Synthesis and characterization of polypropylene-based block copolymers possessing polar segments via controlled radical polymerization

A new method to prepare the polypropylene (PP) macroinitiator for controlled radical polymerization was described. Bromination of terminally-unsaturated PP was carried out by using N-bromosuccinimide and 2,2′-azobis(isobutyronitrile) to give a brominated PP (PP-Br), that has allylic bromide moieties at or near the chain ends. Thus, the obtained PP-Br was successfully used as a macroinitiator for radical polymerization of styrene, methyl methacrylate, and n-butyl acrylate using a copper catalyst system. From ¹H NMR analysis, it was confirmed that the chain extension polymerization was certainly initiated from allylic bromide moieties with high efficiency, leading to the PP-based block copolymers linking the polar segment. From differential scanning calorimetry, it was observed that peak melting temperature of block copolymers was higher than that of PP-Br and the obtained PP-PS block copolymers with different compositions of each segment demonstrated the unique morphological features due to the microphase separation between both segments. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 812–823, 2009