Straightforward Access to Block and Gradient Light‐Responsive Poly(2‐Oxazoline)S via Cationic Ring Opening Polymerization Of 2‐Azobenzenyl‐2‐Oxazoline

Abstract Light‐responsive polymers are a prospective area of smart materials. The increasing number of potential applications of these materials require the development of new polymers sensitive to external irradiation. However, most of the polymers reported so far are represented by poly(meth)acrylates. In this work, the straightforward approach is proposed to the synthesis of light‐responsive poly(2‐oxazoline)s via cationic ring‐opening polymerization of 2‐azobenzenyl‐2‐oxazoline (2‐(4‐(phenyldiazenyl)phenyl)‐2‐oxazoline). Polymerization kinetics studies reveal significant activity of the new monomer in both homopolymerization and copolymerization with 2‐ethyl‐2‐oxazoline. The difference in monomer reactivity allows obtaining both gradient and block copolymers via simultaneous or subsequent one‐pot polymerization, respectively, leading to a set of well‐defined gradient and block copoly(2‐oxazoline)s with 10–40% of azobenzene units. Due to their amphiphilic nature, the materials self‐assemble in water, which is proven by dynamic light scattering and transmission electron microscopy. The change in polarity caused by the isomerization of azobenzene fragments in response to UV light irradiation results in a change of nanoparticle size. The obtained results provide a new impulse for the development of light‐responsive materials based on poly(2‐oxazoline)s.