Macrocyclic Side-Chain Monomers for Photoinduced ATRP: Synthesis and Properties versus Long-Chain Linear Isomers

The photoinduced atom transfer radical polymerization of traditionally challenging hydrophobic monomers (lauryl C-12, stearyl C-18, and docosyl C-22-acrylate) and novel cyclic isomers (C-12) C-16, and C-17) is reported. By the judicious selection of commercially available solvents and catalytic systems, polymers with a high degree of control over dispersity (D approximate to 1.1) and end-group fidelity were obtained over a wide range of molecular weights. This level of control provides access to unique hydrophobic materials (random, block, and homopolymers) with significant differences in properties observed due to the isomeric form of the hydrocarbon side chain (macrocyclic versus linear).