2.2 Ethylene Polymerization in the NMR Tube: Direct Insight into the Catalytic Action
Using Enriched
13
C Ethylene [12, 17, 18] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3 Kinetic Analysis in a Plug Flow Reactor [13, 16] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3 Stereorigid Bridged Metallocene Catalysts in Connection with MAO as Activator . . . . . . . 20
3.1 Mechanism of Stereochemical Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.2 Stereospecific Propylene Polymerization: The Rotation Effect, an Insight into
Mechanistic Detail . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4 Silica-Supported Metallocene/MAO Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.1 Polymerization Kinetics and Polymer Particle Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
5 Video Microscopy for the Investigation of Gas-Phase Polymerization . . . . . . . . . . . . . . . . . . . . 30
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
1 Introduction
Within the programme “Historical Landmarks of Chemistry”
1 [1], on the 8th May
2008 the Gesellschaft Deutscher Chemiker (GDCh, Society of German Chemists)
and the Max-Planck-Institut fu ¨r Kohlenforschung (Max Planck Institute for Coal
Research) in Mu ¨lheim an der Ruhr honoured the achievements of Karl Ziegler,
whose pioneering research in the field of organic chemistry led to a revolution
in organometallic catalysis and organometallic chemistry (Fig. 1). In 1953, he
submitted a patent application describing the preparation of high molecular weight
polyethylene at normal pressure and room temperature with the help of so-called
metallorganische Mischkatalysatoren (organometallic mixed-catalysts) formed by
treating transition metal compounds with alkyl-aluminium species and this led to
an unprecedented growth in the industrial production of polyolefins. Polyolefins,
such as polypropylene and polyethylene, are inexpensive, ecologically acceptable
synthetic polymers that find use in a whole range of products and make up
over half of the 250 million tons of synthetic polymers produced annually. The
discovery also accelerated the development of homogeneous catalysis using soluble
organometallic complexes. This has become one of the most innovative fields in
modern chemistry and is of considerable importance in the production of organic
compounds by the pharmaceutical and chemical industries. Karl Ziegler and the
chemistry associated with his name found world-wide acclaim, and in 1963
he was awarded the Nobel Prize for Chemistry along with the Italian Giulio
Natta who had determined the stereochemistry of the polypropylene formed using
Ziegler catalysts.
1 The programme “Historical Landmarks of Chemistry” (Historische Sta ¨tten der Chemie) was
instigated by the GDCh in order to draw the attention of the general public to research of particular
significance to the development of chemistry in Germany. The objective is ultimately to further
an interest in the cultural inheritance of chemistry while emphasizing its historical basis. The
locations where important scientists made their most significant discoveries are recalled in an
inaugural act with the unveiling of a plaque and with the publication of a booklet [1] describing
their work and its present day relevance.
2
G. Fink
Using Enriched
13
C Ethylene [12, 17, 18] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3 Kinetic Analysis in a Plug Flow Reactor [13, 16] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3 Stereorigid Bridged Metallocene Catalysts in Connection with MAO as Activator . . . . . . . 20
3.1 Mechanism of Stereochemical Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.2 Stereospecific Propylene Polymerization: The Rotation Effect, an Insight into
Mechanistic Detail . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4 Silica-Supported Metallocene/MAO Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.1 Polymerization Kinetics and Polymer Particle Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
5 Video Microscopy for the Investigation of Gas-Phase Polymerization . . . . . . . . . . . . . . . . . . . . 30
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
1 Introduction
Within the programme “Historical Landmarks of Chemistry”
1 [1], on the 8th May
2008 the Gesellschaft Deutscher Chemiker (GDCh, Society of German Chemists)
and the Max-Planck-Institut fu ¨r Kohlenforschung (Max Planck Institute for Coal
Research) in Mu ¨lheim an der Ruhr honoured the achievements of Karl Ziegler,
whose pioneering research in the field of organic chemistry led to a revolution
in organometallic catalysis and organometallic chemistry (Fig. 1). In 1953, he
submitted a patent application describing the preparation of high molecular weight
polyethylene at normal pressure and room temperature with the help of so-called
metallorganische Mischkatalysatoren (organometallic mixed-catalysts) formed by
treating transition metal compounds with alkyl-aluminium species and this led to
an unprecedented growth in the industrial production of polyolefins. Polyolefins,
such as polypropylene and polyethylene, are inexpensive, ecologically acceptable
synthetic polymers that find use in a whole range of products and make up
over half of the 250 million tons of synthetic polymers produced annually. The
discovery also accelerated the development of homogeneous catalysis using soluble
organometallic complexes. This has become one of the most innovative fields in
modern chemistry and is of considerable importance in the production of organic
compounds by the pharmaceutical and chemical industries. Karl Ziegler and the
chemistry associated with his name found world-wide acclaim, and in 1963
he was awarded the Nobel Prize for Chemistry along with the Italian Giulio
Natta who had determined the stereochemistry of the polypropylene formed using
Ziegler catalysts.
1 The programme “Historical Landmarks of Chemistry” (Historische Sta ¨tten der Chemie) was
instigated by the GDCh in order to draw the attention of the general public to research of particular
significance to the development of chemistry in Germany. The objective is ultimately to further
an interest in the cultural inheritance of chemistry while emphasizing its historical basis. The
locations where important scientists made their most significant discoveries are recalled in an
inaugural act with the unveiling of a plaque and with the publication of a booklet [1] describing
their work and its present day relevance.
2
G. Fink