posted on 2021-06-08, 20:07authored byXiaotian Zhao, Wanqiu Huang, Shibo Lin, Xi Chen, Xirui Guo, Dehong Zou, Guodong Ye
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.