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Updated: Feb 23, 2026

Facile Preparation of Ultrafine Aluminum Hydroxide Particles with or without Mesoporous MCM-41 in Ambient Environments
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Formation, Structure, and Composition of Methylaluminoxane.

Mikko Linnolahti1, Scott Collins2

  • 1Department of Chemistry, University of Eastern Finland, Joensuu Campus, FI-80101, Joensuu, Finland.

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
|September 1, 2017
PubMed
Summary

Methylaluminoxane (MAO), a key activator in olefin polymerization, forms stable cage structures with associated trimethylaluminum (TMA). These reactive sites explain MAO's catalytic function, with structures evolving from chains to cages as size increases.

Keywords:
ab initio calculationscage compoundshomogeneous catalysispolymerizationstructure elucidation

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Area of Science:

  • Polymer Chemistry
  • Organometallic Chemistry
  • Computational Chemistry

Background:

  • Methylaluminoxane (MAO) is the standard activator for olefin polymerization.
  • The precise structure and formation mechanism of MAO remain poorly understood.
  • Trimethylaluminum (TMA) is the precursor for MAO synthesis.

Purpose of the Study:

  • To elucidate the thermodynamic formation pathways of MAO through computational simulations.
  • To determine the stable structures of MAO in the realistic size domain.
  • To correlate MAO structure with its function as a catalyst activator.

Main Methods:

  • Large-scale, systematic quantum chemical calculations.
  • Simulation of controlled hydrolysis of trimethylaluminum (TMA).
  • Mass spectrometric analysis of MAO anions.

Main Results:

  • MAO favors cage-like structures, often containing associated TMA, across various sizes.
  • Observed structural transitions from chains to rings to sheets to cages with increasing size.
  • Identified the most stable cage structure as (MeAlO)16(Me3Al)6, a tubular form with MW 1360 g/mol.
  • Mass spectrometry confirmed major and minor anion species, aligning with computational findings.

Conclusions:

  • MAO's cage structures with associated TMA are crucial for its role as a catalyst activator.
  • Computational and experimental results provide a consistent understanding of MAO's size-dependent structural evolution.
  • The study clarifies the long-standing structural ambiguity of MAO, essential for olefin polymerization catalysis.