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The kinetics of hydrolytic polymerization of ε‐caprolactam. II. Determination of the kinetic and thermodynamic constants by least‐squares curve fitting
Author(s) -
Tai Kazuo,
Teranishi Hiroichi,
Arai Yoshihiro,
Tagawa Takashi
Publication year - 1980
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1980.070250108
Subject(s) - caprolactam , reaction rate constant , thermodynamics , chemistry , kinetics , kinetic energy , polymerization , hydrolysis , natta , polymer chemistry , polymer , organic chemistry , physics , quantum mechanics
The kinetic and thermodynamic constants of the hydrolytic polymerization of ∂‐caprolactam were determined by least‐squares curve fitting. The calculations were carried out using observed kinetic data such as concentration of ∂‐caprolactam ([CL]), endgroup ([EG]), and ∂‐aminocaproic acid ([ACA]) and time derivatives of each concentration (rates) ∂[CL]/∂ t , ∂[EG]/∂ t , and ∂[ACA]/∂ t . The sets of the converged constants are obtained for the initial water concentrations of 0.42, 0.82, and 1.18 mole/kg. An averaged set of the constants applicable for this range of the initial composition was also evaluated. The compatibility between observed and calculated concentration and rate curves was improved by the use of the newly developed sets of the constants. The mechanism of the polycondensation reaction is also discussed, based on the rate and kinetic constants obtained by this work.