Abstract
The dynamics of in-core perfluorinated alkyl pendants in microgel star polymers were investigated by 19F nuclear magnetic resonance spectroscopy and 19F spin–spin relaxation time (T2) measurements, to elucidate the origin of the efficient encapsulation of perfluorinated guests into the fluorous microgel cores. Fluorinated microgel star polymers were prepared by the linking reaction of chlorine-capped poly(methyl methacrylate) arms with dimethacrylate linking agents and a perfluorinated methacrylate via ruthenium-catalyzed living radical polymerization. Temperature-dependent T2 measurements revealed the reduced thermodynamic mobility of the perfluorinated pendants indicative of their accumulation and thus aggregation in the core network. Fluorinated microgel star polymers accordingly provide stable “fluorous compartments” where the encapsulation of perfluoromethylcyclohexane (PFMCH) in DMF is better attained and more efficient than that in the corresponding block copolymer micelles.
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