Aroylacetylene-Based Amino-Yne Click Polymerization toward Nitrogen-Containing Polymers

Synthesis of nitrogen-containing polymers has always been a hot research topic for their broad applications as functional materials. In this work, we established new, spontaneous, and atom-economic amino-yne click polymerization for the construction of regio-/stereoregular nitrogen-containing polymers. Aroylacetylenes, which could be facilely prepared without using water-sensitive ethynylmagnesium bromide and harsh reaction conditions, could be polymerized with amines in the absence of any catalyst under ambient conditions, and poly­(β-enaminone)­s with high weight-average molecular weights (M_w of up to 49 400) could be produced in excellent yields (up to 99%). Moreover, sole E-isomer-containing polymers could be obtained efficiently from the click polymerization of aroylacetylenes and secondary amines, whereas absolute Z-configuration products were prepared when using primary amines. In addition, poly­(β-enaminone)­s could be degraded upon the addition of Lewis acid and primary amines in aqueous solution and definite compounds could be generated, proving their wide application prospects as degradable nitrogen-containing polymers.