Analysis of Polymer Additives and Impurities by Liquid Chromatography/Mass Spectrometry and Capillary Electrophoresis/Mass Spectrometry

  • Wolfgang Buchberger
  • Martin Stiftinger
Part of the Advances in Polymer Science book series (POLYMER, volume 248)


The analysis of polymeric materials can be quite challenging because such samples are often of complex nature due to the presence of various groups of additives, compounding ingredients, and fillers. Of special importance are stabilizers that protect the material from degradation by thermal stress during manufacture or from environmental impact during use. Apart from intact stabilizers, the degradation products of stabilizers should also be identified to understand the reactions occurring in a polymeric material. In all cases, the optimization of performance of a polymer as well as the reduction of production costs requires adequate analytical methods, whereby high-performance liquid chromatography plays a major role. As outlined in this review, mass spectrometry with atmospheric pressure ionization has become state-of-the-art for identification of components in polymeric materials after separation by liquid chromatography. These ionization techniques include electrospray ionization, atmospheric pressure chemical ionization, and atmospheric pressure photoionization. The latter technique shows various advantages such as low detection limits and applicability to a wide range of structurally different polymer additives. Besides chromatography, capillary electrophoresis has demonstrated some potential for separation of polymer stabilizers and for characterization of polymers, but its importance is still limited in comparison with liquid chromatography. As an alternative to the combination of chromatography with mass spectrometric detection, direct mass spectrometric techniques for solid polymer samples are emerging. These techniques provide new tools for quick screening procedures at the same time as avoiding tedious sample preparation.


Additives Capillary electrophoresis Liquid chromatography Mass spectrometry Polymeric materials 



Atmospheric pressure chemical ionization


Atmospheric pressure photoionization


Atmospheric solid analysis probe


Capillary electrophoresis


Capillary zone electrophoresis


Direct analysis in real time


Desorption electrospray ionization


Electroosmotic flow


Electrospray ionization


Gas chromatography


Hindered amine light stabilizers


High-performance liquid chromatography


Matrix-assisted laser desorption/ionization


Microemulsion electrokinetic chromatography


Micellar electrokinetic chromatography


Mass spectrometry


Normal phase


Reversed phase


Size-exclusion chromatography


Supercritical fluid chromatography


Secondary ion mass spectrometry




Ultrahigh-performance liquid chromatography



This work was funded partly by the COMET K-Project APMT (project number 825344) and by the FFG SolPol Projects (project numbers 825444 and 827788).


  1. 1.
    Reingruber E, Himmelsbach M, Sauer C, Buchberger W (2010) Identification of degradation products of antioxidants in polyolefins by liquid chromatography combined with atmospheric pressure photoionisation mass spectrometry. Polym Degrad Stab 95:740–745CrossRefGoogle Scholar
  2. 2.
    Green S, Bai S, Cheatham M, Cong R, Yau W (2010) Determination of antioxidants in polyolefins using total dissolution methodology followed by RPLC. J Sep Sci 33:3455–3462CrossRefGoogle Scholar
  3. 3.
    Coulier L, Kaal ER, Tienstra M, Hankemeier T (2005) Identification and quantification of (polymeric) hindered-amine light stabilizers in polymers using pyroylsis-gas chromatography-mass spectrometry and liquid chromatography-ultraviolet absorbance detection-evaporative light scattering detection. J Chromatogr A 1062:227–238CrossRefGoogle Scholar
  4. 4.
    Wang FC (2000) Polymer additive analysis by pyrolysis-gas chromatography. IV. Antioxidants. J Chromatogr A 891(2):325–336CrossRefGoogle Scholar
  5. 5.
    Barnes KA, Damant AP, Startin JR, Castle L (1995) Qualitative liquid chromatographic-atmospheric pressure chemical ionisation mass spectrometric analysis of polyethylene terephthalate oligomers. J Chromatogr A 712:191–199CrossRefGoogle Scholar
  6. 6.
    Vandenburg HJ, Clifford AA, Bartle KD, Carroll J, Newton I, Garden LM, Dean JR, Costley CT (1997) Analytical extraction of additives from polymers. Analyst 122:101R–115RCrossRefGoogle Scholar
  7. 7.
    Stiftinger M (2012) PhD Thesis, Johannes-Kepler-University Linz (in preparation)Google Scholar
  8. 8.
    Farajzadeh MA, Eskandar SG, Ranji A, Feyz E (2007) HPLC technique for quantitation of Chimassorb 944, and its evaluation in analysis of real and standard samples of polyolefins. Microchim Acta 159:363–369CrossRefGoogle Scholar
  9. 9.
    Vandenburg HJ, Clifford AA, Bartle KD, Carlson RE, Carroll J, Newton ID (1999) A simple solvent selection method for accelerated solvent extraction of additives from polymers. Analyst 124:1707–1710CrossRefGoogle Scholar
  10. 10.
    Garrido-Lopez A, Tena MT (2005) Experimental design approach for the optimisation of pressurised fluid extraction of additives from polyethylene films. J Chromatogr A 1099:75–83CrossRefGoogle Scholar
  11. 11.
    De Paepe A, Erlandsson B, Östelius J, Gasslander U, Arbin A (2006) An Alternative method for determination of additives in polypropylene using supercritical fluid extraction and enhanced solvent extraction. J Liq Chromatogr Rel Technol 29:1541–1559CrossRefGoogle Scholar
  12. 12.
    Vandenburg HJ, Clifford AA, Bartle KD, Carroll J, Newton ID (1999) Comparison of pressurised fluid extraction and microwave assisted extraction with atmospheric pressure methods for extraction of additives from polypropylene. Analyst 124:397–400CrossRefGoogle Scholar
  13. 13.
    Marcato B, Vianello M (2000) Microwave-assisted extraction by fast sample preparation for the systematic analysis of additives in polyolefins by high-performance liquid chromatography. J Chromatogr A 869:285–300CrossRefGoogle Scholar
  14. 14.
    Dopico Garcia MS, López VJM, Bouza R, Abad MJ, González Soto E, González Rodrıguez MV (2004) Extraction and quantification of antioxidants from low-density polyethylene by microwave energy and liquid chromatography. Anal Chim Acta 521:179–188CrossRefGoogle Scholar
  15. 15.
    Smith SH, Taylor LT (2002) Extraction of various additives from polystyrene and their subsequent analysis. Chromatographia 56:165–169CrossRefGoogle Scholar
  16. 16.
    Ashraf-Khorassani M, Nazem N, Taylor LT (2003) Feasibility of supercritical fluid extraction with on-line coupling of reversed-phase liquid chromatography for quantitative analysis of polymer additives. J Chromatogr A 995:227–232CrossRefGoogle Scholar
  17. 17.
    Thilen M, Shishoo R (2000) Optimization of experimental parameters for the quantification of polymer additives using SFE/HPLC. J Appl Polym Sci 76:938–946CrossRefGoogle Scholar
  18. 18.
    Fu C (2010) Diploma Thesis, Johannes-Kepler-University LinzGoogle Scholar
  19. 19.
    Kim BH, Yang DK, Ok JH (2007) Analysis of polymer additives in high-temperature liquid chromatography. J Chromatogr Sci 45:16–21Google Scholar
  20. 20.
    Noguerol-Cal R, Lopez-Vilarino JM, Gonzalez-Rodriguez MV, Barral-Losada LF (2007) Development of an ultraperformance liquid chromatography method for improved determination of additives in polymeric materials. J Sep Sci 30:2452–2459CrossRefGoogle Scholar
  21. 21.
    Gaudin K, Ho-Sung H, Bleton J, Joseph-Charles J, Dallet P, Puig P, Dubost JP (2007) Determination of N, N´-ethylenebisstearamide additive in polymer by normal phase liquid chromatography with evaporative light scattering detection. J Chromatogr A 1167:27–34CrossRefGoogle Scholar
  22. 22.
    Raynor MW, Bartle KD, Davies IL, Williams A, Clifford AA, Chalmers JM, Cook BW (1988) Polymer additive characterization by capillary supercritical fluid chromatography/fourier transform infrared microspectrometry. Anal Chem 60:427–433CrossRefGoogle Scholar
  23. 23.
    Carrott MJ, Jones DC, Davidson G (1998) Identification and analysis of polymer additives using packed-column supercritical fluid chromatography with APCI mass spectrometric detection. Analyst 123:1827–1833CrossRefGoogle Scholar
  24. 24.
    Andersen T, Skuland IL, Holm A, Trones R, Greibrokk T (2004) Temperature-programmed packed capillary liquid chromatography coupled to evaporative light-scattering detection and electrospray ionization time-of-flight mass spectrometry for characterization of high-molecular-mass hindered amine light stabilizers. J Chromatogr A 1029:49–56CrossRefGoogle Scholar
  25. 25.
    Noguerol-Cal R, López-Vilarino JM, Fernandez-Martinez G, Gonzales-Rodriquez MV, Barral-Losada LF (2010) Liquid chromatographic methods to analyze hindered amines light stabilizers (HALS) levels to improve safety in polyolefins. J Sep Sci 33:2698–2706CrossRefGoogle Scholar
  26. 26.
    Reisinger M (2010) Diploma Thesis, Johannes Kepler-University LinzGoogle Scholar
  27. 27.
    Haddad PR (2004) Ion chromatography. Anal Bioanal Chem 379:341–343CrossRefGoogle Scholar
  28. 28.
    Gill M, Garber MJ, Yousheng H, Jenke D (2010) Development and validation of an HPLC-MS-MS method for quantitating bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770) and a related substance in aqueous extract of plastic materials. J Chromatogr Sci 48:200–207Google Scholar
  29. 29.
    Gonzalez-Rodriguez MV, Dopico-Garcia MS, Noguerol-Cal R, Carballeira-Amarelo T, Lopez-Vilarino JM, Fernandez-Martinez G (2010) Application of liquid chromatography in polymer non-ionic antistatic additives analysis. J Sep Sci 33:3595–3603CrossRefGoogle Scholar
  30. 30.
    Larsen BS, Kaiser MA, Botelho M, Wooler GR, Buxton LW (2005) Comparison of pressurized solvent and reflux extraction methods for the determination of perfluorooctanoic acid in polytetrafluoroethylene polymers using LC-MS-MS. Analyst 130:59–62CrossRefGoogle Scholar
  31. 31.
    Himmelsbach M, Buchberger W, Reingruber E (2009) Determination of polymer additives by liquid chromatography coupled with mass spectrometry. A comparison of atmospheric pressure photoionization (APPI), atmospheric pressure chemical ionization (APCI), and electrospray ionization (ESI). Polym Degrad Stab 94:1213–1219CrossRefGoogle Scholar
  32. 32.
    Schnöller J, Pittenauer E, Hutter H, Allmaier G (2009) Analysis of antioxidants in insulation cladding of copper wire: a comparison of different mass spectrometric techniques (ESI-IT, MALDI-RTOF and RTOF-SIMS). J Mass Spectrom 44:1724–1732Google Scholar
  33. 33.
    Hayen H, Alvarez-Grima MM, Debnath SC, Noordermeer JWM, Karst U (2004) Liquid chromatography/coordination ion spray mass spectrometry for the analysis of rubber vulcanization products. Anal Chem 76:1063–1068CrossRefGoogle Scholar
  34. 34.
    Block C, Wynants L, Kelchtermans M, De Boer R, Compernolle F (2006) Identification of polymer additives by liquid chromatography-mass spectrometry. Polym Degrad Stab 91:3163–3173CrossRefGoogle Scholar
  35. 35.
    Schlummer M, Brandl F, Mäurer A, van Eldik R (2005) Analysis of flame retardant additives in polymer fractions of waste of electric and electronic equipment (WEEE) by means of HPLC-UV/MS and GPC-HPLC-UV. J Chromatogr A 1064:39–51CrossRefGoogle Scholar
  36. 36.
    Desmazieres B, Buchmann W, Terrier P, Tortajada J (2008) APCI interface for LC- and SEC-MS analysis of synthetic polymers: Advantages and limits. Anal Chem 80:783–792CrossRefGoogle Scholar
  37. 37.
    Duderstadt RE, Fischer SM (2008) Effect of organic mobile phase composition on signal responses for selected polyalkene additive compounds by liquid chromatography – mass spectrometry. J Chromatogr A 1193:70–78CrossRefGoogle Scholar
  38. 38.
    Robb DB, Covey TR, Bruins AP (2000) Atmospheric pressure photoionization: an ionization method for liquid chromatography – mass spectrometry. Anal Chem 72:3653–3659CrossRefGoogle Scholar
  39. 39.
    Robb DB, Blades MW (2008) State-of-the-art in atmospheric pressure photoionization for LC/MS. Anal Chim Acta 627:34–49CrossRefGoogle Scholar
  40. 40.
    Marchi I, Rudaz S, Veuthey JL (2009) Atmospheric pressure photoionization for coupling liquid chromatography to mass spectrometry: A review. Talanta 78:1–18CrossRefGoogle Scholar
  41. 41.
    Hommerson P, Khan AM, Bristow T, Niessen W, de Jong GJ, Somsen GW (2007) Photon-independent gas-phase-ion formation in capillary electrophoresis-mass spectrometry using atmospheric pressure photoionization. Anal Chem 79:5351–5357CrossRefGoogle Scholar
  42. 42.
    Reingruber E, Buchberger W (2010) Analysis of polyolefin stabilizers and their degradation products. J Sep Sci 33:3463–3475CrossRefGoogle Scholar
  43. 43.
    Pan C (2009) Diploma Thesis, Johannes-Kepler-University LinzGoogle Scholar
  44. 44.
    Hilder EF, Klampfl CW, Buchberger W, Haddad PR (2001) Separation of hydrophobic polymer additives by microemulsion electrokinetic chromatography. J Chromatogr A 922:293–302CrossRefGoogle Scholar
  45. 45.
    Himmelsbach M, Haunschmidt M, Buchberger W, Klampfl CW (2007) Microemulsion electrokinetic chromatography with on-line atmospheric pressure photoionization mass spectrometric detection. Anal Chem 79:1564–1568CrossRefGoogle Scholar
  46. 46.
    Vo TDT, Himmelsbach M, Haunschmidt M, Buchberger W, Schwarzinger C, Klampfl CW (2008) Improved analysis of melamine-formaldehyde resins by capillary zone electrophoresis – mass spectrometry using ion-trap and quadrupole-time-of-flight mass spectrometers. J Chromatogr A 1213:83–87CrossRefGoogle Scholar
  47. 47.
    Kaal ER, Alkema G, Kurano M, Geissler M, Janssen HG (2007) On-line size exclusion chromatography-pyrolysis-gas chromatography-mass spectrometry for copolymer characterization and additive analysis. J Chromatogr A 1143:182–189CrossRefGoogle Scholar
  48. 48.
    Takats Z, Wiseman JM, Gologan B, Cooks RG (2004) Mass spectrometry sampling under ambient conditions with desorption electrospray ionization. Science 306:471–473CrossRefGoogle Scholar
  49. 49.
    Reiter SM, Buchberger W, Klampfl CW (2011) Rapid identification and semi-quantitative determination of polymer additives by desorption electrospray ionization/time-of-flight mass spectrometry. Anal Bioanal Chem 400:2317–2322CrossRefGoogle Scholar
  50. 50.
    Cody RB, Laramee JA, Durst HD (2005) Versatile new ion source for the analysis of materials in open air under ambient conditions. Anal Chem 77:2297–2302CrossRefGoogle Scholar
  51. 51.
    Haunschmidt M, Klampfl CW, Buchberger W, Hertsens R (2010) Rapid identification of stabilisers in polypropylene using time-of-flight mass spectrometry and DART as ion source. Analyst 135:80–85CrossRefGoogle Scholar
  52. 52.
    Eberherr W, Buchberger W, Hertsens R, Klampfl CW (2010) Investigations on the coupling of high-performance liquid chromatography to direct analysis in real time mass spectrometry. Anal Chem 82:5792–5796CrossRefGoogle Scholar
  53. 53.
    Trimpin S, Wijerathne K, McEwan CN (2009) Rapid methods of polymer and polymer additives identification: Multi-sample solvent-free MALDI, pyrolysis at atmospheric pressure, and atmospheric solids analysis probe mass spectrometry. Anal Chim Acta 654:20–25CrossRefGoogle Scholar
  54. 54.
    Weng LT, Chan CM (2006) SSIMS analysis of organics, polymer blends and interfaces. Appl Surf Sci 252:6570–6574CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2011

Authors and Affiliations

  1. 1.Institute of Analytical ChemistryJohannes-Kepler-University LinzLinzAustria

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