Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching
This invention relates to catalyst compositions, methods, and polymers encompassing at least one Group 4 metallocene compound comprising bridging η 5 -cyclopentadienyl-type ligands, typically in combination with at least one cocatalyst, and at least one activator. The compositions and methods disclosed herein provide ethylene polymers with low levels of long chain branching.
1. A process for polymerizing olefins, the process comprising:
contacting an olefin monomer and an optional comonomer with a catalyst composition under polymerization conditions to form a polymer;
wherein the catalyst composition comprises a contact product of: a) at least one ansa-metallocene; b) optionally, at least one organoaluminum compound; and c) at least one activator, wherein:
a) the at least one ansa-metallocene comprises a compound having the formula:
(X 1 )(X 2 )(X 3 )(X 4 )M 1 , wherein
M 1 is titanium, zirconium, or hafnium;
(X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;
one substituent on (X 1 ) and (X 2 ) is a bridging group having the formula ER 1 R 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group;
at least one substituent on (X 1 ) is a substituted or an unsubstituted alkenyl group having up to 20 carbon atoms;
at least one substituent on (X 2 ) is an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; or a halide;
(X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR A 2 or SO 3 R A , wherein R A is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and
any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen;
b) the at least one organoaluminum compound comprises a compound having the formula:
Al(X 5 ) n (X 6 ) 3−n ,
wherein (X 5 ) is a hydrocarbyl having from 1 to 20 carbon atoms; (X 6 ) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive; and
c) the at least one activator is selected independently from:
i) an activator-support selected from a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-exchangeable activator-support, or any combination thereof;
ii) an organoboron compound or an organoborate compound; or
iii) a combination thereof;
wherein the at least one organoaluminum compound is optional when at least one of (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 .
2. The process of claim 1 , wherein the olefin monomer is ethylene.
3. The process of claim 2 , wherein the comonomer is 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-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-hexene, 1-octene, 1-decene, or styrene.
4. The process of claim 1 , wherein the process is conducted in a slurry reactor, a gas phase reactor, a solution reactor, a high pressure tubular reactor, a high pressure autoclave reactor, or a combination thereof.
5. The process of claim 1 , wherein:
a) the at least one ansa-metallocene comprises a compound having the formula:
M 1 is zirconium or hafnium;
X is, independently, F, Cl, Br, or I;
E is C or Si;
R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group;
R 3A and R 3B are independently H or methyl;
n is an integer from 0 to 10, inclusive; and
R 4A and R 4B are independently an aliphatic group, an aromatic group, a cyclic group, or a combination of aliphatic and cyclic groups, any of which having from 1 to 12 carbon atoms;
b) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-isopropylaluminum, tri-n-butylaluminum, tri-sec-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; and
c) the at least one activator comprises a solid oxide treated with an electron-withdrawing anion, wherein
the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, or zinc oxide, a mixed oxide thereof, or any combination thereof; and
the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, or substituted or unsubstituted alkylsulfate, or any combination thereof.
6. The process of claim 1 , wherein:
a) the at least one ansa-metallocene comprises a compound having the formula:
M 1 is zirconium or hafnium;
X is F, Cl, Br, or I;
E is C or Si;
R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group;
R 3A and R 3B are independently H, methyl, allyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl;
n is 1 or 2; and
R 4A and R 4B are independently an aliphatic group, an aromatic group, a cyclic group, or a combination of aliphatic and cyclic groups, any of which having from 1 to 12 carbon atoms;
b) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-isopropylaluminum, tri-n-butylaluminum, tri-sec-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof; and
c) the at least one activator is an activator-support selected from bromided alumina, chlorided alumina, fluorided alumina, sulfated alumina, phosphated alumina, bromided silica-alumina, chlorided silica-alumina, fluorided silica-alumina, sulfated silica-alumina, bromided silica-zirconia, chlorided silica-zirconia, fluorided silica-zirconia, sulfated silica-zirconia, fluorided aluminophosphate, or any combination thereof.
7. The process of claim 1 , wherein:
a) the at least one ansa-metallocene comprises a compound having the formula:
M 1 is zirconium or hafnium;
X is Cl, Br, or I;
E is C or Si;
R 1 and R 2 are independently methyl or phenyl, wherein at least one of R 1 and R 2 is phenyl;
R 3A and R 3B are independently H or methyl;
n is an integer from 0 to 10, inclusive; and
R 4A and R 4B are t-butyl;
b) the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof; and
c) the at least one activator comprises a sulfated solid oxide.
8. The process of claim 1 , wherein the at least one ansa-metallocene is:
9. A process for polymerizing olefins, the process comprising:
contacting an olefin monomer and an optional comonomer with a catalyst composition under polymerization conditions to form a polymer;
wherein the catalyst composition comprises a contact product of: a) at least one ansa-metallocene; and b) at least one activator, wherein:
a) the at least one ansa-metallocene comprises a compound having the formula:
(X 1 )(X 2 )(X 3 )(X 4 )M 1 , wherein
M 1 is titanium, zirconium, or hafnium;
(X 1 ) and (X 2 ) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;
one substituent on (X 1 ) and (X 2 ) is a bridging group having the formula ER 1 R 2 , wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X 1 ) and (X 2 ), and wherein R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group;
at least one substituent on (X 1 ) is a substituted or an unsubstituted alkenyl group having up to 20 carbon atoms;
at least one substituent on (X 2 ) is an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; or a halide;
(X 3 ) and (X 4 ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; 4) OBR A 2 or SO 3 R A , wherein R A is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; wherein at least one of (X 3 ) and (X 4 ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; and
any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms; a halide; or hydrogen; and
b) the at least one activator is selected independently from:
i) an activator-support selected from a solid oxide treated with an electron-withdrawing anion, a layered mineral, an ion-exchangeable activator-support, or any combination thereof;
ii) an organoaluminoxane compound;
iii) an organoboron compound or an organoborate compound; or
iv) any combination thereof.
10. The process of claim 9 , wherein the olefin monomer is ethylene.
11. The process of claim 10 , wherein the comonomer is 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-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-hexene, 1-octene, 1-decene, or styrene.
12. The process of claim 9 , wherein the process is conducted in a slurry reactor, a gas phase reactor, a solution reactor, a high pressure tubular reactor, a high pressure autoclave reactor, or a combination thereof.
13. The process of claim 9 , wherein:
a) the at least one ansa-metallocene comprises a compound having the formula:
M 1 is zirconium or hafnium;
X is, independently, H, BH 4 , methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH 2 CMe 2 Ph; CH 2 SiMe 2 Ph; CH 2 CMe 2 CH 2 Ph; or CH 2 SiMe 2 CH 2 Ph;
E is C or Si;
R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group;
R 3A and R 3B are independently H or methyl;
n is an integer from 0 to 10, inclusive; and
R 4A and R 4B are independently an aliphatic group, an aromatic group, a cyclic group, or a combination of aliphatic and cyclic groups, any of which having from 1 to 12 carbon atoms; and
b) the at least one activator comprises a solid oxide treated with an electron-withdrawing anion, wherein
the solid oxide is silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, or zinc oxide, a mixed oxide thereof, or any combination thereof; and
the electron-withdrawing anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted arenesulfonate, or substituted or unsubstituted alkylsulfate, or any combination thereof.
14. The process of claim 9 , wherein:
a) the at least one ansa-metallocene comprises a compound having the formula:
M 1 is zirconium or hafnium;
X is, independently, H, BH 4 , methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH 2 CMe 2 Ph; CH 2 SiMe 2 Ph; CH 2 CMe 2 CH 2 Ph; or CH 2 SiMe 2 CH 2 Ph;
E is C or Si;
R 1 and R 2 are independently an alkyl group or an aryl group, either of which having up to 10 carbon atoms, or hydrogen, wherein at least one of R 1 and R 2 is an aryl group;
R 3A and R 3B are independently H, methyl, allyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl;
n is 1 or 2; and
R 4A and R 4B are independently an aliphatic group, an aromatic group, a cyclic group, or a combination of aliphatic and cyclic groups, any of which having from 1 to 12 carbon atoms;
b) the at least one activator is an activator-support selected from bromided alumina, chlorided alumina, fluorided alumina, sulfated alumina, phosphated alumina, bromided silica-alumina, chlorided silica-alumina, fluorided silica-alumina, sulfated silica-alumina, bromided silica-zirconia, chlorided silica-zirconia, fluorided silica-zirconia, sulfated silica-zirconia, fluorided aluminophosphate, or any combination thereof.
15. The process of claim 9 , wherein:
a) the at least one ansa-metallocene comprises a compound having the formula:
M 1 is zirconium or hafnium;
X is, independently, H, BH 4 , methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH 2 CMe 2 Ph; CH 2 SiMe 2 Ph; CH 2 CMe 2 CH 2 Ph; or CH 2 SiMe 2 CH 2 Ph;
E is C or Si;
R 1 and R 2 are independently methyl or phenyl, wherein at least one of R 1 and R 2 is phenyl;
R 3A and R 3B are independently H or methyl;
n is an integer from 0 to 10, inclusive; and
R 4A and R 4B are t-butyl; and
b) the at least one activator comprises a sulfated solid oxide.
16. A process for polymerizing olefins, the process comprising:
contacting an olefin monomer and an optional comonomer with a catalyst composition under polymerization conditions to form a polymer;
wherein the catalyst composition comprises a contact product of: a) at least one ansa-metallocene; b) optionally, at least one organoaluminum compound; and c) at least one activator, wherein:
a) the ansa-metallocene has the formula:
M 2 is Zr or Hf;
(R 5A ) and (R 5B ) are independently a hydrocarbyl group or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or hydrogen;
n is an integer from 0 to 10, inclusive; and
(X 3A ) and (X 4A ) are independently: 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms; or 4) OBR A 2 or SO 3 R A , wherein R A is an alkyl group or an aryl group, any of which having up to 12 carbon atoms;
b) the at least one organoaluminum compound comprises a compound having the formula:
Al(X 5 ) n (X 6 ) 3−n ,
wherein (X 5 ) is a hydrocarbyl having from 1 to 20 carbon atoms; (X 6 ) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride; and n is a number from 1 to 3, inclusive; and
c) the at least one activator is selected independently from:
i) an activator-support selected from a solid oxide treated with an electron-withdrawing anion, a layered mineral, and an ion-exchangeable activator-support, or any combination thereof;
ii) an organoaluminoxane compound;
iii) an organoboron compound or an organoborate compound; or
iv) any combination thereof,
wherein the at least one organoaluminum compound is optional when: 1) at least one of (X 3A ) and (X 4A ) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH 4 ; 2) the at least one activator comprises an organoaluminoxane compound; or 3) both conditions 1 and 2 are present.
17. The process of claim 16 , wherein the olefin monomer is ethylene.
18. The process of claim 17 , wherein the comonomer is 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-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-hexene, 1-octene, 1-decene, or styrene.
19. The process of claim 16 , wherein the process is conducted in a slurry reactor, a gas phase reactor, a solution reactor, a high pressure tubular reactor, a high pressure autoclave reactor, or a combination thereof.
20. The process of claim 16 , wherein the at least one ansa-metallocene is: