Multiple detection SEC and capillary electrophoresis as complementary separation and characterization methods for branched polymers and polyelectrolytes — ASN Events
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  3. Multiple detection SEC and capillary electrophoresis as complementary separation and characterization methods for branched polymers and polyelectrolytes

Multiple detection SEC and capillary electrophoresis as complementary separation and characterization methods for branched polymers and polyelectrolytes (#61)

Patrice Castignolles 1 , Alison R Maniego 1 2 , Jean-Baptiste Lena 1 2 , Adam Sutton 1 2 , Yohann Guillaneuf 3 , Marianne Gaborieau 2
  1. Australian Centre for Research On Separation Sciencem School of Science and Health, University of Western Sydney, Parramatta, NSW, Australia
  2. Nanoscale Organisation and Dynamics Group (NANO), School of Science and Heath, University of Western Sydney, Parramatta, NSW, Australia
  3. Institut de Chimie Radicalaire, Aix-Marseille University, Marseille, France

Size-exclusion Chromatography (SEC or GPC) separates by hydrodynamic volume, not molar mass,1  although the latest is the quantity usually determined by the method. Polyacrylates have a broad range of applications in paints, coatings etc.2  Unwanted side reactions during their synthesis make the microstructure of the polyacrylates branched.3  Using multiple detection, we have shown that statistical branching leads to significant band broadening in SEC of poly(alkyl acrylates)2,4  as well as poly(acrylic acid). The band broadening is quantified by the determination of the local dispersity, which in turn enable us to evaluate the accuracy of the determined distribution of molecular weights.5,6 When local dispersities are significantly above unity, we propose hydrodynamic volume distributions7,8 as an alternative for meaningful and accurate characterization of polymers size9,10 .

Free solution capillary electrophoresis (CE) allows higher throughput and cheaper characterization of poly(acrylic acid) and its salts. Complete characterization is obtained for oligomers,11  as revealed using CE-ESI TOF MS12 . In the case of polymers, free solution CE separates the poly(acrylic acid) salts by their topology (as well as end-groups) and is thus complementary to SEC. The method is also successfully applied to the characterization of copolymers of poly(acrylic acid).

  1. M. Gaborieau, J. Nicolas, M. Save, B. Charleux, J.-P. Vairon, R.G. Gilbert, P. Castignolles, Journal of Chromatography A 1190 (2008) 215.
  2. M. Gaborieau, P. Castignolles, Analytical and Bioanalytical Chemistry 399 (2011) 1413.
  3. P. Castignolles, R. Graf, M. Parkinson, M. Wilhelm, M. Gaborieau, Polymer 50 (2009) 2373.
  4. O. Colombani, O.l. Langelier, E. Martwong, P. Castignolles, Journal of Chemical Education 88 (2011) 116.
  5. T. Junkers, M. Schneider-Baumann, S.S.P. Koo, P. Castignolles, C. Barner-Kowollik, Macromolecules 43 (2010) 10427.
  6. P. Castignolles, Macromolecular Rapid Communications 30 (2009) 1995
  7. P. Castignolles, M. Gaborieau, Journal of Separation Science 33 (2010) 3564.
  8. M. Gaborieau, R.G. Gilbert, A. Gray-Weale, J.M. Hernandez, P. Castignolles, Macromolecular Theory and Simulations 16 (2007) 13.
  9. J.M. Hernández, M. Gaborieau, P. Castignolles, M.J. Gidley, A.M. Myers, R.G. Gilbert, Biomacromolecules 9 (2008) 954.
  10. G. Delaittre, M. Save, M. Gaborieau, P. Castignolles, J. Rieger, B. Charleux, Polymer Chemistry 3 (2012) 1526.
  11. P. Castignolles, M. Gaborieau, E.F. Hilder, E. Sprong, C.J. Ferguson, R.G. Gilbert, Macromolecular Rapid Communications 27 (2006) 42.
  12. M. Gaborieau, T.J. Causon, Y. Guillaneuf, E.F. Hilder, P. Castignolles, Australian Journal of Chemistry 63 (2010) 1219.