Recycling gradient-elution liquid chromatography for the analysis of chemical-composition distributions of polymers

Leon E. Niezen; Bastiaan B.P. Staal; Christiane Lang; Harry J.A. Philipsen; Bob W.J. Pirok; Govert W. Somsen; Peter J. Schoenmakers

doi:10.1016/j.chroma.2022.463386

Recycling gradient-elution liquid chromatography for the analysis of chemical-composition distributions of polymers

Leon E. Niezen^*
, Bastiaan B.P. Staal
, Christiane Lang
, Harry J.A. Philipsen
, Bob W.J. Pirok
, Govert W. Somsen
, Peter J. Schoenmakers

^*Corresponding author for this work

AIMMS

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

Synthetic polymers typically show dispersity in molecular weight and potentially in chemical composition. For the analysis of the chemical-composition distribution (CCD) gradient liquid chromatography may be used. The CCD obtained using this method is often convoluted with an underlying molecular-weight distribution (MWD). In this paper we demonstrate that the influence of the MWD can be reduced using very steep gradients and that such gradients are best realized utilizing recycling gradient liquid chromatography (LC↻LC). This method allows for a more-accurate determination of the CCD and the assessment of (approximate) critical conditions (if these exist), even when high-molecular-weight standards of narrow dispersity are not readily available. The performance and usefulness of the approach is demonstrated for several polystyrene standards, and for the separation of statistical copolymers consisting of styrene/methyl methacrylate and methyl methacrylate/butyl methacrylate. For the latter case, approximate critical compositions of the copolymers were calculated from the critical compositions of two homopolymers and one copolymer of known chemical composition, allowing for a determination of the CCD of unknown samples. Using this approach it is shown that the copolymers elute significantly closer to the predicted critical compositions after recycling of the gradient. This is most clear for the lowest-molecular-weight copolymer (M_w = 4.2 kDa), for which the difference between measured and predicted elution composition decreases from 7.9% without recycling to 1.4% after recycling.

Original language	English
Article number	463386
Pages (from-to)	1-11
Number of pages	11
Journal	Journal of Chromatography A
Volume	1679
Early online date	28 Jul 2022
DOIs	https://doi.org/10.1016/j.chroma.2022.463386
Publication status	Published - 30 Aug 2022

Bibliographical note

Funding Information:
LN acknowledges the UNMATCHED project, which is supported by BASF, DSM and Nouryon and receives funding from the Dutch Research Council (NWO) in the framework of the Innovation Fund for Chemistry (CHIPP Project 731.017.303) and from the Ministry of Economic Affairs in the framework of the “TKI-toeslagregeling”. BP acknowledges the Agilent UR grant #4354.

Funding Information:
LN acknowledges the UNMATCHED project, which is supported by BASF, DSM and Nouryon and receives funding from the Dutch Research Council (NWO) in the framework of the Innovation Fund for Chemistry (CHIPP Project 731.017.303) and from the Ministry of Economic Affairs in the framework of the “TKI-toeslagregeling”. BP acknowledges the Agilent UR grant #4354. This work was performed in the context of the Chemometrics and Advanced Separations Team (CAST) within the Centre for Analytical Sciences Amsterdam (CASA). The valuable contributions of the CAST members are gratefully acknowledged.

Publisher Copyright:
© 2022

Funding

LN acknowledges the UNMATCHED project, which is supported by BASF, DSM and Nouryon and receives funding from the Dutch Research Council (NWO) in the framework of the Innovation Fund for Chemistry (CHIPP Project 731.017.303) and from the Ministry of Economic Affairs in the framework of the “TKI-toeslagregeling”. BP acknowledges the Agilent UR grant #4354. LN acknowledges the UNMATCHED project, which is supported by BASF, DSM and Nouryon and receives funding from the Dutch Research Council (NWO) in the framework of the Innovation Fund for Chemistry (CHIPP Project 731.017.303) and from the Ministry of Economic Affairs in the framework of the “TKI-toeslagregeling”. BP acknowledges the Agilent UR grant #4354. This work was performed in the context of the Chemometrics and Advanced Separations Team (CAST) within the Centre for Analytical Sciences Amsterdam (CASA). The valuable contributions of the CAST members are gratefully acknowledged.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 12 Responsible Consumption and Production

Keywords

Gradient elution
Gradient Recycling
Liquid Chromatography
Polymer analysis

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10.1016/j.chroma.2022.463386

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title = "Recycling gradient-elution liquid chromatography for the analysis of chemical-composition distributions of polymers",

abstract = "Synthetic polymers typically show dispersity in molecular weight and potentially in chemical composition. For the analysis of the chemical-composition distribution (CCD) gradient liquid chromatography may be used. The CCD obtained using this method is often convoluted with an underlying molecular-weight distribution (MWD). In this paper we demonstrate that the influence of the MWD can be reduced using very steep gradients and that such gradients are best realized utilizing recycling gradient liquid chromatography (LC↻LC). This method allows for a more-accurate determination of the CCD and the assessment of (approximate) critical conditions (if these exist), even when high-molecular-weight standards of narrow dispersity are not readily available. The performance and usefulness of the approach is demonstrated for several polystyrene standards, and for the separation of statistical copolymers consisting of styrene/methyl methacrylate and methyl methacrylate/butyl methacrylate. For the latter case, approximate critical compositions of the copolymers were calculated from the critical compositions of two homopolymers and one copolymer of known chemical composition, allowing for a determination of the CCD of unknown samples. Using this approach it is shown that the copolymers elute significantly closer to the predicted critical compositions after recycling of the gradient. This is most clear for the lowest-molecular-weight copolymer (Mw = 4.2 kDa), for which the difference between measured and predicted elution composition decreases from 7.9\% without recycling to 1.4\% after recycling.",

keywords = "Gradient elution, Gradient Recycling, Liquid Chromatography, Polymer analysis",

author = "Niezen, \{Leon E.\} and Staal, \{Bastiaan B.P.\} and Christiane Lang and Philipsen, \{Harry J.A.\} and Pirok, \{Bob W.J.\} and Somsen, \{Govert W.\} and Schoenmakers, \{Peter J.\}",

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AU - Niezen, Leon E.

AU - Staal, Bastiaan B.P.

AU - Lang, Christiane

AU - Philipsen, Harry J.A.

AU - Pirok, Bob W.J.

AU - Somsen, Govert W.

AU - Schoenmakers, Peter J.

N1 - Funding Information: LN acknowledges the UNMATCHED project, which is supported by BASF, DSM and Nouryon and receives funding from the Dutch Research Council (NWO) in the framework of the Innovation Fund for Chemistry (CHIPP Project 731.017.303) and from the Ministry of Economic Affairs in the framework of the “TKI-toeslagregeling”. BP acknowledges the Agilent UR grant #4354. Funding Information: LN acknowledges the UNMATCHED project, which is supported by BASF, DSM and Nouryon and receives funding from the Dutch Research Council (NWO) in the framework of the Innovation Fund for Chemistry (CHIPP Project 731.017.303) and from the Ministry of Economic Affairs in the framework of the “TKI-toeslagregeling”. BP acknowledges the Agilent UR grant #4354. This work was performed in the context of the Chemometrics and Advanced Separations Team (CAST) within the Centre for Analytical Sciences Amsterdam (CASA). The valuable contributions of the CAST members are gratefully acknowledged. Publisher Copyright: © 2022

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N2 - Synthetic polymers typically show dispersity in molecular weight and potentially in chemical composition. For the analysis of the chemical-composition distribution (CCD) gradient liquid chromatography may be used. The CCD obtained using this method is often convoluted with an underlying molecular-weight distribution (MWD). In this paper we demonstrate that the influence of the MWD can be reduced using very steep gradients and that such gradients are best realized utilizing recycling gradient liquid chromatography (LC↻LC). This method allows for a more-accurate determination of the CCD and the assessment of (approximate) critical conditions (if these exist), even when high-molecular-weight standards of narrow dispersity are not readily available. The performance and usefulness of the approach is demonstrated for several polystyrene standards, and for the separation of statistical copolymers consisting of styrene/methyl methacrylate and methyl methacrylate/butyl methacrylate. For the latter case, approximate critical compositions of the copolymers were calculated from the critical compositions of two homopolymers and one copolymer of known chemical composition, allowing for a determination of the CCD of unknown samples. Using this approach it is shown that the copolymers elute significantly closer to the predicted critical compositions after recycling of the gradient. This is most clear for the lowest-molecular-weight copolymer (Mw = 4.2 kDa), for which the difference between measured and predicted elution composition decreases from 7.9% without recycling to 1.4% after recycling.

AB - Synthetic polymers typically show dispersity in molecular weight and potentially in chemical composition. For the analysis of the chemical-composition distribution (CCD) gradient liquid chromatography may be used. The CCD obtained using this method is often convoluted with an underlying molecular-weight distribution (MWD). In this paper we demonstrate that the influence of the MWD can be reduced using very steep gradients and that such gradients are best realized utilizing recycling gradient liquid chromatography (LC↻LC). This method allows for a more-accurate determination of the CCD and the assessment of (approximate) critical conditions (if these exist), even when high-molecular-weight standards of narrow dispersity are not readily available. The performance and usefulness of the approach is demonstrated for several polystyrene standards, and for the separation of statistical copolymers consisting of styrene/methyl methacrylate and methyl methacrylate/butyl methacrylate. For the latter case, approximate critical compositions of the copolymers were calculated from the critical compositions of two homopolymers and one copolymer of known chemical composition, allowing for a determination of the CCD of unknown samples. Using this approach it is shown that the copolymers elute significantly closer to the predicted critical compositions after recycling of the gradient. This is most clear for the lowest-molecular-weight copolymer (Mw = 4.2 kDa), for which the difference between measured and predicted elution composition decreases from 7.9% without recycling to 1.4% after recycling.

KW - Gradient elution

KW - Gradient Recycling

KW - Liquid Chromatography

KW - Polymer analysis

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M1 - 463386

ER -

Recycling gradient-elution liquid chromatography for the analysis of chemical-composition distributions of polymers

Abstract

Bibliographical note

Funding

UN SDGs

Keywords

Access to Document

Persistent URL (handle)

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