Polymerization and Polymer Properties Polymerization kinetics and
thermodynamics. Detailed modelling of the free radical homo- and co-polymerizations of
vinyl monomers. Preparation of oligomeric and functional polymers.
Polymerization Kinetics
- As an extension of earlier work which revealed the chain length
dependence of the termination rate constants in free radical polymerization, we are using
a new pulsed-laser technique to measure the propagation rate constant and have extended
this work to co-polymerization. This has led to the observation that penultimate units do
affect radical reactivity in many co-polymerizations. Work continues to attempt to
generalize this observation.
Short Polymers
- A method of making low molecular weight polymers uses a catalytic
chain transfer agent (an organo-cobalt compound) to make oligomeric chains which are
actually "macromers;" i.e. they have a functional group on them which permits
their use in subsequent polymerization reactions. We are studying their behaviour in
making comb-like copolymers.
- In another study, tubular reactors are being investigated to make
polymers of medium length. Fouling aspects of these reactors are being quantified.
The magnitude of the “gel effect” in homo- and co-polymerizations of STY and
MMA.
Influence of STY mole fraction, f1 on the overall rate constant, kp,
for propagation in the co-polymerization of STY/MMA as determined by pulsed laser
experiments. Dashed line is classic theory, solid line is penultimate unit model.
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- "The Rate of Copolymerization of Styrene and
Methyl-methacrylate, I. Low Conversion Kinetics", O'Driscoll, K.F. and Huang, J., Eur.
Polym. J. 25, 629-633 (1989).
- "Optimization of a Batch Polymerization Reactor at the Final
Stage of Conversion", O'Driscoll, K.F., Ponnuswamy, S.R. and Penlidis, A., ACS
Symposium Series 404, 321-336 (1989).
- "Determination of Propagation Rate Constants Using a Pulsed
Laser Technique", Davis, T.P., O'Driscoll, K.F., Piton, M.C. and Winnik, M.A., Macromolecules
22, 2785-2788 (1989).
- "Monte Carlo Estimation of Kinetic Parameters in Polymerization
Reactions", Duever, T.A., O'Driscoll, K.F. and Reilly, P.M., J. Poly. Sci., Polymer
Chemistry Edition 26, 965-971 (1988).
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