http://www.cnr.it/ontology/cnr/individuo/prodotto/ID189225
Facing Unexpected Reactivity Paths with ZrIV-Pyridylamido Polymerization Catalysts (Articolo in rivista)
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- Facing Unexpected Reactivity Paths with ZrIV-Pyridylamido Polymerization Catalysts (Articolo in rivista) (literal)
- Anno
- 2012-01-01T00:00:00+01:00 (literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
- 10.1002/chem.201102194 (literal)
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- Luconi L; Rossin A.; Tuci G.; Tritto I.; Boggioni L.; Klosin J.J.; Theriault C.N.; Giambastiani G. (literal)
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- http://onlinelibrary.wiley.com/doi/10.1002/chem.201102194/abstract;jsessionid=A2B64B621AD5496AD50FA559A1A76968.d03t01?systemMessage=Wiley+Online+Library+will+be+disrupted+on+27+October+from+10%3A00-12%3A00+BST+%2805%3A00-07%3A00+EDT%29+for+essential+maintenance (literal)
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- Luconi L.; Rossin, A.; Tuci, G.; Giambastiani, G.: ICCOM CNR, Inst Chem OrganoMetall Cpds, I-50019 Florence, Italy
Tritto I.: ISMAC CNR, Inst Macromol Studies, I-20133 Milan, Italy
Boggioni L.: ISMAC CNR, Inst Macromol Studies, I-20133 Milan, Italy
Klosin, J.J.; Theriault, C.N.: Dow Chem Co USA, Corp R&D, Midland, MI 48674 USA (literal)
- Titolo
- Facing Unexpected Reactivity Paths with ZrIV-Pyridylamido Polymerization Catalysts (literal)
- Abstract
- This work provides original insights to the better understanding of the complex structure-activity relationship of ZrIV-pyridylamido-based olefin polymerization catalysts and highlights the importance of the metal-precursor choice (Zr(NMe2)4 vs. Zr(Bn)4) to prepare precatalysts of unambiguous identity. A temperature-controlled and reversible ?-bond metathesis/protonolysis reaction is found to take place on the ZrIV-amido complexes in the 298-383 K temperature range, changing the metal coordination sphere dramatically (from a five-coordinated tris-amido species stabilized by bidentate monoanionic {N,N-} ligands to a six-coordinated bis-amido-mono-amino complexes featured by tridentate dianionic {N-,N,C-} ligands). Well-defined neutral ZrIV-pyridylamido complexes have been prepared from Zr(Bn)4 as metal source. Their cationic derivatives [ZrIV{N-,N,C-}Bn]+[B(C6F5)4]- have been successfully applied to the room-temperature polymerization of 1-hexene with productivities up to one order of magnitude higher than those reported for the related HfIV state-of-the-art systems. Most importantly, a linear increase of the poly(1-hexene) Mn values (30-250 kg mol-1) has been observed upon catalyst aging. According to that, the major active species (responsible for the increased Mn polymer values) in the aged catalyst solution, has been identified. (literal)
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