Design of Topology‐Controlled Polyethers toward Robust Cooperative Hydrogen Bonding

Abstract

Topology control of polymers is critical for determining their physical properties and potential applications; in particular, topologies that incorporate numerous hydrogen bonding (H-bonding) donors and acceptors along the polymer chains considerably influence the formation of different inter- and intramolecular H-bonding motifs. In this study, the high-level control of inter- and intramolecular H-bonding is investigated in topology-controlled poly(glycidoxy carbonyl benzoic acid)s (PGCs). Three types of topology-controlled PGCs (i.e., linear, hyperbranched, and branched cyclic structures having a similar degree of polymerization) are prepared by introducing aromatic carboxylic acids into the corresponding polyglycidols (PGs) via quantitative post-polymerization modification with phthalic anhydride. The obtained three types of PGCs demonstrated the high-level interplay between the inter- and intramolecular H-bonding in polymer chains by exhibiting the pH-dependent self-association properties in the solution state and the strong adhesion properties in the bulk state with high transparency. Interestingly, the dramatically enhanced adhesive property by 2.6-fold is demonstrated by simple mixing of branched cyclic PGC and topology-controlled PGs to promote the cooperative H-bonding between polymer chains. The new class of cooperative H-bonding is anticipated between topology-controlled polymers to contribute to the development of advanced adhesive and the high potential in biological and biomedical applications due to its excellent biocompatibility.