RAFT-mediated synthesis of poly(N-(2-hydroxypropyl)methacrylamide-b-4-vinylpyridine) by conventional and microwave heating

We report the synthesis of N-(2-hydroxypropyl)methacrylamide (HPMA) macroCTA and HPMA-b-4-Vinylpyridine block copolymers via reversible addition-fragmentation chain transfer (RAFT) reaction. Polymerization was carried out in dimethylformamide (DMF) at 70 °C using 4-Cyano-4(thiobenzoylthio) pentanoic acid as chain transfer agent and AIBN as an initiator. Control over molecular weight and composition was achieved by altering the CTA, monomer and initiator feed ratio. The controlled living character of the polymerization was verified with pseudo-first-order kinetic plots, a linear increase of the molecular weight with conversion, and low polydispersities (PDIs ≤ 1.2). Effect of microwave heating on the homo- and copolymer formation was investigated and the rates were significantly higher than those observed under conventional heating conditions. These polymerization reactions were in controlled fashion resulting in polymers with low PDIs, too. These polymers have a great potential to be used in developing delivery vehicles and conjugates for further drug or gene delivery applications.