Adv Polym Sci (2013) 257: 1–36
DOI: 10.1007/12_2013_225
© Springer-Verlag Berlin Heidelberg 2013
Published online: 14 June 2013
Contributions to the Ziegler–Natta Catalysis:
An Anthology
Gerhard Fink
Abstract This anthology summarizes contributions to Ziegler–Natta catalysis that
have led through novel experimental methods to well-founded results, to continuing
conclusions, and to increasing knowledge about the course of this catalysis. The
complex and manifold mechanism has been elucidated in extensive kinetic studies
in a half continuous tank reactor, in a plug flow reactor with oligomer distribution
analysis as an additional “measuring instrument,” by dynamic NMR spectroscopy
with line shape analysis, through use of
13
C-enriched reacting ethylene as a
molecular surveyor, and by observation of the individual behavior of a large
number of particles with supported catalysts by transmission electron microscopy
and video microscopy. The synopsis of the results of the different experimental
methods gives assurance that we are safely on the right path.
Keywords Catalysis Á Kinetic analysis Á Mechanistic detail Á Stereospecific
polymerization Á Silica-supported Metallocene/MAO catalysts Á Videomicroscopy
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1 Biographical Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Early Soluble Unbridged Metallocene Catalysts in Connection with Alkyl Aluminum
Chlorides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.1 Kinetic Analysis by Means of a Half Continuous Stirred Tank Reactor: Ethylene
Polymerization with an In Situ Start [11] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
G. Fink (*)
Max-Planck-Institut fu ¨r Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mu ¨lheim an der Ruhr,
Germany
e-mail: fink@mpi-muelheim.mpg.de
Studies with W. Zoller, R. Rottler, D. Schnell, W. Fenzl, R. Mynott, N. Herfert, J. van der Leek,
M. Reffke, R. Kleinschmidt, R. Goretzki, K Angermund, V. Jensen, W. Thiel, B. Tesche,
B. Steinmetz, C. Przybyla, J. Zechlin, B. Weimann, K. Hauschild, F. Korber, S. Knoke,
A. Alexiades, and D. Ferrari.
DOI: 10.1007/12_2013_225
© Springer-Verlag Berlin Heidelberg 2013
Published online: 14 June 2013
Contributions to the Ziegler–Natta Catalysis:
An Anthology
Gerhard Fink
Abstract This anthology summarizes contributions to Ziegler–Natta catalysis that
have led through novel experimental methods to well-founded results, to continuing
conclusions, and to increasing knowledge about the course of this catalysis. The
complex and manifold mechanism has been elucidated in extensive kinetic studies
in a half continuous tank reactor, in a plug flow reactor with oligomer distribution
analysis as an additional “measuring instrument,” by dynamic NMR spectroscopy
with line shape analysis, through use of
13
C-enriched reacting ethylene as a
molecular surveyor, and by observation of the individual behavior of a large
number of particles with supported catalysts by transmission electron microscopy
and video microscopy. The synopsis of the results of the different experimental
methods gives assurance that we are safely on the right path.
Keywords Catalysis Á Kinetic analysis Á Mechanistic detail Á Stereospecific
polymerization Á Silica-supported Metallocene/MAO catalysts Á Videomicroscopy
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1 Biographical Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Early Soluble Unbridged Metallocene Catalysts in Connection with Alkyl Aluminum
Chlorides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.1 Kinetic Analysis by Means of a Half Continuous Stirred Tank Reactor: Ethylene
Polymerization with an In Situ Start [11] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
G. Fink (*)
Max-Planck-Institut fu ¨r Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mu ¨lheim an der Ruhr,
Germany
e-mail: fink@mpi-muelheim.mpg.de
Studies with W. Zoller, R. Rottler, D. Schnell, W. Fenzl, R. Mynott, N. Herfert, J. van der Leek,
M. Reffke, R. Kleinschmidt, R. Goretzki, K Angermund, V. Jensen, W. Thiel, B. Tesche,
B. Steinmetz, C. Przybyla, J. Zechlin, B. Weimann, K. Hauschild, F. Korber, S. Knoke,
A. Alexiades, and D. Ferrari.