[미국특허]
Half-metallocene compounds and catalyst compositions
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/6592
C08F-004/642
C08F-010/00
C08F-210/16
C08F-004/76
C07F-017/00
C08F-004/659
출원번호
US-0277140
(2014-05-14)
등록번호
US-9062134
(2015-06-23)
발명자
/ 주소
Ding, Errun
Martin, Joel L.
Masino, Albert P.
Yang, Qing
Yu, Youlu
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould
인용정보
피인용 횟수 :
1인용 특허 :
71
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 of olefins also are provided.
대표청구항▼
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 a hybrid metallocene compound and an activ
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 a hybrid metallocene compound and an activator, and wherein the hybrid metallocene compound has the formula: wherein:M is Zr or Hf;X1 and X2 independently are a halide or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof; andX3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, wherein any substituents on X3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof. 2. The process of claim 1, wherein: the process is conducted in a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof; andthe catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof. 3. The process of claim 2, wherein: the olefin polymer has less than about 0.002 long chain branches per 1000 total carbon atoms;the olefin polymer has a ratio of Mw/Mn in a range from about 3 to about 20;the olefin polymer has a ratio of vinyl end groups to saturated end groups in a range from about 0.4 to about 0.9; orany combination thereof. 4. The process of claim 1, wherein the activator comprises a solid oxide treated with an electron-withdrawing anion. 5. The process of claim 4, wherein: the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof;the activator comprises a fluorided solid oxide and/or a sulfated solid oxide;X1 and X2 are Cl; andX3 is a substituted or unsubstituted cyclopentadienyl group. 6. The process of claim 1, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. 7. The process of claim 6, wherein: the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof;X1 and X2 are Cl; andX3 is a substituted or unsubstituted cyclopentadienyl group. 8. 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 a hybrid metallocene compound and an activator, and wherein the 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; andX3 is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group, wherein any substituents on X3 independently are a hydrogen atom or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof. 9. The process of claim 8, wherein: the process is conducted in a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof; andthe catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof. 10. The process of claim 9, wherein: the olefin polymer has less than about 0.002 long chain branches per 1000 total carbon atoms;the olefin polymer has a ratio of Mw/Mn in a range from about 3 to about 20;the olefin polymer has a ratio of vinyl end groups to saturated end groups in a range from about 0.4 to about 0.9; orany combination thereof. 11. The process of claim 8, wherein the activator comprises a solid oxide treated with an electron-withdrawing anion. 12. The process of claim 11, wherein: the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof;the activator comprises a fluorided solid oxide and/or a sulfated solid oxide;X1 and X2 are Cl; andX3 is a substituted or unsubstituted cyclopentadienyl group. 13. The process of claim 8, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. 14. The process of claim 13, wherein: the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof;X1 and X2 are Cl; andX3 is a substituted or unsubstituted cyclopentadienyl group. 15. The process of claim 8, wherein the hybrid metallocene compound is: 16. 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 a hybrid metallocene compound and an activator-support comprising a solid oxide treated with an electron-withdrawing anion, and wherein the 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, wherein 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, —NH—RA, —PH—RA, —S—RA, —O—Si—RB3, or —O—C—RB3;wherein: RA is an aryl group substituted with a first alkoxy group and a second substituent selected from an alkyl, cycloalkyl, or second alkoxy group, wherein any additional substituents on RA independently are a hydrogen atom or an alkyl, cycloalkyl, or alkoxy group; andeach RB independently is a substituted or unsubstituted aliphatic, aromatic, or cyclic group, or a combination thereof. 17. The process of claim 16, wherein: the process is conducted in a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof; andthe catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof. 18. The process of claim 17, wherein: the olefin polymer has less than about 0.002 long chain branches per 1000 total carbon atoms;the olefin polymer has a ratio of Mw/Mn in a range from about 3 to about 20;the olefin polymer has a ratio of vinyl end groups to saturated end groups in a range from about 0.4 to about 0.9; orany combination thereof. 19. The process of claim 17, wherein: X1 and X2 independently are a methyl group, a phenyl group, a benzyl group, or a halide; andX4 is —O—RA, wherein RA is a 2,6-disubstituted aryl group, wherein the substituent at the 2-position is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, and the substituent at the 6-position is a methyl group, an ethyl group, a propyl group, a n-butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. 20. The process of claim 19, wherein: X3 is an unsubstituted cyclopentadienyl group;the catalyst composition further comprises an organoaluminum compound; andthe activator-support comprises a fluorided solid oxide, a sulfated solid oxide, or a combination thereof. 21. The process of claim 17, wherein: X1 and X2 independently are a methyl group, a phenyl group, a benzyl group, or a halide; andX4 is —O—Si—RB3, or —O—C—RB3, wherein each RB independently is a phenyl group, a benzyl group, a tolyl group, a xylyl group, a methyl benzyl group, a 1-ethenyl-2-phenyl group, or a 1-ethynyl-2-phenyl group. 22. The process of claim 21, wherein: X3 is a substituted or unsubstituted cyclopentadienyl or indenyl group;the catalyst composition further comprises an organoaluminum compound; andthe activator-support comprises a fluorided solid oxide, a sulfated solid oxide, or a combination thereof. 23. The process of claim 16, wherein X4 is: 24. The process of claim 16, wherein the hybrid metallocene compound has the formula: wherein in formula (II): X1 and X2 independently are a methyl group, a phenyl group, a benzyl group, or a halide;each RC 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;n is an integer from 0 to 5, inclusive;X4 is —O—RA, —O—Si—RB3, or —O—C—RB3;wherein: RA is a 2,6-disubstituted aryl group, wherein the substituent at the 2-position is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, and the substituent at the 6-position is a methyl group, an ethyl group, a propyl group, a n-butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; andeach RB independently is a phenyl group, a benzyl group, a tolyl group, a xylyl group, a methyl benzyl group, a 1-ethenyl-2-phenyl group, or a 1-ethynyl-2-phenyl group.
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