[미국특허]
Nano-linked heteronuclear metallocene catalyst compositions and their polymer products
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/642
C08F-004/6592
B01J-031/22
C07F-017/00
출원번호
US-0398142
(2012-02-16)
등록번호
US-8426536
(2013-04-23)
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 :
1인용 특허 :
71
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 (IA)=(IB); wherein: (IA) is (IB) is wherein:X1, X2, X13, and X14 independently are hydrogen; BH4; a halide; a hydrocarbyl group, hydrocarbyloxide group, hydrocarbyloxylate group, hydrocarbylamino group, or hydrocarbylsilyl group, any of which h
1. A dinuclear metallocene compound having the formula (IA)=(IB); wherein: (IA) is (IB) is wherein:X1, X2, X13, and X14 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 and X15 independently are a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X3 and X15 independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;X4 and X16 independently are a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X4 and X16 other than an alkenyl linking group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;M1 and M4 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;with the proviso that (IA) is not the same as (IB). 2. The compound of claim 1, wherein: X1, X2, X13, and X14 independently are Cl, a methyl group, a phenyl group, or a benzyl group; andeach n independently is 0, 1, 2, 3, 4, 5, or 6. 3. The compound of claim 2, wherein: X3 and X15 independently are a substituted or unsubstituted cyclopentadienyl group;X4 and X16 independently are a substituted cyclopentadienyl or substituted indenyl group;M1 and M4 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 a catalyst composition with an olefin monomer and an optional olefin comonomer under polymerization conditions to produce an olefin polymer, wherein: the catalyst composition comprises a contact product of the dinuclear metallocene compound of claim 1; an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an activator-support, or any combination thereof; and an optional organoaluminum compound. 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 (IIA)=(IIB); wherein: (IIA) is (IIB) is wherein:X5, X6, X17, and X18 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 and X19 independently are a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X7 and X19 other than a bridging group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;X8 and X20 independently are a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X8 and X20 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 and A3 independently are 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 and A3 independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;M2 and M5 independently are Zr, Hf, or Ti;each E independently 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;with the proviso that (IIA) is not the same as (IIB). 11. The compound of claim 10, wherein: X5, X6, X17, and X18 independently are Cl, a methyl group, a phenyl group, or a benzyl group;A1 and A3 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. 12. The compound of claim 11, wherein: X7 and X19 independently are substituted fluorenyl groups;X8 and X20 independently are a substituted cyclopentadienyl group or substituted indenyl group;M2 and M5 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 a catalyst composition with an olefin monomer and an optional olefin comonomer under polymerization conditions to produce an olefin polymer, wherein: the catalyst composition comprises a contact product of the dinuclear metallocene compound of claim 10; an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an activator-support, or any combination thereof; and an optional organoaluminum compound. 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 (IIIA)=(IIIB); wherein: (IIIA) is (IIIB) is wherein:X9, X10, X21, and X22 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;X11, X12, X23, and X24 independently are a substituted cyclopentadienyl, indenyl, or fluorenyl group, any substituents on X11, X12, X23, and X24 other than a bridging group independently are a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group;A2 and A4 independently are 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 and A4 other than an alkenyl linking group independently are a hydrogen atom, or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;M3 and M6 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;with the proviso that (IIIA) is not the same as (IIIB). 20. The compound of claim 19, wherein: X9, X10, X21, and X22 independently are Cl, a methyl group, a phenyl group, or a benzyl group;A2 and A4 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: at least one of X11 and X12 is a substituted fluorenyl group;at least one of X23 and X24 is a substituted fluorenyl group;M3 and M6 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 a catalyst composition with an olefin monomer and an optional olefin comonomer under polymerization conditions to produce an olefin polymer, wherein: the catalyst composition comprises a contact product of the dinuclear metallocene compound of claim 19; an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an activator-support, or any combination thereof; and an optional organoaluminum compound. 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. 28. The process of claim 7, wherein the catalyst composition is contacted with ethylene and a comonomer selected from 1-butene, 1-hexene, 1-octene, or a combination thereof. 29. The process of claim 16, wherein the catalyst composition is contacted with ethylene and a comonomer selected from 1-butene, 1-hexene, 1-octene, or a combination thereof. 30. The process of claim 25, wherein the catalyst composition is contacted with ethylene and a comonomer selected from 1-butene, 1-hexene, 1-octene, or a combination thereof.
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상세보기
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