Polymerization of Styrene Sulfonate Ethyl Ester by ATRP: Synthesis and Characterization of Macromonomers for Suzuki Polycondensation

Summary: Macromonomers from SSE were synthesized via ATRP with initiators carrying functional groups that are polymerizable by Suzuki polycondensation. The material obtained had a monomodal molar mass distribution with a polydispersity of 1.3–1.6. The reaction kinetics in bulk and in solution were monitored by in situ 1H NMR spectroscopy. Rate constants and the activation energy for SSE polymerization were determined to be k = 5.5 · 10−5 s−1 (DMF, 60 °C), 6.6 · 10−4 s−1/1.4 · 10−3 s−1/4.8 · 10−3 s−1 (bulk, 45/60/75 °C), Ea = 60.1 kJ · mol−1 (bulk). Hydrolysis yielded the corresponding macromonomers of poly(styrene sulfonic acid). Monomer conversion for different reaction temperatures and exponential fit to the data for the SSE polymerization in bulk.