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

ABSTRACT A simple and facile strategy for the functionalization of commercial poly(ε‐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 Activated monomer oligomerization of allyl glycidyl ether using poly(ε‐caprolactone)‐diols (PCLs) as macroinitiators in combination with thiol–ene chemistry provides a convenient synthetic route for the synthesis of new furyl end‐block functionalized PCLs.