Macromolecules, Vol.39, No.13, 4386-4394, 2006
Nanophasic amphiphilic conetworks with a fluorophilic phase
Amphiphilic conetworks, generally considered as hydrophilic/ hydrophobic materials, are recently gaining great interest due to their wide range of possible applications in catalysis, sensors, and biomedical applications. However, little is known about conetworks with highly fluorinated phases. Here, we describe two readily available methods that allow the synthesis of nanophase separated hydrophobic/fluorophilic and hydrophilic/ fluorophilic conetworks. The first kind was achieved by the novel "hot plate technique", which allows to homogenize a mixture of the perfluoro-tagged 1H, 1H, 2H, 2H-hexadecylfluorodecyl acrylate and a dimethacrylate terminated poly( dimethylsiloxane). Upon photopolymerization, nanophase separated conetworks in all compositions were obtained. Further, hydrophilic/ fluorophilic conetworks could be accessed by applying the precursor approach for the synthesis of amphiphilic conetworks. To this end, 2-hydroxyethyl acrylate was modified with a perfluoro-tagged silane, mixed with dimethacrylate-terminated perfluoropolyether, photopolymerized, and subsequently deprotected. The amphiphilic behavior as well as the nanophase morphology of all conetworks was proven with swelling experiments, AFM, TEM, and DSC measurements. Preliminary results show the great affinity of the hydrophilic/ fluorophilic conetworks to the catalytically important enzyme lipase, indicating their potential as phase transfer matrix for biotransformations in perfluorinated solvents and supercritical fluids.