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 C12, stearyl C18, and docosyl C22-acrylate) and novel cyclic isomers (C12, C16, and C17) is reported. By the judicious selection of commercially available solvents and catalytic systems, polymers with a high degree of control over dispersity (Đ ≈ 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).