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The subject deals with all aspects of the description and mathematical modelling of polymerization reactors. It includes treatment of reaction kinetics, population balances, description of molecular architecture by distribution functions, effect of phase and reaction equilibrium on polymerization, gas-dispersion and liquid-dispersion reactors, effects of thermodynamics on polymerization, control of polymerization reactors, down-stream processing of polymerization products and preparation of polymeric foams.
Last update: Pátková Vlasta (16.11.2018)
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Young R.J., Lovell P.A.: Introduction to Polymers, Chapman & Hall (1991).
Morbidelli M.: Polymer reaction and colloid engineering (PDF file). https://www.ethz.ch/content/dam/ethz/special-interest/chab/icb/morbidelli-dam/documents/Education/PRCE/Series2016/PRCE_Lecture_Notes.pdf Last update: Pátková Vlasta (16.11.2018)
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1. Polymers – amorphous, crystalline, semi-crystalline. DSC characterization. Polymer molecular architecture – chain-length distribution, distributions for copolymers, branching, tacticity. GPC. 2. Method of polymer moments applied to chain-length distribution. Various distributions (NCLD, WCLD, NMWD, WMWD) and their characteristics related to moments (average chain length, polydispersity). Physical interpretation of polymer moments. 3. Types of polymerization kinetics. Method of polymer moments applied to processing of a simple polymerization kinetics. 4. Polycondensation. Carothers and Flory theories. Chain-length distribution of polymers prepared by polycondensation. Reaction kinetics of polycondensation. 5. Polycondensation. Non-stoichiometric ratio of reactants. Effect of reaction equilibrium. Effect of phase equilibrium and diffusion. Geling. 6. Free-radical polymerization kinetics. Reaction mechanism, rate of polymerization and average chain length. Chain transfer to solvent and to polymer. Ceiling temperature. 7. Chain-length distribution in free-radical polymerization for live and dead chains. Effect of temperature on polymerization rate and average chain length. Geling effect. 8. Copolymerization in free-radical polymerization. Reactivity ratios. Copolymer composition and composition drift during batch copolymerization. Sequence lengths. 9. Reactors for free-radical (co)polymerization. Polymerization in bulk, solution, suspension and emulsion. Colloidal stability (DLVO theory) in emulsions. 10. Emulsion polymerization. Critical micelle concentration (CMC). Phase behavior and stages of emulsion polymerization. Average number of radicals per particle. Rate of polymerization and average chain length in emulsion polymerization. 11. Catalytic polymerization and copolymerization. Ziegler-Natta catalysis. Types of catalyst sites. Stereoregularity. Catalytic activity and its evolution in time. 12. Reactors for catalytic polymerization – in solution, in slurry, in gas dispersion. Heat removal from fluidized bed reactor. Particle growth in slurry and gas dispersion reactors. Particle overheating. 13. Basic thermodynamics of polymer-solvent systems. Flory-Huggins theory. Enthalpy and entropy of mixing. Gibbs energy of mixing – bimodal and spinodal points. Phase diagrams. Hildebrand solubility parameter. 14. Rheology of polymer solutions. Mark-Houwing equation. Intrinsic viscosity of polymer solution. Rheology of polymer melts and its dependence on molecular weight of polymer. Melt flow index. 15. Measurement of MWD (molecular weight distribution) or molecular weight based on viscosity, gel permeation chromatography, osmometry, light scattering, FFF (field flow fractionation), ultracentrifugation, etc. 16. Crystalline, amorphous and semi-crystalline polymers. Lamellas and spherulites. Double-emulsion morphology (e.g., high-impact polystyrene). Melting temperature and glass-transition temperature. Simple morphological models of ion exchange membranes (Nafion). 17. Mechanical properties of polymer. Types of stress-strain curves. Concepts of strength and toughness. Deformation and failure mechanisms in polymers. 18. Visco-elasticity and simple Maxwell and Kelvin-Voight models. Loss and storage moduli.
Last update: Pátková Vlasta (16.11.2018)
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