Study of the Reaction between Nitroxide-Terminated Polymers and Thiuram Disulfides. Toward a Method of Functionalization of Polymers Prepared by Nitroxide Mediated Free “Living” Radical Polymerization

Nitroxide-terminated polystyrenes resulting from “living” free radical polymerization processes have been “functionalized” by combination reaction with thiuram disulfide compounds, i.e., tetraethyl thiuram disulfide ( 3a ), and N, N ‘-diethyl- N, N ‘-bis{2-((trimethylsilyl)oxy)ethyl} thiuram disulfide ( 3c ). The quantitative substitution of the nitroxide moiety by the dithiocarbamate group has been characterized by 1 H NMR, 13 C NMR, and IR spectroscopy, MALDI-TOF mass spectrometry, ESI mass spectrometry, and LSI mass spectrometry. The reaction has also been studied on a model compound.