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Detailed study of polystyrene solubility using pyrolysis–gas chromatography–mass spectrometry and combination with size-exclusion chromatography

Abstract

Measuring polymer solubility accurately and precisely is challenging. This is especially true at unfavourable solvent compositions, when only very small amounts of polymer dissolve. In this paper, pyrolysis–gas chromatography–mass spectrometry (Py-GC-MS) is demonstrated to be much more informative and sensitive than conventional methods, such as ultraviolet spectroscopy. By using a programmed-temperature-vapourisation injector as the pyrolysis chamber, we demonstrate that Py-GC-MS can cover up to five orders of magnitude in dissolved polymer concentrations. For polystyrene, a detection limit of 1 ng mL−1 is attained. Dissolution in poor solvents is demonstrated to be discriminating in terms of the analyte molecular weight. Py-GC-MS additionally can yield information on polymer composition (e.g. in case of copolymers). In combination with size-exclusion chromatography, Py-GC-MS allows us to estimate the molecular weight distributions of minute amounts of a dissolved polymer and variations therein as a function of time.

SEC/-/Py-GC-MS (reconstructed, chromatograms) of dissolved polymer in ACN/THF%.

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References

  1. García MT, Gracia I, Duque G, Lucas AD, Rodríguez JF (2009) Waste Manage (Oxford) 29:1814–1814

    Article  Google Scholar 

  2. Pappa G, Boukouvalas C, Giannaris C, Ntaras N, Zografos V, Magoulas K, Lygeros A, Tassios D (2001) Resour Conserv Recycl 34:33–44

    Article  Google Scholar 

  3. Poulakis JG, Papaspyrides CD (1997) Resour Conserv Recycl 20:31–41

    Article  Google Scholar 

  4. Nauman B (1994) JCLE. US Patent 5 278 282. Rensselaer Polytechnic Institute

  5. Yoshiaki Mizumoto SH (1977) US Patent 4 031 039. Mitsubishi Jukogyo Kabushiki Kaisha

  6. Kurtz SM, Devine JN (2007) Biomaterials 28:4845–4869

    CAS  Article  Google Scholar 

  7. Chojnacka A, Ghaffar A, Feilden A, Treacher K, Janssen H-G, Schoenmakers P (2011) Anal Chim Acta 706:305–311

    CAS  Article  Google Scholar 

  8. Shively ML, Coonts BA, Renner WD, Southard JL, Bennett AT (1995) J Controlled Release 33:237–243

    CAS  Article  Google Scholar 

  9. Miller-Chou BA, Koenig JL (2003) Prog Polym Sci 28:1223–1270

    CAS  Article  Google Scholar 

  10. Moore SJ, Wanke SE (2001) Chem Eng Sci 56:4121–4129

    CAS  Article  Google Scholar 

  11. Voit BI (2003) Comptes Rendus Chimie 6:821–832

    CAS  Article  Google Scholar 

  12. Bozdogan AE (2004) Polymer 45:6415–6424

    CAS  Article  Google Scholar 

  13. Mieczkowski R (1989) Eur Polym J 25:1055–1076

    CAS  Article  Google Scholar 

  14. Bustamante P, Navarro-Lupión J, Escalera B (2005) Eur J Pharm Sci 24:229–237

    CAS  Article  Google Scholar 

  15. Bordes C, Fréville V, Ruffin E, Marote P, Gauvrit JY, Briançon S, Lantéri P (2010) Int J Pharm 383:236–243

    CAS  Article  Google Scholar 

  16. Chen Y, Zhang Y, Ke F, Zhou J, Wang H, Liang D (2011) Polymer 52:481–488

    CAS  Article  Google Scholar 

  17. Ochi K, Saito T, Kojima K (1999) Fluid Phase Equilib 158–160:847–851

    Article  Google Scholar 

  18. Haken JK, Ho DKM (1976) J Chromatogr A 126:239247

    Article  Google Scholar 

  19. Liu H, Fu R, Zhu P, Ye M, Shi L (1990) J Anal Appl Pyrolysis 18:7989

    Article  Google Scholar 

  20. Fuh M-RS, Wang G-Y (1998) Anal Chim Acta 371:89–96

    CAS  Article  Google Scholar 

  21. Wang FC-Y, Dettloff ML, Null MJ, White JE (2000) J Chromatogr A 886:217–224

    CAS  Article  Google Scholar 

  22. Tienpont B, David F, Vanwalleghem F, Sandra P (2001) J Chromatogr A 911:235–247

    CAS  Article  Google Scholar 

  23. Lee YS, Lee W-K, Cho S-G, Kim I, Ha C-S (2007) J Anal Appl Pyrolysis 78:85–94

    CAS  Article  Google Scholar 

  24. Antić VV, Antić MP, Kronimus A, Oing K, Schwarzbauer J (2011) J Anal Appl Pyrolysis 90:93–99

    Article  Google Scholar 

  25. Kaal E, Janssen H-G (2008) J Chromatogr A1184:43–60

    Article  Google Scholar 

  26. Kaal E, Kolk AHJ, Kuijper S, Janssen H-G (2009) J ChromatogrA 1216:6319–6325

    CAS  Article  Google Scholar 

  27. Kaal ER, Alkema G, Kurano M, Geissler M, Janssen H-G (2007) J Chromatogr A1143:182–189

    Article  Google Scholar 

Download references

Acknowledgments

This work forms a part of the research programme of the Dutch Polymer Institute (project #622, technology area HTE).

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Correspondence to Aleksandra Chojnacka.

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Chojnacka, A., Janssen, HG. & Schoenmakers, P. Detailed study of polystyrene solubility using pyrolysis–gas chromatography–mass spectrometry and combination with size-exclusion chromatography. Anal Bioanal Chem 406, 459–465 (2014). https://doi.org/10.1007/s00216-013-7461-5

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  • DOI: https://doi.org/10.1007/s00216-013-7461-5

Keywords

  • Pyrolysis–gas chromatography–mass spectrometry (Py-GC-MS)
  • Size-exclusion chromatography (SEC)
  • Off-line size-exclusion chromatography/pyrolysis–gas chromatography–mass spectrometry (SEC/-/Py-GC-MS)
  • Polystyrene (PS)
  • Polymer solubility
  • Low-detection limit