LAUSR

Polymerization of allyl ether monomers has previously been considered a free-radical addition polymerization mechanism, but it is difficult to achieve because of the high electron density of their double bond. To interpret the mechanism of photopolymerization, we therefore proposed a radical-mediated cyclization (RMC) reaction, which has been validated by results from quantum chemistry calculations and real-time infrared observation. Our RMC reaction begins with the radical abstracting one allylic hydrogen atom from the methylene group of allyl ether to generate an allyl ether radical with a delocalized π33 bond. Then, the radical reacts with the double bond of a second allyl ether molecule to form a five-membered cyclopentane-like ring (CP) radical. The CP radical abstracts a hydrogen atom from a third ether molecule. At last, a new allyl ether radical is generated and the next circulation as chain propagation begins. The distortion/interaction model was employed to explore the transient state of reaction, and real-time infrared was chosen to clarify the RMC reaction mechanism initiated by different photoinitiators. These results demonstrated that the RMC mechanism can give new insights into these fundamental processes.