Propargyl Amines as Simple Alkyne Initiators for Chain‐Growth Controlled/“Living” Click Polymerization

Recently, we have reported chain‐growth controlled/“living” click polymerization as bi‐directional polyaddition employing copper‐catalyzed azide‐alkyne cycloaddition. In this study, we report simple propargyl amines as the initiator for controlled/“living” click polymerization, some of which are commercially available and contribute to even simpler polymerization processes. By employing tripropargyl or dipropargyl amine, the polymerization of azide‐alkyne AB monomer proceeded well in a well‐controlled manner, which was comparable to that with complicated initiators in the previously reported studies. Furthermore, monomer addition experiments and post‐polymerization modification using the alkyne termini of the resulting polymers were also demonstrated, which would be a convenient pathway to access novel end‐functional polymer materials. This approach not only simplifies the polymerization process but also holds promise for facilitating the development of new end‐functional polymers.