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Mechanism and Kinetics of the Spontaneous Thermal Copolymerization of Styrene/Maleic Anhydride. Experimental and Simulation Studies in the Presence of 4‐oxo‐TEMPO
Author(s) -
MotaMorales Josué D.,
QuinteroOrtega Iraís,
SaldívarGuerra Enrique,
LunaBárcenas Gabriel,
AlboresVelasco Martha,
Percino Judith,
Chapela Víctor,
Ocampo Miguel A.
Publication year - 2010
Publication title -
macromolecular reaction engineering
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 32
eISSN - 1862-8338
pISSN - 1862-832X
DOI - 10.1002/mren.200900061
Subject(s) - copolymer , maleic anhydride , kinetics , styrene , kinetic energy , bar (unit) , polymer chemistry , thermodynamics , materials science , chemistry , crystallography , physics , nuclear magnetic resonance , quantum mechanics , polymer , meteorology
The mechanism and kinetics of the spontaneous copolymerization of styrene (S) and maleic anhydride (MA) in the presence of 4‐oxo‐TEMPO nitroxide (N) were studied. Experiments were performed at 125 °C varying the S/MA and the N/S ratios and the evolution of conversion was measured by dilatometry up to 20% conversion. Clean induction periods or severe retardation in the initial stage of the reaction were observed. From a proposed kinetic mechanism a mathematical model was built, which was used for fitting the relevant kinetic constants for the self‐initiation steps, and the ratio ${{\bar {k}_{\rm p} } \mathord{\left/ {\vphantom {{\bar {k}_{\rm p} } {\bar {k}_{\rm t}^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} }}} \right. \kern-\nulldelimiterspace} {\bar {k}_{\rm t}^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} }}$ . The model performs well in certain concentration regimes, but it remains a challenge to completely understand this complex system in other concentration regimes.