On the mechanism of olefin polymerization by titanocene/MAO catalysts: Relationships between metathesis and addition polymerization

Ethylene polymerizations and norbornene oligomerizations catalysed by Cp2Ti13CH3Cl/MAO (Cp: cyclopentadienyl; MAO: methylaluminoxane) mixtures have been carried out at different temperatures (from ‐20°C to 20°C), in order to test the validity of carbene mechanisms in α‐olefin polymerizations. Depend...

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Bibliographic Details
Published in:Macromolecular chemistry and physics 1997-05, Vol.198 (5), p.1347-1361
Main Authors: Tritto, Incoronata, Li, San Xi, Boggioni, Laura, Sacchi, Maria Carmela, Locatelli, Paolo, O'Neill, Aideen
Format: Article
Language:English
Subjects:
Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
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Summary:Ethylene polymerizations and norbornene oligomerizations catalysed by Cp2Ti13CH3Cl/MAO (Cp: cyclopentadienyl; MAO: methylaluminoxane) mixtures have been carried out at different temperatures (from ‐20°C to 20°C), in order to test the validity of carbene mechanisms in α‐olefin polymerizations. Depending on the temperature, different ratios of the cationic species [Cp2Ti13CH3]+[Cl · MAO]− and precursors of the alkylidene Cp2Ti = 13CH2 exist. The in situ polymerization of 13C enriched ethylene was monitored by 13C NMR spectroscopy. Moreover, catalytic activity was determined and polyethylene samples were analyzed by 13C NMR and gel permeation chromatography (GPC). The following evidence has been provided against the carbene mechanism in the α‐olefin polymerization with titanocene based catalysts: (a) in the in situ ethylene polymerization experiments the appearance of polyethylene signals is concurrent with the decrease of cationic [Cp2Ti13CH3]+[Cl · MAO]− signals and is not related to the intensity of the alkylidene Cp2Ti = 13CH2 signals; (b) from the 13C NMR analysis of polyethylene chain‐end groups the 13C enrichment of Cp2Ti13CH3Cl has only been found in the methyl chain‐end group and not in the methylene of the propyl chain‐end group, as should have been the case if the carbene mechanism had been valid; (c) from norbornene oligomerization (at 0°C) the addition product 2‐13C enriched methyl‐norbornane has been identified. Moreover, the identification of a 13C enriched methylidene‐norbornane dimer at higher temperatures has revealed the possibility of norbornene addition to titanium carbenes through the formation of titanacyclobutane without the opening of the norbornene ring. However, this process requires higher energies with respect to the Cossee type insertion.
ISSN:1022-1352
1521-3935
DOI:10.1002/macp.1997.021980505