Abstract
In order to investigate effects of an electron donor in propylene polymerization (in gas and slurry phase reactions each) by using a 3rd generation Ziegler-Natta catalyst, the catalytic activities were measured before and after the addition of an electron donor. And physical properties of produced polymer were estimated. Polymerization rate was decreased with increasing EB/A1 mole ratio because atactic sites on catalyst were selectively poisoned by the addition of the electron donor, and consequently total number of active sites were diminished. It was found that the overall reaction order was the 2nd order, and a reaction rate form was suggested by using a CO inhibition technique. Catalyst deactivation was due to the formation of dense isotactic polypropylene on the catalyst at the beginning of polymerization so that monomers had the difficulties in diffusion into catalyst surface through the dense polymer. From the measurements of polymer physical properties, probability of active site transitions from atactic→low isotactic→high isotactic sites could be considered, which may be due to the formation of a complex between co-catalyst and electron donor.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Brockmeier, N. F. and Rogan, J. B., “Propylene Polymerization Kinetics in a Semi-Batch Reactor by Use of a Supported Catalyst”,Ind. Eng. Chem. Prod. Res. Dev.,24(2), 278(1985).
Brockmeier, N. F., “Latest Commercial Technology for Propylene Polymerization”. Transition Metal Catalyzed Polymerizations, Alkenes and Dienes B.: Harwood Academic PublishersNew York (1983).
Chadwick, J. C., “Effects of Pro-Catalyst Composition on the Stereospecificity of a Ziegler-Natta Catalyst System”,Makromol. Chem.,193, 1463(1992).
Choi, K. Y., “Polymerization of Olefins through Heterogeneous Catalysis, II. Kinetics of Gas Phase Polymerization with Ziegler-Natta Catalysts”,J. of Appl. Polym. Sci,30, 1065(1985).
Choung, S. J., Technical Report of “PO Polymerization Catalyst Research”, 2nd Year (1994).
Doi, Y., Murata, M., Yano, K. and Keii, T., “Gas-Phase Polymerization of Propene with the Supported Ziegler Catalyst: TiCl4/MgCl2/C6H5COOC2H5/Al(C2H5)3”,Ind. Eng. Chem. Pro. Res. Dev.,21, 580(1982).
Floyd, S., Choi, K. Y., Taylor, T. W. and Ray, W. H., “Polymerization of Olefins through Heterogeneous Catalysis, III. Polymer Particle Modeling with an Analysis Intraparticle Heat and Mass Transfer Effects”,J. of Appl. Polym. Sci.,32, 2935 (1986a).
Floyd, S., Choi, K. Y., Taylor, T. W. and Ray, W. H., “Modeling of Heat and Mass Transfer Resistance in the Polymer Particle”,J. of Appl. Polym. Sci.,31, 2231 (1986b).
Floyd, S., Heiskanen, T., Taylor, T. W., Mann, G. E. and Ray, W. H., “Effect of Heat and Mass Transfer Polymerization Behavior and Polymer Properties”,J. of Appl. Polym. Sci,33, 1021 (1987).
Härkönen, M., Seppälä, J. V. and Väänänen, T., “Effect of the Structure of External Alkoxy Silane Donor in High Activity Ziegler-Natta Catalyst on the Microstructure of Polypropylene”,Studies in Surface Science and Catalysis,56, 87(1990).
Kang, S. C., “The Present Status of Olefin Polymerization Catalyst and Manufacturing Technique”,Catalysis,4(1), 51 (1988).
Kakugo, M., “Microtacticity Distribution of Polypropylenes Prepared with Heterogeneous Ziegler-Natta Catalysts”,Macromolecules,21, 314(1988).
Kashiwa, N., “The Role of Ester in High Activity and High Stereoselectivity Catalyst”, Transition Metal Catalyzed Polymerizations, Alkenes and Dienes, A.: Harwood Academic Publishers, New York (1983).
Keii, T., Suzuki, E., Tamura, M. and Doi, Y., “A Kinetic Study on the Role of Ethyl Benzoate Additive Durint Propene Polymerization with Magnesium Chloride Supported Ziegler-Catalyst”, Transition Metal Catalyzed Polymerizations, Alkenes and Dienes, A.: Harwood Academic Publishers, New York (1983).
Kim, H.K., “Polypropylene(I)”, Honam Oil,1, 14(1991).
Koura, H., “Process of Propylene Polymerization and Catalyst Developement”,Shokubai,35(1), 40(1993).
Langer, A. W., “Effect of Hindered Amines on Supported Catalysts for Polypropylene”, Transition Metal Catalyzed Polymerizations, Alkenes and Dienes, A.: Harwood Academic Publishers, New York (1983).
Lee, C. S., “Producing Process of Polypropylene”, Honam Oil,3, 14 (1987).
Miyatake, T., “Microtacticity Distribution of Polypropylenes Prepared with MgCl2 Supported Ti Catalyst System”,Studies in Surface Science and Catalysis,56, 155 (1990).
Okano, T., “Effect Silane Compounds on Catalyst Isospecificity A Plausible Model Based on MO Calculation”,Studies in Surface Science and Catalysis,56, 177 (1990).
Pino, P., Guastalla, G., Rotzinger, B. and Mülhaupt, R., “Stereospecific Polymerization of Propylene: An Outlook 25 Years after its Discovery”, Transition Metal Catalyzed Polymerizations, Alkenes and Dienes, A.: Harwood Academic Publishers, New York (1983).
Soga, K. and Park, J. R., “Easy Convection of Aspecific into Isospecific Sites”,Studies in Surface Science and Catalysis,56, 131 (1990).
Spitz, R., “The Function of Ethyl Benzoate (EB) in Stereospecific Catalysts for Polymerization of Propene Supported on MgCl2”, Transition Metal Catalyzed Polymerizations, Alkenes and Dienes, A.: Harwood Academic Publishers, New York (1983).
Sacchi, M. C., “13C NMR Investigation on Lewis Base Activation Effect in High Yield Supported Ziegler-Natta Catalysts”,Studies in Surface Science and Catalysis,56, 185 (1990).
Sugano, T., “A New Electron Donor for the Stereospecific Polymerization of Propylene”,Studies in Surface Science and Catalysis,56, 201 (1990).
Taylor, T. W., Choi, K. Y., Yuan, H. and Ray, W. H., “Physico-chemical Kinetics of Liquid Phase Propylene Polymerization”, Transition Metal Catalyzed Polymerizations, Alkenes and Dienes, A.: Harwood Academic Publishers, New York (1983).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Lim, SY., Choung, SJ. & Song, KH. Studies on the effects of external electron donor in propylene polymerization. Korean J. Chem. Eng. 13, 21–29 (1996). https://doi.org/10.1007/BF02705884
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF02705884