Recent Advances in Direct Synthesis of Functional Polymers of Intrinsic Microporosity Based on (Super)Acid Catalysis

Abstract Polymers of intrinsic microporosity (PIMs) are an emerging class of amorphous organic porous materials with solution processability, which are widely used in a multitude of fields such as gas separation, ion conduction, nanofiltration, etc. PIMs have adjustable pore structure and functional pore wall, so it can achieve selective sieving for specific substances. In order to meet the functional requirements of PIMs, two principal methods are used to synthesize functional PIMs, namely, post‐modification of PIMs precursors and functionalization of monomers. A number of post‐modification routes have been reported, however, the direct synthesis of functional PIMs with diverse groups still remains a challenge. The synthesis of PIMs through the acid‐catalyzed polyhydroxyalkylation has been demonstrated to be an effective solution, exhibiting the advantages of wider substrates range, milder reaction conditions, and higher molecular weight. Recently, a series of functional substrates for direct synthesis of PIMs have been proposed. This article presents a review and summary of recent advances in synthesizing PIMs via acid‐catalyzed polyhydroxyalkylation, and the synthesis route and structure‐activity relationship are emphasized, which provides a versatile platform for the direct synthesis of functional PIMs.