Fast and effective copper(0)-mediated simultaneous chain- and step-growth radical polymerization at ambient temperature.

ABSTRACT Vinyl-conjugated monomer (methyl acrylate, MA) and allyl 2-bromopropanoate (ABP)-possessing unconjugated CC and active CBr bonds were polymerized via the Cu(0)-mediated simultaneous chain- and step-growth radical polymerization at ambient temperature using Cu(0) as catalyst, N, N, N′, N″, N″-pentamethyldiethylenetriamine as ligand and dimethyl sulfoxide as solvent. The conversion was reached higher than 98% within 20 h. The obtained polymers showed block structure consisting of polyester and vinyl polymer moieties. The Cu(0)-catalyzed simultaneous chain- and step-growth radical polymerization mechanism was demonstrated by NMR, matrix-assisted laser desorption ionization time-of-flight, and GPC analyses. Furthermore, the obtained copolymers of MA and ABP were further modified with poly( N-isopropylamide) through radical thiol-ene 'click' chemistry from the terminal double bond. The thermoresponsive behavior of this block copolymer was investigated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3907-3916 [ABSTRACT FROM AUTHOR]