Principles and potential of solvent gradient size-exclusion chromatography for polymer analysis

Leon E. Niezen; Jordy D. Kruijswijk; Gerben B. van Henten; Bob W.J. Pirok; Bastiaan B.P. Staal; Wolfgang Radke; Harry J.A. Philipsen; Govert W. Somsen; Peter J. Schoenmakers

doi:10.1016/j.aca.2023.341041

Principles and potential of solvent gradient size-exclusion chromatography for polymer analysis

Leon E. Niezen^*, Jordy D. Kruijswijk, Gerben B. van Henten, Bob W.J. Pirok, Bastiaan B.P. Staal, Wolfgang Radke, Harry J.A. Philipsen, Govert W. Somsen, Peter J. Schoenmakers

^*Corresponding author for this work

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

Abstract

The properties of a polymeric material are influenced by its underlying molecular distributions, including the molecular-weight (MWD), chemical-composition (CCD), and/or block-length (BLD) distributions. Gradient-elution liquid chromatography (LC) is commonly used to determine the CCD. Due to the limited solubility of polymers, samples are often dissolved in strong solvents. Upon injection of the sample, such solvents may lead to broadened or poorly shaped peaks and, in unfavourable cases, to “breakthrough” phenomena, where a part of the sample travels through the column unretained. To remedy this, a technique called size-exclusion-chromatography gradients or gradient size-exclusion chromatography (gSEC) was developed in 2011. In this work, we aim to further explore the potential of gSEC for the analysis of the CCD, also in comparison with conventional gradient-elution reversed-phase LC, which in this work corresponded to gradient-elution reversed-phase liquid chromatography (RPLC). The influence of the mobile-phase composition, the pore size of the stationary-phase particles, and the column temperature were investigated. The separation of five styrene/ethyl acrylate copolymers was studied with one-dimensional RPLC and gSEC. RPLC was shown to lead to a more-accurate CCD in shorter analysis time. The separation of five styrene/methyl methacrylate copolymers was also explored using comprehensive two-dimensional (2D) LC involving gSEC, i.e. SEC × gSEC and SEC × RPLC. In 2D-LC, the use of gSEC was especially advantageous as no breakthrough could occur.

Original language	English
Article number	341041
Pages (from-to)	1-9
Number of pages	9
Journal	Analytica Chimica Acta
Volume	1253
Early online date	4 Mar 2023
DOIs	https://doi.org/10.1016/j.aca.2023.341041
Publication status	Published - 1 May 2023

Bibliographical note

Funding Information:
This research was performed within 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 Agilent (UR grant #4354). LN, JK, GH and BP are part 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.

Funding Information:
This research was performed within 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 Agilent ( UR grant #4354 ).

Publisher Copyright:
© 2023 The Authors

Keywords

Breakthrough
Chemical composition
Gradient-elution liquid chromatography
Polymer analysis
SEC-Gradients
Size-exclusion chromatography

UN SDGs

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

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title = "Principles and potential of solvent gradient size-exclusion chromatography for polymer analysis",

abstract = "The properties of a polymeric material are influenced by its underlying molecular distributions, including the molecular-weight (MWD), chemical-composition (CCD), and/or block-length (BLD) distributions. Gradient-elution liquid chromatography (LC) is commonly used to determine the CCD. Due to the limited solubility of polymers, samples are often dissolved in strong solvents. Upon injection of the sample, such solvents may lead to broadened or poorly shaped peaks and, in unfavourable cases, to “breakthrough” phenomena, where a part of the sample travels through the column unretained. To remedy this, a technique called size-exclusion-chromatography gradients or gradient size-exclusion chromatography (gSEC) was developed in 2011. In this work, we aim to further explore the potential of gSEC for the analysis of the CCD, also in comparison with conventional gradient-elution reversed-phase LC, which in this work corresponded to gradient-elution reversed-phase liquid chromatography (RPLC). The influence of the mobile-phase composition, the pore size of the stationary-phase particles, and the column temperature were investigated. The separation of five styrene/ethyl acrylate copolymers was studied with one-dimensional RPLC and gSEC. RPLC was shown to lead to a more-accurate CCD in shorter analysis time. The separation of five styrene/methyl methacrylate copolymers was also explored using comprehensive two-dimensional (2D) LC involving gSEC, i.e. SEC × gSEC and SEC × RPLC. In 2D-LC, the use of gSEC was especially advantageous as no breakthrough could occur.",

keywords = "Breakthrough, Chemical composition, Gradient-elution liquid chromatography, Polymer analysis, SEC-Gradients, Size-exclusion chromatography",

author = "Niezen, {Leon E.} and Kruijswijk, {Jordy D.} and {van Henten}, {Gerben B.} and Pirok, {Bob W.J.} and Staal, {Bastiaan B.P.} and Wolfgang Radke and Philipsen, {Harry J.A.} and Somsen, {Govert W.} and Schoenmakers, {Peter J.}",

note = "Funding Information: This research was performed within 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 Agilent (UR grant #4354). LN, JK, GH and BP are part 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. Funding Information: This research was performed within 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 Agilent ( UR grant #4354 ). Publisher Copyright: {\textcopyright} 2023 The Authors",

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AU - Staal, Bastiaan B.P.

AU - Radke, Wolfgang

AU - Philipsen, Harry J.A.

AU - Somsen, Govert W.

AU - Schoenmakers, Peter J.

N1 - Funding Information: This research was performed within 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 Agilent (UR grant #4354). LN, JK, GH and BP are part 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. Funding Information: This research was performed within 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 Agilent ( UR grant #4354 ). Publisher Copyright: © 2023 The Authors

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N2 - The properties of a polymeric material are influenced by its underlying molecular distributions, including the molecular-weight (MWD), chemical-composition (CCD), and/or block-length (BLD) distributions. Gradient-elution liquid chromatography (LC) is commonly used to determine the CCD. Due to the limited solubility of polymers, samples are often dissolved in strong solvents. Upon injection of the sample, such solvents may lead to broadened or poorly shaped peaks and, in unfavourable cases, to “breakthrough” phenomena, where a part of the sample travels through the column unretained. To remedy this, a technique called size-exclusion-chromatography gradients or gradient size-exclusion chromatography (gSEC) was developed in 2011. In this work, we aim to further explore the potential of gSEC for the analysis of the CCD, also in comparison with conventional gradient-elution reversed-phase LC, which in this work corresponded to gradient-elution reversed-phase liquid chromatography (RPLC). The influence of the mobile-phase composition, the pore size of the stationary-phase particles, and the column temperature were investigated. The separation of five styrene/ethyl acrylate copolymers was studied with one-dimensional RPLC and gSEC. RPLC was shown to lead to a more-accurate CCD in shorter analysis time. The separation of five styrene/methyl methacrylate copolymers was also explored using comprehensive two-dimensional (2D) LC involving gSEC, i.e. SEC × gSEC and SEC × RPLC. In 2D-LC, the use of gSEC was especially advantageous as no breakthrough could occur.

AB - The properties of a polymeric material are influenced by its underlying molecular distributions, including the molecular-weight (MWD), chemical-composition (CCD), and/or block-length (BLD) distributions. Gradient-elution liquid chromatography (LC) is commonly used to determine the CCD. Due to the limited solubility of polymers, samples are often dissolved in strong solvents. Upon injection of the sample, such solvents may lead to broadened or poorly shaped peaks and, in unfavourable cases, to “breakthrough” phenomena, where a part of the sample travels through the column unretained. To remedy this, a technique called size-exclusion-chromatography gradients or gradient size-exclusion chromatography (gSEC) was developed in 2011. In this work, we aim to further explore the potential of gSEC for the analysis of the CCD, also in comparison with conventional gradient-elution reversed-phase LC, which in this work corresponded to gradient-elution reversed-phase liquid chromatography (RPLC). The influence of the mobile-phase composition, the pore size of the stationary-phase particles, and the column temperature were investigated. The separation of five styrene/ethyl acrylate copolymers was studied with one-dimensional RPLC and gSEC. RPLC was shown to lead to a more-accurate CCD in shorter analysis time. The separation of five styrene/methyl methacrylate copolymers was also explored using comprehensive two-dimensional (2D) LC involving gSEC, i.e. SEC × gSEC and SEC × RPLC. In 2D-LC, the use of gSEC was especially advantageous as no breakthrough could occur.

KW - Breakthrough

KW - Chemical composition

KW - Gradient-elution liquid chromatography

KW - Polymer analysis

KW - SEC-Gradients

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Principles and potential of solvent gradient size-exclusion chromatography for polymer analysis

Abstract

Bibliographical note

Keywords

UN SDGs

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