Controlled Synthesis of High-Molecular-Weight Polystyrene and Its Block Copolymers by Emulsion Organotellurium-Mediated Radical Polymerization

Structurally controlled high-molecular-weight (HMW) polystyrenes (PSts) and block copolymers consisting of HMW PSt segments were successfully synthesized by emulsion organotellurium-mediated radical polymerization (TERP). The hydrophilicity of the organotellurium group of TERP chain transfer agents (CTAs) was important for success, and CTAs 1b and 1c with di- and tetraethylene glycol units were suitable. By using 1b and 1c and using hexadecyltrimethylammonium bromide (CTAB) as the surfactant, PSts with MWs over 1 million and with low dispersity (Đ < 1.6) were synthesized with >96% monomer conversion. Because of the high monomer conversion, high end-group fidelity, and rapid monomer diffusion to polymer particles, HMW block copolymers with low dispersity were successfully synthesized by adding a second monomer after converting the first monomer without isolating the macroinitiators. Despite recent developments in reversible-deactivation radical polymerization (RDRP), the synthesis of HMW polymers, particularly PSts and block copolymers, has been a formidable challenge. This method provides a valuable route for fabricating polymer materials based on HMW PSts.