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Non‐Hydrolytic Route to Aluminoxane‐Type Derivative for Metallocene Activation towards Olefin Polymerisation
Author(s) -
Dalet Thomas,
Cramail Henri,
Deffieux Alain
Publication year - 2004
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200400096
Subject(s) - chemistry , methylaluminoxane , toluene , polymer chemistry , monomer , metallocene , polymerization , hydrolysis , benzoic acid , olefin fiber , absorption spectroscopy , photochemistry , catalysis , organic chemistry , polymer , physics , quantum mechanics
Summary: Access to methylaluminoxane‐type derivatives by a non‐hydrolytic route is described. The procedure involves the reaction between trimethylaluminium (TMA) and benzoic acid (BA) at temperatures comprised from 20 to 100 °C in toluene. The structure of the different aluminic derivatives formed for different ratios R = TMA/BA as well as the reaction pathways leading to these products were investigated by 1 H NMR spectroscopy at different temperatures. The monomeric and/or oligomeric “Me 2 AlOAlMe 2 ” species issued from the reaction between BA and TMA were found to methylate and then activate (cationize) rac ‐Et(Ind) 2 ZrCl 2 as shown by UV/visible spectroscopy analysis. This is further confirmed by successful hex‐1‐ene polymerisations carried out in the presence of such activators.UV/visible absorption spectrum of rac ‐Et(Ind) 2 ZrCl 2 in toluene recorded in the presence of various amounts of MAO 20° ( R = 3).