Photomediated Cationic Ring-Opening Polymerization of Cyclosiloxanes with Temporal Control

Precision synthesis of polyorganosiloxanes and temporal control over the polymerization process during ring-opening polymerization (ROP) of cyclosiloxanes remain challenging due to the occurrence of side reactions, e.g., intramolecular transfer (backbiting) and intermolecular chain transfer, and irreversible catalyst transformation. In this study, a merocyanine-based photoacid catalyst is developed for cationic ROP of different cyclosiloxanes. A series of well-defined cyclotrisiloxane polymers with predetermined molar masses and low dispersities (Đ < 1.30) are successfully synthesized under various conditions (i.e., different catalyst loadings, initiator concentrations, solvents, and monomer types). Mechanistic insights by experiments and theoretical calculations suggest that the cationic active species, siloxonium ions, are combined with the catalyst anions to form tight ion pairs, thereby attenuating the reactivity of active species and subsequently minimizing side reactions. An efficient photocatalytic cycle is established among the catalyst, monomer, and polymer chain due to the rapid and reversible isomeric phototransformation of the catalyst, which endows the polymerization process with excellent temporal control. Successful in situ chain extension further confirms the controlled characteristics of photomediated CROP. This as-developed polymerization strategy effectively addresses long-standing challenges in the field of polyorganosiloxane synthesis.