Synthesis, characterization, and aqueous self‐assembly of amphiphilic poly(ethylene oxide)‐functionalized hyperbranched fluoropolymers

Abstract

AbstractComplex amphiphilic polymers were synthesized via core‐first polymerization followed by alkylation‐based grafting of poly(ethylene oxide) (PEO). Inimer 1‐(4′‐(bromomethyl)benzyloxy)‐2,3,5,6‐tetrafluoro‐4‐vinylbenzene was synthesized and subjected to atom transfer radical self‐condensing vinyl polymerization to afford hyperbranched fluoropolymer (HBFP) as the hydrophobic core component with a number‐averaged molecular weight of 29 kDa and polydispersity index of 2.1. The alkyl halide chain ends on the HBFP were allowed to undergo reaction with monomethoxy‐terminated poly(ethylene oxide) amine (PEOx‐NH2) at different grafting numbers and PEO chain lengths to afford PEO‐functionalized HBFPs [(PEOx)y‐HBFPs], with x = 15 while y = 16, 22, or 29, x = 44 while y = 16, and x = 112 while y = 16. The amphiphilic, grafted block copolymers were found to aggregate in aqueous solution to give micelles with number‐averaged diameters (Dav) of 12–28 nm, as measured by transmission electron microscopy (TEM). An increase of the PEO:HBFP ratio, by increase in either the grafting densities (y values) or the chain lengths (x values), led to decreased TEM‐measured diameters. These complex, amphiphilic (PEOx)y‐HBFPs, with tunable sizes, might find potential applications as nanoscopic biomedical devices, such as drug delivery vehicles and 19F magnetic resonance imaging agents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3487–3496, 2010