Multicomponent Polymerization of Alkynes, Isocyanides, and Isocyanates toward Heterocyclic Polymers

Abstract

Multicomponent polymerization (MCP) based on isocyanides, among the tremendous synthetic methodologies, is a powerful tool for the synthesis of functional heterocyclic polymers such as poly(maleimide)s (PMDs), which should be further developed. In this work, an atom-economic and catalyst-free MCP of activated alkynes, diisocyanides, and diisocyanates was fully explored. PMDs with high weight-average molecular weights (M w up to 29,000) were facilely produced in satisfactory yields (up to 85%). The resultant polymers show excellent solubility, high thermal stability, and good film-forming ability, and their thin films possess high refraction indices in a range of 1.614−1.710 at 632.8 nm. Therefore, this work not only supplements the isocyanide-based MCPs but also enriches the family of polymerization reactions based on triple-bond building blocks.

Multicomponent Spiropolymerization of Diisocyanides, Activated Alkynes, and Bis-Anhydrides

“…Compared with those before acidolysis, the FT-IR spectra of P1a3f after acidolysis showed that two new vibration peaks appeared at 1672 and 1613 cm –1 . They are successively attributed to the CO of butenolide and the N–H of the secondary amine (Figure S38), that is, the CN bonds in the main chain were hydrolyzed by a strong acid, and spiropolymers were degraded into small molecular segments, which is the same as previously reported polymers with similar structures …”

“…They are successively attributed to the C�O of butenolide and the N−H of the secondary amine (Figure S38), that is, the C�N bonds in the main chain were hydrolyzed by a strong acid, and spiropolymers were degraded into small molecular segments, which is the same as previously reported polymers with similar structures. 56 Among all of the different types of drugs for the treatment of stomach diseases, bismuth potassium citrate and other drugs for the treatment of superficial gastric diseases only need to act on the surface of the stomach. 57−59 Moreover, these drugs should have restricted absorption through the gastrointestinal tract into the blood system, which reduces side effects on the liver, kidney, and nerves.…”

Transcending the Trade-off in Refractive Index and Abbe Number for Highly Refractive Polymers: Synergistic Effect of Polarizable Skeletons and Robust Hydrogen Bonds

“…High-refractive-index polymers (HRIPs) have attracted worldwide attention in the field of optical devices from the viewpoint of enhancing performance and flexibility. − To date, numerous HRIPs bearing highly polarizable groups with a small volume (e.g., aromatics − and heteroatoms − ) have been reported to display high refractive indices greater than 1.7. The desired refractive index (RI, n ) values of optical polymers have been increased alongside the rapid development of photonic technologies; for example, transparent materials with RI values exceeding 1.8 are required for use as LED encapsulants in order to enhance the light extraction efficiency .…”

Activated Internal Alkyne‐Based Polymerization†

“…Recently, Qin and coworkers explored a catalyst‐free MCP of DAADs, diisocyanides and diisocyanates to prepare soluble and thermally stable poly(maleimide)s with high M w values (up to 29000) in satisfactory yields (up to 85%) (Scheme 8c). [ 85 ] The resultant polymers displayed excellent film‐forming ability, and their thin films possessed high refractive indices (up to 1.71 at 632.8 nm).…”