Organocatalytic [2 + 2] Photopolymerization under Visible Light: Accessing Sustainable Polymers from Cinnamic Acids

Herein, the successful development of a metal-free, solution [2 + 2] photopolymerization of natural cinnamic acid-derived bisolefinic monomers is reported, which is enabled by a strategy based on direct triplet state access via energy transfer catalysis. 2,2'-Methoxythioxanthone has been identified as an effective organic photocatalyst for the [2 + 2] photopolymerization in solution, which can be excited by visible light and activate the biscinnamate monomers via triplet energy transfer. This method features its metal-free conditions, visible light utilization, solution polymerization, and abundant biomass-based feedstock, as well as processable polymer products, which is different from the rigid, insoluble products obtained from solid-state photopolymerization. This solution polymerization method also shows a good compatibility to monomer structures; cinnamic acid-derived bisolefinic monomers with different linkers, including diamine, natural diol, and bisphenol, can all readily undergo [2 + 2] photopolymerization, and be transformed into colorless, sustainable polymers.