Ziegler Catalysts: Recent Scientific Innovations and Technological Improvements PDF
Preview Ziegler Catalysts: Recent Scientific Innovations and Technological Improvements
G. Fink, R. Miilhaupt, H. H. Brintzinger Ziegler Catalysts Recent Scientific Innovations and Technological Improvements With 267 Figures and 124 Tables Springer-Verlag Berlin Heidelberg New York London Paris Tokyo HongKong Barcelona Budapest Editors: Prof. Dr. Gerhard Fink Max-Planck-Institut fUr Kohlenforschung Kaiser-Wilhelm-Platz 1 D-45470 Miilheim, Germany Prof. Dr. Rolf Miilhaupt Albert-Ludwigs-U niversitiit Freiburg Institut fUr Makromolekulare Chemie Hermann-Staudinger-Haus Stefan-Meier-StraBe 31 D-79104 Freiburg, Germany Prof. Dr. Hans H. Brintzinger Universitiit Konstanz D-78434 Konstanz, Germany ISBN -13 :978-3-642-79138-3 e-ISBN-13 :978-3-642-79136-9 DOl: 10.1007/978-3-642-79136-9 Library of Congress Cataloging-in-Publication Data Fink, G. (Gerhard), 1939-Ziegler catalysts: recent scientific innovations and technological improve ments/G. Fink, R. Miilhaupt, H.H. Brintzinger. p. cm. Includes index. ISBN-13 :978-3-642-79138-3 1. Ziegler-Natta catalysts-Congresses. I. Miilhaupt, R. (Roll), 1954-. II. Brintzinger, H.H. (Hans H.), 1935-. III. Title. TP159.C3F56 1995 547'.41204595--dc20 94-46542 CIP This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, re-use of illustrations, recitation, broadcasting, reproduction microfilms or in other ways, and storage in data banks. Duplication of this publication or parts thereof is only permitted under the provisions of the German Copyright Law of September 9, 1965, in its current version, and a copyright fee must always be paid. © Springer-Verlag Berlin Heidelberg 1995 Softcover reprint of the hardcover 1st edition 1995 The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: Macmillan India Ltd., Bangalore-25 SPIN: 10127236 02/3020 543210 - Printed on acid-free paper Karl Ziegler Preface In 1953 Karl Ziegler discovered that the activation of transition metal com pounds with aluminium alkyls led to the formation of unusual organometallic catalysts which were able to oligomerize and polymerize ethene. In contrast to the industrial free radical ethene polymerization, developed by leI during the mid-thirties, Ziegler's polyinsertion process did not require high ethene pressures and high polymerization temperatures. This spectacular breakthrough had a significant impact on the advancement of science and represents a milestone in polyolefin technology. Today polyinsertion reactions are widely applied as versatile synthetic method in polymer chemistry. Ziegler's ethene oligomeriz ation ("Aufbaureaktion") is used to produce 1-0lefins and surfactants. His low pressure polyethylene process had set the stage for the development of modern polyolefin processes. The potential of this novel synthetic method was expanded substantially in 1954, when Natta prepared and characterized isotactic poly propene. Since then several generations of catalysts and processes have been introduced on the commercial scale to produce a large variety of materials ranging from commodity thermoplastics to rubbers, e.g., high density poly ethylene (HDPE), linear low density polyethylene (LLDPE), isotactic poly propylene, ethene/propene rubber (EPR), ethene/propene/diene rubber (EPDM), cis- and trans-poly(1,3-butadiene) or poly (1,3-isoprene). Forty years after Ziegler's discovery, transition metal catalyzed olefin and diolefin polymerization continues to represent one of the most active and exciting areas of research in academic and industrial laboratories. Since the mid- 1980s, outstanding scientific achievement, innovation, and process improve ments have revolutionized polyolefin technology. New generations of supported Ziegler-Natta catalysts give unprecedented control of both polymer micro structures and polymer morphologies. With spherical magnesium chloride supported Lewis-base-modified catalysts as templates, spherical pellet-sized polyolefin replicas are formed and the need for pelletizing extrusion is elimina ted. Today catalyst productivity exceeds 1 ton polymer/g transition metal and eliminates polymer purification steps, e.g., extraction of catalyst residues and low molecular weight stereoirregular by-products. During the mid-1980s the dis covery of stereospecific ansa-metallocene-based catalysts again revolutionized polymer synthesis and polyolefin technology. Such metallocene catalysts essen tially consist of one type of catalytically active sites which are tailored to produce VIII Preface virtually all feasible polymer microstructures. Syndiotactic, hemiisotactic, and stereoblock poly(1-olefins) as well as novel cycloaliphatic polyolefins are now becoming available in commercial quantities. Moreover, microstructure, mo lecular weight, endgroup composition, and comonomer incorporation can be varied independently. In contrast to the state-of-the art multi-site supported catalysts, the novel generation of single-site catalysts greatly facilitates elucida tion of the basic reaction mechanisms accounting for stereochemical and molecular weight control. Remarkable progress has also been achieved in ring opening metathesis polymerization ("ROMP") of cycloolefin monomers, e.g., RIM processes for dicyclopentadiene poiymerization and living or stereospecific polymerization of norbornene and polar norbornene derivatives. These recent advances have greatly stimulated research in the fields of organometallic chemistry, catalysis, polymer chemistry, and polymer engineering. The recent landmark discoveries offer attractive potential for the development of new, environmentally friendly, versatile classes of poly olefin materials and expand the frontiers of polyolefin technology. Novel commodity and high value-in-use materials can be obtained by fine-tuning the catalyst structures. The international symposium "40 Years Ziegler Catalysts" in honor of Karl Ziegler was held in Freiburg, Germany on September 1-3, 1993 and organized jointly by the Freiburger Materialforschungszentrum (Prof. R. Miilhaupt) of the Albert-Ludwigs University in Freiburg and the Max-Planck-Institut fiir Kohlenforschung (Prof. G. Fink) in Miilheim a.d. Ruhr in close collaboration with Prof. H. Brintzinger (University of Konstanz). The objectives of this conference were twofold: to commemorate Karl Ziegler's pioneering research achievements and to review recent advances in the development of metallocene based and heterogeneous catalysts, new processes and materials, and recent progress in the understanding of reaction mechanisms. Another important objective, especially of the workshop "Mechanisms and Models in Ziegler-Natta Catalysis", chaired by Prof. H. Brintzinger in a special session following the symposium, was to review and discuss the status and prospects of models and modelling in the understanding of the basic reaction mechanisms, emphasizing the future prospects of computer-assisted catalyst design and reaction engineering. The symposium, the workshop, and this monograph would not have been possible without financial support by the Max-Planck-Institut fUr Kohlenfor schung, Ciba-Geigy AG, Shell Research, BASF AG, and Hoechst AG. The organizers would like to express their special thanks to all the authors who were willing to prepare manuscripts and all the participants who contributed to the discussion and the exchange of ideas. Hans H. Brintzinger, University of Konstanz, Gerhard Fink, Max-Planck-Institut fUr Kohlenforschung, Miilheim a.d. Ruhr, Rolf Miilhaupt, Freiburger Materialforschungszentrum, Freiburg i.Br. Contributors Albizzati, E. 413 Fan, L. 291 Altomare, A. 455 Feast, W. J. 469 Angermund, K. 251 Fink, G. 159 Antberg, M. 83 Atwood, J.L. 111 Giannini, U. 413 Aulbach, M. 83 Gibson, V. C. 469 Guerra, G. 237 Bachmann, B. 83 Guyot, A. 401 Beck, S. 181 Bercaw, J. E. 317 Bilda, D. 387 Haftka, S. 83 Bliemeister, J. 57 Hagendorf, W. 57 Bohm, L. L. 387 Hajela, S. 317 Breuers, W. 387 Hanuschik, A. 251 Brintzinger, H.-H. 181 Harder, A. 57 Burger, B. J. 317 Haselwander, T. 181 Heitmann, B. 57 Carlini, C. 455 Herfert, N. 159 Cavallo, L. 237 Herzog, T. A. 317 Chacon, S. T. 317 Hungenberg, K. D. 363 Chadwick, J. C. 427 Chien, J. C. W. 199 Kaminaka, M. 333 Ciardelli, F. 455 Kaminsky, W. 149 Corradini, P. 237 Kells, A. M. 343 Cotter, W. D. 317 Kerth, J. 363 Coughlin, E. B. 317 Khosravi, E. 469 Kim, H. J. 333 Den Dauw, K. 111 Koga, N. 275 Dolle, V. 83 Kohn, R. 317 Doyle, M. J. 481 Kiiber, F. 83 Drent, E. 481 Elder, M. J. 99 Langhauser, F. 363 Enderle, H. F. 387 Lecht, R. 387 Ewen, J. A. 99 Longo, P. 217 X Contributors Marczinke, B. 363 Sinn, H. 57 Marshall, E. L. 469 Smith, C. A. 413 Martin, H. 15 Soga, K. 333 McKenzie, 1. D. 343 Spaleck, W. 83 Miller, S. A. 441 Spitz, R. 401 Mitchell, J. 317 Montag, P. 159 Tait, P. J. T. 343 Morini, G. 413 Tikwe, L. 57 Morokuma, K. 275 Moscardi, G. 237 Urlass, K. 57 Miilhaupt, R. 35 Nafpliotis, L. 111 Vacatello, M. 237 Noll, A. 149 Van Broekhoven, J. A. M. 481 Nolte, M. 251 Vereecke, D. 111 Von Thienen, N. 57 Ostoja Starzewski, K. A. 497 Waymouth, R. M. 441 Pasquet, V. 401 Wilke, G. 1 Patin, M. 401 Wilson, B. 469 Peters, L. 111 Winter, A. 83 Piers, W. E. 317 Winter, H. 57 Proto, A. 217 Wong, P. K. 481 Woo, T. K. 291 Razavi, A. 111 Rohrmann, J. 83 Yoshida, T. 275 Schimmel, I. 57 Schlund, R. 363 Zambelli, A. 217 Schmedt, E. 57 Zarncke, O. 57 Schnuchel, W. 57 Ziegler, R. 413 Shapiro, P. J. 317 Ziegler, T. 291 Shiono, T. 333 Zohuri, G. H. 343 Contents 1. Karl Ziegler-The Last Alchemist G. Wilke . .............. . 1 2. Patent Right Aspects in Connection with Four Decades of Ziegler Catalysts H. Martin . ............................ . 15 3. Novel Polyolefin Materials and Processes: Overview and Prospects R. Mfilhaupt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 35 4. The Role of MAO-Activators J. Bliemeister, W. Hagendorf, A. Harder, B. Heitmann, I. Schimmel, E. Schmedt, W. Schnuchel, H. Sinn, L. Tikwe, N. von Thienen, K. Urlass, H. Winter, and O. Zarncke . . . . . . . . . . . . . . . . . .. 57 5. New Isotactic Polypropylenes via Metallocene Catalysts W. Spaleck, M. Antberg, M. Aulbach, B. Bachmann, V. Dolle, S. Haftka, F. Kfiber, J. Rohrmann, and A. Winter . . . . . .. 83 6. Isospecific Pseudo-Helical Zirconocenium Catalysts J. A. Ewen and M. J. Elder . . . . . . . . . . . . . . . . . . . . . . . .. 99 7. Manipulation of the Ligand Structure as an Effective and Versatile Tool for Modification of Active Site Properties in Homogeneous Ziegler-Natta Catalyst Systems A. Razavi, D. Vereecke, L. Peters, K. Den Dauw, L. Nafpliotis, and J.L. Atwood. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 8. Polymerization of Phenyl Substituted Cyclic Olefins with Metallocene/A luminoxane Catalysts W. Kaminsky and A. Noll. . . . . . . . . . . . . . . .. . ...... 149 9. The Relationship Between Kinetics and Mechanisms G. Fink, N. Herfert, and P. Montag . .................... 159 XII Contents 10. Binuclear Titanocene and Zirconocene Cations with fl-Cl and j1-Ch3-Bridges in Metallocene-Based Ziegler-Natta Catalyst Systems - Solution-NMR Studies T. Haselwander, S. Beck, and H.-H. Brintzinger . ............. 181 11. Advances in Ziegler Catalysts J. C. W. Chien. . . . . . . ... . .... 199 12. Stereochemistry of Polymerization of Some IX-Olefins in the Presence of Ziegler-Type Catalysts A. Zambelli, A. Proto, and P. Longo . . . . . . . . . . . . . .. .... 217 13. Models for the Explanation of the Stereospecific Behavior of Ziegler-Natta Catalysts P. Corradini, G. Guerra, L. Cavallo, G. Moscardi, and M. Vacatello .................. , .......... 237 14. Forcefield Calculations on Zirconocene Compounds K. Angermund, A. Hanuschik, and M. Nolte . ............... 251 15. Theoretical Studies on Olefin Polymerization Using Group 4 Metallocene Catalysts N. Koga, T. Yoshida, and K. Morokuma. . . . . . . . . .... 275 16. A Combined Density Functional and Molecular Mechanics Study on Olefin Polymerization by Metallocene Catalysts T. K. Woo, L. Fan, and T. Ziegler . .................... 291 17. Olefin Polymerization with Single Component Organoscandium and Organoyttrium Catalysts B. J. Burger, W. D. Cotter, E. B. Coughlin, S. T. Chacon, S. Hajela, T. A. Herzog, R. Kahn, J. Mitchell, W. E. Piers, P. J. Shapiro, and J. E. Bercaw ............... 317 18. Heterogeneous Metallocene Catalysts K. Soga, M. Kaminaka, H. J. Kim, and T. Shiono ........... 333 19. Kinetic Studies on Propene Polymerization Using Magnesium Dichloride Supported Ziegler-Natta Catalysts P. J. T. Tait, G. H. Zohuri, A. M. Kells, and L. D. McKenzie ..... 343 20. Gas Phase Polymerization of Olefins with Ziegler-Natta and MetallocenejA luminoxane Catalysts: a Comparison K. D. Hungenberg, J. Kerth, F. Langhauser, B. Marczinke, and R. Schlund. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
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