[미국특허]
Half-metallocene catalyst compositions and their polymer products
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/02
C08F-004/642
C08F-004/6592
B01J-031/22
출원번호
US-0949022
(2010-11-18)
등록번호
US-8110640
(2012-02-07)
발명자
/ 주소
McDaniel, Max P.
Thorn, Matthew G.
Benham, Elizabeth A.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould P.C.
인용정보
피인용 횟수 :
14인용 특허 :
67
초록▼
The present invention provides polymerization catalyst compositions employing half-metallocene compounds with a heteroatom-containing ligand bound to the transition metal. Methods for making these hybrid metallocene compounds and for using such compounds in catalyst compositions for the polymerizati
The present invention provides polymerization catalyst compositions employing half-metallocene compounds with a heteroatom-containing ligand bound to the transition metal. Methods for making these hybrid metallocene compounds and for using such compounds in catalyst compositions for the polymerization and copolymerization of olefins are also provided.
대표청구항▼
1. A catalyst composition comprising a contact product of at least one hybrid metallocene compound and at least one activator-support, wherein: the at least one hybrid metallocene compound has the formula: wherein:M is Zr, Hf, or Ti;X1 and X2 independently are a halide or a substituted or unsubstit
1. A catalyst composition comprising a contact product of at least one hybrid metallocene compound and at least one activator-support, wherein: the at least one hybrid metallocene compound has the formula: wherein:M is Zr, Hf, or Ti;X1 and X2 independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;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 aliphatic, aromatic, or cyclic group, or a combination thereof;X4 is —O—RA, wherein RA is an aryl group substituted with at least one alkenyl substituent, any substituents on RA other than the at least one alkenyl substituent independently are a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group; andthe at least one activator-support comprises a solid oxide treated with an electron-withdrawing anion, wherein:the solid oxide is silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, any mixed oxides thereof, or any mixture thereof; andthe electron-withdrawing anion is fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, or any combination thereof. 2. The catalyst composition of claim 1, wherein each substituent on X3 independently is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a n-butyl group, a t-butyl group, or a hexyl group. 3. The catalyst composition of claim 1, wherein the at least one alkenyl substituent on RA is an ethenyl, propenyl, butenyl, pentenyl, or hexenyl group. 4. The catalyst composition of claim 1, wherein RA is substituted with one alkenyl substituent and with a methyl, ethyl, propyl, n-butyl, t-butyl, methoxy, ethoxy, propoxy, or butoxy group. 5. The catalyst composition of claim 1, wherein the at least one activator-support is 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, or any combination thereof. 6. The catalyst composition of claim 1, wherein the catalyst composition further comprises at least one organoaluminum compound having the formula: Al(X5)m(X6)3-m; wherein: X5 is a hydrocarbyl;X6 is an alkoxide or an aryloxide, a halide, or a hydride; andm is from 1 to 3, inclusive. 7. The catalyst composition of claim 1, wherein: M is Zr or Ti;X1 and X2 independently are a methyl group, a phenyl group, a benzyl group, or a halide;X3 is a substituted or unsubstituted cyclopentadienyl or indenyl group; andRA is substituted with an ethenyl, propenyl, butenyl, pentenyl, or hexenyl group; anda methyl, ethyl, propyl, n-butyl, t-butyl, methoxy, ethoxy, propoxy, or butoxy group. 8. The catalyst composition of claim 7, wherein the catalyst composition further comprises at least one organoaluminum compound, and wherein the at least one organoaluminum compound is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, diethylaluminum ethoxide, tri-n-butylaluminum, diisobutylaluminum hydride, triisobutylaluminum, diethylaluminum chloride, or any combination thereof. 9. A process for polymerizing olefins comprising contacting the catalyst composition of claim 1 with at least one olefin monomer and optionally at least one olefin comonomer under polymerization conditions to produce a polymer or copolymer. 10. The process of claim 9, wherein the catalyst composition and the at least one olefin monomer and the optional at least one olefin comonomer are contacted in a gas phase reactor, a loop reactor, or a stirred tank reactor. 11. The process of claim 9, wherein the at least one olefin monomer comprises ethylene, propylene, or styrene. 12. The process of claim 9, wherein: M is Zr or Ti;X1 and X2 independently are a methyl group, a phenyl group, a benzyl group, or a halide;X3 is a substituted or unsubstituted cyclopentadienyl or indenyl group; andRA is substituted with an ethenyl, propenyl, butenyl, pentenyl, or hexenyl group; anda methyl, ethyl, propyl, n-butyl, t-butyl, methoxy, ethoxy, propoxy, or butoxy group; andthe at least one activator-support is 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, or any combination thereof. 13. The process of claim 12, wherein the catalyst composition further comprises at least one organoaluminum compound having the formula: Al(X5)m(X6)3-m; wherein: X5 is a hydrocarbyl;X6 is an alkoxide or an aryloxide, a halide, or a hydride; andm is from 1 to 3, inclusive. 14. A catalyst composition comprising a contact product of at least one hybrid metallocene compound and at least one activator, wherein: the at least one hybrid metallocene compound has the formula: wherein:M is Zr, Hf, or Ti;X1 and X2 independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof;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 aliphatic, aromatic, or cyclic group, or a combination thereof;X4 is —O—RA, wherein RA is an aryl group substituted with at least one alkenyl substituent, any substituents on RA other than the at least one alkenyl substituent independently are a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, or alkoxy group; andthe at least one activator is at least one aluminoxane compound, at least one organoboron or organoborate compound, at least one ionizing ionic compound, or any combination thereof. 15. The catalyst composition of claim 14, wherein the catalyst composition further comprises at least one organoaluminum compound having the formula: Al(X5)m(X6)3-m; wherein: X5 is a hydrocarbyl;X6 is an alkoxide or an aryloxide, a halide, or a hydride; andm is from 1 to 3, inclusive. 16. The catalyst composition of claim 14, wherein: M is Zr or Ti;X1 and X2 independently are a methyl group, a phenyl group, a benzyl group, or a halide;X3 is a substituted or unsubstituted cyclopentadienyl or indenyl group; andRA is substituted with an ethenyl, propenyl, butenyl, pentenyl, or hexenyl group; anda methyl, ethyl, propyl, n-butyl, t-butyl, methoxy, ethoxy, propoxy, or butoxy group. 17. The catalyst composition of claim 16, wherein the catalyst composition further comprises at least one organoaluminum compound, and wherein the at least one organoaluminum compound is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, diethylaluminum ethoxide, tri-n-butylaluminum, diisobutylaluminum hydride, triisobutylaluminum, diethylaluminum chloride, or any combination thereof. 18. A process for polymerizing olefins comprising contacting the catalyst composition of claim 14 with at least one olefin monomer and optionally at least one olefin comonomer under polymerization conditions to produce a polymer or copolymer. 19. The process of claim 18, wherein the catalyst composition and the at least one olefin monomer and the optional at least one olefin comonomer are contacted in a gas phase reactor, a loop reactor, or a stirred tank reactor. 20. The process of claim 18, wherein the at least one olefin monomer comprises ethylene, propylene, or styrene. 21. The process of claim 18, wherein: M is Zr or Ti;X1 and X2 independently are a methyl group, a phenyl group, a benzyl group, or a halide;X3 is a substituted or unsubstituted cyclopentadienyl or indenyl group; andRA is substituted with an ethenyl, propenyl, butenyl, pentenyl, or hexenyl group; anda methyl, ethyl, propyl, n-butyl, t-butyl, methoxy, ethoxy, propoxy, or butoxy group. 22. The process of claim 21, wherein the catalyst composition further comprises at least one organoaluminum compound having the formula: Al(X5)m(X6)3-m; wherein: X5 is a hydrocarbyl;X6 is an alkoxide or an aryloxide, a halide, or a hydride; andm is from 1 to 3, inclusive.
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상세보기
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