Multicomponent Spiropolymerization of Diisocyanides, Diethyl Acetylenedicarboxylate, and Halogenated Quinones

Multicomponent spiropolymerization (MCSP) provides an efficient synthetic tool for the construction of spiropolymers based on nonspiro monomers. In this study, a method of MCSP using diisocyanides 1, diethyl acetylenedicarboxylate 2, and halogenated quinones 3 is developed for the in situ construction of bis-spiropolymers with high molecular weights (M_w up to 29 200) and good yields (up to 87.7%) under mild reaction conditions. The structure of the obtained bis-spiropolymers is confirmed by gel permeation chromatography, Fourier transform infrared spectroscopy, and nuclear magnetic resonance analysis. Halogenated bis-spiropolymers show good thermal stability, good solubility, and film-forming ability. The photosensitizer rhodamine B is used as a doping agent to induce the photodegradation of the polymer P1a3c into small-molecule segments, which results in the slow release of halogenated spiro-groups under irradiation with simulated sunlight. This finding reveals that P1a3c has the potential to be applied in pesticides. Therefore, this MCSP is a novel method for preparing halogen-containing bis-spiropolymers, which accelerates the development of multifunctional polymer materials.