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. 2017 Jul 28:1508:16-23.
doi: 10.1016/j.chroma.2017.05.050. Epub 2017 May 25.

Analysis using size exclusion chromatography of poly(N-isopropyl acrylamide) using methanol as an eluent

Thomas Swift  1 , Richard Hoskins  2 , Richard Telford  3 , Richard Plenderleith  4 , David Pownall  5 , Stephen Rimmer  6
Affiliations

Analysis using size exclusion chromatography of poly(N-isopropyl acrylamide) using methanol as an eluent

Thomas Swift et al. J Chromatogr A. .

Abstract

Size Exclusion Chromatography is traditionally carried out in either aqueous or non-polar solvents. A system to present molar mass distributions of polymers using methanol as a mobile phase is presented. This is shown to be a suitable system for determining the molar mass distributions poly(N-isopropylacrylamide)s (PNIPAM); a polymer class that is often difficult to analyze by size exclusion chromatography. DOSY NMR was used to provide intrinsic viscosity data that was used in conjunction with a viscometric detector to provide absolute calibration. Then the utility of the system was shown by providing the absolute molar mass distributions of dispersed highly branched PNIPAM with biologically functional end groups.

Keywords: DOSY NMR; Intrinsic viscosity; Methanol; PNIPAM; SEC; Size exclusion chromatography.

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Figures

Fig. 1
Fig. 1
1H NMR (A), 1H DOSY NMR (in D2O) (B), and FTIR (C) spectra of PNIPAM 9. Expanded spectra and additional information are shown in the electronic Supporting information.
Fig. 2
Fig. 2
MHS Plot for PEO of varying molar masses calculated from NMR diffusion measurements (♦) compared to measurements from previous studies (dilute solution viscometry) with calculated K and α , , , , , , .
Fig. 3
Fig. 3
Calibration of Agilent PolarGel columns with linear PNIPAM polymers.
Fig. 4
Fig. 4
Molar mass distribution (A) and MHS plot (B) and raw detector responses (C) of linear PNIPAM 8 over three repeat measurements of SEC Methanol as the eluent.
Fig. 5
Fig. 5
Analysis of HB-PNIPAM. SEC chromatograms, derived from differential refractive index, ultra-violet light absorbance or differential viscometry detectors. HB-PNIPAM with feed ratio of NIPAM:VBP a) 15:1 b) 85:1.
Fig. 6
Fig. 6
Molar Mass Distributions of HB-PNIPAMs (PNIPAM: VBP feed molar ratio shown to the right) determined by Methanol GPC. INSET: Distributions obtained using polystyrene columns with: a. THF as eluent (see Supporting information) or b. previously published distributions using DMF as eluent .
Fig. 7
Fig. 7
Plots of Log[η] versus logM for HB-PNIPAM (PNIPAM:VBP molar feed ratio shown to the right) determined by Methanol SEC.
Fig. 8
Fig. 8
RH Distributions of HB PNIPAM (PNIPAM:VBP molar feed ratio shown to the right) determined by Methanol SEC.
Fig. 9
Fig. 9
Cumulative Molar Mass Distributions of HB PNIPAM Polymers (PNIPAM:VBP molar feed ratio shown to the right) determined by Methanol SEC.
Fig. 10
Fig. 10
Molar Mass Distributions of chain end functionalized HB-PNIPAMs, obtained from HB-PNIPAM modified polymers with initial feed ratios of 25:1.
See this image and copyright information in PMC

References

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