Theoretical Aspects of Iterative Coupling for Linear Oligomers and Polymers

Abstract

A conceptual study of iterative coupling (IC) is performed, providing a unified description and new research directions. IC chain growth rates and functional group choice are analyzed, guiding construction of efficient schemes. The concept of cycle efficiency is defined as a more complete metric of experimental implementations of IC, and then applied to the main linear and exponential IC processes. The mathematical relations between individual reactions, cycles, and the iterative process as a whole are studied. Finally, macromolecule IC is proposed as a strikingly complementary process to standard IC, with potential to reduce the dispersity of non‐uniform samples. Due to its connection with the central limit theorem of statistics, it provides an unusually robust, powerful, and general method for scalable production of polymer samples with narrow distribution. In all, this contribution assists development of improved IC processes targeting low dispersity linear oligomers and polymers.