Tertiary Amine Based Amino-yne Click Polymerization toward Multifunctional Poly(beta-ammonium acrylate)s

Polyelectrolytes possess many unique properties because of their charged groups, which have been widely utilized in the construction of functional materials. However, the synthesis of polyelectrolytes was often carried out under harsh conditions such as high temperature or precious metal catalyst. In this work, we innovatively proposed tertiary amine self-initiation strategy to realize the click reaction of activated alkynes, tertiary amines and protic acids. Accordingly, tertiary amine-based amino-yne click polymerization was successfully established and a series of main-chain charged polyelectrolytes were efficiently prepared under ambient conditions. The resultant poly(beta-ammonium acrylate)s (PAAs) exhibit ionic cluster luminescence and it can be easily regulated through altering anions. Furthermore, we utilized thiophenol compounds achieving the degradation and reconstruction of PAAs. The refractive indices of reconstructed polymers have been greatly improved (Δn = 0.2). Through tertiary amine-based amino-yne click polymerization in this work, amino acid was easily introduced into the polymers. The resultant polyelectrolyte shows astonishing adhesive ability for various substrates. The adhesive strength and work of debonding for stainless steel can reach 6.4 MPa and 14315 Nm-1, respectively. These results demonstrate the high efficiency of tertiary amine-based amino-yne click reactions and the tunability of polymer structures, which indicates the infinite potential for the preparation and application of multifunctional PAA.