Synthesis of Zwitterionic Copolymers via Copper-Mediated Aqueous Living Radical Grafting Polymerization on Starch

[2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) is a well-studied sulfobetaine-methacrylate as its zwitterionic structure allows the synthesis of polymers with attractive properties like antifouling and anti-polyelectrolyte behavior. In the present work, we report the Cu⁰-mediated living radical polymerization (Cu⁰-mediated LRP) of SBMA in sodium nitrate aqueous solution instead of previously reported solvents like trifluoroethanol and sodium chloride aqueous/alcoholic solution. Based on this, starch-g-polySBMA (St-g-PSBMA) was also synthesized homogeneously by using a water-soluble waxy potato starch-based macroinitiator and CuBr/hexamethylated tris(2-aminoethyl)amine (Me₆TREN) as the catalyst. The structure of the macroinitiator was characterized by ¹H-NMR, ¹³C-NMR, gHSQC, and FT-IR, while samples of PSBMA and St-g-PSBMA were characterized by ¹H-NMR and FT-IR. Monomer conversion was monitored by ¹H-NMR, on the basis of which the reaction kinetics were determined. Both kinetic study and GPC results indicate reasonable controlled polymerization. Furthermore, a preliminary study of the thermal response behavior was also carried through rheological tests performed on aqueous solutions of the prepared materials. Results show that branched zwitterionic polymers are more thermal-sensitive than linear ones.