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Visible control over ring-shaped polymer structures
A new photochemical process allows the targeted production of cyclic polymer structures – without unwanted cross-linking. Researchers present an organocatalyzed, light-driven radical process that could provide new impetus for the development of functional coating systems.
A research team led by Gaoyuan Yu and Dian-Feng Chen has developed a new process for controlled radical cyclopolymerisation. The focus is on novel methacrylate and acrylamide crotonate hybrid monomers that are polymerised under visible light. The process uses an organocatalysed photoredox-active ATRP strategy (atom transfer radical polymerisation) for initiation. The polymerisation occurs via a sequential cascade of intramolecular ring formation and intermolecular chain extension.
The result is structure-defined homopolymers and block copolymers with recurring cyclic units – without any unwanted network formation. The cyclic structure gives the polymers special properties, for example in terms of flexibility or stability, which makes them interesting for functional coatings and special applications.
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Light intensity and additives control polymer growth
Another key finding of the study is the high degree of control over the polymer architecture. The researchers were able to show that parameters such as light intensity and the targeted use of additives have a significant influence on chain length and cycle formation. This enables fine-tuning of the macromolecular structure during synthesis – a decisive advantage for the development of customised coating systems with defined properties.
The results demonstrate the potential of photocontrolled organocatalytic polymerisations for demanding coating applications – especially where conventional radical processes reach their limits. The research paves the way for new material solutions in the field of functional polymers.
Source: Polymer Chemistry, Issue 13, 2025, DOI: 10.1039/d4py01813a
