Dual roles of 4-N,N-dimethylaminostyrene as both catalyst and monomer in reversible complexation mediated polymerization for the synthesis of functional polystyrene and polystyrene-block-polyisoprene-block-polystyrene

A styrene derivative, 4-N,N-dimethylaminostyrene (MAS), serving as both catalyst and monomer was exploited in reversible complexation mediated polymerization (RCMP). Radical trap experiment and UV–vis spectroscopy analysis revealed that MAS as a catalyst could abstract iodine from iodine-containing compound to generate propagating radical species. Kinetic studies demonstrated that the polymerization of styrene in the presence of MAS proceeded in a “living”/controlled manner, affording polymers with controlled molecular weights and narrow molecular weight distributions. The livingness of the obtained polymer was confirmed by chain extension. Determined by water contact angle measurement, incorporation of MAS into the polymer led to the enhancement of surface energy. Moreover, using α,ω-bis(2-iodo-2-phenylacetoxy)-end functionalized cis-1,4-polyisoprene as a macroinitiator which was synthesized through cross-metathesis of cis-1,4-polyisoprene with cis-1, 4-bis(2-iodo-2-phenylacetoxy)-2-butene, the polymerization of styrene in the presence of MAS also exhibited typical features of “living”/controlled radical polymerization to yield polystyrene-block-polyisoprene-block-polystyrene.