Controlled radical polymerization of N-vinylpyrrolidone by reversible addition-fragmentation chain transfer process

Poly(N-vinylpyrrolidone) (PNVP) was polymerized by RAFT process using diphenyldithiocarbamate of diethylmalonate (DPCM) as the reversible chain transfer agent in the presence of a small percentage of a conventional radical initiator (AIBN). The molar mass of the polymers synthesized by this method was found to increase with conversion and time. The presence of end group in the polymer chain could be confirmed by ¹H NMR spectra. The molar masses calculated using ¹H NMR spectroscopy and static light scattering (SLS) showed good agreement with the theoretical molar masses. The RAFT compound was fully consumed during the initial stages of the polymerization itself. The controlled nature of these polymers was further confirmed by generating diblock copolymers by sequential addition of monomers such as styrene or n-butyl acrylate (n-BA). PNVP efficiently participated as a macro-RAFT reagent, and cross-over reaction between the two blocks efficiently occurred. The successful diblock copolymer synthesis using PNVP as macro-transfer reagent further confirms the "controlled" nature of such synthetic procedure.