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Normal-phase (temperature gradient) interaction chromatography – A powerful tool for the characterisation of high molecular weight chain-end functionalised polymers

Hutchings, Lian R.; Agostini, S.; Oti, Matthew E.; Keth, Jennifer

Normal-phase (temperature gradient) interaction chromatography – A powerful tool for the characterisation of high molecular weight chain-end functionalised polymers Thumbnail


Authors

S. Agostini

Matthew E. Oti

Jennifer Keth



Abstract

We report here, for the first time, quantitative analysis of end-group functionalisation and the extent of end-group modification of polymers with molar mass up to 200,000 g mol−1, using a combination of isothermal and temperature gradient interaction chromatography. At such high molecular weights, other common analytical techniques such as MALDI-ToF-MS and NMR spectroscopy are simply unable to offer any quantitative insight into the end-group functionality of polymers. Thus, normal phase isothermal interaction chromatography (NP-IIC) has been used to characterise a series of polystyrene samples, with identical molar mass (c. 90,000 g mol−1), each carrying a single chain-end functionality of varying polarity, introduced via a series of end-group transformation reactions – from silyl-protected alcohol → primary alcohol → alkyl bromide. It is shown that the polarity of the functional group dictates the elution volume of the polymers and that NP-IIC could be used to monitor the quantitative end-group transformation. Thus, rather than estimating the success of the transformation reaction from the very small peaks observed in 1H NMR spectra, NP-IIC gives clear chromatographic peaks, whose retention volumes change dramatically only as a consequence of each new chain-end functional group. We also describe the analysis, by a combination of normal phase isothermal and temperature gradient interaction chromatography, of a series of linear polybutadiene samples of varying molar mass (28,000–200,000 g mol−1) each carrying a single primary alcohol functionality at the chain-end. The primary alcohol functionality enabled the separation of functionalised and non-functionalised polymers, which eluted at different retention volumes despite identical molecular weights. It is all the more remarkable that complete (baseline) resolution can be achieved for two polymers with an identical molar mass (<200,000 g mol−1), which differ only in that one sample is functionalised with a single primary alcohol group.

Citation

Hutchings, L. R., Agostini, S., Oti, M. E., & Keth, J. (2015). Normal-phase (temperature gradient) interaction chromatography – A powerful tool for the characterisation of high molecular weight chain-end functionalised polymers. European Polymer Journal, 73, 105-115. https://doi.org/10.1016/j.eurpolymj.2015.10.010

Journal Article Type Article
Acceptance Date Oct 8, 2015
Online Publication Date Oct 8, 2015
Publication Date Dec 1, 2015
Deposit Date Nov 3, 2015
Publicly Available Date Mar 28, 2024
Journal European Polymer Journal
Print ISSN 0014-3057
Electronic ISSN 1873-1945
Publisher Elsevier
Peer Reviewed Peer Reviewed
Volume 73
Pages 105-115
DOI https://doi.org/10.1016/j.eurpolymj.2015.10.010
Keywords Polymer characterisation, Temperature gradient interaction chromatography (TGIC), Anionic polymerisation, End-functionalised polymers.

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