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A kinetic investigation of the in situ polymerization of methyl methacrylate under supercritical fluid CO 2 conditions using high‐pressure DSC
Author(s) -
Lu Shiying,
Zhang Zhiyi,
Nawaby A. Victoria,
Day Michael
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.20574
Subject(s) - supercritical fluid , polymerization , kinetics , methyl methacrylate , isothermal process , activation energy , kinetic energy , polymer chemistry , materials science , degree of polymerization , order of reaction , solvent , chemistry , thermodynamics , reaction rate constant , polymer , organic chemistry , physics , quantum mechanics
The polymerization kinetics of methyl methacrylate (MMA) under supercritical fluid CO 2 was studied by using high‐pressure DSC. The results indicate that CO 2 can significantly reduce the cage effect and improve the chain propagation reactions, with the observed solvent‐like effects being enhanced by increased CO 2 pressures. The polymerization of MMA under isothermal conditions and 56 atm of CO 2 was characterized by a first‐order kinetic rate expression over the conversion range 20–80%. The apparent activation energy for the reaction was found to be 51.6 kJ/mol, which is less than the value reported under ambient conditions (68.2 kJ/mol). The polymerization kinetics were also evaluated under nonisothermal conditions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1236–1239, 2004