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Volumn 129, Issue 22, 2007, Pages 7065-7076

Penultimate effect in ethylene-styrene copolymerization and the discovery of highly active ethylene-styrene catalysts with increased styrene reactivity

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; COPOLYMERIZATION; CRYSTAL STRUCTURE; REACTION KINETICS; STYRENE;

EID: 34250206624     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja070061y     Document Type: Article
Times cited : (68)

References (77)
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    • U.S. Patent 6,670,432 B1, 2003 The Dow Chemical Company
    • (b) Timmers, F. J. U.S. Patent 6,670,432 B1, 2003 (The Dow Chemical Company).
    • Timmers, F.J.1
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    • 3 produced, in addition to ES polymers, substantial amounts of polyethylene and polystyrene homopolymer impurities.
    • 3 produced, in addition to ES polymers, substantial amounts of polyethylene and polystyrene homopolymer impurities.
  • 9
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    • (d) Xu, G. Macromolecules 1998, 31, 2395-2402.
    • (1998) Macromolecules , vol.31 , pp. 2395-2402
    • Xu, G.1
  • 21
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    • For a review on ethylene-styrene polymerization, see
    • For a review on ethylene-styrene polymerization, see: Pellecchia, C.; Oliva, L. Rubber Chem. Technol. 1999, 72, 553-558.
    • (1999) Rubber Chem. Technol , vol.72 , pp. 553-558
    • Pellecchia, C.1    Oliva, L.2
  • 51
  • 52
    • 84972924919 scopus 로고    scopus 로고
    • The convention used for assigning carbon methylene labels such as αβ describes the position relative to the nearest methine carbon in both directions along the polymer chain. Randall, J. C. Rev. Macromol. Chem. Phys. 1989, C29, 201-317
    • The convention used for assigning carbon methylene labels such as αβ describes the position relative to the nearest methine carbon in both directions along the polymer chain. Randall, J. C. Rev. Macromol. Chem. Phys. 1989, C29, 201-317.
  • 53
    • 34250160302 scopus 로고    scopus 로고
    • The substituent effect parameter and corrective terms were taken from ref 11. The values for a phenyl substituent were obtained from: Pretsch, E.; Clerc, T.; Seible, J.; Simon, W. Tables of Spectral Data for Structure Determination of Organic Compounds; Springer-Verlag: 1989.
    • The substituent effect parameter and corrective terms were taken from ref 11. The values for a phenyl substituent were obtained from: Pretsch, E.; Clerc, T.; Seible, J.; Simon, W. Tables of Spectral Data for Structure Determination of Organic Compounds; Springer-Verlag: 1989.
  • 54
    • 34250191923 scopus 로고    scopus 로고
    • A pair of αβ peaks of equal intensity arises from the relative stereochemical arrangement (rac and meso) of the phenyl substituents on either side of αβ methylene units.
    • A pair of αβ peaks of equal intensity arises from the relative stereochemical arrangement (rac and meso) of the phenyl substituents on either side of αβ methylene units.
  • 55
    • 34250183542 scopus 로고    scopus 로고
    • This assumption is not necessary for the kinetic modeling as described herein since the polymers possess reasonably high molecular weights, and end group effects are near zero. This is opposed to low molecular weight oligomers, where chemical shift differences may be observed due to differences in proximity to the end group
    • This assumption is not necessary for the kinetic modeling as described herein since the polymers possess reasonably high molecular weights, and end group effects are near zero. This is opposed to low molecular weight oligomers, where chemical shift differences may be observed due to differences in proximity to the end group.
  • 56
    • 34250206065 scopus 로고    scopus 로고
    • Unpublished results
    • Unpublished results.
  • 59
  • 60
    • 34250168405 scopus 로고    scopus 로고
    • See Supporting Information for details
    • See Supporting Information for details.
  • 65
    • 34250220766 scopus 로고    scopus 로고
    • In theory, silylation could also occur at a quaternary carbon in the Cp. However, due to steric effects this scenario is not very likely
    • In theory, silylation could also occur at a quaternary carbon in the Cp. However, due to steric effects this scenario is not very likely.
  • 68
    • 14844335717 scopus 로고    scopus 로고
    • A lower quality structure of 1 has recently been published. Nishii, K.; Ikeda, T.; Akita, M.; Shiono T. J. Mol. Catal. A: Chem. 2005, 231, 241-246.
    • A lower quality structure of 1 has recently been published. Nishii, K.; Ikeda, T.; Akita, M.; Shiono T. J. Mol. Catal. A: Chem. 2005, 231, 241-246.
  • 69
    • 0003315619 scopus 로고    scopus 로고
    • For other Ti-diphenylbutadiene complexes, see: a
    • For other Ti-diphenylbutadiene complexes, see: (a) Spencer, M. D.; Wilson, S. R.; Girolami, G. S. Organometallics 1997, 16, 3055-3067.
    • (1997) Organometallics , vol.16 , pp. 3055-3067
    • Spencer, M.D.1    Wilson, S.R.2    Girolami, G.S.3
  • 71
    • 0035948489 scopus 로고    scopus 로고
    • Heteroatom Cp and indenyl substitution was shown to exert a considerable electronic effect on the geometry of CGC complexes: (a) Klosin, J, Kruper, W. J, Jr, Nickias, P. N, Roof, G. R, De Waele, P, Abboud, K. A. Organometallics 2001, 20, 2663-2665
    • Heteroatom Cp and indenyl substitution was shown to exert a considerable electronic effect on the geometry of CGC complexes: (a) Klosin, J.; Kruper, W. J., Jr.; Nickias, P. N.; Roof, G. R.; De Waele, P.; Abboud, K. A. Organometallics 2001, 20, 2663-2665.
  • 74
    • 34250219725 scopus 로고    scopus 로고
    • Both 2 and 3 were found to be somewhat less efficient than 1 in ethylene/1-octene polymerization processes. Octene reactivity was found to be comparable for 1 and 2 but much higher for 3 which is consistent with 3 offering a less congested active site. Interestingly, while the molecular weight of ES polymers was found to be the highest for 3 and the lowest for 1, the molecular weight trend is reversed for EO polymerization. See Supporting Information for details.
    • Both 2 and 3 were found to be somewhat less efficient than 1 in ethylene/1-octene polymerization processes. Octene reactivity was found to be comparable for 1 and 2 but much higher for 3 which is consistent with 3 offering a less congested active site. Interestingly, while the molecular weight of ES polymers was found to be the highest for 3 and the lowest for 1, the molecular weight trend is reversed for EO polymerization. See Supporting Information for details.
  • 75
    • 34250214262 scopus 로고    scopus 로고
    • Catalysts 3a and 3b exhibit comparable ES polymerization performance.
    • Catalysts 3a and 3b exhibit comparable ES polymerization performance.
  • 76
    • 34250219344 scopus 로고    scopus 로고
    • See Supporting Information for details
    • See Supporting Information for details.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.