The anionic polymerization of ∈‐caprolactam initiated with magnesium initiators was studied in the interval 180–250°C. ∈‐Caprolactam magnesium bromide was much more active than magnesium di(∈‐caprolactamate) and the activity of both depended on the way of their preparation. The polymerizations obey the zero order kinetics with respect to the monomer.
SUMMARY: The non-activated polymerization of e-caprolactam initiated with the sodium salt of e-caprolactam (CLNa), which was prepared in situ with sodium methoxide, was studied in the temperature range 170 -230 8C and at CLNa concentrations from 0.20 to 1.0 mol-%, and at 190 8C 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 N mol -1 ) as well as for the stage characterized by a zero-order reaction with respect to the monomer (E a = 120 kJ N 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.
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