[미국특허]
Metallocene and half sandwich dual catalyst systems for producing broad molecular weight distribution polymers
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/642
C08F-004/653
C08F-004/6592
C08F-210/16
C08F-004/76
C08F-004/659
C08F-010/02
C08F-010/00
C08L-023/00
C08L-023/04
C08L-023/10
출원번호
US-0493384
(2014-09-23)
등록번호
US-9273159
(2016-03-01)
발명자
/ 주소
Ding, Errun
Yang, Qing
Yu, Youlu
Guatney, Lloyd W.
Askew, Jim B.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould P.C
인용정보
피인용 횟수 :
1인용 특허 :
61
초록
Disclosed herein are polymerization processes for the production of olefin polymers. These polymerization processes can use a dual catalyst system containing a zirconium or hafnium based metallocene compound and a titanium based half-metallocene compound containing an indenyl group.
대표청구항▼
1. A catalyst composition capable of producing an ethylene polymer having a ratio of high load melt index to melt index in a range from about 30 to about 350, the catalyst composition comprising: catalyst component I comprising a zirconium or hafnium based metallocene compound;catalyst component II
1. A catalyst composition capable of producing an ethylene polymer having a ratio of high load melt index to melt index in a range from about 30 to about 350, the catalyst composition comprising: catalyst component I comprising a zirconium or hafnium based metallocene compound;catalyst component II comprising a titanium based half-metallocene compound having formula (IIA): wherein: InA is a substituted or unsubstituted indenyl group; andX1, X2, and X3 independently are a monoanionic ligand;an activator; andoptionally, a co-catalyst. 2. The composition of claim 1, wherein: a weight ratio of catalyst component I to catalyst component II is in a range of from about 10:1 to about 1:10;the catalyst composition comprises only one zirconium or hafnium based metallocene compound, and only one titanium based half-metallocene compound containing an indenyl group; andthe activator comprises an activator-support, the activator-support comprising a solid oxide treated with an electron-withdrawing anion. 3. The composition of claim 1, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. 4. The composition of claim 1, wherein X1, X2, and X3 independently are a halide or C1 to C18 hydrocarbyl group. 5. The composition of claim 1, wherein InA is an unsubstituted indenyl group. 6. The composition of claim 1, wherein: each substituent on InA independently is H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group; andX1, X2, and X3 independently are H, BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, a C1 to C36 hydrocarbylaminyl group, a C1 to C36 hydrocarbylsilyl group, a C1 to C36 hydrocarbylaminylsilyl group, OBR12, or OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group. 7. The composition of claim 1, wherein: each substituent on InA independently is H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, or an allyldimethylsilyl group; andX1, X2, and X3 independently are a halide or C1 to C18 hydrocarbyl group. 8. The composition of claim 1, wherein catalyst component II comprises: or any combination thereof. 9. The composition of claim 1, wherein catalyst component I comprises an unbridged metallocene compound having formula (IA): wherein:M is Zr or Hf,CpA and CpB independently are a substituted or unsubstituted cyclopentadienyl or indenyl group; andX4 and X5 independently are a monoanionic ligand. 10. The composition of claim 9, wherein CpA and CpB independently are an unsubstituted cyclopentadienyl or indenyl group. 11. The composition of claim 1, wherein catalyst component I comprises a bridged metallocene compound having formula (IB): wherein:M is Zr or Hf;CpC is a substituted cyclopentadienyl, indenyl, or fluorenyl group;X4 and X5 independently are a monoanionic ligand;RX and RY independently are H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbylsilyl group; andE is a bridging group selected from: a bridging group having the formula >EARARB, wherein EA is C or Si, and RA and RB independently are H or a C1 to C18 hydrocarbyl group,a bridging group having the formula —CRCRD—CRERF-n wherein RC, RD, RE, and RF independently are H or a C1 to C18 hydrocarbyl group, ora bridging group having the formula —SiRGRH—SiRIRJ—, wherein RG, RH, RI, and RJ independently are H or a C1 to C18 hydrocarbyl group. 12. The composition of claim 11, wherein: RX and RY independently are H or a C1 to C12 hydrocarbyl group; andE is a bridging group having the formula >EARARB, wherein EA is C or Si, and RA and RB independently are a C1 to C12 hydrocarbyl group. 13. A catalyst composition comprising: catalyst component I comprising a zirconium or hafnium based metallocene compound;catalyst component II comprising a titanium based half-metallocene compound having formula (IIA): wherein: InA is a substituted or unsubstituted indenyl group; andX1, X2, and X3 independently are a monoanionic ligand;an activator-support; andoptionally, a co-catalyst;wherein the catalyst composition has an activity of greater than about 100 grams of polyethylene per gram of the activator-support per hour, under slurry polymerization conditions using isobutane as the diluent, at a polymerization temperature of 90° C. and a reactor pressure of 390 psig. 14. The composition of claim 13, wherein catalyst component I comprises an unbridged zirconium or hafnium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group. 15. The composition of claim 13, wherein: the activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof; andthe co-catalyst comprises an organoaluminum compound, the organoaluminum compound comprising 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. 16. The composition of claim 13, wherein: a weight ratio of catalyst component I to catalyst component II is in a range of from about 4:1 to about 1:4; andthe activator-support comprises fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, or any combination thereof. 17. The composition of claim 13, wherein X1, X2, and X3 independently are a halide or a C1 to C18 hydrocarbyl group. 18. The composition of claim 17, wherein: a weight ratio of catalyst component I to catalyst component II is in a range of from about 4:1 to about 1:4; andthe activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide. 19. The composition of claim 13, wherein InA is an unsubstituted indenyl group. 20. The composition of claim 13, wherein X1, X2, and X3 are Cl.
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.
Yang, Qing; McDaniel, Max P.; Crain, Tony R.; Yu, Youlu, Catalysts for producing broad molecular weight distribution polyolefins in the absence of added hydrogen.
Yang, Qing; McDaniel, Max P.; Crain, Tony R.; Yu, Youlu, Catalysts for producing broad molecular weight distribution polyolefins in the absence of added hydrogen.
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.
Jensen,Michael D.; Martin,Joel L.; McDaniel,Max P.; Yang,Qing; Thorn,Matthew G.; Benham,Elizabeth A.; Cymbaluk,Ted H.; Sukhadia,Ashish M.; Krishnaswamy,Rajendra K.; Kertok,Mark E., Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength.
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.
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.
Hottovy John D. ; Hensley Harvey D. ; Przelomski David J. ; Cymbaluk Teddy H. ; Franklin ; III Robert K. ; Perez Ethelwoldo P., High solids slurry polymerization.
Reed Marion G. (Hacienda Heights CA) Jaffe Joseph (Berkeley CA), Hydrocarbon hydroconversion process employing hydroxy-aluminum stabilized catalysts supports.
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.
Shamshoum Edwar S. ; Rauscher David J., Method of olefin polymerization utilizing hydrogen pulsing, products made therefrom, and method of hydrogenation.
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.
Sukhadia, Ashish M.; Martin, Joel L.; Yang, Qing; Jayaratne, Kumudini C.; Lanier, J. Todd, Polyethylene film having improved mechanical and barrier properties and method of making same.
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.; 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.
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.
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.
Ewen John A. (Houston TX) Welborn ; Jr. Howard C. (Houston TX), Process and catalyst for producing polyethylene having a broad molecular weight distribution.
Ewen John A. (Houston TX) Welborn ; Jr. Howard C. (Houston TX), Process and catalyst for producing polyethylene having a broad molecular weight distribution.
Hasegawa Saiki (Mie-ken JPX) Yasuda Hisami (Mie-ken JPX) Yano Akihiro (Mie-ken JPX), Process for producing a
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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.
Yang, Qing; McDaniel, Max P.; Martin, Joel L.; Crain, Tony R.; Muninger, Randy S.; Lanier, Jerry T.; Fodor, Jeff S.; Deslauriers, Paul J.; Tso, Chung C.; Rohlfing, David C., Process for producing broader molecular weight distribution polymers with a reverse comonomer distribution and low levels of long chain branches.
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.
Hlavinka, Mark L.; Ding, Errun; DesLauriers, Paul; Inn, Yongwoo; Cui, Lili; Yang, Qing; Sukhadia, Ashish M.; St. Jean, Guylaine; Buck, Richard M., Higher density polyolefins with improved stress crack resistance.
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