Aryl-based perfluoroalkoxides: How length and branching of the fluorinated initiator Influences the polymerization of hexafluoropropylene xxide (HFPO)

Fluoropolymers are relied upon in many industries, especially those that deal with harsh environments. Industrial hexafluoropropylene oxide (HFPO) polymers are monofunctional, limiting application. Generation of novel aryl initiation would allow for telechelic polymers increasing their potential range of application. In this thesis I looked at the effects CF2 chain length and α-branching of novel arylperfluoroalkoxide initiators had on the polymerization of HFPO. Our secondary focus was to identify the most stable perfluoroarylalkoxide initiator. The efficacy of these initiators was determined by the ratio of chain transfer, polymer length and distributions DPn, Mn, Mw and PDI as well as synthetic challenges. I found that as α-CF3 branching increased polymer length and distributions decreased and chain transfer increased. As alkoxide CF2 length increased there was only a small positive change. Cesium 1,1,2,2-tetrafluoro-2-phenylethan-1-olate was found to have the greatest polymer length and distributions whereas cesium 1,1,2,2,3,3-hexafluoro-3-phenylpropan-1-olate was found to have the least chain transfer.