Light-Mediated Atom Transfer Radical Polymerization of Semi-Fluorinated (Meth)acrylates: Facile Access to Functional Materials

Emre H. Discekici, Athina Anastasaki, Revital Kaminker, Johannes Willenbacher, Nghia P. Truong, Carolin Fleischmann, Bernd Oschmann, David J. Lunn, Javier Read De Alaniz, Thomas P. Davis, Christopher M. Bates, Craig Jon Hawker

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79 Citations (Scopus)


A highly efficient photomediated atom transfer radical polymerization protocol is reported for semi-fluorinated acrylates and methacrylates. Use of the commercially available solvent, 2-trifluoromethyl-2-propanol, optimally balances monomer, polymer, and catalyst solubility while eliminating transesterification as a detrimental side reaction. In the presence of UV irradiation and ppm concentrations of copper(II) bromide and Me6-TREN (TREN = tris(2-aminoethyl amine)), semi-fluorinated monomers with side chains containing between three and 21 fluorine atoms readily polymerize under controlled conditions. The resulting polymers exhibit narrow molar mass distributions (D ≈ 1.1) and high end group fidelity, even at conversions greater than 95%. This level of control permits the in situ generation of chain-end functional homopolymers and diblock copolymers, providing facile access to semi-fluorinated macromolecules using a single methodology with unprecedented monomer scope. The results disclosed herein should create opportunities across a variety of fields that exploit fluorine-containing polymers for tailored bulk, interfacial, and solution properties.

Original languageEnglish
Pages (from-to)5939-5945
Number of pages7
JournalJournal of the American Chemical Society
Issue number16
Publication statusPublished - 26 Apr 2017

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