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Polymerization of methyl methacrylate at high temperature with 1‐butanethiol as chain transfer agent
Author(s) -
Fenouillot F.,
Terrisse J.,
Rimlinger T.
Publication year - 1999
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/(sici)1097-4628(19990620)72:12<1589::aid-app12>3.0.co;2-s
Subject(s) - polymerization , chain transfer , transfer agent , dispersity , polymer chemistry , molar mass distribution , methyl methacrylate , monomer , radical polymerization , catalytic chain transfer , bulk polymerization , polymer , living polymerization , kinetic chain length , chain termination , organic peroxide , methacrylate , materials science , chemistry , organic chemistry , copolymer
The free‐radical polymerization of methyl methacrylate (MMA) at high temperature (120 to 180°C) has been studied in the presence of di‐tertiobutyle peroxide as an initiator and 1‐butanethiol as a chain transfer agent. No solvent was used, and the polymerization was run to high monomer conversion. Based on the experimental data collected with a dilatometric reactor, the features of the reaction have been pointed out. Working at high temperature with a chain transfer agent proved efficient to reduce the intensity of the gel effect and control the molecular weight obtained. At a temperature up to 170°C, however, the burn‐out of the initiator limits the final conversion, and the increase of the polymerization rate during the gel effect has been more difficult to detect and quantify. An empirical expression of the termination rate constant has been adopted to describe the autoacceleration and predict the conversion versus time curves and the average molecular weight of the polymer obtained. The mathematical model includes two adjustable parameters that have been determined as a function of the temperature and the initial concentration of the chain transfer agent. The agreement between the predicted and experimental data on conversion and molecular weight was good, while the polydispersity index was often underestimated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1589–1599, 1999