Characterization of complex polyether polyols using comprehensive two-dimensional liquid chromatography hyphenated to high-resolution mass spectrometry

Gino Groeneveld*, Melissa N. Dunkle, Marian Rinken, Andrea F.G. Gargano, Ayako de Niet, Matthias Pursch, Edwin P.C. Mes, Peter J. Schoenmakers

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Polyether polyols are often used in formulated systems, but their complete characterization is challenging, because of simultaneous heterogeneities in chemical composition, molecular weight and functionality. One-dimensional liquid chromatography–mass spectrometry is commonly used to characterize polyether polyols. However, the separation power of this technique is not sufficient to resolve the complexity of such samples entirely. In this study, comprehensive two-dimensional liquid chromatography hyphenated with high-resolution mass spectrometry (LC × LC-HRMS) was used for the characterization of (i) castor oil ethoxylates (COEs) reacted with different mole equivalents of ethylene oxide and (ii) a blended formulation consisting of glycerol ethoxylate, glycerol propoxylate and glycerol ethoxylate-random-propoxylate copolymers. Retention in the first (hydrophilic-interaction-chromatography) dimension was mainly governed by degree of ethoxylation, while the second reversed-phase dimension resolved the samples based on degree of propoxylation (blended formulation) or alkyl chain length (COEs). For different COE samples, we observed the separation of isomer distributions of various di-, tri- and tetra-esters, and such positional isomers were studied by tandem mass spectrometry (LC–MS/MS). This revealed characteristic fragmentation patterns, which allowed discrimination of the isomers based on terminal or internal positioning of the fatty-acid moieties and provided insight in the LC × LC retention behavior of such species.

Original languageEnglish
Pages (from-to)128-138
Number of pages11
JournalJournal of Chromatography A
Volume1569
DOIs
Publication statusPublished - 28 Sept 2018

Funding

This publication has been written as part of the Open Technology Programme (IWT-STW collaboration), project number 14624 (DEBOCS), which is financed by the Netherlands Organization for Scientific Research (NWO) . Andrea Gargano acknowledges the NWO-VENI grant IPA (722.015.009) for funding. Appendix A

FundersFunder number
NWO-VENI
Netherlands Organization for Scientific Research
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
International Permafrost Association722.015.009

    Keywords

    • Biobased polyols
    • Blended formulations
    • Castor oil ethoxylates
    • Comprehensive two-dimensional liquid chromatography
    • EO/PO random copolymers
    • LC × LC-HRMS

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