A novel azo‐containing dithiocarbamate used for living radical polymerization of methyl acrylate and styrene

Abstract

AbstractA novel azo‐containing dithiocarbamate, 1‐phenylethyl N,N‐(4‐phenylazo) phenylphenyldithiocarbamate (PPADC), was successfully synthesized and used to mediate the polymerization of methyl acrylate (MA) and styrene (St). In the presence of PPADC, the reversible addition‐fragmentation chain transfer (RAFT) polymerization was well controlled in the case of MA, however, the slightly ill‐controlled in the case of St. Interestingly, the polymerization of St could be well‐controlled when using PPADC as the initiator in the presence of CuBr/PMDETA via atom transfer radical polymerization (ATRP) technique. In the cases of RAFT polymerization of MA and ATRP of St, the kinetic plots were both of first‐order, and the molecular weight of the polymer increased linearly with the monomer conversion while keeping the relatively narrow molecular weight distribution (Mw/Mn). The molecular weight of the polymer measured by gel permeation chromatographer (GPC) was also close to the theoretical value (Mn(th)). The obtained polymer was characterized by 1H‐NMR analysis, ultraviolet absorption, FTIR spectra analysis and chain‐extension experiments. Furthermore, the photoresponsive behaviors of azobenzene‐terminated poly(methyl acrylate) (PMA) and polystyrene (PS) were similar to PPADC. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5626–5637, 2008