Polymerization of styrene and cyclization to macrocyclic polystyrene in a one-pot, two-step sequence

Dibrominated polystyrene (BrPStBr) was produced by atom transfer radical polymerization (ATRP) at 80 °C, using the bifunctional initiator benzal bromide to afford the telechelic precursor. The ATRP reaction was stopped around 40% monomer conversion and directly converted into an radical trap-assisted atom transfer radical coupling (RTA-ATRC) reaction by lowering the temperature to 50 °C, and adding the radical trap 2-methyl-2-nitrosopropane (MNP) along with additional catalyst, reducing agent, and ligand to match ATRC-type reaction conditions. In an attempt to induce intramolecular coupling, rather than solely intermolecular coupling and elongation, the total reaction volume was increased by the addition of varying amounts of THF. Cyclization, along with intermolecular coupling and elongation, occurred in all cases, with the extent of ring closure a function of the total reaction volume. The cyclic portion of the coupled product was found to have a 〈G〉 value around 0.8 by GPC analysis, consistent with the reduction in hydrodynamic volume of a cyclic polymer compared to its linear analog. Analysis of the sequence by 1H NMR confirmed that propagation was suppressed nearly completely during the RTA-ATRC phase, with percent monomer conversion remaining constant after the ATRP phase.