Metallocene and other transition metal complexes activated by methylaluminoxane are highly active catalysts for the polymerization of olefins, diolefins, and styrene, which was discovered at the University of Hamburg about 25 years ago. These catalysts allow the synthesis of polymers with a highly defined microstructure, tacticity, and stereoregularity, as well as new copolymers with superior properties such as film clarity, tensile strength, and lower extractables. A better understanding of the mechanism of olefin polymerization leads to findings of other new single site catalysts. The development of the metallocene/MAO‐catalysts from their discovery to their present state of the art is presented. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3911–3921, 2004

50 years ago, Karl Ziegler and Giulio Natta were awarded the Nobel Prize for their discovery of the catalytic polymerization of ethylene and propylene using titanium compounds and aluminum-alkyls as co-catalysts. Polyolefins have grown to become one of the biggest of all produced polymers. New metallocene/methylaluminoxane (MAO) catalysts open the possibility to synthesize polymers with highly defined microstructure, tacticity, and steroregularity, as well as long-chain branched, or blocky copolymers with excellent properties. This improvement in polymerization is possible due to the single active sites available on the metallocene catalysts in contrast to their traditional counterparts. Moreover, these catalysts, half titanocenes/MAO, zirconocenes, and other single site catalysts can control various important parameters, such as co-monomer distribution, molecular weight, molecular weight distribution, molecular architecture, stereo-specificity, degree of linearity, and branching of the polymer. However, in most cases research in this area has reduced academia as olefin polymerization has seen significant advancements in the industries. Therefore, this paper aims to further motivate interest in polyolefin research in academia by highlighting promising and open areas for the future.

Metallocenes and other transition metal complexes, activated by methylaluminoxane allow the synthesis of polyolefins with a highly defined microstructure, tacticity, and stereoregularity. New copolymers, long chain branched polymers, and polyolefin nanocomposites are produced by these highly active catalysts. A better understanding of the structure of active sites for the olefin polymerization will lead to findings of new and simpler co-catalysts. Ethene or propene can be copolymerized with 1-olefin macromers with chain lengths up to 12 000 g mol⁻¹ as well as with cyclic olefins. Polypropenes of high molecular weight and filled with multi-walled carbon nanotubes show exciting new physical and mechanical properties and are prepared by in situ polymerization. These, and other polyolefin specialities, will be new future materials in a wide range of applications.