Dual metallocene catalyst systems for decreasing melt index and increasing polymer production rates
The present invention provides dual catalyst systems and polymerization processes employing these dual catalyst systems. The disclosed polymerization processes can produce olefin polymers at higher production rates, and these olefin polymers may have a higher molecular weight and/or a lower melt index.
1. An olefin polymerization process, the process comprising:
contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound,
wherein an amount of the olefin polymer produced per hour by the process is at least 10% greater than an amount of an olefin polymer obtained per hour under the same polymerization conditions without catalyst component II;
wherein a molar ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 6:1 to about 75:1;
wherein a melt index (MI) of the olefin polymer produced by the process is at least 10% less than a MI of an olefin polymer obtained under the same polymerization conditions without catalyst component II;
wherein catalyst component I comprises:
a compound having formula (C);
a compound having formula (D); or
any combination thereof, wherein:
formula (C) is
wherein:
M 3 is Zr or Hf;
X 4 and X 5 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH 4 ; OBR 2 or SO 3 R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
E 3 is a bridging group selected from:
a cyclic or heterocyclic bridging group having up to 18 carbon atoms,
a bridging group having the formula >E 3A R 7A R 8A , wherein E 3A is C or Si, and R 7A and R 8A are independently H or a hydrocarbyl group having up to 18 carbon atoms,
a bridging group having the formula —CR 7B R 8B —CR 7C R 8C —, wherein R 7B , R 8B , R 7C , and R 8C are independently H or a hydrocarbyl group having up to 10 carbon atoms, or
a bridging group having the formula —SiR 7D R 8D —SiR 7E R 8E —, wherein R 7D , R 8D , R 7E , and R 8E are independently H or a hydrocarbyl group having up to 10 carbon atoms;
R 9 and R 10 are independently H or a hydrocarbyl group having up to 18 carbon atoms; and
Cp 1 is a cyclopentadienyl or indenyl group, any substituent on Cp 1 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms; and
formula (D) is
wherein:
M 4 is Zr or Hf;
X 6 and X 7 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH 4 ; OBR 2 or SO 3 R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
E 4 is a bridging group selected from:
a cyclic or heterocyclic bridging group having up to 18 carbon atoms,
a bridging group having the formula >E 4A R 12A R 13A , wherein E 4A is C or Si, and R 12A and R 13A are independently H or a hydrocarbyl group having up to 18 carbon atoms,
a bridging group having the formula —CR 12B R 13B —CR 12C R 13C —, wherein R 12B , R 13B , R 12C , and R 13C are independently H or a hydrocarbyl group having up to 10 carbon atoms, or
a bridging group having the formula —SiR 12D R 13D —SiR 12E R 13E —, wherein R 12D , R 13D , R 12E , and R 13E are independently H or a hydrocarbyl group having up to 10 carbon atoms; and
R 14 ,R 15 ,R 16 , and R 17 are independently H or a hydrocarbyl group having up to 18 carbon atoms; and
wherein catalyst component II comprises:
a compound having the formula
or any combination thereof, wherein:
M 5 is Zr or Hf;
X 8 and X 9 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH 4 ; OBR 2 or SO 3 R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
Cp 2 and Cp 3 are independently a cyclopentadienyl or indenyl, any substituent on Cp 2 and Cp 3 is independently H or a hydrocarbyl group having up to 18 carbon atoms; and
E 5 is a bridging group having the formula —(CH 2 ) n —, wherein n is an integer from 2 to 8, inclusive.
2. The process of claim 1 , wherein the amount of the olefin polymer produced per hour by the process is from about 10% to about 40% greater than the amount of the olefin polymer obtained per hour under the same polymerization conditions without catalyst component II.
3. The process of claim 1 , wherein:
a melt index of the olefin polymer produced by the process is in a range from about 0.1 to about 5 g/10 min; or
a density of the olefin polymer produced by the process is in a range from about 0.89 to about 0.94 g/cm 3 ; or
both.
4. The process of claim 1 , wherein the polymerization process is conducted in the presence of hydrogen at a weight ratio of hydrogen to the olefin monomer in a range from about 10 ppm to about 200 ppm.
5. The process of claim 1 , wherein the activator-support comprises a solid oxide treated with an electron-withdrawing anion, wherein:
the solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; and
the electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, or any combination thereof.
6. The process of claim 1 , wherein the activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.
7. The process of claim 1 , wherein the organoaluminum compound 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.
8. The process of claim 1 , wherein the catalyst composition further comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.
9. The process of claim 1 , wherein catalyst component I comprises a compound having formula (C), and wherein:
X 4 and X 5 are independently F, Cl, Br, I, benzyl, phenyl, or methyl;
E 3 is a bridging group selected from:
a cyclopentyl or cyclohexyl group,
a bridging group having the formula >E 3A R 7A R 8A , wherein E 3A is C or Si, and R 7A and R 8A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl,
a bridging group having the formula —CR 7B R 8B —CR 7C R 8C —, wherein R 7B , R 8B , R 7C , and R 8C are independently H or methyl, or
a bridging group having the formula —SiR 7D R 8D —SiR 7E R 8E —, wherein R 7D , R 8D , R 7E , and R 8E are independently H or methyl; and
R 9 and R 10 are independently H or t-butyl.
10. The process of claim 1 , wherein catalyst component I comprises a compound having formula (D), and wherein:
X 6 and X 7 are independently F, Cl, Br, I, benzyl, phenyl, or methyl;
E 4 is a bridging group selected from:
a cyclopentyl or cyclohexyl group,
a bridging group having the formula >E 4A R 12A R 13A , wherein E 4A is C or Si, and R 12A and R 13A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl,
a bridging group having the formula —CR 12B R 13B —CR 12C R 13C —, wherein R 12B , R 13B , R 12C , and R 13C are independently H or methyl, or
a bridging group having the formula —SiR 12D R 13D —SiR 12E R 13E —, wherein R 12D , R 13D , R 12E , and R 13E are independently H or methyl; and
R 14 , R 15 , R 16 , and R 17 are independently H or t-butyl.
11. The process of claim 1 , wherein the catalyst composition comprises an activator-support; an organoaluminum compound; only one compound having formula (C) or formula (D); and only one compound selected from
or a compound having the formula
12. The process of claim 1 , wherein the process is conducted in a batch reactor, slurry reactor, gas-phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, or a combination thereof.
13. The process of claim 1 , wherein the olefin monomer is ethylene, and the olefin comonomer comprises propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.
14. An olefin polymerization process, the process comprising:
contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound,
wherein an amount of the olefin polymer produced per hour by the process is at least 10% greater than an amount of an olefin polymer obtained per hour under the same polymerization conditions without catalyst component II;
wherein a melt index (MI) of the olefin polymer produced by the process is at least 10% less than a MI of an olefin polymer obtained under the same polymerization conditions without catalyst component II;
wherein a molar ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 8:1 to about 15:1;
wherein catalyst component I comprises a metallocene compound having the formula:
wherein:
M is Zr or Hf;
X 1 and X 2 are independently F, Cl, Br, I, benzyl, phenyl, or methyl;
R 1 and R 2 are independently H or an alkyl, alkenyl, or aryl group having up to 12 carbon atoms;
R 3 and R 4 are independently H or an alkyl group having up to 12 carbon atoms; and
R 5 is H or an alkyl or alkenyl group having up to 12 carbon atoms;
wherein catalyst component II comprises:
or a combination thereof;
wherein the activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof; and
wherein the organoaluminum compound 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.
15. The process of claim 14 , wherein:
X 1 and X 2 are independently Cl, benzyl, phenyl, or methyl;
R 1 and R 2 are independently methyl, ethyl, propyl, butyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, benzyl, or phenyl;
R 3 and R 4 are independently H or t-butyl; and
R 5 is H, methyl, ethyl, propyl, butyl, ethenyl, propenyl, butenyl, pentenyl, or hexenyl.
16. The process of claim 14 , wherein the catalyst composition is contacted with ethylene and a comonomer comprising 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or a combination thereof.
17. The process of claim 16 , wherein:
catalyst component I is:
or a combination thereof; and
catalyst component II is:
18. An olefin polymerization process, the process comprising:
contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound,
wherein an amount of the olefin polymer produced per hour by the process is at least 10% greater than an amount of an olefin polymer obtained per hour under the same polymerization conditions without catalyst component II;
wherein a molar ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 6:1 to about 75:1;
wherein a weight-average molecular weight (Mw) of the olefin polymer produced by the process is at least 10% greater than a weight-average molecular weight (Mw) of an olefin polymer obtained under the same polymerization conditions without catalyst component II;
wherein catalyst component I comprises:
a compound having formula (C);
a compound having formula (D); or
any combination thereof, wherein:
formula (C)is
wherein:
M 3 is Zr or Hf;
X 4 and X 5 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH 4 ; OBR 2 or SO 3 R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
E 3 is a bridging group selected from:
a cyclic or heterocyclic bridging group having up to 18 carbon atoms,
a bridging group having the formula >E 3A R 7A R 8A , wherein E 3A is C or Si, and R 7A and R 8A are independently H or a hydrocarbyl group having up to 18 carbon atoms,
a bridging group having the formula —CR 7B R 8B —CR 7C R 8C —, wherein R 7B , R 8B , R 7C , and R 8C are independently H or a hydrocarbyl group having up to 10 carbon atoms, or
a bridging group having the formula —SiR 7D R 8D —SiR 7E R 8E —, wherein R 7D , R 8D , R 7E , and R 8E are independently H or a hydrocarbyl group having up to 10 carbon atoms;
R 9 and R 10 are independently H or a hydrocarbyl group having up to 18 carbon atoms; and
Cp 1 is a cyclopentadienyl or indenyl group, any substituent on Cp 1 is H or a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbon atoms; and
formula (D) is
wherein:
M 4 is Zr or Hf;
X 6 and X 7 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH 4 ; OBR 2 or SO 3 R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
E 4 is a bridging group selected from:
a cyclic or heterocyclic bridging group having up to 18 carbon atoms,
a bridging group having the formula >E 4A R 12A R 13A , wherein E 4A is C or Si, and R 12A and R 13A are independently H or a hydrocarbyl group having up to 18 carbon atoms,
a bridging group having the formula —CR 12B R 13B —CR 12C R 13C —, wherein R 12B , R 13B , R 12C , and R13C are independently H or a hydrocarbyl group having up to 10 carbon atoms, or
a bridging group having the formula —SiR 12D R 13D —SiR 12E R 13E —, wherein R 12D , R 13D , R 12E , and R 17 are independently H or a hydrocarbyl group having up to 10 carbon atoms; and
R 14 , R 15 , R 16 , and R 17 are independently H or a hydrocarbyl group having up to 18 carbon atoms; and
wherein catalyst component II comprises:
a compound having the formula
or any combination thereof, wherein:
M 5 is Zr or Hf;
X 8 and X 9 are independently F; Cl; Br; I; methyl; benzyl; phenyl; H; BH 4 ; OBR 2 or SO 3 R, wherein R is an alkyl or aryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilyl group, any of which having up to 18 carbon atoms;
Cp 2 and Cp 3 are independently a cyclopentadienyl or indenyl, any substituent on Cp 2 and Cp 3 is independently H or a hydrocarbyl group having up to 18 carbon atoms; and
E 5 is a bridging group having the formula —(CH 2 ) n —, wherein n is an integer from 2 to 8, inclusive.
19. The process of claim 18 , wherein:
the catalyst composition is contacted with ethylene and a comonomer comprising 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or a combination thereof;
the activator-support comprises a solid oxide treated with an electron-withdrawing anion; and
the molar ratio of catalyst component I to catalyst component II is in a range from about 8:1 to about 25:1.
20. The process of claim 19 , wherein:
a melt index of the olefin polymer produced by the process is in a range from about 0.1 to about 5 g/10 min; or
a density of the olefin polymer produced by the process is in a range from about 0.89 to about 0.94 g/cm 3 ; or
both.
21. The process of claim 20 , wherein:
catalyst component I comprises a metallocene compound having the formula:
wherein:
M is Zr or Hf;
X 1 and X 2 are independently F, Cl, Br, I, benzyl, phenyl, or methyl;
R 1 and R 2 are independently H or an alkyl, alkenyl, or aryl group having up to 12 carbon atoms;
R 3 and R 4 are independently H or an alkyl group having up to 12 carbon atoms; and
R 5 is H or an alkyl or alkenyl group having up to 12 carbon atoms;
the activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof; and
the organoaluminum compound 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.
22. The process of claim 21 , wherein the catalyst composition comprises the activator-support, the organoaluminum compound, only one compound having formula (A), and only one compound selected from:
or a compound having the formula
23. The process of claim 22 , wherein:
catalyst component I is:
and
catalyst component II is: