
27. The process of claim 15 wherein the unsaturated PAO product is represented by the following formula (F-1):
where R 1 , R 2a , R 2b , R 3 , each of R 4 and R 5 , R 6 , and R 7 , the same or different at each occurrence, independently represents a hydrogen or a substituted or unsubstituted hydrocarbyl, and n is a non-negative integer corresponding to the degree of polymerization, where R 1 is not hydrogen, and both R 2a and R 2b are hydrogen and n is 0.
28. The process of claim 16 wherein the unsaturated PAO product is represented by the following formula (F-1):
where R 1 , R 2a , R 2b , R 3 , each of R 4 and R 5 , R 6 , and R 7 , the same or different at each occurrence, independently represents a hydrogen or a substituted or unsubstituted hydrocarbyl, and n is a non-negative integer corresponding to the degree of polymerization, where R 1 is not hydrogen, and both R 2a and R 2b are hydrogen and n is 0.
29. The process of claim 17 wherein the unsaturated PAO product is represented by the following formula (F-1):
where R 1 , R 2a , R 2b , R 3 , each of R 4 and R 5 , R 6 , and R 7 , the same or different at each occurrence, independently represents a hydrogen or a substituted or unsubstituted hydrocarbyl, and n is a non-negative integer corresponding to the degree of polymerization, where R 1 is not hydrogen, and both R 2a and R 2b are hydrogen and n is 0.
30. The process of claim 1 wherein the C 6 -C 32 alpha-olefin, the metallocene compound and the activator are contacted in the solution phase, bulk phase, or slurry phase in a continuous stirred tank reactor or a continuous tubular reactor.
31. The process of claim 1 wherein the process is carried out in a continuous operation, where feeds and catalyst system components are continuously and/or simultaneously added to a reactor so to maintain a constant ratio of catalyst system and feed olefins; and the reaction mixture is continuously withdrawn from the reactor.
32. The process of claim 1 wherein the process is carried out in a continuous operation, where feeds and catalyst system components are continuously and/or simultaneously added to a continuous stirred tank reactor so to maintain a constant ratio of catalyst system and feed olefins; and the reaction mixture is continuously withdrawn from the reactor.
33. The process of claim 1 wherein the process is a continuous processes.
34. The process of claim 1 wherein the process is a continuous processes which includes the steps of: a) continuously introducing a feed stream comprising at least 10 mol % of the one or more C 6 to C 24 alpha-olefins into a reactor, b) continuously introducing the metallocene compound and the activator into the reactor, and c) continuously withdrawing the PAO product from the reactor.
35. The process of claim 1 wherein the process is carried out in a continuous stirred tank reactor or plug flow reactor.
36. The process of claim 1 , wherein the feed comprises octene.
37. The process of claim 1 , wherein the feed comprises decene.
38. The process of claim 1 , wherein the feed comprises octene, decene and dodecene.
39. The process of claim 1 , wherein the feed comprises octene and dodecene.
40. The process of claim 1 , wherein the feed comprises a single alpha-C 6 -C 32 olefin monomer or a combination of two or more alpha-C 6 -C 32 olefin monomers.
41. The process of claim 1 , wherein the feed comprises a single alpha-olefin monomer selected from the group consisting of: hexene, heptene, octene, nonene, decene, dodecene, and tetradecene.
42. The process of claim 1 , wherein the feed comprises two or more alpha-olefin monomers selected from the group consisting of: hexene, heptene, octene, nonene, decene, dodecene, and tetradecene.
43. The process of claim 1 , wherein the PAO is a homopolymer of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene or 1-tetradecene.
44. The process of claim 1 , wherein the PAO is a copolymer of decene and one or more of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-undecene, 1-dodecene or 1-tetradecene.
45. The process of claim 1 , wherein the PAO is a copolymer of two or more of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene or 1-tetradecene.