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Polymerization of lactams, 92. Non‐activated anionic polymerization of ϵ ‐caprolactam initiated with the sodium salt of ϵ ‐caprolactam
Author(s) -
Havlice Jiří,
Broz�ek Jiří,
Šáchová Monika,
Nováková Václava,
Roda Jan
Publication year - 1999
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/(sici)1521-3935(19990501)200:5<1200::aid-macp1200>3.0.co;2-b
Subject(s) - caprolactam , polymerization , chemistry , polymer chemistry , anionic addition polymerization , bulk polymerization , monomer , polymer , radical polymerization , organic chemistry
The non‐activated polymerization of ε ‐caprolactam initiated with the sodium salt of ε ‐caprolactam (CLNa), which was prepared in situ with sodium methoxide, was studied in the temperature range 170–230°C and at CLNa concentrations from 0.20 to 1.0 mol‐%, and at 190°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·mol –1 ) as well as for the stage characterized by a zero‐order reaction with respect to the monomer ( E a = 120 kJ·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.