[미국특허]
Ziegler-natta—metallocene dual catalyst systems with activator-supports
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/00
C08F-210/00
C08F-210/02
C08F-210/16
C08F-004/659
출원번호
US-0622114
(2017-06-14)
등록번호
US-9926393
(2018-03-27)
발명자
/ 주소
Ding, Errun
Tso, Chung C.
Yu, Youlu
Yang, Qing
Buck, Richard M.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould P.C.
인용정보
피인용 횟수 :
0인용 특허 :
87
초록
Catalyst systems having both a metallocene catalyst component and a Ziegler-Natta component are disclosed. Such catalyst systems can contain a metallocene compound, an activator-support, an organoaluminum compound, and a Ziegler-Natta component comprising titanium supported on magnesium chloride.
대표청구항▼
1. An olefin polymerization process, the process comprising: contacting (i) a metallocene compound, (ii) a Ziegler-Natta component comprising titanium supported on MgCl2, (iii) an activator-support, and (iv) an organoaluminum compound, to form a catalyst composition; andcontacting the catalyst compo
1. An olefin polymerization process, the process comprising: contacting (i) a metallocene compound, (ii) a Ziegler-Natta component comprising titanium supported on MgCl2, (iii) an activator-support, and (iv) an organoaluminum compound, to form a catalyst composition; andcontacting the catalyst composition with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer. 2. The process of claim 1, wherein the catalyst composition has a catalyst activity greater than about 1,000 g/g/hr, under slurry polymerization conditions with triisobutylaluminum in the catalyst composition, using isobutane as the diluent, at a polymerization temperature of 80° C. and a reactor pressure of 260 psig. 3. The process of claim 1, wherein: the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof; andthe activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide. 4. The process of claim 3, wherein the polymerization reactor system comprises a single loop slurry reactor. 5. The process of claim 1, wherein: a weight percentage of magnesium, based on the weight of the Ziegler-Natta component, is in a range from about 0.1 to about 10 wt. %; anda weight percentage of titanium, based on the weight of the Ziegler-Natta component, is in a range from about 0.1 to about 10 wt. %. 6. The process of claim 5, wherein: a weight ratio of the metallocene compound to the activator-support is in a range from about 1:10 to about 1:10,000;a weight ratio of the activator-support to the organoaluminum compound is in a range from about 1:3 to about 200:1; anda molar ratio of the metallocene compound to titanium is in a range from about 3:1 to about 1:5. 7. The process of claim 1, wherein the olefin polymer comprises an ethylene/alpha-olefin copolymer. 8. A process to produce a catalyst composition, the process comprising: (a) contacting an activator-support and an organoaluminum compound for a first period of time to form a precontacted mixture; and(b) contacting the precontacted mixture with a metallocene compound and a Ziegler-Natta component comprising titanium supported on MgCl2 for a second period of time to form the catalyst composition. 9. The process of claim 8, wherein an activity of the catalyst composition is greater than that of a catalyst system obtained by first combining the activator-support and the metallocene compound, and then combining the organoaluminum compound and the Ziegler-Natta component, under the same polymerization conditions. 10. The process of claim 8, wherein: a weight percentage of magnesium, based on the weight of the Ziegler-Natta component, is in a range from about 0.1 to about 10 wt. %;a weight percentage of titanium, based on the weight of the Ziegler-Natta component, is in a range from about 0.1 to about 10 wt. %;a molar ratio of the metallocene compound to titanium is in a range from about 3:1 to about 1:5;a weight ratio of the metallocene compound to the activator-support is in a range from about 1:10 to about 1:10,000; anda weight ratio of the activator-support to the organoaluminum compound is in a range from about 1:3 to about 200:1. 11. The process of claim 8, wherein: the activator-support comprises fluorided alumina, fluorided silica-alumina, fluorided silica-zirconia, fluorided silica-coated alumina, fluorided-chlorided silica-coated alumina, sulfated alumina, sulfated silica-alumina, sulfated silica-coated alumina, or any combination thereof;the metallocene compound comprises a bridged zirconium or hafnium based metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group, and a phenyl substituted bridging group; andthe catalyst composition has a catalyst activity in a range from about 1,500 to about 10,000 g/g/hr, under slurry polymerization conditions, with triisobutylaluminum in the catalyst composition, using isobutane as the diluent, at a polymerization temperature of 80° C. and a reactor pressure of 260 psig. 12. An olefin polymerization process, the olefin polymerization process comprising contacting the catalyst composition produced by the process of claim 8 with ethylene and an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer, wherein: step (a) is conducted in a precontacting vessel prior to the introduction of the catalyst composition into a polymerization reactor within the polymerization reactor system; andthe olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof. 13. The process of claim 1, wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof. 14. The process of claim 13, wherein: the activator-support comprises fluorided alumina, fluorided silica-alumina, fluorided silica-zirconia, fluorided silica-coated alumina, fluorided-chlorided silica-coated alumina, sulfated alumina, sulfated silica-alumina, sulfated silica-coated alumina, or any combination thereof; andthe metallocene compound comprises a bridged zirconium or hafnium based metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group, and a phenyl substituted bridging group. 15. The process of claim 14, wherein a molar ratio of the metallocene compound to titanium is in a range from about 3:1 to about 1:5. 16. The process of claim 13, wherein the olefin polymer is characterized by the following polymer fractions in an ATREF test: from about 1 to about 18 wt. % of the polymer eluted below a temperature of 40° C.;from about 1 to about 15 wt. % of the polymer eluted between 76 and 86° C.;from about 27 to about 60 wt. % of the polymer eluted above a temperature of 86° C.;and the remaining percentage of the polymer eluted between 40 and 76° C. 17. The process of claim 8, wherein the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide. 18. The process of claim 17, wherein: the metallocene compound comprises a bridged or unbridged, zirconium or hafnium based metallocene compound with two substituted or unsubstituted indenyl groups; anda molar ratio of the metallocene compound to titanium is in a range from about 10:1 to about 1:10. 19. The process of claim 17, wherein: the metallocene compound comprises a bridged zirconium or hafnium based metallocene compound with an alkenyl-substituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; anda molar ratio of the metallocene compound to titanium is in a range from about 5:1 to about 1:5.
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상세보기
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