[미국특허]
Nano-linked heteronuclear metallocene catalyst compositions and their polymer products
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/64
C08F-004/642
C08F-004/6592
B01J-031/22
출원번호
US-0034036
(2011-02-24)
등록번호
US-8143430
(2012-03-27)
발명자
/ 주소
Murray, Rex E.
Jayaratne, Kumudini C.
Yang, Qing
Martin, Joel L.
Glass, Gary L.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould P.C.
인용정보
피인용 횟수 :
8인용 특허 :
69
초록
The present invention provides polymerization catalyst compositions employing novel heterodinuclear metallocene compounds. Methods for making these new dinuclear metallocene compounds and for using such compounds in catalyst compositions for the polymerization of olefins are also provided.
대표청구항▼
1. A dinuclear metallocene compound having the formula: wherein: X1, X2, X5, and X6 independently are hydrogen; BH4; a halide; a hydrocarbyl group, hydrocarbyloxide group, hydrocarbyloxylate group, hydrocarbylamino group, or hydrocarbylsilyl group, any of which having up to 20 carbon atoms; or OBRA
1. A dinuclear metallocene compound having the formula: wherein: X1, X2, X5, and X6 independently are hydrogen; BH4; a halide; a hydrocarbyl group, hydrocarbyloxide group, hydrocarbyloxylate group, hydrocarbylamino group, or hydrocarbylsilyl group, any of which having up to 20 carbon atoms; or OBRA2 or SO3RA, wherein RA is an alkyl group or aryl group having up to 12 carbon atoms;X3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X3 independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;X4 is a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X4 other than an alkenyl linking group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;X7 is a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X7 other than a bridging group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;X8 is a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X8 other than a bridging group and an alkenyl linking group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;A1 is a substituted or unsubstituted bridging group comprising either a cyclic group of 5 to 8 carbon atoms, a bridging chain of 2 to 5 carbon atoms, or a carbon, silicon, germanium, tin, boron, nitrogen, or phosphorus bridging atom, any substituents on A1 independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;M1 and M2 independently are Zr, Hf, or Ti;E is carbon or silicon;each RX, RY, and RZ independently is a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; andeach n independently is an integer in a range from 0 to 12, inclusive. 2. The compound of claim 1, wherein: X1, X2, X5, and X6 independently are Cl, a methyl group, a phenyl group, or a benzyl group;A1 comprises a carbon bridging atom, a silicon bridging atom, or a bridging chain of 2 to 5 carbon atoms; andeach n independently is 0, 1, 2, 3, 4, 5, or 6. 3. The compound of claim 2, wherein: X3 is a substituted or unsubstituted cyclopentadienyl group;X4 is a substituted cyclopentadienyl or substituted indenyl group;X7 is a substituted fluorenyl group;X8 is a substituted cyclopentadienyl group or substituted indenyl group;M1 and M2 independently are Zr or Hf; andeach RX, RY, and RZ independently is a hydrogen atom or a methyl group. 4. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 1 and an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. 5. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 1 and an activator-support, wherein the activator-support comprises a solid oxide treated with an electron-withdrawing anion, and wherein: the solid oxide comprises silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; andthe electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, or any combination thereof. 6. The catalyst composition of claim 5, further comprising an organoaluminum compound, 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. 7. A process for polymerizing olefins, the process comprising contacting the catalyst composition of claim 5 and an optional organoaluminum compound with an olefin monomer and an optional olefin comonomer under polymerization conditions to produce an olefin polymer. 8. The process of claim 7, wherein the olefin monomer comprises 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 mixtures thereof. 9. The process of claim 7, wherein the process is conducted in a polymerization reactor system comprising a slurry reactor, a loop slurry reactor, a gas phase reactor, a fluidized bed reactor, a solution reactor, a tubular reactor, an autoclave reactor, or any combination thereof. 10. A dinuclear metallocene compound having the formula: wherein: X1, X2, X9, and X10 independently are hydrogen; BH4; a halide; a hydrocarbyl group, hydrocarbyloxide group, hydrocarbyloxylate group, hydrocarbylamino group, or hydrocarbylsilyl group, any of which having up to 20 carbon atoms; or OBRA2 or SO3RA, wherein RA is an alkyl group or aryl group having up to 12 carbon atoms;X3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X3 independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;X4 is a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X4 other than an alkenyl linking group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;X11 and X12 independently are a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X11 and X12 other than a bridging group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;A2 is a substituted bridging group comprising either a silicon bridging atom, a germanium bridging atom, a tin bridging atom, a carbon bridging atom, or a bridging chain of 2 to 5 carbon atoms, any substituents on A2 other than the alkenyl linking group independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;M1 and M3 independently are Zr, Hf, or Ti;each RX, RY, and RZ independently is a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; andeach n independently is an integer in a range from 0 to 12, inclusive. 11. The compound of claim 10, wherein: X1, X2, X9, and X10 independently are Cl, a methyl group, a phenyl group, or a benzyl group;A2 comprises a carbon bridging atom, a silicon bridging atom, or a bridging chain of 2 to 5 carbon atoms; andeach n independently is 0, 1, 2, 3, 4, 5, or 6. 12. The compound of claim 11, wherein: X3 is a substituted or unsubstituted cyclopentadienyl group;X4 is a substituted cyclopentadienyl or substituted indenyl group;at least one of X11 and X12 is a substituted fluorenyl group;M1 and M3 independently are Zr or Hf; andeach RX, RY, and RZ independently is a hydrogen atom or a methyl group. 13. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 10 and an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. 14. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 10 and an activator-support, wherein the activator-support comprises a solid oxide treated with an electron-withdrawing anion, and wherein: the solid oxide comprises silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; andthe electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, or any combination thereof. 15. The catalyst composition of claim 14, further comprising an organoaluminum compound, 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. 16. A process for polymerizing olefins, the process comprising contacting the catalyst composition of claim 14 and an optional organoaluminum compound with an olefin monomer and an optional olefin comonomer under polymerization conditions to produce an olefin polymer. 17. The process of claim 16, wherein the olefin monomer comprises 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 mixtures thereof. 18. The process of claim 16, wherein the process is conducted in a polymerization reactor system comprising a slurry reactor, a loop slurry reactor, a gas phase reactor, a fluidized bed reactor, a solution reactor, a tubular reactor, an autoclave reactor, or any combination thereof. 19. A dinuclear metallocene compound having the formula: wherein: X5, X6, X9, and X10 independently are hydrogen; BH4; a halide; a hydrocarbyl group, hydrocarbyloxide group, hydrocarbyloxylate group, hydrocarbylamino group, or hydrocarbylsilyl group, any of which having up to 20 carbon atoms; or OBRA2 or SO3RA, wherein RA is an alkyl group or aryl group having up to 12 carbon atoms;X7, X11, and X12 independently are a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X7, X11, and X12 other than a bridging group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;X8 is a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X8 other than a bridging group and an alkenyl linking group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;A1 is a substituted or unsubstituted bridging group comprising either a cyclic group of 5 to 8 carbon atoms, a bridging chain of 2 to 5 carbon atoms, or a carbon, silicon, germanium, tin, boron, nitrogen, or phosphorus bridging atom, any substituents on A1 independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;A2 is a substituted bridging group comprising either a silicon bridging atom, a germanium bridging atom, a tin bridging atom, a carbon bridging atom, or a bridging chain of 2 to 5 carbon atoms, any substituents on A2 other than the alkenyl linking group independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;M2 and M3 independently are Zr, Hf, or Ti;E is carbon or silicon;each RX, RY, and RZ independently is a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; andeach n independently is an integer in a range from 0 to 12, inclusive. 20. The compound of claim 19, wherein: X5, X6, X9, and X10 independently are Cl, a methyl group, a phenyl group, or a benzyl group;A1 and A2 independently comprise a carbon bridging atom, a silicon bridging atom, or a bridging chain of 2 to 5 carbon atoms; andeach n independently is 0, 1, 2, 3, 4, 5, or 6. 21. The compound of claim 20, wherein: X7 is a substituted fluorenyl group;X8 is a substituted cyclopentadienyl group or substituted indenyl group;at least one of X11 and X12 is a substituted fluorenyl group;M2 and M3 independently are Zr or Hf; andeach RX, RY, and RZ independently is a hydrogen atom or a methyl group. 22. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 19 and an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. 23. A catalyst composition comprising a contact product of the dinuclear metallocene compound of claim 19 and an activator-support, wherein the activator-support comprises a solid oxide treated with an electron-withdrawing anion, and wherein: the solid oxide comprises silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; andthe electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, or any combination thereof. 24. The catalyst composition of claim 23, further comprising an organoaluminum compound, 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. 25. A process for polymerizing olefins, the process comprising contacting the catalyst composition of claim 23 and an optional organoaluminum compound with an olefin monomer and an optional olefin comonomer under polymerization conditions to produce an olefin polymer. 26. The process of claim 25, wherein the olefin monomer comprises 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 mixtures thereof. 27. The process of claim 25, wherein the process is conducted in a polymerization reactor system comprising a slurry reactor, a loop slurry reactor, a gas phase reactor, a fluidized bed reactor, a solution reactor, a tubular reactor, an autoclave reactor, or any combination thereof.
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상세보기
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