IPC분류정보
| 국가/구분 |
United States(US) Patent
등록
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| 국제특허분류(IPC7판) |
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| 출원번호 |
US-0899735
(2010-10-07)
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| 등록번호 |
US-8629292
(2014-01-14)
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발명자
/ 주소 |
- Buck, Richard M.
- Yang, Qing
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| 출원인 / 주소 |
- Chevron Phillips Chemical Company LP
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| 대리인 / 주소 |
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| 인용정보 |
피인용 횟수 :
4 인용 특허 :
94 |
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 method of making a stereo-enriched ansa-metallocene compound having formula (I): E(CpRAn)2M(NR2)m (I), the method comprising: reacting a compound having formula (II): E(CpRAn)2MA2 (II)with an unchelated amine compound having formula (III): M(NR2)mXpLq (III); wherein: M is Ti, Zr, Hf, Cr, Sc,
1. A method of making a stereo-enriched ansa-metallocene compound having formula (I): E(CpRAn)2M(NR2)m (I), the method comprising: reacting a compound having formula (II): E(CpRAn)2MA2 (II)with an unchelated amine compound having formula (III): M(NR2)mXpLq (III); 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, p is 2, and q is 0, 1, or 2 when M is Ti, Zr, or Hf;m is 1, p is 2, and q is 0, 1, 2, or 3 when M is Cr, Sc, Y, La, or a lanthanide;n is 0, 1, 2, 3, or 4 when Cp is an indenyl group;n is 1, 2, 3, or 4 when Cp is a cyclopentadienyl or a fluorenyl group;each MA independently is Li, Na, K, SiRB3, AlRB2, SnRB3, ½ Mg, ½ Zn, MgX, or ZnX, wherein RB is an alkyl group having up to 18 carbon atoms;each X independently is triflate, a halide, or a sulfonate; andeach L independently is a neutral Lewis base donor ligand. 2. The method of claim 1, wherein a molar ratio of rac isomer to meso isomer of the ansa-metallocene compound having formula (I) is greater than about 5:1. 3. The method of claim 2, further comprising a step of isolating the rac isomer. 4. The method of claim 1, further comprising a step of converting the stereo-enriched ansa-metallocene compound having formula (I) to a compound having formula (V): E(CpRAn)2M(Cl)m (V). 5. The method of claim 1, wherein: 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 atoms; andeach R independently is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or trimethylsilyl. 6. The method of claim 5, wherein: each MA independently is Li, Na, or K;each X independently is F, Cl, Br, or I; andE is a bridging chain having the formula —(CR10AR10B)u— or the formula —(SiR11AR11B)v—, wherein: u is 3, 4, or 5;v is 2, 3, or 4, andR10A, R10B, R11A, and R11B are independently H, methyl, ethyl,propyl, butyl, allyl, butenyl, pentenyl, phenyl, or benzyl. 7. The method of claim 5, wherein E is a substituted bridging chain of 2 silicon atoms. 8. The method of claim 5, wherein E is a substituted or unsubstituted bridging chain of 3, 4, or 5 carbon atoms. 9. The method of claim 1, wherein: M is Ti, Zr, or Hf;Cp is a cyclopentadienyl or a fluorenyl group;n is 1 or 2;E is a substituted or unsubstituted bridging chain of 3 to 6 carbon atoms or 2 to 6 silicon 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. 10. The method of claim 9, wherein: each MA independently is Li, Na, or K;each X independently is F, Cl, Br, or I; andE is a bridging chain having the formula —(CR10AR10B)u— or the formula —(SiR11AR11B)v—, wherein: u is 3, 4, or 5;v is 2, 3, or 4, andR10A, R10B, R11A, and R11B are independently H, methyl, ethyl, propyl, butyl, allyl, butenyl, pentenyl, phenyl, or benzyl. 11. The method of claim 1, wherein: q is 2; andeach L independently is THF, acetonitrile, a pyridine, an ether, a thioether, an amine, an isocyanide, or a phosphine. 12. The method of claim 1, wherein the stereo-enriched ansa-metallocene compound having formula (I) comprises: 13. The method of claim 1, wherein the unchelated amine compound having formula (III) comprises: or a combination thereof. 14. The method of claim 1, wherein a molar ratio of the compound having formula (II) to the unchelated amine compound having formula (III) is in a range from about 1.2:1 to about 1:1.2. 15. The method of claim 1, wherein the reacting is conducted in the presence of a solvent, and wherein the solvent comprises an ether, an aliphatic hydrocarbon, an aromatic hydrocarbon, or any combination thereof. 16. A method of making a stereo-enriched ansa-metallocene compound having formula (I): E(CpRAn)2M(NR2)m (I), the method comprising: (a) contacting a compound having formula (IV): E(CpRAn)2 (IV),with a strong base in the presence of a solvent to form an intermediate mixture comprising a dianion of the compound having formula (IV); and(b) contacting the intermediate mixture comprising the dianion of the compound having formula (IV) with an unchelated amine compound having formula (III): M(NR2)mXpLq (III); wherein: the strong base comprises an alkyl lithium, and alkyl sodium, an alkyl potassium, LiCH2SiMe3, LiCH2Ph, LiH, NaH, KH, or any combination thereof;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, p is 2, and q is 0, 1, or 2 when M is Ti, Zr, or Hf;m is 1, p is 2, and q is 0, 1, 2, or 3 when M is Cr, Sc, Y, La, or a lanthanide;n is 0, 1, 2, 3, or 4 when Cp is an indenyl group;n is 1, 2, 3, or 4 when Cp is a cyclopentadienyl or a fluorenyl group;each X independently is triflate, a halide, or a sulfonate; andeach L independently is a neutral Lewis base donor ligand. 17. The method of claim 16, wherein a molar ratio of rac isomer to meso isomer of the ansa-metallocene compound having formula (I) is greater than about 5:1. 18. The method of claim 16, wherein the strong base comprises MeLi, n-BuLi, t-BuLi, n-hexylLi, LiCH2SiMe3, LiCH2Ph, LiCH2CMe3, LiH, NaH, KH, or any combination thereof. 19. The method of claim 1, wherein: M is Ti, Zr, or Hf;Cp is an indenyl group;n is 0, 1, or 2;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;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; anda molar ratio of rac isomer to meso isomer of the ansa-metallocene compound having formula (I) is in a range from about 5:1 to about 100:1. 20. The method of claim 19, wherein: R11A and R11B are independently H, methyl, ethyl, propyl butyl, allyl, butenyl, pentenyl, phenyl, or benzyl;each R independently is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, noyl, or decyl;each 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;each L independently is THF, acetonitrile, a pyridine, and either, a thioether, an amine, an isocyanide, or a phosphine; anda molar ratio of rac isomer to meso isomer of the ansa-metallocene compound having formula (I) is in a range from about 5:1 to about 90:1. 21. The method of claim 20, wherein: q is 2;each MA independently is Li, Na, or K; andeach X independently is F, Cl, Br, or I. 22. The method of claim 21, wherein n is 0.
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