Reaction Environment Effect on the Kinetics of Radical Thiol–Ene Polymerizations in the Presence of Amines and Thiolate Anions

Because of facile implementation, quantitative conversions, and an insensitivity to oxygen, water, and most organic functional groups, radical-mediated thiol–ene coupling (TEC) reactions have emerged as a valuable tool in macromolecule synthesis. It was recently demonstrated that the kinetics and conversions of thiyl radical-mediated reactions are adversely affected in the presence of basic amines by the formation of retardive thiolate anions. Herein, the performance of TEC polymerizations is evaluated under a variety of reaction environments with the intention to aid in the optimal formulation design of TEC reactions in the presence of amines. Results from both bulk and aqueous-phase network photopolymerizations established that sensitivity to amine basicity and pH is dependent on the thiol acidity, although norbornene-type alkenes exhibit a unique ability to achieve high conversions, where allyl ethers, vinyl ether, and vinyl siloxanes are highly inhibited. Additionally, the protic solvents such as alcohols and acetic acid are established as ideal solvents or additives to suppress or eliminate amine-induced retardation.