Polymer Synthesis Based on Self‐Accelerating 1,3‐Dipolar Cycloaddition Click Reactions^†

Abstract

This review reports our recent work on developing polymer synthesis methods based on a self‐accelerating double‐strain‐promoted 1,3‐dipole‐alkyne cycloaddition (DSPDAC) click reaction. In DSPDAC, the cycloaddition of 1,3‐dipole with the first alkyne of sym‐dibenzo‐1,5‐cyclooctadiene‐3,7‐diyne (DIBOD) activates the second unreacted alkyne, which reacts with 1,3‐dipole much faster than the original alkyne of DIBOD. When using DIBOD and bis‐dipole compounds as monomer pairs, the self‐accelerating property of DSPDAC allows us to develop a stoichiometric imbalance‐promoted step‐growth polymerization method. It could produce polymers with ultrahigh molecular weight in the presence of excess DIBOD monomers. When using DIBOD to ring‐close linear polymers with 1,3‐dipole end groups, the self‐accelerating property of DSPDAC facilitates us to develop a unique bimolecular ring‐closure method. It could efficiently prepare pure cyclic polymers in the presence of excess DIBOD small linkers to linear polymer precursors.

Synthesis of thermo-responsive polymer gels composed of star-shaped block copolymers by copper-catalyzed living radical polymerization and click reaction

“…The click reaction is very effective for modifying the ends of polymer chains. One of the outstanding contributions in the click reaction is the introduction of a double strain-promoted azide – alkyne cycloaddition (DSPAAC) reaction through the bimolecular homodifunctional method, utilizing sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DIBOD) as the small difunctional linker [ 25 , 26 ]. DSPAAC’s distinct advantage lies in its self-accelerating nature, surpassing traditional azide – alkyne click reactions.…”

Self‐Accelerating Diels–Alder Reaction for Preparing Polymers of Intrinsic Microporosity

“…[13] Recently, we developed a library of self-accelerating click reactions based on 1,3-dipolar cycloaddition of sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DIBOD) and various 1,3-dipoles. [14] In these reactions, the [3+2] cycloaddition of the 1,3-dipole with the first alkyne of DIBOD fused a five-membered ring to DIBOD and increased the ring strain of DIBOD. This activated the second unreacted alkyne moiety and allowed it to react with the 1,3-dipole much faster than the original alkyne of DIBOD.…”

“…To eliminate the side effects of non‐stoichiometry on molecular weight, a unique type of stoichiometric imbalance‐promoted step‐growth polymerization method has been developed using the self‐accelerating reactions as polymerization reactions [13] . Recently, we developed a library of self‐accelerating click reactions based on 1,3‐dipolar cycloaddition of sym‐dibenzo‐1,5‐cyclooctadiene‐3,7‐diyne (DIBOD) and various 1,3‐dipoles [14] . In these reactions, the [3+2] cycloaddition of the 1,3‐dipole with the first alkyne of DIBOD fused a five‐membered ring to DIBOD and increased the ring strain of DIBOD.…”

Rational design of a multi-in-one heterofunctional agent for versatile topological transformation of multisite multisegmented polystyrenes

“…[24][25][26][27][28][29][30][31] Among them, linker-reactive multisite multisegmented polymers (LMMPs) with linear or nonlinear architectures are an important subclass of ATPs. [8][9][10][11][16][17][18][19][27][28][29][30][31][32][33][34][35][36][37] Owing to multiple functionalities and variable segment numbers, they can exhibit some interesting features and unique properties. First, the reactive sites present in neighboring polymer segments can endow LMMPs with versatile topological transformations via coupling, cleavage and polymerization.…”