We developed a recyclable catalytic system for the metal-free cationic polymerization under ambient conditions, which provides mild and environmentally friendly polymerization condition as well as unique polymer topology.

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.

The topologies of polymers can impact the performance of polymeric materials, including their chemical and physical properties. In this work, a dynamic covalent bond of boronate ester was introduced by...

Tri-N-heterocyclic carbene coordinated copper catalysts promoted the efficient synthesis of ultralow-branched cyclic polyglycerol (DB = 0.08–0.18).