Isotactic poly(acrylonitrile) via ultraviolet irradiation of acrylonitrile-urea canal complex

Isotactic poly(acrylonitrile) (PAN) has been prepared by means of a conventional ultraviolet (UV) irradiation apparatus without γ-ray sources; an acrylonitrile-urea canal complex was directly formed at the surface of the UV (Hg) emission tube at low temperatures (∼ −78°C). When the complex was UV-irradiated at this temperature, a stereoregular polymer was formed in the canal. The 13C-NMR analyses indicate that (1) these PAN are rich in isotactic configuration, (2) the extent of the isotactic triad is in the range of 56−71%, and (3) the penultimate unit effect, 4 (mm) (rr)/(mr)2, is linearly correlated with the ultimate unit effect, (mm)/(rr). From the plots of log{4(mm)(rr)/(mr)2} vs log{(mm)/(rr)}, the anomaly in the polymerization of AN is discussed. The molecular characteristics of the UV canal PAN such as molecular weight, etc., were briefly noted. © 1995 John Wiley & Sons, Inc.