Adv Polym Sci (2013) 258: 279–310
DOI: 10.1007/12_2013_219
# Springer-Verlag Berlin Heidelberg 2013
Published online: 12 June 2013
Polyolefin Nanocomposites and Hybrid
Catalysts
Markus Stu ¨rzel, Alexander Kurek, Melanie Anselm, Tobias Halbach,
and Rolf Mu ¨ lhaupt
Abstract The interplay of single- and multi-site catalysts with nanoparticles,
nanostructure formation, and polymer crystallization represents the key to the
development of advanced polyolefin materials for sustainable development. In
polymerization filling technology, catalysts are supported on a great variety of
nanofillers. In contrast to melt compounding, effective nanoparticle dispersion is
readily achieved during catalytic olefin polymerization, independent of polyolefin
molar mass. Novel families of in situ-formed polyolefin carbon hybrid materials are
based upon single- and multi-layer graphene. Supported multi-site catalysts
produce reactor blends as all “polyolefin” nanocomposites, reinforced by in
situ-formed shish–kebab-like ultrahigh molecular weight polyolefin nanofibers.
Keywords Catalysis Á Molecular reinforcement Á Nanocomposites Á Olefin
polymerization Á Polymerization filling Á Polyolefin Á Reactor blends Á Single-site
catalyst Á Ziegler–Natta
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
2 Polyolefin Nanocomposites and Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
2.1 Polymerization Filling and In situ Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
2.2 Polyolefin Carbon Hybrid Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
2.3 “All Polyolefin” Composites and Hybrid Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
3 Summary, Conclusions, and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
M. Stu ¨rzel, A. Kurek, M. Anselm, T. Halbach and R. Mu ¨lhaupt (*)
Freiburg Materials Research Center and Institute for Macromolecular Chemistry,
Stefan-Meier-Strasse 31, 79104 Freiburg, Germany
e-mail: rolfmuelhaupt@web.de
DOI: 10.1007/12_2013_219
# Springer-Verlag Berlin Heidelberg 2013
Published online: 12 June 2013
Polyolefin Nanocomposites and Hybrid
Catalysts
Markus Stu ¨rzel, Alexander Kurek, Melanie Anselm, Tobias Halbach,
and Rolf Mu ¨ lhaupt
Abstract The interplay of single- and multi-site catalysts with nanoparticles,
nanostructure formation, and polymer crystallization represents the key to the
development of advanced polyolefin materials for sustainable development. In
polymerization filling technology, catalysts are supported on a great variety of
nanofillers. In contrast to melt compounding, effective nanoparticle dispersion is
readily achieved during catalytic olefin polymerization, independent of polyolefin
molar mass. Novel families of in situ-formed polyolefin carbon hybrid materials are
based upon single- and multi-layer graphene. Supported multi-site catalysts
produce reactor blends as all “polyolefin” nanocomposites, reinforced by in
situ-formed shish–kebab-like ultrahigh molecular weight polyolefin nanofibers.
Keywords Catalysis Á Molecular reinforcement Á Nanocomposites Á Olefin
polymerization Á Polymerization filling Á Polyolefin Á Reactor blends Á Single-site
catalyst Á Ziegler–Natta
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
2 Polyolefin Nanocomposites and Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
2.1 Polymerization Filling and In situ Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
2.2 Polyolefin Carbon Hybrid Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
2.3 “All Polyolefin” Composites and Hybrid Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
3 Summary, Conclusions, and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
M. Stu ¨rzel, A. Kurek, M. Anselm, T. Halbach and R. Mu ¨lhaupt (*)
Freiburg Materials Research Center and Institute for Macromolecular Chemistry,
Stefan-Meier-Strasse 31, 79104 Freiburg, Germany
e-mail: rolfmuelhaupt@web.de