Abstract
The control of polymer particle size and PSD is of industrial importance. Very fine particles pack poorly, thereby limiting reactor capacity, and present a dust explosion hazard. In olefin polymerization, a particle size distribution (PSD) in the polymerization reactor has been derived using population balances. Three reasonable reaction mechanisms for Ziegler-Natta catalysts, i.e., a simple reaction model, an active site reduction model, and a two sites model, have been used to derive the average number of active sites. It was observed that the PSD depends not only on residence time, but also on the reaction mechanism. It was also found that multiple active sites change the PSD slightly. The PSD, however, does not depend on initial catalyst volume.
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References
Blackley, D. C, “Theory of Kinetics of Compartmentalized Free-Radical Polymerization Reactions “, in I. Piirma ed., Emulsion Polymerization, Academic Press (1982).
Brockmeier, N. F., “Propylene Polymerization Kinetics in Gas Phase Reactors Using Titanium Trichloride Catalyst”, in J. N. Henderson and T. C. Bouton, ed., Polymerization Reactors and Processes, ACS Symp. Ser., 104 (1979).
Carson, I. G., “Particle Size Distribution of Polypropylene Produced in Continuous Polymerisation”,Die. Angew. Makromol. Chem.,161, 145 (1988).
de Carvalho, AB., Gloor, P.E. and Hamielec, A.E., “A Kinetic Mathematical Model of Heterogeneous Ziegler-Natta Copolymerization”,Polymer,30, 280 (1989).
Chien, J.C.W., “Recent Advances in Supported High Mileage Catalysts for Olefin Polymerization”, in R.P. Quirk ed., Transition Metal Catalyzed Polymerization, Ziegler-Natta and Metathesis Polymerizations, Cambridge University Press, 55 (1989).
Chien, J.C.W., and Kuo, K.I., “Magnesium Chloride Supported High Mileage Catalyst for Olefin Polymerization. VIII. Decay and Transformation of Active Sites”,J. Polym. Sci. Polym. Chem.,23, 761 (1985).
Choi, K. Y. and Ray, W. H., “The Dynamic Behavior of Continuous Stirred-Bed Reactors for the Solid Catalyzed Gas Phase Polymerization of Propylene”,Chem. Eng. Sci.,43 (10), 2587 (1988).
Eirich, F. and Mark, H., “Vinyl Type Polymerization at Solid Surfaces and with Complex Catalysts”,J. Colloid Sci.,11, 748 (1956).
Floyd, S., Choi, K.Y., Taylor, T.W. and Ray, W.H., “Polymerization of Olefins through Heterogeneous Catalysis. III. Polymer Particle Modelling with an Analysis of Intraparticle Heat and Mass Transfer Effects”,J. Appl. Poly. Sci.,32, 2935 (1986a).
Floyd, S., Choi, K.Y., Taylor, T.W. and Ray, W.H., “Polymerization of Olefins through Heterogeneous Catalysis. IV. Modeling of Heat and Mass Transfer Resistance in the Polymer Particle Boundary Layer”,J. Appl. Poly. Sci,31, 2131 (1986b).
Floyd, S., Heiskanen, T., Taylor, T. W., Mann, G. E. and Ray, W. H., “Polymerization of Olefins through Heterogeneous Catalysis. VI. Effect of Particle Heat and Mass Transfer on Polymerization Behavior and Polymer Properties”,J. Appl. Poly. Sci,33, 1021 (1987).
Giannetti, E., “Emulsion Polymerization. 3. Theory of Emulsion Copolymerization Kinetics”,Macromolecule,22, 2094 (1989).
Hutchinson, R.A., Chen, C.M. and Ray, W.H., “Polymerization of Olefins through Heterogeneous Catalysis. X: Modeling of Particle Growth and Morphology”,J. Appl. Poly. Sci,44, 1389 (1992).
Karol, F. J., “Studies with High Activity Catalysts for Olefin Polymerization”,Catal. Rev. Sci Eng.,26(3/4), 557 (1984).
Kiparissides, C., MacGregor, J. F. and Hamielec, A. E., “Continuous Emulsion Polymerization. Modeling Oscillations in Vinyl Acetate Polymerization”,J. Appl. Poly. Sci.,23, 401 (1979).
Kissin, Y. V., “Isospecific Polymerization of Olefins with Heterogeneous Ziegler-Natta Catalysts”, Springer-Verlag, New York (1985).
Kissin, Y. V., “Principles of Polymerizations with Ziegler-Natta Catalysts”, in N. P. Cheremisinoff ed., Handbook of Polymer Science and Technology. Vol. 1: Synthesis and Properties, Marcel Dekker (1989).
Kuo, C., “Magnesium Chloride Supported High-Activity Catalyst for Olefin Polymerization”, Ph. D. Thesis, University of Massachusetts, Amherst (1985).
McAuley, K. B., MacGregor, J. F. and Hamielec, A. E., “A Kinetic Model for Industrial Gas-Phase Ethylene Copolymerization”,AIChE J.,36(6), 837 (1990).
Min, K. W., “The Modeling and Simulation of Emulsion Polymerization Reactors”, Ph. D. Thesis, SUNY, Buffalo, 1976.
O’Toole, J. T., “Kinetics of Emulsion Polymerization”,J. Appl. Poly. Sci.,9, 1291 (1965).
Rawlings, J. B., “Simulation and Stability of Continuous Emulsion Polymerization Reactors”, Ph. D. Thesis, University of Wisconsin, Madison (1985).
Rincon-Rubio, L.M., Wilen, C.E. and Lindfors, L.E., “A Kinetic Model for the Polymerization of Propylene over a Ziegler-Natta Catalyst”,Eur. Polym. J.,26(2), 171 (1990).
Saltman, W. H., “A Kinetic Mechanism for the Heterogeneous Stereospecific Polymerization of Propylene”,J. Poly. Sci,46, 375 (1960).
Schnauβ, A. and Reichert, K. H., “Modelling the Kinetics of Ethylene Polymerization with Ziegler-Natta Catalysts”,Makromol. Chem., Rapid Commum.,11, 315 (1990).
Soga, K., Chen, S. I. and Ohnishi, R., “Effect of Ethyl Benzoate on the Copolymerization of Ethylene with Higher α -Olefins over TiCl4/MgCl2 Catalytic Systems”,Polymer Bull,10, 168 (1983).
Soga, K., Sano, T. and Ohnishi, R., “Copolymerization of Ethylene with Propylene over the Thermally-Reduced γ Al2O3-Supported TiCl4 Catalyst”,Polymer Bull,4, 157 (1981).
Stockmayer, W. H., “Note on the Kinetics of Emulsion Polymerization”,J. Poly. Sci.,24, 314 (1957).
Tait, P. J. T., “Monoalkene Polymerization: Ziegler-Natta and Transition Metal Catalysts”, in G. Allen and J. C. Bevington ed., Comprehensive Polymer Science: The Synthesis, Characterization, Reactions & Applications of Polymers, Pergamon Press (1989).
Tait, P.J. T. and Watkins, N. D., “Monoalkene Polymerization: Mechanisms”, in G. Allen and J. C. Bevington ed., Comprehensive Polymer Science: The Synthesis, Characterization, Reactions & Applications of Polymers, Pergamon Press (1989).
Vesely, K., Ambroz, J., Vilim, R. and Hamrick, O., “Influence of Donor-Type Impurities on the Polymerization of Propylene Catalyzed by Titanium Trichloride-Triethyl Aluminum System”,J. Poly. Sci,55, 25 (1961).
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Kim, J.Y., Conner, W.C. & Laurence, R.L. Particle size distribution in olefin continuous stirred-bed polymerization reactors. Korean J. Chem. Eng. 15, 262–272 (1998). https://doi.org/10.1007/BF02707081
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DOI: https://doi.org/10.1007/BF02707081