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Polymers 2011, 3(4), 1944-1971; doi:10.3390/polym3041944

Threshold Particle Diameters in Miniemulsion Reversible-Deactivation Radical Polymerization

Department of Materials Science and Engineering, University of Fukui, 3-9-1 Bunkyo, Fukui 901-8507, Japan
Received: 7 September 2011 / Revised: 17 October 2011 / Accepted: 9 November 2011 / Published: 11 November 2011
(This article belongs to the Special Issue Living Polymerization Techniques)

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, . 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 . On the other hand, for  the polymerization rate is suppressed because of a large statistical variation of monomer concentration among particles. View Full-Text
Keywords: controlled/living radical polymerization; emulsion polymerization; stable-radical-mediated polymerization (SRMP); atom-transfer radical polymerization (ATRP); reversible-addition-fragmentation chain-transfer polymerization (RAFT); polymerization kinetics controlled/living radical polymerization; emulsion polymerization; stable-radical-mediated polymerization (SRMP); atom-transfer radical polymerization (ATRP); reversible-addition-fragmentation chain-transfer polymerization (RAFT); polymerization kinetics
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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Tobita, H. Threshold Particle Diameters in Miniemulsion Reversible-Deactivation Radical Polymerization. Polymers 2011, 3, 1944-1971.

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