[미국특허]
Cyclobutylidene-bridged metallocenes and catalyst systems containing the same
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/6592
C08F-004/642
C08F-210/16
C08F-210/02
C08F-004/659
C08F-010/02
출원번호
US-0790038
(2015-07-02)
등록번호
US-9359460
(2016-06-07)
발명자
/ 주소
Praetorius, Jeremy M.
Cruz, Carlos
Yang, Qing
McDaniel, Max P.
Barr, Jared L.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould P.C.
인용정보
피인용 횟수 :
4인용 특허 :
44
초록
Disclosed herein are catalyst compositions containing cyclobutylidene-bridged metallocene compounds. These catalyst compositions can be used for the polymerization of olefins.
대표청구항▼
1. A catalyst composition comprising a metallocene compound, an activator, and an optional co-catalyst, wherein the metallocene compound has the formula: wherein: M is Ti, Zr, or Hf;Cp is a cyclopentadienyl group with an alkyl and/or an alkenyl substituent;X1 and X2 independently are a monoanionic
1. A catalyst composition comprising a metallocene compound, an activator, and an optional co-catalyst, wherein the metallocene compound has the formula: wherein: M is Ti, Zr, or Hf;Cp is a cyclopentadienyl group with an alkyl and/or an alkenyl substituent;X1 and X2 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;a catalyst activity of the catalyst composition is greater than about 350,000 grams of ethylene homopolymer per millimole of the metallocene compound per hour, under slurry polymerization conditions, with a triisobutylaluminum co-catalyst, using isobutane as a diluent, and with a polymerization temperature of 80° C. and a reactor pressure of 340 psig; anda catalyst activity of the catalyst composition is greater than about 1,500,000 grams of ethylene/1-hexene copolymer per millimole of the metallocene compound per hour, under slurry polymerization conditions, with a triisobutylaluminum co-catalyst, using isobutane as a diluent, and with a polymerization temperature of 80° C. and a reactor pressure of 340 psig. 2. 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. 3. The composition of claim 1, wherein the catalyst composition comprises a co-catalyst, and wherein the activator comprises an activator-support, the activator-support comprising a solid oxide treated with an electron-withdrawing anion. 4. The composition of claim 1, wherein M is Zr or Hf;Cp is a cyclopentadienyl group with a C3 to C8 terminal alkenyl substituent; andRX and RY independently are H or a C1 to C12 hydrocarbyl group. 5. The composition of claim 4, wherein X1 and X2 independently are a halide or a C1 to C12 hydrocarbyl group. 6. The composition of claim 5, wherein the catalyst composition comprises an organoaluminum co-catalyst, and the activator comprises a fluorided solid oxide and/or a sulfated solid oxide. 7. The composition of claim 1, wherein a copolymer catalyst activity of the catalyst composition is greater than that of a catalyst system containing a metallocene compound with a different cycloalkyl bridging group. 8. The composition of claim 1, wherein: the catalyst composition comprises an organoaluminum co-catalyst;the activator comprises a fluorided solid oxide and/or a sulfated solid oxide;M is Zr or Hf;RX and RY independently are H or a C1 to C12 hydrocarbyl group; andX1 and X2 independently are a halide or a C1 to C12 hydrocarbyl group. 9. The composition of claim 8, wherein: the catalyst activity of the catalyst composition is in a range from greater than about 350,000 grams to about 1,250,000 grams of ethylene homopolymer per millimole of the metallocene compound per hour, under slurry polymerization conditions, with a triisobutylaluminum co-catalyst, using isobutane as a diluent, and with a polymerization temperature of 80° C. and a reactor pressure of 340 psig; andthe catalyst activity of the catalyst composition is in a range from greater than about 1,500,000 grams to about 4,000,000 grams of ethylene/1-hexene copolymer per millimole of the metallocene compound per hour, under slurry polymerization conditions, with a triisobutylaluminum co-catalyst, using isobutane as a diluent, and with a polymerization temperature of 80° C. and a reactor pressure of 340 psig. 10. A catalyst composition comprising a metallocene compound, an activator, and an optional co-catalyst, wherein the metallocene compound has the formula: wherein: M is Ti, Zr, or Hf;Cp is a cyclopentadienyl group with an alkyl and/or an alkenyl substituent;X1 and X2 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;a catalyst activity of the catalyst composition has a copolymer:homopolymer activity ratio in a range from about 2.5:1 to about 5:1;a copolymer:homopolymer activity ratio of the catalyst composition is greater than that of a catalyst system containing a metallocene compound with a different cycloalkyl bridging group; anda copolymer catalyst activity of the catalyst composition is greater than that of a catalyst system containing a metallocene compound with a different cycloalkyl bridging group. 11. The composition of claim 10, wherein: M is Zr or Hf;Cp is a cyclopentadienyl group with a C3 to C8 terminal alkenyl substituent; andRX and RY independently are H or a C1 to C12 hydrocarbyl group. 12. The composition of claim 11, wherein X1 and X2 independently are a halide or a C1 to C12 hydrocarbyl group. 13. The composition of claim 12, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. 14. The composition of claim 12, wherein the catalyst composition comprises a co-catalyst, and wherein the activator comprises an activator-support, the activator-support comprising a solid oxide treated with an electron-withdrawing anion. 15. The composition of claim 10 wherein: the catalyst composition comprises an organoaluminum co-catalyst;the activator comprises a fluorided solid oxide and/or a sulfated solid oxide;M is Zr or Hf;RX and RY independently are H or a C1 to C12 hydrocarbyl group; andX1 and X2 independently are a halide or a C1 to C12 hydrocarbyl group. 16. The composition of claim 10, wherein: the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof;M is Zr or Hf;RX and RY independently are H or a C1 to C12 hydrocarbyl group; andX1 and X2 independently are a halide or a C1 to C12 hydrocarbyl group. 17. A catalyst composition comprising a metallocene compound, an activator, and an optional co-catalyst, wherein the metallocene compound has the formula: wherein: M is Ti, Zr, or Hf;Cp is a cyclopentadienyl group with an alkyl and/or an alkenyl substituent;X1 and X2 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; anda catalyst activity of the catalyst composition has a copolymer:homopolymer activity ratio in a range from about 2.5:1 to about 5:1. 18. The composition of claim 17, wherein: M is Zr or Hf;Cp is a cyclopentadienyl group with a C3 to C8 terminal alkenyl substituent; andRX and RY independently are H or a C1 to C12 hydrocarbyl group. 19. The composition of claim 18, wherein X1 and X2 independently are a halide or a C1 to C12 hydrocarbyl group. 20. The composition of claim 19, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. 21. The composition of claim 19, wherein the catalyst composition comprises a co-catalyst, and wherein the activator comprises an activator-support, the activator-support comprising a solid oxide treated with an electron-withdrawing anion. 22. The composition of claim 17, wherein: the catalyst composition comprises an organoaluminum co-catalyst;the activator comprises a fluorided solid oxide and/or a sulfated solid oxide;M is Zr or Hf;RX and RY independently are H or a C1 to C12 hydrocarbyl group; andX1 and X2 independently are a halide or a C1 to C12 hydrocarbyl group. 23. The composition of claim 17, wherein: the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof;M is Zr or Hf;Rx and RY independently are H or a C1 to C12 hydrocarbyl group; andX1 and X2 independently are a halide or a C1 to C12 hydrocarbyl group.
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