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15) Monteiro, M. J. J. Polym. , Part A: Polym. Chem. 2005, 43, 3189- 3204. ; Gilbert, R. ; Hutchinson, R. ; Manders, B. ; Russell, G. ; Schweer, J. Macromol Chem. Phys. 1995, 196, 3267-3280. ; ACS Symposium Series; American Chemical Society: Washington, DC, 2009. ; Immergut, E. ; Grulke, E. A. ; J. Wiley &Sons: New York, 1999. (18) Tulig, T. ; Tirrell, M. Macromolecules 1981, 14, 1501-1511. (19) Tulig, T. ; Tirrell, M. Macromolecules 1982, 15, 459-463. (20) De Gennes, P. G. Scaling Concepts in Polymer Physics; Cornell University Press: Ithaca, NY, 1979.
ACS Symposium Series; American Chemical Society: Washington, DC, 2009. ch004 55 Figure 2. 0) and dependence of m contents on [thiourea]0/[M]0 in radical polymerization of NIPAM in CH2Cl2 at –78 °C: [M]0/[thiourea]0/[n-Bu3B]0 = 500/0-750/50 mM, with O2. The isospecificities in these polymerizations were lower than the reported ones mediated by metal triflates (20b). ; the m value for DMAM is the highest (m = 74%) and that for NIPAM is almost the same (m = 68%) with the reported highest value for the substituted N-oxide derivatives in CHCl3 at –60 °C (24e).
Figure 1 plots the dependence of the isotactic contents (m) on the amounts of the additives (1–3) in CH2Cl2 at –78 °C. Upon increasing the initial concentrations of 1 and 2, the m values increased from 55% to about 75% although the dependences were slightly different. In contrast, there were almost no changes due to 3. ; ACS Symposium Series; American Chemical Society: Washington, DC, 2009. ch004 53 Figure 1. 0) and dependence of m contents on [thiourea]0/[M]0 in radical polymerization of DMAM in CH2Cl2 at –78 °C: [M]0/[thiourea]0/[n-Bu3B]0 = 500/0-750/50 mM, with O2.