Catalyst‐Free Four‐Component Polymerization of Propiolic Acids, Benzylamines, Organoboronic Acids, and Formaldehyde toward Functional Poly(propargylamine)s

Abstract

Multicomponent polymerizations (MCPs) are a group of fascinating polymer synthesis approaches that are developed rapidly in the recent decade. As a popular alkyne‐based MCP, the A3‐polycouplings of alkynes, aldehydes, and amines are developed for the synthesis of poly(propargylamine)s under the catalysis of metal catalysts. In this work, through the design of carboxylic acid group‐activated alkyne monomers, a catalyst‐free, four‐component polymerization of propiolic acids, benzylamines, organoboronic acids, and formaldehyde is reported under mild condition at 45 °C in dichloroethane. This four‐component polymerization is applicable to different monomer structures, which can afford seven poly(propargylamine)s with up to 94% yields and molecular weights of up to 13 900 g mol−1. Moreover, the poly(propargylamine)s demonstrate good solubility and processibility, high thermal stability and light refractivity, unique photophysical property, and so on. The simple monomers, mild condition, low cost, high efficiency, and procedure simplicity of this catalyst‐free four‐component polymerization demonstrates an elegant example of functional polymer synthesis.

Activated Internal Alkyne‐Based Polymerization†

“…Additionally, with TPE and tertiary amine moieties embedded in the polymer skeletons, these poly(propargylamine)s displayed unique AIE feature and citric acid‐triggered fluorescence enhancement, which are applicable in luminescent materials. [ 51 ]…”

Imine-based multicomponent polymerization: Concepts, structural diversity and applications

“…15). [122] The A 3 -coupling-Petasis five-center four-component polymerization (AP-5C-4CP) was carried out without catalyst under mild conditions (45°C) in dichloroethane for 10 hours. Formaldehyde and aromatic alkynyl carboxylic acids were used as monofunctional reagents whereas dibenzylamines and diboronic acids compounds containing aromatic fluorene or tetraphenylethene served as difunctional monomers (Fig.…”

“…Moreover, the photoluminescence was enhanced upon addition of citric acid. [122] This phenomenon was attributed either to the protonation of the amines or a further ionic crosslinking that induced aggregations.…”

Multicomponent Spiropolymerization of Diisocyanides, Diethyl Acetylenedicarboxylate, and Halogenated Quinones

“…Multicomponent polymerization (MCP) has attracted the attention of scientists for the development of new polymers. [19][20][21][22][23][24][25][26] Triple-bond compounds, such as alkynes [27][28][29][30][31][32][33][34] and isonitriles, [35][36][37] are widely used in MCPs with various chemical structures. For example, Arndtsen's group synthesized a series of pyrrole-containing -conjugated polymers by MCP of diimines, diacid chlorides, and alkynes.…”