Effect of the Z- and Macro‐R‐Group on the Thermal Desulfurization of Polymers Synthesized with Acid/Base "Switchable" Dithiocarbamate RAFT Agents

Thermolysis is examined as a method for complete desulfurization of reversible addition‐fragmentation chain transfer (RAFT)‐synthesized polymers prepared with acid/base "switchable" N‐methyl‐N‐pyridyldithiocarbamates [R—S₂CZ or R—S₂CZH⁺]. Macro‐RAFT agents from more activated monomers (MAMs) (i.e., styrene (St), N‐isopropylacrylamide (NIPAm), and methyl methacrylate (MMA)) with R—S₂CZH⁺ and less activated monomers (LAMs) (i.e., vinyl acetate (VAc) and N‐vinylpyrolidone (NVP)) with R—S₂CZ are prepared by RAFT polymerization and analyzed by thermogravimetric analysis. In all cases, a mass loss consistent with loss of the end group (Z—CS₂H) is observed at temperatures lower than, and largely discrete from, that required for further degradation of the polymer. The temperatures for end group loss and the new end groups formed are strongly dependent on the identity of the R—(P)<i>_n</i> and the state of the pyridyl Z group; increasing in the series poly(MMA) < poly(St) ∼ poly(NIPAm) << poly(VAc) ∼ poly(NVP) for —S₂CZ and poly(MMA) < poly(St) ∼ poly(NIPAm) for —S₂CZH⁺. Clean end group removal is possible for poly(St) and poly(NVP). For poly(NIPAm), the thiocarbonyl chain end is removed, but the end group identity is less certain. For poly(MMA) and poly(VAc), some degradation of the polymer accompanies end group loss under the conditions used and further refinement of the process is required.