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- W4232585596 abstract "<p>Methylalumoxane (MAO), a perennially useful activator for olefin polymerization precatalysts, is famously intractable to structural elucidation, consisting as it does of a complex mixture of oligomers generated from hydrolysis of pyrophoric trimethylaluminum (TMA). Electrospray ionization mass spectrometry (ESI-MS) is capable of studying those oligomers that become charged during the activation process. We’ve exploited that ability to probe the synthesis of MAO in real time, starting less than a minute after the mixing of H<sub>2</sub>O and TMA and tracking the first half hour of reactivity. We find that the process does not involve an incremental build-up of oligomers; instead, oligomerization to species containing 12-15 aluminum atoms happens within a minute, with slower aggregation to higher molecular weight ions. The principal activated product of the benchtop synthesis is the same as that observed in industrial samples, namely [(MeAlO)<sub>16</sub>(Me<sub>3</sub>Al)<sub>6</sub>Me]<sup>–</sup>, and we have computationally located a new sheet structure for this ion 94 kJ mol<sup>-1</sup> lower in Gibbs energy than any previously calculated.</p>" @default.
- W4232585596 created "2022-05-12" @default.
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- W4232585596 date "2020-08-20" @default.
- W4232585596 modified "2023-09-29" @default.
- W4232585596 title "Real-Time Analysis of Methylalumoxane Formation" @default.
- W4232585596 doi "https://doi.org/10.26434/chemrxiv.12830942" @default.
- W4232585596 hasPublicationYear "2020" @default.
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