[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
C08F-004/659
출원번호
US-0517158
(2014-10-17)
등록번호
US-9303106
(2016-04-05)
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 :
8인용 특허 :
51
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. A process to produce a catalyst composition, the process comprising: (i) contacting an activator-support and a solid metallocene compound for a first period of time to form a precontacted mixture; and(ii) contacting the precontacted mixture with an organoaluminum compound for a second period of t
1. A process to produce a catalyst composition, the process comprising: (i) contacting an activator-support and a solid metallocene compound for a first period of time to form a precontacted mixture; and(ii) contacting the precontacted mixture with an organoaluminum compound for a second period of time to produce the catalyst composition;wherein an activity of the catalyst composition is from about 5% to about 100% 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 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. 3. The process of claim 1, wherein in step (i), at least one of the activator-support and the solid metallocene compound is a dry solid. 4. The process of claim 1, wherein: the activator-support comprises a fluorided solid oxide, a sulfated solid oxide, a phosphated solid oxide, or a combination thereof; andthe solid metallocene compound comprises a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group. 5. The process of claim 1, wherein: the first period of time is at least about 15 seconds; andthe activity of the catalyst composition is from about 5% to about 75% 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. 6. The process of claim 1, 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; andthe activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof. 7. The process of claim 1, 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. 8. A process to produce a catalyst composition, the process comprising contacting, in any order: (a) an activator-support;(b) a solid metallocene compound; and(c) an organoaluminum compound; to produce the catalyst composition; wherein an activity of the catalyst composition is from about 5% to about 100% 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. 9. The process of claim 8, wherein the process comprises comprising contacting a slurry of the activator-support in a first diluent, a slurry of the solid metallocene compound in a second diluent, and the organoaluminum compound. 10. The process of claim 8, wherein the process comprises comprising contacting a slurry of the activator-support in a first diluent, a slurry of the solid metallocene compound in a second diluent, and a solution of the organoaluminum compound. 11. The process of claim 8, wherein at least one of the activator-support and the solid metallocene compound is a dry solid. 12. The process of claim 8, wherein: the solid metallocene compound comprises a bridged metallocene compound; andthe activator-support comprises sulfated alumina. 13. The process of claim 8, wherein: the activator-support comprises a fluorided solid oxide, a sulfated solid oxide, or a combination thereof;the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof; andthe 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. 14. The process of claim 8, wherein the activity of the catalyst composition is from about 5% to about 75% 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. 15. The process of claim 1, wherein: the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide; andthe 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. 16. The process of claim 15, wherein the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof. 17. The process of claim 1, wherein: the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide; andthe solid metallocene compound comprises an unbridged zirconium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group. 18. The process of claim 2, wherein the first diluent and the second diluent independently comprise propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, or combinations thereof. 19. The process of claim 8, wherein: the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide; andthe 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. 20. The process of claim 19, wherein the activator-support comprises fluorided silica-alumina, fluorided silica-coated alumina, sulfated alumina, or a combination thereof. 21. The process of claim 9, wherein the first diluent and the second diluent independently comprise propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, n-hexane, or combinations thereof. 22. The process of claim 13, wherein: 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.
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