Unprecedented Sequence Control and Sequence-Driven Properties in A Series of AB-Alternating Copolymers Consisting Solely of Acrylamide Units

Abstract

In this article, we report a method to synthesize a series of alternating copolymers that consist exclusively of acrylamide units. Crucial to realizing the unprecedented polymer synthesis is the design of a divinyl monomer that contains acrylate and acrylamide moieties connected via two activated ester bonds. This elaborate design, which is based on the reactivity ratio of the embedded vinyl groups, allows a “selective” cyclopolymerization, wherein the intramolecular and intermolecular propagation are repeated alternately under dilute conditions. The addition of an amine to the resulting cyclopolymers afforded two different acryl amide units, i.e., an amine‐substituted acryl amide and a 2‐hydroxy‐ethyl‐substituted acryl amide in alternating sequence. Using this method, we were able to furnish ten types of alternating copolymers; some of these exhibit unique properties in solution and in the bulk, which are clearly different from those of the corresponding random copolymers, and we attributed the observed differences to the alternating sequence.