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Published: Kem. Ind. 64 (7-8) (2015) 363−379
Paper reference number: KUI-16/2014
Paper type: Review
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Sixtieth Anniversary of Ziegler-Natta Catalysts and Stereospecific Polymerization

Z. Janović and Z. Veksli


This review article highlights the history of the discoveries of organometallic catalysts and stereospecific polymerization of α-olefins, dienes and a number of vinyl monomers by Karl Ziegler and Giulio Natta sixty years ago, their developments and recent progress. As one of the most important achievements in the field of catalysis, macromolecular science and polymer materials, their inventors were awarded the Nobel Prize in Chemistry in 1963 “for their discoveries in the field of chemistry and technology of high polymers”. These discoveries have stimulated an intensive, both basic and applied research all over the world, up to the present times, leading to great development of the polymer industry. The important biographical data and scientific advancements of K. Ziegler and G. Natta are presented as well. Karl Ziegler, a German scientist, Director of Max Planck Institute for Coal Research in Mülheim, besides many scientific achievements, in 1953 discovered a new process for the polymerization of ethylene into linear polyethylene under mild conditions by using titanium chloride and alkyl aluminium catalytic system that was superior to all existing polymerization. Giulio Natta, an Italian scientist, Director of the Department of Industrial Chemistry at Polytechnic, University of Milan, besides many achievements in petrochemical processes, in 1954 obtained for the first time isotactic polypropylene and Montecatini Co. started its production already in 1958. He conducted pioneering studies on the chain microstructure of synthetic organic polymers and postulated the mechanisms of stereospecific polymerizations. Since the discovery of the Zeigler-Natta catalyst, stereospecific polymerization and processes, significant developments have occurred. The breakthrough in polymerization processes such as fluid bed, liquid phase loop reactor and reactor granule technology led to significant development and growth of polyolefin production. In the 1980s, a new family of transition metal complexes known as metallocene catalysts were discovered, based on biscyclopentadienyl and transition metal as Zr, Hf and Ti and appropriate cocatalysts. There major advantage is solubility, high catalytic activity, and the easy tailoring of the polymer microstructure. In 1986, the first synthesis of syndiotactic polystyrene was performed using monocyclopentadienyl/titanium chloride catalyst. The development of catalysts based on diimine complexes of nickel and palladium, and of phenoxy-imino complexes of zirconium and nickel, resulted in polyolefins of different structure and morphology, and many new copolymers of ethylene particularly with polar monomers, producing a variety of new functional polymers, reactive oligomers, and block copolymers. The described discoveries of organometallic catalysts and their applications are one of the most valid models and sources of inspiration for the progress in chemistry and chemical engineering.

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Karl Ziegler, Giulio Natta, Ziegler-Natta catalysts, metallocene catalysts, stereospecific polymerization, polyolefins