Column-Based Chromatographic Techniques

  • Harald Pasch
  • Muhammad Imran Malik
Part of the Springer Laboratory book series (SPLABORATORY)


Crystallization-based fractionation techniques are powerful methods for the chemical composition fractionation of semi-crystalline polyolefins. The non-crystallizing part cannot be fractionated and is obtained as a bulk fraction. As alternative methods, column-based separation techniques can be used. These techniques fractionate polyolefins regardless of crystallinity based on molecular size, chemical composition and/or branching. In this chapter, experimental approaches for the molar mass analysis by size exclusion chromatography and the chemical composition analysis by different means of interaction chromatography will be presented. The dual molar mass/chemical composition fractionation by two-dimensional liquid chromatography will be highlighted and examples for comprehensive analysis will be given.


High Performance Liquid Chromatography Molar Mass Size Exclusion Chromatography Evaporative Light Scatter Detector High Molar Mass 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


  1. 1.
    Francuskiewicz F (1994) Polymer fractionation. Springer, BerlinCrossRefGoogle Scholar
  2. 2.
    Mori S, Barth HG (1999) Size exclusion chromatography. Springer, BerlinCrossRefGoogle Scholar
  3. 3.
    Striegel AM, Yau WW, Kirkland JJ, Bly DD (2009) Modern size-exclusion liquid chromatography. John Wiley, Hoboken, NJCrossRefGoogle Scholar
  4. 4.
    Pasch H, Trathnigg B (1998) HPLC of polymers. Springer, BerlinGoogle Scholar
  5. 5.
    Pasch H, Trathnigg B (2013) Multidimensional HPLC of polymers. Springer, BerlinCrossRefGoogle Scholar
  6. 6.
    Pasch H, Malik I, Macko T (2013) Adv Polym Sci 251:77CrossRefGoogle Scholar
  7. 7.
    Housaki T, Satoh K, Nishikida K, Morimoto M (1988) Makromol Chem Rapid Commun 9:525CrossRefGoogle Scholar
  8. 8.
    Nishikida K, Housaki T, Morimoto M, Kinoshita T (1990) J Chromatogr A 517:209CrossRefGoogle Scholar
  9. 9.
  10. 10.
  11. 11.
  12. 12.
    Markovich RP, Hazlitt LG, Smith-Courtney L (1993) In: Provder T (ed) Chromatography of polymers. Characterization by SEC and FFF, ACS symposium series 521. American Chemical Society, Washington, DCGoogle Scholar
  13. 13.
    DesLauriers PJ (2004) Measuring compositional heterogeneity in polyolefins using SEC/FTIR spectroscopy. In: Striegel A (ed) Multiple detection in size exclusion chromatography. ACS symposium series 893. American Chemical Society, Washington, DCGoogle Scholar
  14. 14.
    Pang S, Rudin A (1992) Polymer 33:1949CrossRefGoogle Scholar
  15. 15.
    Wintermantel M, Antonietti M, Schmidt M (1993) J Appl Polym Sci Appl Polym Symp 52:91CrossRefGoogle Scholar
  16. 16.
    Degoulet C, Nicolai T, Durand D, Busnel JP (1995) Macromolecules 28:6819–6824CrossRefGoogle Scholar
  17. 17.
    Jackson C, Chen YJ, Mays JW (1996) J Appl Polym Sci 61:865CrossRefGoogle Scholar
  18. 18.
    Yau WW, Arora KS (1994) Polym Mater Sci Eng 69:210Google Scholar
  19. 19.
    Jackson C, Barth HG (1994) Trends Polym Sci 2:203Google Scholar
  20. 20.
    Yau WW (1990) Chemtracts-Macromol Chem 1:1Google Scholar
  21. 21.
    Rao B, Balke ST, Mourey TH, Schunk TC (1996) J Chromatogr A 755:27CrossRefGoogle Scholar
  22. 22.
    Ying Q, Xie P, Liu Y, Qian R (1986) J Liq Chromatogr 9:1233CrossRefGoogle Scholar
  23. 23.
    Ibhadon AO (1991) J Appl Polym Sci 42:1887CrossRefGoogle Scholar
  24. 24.
    Ying Q, Ye M (1985) Macromol Chem Rapid Commun 6:105CrossRefGoogle Scholar
  25. 25.
    Pasti L, Melucci D, Contado C, Dondi F, Mingozzi I (2002) J Sep Sci 25:69CrossRefGoogle Scholar
  26. 26.
    Sun T, Brant P, Chance RR, Graessley WW (2001) Macromolecules 34:6812CrossRefGoogle Scholar
  27. 27.
    Parth M, Aust N, Lederer K (2003) Int J Polym Anal Charact 8:175CrossRefGoogle Scholar
  28. 28.
    Mes EPC, De Jonge H, Klein T, Welz RR, Gillespie DT (2007) J Chromatogr A 1154:31CrossRefGoogle Scholar
  29. 29.
    Barth HG, Carlin FJ Jr (1984) J Liq Chromatogr 7:1717CrossRefGoogle Scholar
  30. 30.
    Pasch H (2012) Chromatography. In: Matyjaszewski K, Moeller M (eds) Polymer science: a comprehensive reference, vol 2. Elsevier, Amsterdam, pp 33–64Google Scholar
  31. 31.
    Provder T, Barth HG, Urban MW (eds) (1995) Chromatographic characterization of polymers. Adv Chem Ser 247. American Chemical Society, Washington, DCGoogle Scholar
  32. 32.
    Chu B (1995) Scattering methods in polymer science. Prentice Hall, LondonGoogle Scholar
  33. 33.
    Chu B (1997) Appl Optic 36:7645CrossRefGoogle Scholar
  34. 34.
    Dhenin V, Rose LJ (2000) Polym Prepr 41:285CrossRefGoogle Scholar
  35. 35.
    DesLauriers PJ, Battiste DR (1995) ANTEC-SPE 53:3639Google Scholar
  36. 36.
    DesLauriers PJ, Rohlfing DC, Hsieh ET (2002) Polymer 43:159CrossRefGoogle Scholar
  37. 37.
    Piel C, Albrecht A, Neubauer C, Klampfl CW, Reussner J (2001) Anal Bioanal Chem 400:2607CrossRefGoogle Scholar
  38. 38.
    Tackx P, Bremmers S (1997) Proceedings of the ISPAC-10, Toronto, p 42Google Scholar
  39. 39.
    Albrecht A, Brüll R, Macko T, Malz F, Pasch H (2009) Macromol Chem Phys 210:1319CrossRefGoogle Scholar
  40. 40.
    Albrecht A, Brüll R, Macko T, Sinha P, Pasch H (2008) Macromol Chem Phys 209:1909CrossRefGoogle Scholar
  41. 41.
    Heinz LC, Graef S, Macko T, Brüll R, Balk S, Keul H, Pasch H (2005) e-polymers no. 54Google Scholar
  42. 42.
    Macko T, Schulze U, Brüll R, Albrecht A, Pasch H, Fonagy T, Haeussler L, Ivan B (2008) Macromol Chem Phys 209:404CrossRefGoogle Scholar
  43. 43.
    de Goede S, Brüll R, Pasch H, Marshall N (2003) Macromol Symp 193:35CrossRefGoogle Scholar
  44. 44.
    de Goede S, Brüll R, Pasch H, Marshall N (2004) e-polymers no. 012Google Scholar
  45. 45.
    de Goede E, Mallon P, Pasch H (2010) Macromol Mater Eng 295:366CrossRefGoogle Scholar
  46. 46.
    de Goede E, Mallon P, Pasch H (2012) Macromol Mater Eng 297:26CrossRefGoogle Scholar
  47. 47.
    de Goede E, Mallon P, Pasch H (2011) Macromol Mater Eng 296:1018CrossRefGoogle Scholar
  48. 48.
    Graef S, Brüll R, Pasch H, Wahner UM (2003) e-polymers no. 005Google Scholar
  49. 49.
    Luruli N, Pipers T, Brüll R, Grumel V, Pasch H, Mathot VBF (2007) J Polym Sci Polym Phys 45:2956CrossRefGoogle Scholar
  50. 50.
    Kearney T, Dwyer JL (2008) Am Lab 40:8Google Scholar
  51. 51.
    Hiller W, Pasch H, Macko T, Hoffmann M, Ganz J, Spraul M, Braumann U, Streck R, Mason J, van Damme F (2006) J Magn Reson 183:290CrossRefGoogle Scholar
  52. 52.
    Frauenrath H, Balk S, Keul H, Höcker H (2001) Macromol Rapid Commun 22:1147CrossRefGoogle Scholar
  53. 53.
    Smallcombe SH, Patt SL, Keifer PA (1995) J Magn Reson A 117:295CrossRefGoogle Scholar
  54. 54.
    Hiller W, Sinha P, Hehn M, Pasch H (2014) Prog Polym Sci 39:979CrossRefGoogle Scholar
  55. 55.
    Zhou Z, Kuemmerle R, Stevens JC, Redwine D, He Y, Qiu X, Cong R, Klosin J, Montanez N, Roof G (2009) J Magn Reson 200:328CrossRefGoogle Scholar
  56. 56.
    Zhou Z, Stevens JC, Klosin J, Kuemmerle R, Qiu X, Redwine D, Cong R, Taha A, Winniford B, Chauvel P, Montanez N (2009) Macromolecules 42:2291CrossRefGoogle Scholar
  57. 57.
    Cong R, de Groot AW, Parrott A, Yau W, Hazlitt L, Brown R, Miller MD, Zhou Z (2011) Macromolecules 44:3062CrossRefGoogle Scholar
  58. 58.
    Berek D (2000) Prog Polym Sci 25:873CrossRefGoogle Scholar
  59. 59.
    Chang T (2003) Adv Polym Sci 163:1CrossRefGoogle Scholar
  60. 60.
    Macko T, Pasch H, Kazakevich YV, Fadeev AY (2003) J Chromatogr A 988:69CrossRefGoogle Scholar
  61. 61.
    Macko T, Pasch H, Denayer JF (2003) J Chromatogr A 1002:55CrossRefGoogle Scholar
  62. 62.
    Macko T, Brüll R, Pasch H (2003) Chromatographia 57:S39CrossRefGoogle Scholar
  63. 63.
    Macko T, Denayer JF, Pasch H, Baron GV (2003) J Sep Sci 26:1569CrossRefGoogle Scholar
  64. 64.
    Macko T, Denayer JF, Pasch H, Pan L, Li J, Raphael A (2004) Chromatographia 59:461Google Scholar
  65. 65.
    Macko T, Pasch H, Denayer JF (2005) J Sep Sci 28:59CrossRefGoogle Scholar
  66. 66.
    Wang X, Rusa CC, Hunt MA, Tonelli AE, Macko T, Pasch H (2005) Macromolecules 38:12040Google Scholar
  67. 67.
    Macko T, Brüll R, Brinkmann C, Pasch H (2009) J Autom Methods Manag Chem ID 357026 (electronic journal)Google Scholar
  68. 68.
    Macko T, Pasch H, Brüll R (2006) J Chromatogr A 1115:81CrossRefGoogle Scholar
  69. 69.
    Macko T, Pasch H, Milonjic SK, Hiller W (2006) Chromatographia 64:183CrossRefGoogle Scholar
  70. 70.
    Macko T, Brüll R, Zhu Y, Wang Y (2010) J Sep Sci 33:3446CrossRefGoogle Scholar
  71. 71.
    Heinz LC, Macko T, Williams A, O’Donohue S, Pasch H (2006) The Column (electronic journal), February 13Google Scholar
  72. 72.
  73. 73.
    Monrabal B (2013) Adv Polym Sci 257:203CrossRefGoogle Scholar
  74. 74.
    Heinz LC, Macko T, Pasch H, Weiser MS, Mülhaupt R (2006) Int J Polym Anal Charact 11:47CrossRefGoogle Scholar
  75. 75.
    Macko T, Hunkeler D (2003) Adv Polym Sci 163:61Google Scholar
  76. 76.
    Heinz LC, Pasch H (2005) Polymer 46:12040CrossRefGoogle Scholar
  77. 77.
    Albrecht A, Heinz LC, Lilge D, Pasch H (2007) Macromol Symp 257:46CrossRefGoogle Scholar
  78. 78.
    Weiser MS, Thomann Y, Heinz LC, Pasch H, Mülhaupt R (2006) Polymer 47:4505CrossRefGoogle Scholar
  79. 79.
    Dolle V, Albrecht A, Brüll R, Macko T (2011) Macromol Chem Phys 212:959CrossRefGoogle Scholar
  80. 80.
    Albrecht A, Brüll R, Macko T, Pasch H (2007) Macromolecules 40:5545CrossRefGoogle Scholar
  81. 81.
    Pasch H, Albrecht A, Brüll R, Macko T, Hiller W (2009) Macromol Symp 282:71CrossRefGoogle Scholar
  82. 82.
  83. 83.
    Gilbert MT, Knox JH, Kaur B (1982) Chromatographia 16:138CrossRefGoogle Scholar
  84. 84.
    Macko T, Pasch H, Wang Y (2009) Macromol Symp 282:93CrossRefGoogle Scholar
  85. 85.
    Macko T, Pasch H (2009) Macromolecules 42:6063CrossRefGoogle Scholar
  86. 86.
    Macko T, Brüll R, Wang Y (2009) Polym Prepr 50:228Google Scholar
  87. 87.
    Macko T, Brüll R, Alamo RG, Thomann Y, Grumel V (2009) Polymer 50:5443CrossRefGoogle Scholar
  88. 88.
    Macko T, Brüll R, Wang Y, Thomann Y (2009) The Column (electronic journal) 4:15Google Scholar
  89. 89.
    Macko T, Brüll R, Wang Y, Coto B, Suarez I (2011) J App Polym Sci 122:3211CrossRefGoogle Scholar
  90. 90.
    Macko T, Cutillo F, Bussico V, Brüll R (2010) Macromol Symp 298:182CrossRefGoogle Scholar
  91. 91.
    Chitta R, Macko T, Brüll R, van Doremaele G, Heinz LC (2011) J Polym Sci Polym Chem 49:1840CrossRefGoogle Scholar
  92. 92.
    Macko T, Brüll R, Alamo RG, Stadler FJ, Losio S (2011) Anal Bioanal Chem 399:1547CrossRefGoogle Scholar
  93. 93.
    Buback M, Wittkowski L, Lehmann SA, Mähling FO (1999) Macromol Chem Phys 200:1935CrossRefGoogle Scholar
  94. 94.
    Kisparissidis C, Baltsas A, Papadopoulos S, Congalidis JP, Richards JR, Kelly MB, Ye Y (2005) Ind Eng Chem Res 44:2592CrossRefGoogle Scholar
  95. 95.
    Kisparissidis C, Verros G, MacGregor JF (1993) J Macromol Sci Rev C33:437CrossRefGoogle Scholar
  96. 96.
    Findenegg GH, Liphard M (1987) Carbon 25:119CrossRefGoogle Scholar
  97. 97.
    Baukema PR, Hopfinger AJ (1982) J Polym Sci Polym Phys Ed 20:399CrossRefGoogle Scholar
  98. 98.
    Lipatov YS, Sergeeva LM (1974) Adsorption of polymers. Wiley, New York, NYGoogle Scholar
  99. 99.
    Lochmüller CH, Moebus MA, Liu QC, Jung C, Elomaa M (1996) J Chromatogr Sci 34:69CrossRefGoogle Scholar
  100. 100.
    Lee HC, Chang T (1996) Polymer 37:5747CrossRefGoogle Scholar
  101. 101.
    Im K, Park S, Cho D, Chang T, Lee K, Choi N (2004) Anal Chem 76:2638CrossRefGoogle Scholar
  102. 102.
    Monrabal B, Lopez E, Romero L (2013) Macromol Symp 330:9CrossRefGoogle Scholar
  103. 103.
    Nakano S, Goto Y (1981) J Appl Polym Sci 26:4217CrossRefGoogle Scholar
  104. 104.
    Ortin A, Monrabal B, Sancho-Tello J (2007) Macromol Symp 257:13CrossRefGoogle Scholar
  105. 105.
    Monrabal B (2012) Advances in microstructure characterization of polyolefins. In: Proceedings of the Chemelot International Polyolefins Symposium (CIPS), Maastricht, 7–10 October 2012Google Scholar
  106. 106.
    Ginzburg A, Macko T, Dolle V, Brüll R (2010) J Chromatogr A 1217:6867CrossRefGoogle Scholar
  107. 107.
    Ginzburg A, Macko T, Dolle V, Brüll R (2011) Eur Polym J 47:319CrossRefGoogle Scholar
  108. 108.
    Roy A, Miller MD, Meunier DM, de Groot AW, Winniford WL, van Damme FA, Pell RJ, Lyons JW (2010) Macromolecules 43:3710CrossRefGoogle Scholar
  109. 109.
    Lee D, Miller MD, Meunier DM, Lyons JW, Bonner JM, Pell RJ, Li Pi Chan C, Huang T (2011) J Chromatogr A 1218:7173CrossRefGoogle Scholar
  110. 110.
    Bashir MA, Brüll A, Radke W (2005) Polymer 46:3223CrossRefGoogle Scholar
  111. 111.
    Cheruthazhekatt S, Harding GW, Pasch H (2013) J Chromatogr A 1286:69CrossRefGoogle Scholar
  112. 112.
    Sperling LH (2006) Introduction to physical polymer science, 4th edn. John Wiley, Hoboken, NJGoogle Scholar
  113. 113.
    Cheruthazhekatt S, Pijpers TFJ, Harding GW, Mathot VBF, Pasch H (2012) Macromolecules 45:2025CrossRefGoogle Scholar
  114. 114.
    Cheruthazhekatt S, Pijpers TFJ, Harding GW, Mathot VBF, Pasch H (2012) Macromolecules 45:5866CrossRefGoogle Scholar

Copyright information

© Springer International Publishing Switzerland 2014

Authors and Affiliations

  • Harald Pasch
    • 1
  • Muhammad Imran Malik
    • 2
  1. 1.Department of Chemistry and Polymer ScienceUniversity of StellenboschMatielandSouth Africa
  2. 2.International Center for Chemical and Biological Sciences (ICCBS) H.E.J. Research Institute of ChemistryUniversity of KarachiKarachiPakistan

Personalised recommendations