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Table of contents
1 Introduction
1.1 Motivation
1.2 Outline of the thesis
2 Emulsion polymerization principles
2.1 Introduction
2.1.1 Uses of emulsion polymerization
2.1.2 Technical interest of emulsion polymerization
2.1.3 Economic aspects
2.2 Components of an emulsion polymerization
2.3 Sites of polymerization
2.4 Advantages and drawbacks
2.5 Process description
2.6 Kinetics and mechanisms
2.6.1 Free radical polymerization
2.6.2 Rate of polymerization
2.6.3 Number of polymer particles
2.6.4 Average number of radicals per particle
2.6.5 Monomer concentration [M]
2.7 Other kinetic effects
2.7.1 Electrolyte concentration
2.7.2 Emulsifier structure
2.7.3 Nonionic emulsifiers
2.7.4 Monomer to water ratio
2.7.5 Temperature
2.7.6 Agitation
2.7.7 Conversion
2.7.8 Gel effect
2.8 Reactor engineering
2.8.1 Batch reactor
2.8.2 Semibatch reactor
2.8.3 Continuous reactor
3 Modeling and simulation of emulsion polymerization
3.1 Introduction
3.2 Modeling of emulsion polymerization
3.2.1 Initiator balance
3.2.2 Monomer balance
3.2.3 Average number of radicals per particle ¯n
3.2.4 Radicals in the aqueous phase
3.2.5 Monomer phase distribution
3.2.6 Moments of dead chains
3.2.7 Energy balance equations
3.3 Experimental validation of the model
3.4 Conclusion
4 Dynamic optimization of vinyl acetate polymerization
4.1 Dynamic optimization fundamentals
4.1.1 Introduction
4.1.2 Problem definition
4.1.3 Analytical methods
4.1.4 Numerical methods
4.2 Dynamic optimization of emulsion polymerization
4.3 Case study : Vinyl acetate emulsion polymerization
4.3.1 Process operation
4.3.2 Minimization of batch time with T as control variable
4.3.3 Minimization of batch time with reactor T and qI as control variables
4.3.4 Minimization of batch time with T, qI and qM as control variables
4.4 Conclusion
5 Nonlinear geometric control and state estimation
5.1 Nonlinear geometric control fundamentals
5.1.1 Differential geometry concepts
5.1.2 Input/output linearization
5.1.3 Su-Hunt-Meyer linearization (or input/state linearization)
5.2 State estimation
5.2.1 State estimation principles
5.2.2 Extended Kalman filter (EKF)
6 Nonlinear control of vinyl acetate polymerization
6.1 Control of emulsion polymerization
6.2 Simulation of the nonlinear geometric control
6.2.1 Controller design
6.2.2 Extended Kalman filter
6.2.3 Simulations results for the current operation of the industrial reactor
6.3 Control under optimal conditions
6.3.1 Optimal temperature control with optimal feed policies (qI and qM)
6.4 Conclusion
7 Conclusions and perspectives
