Fluorinated polyhedral oligomeric silsesquioxane-based shape amphiphiles: Molecular design, topological variation, and facile synthesis

Citation data:

Polymer Chemistry, ISSN: 1759-9954, Vol: 3, Issue: 8, Page: 2112-2120

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https://ideaexchange.uakron.edu/polymerengin_ideas/1384; https://works.bepress.com/kevin_cavicchi/12
He, Jinlin; Yue, Kan; Liu, Yuging; Yu, Xinfei; Ni, Peihong; Cavicchi, Kevin; Quirk, Roderic P.; Chen, Er-Qiang; Cheng, Stephen Z. D.; Zhang, Wen-Bin
Royal Society of Chemistry (RSC); The Royal Society of Chemistry
Chemical Engineering; Biochemistry, Genetics and Molecular Biology; Materials Science; Chemistry; Engineering
article description
This paper reports the design and synthesis of fluoroalkyl-functionalized polyhedral oligomeric silsesquioxane (FPOSS)-based shape amphiphiles with two distinct topologies: (i) mono-tethered FPOSS-poly(ε-caprolactone) (PCL) and (ii) FPOSS tethered with two polymer chains possessing different compositions, namely, polystyrene (PS) and PCL, denoted as PS-(FPOSS)-PCL. The synthetic strategy features an efficient "growing-from" and "click- functionalization" approach. From a monohydroxyl-functionalized heptavinyl POSS, a PCL chain was grown via ring opening polymerization (ROP) of ε-caprolactone; subsequent thiol-ene "click" chemistry with 1H,1H,2H,2H-perfluoro-1-decanethiol allowed the facile introduction of seven perfluorinated alkyl chains onto the POSS head. Similarly, PS-(FPOSS)-PCL was synthesized from a PS precursor bearing both hydroxyl group and heptavinyl POSS at the ω-end, which was prepared by living anionic polymerization and hydrosilylation. The compounds were fully characterized byH NMR,C NMR, FT-IR spectroscopy, MALDI-TOF mass spectrometry, and size exclusion chromatography. The introduction of perfluorinated molecular cluster into polymers is expected to make them surface-active while the interplay between crystallization and fluorophobic/fluorophilic bulk phase separation in these shape amphiphiles shall lead to intriguing self-assembly behavior and novel hierarchical structures. This study has demonstrated FPOSS as a versatile building block in the construction of shape amphiphiles and established a general and efficient method to introduce such fluorous molecular clusters into polymers. © 2012 The Royal Society of Chemistry.