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A kinetic study on the autocatalytic cure reaction of a cyanate ester resin
Author(s) -
Chen ChingChung,
Don TrongMing,
Lin TaiHung,
Cheng LiaoPing
Publication year - 2004
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.20314
Subject(s) - autocatalysis , cyanate ester , curing (chemistry) , cyanate , exothermic reaction , reaction rate constant , order of reaction , isothermal process , activation energy , kinetics , materials science , reaction rate , kinetic energy , differential scanning calorimetry , polymer chemistry , thermosetting polymer , thermodynamics , chemistry , composite material , catalysis , organic chemistry , epoxy , physics , quantum mechanics
Abstract The cure of a novolac‐type cyanate ester monomer, which reacts to form a polycyanurate network, was investigated by using differential scanning calorimeter. The conversions and the rates of cure were determined from the exothermic curves at several isothermal temperatures (513–553 K). The experimental data, showing an autocatalytic behavior, conforms to the kinetic model proposed by Kamal, which includes two reaction orders, m and n , and two rate constants, k 1 and k 2 . These kinetic parameters for each curing temperature were obtained by using Kenny's graphic‐analytical technique. The overall reaction order was about 1.99 ( m = 0.99, n = 1.0) and the activation energies for the rate constants, k 1 and k 2 , were 80.9 and 82.3 kJ/mol, respectively. The results show that the autocatalytic model predicted the curing kinetics very well at high curing temperatures. However, at low curing temperatures, deviation from experimental data was observed after gelation occurred. The kinetic model was, therefore, modified to predict the cure kinetics over the whole range of conversion. After modification, the overall reaction order slightly decreased to be 1.94 ( m = 0.95, n = 0.99), and the activation energies for the rate constants, k 1 and k 2 , were found to be 86.4 and 80.2 kJ/mol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3067–3079, 2004