Exploration of the Bulk Atom Transfer Radical Polymerization of Styrene

Abstract

ABSTRACTThe synthesis of well‐defined polystyrene by atom transfer radical polymerization (ATRP) is reported. The effects of temperature, initiators, catalysts, and ligands on styrene bulk ATRP were investigated in detail. Results indicated that the initiator activity for a given monomer needs careful matching to bring about a match of the chain‐initiation and chain‐propagation rates. The higher activity is not necessarily the better. Thus, the less reactive monomer, styrene, was efficiently initiated by 1‐phenylethyl bromide (1‐PEBr), which only has a moderate initiator activity. Similarly, the catalyst system had to be carefully matched to achieve a real controlled/living radical polymerization. Controlled/living bulk ATRP of styrene was achieved by using 1‐PEBr as initiator, copper(I) bromide as catalyst, and N,N,N′,N′′,N′′‐ pentamethyldiethyllenetriamine as ligand at 90°C. After 4 h, the monomer conversion reached 51.8%, the practical molecular weight of polystyrene coincided well with the theoretical molecular weight of polystyrene, and the molecular weight distribution was 1.15. © 2013 Wiley Periodicals, Inc. Adv Polym Technol 2013, 32, 21371; View this article online at wileyonlinelibrary.com. DOI 10.1002/adv.21371