Chain‐growth branching radical polymerization: an inibramer strategy

Branched polymers are considered as more synthetically scalable and accessible alternatives of dendrimers with similar properties such as low viscosity, high solubility, and high degree of end group functionality. However, traditional synthetic strategies towards branched polymers have limited control over molecular weight and degree of branching due to the step‐growth reaction mechanism of the branching polymerization. To achieve a better control over the branching polymerization, a chain‐growth controlled polymerization pathway can be realized by employing a rationally designed comonomer called inibramer (initiator + monomer + branching junction creator) where the initiating site is exclusively active after the monomer is polymerized. In this minireview, recent developments on inibramer design are reviewed. The directions for incorporating new types of inibramers to produce dendrimer‐like polymers and broaden their applications are discussed. © 2021 Society of Industrial Chemistry. An inibramer allows a chain‐growth polymerization to produce branched polymers with a polymerization‐induced activation of the initiating site. The application of inibramers in reversible deactivation radical polymerization enables the facile and efficient construction of complex architectures from a broad range of monomers.