Abstract
The development of the homogeneous metallocene/methylaluminoxane catalyst for the polymerization of olefin has widely increased the possibilities in controlling the polymer composition, polymer structure, tacticity and special properties with high precision compared to the heterogeneous Ziegler–Natta and Phillips catalysts. Metallocene catalysts allow the synthesis of isotactic, isoblock, syndiotactic, stereoblock or atactic polymers, as well as polyolefin composite materials with superior properties and low content of extractables. The homogeneous character of metallocene-based catalysts leads to a better understanding of the mechanism of the olefin polymerization and allows the synthesis of optically active olefin oligomers using chiral transition metal complexes. These single-site catalysts are able to copolymerize ethene and propene with short- and long-chained α-olefins, cyclic olefins, or polar vinyl monomers such as ethers, alcohols or esters. Such copolymers are suitable for blends of polyolefins with polyethers and other polar polymers because of an excellent adhesion of the two polymers. In the future, polyolefin nanocomposites and tailored copolymers open up the approach to new classes of materials with great property combinations such as improved stiffness, high gas barrier properties, significant flame retardancy, and high crystallization rates.
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References
Bochmann M (2010) The chemistry of catalyst activation: the case of group 4 polymerization catalysts. Organometallics 29:4711–4740
Boggioni L, Tritto I (2014) Propene-cycloolefin polymerization. Polyolefins J 1:61–75
Coates GW (2000) Precise control of polyolefin stereochemistry using single-site metal catalysts. Chem Rev 100:1223–1252
Delferro M, Marks TJ (2011) Multinuclear olefin polymerization catalysts. Chem Rev 111:2450–2485
Ewen JA, Jones RL, Razavi A, Ferrara JP (1988) Syndiospecific propylene polymerization with group IVB metallocenes. J Am Chem Soc 110:6255–6256
Frediani M, Bianchini C, Kaminsky W (2006) Low density polyethylene by tandem catalysis with single site Ti(IV)/Co(II) catalysts. Kinet Catal 47:207–212
Hlatky GG (2000) Heterogeneous single-site catalysts for olefin polymerization. Chem Rev 100:1347–1376
Kaminsky W (2012) Discovery of methylaluminoxane as cocatalyst for olefin polymerization. Macromolecules 45:3289–3297
Kaminsky W (Ed) (2013) Polyolefins: 50 years after Ziegler and Natta. Vol I and II, Advances in Polymer Science 257 and 258. Springer, Heidelberg
Kaminsky W (2014) Metallocene based polyolefin nanocomposites. Materials 7:5069–5108
Kaminsky W, Fernandez M (2008) New polymers by copolymerization of olefins with bio oil components. Eur J Lipid Sci Technol 110:841–845
Kaminsky W, Fernandez M (2015) Discovery and development of metallocene based polyolefins with special properties. Polyolefins J 2:1–16
Kaminsky W, Luinstra GA (2010) Olefin polymerization by metallocene catalysis. In: Reschetilowski W, Hönle (eds) Edition Ostwald: on catalysis, vol 2. VWB, Berlin, pp 186–214
Kaminsky W, Külper K, Brintzinger HH, Wild FR (1985) Polymerization of propene and butene with a chiral zirconocene and methylalumoxane as cocatalyst. Angew Chem Int Ed Engl 24:507–508
Kaminsky W, Ahlers A, Möller-Lindenhof N (1989) Asymmetric oligomerization of propene and 1-butene with a zirconocene/alumoxane catalyst. Angew Chem Int Ed Engl 28:1216–1218
Kaminsky W, Funck A, Klinke C (2008) In-situ polymerization of olefins on nanoparticles or fibers by metallocene catalysts. Top Catal 48:84–90
Kaminsky W, Boggioni L, Tritto I (2012) Cycloolefin polymerization. A Comprehensive Ref: Matyjaszewski K, Möller M (eds) Polym Sci 3:843–873
Kawai K, Fujita T (2009) Metal catalysts in olefin polymerization. Top Organomet Chem 26:3–46
Lozano K, Bonilla-Rios J, Barrera EV (2001) Nanofiber reinforced thermoplastic composites: thermoanalytic and mechanical analysis. J Appl Polym Sci 80:1162–1172
McNally T, Poetschke P (eds) (2011) Polymer-carbon nanotube composites: preparation, properties, and applications. Woodhead, Cambridge
Nomura K, Liu KJ (2011) Half-titanocenes for precise olefin polymerization: effect of ligand substituents and some mechanistic aspects. Dalton Trans 40:7666–7682
Pino P, Cioni P, Wei J (1987) Asymmetric hydrooligomerization. J Am Chem Soc 109:6189–6191
PlasticsEurope (2015) Production of plastics worldwide. Statistica. http://www.plasticseurope.org
Razavi A (2013) Syndiotactic polypropylene: discovery, development, and industrialization via bridged metallocene catalysts. Adv Polym Sci 258:43–116
Rieger B, Baugh LS, Kacker S, Striegler S (eds) (2003) Late transition metal polymerization catalysis. Wiley-VCH, Weinheim
Säppälä J, Kokko E, Lehmus P, Malmberg AP, Hakala K, Lipponen S, Löfgren B (2013) Functional polyolefins through polymerization by using bis(indenyl)zirconium catalysts. Adv Polym Sci 258:179–232
Schäfer A, Karl E, Zsolnai L, Huttner G, Brintzinger HH (1987) ansa-Metallocene derivates. XII Diastereomeric derivatization and enantiomer separation of ethylenebis(tetrahydroindenyl)titanium and zirconium dichlorides. J Organomet Chem 328:87–99
Scheirs J, Kaminsky W (eds) (2000) Metallocene-based polyolefins: preparation, properties, and technology, vols 1 and 2. Wiley, Chichester
Sinn H et al (1995) The role of MAO activators. In: Fink G, Mülhaupt P, Brintzinger HH (eds) Ziegler catalysts. Springer, Berlin, pp 57–82
Stadler FJ, Arikan-Conley B, Kaschta J, Kaminsky W, Münstedt H (2011) Synthesis and characterization of novel ethylene-graft-ethylene/propylene copolymers. Macromolecules 44:5053–5063
Wild FR, Zsolnai L, Huttner G, Brintzinger HH (1982) Ansa-metallocene derivates.IV. Synthesis and molecular structure of chiral ansa-titanocene derivates with bridged tetrahydroindenyl ligands. J Organomet Chem 232:233–247
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Kaminsky, W. The discovery and evolution of metallocene-based olefin polymerization catalysts. Rend. Fis. Acc. Lincei 28 (Suppl 1), 87–95 (2017). https://doi.org/10.1007/s12210-016-0588-5
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DOI: https://doi.org/10.1007/s12210-016-0588-5