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Online Coupling of Two-Dimensional Liquid Chromatography and NMR for the Analysis of Complex Polymers

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Faculty of Chemistry, TU Dortmund, Otto-Hahn-Straße 6, 44227 Dortmund, Germany
Department of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, 7602 Matieland, South Africa
§ German Institute for Polymers, Schlossgartenstraße 6, 64289 Darmstadt, Germany
*Fax: +49 231 755 3771. E-mail: [email protected]
Cite this: Macromolecules 2012, 45, 19, 7740–7748
Publication Date (Web):September 25, 2012
https://doi.org/10.1021/ma301494c
Copyright © 2012 American Chemical Society

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    Abstract

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    For the first time, comprehensive two-dimensional liquid chromatography (2D-LC) of complex polymers is coupled online to 1H NMR. 2D-LC is used to separate mixtures of poly(ethylene oxide)s with regard to chemical composition and molar mass. The present samples contain polymers with different end groups and chain distributions. In the first LC dimension, liquid chromatography at critical conditions (LCCC) is used for the selective separation according to the end groups. Fractions that are then uniform regarding their end groups are automatically transferred into the second LC dimension which separates the fractions regarding their chain length distributions using liquid adsorption chromatography. The eluate from 2D-LC is directly introduced into the 1H NMR for on-flow analysis. The online coupling of one- and two-dimensional chromatography with 1H NMR detection is demonstrated. The NMR is coupled to both individual separations as well as to the entire two-dimensional separation. As a result of this multidimensional analysis quantitative information is obtained on the types and topology of end groups and the chain length distributions within each functionality fraction.

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    1H NMR spectra of alkylphenoxy-terminated PEO, gradient HSQC of sample 5, onflow LAC-NMR of the alkylphenoxy-terminated PEO, and onflow 2D-LCCC-LAC-NMR traces of the C18- and alkylphenoxy-terminated PEO. This material is available free of charge via the Internet at http://pubs.acs.org.

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