Threshold Particle Diameters in Miniemulsion Reversible-Deactivation Radical Polymerization 英文参考文献.docVIP

Polymers 2011, 3, 1944-1971; doi:10.3390/polym3041944 OPEN ACCESS polymers ISSN 2073-4360 /journal/polymers Article Threshold Particle Diameters in Miniemulsion Reversible-Deactivation Radical Polymerization Hidetaka Tobita Department of Materials Science and Engineering, University of Fukui, 3-9-1 Bunkyo, Fukui 901-8507, Japan; E-Mail: tobita@matse.u-fukui.ac.jp; Tel.: +81-776-27-8775; Fax: +81-776-27-8767 Received: 7 September 2011; in revised form: 17 October 2011 / Accepted: 9 November 2011 / Published: 11 November 2011 Abstract: Various types of controlled/living radical polymerizations, or using the IUPAC recommended term, reversible-deactivation radical polymerization (RDRP), conducted inside nano-sized reaction loci are considered in a unified manner, based on the polymerization rate expression, Rp = kp[M]K[Interm]/[Trap]. Unique miniemulsion polymerization kinetics of RDRP are elucidated on the basis of the following two factors: (1) A high single molecule concentration in a nano-sized particle; and (2) a significant statistical concentration variation among particles. The characteristic particle diameters below which the polymerization rate start to deviate significantly (1) from the corresponding bulk polymerization, and (2) from the estimate using the average concentrations, can be estimated by using simple equations. For stable-radical-mediated polymerization (SRMP) and atom-transfer radical polymerization (ATRP), an acceleration window is predicted for the particle diameter range, ,T p ,T . For reversible-addition-fragmentation chain-transfer polymerization (RAFT), degenerative-transfer radical polymerization (DTRP) and also for the conventional nonliving radical polymerization, a significant rate increase occurs for ,R? . On the other hand, for p ,M the polymerization rate is suppressed because of a larg