Quantification of identical and unique segments in ethylene-propylene copolymers using two dimensional liquid chromatography with infra-red detection

Document Type: Original research


1 Fraunhofer Institute for Structural Durability and System Reliability, Division Plastics, Group Material Analytics, Schlossgartenstrasse 6, 64289, Darmstadt, Germany

2 Dutch Polymer Institute (DPI), P.O.Box 902,5600 AX Eindhoven, the Netherlands


Hyphenating High Temperature High Performance Liquid Chromatography (HT-HPLC) with High Temperature Size Exclusion Chromatography (HT-SEC) (High Temperature Two Dimensional Liquid Chromatography (HT-HPLC x HT-SEC or HT 2D-LC)) leads to an isocratic elution in the second dimension, which in turn enables to use IR detector (quantitative detection) for monitoring the eluting polymers. Experimental data obtained from HT 2D-LC with IR detector are usually presented as contour plots, which can be mathematically described in matrices. Quantitative data about chemical composition, molar mass and concentration of all the segments, which are present in a polymer, can be obtained, after calibrating the HPLC separation (HPLC elution volume vs chemical composition), SEC separation (SEC separation vs molar mass) and response of the IR detector (IR response vs mass of the polymer). A new procedure based on subtraction and addition of matrices is described, which enables quantitative comparison of different polymer materials. This procedure enables to determine, which components are present in both materials (i.e., identical components or segments) and which are present only in one from both the materials (i.e., unique segments). Moreover, molar mass distribution, as well as chemical composition distribution of both identical and unique segments is evaluated from experimental data. The procedure was applied on two different ethylene-propylene copolymer samples.


Main Subjects

  1. Pasch H, Trathnigg B (1998) HPLC of Polymers. Springer.
  2. Macko T, Pasch H (2009) Separation of linear polyethylene from isotactic, atactic, and syndiotactic polypropylene by hightemperature adsorption liquid chromatography. Macromolecules 42: 6063-6067
  3. Macko T, Brüll R, Alamo RG, Thomann Y, Grumel V (2009) Separation of propene/1-alkene and ethylene/1-alkene copolymers by hightemperature adsorption liquid chromatography. Polymer 50: 5443-5448
  4. Miller MD, deGroot AW, Lyons JW, Van Damme FA, Winniford BL (2012) Separation of polyolefins based on comonomer content using high-temperature gradient adsorption liquid chromatography with a graphitic carbon column. J Appl Polym Sci 123: 1238-1244
  5. Moore JC (1964) Gel permeation chromatography. I. A new method for molecular weight distribution of high polymers. J Polym Sci Pol Chem 2: 835- 843
  6. Striegel A, Yau WW, Kirkland JJ, Bly DD (2009) Modern size-exclusion liquid Chromatography: Practice of gel permeation and gel filtration chromatography. John Wiley & Sons
  7. Balke ST (1982) Orthogonal chromatography: Chromatographic cross-fractionation of polymers. Separ Purif Rev 11: 1-28
  8. Balke ST, Patel RD (1980) Coupled GPC/HPLC: Copolymer composition and axial dispersion characterization. J Polym Sci Pol Lett Ed 18: 453-456
  9. Rittig F, Pasch H (2008) Multidimensional liquid chromatography in industrial applications: Multidimensional liquid chromatography. John Wiley & Sons, 385-423
  10. Kilz P, Pasch H (2006) Coupled liquid chromatographic techniques in molecular characterization. encyclopedia of analytical chemistry. Wiley & Sons, New York
  11. Malik MI, Pasch H (2014) Novel developments in the multidimensional characterization of segmented copolymers. Progr Polym Sci 39: 87-123
  12. Ortín A, Montesinos J, López E, del Hierro P, Monrabal B, Torres-Lapasió JR, García-Álvarez- Coque MC (2013) Characterization of chemical composition along the molar mass distribution in polyolefin copolymers by GPC using a modern filter-based IR detector. Macromol Symp 330: 63-80
  13. Ginzburg A, Macko T, Malz F, Schroers M, Troetsch-Schaller I, Strittmatter J, Brüll R (2013) Characterization of functionalized polyolefins by high-temperature two-dimensional liquid chromatography. J Chromatogr A 1285: 40-47
  14. Ginzburg A, Macko T, Dolle V, Brüll R (2013) Multidimensional high-temperature liquid chromatography: A new technique to characterize the chemical heterogeneity of Ziegler-Natta based bimodal HDPE. J Appl Polym Sci 129: 1897-1906
  15. Chitta R, Ginzburg A, van Doremaele G, Macko T, Brüll R (2011) Separating ethylene-propylene diene terpolymers according to the content of
  16. diene by HT-HPLC and HT 2D-LC. Polymer 52: 5953-5960
  17. Ginzburg A, Macko T, Dolle V, Brüll R (2011) Characterization of polyolefins by comprehensive high-temperature two-dimensional liquid chromatography (HT 2D-LC). Eur Polym J 47: 319-329
  18. Ginzburg A, Macko T, Dolle V, Brüll R (2010) High-temperature two-dimensional liquid chromatography of ethylene-vinylacetate copolymers. J Chromatogr A 1217: 6867-6874
  19. Roy A, Miller MD, Meunier DM, Degroot AW, Winniford WL, Van Damme FA, Pell RJ, Lyons JW (2010) Development of comprehensive two-dimensional high temperature liquid chromatography × gel permeation chromatography for characterization of polyolefins. Macromolecules 43: 3710-3720
  20. Cheruthazhekatt S, Pasch H (2014) Fractionation and characterization of impact poly(propylene) copolymers by high temperature two-dimensional liquid chromatography. Macromol Symp 337: 51-57
  21. Mekap D, Macko T, Brüll R, Cong R, deGroot W, Parrott A, Yau W (2014) Multiple-injection method in high-temperature two-dimensional liquid chromatography (2D HT-LC). Macromol Chem Phys 215: 314-319
  22. Bhati SS, Macko T, Brüll R, Mekap D (2015) Liquid chromatography at critical conditions of poly(propylene). Macromol Chem Phys 216: 2179-2189
  23. Kilz P, Radke W (2015) Application of two-dimensional chromatography to the characterization of macromolecules and biomacromolecules. Anal Bioanal Chem 407: 193-215
  24. Al Samman M, Radke W, Khalyavina A, Lederer A (2010) Retention behavior of linear, branched, and hyperbranched polyesters in interaction liquid chromatography. Macromolecules 43: 3215-3220
  25. Cheruthazhekatt S, Harding GW, Pasch H (2013) Comprehensive high temperature twodimensional liquid chromatography combined with high temperature gradient chromatographyinfrared spectroscopy for the analysis of impact polypropylene copolymers. J Chromatogr A 1286: 69-82
  26. Monrabal B (2013) Polyolefin characterization: Recent advances in separation techniques: Polyolefins: 50 years after Ziegler and Natta I. Adv Polym Sci 257: 203-251
  27. Chitta R, Macko T, Brüll R, Kalies G (2010) Elution behavior of polyethylene and polypropylene standards on carbon sorbents. J Chromatogr A 1217: 7717-7722
  28. Macko T, Cutillo F, Busico V, Brüll R (2010) Separation of poly(propylene) samples according to tacticity using a hypercarb column. Macromol Symp 298: 182-190 
  29. Mekap D, Macko T, Brüll R, Cong R, deGroot W, Parrott A, Yau W (2013) One-step method for separation and identification of n-alkanes/ oligomers in hdpe using high-temperature high-performance liquid chromatography. Macromolecules 46: 6257-6262
  30. Mekap D, Macko T, Brüll R, Cong R, Parrott A, Cools P, Yau W (2013) Liquid chromatography at critical conditions of polyethylene. Polymer 54: 5518-5524
  31. Arndt JH, Macko T, Brüll R (2013) Application of the evaporative light scattering detector to analytical problems in polymer science. J Chromatogr A 1310: 1-14
  32. Hehn M, Maiko K, Pasch H, Hiller W (2013) Online HPLC–NMR: An efficient method for the analysis of PMMA with respect to tacticity. Macromolecules 46: 7678-7686
  33. Hehn M, Wagner T, Hiller W (2014) Direct quantification of molar masses of copolymers by online liquid chromatography under critical conditions–nuclear magnetic resonance and size exclusion chromatography–nuclear magnetic resonance. Anal Chem 86: 490-497
  34. Sinha P, Hiller W, Bellas V, Pasch H (2012) Analysis of polystyrene-b-polyisoprene copolymers by coupling of liquid chromatography at critical conditions to NMR at critical conditions of polystyrene and polyisoprene. J Separ Sci 35: 1731-1740
  35. Raust J-A, Bruell A, Sinha P, Hiller W, Pasch H (2010) Two-dimensional chromatography of complex polymers, 8. Separation of fatty alcohol ethoxylates simultaneously by end group and chain length. J Separ Sci 33: 1375-1381
  36. Hiller W, Hehn M, Sinha P, Raust J-A, Pasch H (2012) Online coupling of two-dimensional liquid chromatography and NMR for the analysis of complex polymers. Macromolecules 45: 7740- 7748
  37. Hiller W, Pasch H, Macko T, Hofmann M, Ganz J, Spraul M, Braumann U, Streck R, Mason J, Van Damme F (2006) On-line coupling of high temperature GPC and 1H NMR for the analysis of polymers. J Magnetic Res 183: 290-302
  38. Pasch H, Heinz L-C, Macko T, Hiller W (2008) High-temperature gradient HPLC and LC-NMR for the analysis of complex polyolefins. Pure Appl Chem 80: 1747-1762 38. Monrabal B (1994) Crystallization analysis fractionation: A new technique for the analysis of branching distribution in polyolefins. J ApplPolym Sci 52: 491-499
  39. Anantawaraskul S, Soares JP, Wood-Adams P (2005) Fractionation of semicrystalline polymers by crystallization analysis fractionation and temperature rising elution fractionation. Adv Polym Sci 182: 1-54
  40. Monrabal B, Sancho-Tello J, Mayo N, Romero L (2007) Crystallization elution fractionation. A new separation process for polyolefin resins. Macromol Symp 257: 71-79
  41. Macko T, Ginzburg A, Remerie K, Bruell R (2012) Separation of high-impact polypropylene using interactive liquid chromatography. Macromol Chem Phys 213: 937-944
  42. Barth HG, Carlin FJ (1984) A review of polymer shear degradation in size-exclusion chromatography. J Liq Chromatogr 7: 1717-1738.
  43. Shrivastava A, Gupta VB (2011) Methods for the determination of limit of detection and limit of quantitation of the analytical methods. Chron Young Scientists 2: 21-25
  44. Kebritchi A, Nekoomanesh M, Mohammadi F, Khonakdar HA (2014) The role of 1-hexene comonomer content in thermal behavior of medium density polyethylene (MDPE) synthesized using Phillips catalyst. Polyolefins J 1: 117-129