Synthesis of allyl end-block functionalized poly(ε-caprolactone)s and their facile post-functionalization via thiol–ene reaction

A simple and facile strategy for the functionalization of commercial poly(e-caprolactone) diols (PCLs) with pendant functionalities at the polymer chain termini is described. Well-defined allyl-functionalized PCLs with varying numbers of allyl end-block side-groups were synthesized by cationic ring-opening polymerization of allyl glycidyl ether using PCL diols as macroinitiators. Further functionalization of the allyl-functionalized PCLs was realized via the UV-initiated radical addition of a furan-functionalized thiol to the pendant allyl functional groups, showing the suitability for post-modification of the PCL materials. Changes in polymer structure as a result of varying the number of pendant functional units at the PCL chain termini were demonstrated. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 928–939

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