Adv Polym Sci (2013) 258: 1–28
DOI: 10.1007/12_2013_226
# Springer-Verlag Berlin Heidelberg 2013
Published online: 12 June 2013
Methylaluminoxane: Key Component for
New Polymerization Catalysts
Walter Kaminsky and Hansjo ¨rg Sinn
Abstract The use of methylaluminoxane (MAO) as cocatalyst for the polymerization
of olefins and some other vinyl compounds has widely increased the possibilities for
more precisely controlling the polymer composition, polymer structure, tacticity, and
special properties. Highly active catalysts are obtained by different transition metal
complexes such as metallocenes, half-sandwich complexes, and bisimino complexes
combined with MAO. These catalysts allow the synthesis of polyolefins with different
tacticities and stereoregularities, new cycloolefins and other copolymers, and polyolefin composite materials of a purity that cannot be obtained by Ziegler–Natta
catalysts. The single-site character of metallocene/MAO or other transition metal/
MAO catalysts leads to a better understanding of the mechanism of olefin
polymerization.
Keywords Metallocene catalysts Á Methylaluminoxane Á Olefin polymerization Á
Single-site catalysts
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Formation and Structure of MAO . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . .. . . . . 4
3 New Polyolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
W. Kaminsky (*)
Institute for Technical and Macromolecular Chemistry, University of Hamburg,
Bundesstraase 45, 20146 Hamburg, Germany
e-mail: kaminsky@chemie.uni-hamburg.de
H. Sinn
Guest at the Technical University Clausthal,
Institute for Technical and Macromolecular Chemistry, University of Hamburg,
Bundesstraase 45, 20146 Hamburg, Germany
e-mail: sinnalox@t-online.de
DOI: 10.1007/12_2013_226
# Springer-Verlag Berlin Heidelberg 2013
Published online: 12 June 2013
Methylaluminoxane: Key Component for
New Polymerization Catalysts
Walter Kaminsky and Hansjo ¨rg Sinn
Abstract The use of methylaluminoxane (MAO) as cocatalyst for the polymerization
of olefins and some other vinyl compounds has widely increased the possibilities for
more precisely controlling the polymer composition, polymer structure, tacticity, and
special properties. Highly active catalysts are obtained by different transition metal
complexes such as metallocenes, half-sandwich complexes, and bisimino complexes
combined with MAO. These catalysts allow the synthesis of polyolefins with different
tacticities and stereoregularities, new cycloolefins and other copolymers, and polyolefin composite materials of a purity that cannot be obtained by Ziegler–Natta
catalysts. The single-site character of metallocene/MAO or other transition metal/
MAO catalysts leads to a better understanding of the mechanism of olefin
polymerization.
Keywords Metallocene catalysts Á Methylaluminoxane Á Olefin polymerization Á
Single-site catalysts
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Formation and Structure of MAO . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . .. . . . . 4
3 New Polyolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
W. Kaminsky (*)
Institute for Technical and Macromolecular Chemistry, University of Hamburg,
Bundesstraase 45, 20146 Hamburg, Germany
e-mail: kaminsky@chemie.uni-hamburg.de
H. Sinn
Guest at the Technical University Clausthal,
Institute for Technical and Macromolecular Chemistry, University of Hamburg,
Bundesstraase 45, 20146 Hamburg, Germany
e-mail: sinnalox@t-online.de