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

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.

Automated summary

This review discusses a polymer synthesis method based on a self-accelerating double-strain-promoted 1,3-dipole-alkyne cycloaddition (DSPDAC) click reaction, which can produce polymers with ultrahigh molecular weight. The method also demonstrates a stoichiometric imbalance-promoted step-growth polymerization approach and a unique bimolecular ring-closure method.