What question did this study set out to answer?

The aim is to establish a precise method for synthesizing topologically diverse polyrotaxanes using living ring-opening polymerization.

June 12, 2026

Controlled Synthesis of Topologically Diverse Polyrotaxanes by Ring-Opening Polymerization of Mechanically Interlocked Monomers

Key Points

The aim is to establish a precise method for synthesizing topologically diverse polyrotaxanes using living ring-opening polymerization.
Utilized living ring-opening polymerization for synthesis.
Incorporated mechanically interlocked monomers: [2]catenanes and c[1]daisy chains.
Conducted comparative studies on reactivity related to molecular topology.
Achieved predictable molecular weights with narrow dispersities (Đ ≤ 1.19).
Demonstrated topology-dependent reactivity, impacting polymerization kinetics.
Created an accessible route for block copolymer formation.

Abstract

Mechanically interlocked polymers (MIPs) offer unconventional architectures that expand the design space of polymer chemistry, making them an emerging focus of polymer and supramolecular science. Yet their synthesis still lacks the precision and control established in conventional polymer chemistry. We report a living ring-opening polymerization that enables controlled construction of topologically diverse polyrotaxanes from two monomers─2catenanes and c 1daisy chains. The method delivers main-chain and daisy-chain architectures with predictable molecular weights, narrow dispersities ( Đ ≤ 1.19), and block copolymer access. Comparative studies reveal topology-dependent reactivity, underscoring the role of conformational constraints in polymerization kinetics. This unified route establishes a versatile platform for programmable MIP synthesis, bridging molecular topology with materials design and paving the way for next-generation mechanically bonded polymers.

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