Catalyst composition and method for preparing polyethylene
Disclosed are metallocene compounds, catalyst compositions comprising at least one metallocene compound, processes for polymerizing olefins, methods for making catalyst compositions, olefin polymers and articles made from olefin polymers. In an aspect, a metallocene compound and catalyst composition are disclosed in which the metallocene contains at least one indenyl ligand, the indenyl ligand containing at least one halogenated substituent, such as a fluorinated substituent. These metallocene compounds and catalyst compositions can produce polyethylene having unexpectedly low levels of short chain branching.
1. A metallocene compound having the formula:
2. A metallocene compound having the formula:
3. A metallocene compound having the formula:
4. A catalyst composition for polymerizing olefins, the catalyst composition comprising:
a) a first metallocene compound having the formula:
wherein
M 1 is hafnium;
X 1 is an indenyl ligand which is substituted at the 1-position with a group selected independently from
X 2 is [1] an unsubstituted cyclopentadienyl ligand or an unsubstituted indenyl ligand, [2] a cyclopentadienyl ligand which is substituted with at least one hydrocarbyl substituent selected independently from a C 1 -C 12 alkyl or a C 2 -C 12 alkenyl, or [3] an indenyl ligand which is substituted at the 1-position with a group having the formula
wherein X 1 and X 2 are unbridged; and
X 3 and X 4 are each a chloride;
b) optionally, a co-catalyst comprising an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof; and
c) an activator comprising a solid oxide treated with an electron-withdrawing anion (activator-support), an organoboron compound, an organoborate compound, an ionizing ionic compound, an aluminoxane compound, or any combination thereof.
5. The catalyst composition according to claim 4 , wherein the first metallocene compound is selected from:
wherein R 1 is C 6 F 5 or R 1 is H;
wherein R 2 is H and R 3 is H; R 2 is CH 2 CH 2 CH═CH 2 and R 3 is H; R 2 is CH 2 CH 2 CH═CH 2 and R 3 is CH 3 ; R 2 is CH 2 CH═CH 2 and R 3 is H, or R 2 is CH 2 CH═CH 2 and R 3 is CH 3 ;
or
any combination thereof.
6. The catalyst composition according to claim 4 , wherein the catalyst composition further comprises:
d) a second metallocene compound having the formula:
wherein
M 2 is titanium, zirconium, or hafnium;
X 5 is an optionally substituted cyclopentadienyl, indenyl, or fluorenyl ligand, wherein the substituent is selected independently from a C 1 -C 12 hydrocarbyl group;
X 6 is an optionally substituted indenyl or fluorenyl ligand, wherein the substituent is selected independently from a C 1 -C 12 hydrocarbyl group or a C 1 -C 12 heterohydrocarbyl group;
wherein X 5 and X 6 are bridged by a bridging group selected from (>ER B 2 ) x or >BR B , wherein x is an integer from 1 to 3, E in each occurrence is selected independently from a carbon atom or a silicon atom, R B in each occurrence is selected independently from H or a C 1 -C 12 hydrocarbyl group, and wherein optionally, two R B moieties form a C 3 -C 6 cyclic group; and
X 7 and X 8 are independently selected from a halide, hydride, a C 1 -C 20 hydrocarbyl group, a C 1 -C 20 heterohydrocarbyl group, tetrahydroborate, or OBR A 2 or OSO 2 R A wherein R A is independently a C 1 -C 12 hydrocarbyl group.
7. The catalyst composition according to claim 6 , wherein
X 5 is unsubstituted or substituted with a C 1 -C 6 alkyl or C 2 -C 8 alkenyl group, and X 6 is substituted with two substituents selected independently from a C 1 -C 12 hydrocarbyl group; and
R B , in each occurrence, is selected independently from a C 1 -C 6 alkyl or C 2 -C 8 alkenyl group.
8. The catalyst composition according to claim 6 , wherein (>ER B 2 ) x is selected from (—CR B 2 CR B 2 —), (—SiR B 2 SiR B 2 —), (—CR B 2 SiR B 2 —), (—CR B 2 CR B 2 CR B 2 —), (—SiR B 2 CR B 2 CR B 2 —), (—CR B 2 SiR B 2 CR B 2 —), (—SiR B 2 CR B 2 SiR B 2 —), (—SiR B 2 SiR B 2 CR B 2 —), or (—SiR B 2 SiR B 2 SiR B 2 —).
9. A catalyst composition according to claim 6 , wherein (>ER B 2 ) x or >BR B is selected from >CMe 2 , >CPh 2 , >CHMe, >CHPh, >CH(tolyl), >CMeEt, >CMe(CH 2 CH 2 CH 3 ), >CMe(CH 2 CH 2 CH 2 CH 3 ), >CH(CH 2 CH 2 CH═CH 2 ), >CMe(CH 2 CH 2 CH═CH 2 ), >CEt(CH 2 CH 2 CH═CH 2 ), >CPh(CH 2 CH 2 CH═CH 2 ), >SiMe 2 , >SiPh 2 , >SiEt 2 , >Si(tolyl) 2 , (—CH 2 CH 2 —), (—CMe 2 CMe 2 -), (—CH 2 CH 2 CH 2 —), (—CH 2 SiMe 2 CH 2 —), (—CH 2 SiPh 2 CH 2 —), (—SiMe 2 SiMe 2 -), >BMe, >BEt, >BPh, or >B(tolyl).
10. A catalyst composition according to claim 6 , wherein the second metallocene is selected from a compound having the formula:
wherein:
M 4 is zirconium or hafnium;
X 5 in each occurrence is independently F, Cl, Br, I, H, methyl, benzyl, phenyl, or methoxy;
R D in each occurrence is selected independently from H, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 6 -C 10 aryl, C 7 -C 12 aralkyl, or C 1 -C 12 hydrocarbyloxide;
E 1 is C or Si;
R E in each occurrence is selected independently from H, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 6 -C 10 aryl, or C 7 -C 12 aralkyl; and
R F is selected from H, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 6 -C 10 aryl, or C 7 -C 12 aralkyl.
11. A catalyst composition according to claim 6 , wherein the second metallocene is selected from a compound having the formula:
wherein:
M 4 is zirconium or hafnium;
X 5 in each occurrence is independently Cl, Br, methyl, or benzyl;
R D in each occurrence is selected independently from H or t-butyl;
E 1 is C;
R E in a first occurrence is methyl or phenyl, and R E in a second occurrence is methyl, phenyl, or CH 2 CH 2 CH═CH 2 ; and
R F is H or CH 2 CH 2 CH 2 CH═CH 2 .
12. A catalyst composition according to claim 6 , wherein the second metallocene is selected from a compound having the formula:
13. The catalyst composition according to claim 4 , wherein the activator comprises a solid oxide treated with an electron-withdrawing anion, and wherein:
the solid oxide comprises silica, alumina, titania, zirconia, magnesia, boria, calcia, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, magnesium aluminate, titania-zirconia, mullite, boehmite, heteropolytungstates, or any combination thereof; and
the electron-withdrawing anion comprises fluoride, chloride, bromide, iodide, sulfate, bisulfate, fluorosulfate, phosphate, fluorophosphate, triflate, mesylate, tosylate, thiosulfate, C 1 -C 10 alkyl sulfonate, C 6 -C 14 aryl sulfonate, trifluoroacetate, fluoroborate, fluorozirconate, fluorotitanate, or any combination thereof.
14. A catalyst composition according to claim 4 , wherein the activator comprises a solid oxide treated with an electron-withdrawing anion selected from fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, phosphated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, phosphated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, phosphated silica-zirconia, fluorided mullite, chlorided mullite, bromided mullite, sulfated mullite, phosphated mullite, fluorided silica-coated alumina, chlorided silica-coated alumina, bromided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.
15. A catalyst composition according to claim 4 , wherein:
a) the optional co-catalyst has a general formula:
i) M 3 (X 10 ) n (X 11 ) 3-n , wherein M 3 is boron or aluminum and n is from 1 to 3 inclusive;
ii) M 4 (X 10 ) n (X 11 ) 2-n , wherein M 4 is magnesium or zinc and n is from 1 to 2 inclusive; or
iii) M 5 X 10 , wherein M 5 is Li;
b) X 10 is independently hydride or a C 1 to C 20 hydrocarbyl; and
c) X 11 is independently a halide, a hydride, a C 1 to C 20 hydrocarbyl, or a C 1 to C 20 hydrocarbyloxide.
16. A catalyst composition according to claim 4 , wherein the optional co-catalyst comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof.
17. The catalyst composition according to claim 4 , wherein the first metallocene compound has the formula:
18. The catalyst composition according to claim 4 , wherein the first metallocene compound has the formula:
19. The catalyst composition according to claim 4 , wherein the first metallocene compound has the formula:
20. The catalyst composition according to claim 4 , wherein the first metallocene compound has the formula:
21. The catalyst composition according to claim 4 , wherein the first metallocene compound has the formula:
22. The catalyst composition according to claim 4 , wherein the first metallocene compound has the formula:
23. The catalyst composition according to claim 4 , wherein the first metallocene compound has the formula:
24. The catalyst composition according to claim 4 , wherein the first metallocene compound has the formula:
25. The catalyst composition according to claim 4 , wherein the first metallocene compound has the formula:
26. A process for polymerizing olefins, the process comprising contacting at least one olefin monomer and the catalyst composition according to claim 4 under polymerization conditions to form an olefin polymer, wherein the at least one olefin monomer comprises ethylene or ethylene in combination with an olefin co-monomer selected from propylene, butene, pentene, hexene, heptene, octene, styrene, or a combination thereof.