Reversible addition–fragmentation chain transfer mediated radical polymerization of asymmetrical divinyl monomers targeting hyperbranched vinyl polymers

Reversible addition–fragmentation chain transfer (RAFT) mediated radical polymerizations of allyl methacrylate and undecenyl methacrylate, compounds containing two types of vinyl groups with different reactivities, were investigated to provide hyperbranched polymers. The RAFT agent benzyl dithiobenzoate was demonstrated to be an appropriate chain‐transfer agent to inhibit crosslinking and obtain polymers with moderate‐to‐high conversions. The polymerization of allyl methacrylate led to a polymer without branches but with five‐ or six‐membered rings. However, poly(undecenyl methacrylate) showed an indication of branching rather than intramolecular cycles. The hyperbranched structure of poly(undecenyl methacrylate) was confirmed by a combination of ¹H, ¹³C, ¹H–¹H correlation spectroscopy, and distortionless enhancement by polarization transfer 135 NMR spectra. The branching topology of the polymers was controlled by the variation of the reaction temperature, chain‐transfer‐agent concentration, and monomer conversion. The significantly lower inherent viscosities of the resulting polymers, compared with those of linear analogues, demonstrated their compact structure. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 26–40, 2007