UC Santa Cruz

Three novel fluorinated alkoxyamines were synthesized for nitroxide-mediated precipitation polymerization (NMP) of styrene in supercritical carbon dioxide. The polymerizations were conducted in supercritical carbon dioxide without excess free nitroxide to allow for a detailed study on nitroxide partitioning. The addition of a fluorinated moiety allowed for increased partitioning relative to the parent nitroxide into supercritical carbon dioxide. The loss of control over the polymerization due to nitroxide partitioning did not have a significant influence on the polymerization rate. Synthesis of polyfluorinated macroinitiators by atom transfer radical polymerization (ATRP) of fluorinated monomers was explored but thwarted due to a lack of solubility. The increased fluorine content due to polymerization of fluorinated monomers would have allowed direct control over the quantity of fluorine added to the macroinitiator and potentially influenced the quantity of nitroxide partitioning.