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

Authors

  • Wenjun Du,

    1. Departments of Chemistry and Radiology, Washington University in Saint Louis, Saint Louis, Missouri 63130
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  • Yali Li,

    1. Departments of Chemistry and Radiology, Washington University in Saint Louis, Saint Louis, Missouri 63130
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  • Andreas M. Nyström,

    1. Departments of Chemistry and Radiology, Washington University in Saint Louis, Saint Louis, Missouri 63130
    Current affiliation:
    1. Department of Neuroscience and The Swedish Medical Nanoscience Center, Karolinska Institute, SE-17776 Stockholm, Sweden
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  • Chong Cheng,

    1. Departments of Chemistry and Radiology, Washington University in Saint Louis, Saint Louis, Missouri 63130
    Current affiliation:
    1. Department of Chemical and Biological Engineering, the State University of New York at Buffalo, Buffalo, New York 14260
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  • Karen L. Wooley

    Corresponding author
    1. Departments of Chemistry and Radiology, Washington University in Saint Louis, Saint Louis, Missouri 63130
    Current affiliation:
    1. Department of Chemistry, Texas A&M University, College Station, Texas 77842
    • Departments of Chemistry and Radiology, Washington University in Saint Louis, Saint Louis, Missouri 63130
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Abstract

Complex 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

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