[미국특허]
Processes for preparing solid metallocene-based catalyst systems
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/6592
C08F-210/16
C08F-110/02
B01J-037/04
C08F-010/00
C08F-004/659
출원번호
US-0421510
(2017-02-01)
등록번호
US-10059783
(2018-08-28)
발명자
/ 주소
Clark, Kensha M.
Yang, Qing
Glass, Gary L.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould P.C.
인용정보
피인용 횟수 :
0인용 특허 :
55
초록▼
Methods for preparing metallocene-based catalyst systems containing an activator-support are disclosed. These methods can include contacting a solid metallocene compound, an activator-support, and an organoaluminum compound, resulting in catalyst systems with increased catalytic activity as compared
Methods for preparing metallocene-based catalyst systems containing an activator-support are disclosed. These methods can include contacting a solid metallocene compound, an activator-support, and an organoaluminum compound, resulting in catalyst systems with increased catalytic activity as compared to catalyst systems utilizing a solution of the metallocene compound.
대표청구항▼
1. An olefin polymerization process, the olefin polymerization process comprising: (i) contacting an activator-support and a solid metallocene compound for a first period of time to form a precontacted mixture;(ii) contacting the precontacted mixture with an organoaluminum compound for a second peri
1. An olefin polymerization process, the olefin polymerization process comprising: (i) contacting an activator-support and a solid metallocene compound for a first period of time to form a precontacted mixture;(ii) contacting the precontacted mixture with an organoaluminum compound for a second period of time to produce 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;wherein an activity of the catalyst composition is from about 5% to about 150% greater than that of a catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions. 2. The olefin polymerization process of claim 1, wherein: the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, phosphated alumina, or a combination thereof;the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof; andthe olefin monomer comprises ethylene and the olefin comonomer comprises a C3-C10 alpha-olefin. 3. An olefin polymerization process, the olefin polymerization process comprising contacting a catalyst composition with ethylene and an optional olefin comonomer comprising a C3-C10 alpha-olefin in a polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises: (a) an activator-support;(b) a solid metallocene compound; and(c) an organoaluminum compound;wherein an activity of the catalyst composition is from about 5% to about 150% greater than that of a catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions. 4. The olefin polymerization process of claim 3, wherein: the polymerization reactor system comprises 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. 5. The olefin polymerization process of claim 1, wherein in step (i), a slurry of the activator-support in a first diluent is contacted with a slurry of the solid metallocene compound in a second diluent. 6. The olefin polymerization process of claim 5, wherein the first diluent and the second diluent independently comprise propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, or combinations thereof. 7. The olefin polymerization process of claim 1, wherein the solid metallocene compound comprises: an unbridged zirconium or hafnium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group; ora bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group. 8. The olefin polymerization process of claim 1, wherein the olefin polymer is an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer. 9. The olefin polymerization process of claim 1, wherein the olefin polymer is a polypropylene homopolymer or a propylene-based copolymer. 10. The olefin polymerization process of claim 1, wherein the activity of the catalyst composition is from about 5% to about 150% 100% greater than that of the catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions. 11. The olefin polymerization process of claim 10, wherein: the catalyst composition is contacted with ethylene and an olefin comonomer comprising a C3-C10 alpha-olefin;the activator-support comprises sulfated alumina; andthe organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof. 12. The olefin polymerization process of claim 1, wherein the activity of the catalyst composition is from about 5% to about 75% greater than that of the catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions. 13. The olefin polymerization process of claim 12, 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-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof; andthe solid metallocene compound comprises: an unbridged zirconium based metallocene compound containing a cyclopentadienyl and an indenyl group, and with an alkenyl substituent; ora bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group, and with an alkenyl substituent. 14. The olefin polymerization process of claim 3, wherein: the activator-support comprises a fluorided solid oxide, a sulfated solid oxide, or a combination thereof; andthe activity of the catalyst composition is from about 5% to about 150% 100% greater than that of the catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions. 15. The olefin polymerization process of claim 14, wherein the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof. 16. The olefin polymerization process of claim 3, wherein the activity of the catalyst composition is from about 5% to about 75% greater than that of the catalyst system obtained by using a solution of the metallocene compound instead of the solid metallocene compound, under the same polymerization conditions. 17. The olefin polymerization process of claim 16, wherein the solid metallocene compound comprises an unbridged zirconium based metallocene compound containing a cyclopentadienyl and an indenyl group, and with an alkenyl substituent. 18. The olefin polymerization process of claim 16, wherein the solid metallocene compound comprises a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group, and with an alkenyl substituent. 19. The olefin polymerization process of claim 3, wherein: a weight ratio of the solid 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 1:5 to about 1000:1. 20. The olefin polymerization process of claim 19, wherein: the activator-support comprises sulfated alumina; andthe organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof. 21. The olefin polymerization process of claim 16, 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-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof; andthe solid metallocene compound comprises: an unbridged zirconium based metallocene compound containing a cyclopentadienyl and an indenyl group, and with an alkenyl substituent; ora bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group, and with an alkenyl substituent.
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