Catalyst-Free Multicomponent Cyclopolymerizations of Diisocyanides, Activated Alkynes, and 1,4-Dibromo-2,3-Butanedione: a Facile Strategy toward Functional Polyiminofurans Containing Bromomethyl Groups

Polymers containing iminofuran (PIFs) are rarely reported due to the lack of simple and effective synthesis methods. In this work, a novel multicomponent cyclopolymerization (MCCP) of diisocyanides, activated alkynes, and 1,4-dibromo-2,3-butanedione using catalyst-free one-pot reactions under mild conditions to prepare PIFs containing bromomethyl groups is reported. PIFs with good solubility and thermal stability are obtained with high M_ws (up to 19 600) and good yields (up to 89.5%) under optimized polymerization conditions. The structure of the PIFs is characterized by nuclear magnetic resonance, Fourier transform infrared spectroscopy, and gel permeation chromatography. The photophysical properties indicate that polymers P1a2b3 and P1c2b3 have cluster-triggered emission characteristics. Thin films made from PIFs quickly degrade under UV irradiation. Moreover, the obtained polymers are decorated with bromomethyl and carboxylate groups in the side chain, which can be postfunctionalized to prepare multifunctional materials, such as star branched polymers and biomedical carrier materials. Thus, this work not only enriches the field of polymerization based on isocyanates and activated alkynes but also provides a facile strategy toward functional iminofuran polymers.