By Krzysztof Matyjaszewski (Eds.)
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Additional info for Controlled/Living Radical Polymerization. Progress in ATRP, NMP, and RAFT
Macromolecules 1999, 32, 2948. ; ACS Symposium Series; American Chemical Society: Washington, DC, 2000. ch003 Institut für Physikalische Chemie der Georg-August-Universität, Tammannstrasse 6, D-37077 Göttingen, Germany A n almost constant value of chain-length averaged termination rate coefficient, k , is observed during the initial period of free-radical homo- and copolymerizations in bulk and in solution with the extension of this plateau region depending on monomer type and on the particular polymerization conditions.
Am. Chem. , Div. Polym. ) 1997, 38(1), 6. 3. Curran, D . P. Synthesis 1988, 489. 4. Quiclet-Sire, B . ; Zard, S. Z . Pure & Appl. Chem. 1997, 69, 645. 5. Solomon, D . , 1986, U . S. Pat. 4, 581, 429. 6. Georges, M. K . ; Veregin, R. P. ; Kazmaier, P. ; Hamer, G . K . Macromolecules 1993, 26, 2987. 7. ; Finet, J. ; Gnanou, Y. ACS Symp. Ser. 1998, 685, 225. 8. ; Hawker, C. J. J. Am. Chem. Soc. 1999, 121, 3904. 9. ; Muellen, K . ; Hubrich, M. Macromolecules 1998, 31, 5223. 10. ; Florian, S. Angew.
Data in Figure 5. The suitability of this penultimate model to fit kt strongly suggests that steric effects are controlling termination behavior in the initial plateau region of (meth)acrylates. ; ACS Symposium Series; American Chemical Society: Washington, DC, 2000. 46 the terminal and the penultimate segments on the macroradical chain appears to sufficiently account for the shielding action at the free-radical site. Assuming a rate control by steric effects may also explain the similarity in the homo-Vs of D A and D M A : As the shielding effect of the dodecyl group will largely exceed the corresponding action of a methyl group, the addition of a C H group to D A , to yield D M A , will not extensively vary the shielding situation.
Controlled/Living Radical Polymerization. Progress in ATRP, NMP, and RAFT by Krzysztof Matyjaszewski (Eds.)