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Updated: Aug 5, 2025

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Published on: March 31, 2021
Principles and potential of solvent gradient size-exclusion chromatography for polymer analysis
Leon E Niezen1, Jordy D Kruijswijk2, Gerben B van Henten1
1Analytical-Chemistry Group, van 't Hoff Institute for Molecular Sciences, Faculty of Science, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, the Netherlands; Centre for Analytical Sciences Amsterdam (CASA), the Netherlands.
Gradient size-exclusion chromatography (gSEC) offers a solution for polymer analysis challenges. This study compares gSEC with reversed-phase liquid chromatography (RPLC), finding RPLC faster for chemical-composition distribution but gSEC advantageous in 2D-LC to prevent sample breakthrough.
Area of Science:
- Polymer Chemistry
- Analytical Chemistry
- Chromatography
Background:
- Polymer properties depend on molecular distributions like chemical-composition distribution (CCD).
- Conventional gradient-elution liquid chromatography (LC) faces challenges with polymer solubility, leading to peak broadening and breakthrough.
- Gradient size-exclusion chromatography (gSEC), developed in 2011, addresses these limitations.
Purpose of the Study:
- To evaluate the potential of gSEC for CCD analysis.
- To compare gSEC with conventional gradient-elution reversed-phase LC (RPLC).
- To investigate the impact of mobile phase, stationary phase pore size, and temperature on separation.
Main Methods:
- One-dimensional RPLC and gSEC were used to separate styrene/ethyl acrylate copolymers.
- Comprehensive two-dimensional (2D) LC, including SEC × gSEC and SEC × RPLC, was applied to styrene/methyl methacrylate copolymers.
- Investigated influence of mobile-phase composition, stationary-phase pore size, and column temperature.
Main Results:
- RPLC provided a more accurate CCD in a shorter analysis time for one-dimensional separations.
- In 2D-LC, gSEC proved advantageous by preventing sample breakthrough.
- The study explored various chromatographic conditions affecting polymer separation.
Conclusions:
- gSEC is a valuable technique for polymer CCD analysis, particularly in 2D-LC applications.
- RPLC offers faster CCD analysis in one dimension.
- Optimization of chromatographic parameters is crucial for effective polymer characterization.
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