Photocrosslinkable Star Polymers via RAFT-Copolymerizations with N-Ethylacrylate-3,4-dimethylmaleimide

This paper describes the Z-RAFT-star copolymerization of n-butyl acrylate (BA) and N-isopropyl acrylamide (NIPAm), respectively, with N-ethylacrylate-3,4-dimethylmaleimide (1.1), a monomer carrying a UV-reactive unit that undergoes photocrosslinking. Addition of 1.1 slows down the polymerization rate both for BA and for NIPAm polymerization. Double star formation due to radical attack to the 3,4-dimethylmaleimide moiety was found in the case of BA. Dead polymer formation, presumably due to aminolysis as side-reaction, was pronounced in the NIPAm system. These two effects broadened the molar mass distributions, but did not impede the formation of functional star polymers. The composition of the copolymers as well as the reactivity ratios for the applied comonomers were determined via NMR spectroscopy (BA-co-1.1 r1.1 = 2.24 rBA = 0.95; NIPAm-co-1.1 r1.1 = 0.96 rNIPAm = 0.05). In both cases, the comonomer is consumed preferably in the beginning of the polymerization, thus forming gradient copolymer stars with the UV-reactive units being located in the outer sphere.