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Chemo-enzymatic methods are powerful tools for the synthesis of novel materials. By combining the flexibility of chemical synthesis and the high selectivity of enzymes, a variety of functional materials can be achieved. In the present study, a series of α,ω-thiol telechelic oligoesters with varying amount of internal alkenes are prepared using selective lipase catalysis and are subsequently cross-linked by thiol-ene chemistry yielding alkene functional networks. Due to the reactivity of thiols and alkenes almost all present thiol-ene systems consist of two components. This work demonstrates that selective lipase catalysis in combination with renewable monomers with internal alkenes is a promising system for achieving one-component thiol-alkene functional resins with good storage stability and a high degree of thiol end-groups. The developed chemo-enzymatic route yields polymer networks with tailored amount of alkene functionalities in the final thermoset, which facilitate further postmodification. [ABSTRACT FROM AUTHOR]

There is a demand for new sustainable polymeric materials. Vinyl ethers are, in this context, attractive oligomers since they polymerize fast, are non‐toxic, and can be polymerized under ambient conditions. The availability of vinyl ether oligomers is, however, currently limited due to difficulties in synthesizing them without using tedious synthesis routes. This work presents the synthesis of a series of vinyl ether ester oligomers using enzyme catalysis under solvent‐free conditions and the subsequent photoinduced cationic polymerization to form polymer thermosets with Tgs ranging from −10 to 100 °C. The whole process is very efficient as the synthesis takes less than 1 h with no need for purification and the crosslinking is complete within 2 min. This work presents an efficient and benign enzymatic synthesis of vinyl ether ester oligomers for solvent‐free resin applications. The synthesis is complete in less than 1 h and the oligomers are thereafter crosslinked during 2 min with UV‐initiated cationic polymerization, which yielded transparent free‐standing films that have a wide range of Tgs from −10 to 100 °C depending on composition. [ABSTRACT FROM AUTHOR]