Polymerization of lactams, 92 Non-activated anionic polymerization of #epsilon#-caprolactam initiated with the sodium salt of #epsilon#-caprolactam

摘要

The non-activated polymerization of #epsilon#-caprolactam initiated with the sodium salt of #epsilon#-caprolactam (CLNa), which was prepared in situ with sodium methoxide, was studied in the temperature range 170-230 deg C and at CLNa concentrations from 0.20 to .0 mol-, and at 190 deg C in the presence of 2.0-10.0 mol- CLNa. Apparent rate constants and values of apparent activation energy (E_a) were determined for the initial autoaccelerated stage of polymerization (E_a = 230 kJ (centre dot) mol~(-1)) as well as for the stage characterized by a zero-order reaction with respect to the monomer (E_a = 120 kJ (centre dot) mol~(-1)). Non-integral orders of the polyreaction with respect to the initiator indicate a highly complex polymerization mechanism. Degradation reactions accompany the polymerization at high polymer contents.