H. Sasaki et al., PHOTOINITIATED CATIONIC POLYMERIZATION OF OXETANE FORMULATED WITH OXIRANE, Journal of polymer science. Part A, Polymer chemistry, 33(11), 1995, pp. 1807-1816
Photoinitiated cationic polymerization of oxetane, oxirane (epoxide),
and a formulation of both was carried out and their reactivity compare
d. To investigate a formulated system of oxetane and oxirane in photoi
nitiated cationic polymerization, computational and experimental metho
ds were used. In the computational study, we employed a semiempirical
molecular orbital method (AM1). On the other hand, the reactivities of
each system were evaluated and compared experimentally by a real-time
FT-IR method. The computational study reveals that oxetane seems to p
olymerize in S(N)2 mechanism, but two possibilities, of S(N)1 mechanis
m through the a-cleavage and of S(N)2 mechanism through beta-cleavage,
are implied for oxirane. Using the real-time FT-IR method, the formul
ation of oxetane and oxirane was proved to possess rather high reactiv
ities of oxetane toward photoinitiated cationic polymerization. The fo
rmulated system exhibited slightly lower number-average molecular weig
ht than oxetane but higher than oxirane. These experimental observatio
ns are well explained in terms of the calculated reaction paths. (C) 1
995 John Wiley and Sons, Inc.