Separation and identification of oligomeric ethyl silicates by liquid chromatography with electrospray ionization mass spectrometry

Reversed‐phase liquid chromatography coupled with electrospray ionization mass spectrometry was used to study the molecular structures of components and molar mass distributions in ethyl silicate‐40, a versatile liquid precursor for silicon‐based materials. Identity testing by standard spectroscopic techniques showed that a commercial sample of ethyl silicate‐40 was composed of linear/branched ethoxysiloxane oligomers with the silicon atoms ranging from 2 to 12 together with minor monocyclic species. Analysis of the sample by liquid chromatography coupled with evaporative light scattering detection resulted in an elution profile consisting of a series of peak clusters. Peak identification showed that the linear/branched homologous series of oligomers were eluted in the order of increasing number of silicon atoms in the molecules and the time duration (width) of the resulting peak clusters increased in the same fashion corresponding to increasing number of geometric isomers. In addition, small amounts of monocyclic oligomers present in the sample were found to be less retained than each linear/branched counterpart. Finally, the molar mass distribution parameters for ethyl silicate‐40 determined by the developed method were in good agreement with the literature values. Overall, this work demonstrates that reversed‐phase liquid chromatography coupled with electrospray ionization mass spectrometry is an indispensable tool for the comprehensive characterization of complex mixtures of this type.