[미국특허]
Stereoselective synthesis of bridged metallocene complexes
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C07F-017/00
C07F-019/00
출원번호
US-0107072
(2013-12-16)
등록번호
US-9018407
(2015-04-28)
발명자
/ 주소
Buck, Richard M.
Yang, Qing
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould
인용정보
피인용 횟수 :
0인용 특허 :
98
초록
The present invention provides methods of making stereo-enriched ansa-metallocene compounds using an unchelated amine compound. Generally, these methods result in a rac:meso isomer selectivity of the stereo-enriched ansa-metallocene compound of greater than 4:1.
대표청구항▼
1. A racemic ansa-metallocene compound having formula (I): E(CpRAn)2M(NR2)m (I); wherein: M is Ti, Zr, Hf, Cr, Sc, Y, La, or a lanthanide;Cp is a cyclopentadienyl, indenyl, or fluorenyl group;E is a substituted or unsubstituted bridging chain of 2 to 8 silicon, germanium, or tin atoms, wherein any
1. A racemic ansa-metallocene compound having formula (I): E(CpRAn)2M(NR2)m (I); wherein: M is Ti, Zr, Hf, Cr, Sc, Y, La, or a lanthanide;Cp is a cyclopentadienyl, indenyl, or fluorenyl group;E is a substituted or unsubstituted bridging chain of 2 to 8 silicon, germanium, or tin atoms, wherein any substituents on atoms of the bridging chain independently are H or a hydrocarbyl group having up to 18 carbon atoms;each R independently is H, a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxide group having up to 18 carbon atoms, or each NR2 group is a heterocyclic group having up to 18 carbon atoms;each RA independently is H or a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxide group having up to 18 carbon atoms;m is 2 when M is Ti, Zr, or Hf;m is 1 when M is Cr, Sc, Y, La, or a lanthanide;n is 0, 1, 2, 3, or 4 when Cp is an indenyl group; andn is 1, 2, 3, or 4 when Cp is a cyclopentadienyl or a fluorenyl group. 2. The compound of claim 1, wherein: M is Ti, Zr, or Hf;Cp is an indenyl group;n is 0; andE is a substituted or unsubstituted bridging chain of 2 to 6 silicon, germanium, or tin atoms. 3. The compound of claim 2, wherein E is a substituted or unsubstituted bridging chain of 2 silicon, germanium, or tin atoms. 4. The compound of claim 1, wherein: M is Ti, Zr, or Hf;Cp is an indenyl group;n is 0;E is a bridging chain having the formula —(SiR11AR11B)2—, wherein R11A and R11B are independently H, methyl, ethyl, propyl, butyl, allyl, butenyl, pentenyl, phenyl, or benzyl; andeach R independently is H or a hydrocarbyl group having up to 18 carbon atoms, or each NR2 group is a heterocyclic group having up to 18 carbon atoms. 5. The compound of claim 4, wherein E is —SiMe2-SiMe2-. 6. The compound of claim 1, wherein: M is Ti, Zr, or Hf;Cp is an indenyl group;n is 1 or 2; andE is a substituted or unsubstituted bridging chain of 2 silicon, germanium, or tin atoms. 7. The compound of claim 6, wherein: each R independently is H or a hydrocarbyl group having up to 18 carbon atoms, or each NR2 group is a heterocyclic group having up to 18 carbon atoms; andeach RA independently is H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, benzyl, tolyl, or trimethylsilyl. 8. The compound of claim 7, wherein E is a bridging chain having the formula —(SiR11AR11B)2—, wherein R11A and R11B are independently H or a hydrocarbyl group having up to 18 carbon atoms. 9. The compound of claim 7, wherein E is —SiMe2-SiMe2-. 10. A stereo-enriched ansa-metallocene compound having formula (I) and a molar ratio of rac isomer to meso isomer of greater than 4:1: E(CpRAn)2M(NR2)m (I); wherein: M is Ti, Zr, Hf, Cr, Sc, Y, La, or a lanthanide;Cp is a cyclopentadienyl, indenyl, or fluorenyl group;E is a substituted or unsubstituted bridging chain of 3 to 8 carbon atoms or 2 to 8 silicon, germanium, or tin atoms, wherein any substituents on atoms of the bridging chain independently are H or a hydrocarbyl group having up to 18 carbon atoms;each R independently is H, a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxide group having up to 18 carbon atoms, or each NR2 group is a heterocyclic group having up to 18 carbon atoms;each RA independently is H or a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxide group having up to 18 carbon atoms;m is 2 when M is Ti, Zr, or Hf;m is 1 when M is Cr, Sc, Y, La, or a lanthanide;n is 0, 1, 2, 3, or 4 when Cp is an indenyl group; andn is 1, 2, 3, or 4 when Cp is a cyclopentadienyl or a fluorenyl group. 11. The compound of claim 10, wherein: the molar ratio of rac isomer to meso isomer is in a range from about 6:1 to about 100:1;M is Ti, Zr, or Hf;Cp is an indenyl group;n is 0;E is a substituted or unsubstituted bridging chain of 3 to 6 carbon atoms or 2 to 6 silicon, germanium, or tin atoms; andeach R independently is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or trimethylsilyl. 12. The compound of claim 11, wherein E is a substituted or unsubstituted bridging chain of 2 silicon, germanium, or tin atoms. 13. The compound of claim 10, wherein: the molar ratio of rac isomer to meso isomer is in a range from about 5:1 to about 100:1; andthe stereo-enriched ansa-metallocene compound having formula (I) is: 14. The compound of claim 10, wherein: the molar ratio of rac isomer to meso isomer is in a range from about 6:1 to about 100:1;M is Ti, Zr, or Hf;n is 1 or 2;E is a substituted or unsubstituted bridging chain of 3 to 6 carbon atoms or 2 to 6 silicon, germanium, or tin atoms;each R independently is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or trimethylsilyl; andeach RA independently is H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, benzyl, tolyl, or trimethylsilyl. 15. The compound of claim 14, wherein: Cp is an indenyl group; andE is a substituted or unsubstituted bridging chain of 2 silicon, germanium, or tin atoms. 16. A stereo-enriched ansa-metallocene compound having formula (V) and a molar ratio of rac isomer to meso isomer of greater than or equal to 6:1: E(CpRAn)2M(Cl)m (V); wherein: M is Ti, Zr, Hf, Cr, Sc, Y, La, or a lanthanide;Cp is a cyclopentadienyl, indenyl, or fluorenyl group;E is a substituted or unsubstituted bridging chain of 3 to 8 carbon atoms or 2 to 8 silicon, germanium, or tin atoms, wherein any substituents on atoms of the bridging chain independently are H or a hydrocarbyl group having up to 18 carbon atoms;each RA independently is H or a hydrocarbyl, hydrocarbylsilyl, hydrocarbylamino, or hydrocarbyloxide group having up to 18 carbon atoms;m is 2 when M is Ti, Zr, or Hf;m is 1 when M is Cr, Sc, Y, La, or a lanthanide;n is 0, 1, 2, 3, or 4 when Cp is an indenyl group; andn is 1, 2, 3, or 4 when Cp is a cyclopentadienyl or a fluorenyl group. 17. The compound of claim 16, wherein: the molar ratio of rac isomer to meso isomer is in a range from 6:1 to about 100:1;M is Ti, Zr, or Hf;Cp is an indenyl group;n is 0;E is a substituted or unsubstituted bridging chain of 3 to 6 carbon atoms or 2 to 6 silicon, germanium, or tin atoms. 18. The compound of claim 17, wherein E is a substituted or unsubstituted bridging chain of 2 silicon, germanium, or tin atoms. 19. The compound of claim 17, wherein E is —SiMe2-SiMe2-. 20. The compound of claim 16, wherein: the molar ratio of rac isomer to meso isomer is in a range from 6:1 to about 100:1;M is Ti, Zr, or Hf;n is 1 or 2;E is a substituted or unsubstituted bridging chain of 3 to 6 carbon atoms or 2 to 6 silicon, germanium, or tin atoms; andeach RA independently is H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, benzyl, tolyl, or trimethylsilyl. 21. The compound of claim 20, wherein: Cp is an indenyl group; andE is a substituted or unsubstituted bridging chain of 2 silicon, germanium, or tin atoms. 22. The compound of claim 20, wherein E is —SiMe2-SiMe2-.
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