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

Tailoring the Hard–Soft Interface with Dynamic Diels–Alder Linkages in Polyurethanes: Toward Superior Mechanical Properties and Healability at Mild Temperature

“…The synthetic pathway is shown in Figure 1c. Following our previous synthetic design of furan end-block-functionalized PCLs (Scheme S1 and Figures S1 and S2, Supporting Information), 59 we synthesized a PCL polyol with the chain termini attached to the hydroxyl-bearing DA groups (DA-PCL polyol 2, Figure 1c) using the DA reaction between a furan end-functionalized PCL diol (furan-PCL diol 1, Figure 1c) and 3-maleimido-1-propanol with furan-to-maleimide equimolar ratio. The successful occurrence of the DA reaction was evidenced by 1 H NMR (Figure 2) and Fourier transform infrared (FT-IR) (Figure S4, Supporting Information) spectroscopy.…”

Synthesize Hyperbranched Polymers Carrying Two Reactive Handles via CuAAC Reaction and Thiol–Ene Chemistry

“…The utilization of internal reactive groups for conjugation would significantly improve the loading density of guest ingredients and enrich their species in the polymer carrier, which is vital in many applications with requirement of dual functionalities . To completely react the inside alkene groups in HBPs, it was initially hypothesized that an excess amount of thiols to alkene groups would be necessary according to many reported protocols . Thus, the functionalization of HBP(ene) 300 ‐ c ‐Ph with 2.5 equiv.…”

Progress in the Preparation of Functional and (Bio)Degradable Polymers via Living Polymerizations

“…This analog of aliphatic polyesters can be reacted with the chain-end hydroxyl group(s) to perform further functionalization, modifications, or chain extensions. Thus, the limited numbers of functionalizable end(s) thus can be anticipated [ 32 , 33 , 34 ]. However, rendering a variety of functional groups on aliphatic polyester backbones remains challenging since ROP cannot usually tolerate high-polar groups [ 35 , 36 , 37 , 38 , 39 ].…”