Macrocyclic poly(methyl acrylate) and macrocyclic poly(methyl acrylate-block-styrene) synthesized by radical trap-assisted atom transfer radical coupling

Abstract

Dibrominated poly(methyl acrylate) (BrPMABr) was prepared by atom transfer radical polymerization (ATRP), and this unpurified reaction mixture was used directly in a radical trap-assisted atom transfer radical coupling (RTA-ATRC) reaction to achieve cyclic PMA by intramolecular chain-end coupling. When the polymerization-to-cyclization crossover was performed as a one pot-two step sequence simply by the addition of the radical trap 2-methyl-2-nitrosopropane (MNP) and increased amounts of ligand-catalyst complex, cyclic PMA could be formed in yields up to 65% by adjusting the total volume and reactant ratios during the intramolecular RTA-ATRC, based on gel permeation chromatography (GPC) analysis. In analogous intramolecular ATRC trials lacking the radical trap, cyclization was not successful and instead chain extension by continuation of ATRP was observed. When the ATRP reaction mixture containing the BrPMABr precursor was added drop-wise into a redox active solution containing MNP, yields of cyclic polymer were increased up to 85%. The effect of the ligand was studied, with the highest amounts of cyclic product obtained in intramolecular RTA-ATRC reactions using tris[2-(dimethylamino)ethyl]amine (Me6TREN) as the ligand. Cyclic diblock copolymers were also prepared by this method, using telechelic poly(methyl acrylate-block-styrene-block-methyl acrylate) (PMA-b-PS-b-PMA) linear precursors prepared by sequential ATRP reactions.