Adv Polym Sci (2013) 257: 37–58
DOI: 10.1007/12_2013_213
# Springer-Verlag Berlin Heidelberg 2013
Published online: 30 May 2013
Giulio Natta and the Development of
Stereoselective Propene Polymerization
Vincenzo Busico
Abstract 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 TiCl 3 -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.
Keywords Isotactic Á Polypropylene Á Stereocontrol Á Stereoselective polymerization Á Titanium trichloride Á Ziegler–Natta catalysis
Contents
1 Premise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2 ZN Catalysts for Polypropylene: Definition and Genealogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3 From Ziegler’s Metallorganische Mischkatalysator to ZN Catalysts . . . . . . . . . . . . . . . . . . . . . . 40
4 The Structure of TiCl 3 -Based ZN Catalysts for iPP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5 From “Self-Supported” TiCl 3 -Based to MgCl 2 -Supported TiCl 4 -Based ZN Catalysts . . . 50
6 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Appendix: Some Biographic Notes on Giulio Natta . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
V. Busico (*)
Laboratory of Stereoselective Polymerizations (LSP), Department of Chemical Sciences,
Federico II University of Naples, Naples 80126, Italy
e-mail: busico@unina.it
DOI: 10.1007/12_2013_213
# Springer-Verlag Berlin Heidelberg 2013
Published online: 30 May 2013
Giulio Natta and the Development of
Stereoselective Propene Polymerization
Vincenzo Busico
Abstract 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 TiCl 3 -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.
Keywords Isotactic Á Polypropylene Á Stereocontrol Á Stereoselective polymerization Á Titanium trichloride Á Ziegler–Natta catalysis
Contents
1 Premise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2 ZN Catalysts for Polypropylene: Definition and Genealogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3 From Ziegler’s Metallorganische Mischkatalysator to ZN Catalysts . . . . . . . . . . . . . . . . . . . . . . 40
4 The Structure of TiCl 3 -Based ZN Catalysts for iPP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5 From “Self-Supported” TiCl 3 -Based to MgCl 2 -Supported TiCl 4 -Based ZN Catalysts . . . 50
6 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Appendix: Some Biographic Notes on Giulio Natta . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
V. Busico (*)
Laboratory of Stereoselective Polymerizations (LSP), Department of Chemical Sciences,
Federico II University of Naples, Naples 80126, Italy
e-mail: busico@unina.it