Effect of Regioregularity on the Solution Behavior of Polyoctenamer‐ <i>graft</i> ‐poly(ethylene glycols)

Abstract Solution properties of amphiphilic polyoctenamers functionalized with short polyethylene glycol side chains in the 3 rd and 5 th positions are compared using light scattering and diffusion‐ordered spectroscopy. To that end, 3‐ and 5‐ succinyl cyclooctenes are synthesized in several steps, starting from cyclooctene and 1,5‐cyclooctadiene, respectively, then grafted with oligoethylene glycol methyl ether, and involved as monomers in ring‐opening metathesis polymerization on the second‐generation Grubbs catalyst. In the case of 3‐succinyl cyclooctene, the polymerization proceeds in a regio‐ and stereoselective manner to afford macromolecules with full head‐to‐tail regioregularity and trans‐stereoregularity. Although both 3‐ and 5‐functionalized polyoctenamers form micelles in water and chloroform above certain concentrations and exhibit a cloud point on heating, it is found that regularly positioned pendants lower the tendency to aggregation more efficiently, which can be important for all applications involving the use of amphiphilic polymer brushes.