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Screening the Thermodynamics of Trimethylaluminum‐Hydrolysis Products and Their Co‐Catalytic Performance in Olefin‐Polymerization Catalysis
Author(s) -
Linnolahti Mikko,
Laine Anniina,
Pakkanen Tapani A.
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201204450
Subject(s) - exergonic reaction , chemistry , catalysis , olefin fiber , polymerization , monomer , olefin polymerization , molecule , stoichiometry , hydrolysis , metallocene , polymer chemistry , organic chemistry , polymer
Herein, we introduce an approach for the computational screening of stoichiometric reactions between trimethylaluminum (TMA) and water. The thermodynamic products of these reactions are methylaluminoxanes (MAOs) with different compositions, which have the general formula (AlOMe) n (AlMe 3 ) m , in which n describes the degree of oligomerization and m is the number of associated TMA molecules. These reaction products were thoroughly explored up to n =4, thus demonstrating the thermodynamically preferable association of up to four AlMe 3 molecules, that is, TMA molecules in their monomeric form. The relative Lewis acidities of the Al sites in these MAOs were systematically explored and we found that the associated TMA molecules were a key ingredient for co‐catalytic activity in olefin‐polymerization catalysis. This conclusion was supported by computational studies on catalyst activation, which revealed an exergonic insertion of ethene into the metallocene/MAO complex.