A non‐PFT (polymerization filling technique) approach to poly(ethylene‐co‐norbornene)/MWNTs nanocomposites by in situ copolymerization with scandium half‐sandwich catalyst |
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Authors: | Andrea Ravasio Laura Boggioni Incoronata Tritto Cristina D'arrigo Angelo Perico Julia Hitzbleck Jun Okuda |
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Institution: | 1. Istituto per lo Studio delle Macromolecole (ISMAC), Consiglio Nazionale delle Ricerche, Via E. Bassini 15, 20133 Milano, Italy;2. Istituto per lo Studio delle Macromolecole (ISMAC), Consiglio Nazionale delle Ricerche, Via De Marini 6, 16149 Genova, Italy;3. Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, D‐52074 Aachen, Germany |
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Abstract: | The in situ synthesis of ethylene‐co‐norbornene copolymers/multi‐walled carbon nanotubes (MWNTs) nanocomposites was achieved by rare‐earth half‐sandwich scandium precursor Sc(η5‐C5Me4SiMe3)(η1‐CH2SiMe3)2(THF)] (1) activated by Ph3C]B(C6F5)4], through a non‐PFT (Polymerization Filling Technique) approach. MWNTs nanocomposites with low aluminum residue were obtained with excellent yields even though small amounts of triisobutylaluminium were needed as scavenger to prevent catalyst poisoning by MWNT impurities. MWNT bundles were disaggregated and highly coated with Poly(ethylene‐co‐norbornene) P(E‐co‐N)] as revealed by transmission electron microscopy. Interestingly, P(E‐co‐N) copolymers showed Tg over 130 °C as well as norbornene content over 50 mol %; both values were higher than those obtained by the cationic active species in 1 /Ph3C]B(C6F5)4]. A series of copolymerization reactions by 1 /Ph3C]B(C6F5)4]/AliBu3 without MWNTs produced copolymers with the same unexpected features. The NMR analysis revealed the presence of rac‐ENNE and rac‐ENNNE sequences. Thus, AliBu3 changed the stereoirregular alternating copolymer microstructure produced by 1 /Ph3C]B(C6F5)4]. We conclude that AliBu3 is not only a scavenger for CNT impurities, but it reacts with the THF ligand to give coordinatively unsaturated active species. Finally, P(E‐co‐N)/MWNT masterbatches were mixed with commercial TOPAS to produce cyclic olefin copolymer nanocomposites with excellent dispersion of filler. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5709–5719, 2009 |
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Keywords: | catalysis copolymerization nanocomposites polyolefins TEM |
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