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Gelation and Hollow Particle Formation in Nitroxide-Mediated Radical Copolymerization of Styrene and Divinylbenzene in Miniemulsion

✍ Scribed by Per B. Zetterlund; Yuichi Saka; Masayoshi Okubo

Publisher
John Wiley and Sons
Year
2008
Tongue
English
Weight
290 KB
Volume
210
Category
Article
ISSN
1022-1352

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✦ Synopsis

Abstract

Network formation in the nitroxide‐mediated cross‐linking copolymerization of styrene and divinylbenzene (3 or 8.2 mol‐% relative to total monomer) using the nitroxide 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy (TEMPO) at 125 °C can proceed markedly differently in aqueous miniemulsion compared to the corresponding solution polymerization depending on the organic‐phase composition. When the organic phase comprises 54 vol‐% of the hydrophobe tetradecane, gelation occurs at much lower conversion in miniemulsion than in solution, and at significantly lower conversion than predicted by Flory–Stockmayer gelation theory. This is proposed to be a result of an effect of the oil–water interface, whereby the concentration of polymer with pendant unsaturations is higher near the interface than in the particle interior.

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