Table Of ContentG. Fink, R. Miilhaupt, H. H. Brintzinger
Ziegler Catalysts
Recent Scientific Innovations
and Technological Improvements
With 267 Figures and 124 Tables
Springer-Verlag
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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
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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
