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Volumn 39, Issue 24, 2006, Pages 8229-8235

Factors affecting the apparent chain transfer rate constants of chromium metalloradicals: Mechanistic implications

Author keywords

[No Author keywords available]

Indexed keywords

CHAIN TRANSFER; CHROMIUM METALLORADICALS; MAYO METHOD; OLIGOMERIZATION;

EID: 33846125248     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma061574c     Document Type: Article
Times cited : (13)

References (41)
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    • Personal communication from Dr. Steven D. Ittel, DuPont
    • Personal communication from Dr. Steven D. Ittel, DuPont.
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    • and J. Am. Chem. Soc. 2006, 128, 11314.
    • and J. Am. Chem. Soc. 2006, 128, 11314.
  • 14
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    • For recent work on cobalt(II)-catalyzed chain transfer during styrene polymerization see: (a) Pierik, S. C. J.; Vollmerhaus, R.; van Herk, A. M.; German, A. L. Macromol. Symp. 2002, 182, 43-52.
    • For recent work on cobalt(II)-catalyzed chain transfer during styrene polymerization see: (a) Pierik, S. C. J.; Vollmerhaus, R.; van Herk, A. M.; German, A. L. Macromol. Symp. 2002, 182, 43-52.
  • 23
    • 33846181789 scopus 로고    scopus 로고
    • With such a high concentration of 1 the chain-carrying radicals are oligomeric. With CS, 400 for 1 in MMA/toluene (from ref 15, the Mayo equation (eq 4) estimates DPn to be about 3
    • n to be about 3.
  • 24
    • 33846169193 scopus 로고    scopus 로고
    • In the presence of such a high concentration of the chain transfer catalyst 1 no significant amount of other MMA oligomers was generated
    • In the presence of such a high concentration of the chain transfer catalyst 1 no significant amount of other MMA oligomers was generated.
  • 26
    • 33846141293 scopus 로고    scopus 로고
    • In the presence of 5 × 10-5 M of 1, the Mayo equation (eq 4) gives DPn, 150 for the resulting polymer, suggesting that propagation is 150 times faster than chain transfer. Under these conditions the fraction of monomeric radical is very small
    • n = 150 for the resulting polymer, suggesting that propagation is 150 times faster than chain transfer. Under these conditions the fraction of monomeric radical is very small.
  • 27
    • 33846135557 scopus 로고    scopus 로고
    • Chain transfer between the methyl isobutyryl radical 3 and 1 can be ignored not only because the fraction of 3 is very small, but because the rate constant of chain transfer from 3 (eq 13) is smaller than that from chain-carrying radicals eq 2, see ref 7
    • Chain transfer between the methyl isobutyryl radical 3 and 1 can be ignored not only because the fraction of 3 is very small, but because the rate constant of chain transfer from 3 (eq 13) is smaller than that from chain-carrying radicals (eq 2) (see ref 7).
  • 28
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    • As quoted in
    • University of Mainz, Stickler, M, 1984 1986
    • Kouloumbris, M. Dissertation, University of Mainz, 1984. As quoted in: Stickler, M. Makromol. Chem. 1986, 187, 1765-1775.
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  • 29
    • 84934292015 scopus 로고    scopus 로고
    • d of AIBMe in benzene at different temperatures were reported in: Otsu, T.; Yamada, B. J. Macromol. Sci. A: Chem. 1969, 3, 187-196.
    • d of AIBMe in benzene at different temperatures were reported in: Otsu, T.; Yamada, B. J. Macromol. Sci. A: Chem. 1969, 3, 187-196.
  • 30
    • 0024886079 scopus 로고    scopus 로고
    • d in styrene are available at various temperatures in O'Driscoll, K. F.; Huang, J. Eur. Polym. J. 1989, 25, 629-633.
    • d in styrene are available at various temperatures in O'Driscoll, K. F.; Huang, J. Eur. Polym. J. 1989, 25, 629-633.
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    • 4th ed, Brandrup, J, Immergut, E. H, Grulke, E. A, Eds, Wiley-Interscience: New York, and references therein
    • Polymer Handbook, 4th ed.; Brandrup, J., Immergut, E. H., Grulke, E. A., Eds.; Wiley-Interscience: New York, 1999; and references therein.
    • (1999) Polymer Handbook
  • 33
    • 0031079083 scopus 로고    scopus 로고
    • -0.19) in: Suddaby, K. G.; Maloney, D. R.; Haddleton, D. M. Macromolecules 1997, 30, 702-713.
    • -0.19) in: Suddaby, K. G.; Maloney, D. R.; Haddleton, D. M. Macromolecules 1997, 30, 702-713.
  • 34
    • 33846126716 scopus 로고    scopus 로고
    • Written by James Ianni, University of Pennsylvania. A free download is available for academic users at http://www.kintecus.com.
    • Written by James Ianni, University of Pennsylvania. A free download is available for academic users at http://www.kintecus.com.
  • 35
    • 33846129235 scopus 로고    scopus 로고
    • -7 M/s).
    • -7 M/s).
  • 36
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    • 1/2 during chain transfer polymerization with cobalt(H) catalysts.
    • 1/2 during chain transfer polymerization with cobalt(H) catalysts.
  • 37
    • 33846156345 scopus 로고    scopus 로고
    • It is difficult to characterize the polymer formed during the first 20 min of a reaction because of the low conversion
    • It is difficult to characterize the polymer formed during the first 20 min of a reaction because of the low conversion.
  • 38
    • 0037203286 scopus 로고    scopus 로고
    • Critically evaluated termination rate coefficients for free-radical polymerization: (a) Buback, M.; Egorov, M.; Gilbert, R. G.; Kaminsky, V.; Olaj, O. F.; Russell, G. T.; Vana, P.; Zifferer, G
    • Two reviews are available from the IUPAC-sponsored Task Group on
    • Two reviews are available from the IUPAC-sponsored Task Group on "Critically evaluated termination rate coefficients for free-radical polymerization": (a) Buback, M.; Egorov, M.; Gilbert, R. G.; Kaminsky, V.; Olaj, O. F.; Russell, G. T.; Vana, P.; Zifferer, G. Macromol. Chem. Phys. 2003, 203, 2570-2582.
    • (2003) Macromol. Chem. Phys , vol.203 , pp. 2570-2582


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