Catalyst systems and polymerization processes for using the same
Catalyst systems including more than one metallocene catalysts and processes for using the same are provided to produce polyolefin polymers such as polyethylene polymers.
1. A catalyst system comprising the product of the combination of:
(i) a first metallocene catalyst represented by the formula (A):
wherein:
M is Hf or Zr;
each R 1 and R 4 is independently hydrogen, an alkoxide or a C 1 to C 40 substituted or unsubstituted hydrocarbyl group;
each R 2 , R 3 , and R 8 is independently hydrogen, an alkoxide, a C 1 to C 40 substituted or unsubstituted hydrocarbyl group, —CH 2 —SiR′ 3 , or —CH 2 —CR′ 3 , wherein each R′ is independently hydrogen or a C 1 to C 20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not hydrogen and at least one of R 2 and R 3 is —CH 2 —SiR′ 3 or —CH 2 —CR′ 3 ;
each R 7 and R 10 is independently hydrogen, an alkoxide or a C 1 to C 40 substituted or unsubstituted hydrocarbyl group;
R 9 is —CH 2 —SiR′ 3 or —CH 2 —CR′ 3 ;
T is a bridging group; and
each X is, independently, a univalent anionic ligand, two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand;
(ii) a second metallocene catalyst represented by the formula (B):
V v Cp m M 6 G n X 5 q (B),
wherein:
M 6 is a Group 4 metal;
each Cp is, independently, a substituted or unsubstituted cyclopentadienyl group;
G is a heteroatom group represented by the Formula JR* z , wherein J is N, P, O or S, and R* is a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms and z is 1 or 2;
V is a bridging group and y is 0 or 1;
X 5 is a leaving group; and
m=1 or 2, n=0, 1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the metal;
(iii) at least one activator; and
(iv) optionally, at least one support.
2. The catalyst system of claim 1 , wherein M 6 is Hf or Zr and M and M 6 are the same or different.
3. The catalyst system of claim 1 , wherein R 9 and R 3 are, independently, —CH 2 —SiR′ 3 or —CH 2 —CR′ 3 .
4. The catalyst system of claim 1 , wherein R 3 is hydrogen, an alkoxide or a C 1 to C 40 substituted or unsubstituted hydrocarbyl group.
5. The catalyst system of claim 1 , wherein first metallocene catalyst comprises at least 50% racemic compounds.
6. The catalyst system of claim 1 , wherein R 9 and R 3 or R 2 are, independently, —CH 2 —CMe 3 , or —CH 2 —SiMe 3 .
7. The catalyst system of claim 1 , wherein T of the first metallocene is a bridging group comprising a group 14 atom and one or more of a C 1 -C 10 linear hydrocarbyl group or substituted hydrocarbyl group.
8. The catalyst system of claim 1 , wherein each Cp is a cyclopentadiene, indene or fluorene, which may be substituted or unsubstituted, M 6 is zirconium, and each X 5 is, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.
9. The catalyst system of claim 1 , wherein y is 1, m is 1 or 2, n is 1, J is N, and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.
10. The catalyst system of claim 1 , wherein the second metallocene catalyst comprises bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)hafnium dichloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl, bis(1-methyl-3-phenylcyclopentadienyl)zirconium dichloride, bis(1-methyl-3-phenylcyclopentadienyl)zirconium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl, bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dimethyl, bis(tetrahydro-1-indenyl)zirconium dichloride, bis(tetrahydro-1-indenyl)zirconium dimethyl, (n-propyl cyclopentadienyl)(pentamethyl cyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl) (pentamethyl cyclopentadienyl)zirconium dimethyl, rac/meso-(1-ethylindenyl)zirconium dichloride, rac/meso-(1-ethylindenyl)zirconium dimethyl, rac/meso-(1-methylindenyl)zirconium dichloride, rac/meso-(1-methylindenyl)zirconium dimethyl, rac/meso-(1-propylindenyl)zirconium dichloride, rac/meso-(1-propylindenyl)zirconium dimethyl, rac/meso-(1-butylindenyl)zirconium dichloride, rac/meso-(1-butylindenyl)zirconium dimethyl, meso-(1-ethylindenyl) zirconium dichloride, meso-(1-ethylindenyl) zirconium dimethyl, (1-methylindenyl)(pentamethylcyclopentadienyl) zirconium dichloride, (1-methylindenyl)(pentamethyl cyclopentadienyl) zirconium dimethyl, or a mixture thereof.
11. The catalyst system of claim 1 , wherein the second metallocene catalyst comprises rac/meso-(1-ethylindenyl)zirconium dichloride, rac/meso-(1-ethylindenyl)zirconium dimethyl, rac/meso-(1-methylindenyl)zirconium dichloride, rac/meso-(1-methylindenyl)zirconium dimethyl, rac/meso-(1-propylindenyl)zirconium dichloride, rac/meso-(1-propylindenyl)zirconium dimethyl, rac/meso-(1-butylindenyl)zirconium dichloride, rac/meso-(1-butylindenyl)zirconium dimethyl, meso-(1-ethylindenyl) zirconium dichloride, meso-(1-ethylindenyl) zirconium dimethyl, (1-methylindenyl)(pentamethyl cyclopentadienyl) zirconium dichloride, (1-methylindenyl)(pentamethyl cyclopentadienyl) zirconium dimethyl, or a mixture thereof.
12. The catalyst system of claim 1 , wherein the at least one activator comprises an alumoxane, an aluminum alkyl, an ionizing activator, or a mixture thereof.
13. The catalyst system of claim 1 , wherein the at least one activator comprises methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, isobutylalumoxane, alkylalumoxane, modified alkylalumoxane, or a mixture thereof.
14. The catalyst system of claim 1 , wherein the at least one support is present and comprises talc, clay, silica, alumina, silica-alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thoria, aluminum phosphate gel, polyvinylchloride, substituted polystyrene, functionalized or crosslinked organic supports, polystyrene divinyl benzene, graphite, or a mixture thereof.
15. A polymerization process to produce a polyethylene polymer, the process comprising contacting the catalyst system of claim 1 with ethylene and, optionally, one or more C 3 -C 10 alpha-olefin comonomers, under polymerizable conditions to produce the polyethylene polymer.
16. The process of claim 15 , wherein the polymerization process is a gas phase fluidized bed process, a solution phase process, a high pressure process, a slurry phase process, or a combination thereof.
17. The process of claim 15 , wherein the polymerization process is a gas phase fluidized bed polymerization process and further comprises an inert condensing agent.
18. The process of claim 17 , wherein the inert condensing agent comprises n-butane, isobutane, n-pentane, neopentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, or a mixture thereof.
19. The process of claim 15 , wherein the polymerization process occurs in a single reactor.
20. The process of claim 15 , wherein the polyethylene polymer has a density of from 0.890 g/cm 3 to 0.950 g/cm 3 .
21. The process of claim 15 , wherein the polyethylene polymer has a density of from 0.910 g/cm 3 to 0.930 g/cm 3 .
22. The process of claim 15 , wherein the polyethylene polymer has a melt index (I 2 ) of from 0.10 g/10 min to 10 g/10 min.
23. The process of claim 15 , wherein the polyethylene polymer has a melt index (I 2 ) of from 0.50 g/10 min to 5 g/10 min.
24. The process of claim 15 , wherein the polyethylene polymer has a melt index ratio (I 21 /I 2 ) of from 5 to 65.
25. The process of claim 15 , wherein the polyethylene polymer has a melt index ratio (I 21 /I 2 ) of from 20 to 45.