A new approach to multiblock copolymers using atom transfer radical coupling

Atom transfer radical coupling (ATRC) is a method for chain extension of styrene homopolymers prepared by atom transfer radical polymerization (ATRP). This concept is used to produce multiblock copolymers from block copolymers prepared via ATRP of styrene using various macroinitiators. ATRC comprises the reactivation of the dormant species at the chain ends. In the absence of monomer, the active radical species recombine to give chain extension (from polystyrene, PS) or multiblock copolymers (from block copolymers). The application of ATRC to PSblock- poly(bisphenol A carbonate)-block-PS (PS-b-PC-b-PS) was not successful because chain degradation of the PC block occurs. However, poly(phenylene oxide)-block-PS (PPO-b-PS) and PS-b-PPO-b-PS were successfully transformed into tri- and multiblock copolymers by ATRC, although the coupling efficiency is not as high as observed for PS oligomers under similar conditions.