Radiation-induced cryopolymerization of epichlorohydrin

The polymerization of epichlorohydrin occurs in the temperature region of g lass transition as a result of heating of the samples preirradiated at 77 K . The specific heat of polymerization of epichlorohydrin DeltaH was determi ned to be 95.4 +/- 6.0 kJ/mol. The postirradiation polymerization proceeds through the cationic mechanism. The chain propagation rate constant was est imated at k(p) 10(-18)exp(-14 200/RT) cm(3)/s for the temperature range 95- 140 K. The dynamics of postirradiation polymerization of crystalline epichl orohydrin is substantially different from the polymerization dynamics of th e glassy monomer. The polymer yields were found to be 3 and 12% for the cry stalline and the glassy monomer, respectively. Heating of an irradiated gla ssy solution of hydrogen cyanide in epichlorohydrin results in the formatio n of the corresponding copolymer.