Poly(n-butyl acrylate) terminated with benzyl alcohol units (PnBA-MI) of varying molecular weights were synthesized by polymerizing n-butyl acrylate using substituted benzyl alcohol based initiators under atom transfer radical polymerization (ATRP) conditions. Between the ligands bipyridine and PMDETA, the latter ligand showed better control for the polymerization of n-BA. High molecular weight diblock copolymers of poly[(n-butyl acrylate)-block-(3-caprolactone)] were synthesized by ring opening polymerization (ROP) of 3-caprolactone using PnBA-MI which formed thin, flexible and opaque films which are soft to touch. Triblock copolymers of poly[(n-butyl acrylate)-block-(3caprolactone)-block-(L-lactide)] were synthesized in a one pot, two step reaction by the sequential addition of monomers. The molecular weights of PCL and PL segments in the triblock copolymers were comparable. Due to this, the triblock copolymer showed exothermic transition upon cooling well above the T m of PCL block.

Despite the large difference in their nucleophilicity, phenoxide and carboxylate anions take part nearly simultaneously in the aliphatic nucleophilic substitution reaction with 1,4‐dibromo‐2‐butene. This leads to the formation of ether (O) and ester (COO) linkages simultaneously under mild reaction conditions when hydroxyl benzoic acids are employed as nucleophiles. The process yields a new class of polymer broadly classified as unsaturated poly(ether ester) which are potentially functionalizable. This methodology has also been extended for preparing networked polymers by making use of 3,5‐dihydroxybenzoic acid as A3 type monomer. Copyright © 2011 Society of Chemical Industry

A novel approach for ATRP has been developed which enables the polymerization of vinyl monomers including those bearing carboxylic acid groups such as acrylic/methacrylic acid in the free acid form with ppm amounts of copper. The quantity of copper used in the polymerization is comparable to those left in purified polymers obtained by a conventional ATRP process.