Synthesis and reactivity of α,ω-homotelechelic polymers by Cu(0)-mediated living radical polymerization

Abstract

Telechelic poly(n-butyl acrylate) and poly[poly(ethylene glycol) methyl ether acrylate] are obtained with high monomer conversions and narrow molecular weight distributions (Ð<1.2) by Cu(0)-mediated living radical polymerization (SET-LRP). The high end group fidelity of the polymer is confirmed by a combination of 1H NMR and MALDI-ToF-MS analysis. The reactivity of the telechelics is exploited to yield amphiphilic BAB triblocks, by sequential addition of a second monomer, which self-assemble in water. Furthermore, nucleophilic thiol-bromine substitution using 2-mercaptoethanol post-polymerization enables the incorporation of primary alcohols on both the α- and ω-polymer chain ends. The presence and reactivity of hydroxyl end-groups is confirmed upon reaction with isocyanates and further exploited to induce the ring opening polymerization (ROP) of ε-caprolactone.