[미국특허]
High activity catalyst compositions containing silicon-bridged metallocenes with bulky substituents
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C07F-017/00
C08F-004/642
C08F-004/6592
B01J-031/22
출원번호
US-0198009
(2011-08-04)
등록번호
US-8431729
(2013-04-30)
발명자
/ 주소
Martin, Joel L.
Yang, Qing
McDaniel, Max P.
Askew, Jim B.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould P.C.
인용정보
피인용 횟수 :
5인용 특허 :
43
초록
The present invention discloses catalyst compositions employing silicon-bridged metallocene compounds with bulky substituents. Methods for making these silicon-bridged metallocene compounds and for using such compounds in catalyst compositions for the polymerization of olefins also are provided.
대표청구항▼
1. A compound having the formula: or a derivative thereof; wherein: M is Ti, Zr, or Hf;X1 and X2 independently are a monoanionic ligand;RA is a C2 to C18 alkenyl; andn equal to 1. 2. The compound of claim 1, wherein M is Zr or Hf. 3. The compound of claim 1, wherein RA is a C3 to C8 terminal alkeny
1. A compound having the formula: or a derivative thereof; wherein: M is Ti, Zr, or Hf;X1 and X2 independently are a monoanionic ligand;RA is a C2 to C18 alkenyl; andn equal to 1. 2. The compound of claim 1, wherein M is Zr or Hf. 3. The compound of claim 1, wherein RA is a C3 to C8 terminal alkenyl. 4. The compound of claim 1, wherein RA is ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl. 5. The compound of claim 1, wherein X1 and X2 independently are hydrogen; a halide; BH4; a C1 to C18 hydrocarbyl, hydrocarbyloxide, hydrocarbylamino, hydrocarbylsilyl, or hydrocarbylaminosilyl; or OBR12 or OSO2R1, wherein R1 is a C1 to C18 hydrocarbyl. 6. The compound of claim 1, wherein X1 and X2 independently are F, Cl, Br, I, methyl, benzyl, or phenyl. 7. The compound of claim 1, wherein X1 and X2 independently are an alkoxy, an aryloxy, an alkylamino, a dialkylamino, a trihydrocarbylsilyl, or a hydrocarbylaminosilyl. 8. A catalyst composition comprising: (i) a silicon-bridged metallocene compound having formula (I): or a derivative thereof; wherein: M is Ti, Zr, or Hf;X1 and X2 independently are a monoanionic ligand;RA is a C2 to C18 alkenyl; andn equal to 1;(ii) an activator; and(iii) optionally, an organoaluminum compound. 9. The composition of claim 8, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. 10. The composition of claim 8, wherein the activator comprises an activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein: the solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; andthe electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, or any combination thereof. 11. The composition of claim 8, wherein the activator comprises an activator-support comprising 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. 12. The composition of claim 8, wherein the catalyst composition comprises: (i) a silicon-bridged metallocene compound having formula (I), or a derivative thereof;(ii) an activator; and(iii) an organoaluminum compound; 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. 13. The composition of claim 12, wherein the activator comprises an activator-support comprising fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, or any combination thereof. 14. The catalyst composition of claim 13, wherein a catalyst activity of the catalyst composition is greater than about 3,000 grams of polyethylene per gram of metallocene compound per hour under slurry polymerization conditions, using isobutane as a diluent, with a polymerization temperature of 90° C. and a reactor pressure of 390 psig. 15. An olefin polymerization process, the process comprising: contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises:(i) a silicon-bridged metallocene compound having formula (I): or a derivative thereof; wherein: M is Ti, Zr, or Hf;X1 and X2 independently are a monoanionic ligand;RA is a C2 to C18 alkenyl; andn equal to 1;(ii) an activator; and(iii) optionally, an organoaluminum compound. 16. The process of claim 15, wherein the process is conducted in a batch reactor, slurry reactor, gas-phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, or a combination thereof. 17. The process of claim 15, wherein the olefin monomer comprises a C2 to C16 olefin. 18. The process of claim 15, wherein the olefin monomer comprises ethylene, and the olefin comonomer comprises propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, or a mixture thereof. 19. The compound of claim 1, wherein the compound is: or a derivative thereof. 20. The composition of claim 8, wherein: M is Zr or Hf;X1 and X2 independently are F, Cl, Br, I, methyl, benzyl, or phenyl; andRA is a C3 to C8 terminal alkenyl. 21. The process of claim 15, wherein the catalyst composition is contacted with ethylene and a comonomer selected from 1-butene, 1-hexene, 1-octene, or a combination thereof. 22. The process of claim 21, wherein the catalyst composition comprises: (i) a silicon-bridged metallocene compound having formula (I), or a derivative thereof;(ii) an activator; and(iii) an organoaluminum compound; 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. 23. The process of claim 22, wherein: M is Zr or Hf;X1 and X2 independently are F, Cl, Br, I, methyl, benzyl, or phenyl; andRA is a C3 to C8 terminal alkenyl.
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상세보기
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.; Yang, Qing; McDaniel, Max P.; Askew, Jim B., High activity catalyst compositions containing silicon-bridged metallocenes with bulky substituents.
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