Improving the performance of methylalumoxane: A facile and efficient method to trap “free” trimethylaluminum

V Busico, R Cipullo, F Cutillo… - Journal of the …, 2003 - ACS Publications
V Busico, R Cipullo, F Cutillo, N Friederichs, S Ronca, B Wang
Journal of the American Chemical Society, 2003ACS Publications
The presence of “free” trimethylaluminum (TMA) in methylalumoxane (MAO) solutions can
be highly detrimental to the performance of metallocene and “post-metallocene” olefin
polymerization catalysts. The most used strategy to remove “free” TMA is to evaporate MAO
solutions to dryness, until a free-flowing white powder (“solid MAO”) is left. This procedure is
tedious and potentially hazardous, because in some cases the distillate is a concentrated
hydrocarbon solution of TMA. Moreover,“solid MAO” is poorly soluble in common …
The presence of “free” trimethylaluminum (TMA) in methylalumoxane (MAO) solutions can be highly detrimental to the performance of metallocene and “post-metallocene” olefin polymerization catalysts. The most used strategy to remove “free” TMA is to evaporate MAO solutions to dryness, until a free-flowing white powder (“solid MAO”) is left. This procedure is tedious and potentially hazardous, because in some cases the distillate is a concentrated hydrocarbon solution of TMA. Moreover, “solid MAO” is poorly soluble in common polymerization media, and once in solution it can regenerate TMA to some extent. This communication reports on a facile alternative, which consists in the controlled addition of a sterically hindered phenol, such as 2,6-di-tert-butylphenol, effectively trapping “free” TMA. We show here that 2,6-di-tert-butylphenol/MAO solutions activate equally well the dichloro-precursors of well-known zirconocene and bis(phenoxyimine)Ti catalysts, and that their use in propene polymerization results in a substantially higher productivity, polymer stereoregularity, and/or average molecular mass compared with activation by MAO alone.
ACS Publications
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