[미국특허]
Processes for preparing metallocene-based catalyst systems
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/653
C08F-004/6592
C08F-010/00
C08F-210/16
C08F-004/659
C08F-004/52
출원번호
US-0290010
(2016-10-11)
등록번호
US-9944736
(2018-04-17)
발명자
/ 주소
Cymbaluk, Ted H.
McDaniel, Max P.
Yang, Qing
Holtermann, Dennis L.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould P.C.
인용정보
피인용 횟수 :
1인용 특허 :
54
초록▼
Methods for preparing single and dual metallocene catalyst systems containing an activator-support are disclosed. These methods can include precontacting of the activator-support and an organoaluminum compound, as well as sequential contacting of two different metallocene compounds to form a dual me
Methods for preparing single and dual metallocene catalyst systems containing an activator-support are disclosed. These methods can include precontacting of the activator-support and an organoaluminum compound, as well as sequential contacting of two different metallocene compounds to form a dual metallocene catalyst system.
대표청구항▼
1. A process to produce a dual metallocene catalyst composition, the process comprising: (a) contacting a first metallocene compound and an organoaluminum compound with a slurry of an activator-support for a first period of time to form a first mixture; and(b) contacting the first mixture with a sec
1. A process to produce a dual metallocene catalyst composition, the process comprising: (a) contacting a first metallocene compound and an organoaluminum compound with a slurry of an activator-support for a first period of time to form a first mixture; and(b) contacting the first mixture with a second metallocene compound for a second period of time to form the dual metallocene catalyst composition;wherein an activity of the catalyst composition is at least about 10% greater than that of a dual catalyst system obtained by combining the activator-support, a mixture of the first metallocene compound and the second metallocene compound, and the organoaluminum compound, under the same polymerization conditions. 2. The process of claim 1, wherein: the first metallocene compound is less reactive with the activator-support than the second metallocene compound; anda weight ratio of the first metallocene compound to the second metallocene compound is in a range from about 1:10 to about 10:1. 3. The process of claim 1, wherein: the activator-support comprises sulfated alumina;the first metallocene compound comprises a bridged metallocene compound; andthe second metallocene compound comprises an unbridged metallocene compound. 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;the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof;the first metallocene compound comprises a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group; andthe second 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. 5. The process of claim 1, wherein the activity of the catalyst composition is from about 15% to about 100% greater than that of the dual catalyst system obtained by combining the activator-support, the mixture of the first metallocene compound and the second metallocene compound, and the organoaluminum compound, under the same polymerization conditions. 6. An olefin polymerization process, the olefin polymerization process comprising: (a) contacting a first metallocene compound and an organoaluminum compound with a slurry of an activator-support for a first period of time to form a first mixture;(b) contacting the first mixture with a second metallocene compound for a second period of time to form the dual metallocene catalyst composition; and(c) contacting the dual metallocene 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 a Mw of the olefin polymer produced by the polymerization process is greater than a Mw of an olefin polymer produced under the same polymerization conditions using a dual catalyst system obtained by combining the activator-support, a mixture of the first metallocene compound and the second metallocene compound, and the organoaluminum compound. 7. The olefin polymerization process of claim 6, wherein: the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof;the olefin monomer comprises ethylene and the olefin comonomer comprises a C3-C10 alpha-olefin; andthe first metallocene compound produces a higher molecular weight component of the olefin polymer than the second metallocene compound. 8. The olefin polymerization process of claim 7, wherein: the olefin polymer comprises a higher molecular weight component and a lower molecular weight component; anda ratio of the higher molecular weight component to the lower molecular weight component of the olefin polymer produced by the polymerization process is greater than a ratio of the higher molecular weight component to the lower molecular weight component of an olefin polymer produced under the same polymerization conditions using a dual catalyst system obtained by combining the activator-support, a mixture of the first metallocene compound and the second metallocene compound, and the organoaluminum compound. 9. The olefin polymerization process of claim 7, wherein the 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 1, wherein: the activator-support comprises a sulfated solid oxide and/or a fluorided solid oxide;the first metallocene compound comprises a bridged metallocene compound and is less reactive with the activator-support than the second metallocene compound; andthe second metallocene compound comprises an unbridged metallocene compound. 11. The process of claim 10, wherein a weight ratio of the first metallocene compound to the second metallocene compound is in a range from about 1:2 to about 2:1. 12. The olefin polymerization process of claim 6, wherein: the dual metallocene catalyst composition is contacted with ethylene and an olefin comonomer comprising a C3-C10 alpha-olefin; andthe first metallocene compound produces a higher molecular weight component of the olefin polymer than the second metallocene compound. 13. The olefin polymerization process of claim 6, wherein: the activator-support comprises a fluorided solid oxide, a sulfated solid oxide, a phosphated solid oxide, or a combination thereof; andthe olefin polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or a combination thereof. 14. The olefin polymerization process of claim 13, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof. 15. The olefin polymerization process of claim 6, wherein: the activator-support comprises sulfated alumina;the first metallocene compound comprises a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group; andthe second 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. 16. The olefin polymerization process of claim 6, wherein: the first metallocene compound comprises: or both; andthe second metallocene compound comprises: or both. 17. An olefin polymerization process, the olefin polymerization process comprising: (a) contacting a first metallocene compound and an organoaluminum compound with a slurry of an activator-support for a first period of time to form a first mixture;(b) contacting the first mixture with a second metallocene compound for a second period of time to form the dual metallocene catalyst composition; and(c) contacting the dual metallocene 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:the olefin polymer comprises a higher molecular weight component and a lower molecular weight component; anda ratio of the higher molecular weight component to the lower molecular weight component of the olefin polymer produced by the polymerization process is greater than a ratio of the higher molecular weight component to the lower molecular weight component of an olefin polymer produced under the same polymerization conditions using a dual catalyst system obtained by combining the activator-support, a mixture of the first metallocene compound and the second metallocene compound, and the organoaluminum compound. 18. The olefin polymerization process of claim 17, wherein: the first metallocene compound produces the higher molecular weight component of the olefin polymer;the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof; andthe dual metallocene catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof. 19. The olefin polymerization process of claim 18, wherein the activator-support comprises a fluorided solid oxide, a sulfated solid oxide, a phosphated solid oxide, or a combination thereof. 20. The olefin polymerization process of claim 19, wherein: the first metallocene compound comprises a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group; andthe second 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. 21. The olefin polymerization process of claim 20, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof.
Hottovy John D. (Bartlesville OK) Lawrence Frederick C. (Bartlesville OK) Lowe Barry W. (Bartlesville OK) Fangmeier James S. (Bartlesville OK), Apparatus and method for producing ethylene polymer.
McDaniel Max P. ; Benham Elizabeth A. ; Martin Shirley J. ; Collins Kathy S. ; Smith James L. ; Hawley Gil R. ; Wittner Christopher E. ; Jensen Michael D., Compositions that can produce polymers.
McDaniel Max P. ; Collins Kathy S. ; Johnson Marvin M. ; Smith James L. ; Benham Elizabeth A. ; Hawley Gil R. ; Wittner Christopher E. ; Jensen Michael D., Compositions that can produce polymers.
McDaniel, Max P.; Benham, Elizabeth A.; Martin, Shirley J.; Collins, Kathy S.; Smith, James L.; Hawley, Gil R.; Wittner, Christopher E.; Jensen, Michael D., Compositions that can produce polymers.
Yang, Qing; Jayaratne, Kumudini C.; Jensen, Michael D.; McDaniel, Max P.; Martin, Joel L.; Thorn, Matthew G.; Lanier, Jerry T.; Crain, Tony R., Dual metallocene catalysts for polymerization of bimodal polymers.
Yang, Qing; Jayaratne, Kumudini C.; Jensen, Michael D.; McDaniel, Max P.; Martin, Joel L.; Thorn, Matthew G.; Lanier, Jerry T.; Crain, Tony R., Dual metallocene catalysts for polymerization of bimodal polymers.
Degroot,Alexander W.; Stevens,James C.; Desjardins,Sylvie Y.; Weinhold,Jeffrey; Carnahan,Edmund M.; Gillespie,David; Vanderlende,Daniel D., High melt strength polymers and method of making same.
Hottovy John D. ; Hensley Harvey D. ; Przelomski David J. ; Cymbaluk Teddy H. ; Franklin ; III Robert K. ; Perez Ethelwoldo P., High solids slurry polymerization.
Jenkins ; III John M. (So. Charleston WV) Jones Russell L. (Chapel Hill NC) Jones Thomas M. (So. Charleston WV) Beret Samil (Danville CA), Method for fluidized bed polymerization.
Burns, David H.; Verser, Donald W.; Benham, Elizabeth A.; McDaniel, Max P.; Hottovy, John D.; Zellers, Dale A.; Zellers, legal representative, Penny A.; Thurman, Clay K; Lockman, David A.; Lawmaster, John O.; Haberly, Matthew T.; Smith, Thomas H.; Lanier, Jerry T.; Thorn, Matthew G., Multiple component feed methods and systems.
Murray, Rex E.; Jayaratne, Kumudini C.; Yang, Qing; Martin, Joel L.; Glass, Gary L., Nano-linked heteronuclear metallocene catalyst compositions and their polymer products.
McDaniel, Max P.; Johnson, Marvin M.; Randolph, Bruce B.; Collins, Kathy S.; Benham, Elizabeth A.; Jensen, Michael D.; Martin, Joel L.; Hawley, Gil R., Organometal catalyst composition.
Collins, Kathy S.; Palackal, Syriac J.; McDaniel, Max P.; Jensen, Michael D.; Hawley, Gil R.; Farmer, Kenneth R.; Wittner, Christopher E.; Benham, Elizabeth A.; Eaton, Anthony P.; Martin, Joel L., Organometal catalyst compositions.
Max P. McDaniel ; James B. Kimble ; Kathy S. Collins ; Elizabeth A. Benham ; Michael D. Jensen ; Gil R. Hawley ; Joel L. Martin, Organometal catalyst compositions.
Max P. McDaniel ; Kathy S. Collins ; Anthony P. Eaton ; Elizabeth A. Benham ; Michael D. Jensen ; Joel L. Martin ; Gil R. Hawley, Organometal catalyst compositions.
Max P. McDaniel ; Kathy S. Collins ; James L. Smith ; Elizabeth A. Benham ; Marvin M. Johnson ; Anthony P. Eaton ; Michael D. Jensen ; Joel L. Martin ; Gil R. Hawley, Organometal catalyst compositions.
McDaniel, Max P.; Collins, Kathy S.; Benham, Elizabeth A.; Eaton, Anthony P.; Jensen, Michael D.; Martin, Joel L.; Hawley, Gil R.; Hsieh, Eric T., Organometal catalyst compositions.
McDaniel, Max P.; Collins, Kathy S.; Eaton, Anthony P.; Benham, Elizabeth A.; Jensen, Michael D.; Martin, Joel L.; Hawley, Gil R., Organometal catalyst compositions.
McDaniel, Max P.; Shveima, Joseph S.; Smith, James L.; Collins, Kathy S.; Benham, Elizabeth A.; Eaton, Anthony P.; Jensen, Michael D.; Martin, Joel L.; Hawley, Gil R., Organometal catalyst compositions.
McDaniel, Max P.; Collins, Kathy S.; Benham, Elizabeth A.; Eaton, Anthony P.; Jensen, Michael D.; Martin, Joel L.; Hawley, Gil R., Organometal catalyst compositions with solid oxide supports treated with fluorine and boron.
Max P. McDaniel ; Kathy S. Collins ; Anthony P. Eaton ; Elizabeth A. Benham ; Joel L. Martin ; Michael D. Jensen ; Gil R. Hawley, Organometal compound catalyst.
McDaniel, Max P.; Collins, Kathy S.; Hawley, Gil R.; Jensen, Michael D.; Benham, Elizabeth A.; Eaton, Anthony P.; Martin, Joel L.; Wittner, Christopher E., Organometal compound catalyst.
Hawley, Gil R.; McDaniel, Max P.; Wittner, Christopher E.; Jensen, Michael D.; Martin, Joel L.; Benham, Elizabeth A.; Eaton, Anthony P.; Collins, Kathy S., Polymerization catalysts.
Martin,Joel L.; Thorn,Matthew G.; McDaniel,Max P.; Jensen,Michael D.; Yang,Qing; DesLauriers,Paul J.; Kertok,Mark E., Polymerization catalysts and process for producing bimodal polymers in a single reactor.
Yang,Qing; Jensen,Michael D.; Thorn,Matthew G.; McDaniel,Max P.; Martin,Joel L.; Crain,Tony R., Polymerization catalysts for producing high melt index polymers without the use of hydrogen.
Yang, Qing; Jensen, Michael D.; Martin, Joel L.; Thorn, Matthew G.; McDaniel, Max P.; Yu, Youlu; Rohlfing, David C., Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching.
Hanson Donald O. (Bartlesville OK), Process and apparatus for separating diluents from solid polymers utilizing a two-stage flash and a cyclone separator.
Max P. McDaniel ; Anthony P. Eaton ; Elizabeth A. Benham ; Shawn R. Kennedy ; Ashish M. Sukhadia ; Rajendra K. Krishnaswamy ; Kathy S. Collins, Process for producing a polymer composition.
McDaniel Max P. ; Collins Kathy S. ; Johnson Marvin M. ; Smith James L. ; Benham Elizabeth A. ; Hawley Gil R. ; Wittner Christopher E. ; Jensen Michael D., Process for producing polymers using a composition comprising an organometal compound, a treated solid oxide compound, and an organoaluminum compound.
Martin,Joel L.; Benham,Elizabeth A.; Kertok,Mark E.; Jensen,Michael D.; McDaniel,Max P.; Hawley,Gil R.; Yang,Qing; Thorn,Matthew G.; Sukhadia,Ashish M., Resins that yield low haze films and the process for their production.
Szul, John F.; Erickson, Kersten Anne; Mawson, Simon; Schreck, David James; Goode, Mark G.; Daniell, Paul T.; McKee, Matthew G.; Williams, Clark C., Solution feed of multiple catalysts.
※ AI-Helper는 부적절한 답변을 할 수 있습니다.