Giulio Natta and the Development of Stereoselective Propene Polymerization

This chapter looks back at the fascinating history of isotactic polypropylene, the first man-made stereoregular polymer, from the largely serendipitous discovery to the modern technologies for the industrial production of reactor blends with high-yield Ziegler–Natta catalysts featuring highly controlled morphology. This is also the story of a great man, Giulio Natta, winner of the 1963 Nobel Prize in Chemistry, and his team of incredibly talented young coworkers at the Milan Polytechnic, who in just a few years at the end of the 1950s elucidated the structure of the new polymer and that of the novel TiCl3-based catalysts leading to its formation. The pioneering studies that followed on chain microstructure and the origin of the stereocontrol, and the first educated guesses on the nature of the active species, are critically reviewed, and re-visited with the aid of modern experimental and computational tools and methods, to highlight the current picture of what still represents a most important and lively area of polymer science and organometallic catalysis.