Journal of Polymers and the Environment

, Volume 21, Issue 1, pp 24–29 | Cite as

Determination of Mark-Houwink Parameters and Absolute Molecular Weight of Medium-Chain-Length Poly(3-Hydroxyalkanoates)

  • Manoj Nerkar
  • Juliana A. Ramsay
  • Bruce A. Ramsay
  • Marianna Kontopoulou
  • Robin A. Hutchinson
Original Paper

Abstract

Absolute molecular weight distributions were determined for different medium-chain-length poly(3-hydroxyalkanoates) (MCL PHAs) with predominantly 3-hydroxyoctanoate (PHO), 3-hydroxynonanoate (PHN) or 3-hydroxydodecanoate content. This is the first study to estimate the Mark-Houwink constants of these polymers in the commonly employed GPC carrier solvent tetrahydrofuran (THF). The absolute molecular weight averages were determined via triple-detector size exclusion chromatography and combined with analyses using various detectors. Unlike with the short-chain-length poly(3-hydroxybutyrate), PHB, uncorrected polystyrene calibration in THF provided a good estimate (within 10 %) of absolute MW values for these MCL PHAs, irrespective of side chain length. Weight-average MW values ranged from 172,000 Da for PHO to 18,200 for PHN with 30 mol% 3-hydroxyheptanoate, and dispersities of all samples were close to two. Melt viscosity data suggested an entanglement molecular weight around 8 × 104 Da, significantly higher than most polymers.

Keywords

Polyhydroxyalkanoate Medium chain length polyhydroxyalkanoate Viscosity Absolute molecular weight 

References

  1. 1.
    Vaidya A, Pandey R, Mudliar S, Kumar M, Chakrabarti T, Devotta S (2005) Crit Rev Environ Sci Technol 35:429–467CrossRefGoogle Scholar
  2. 2.
    Takagi Y, Yasuda R, Yamaoka M, Yamane T (2004) J Appl Polym Sci 93:2363–2369CrossRefGoogle Scholar
  3. 3.
    Kim DY, Kim HW, Chung MG, Rhee YH (2007) J Microbiol 45:87–97Google Scholar
  4. 4.
    Rai R, Yunos DM, Boccaccini AR, Knowles JC, Barker IA, Howdle SM, Tredwell GD, Keshavarz T, Roy I (2011) Biomacromolecules 12:2126–2136CrossRefGoogle Scholar
  5. 5.
    Nerkar M, Ramsay JA, Ramsay BA, Kontopoulou M (2012) In: Conference on the proceeding of poly processing society 358–359Google Scholar
  6. 6.
    Akita S, Einaga Y, Miyaki Y, Fujita H (1976) Macromolecules 9:774–780CrossRefGoogle Scholar
  7. 7.
    Marchessault RH, Okamura K, Su CJ (1970) Macromolecules 3:735–740CrossRefGoogle Scholar
  8. 8.
    Miyaki Y, Einaga Y, Hirosye T, Fujita H (1977) Macromolecules 10:1356–1364CrossRefGoogle Scholar
  9. 9.
    Cornibert J, Marchessault RH, Benoit H, Weill G (1970) Macromolecules 3:741–746CrossRefGoogle Scholar
  10. 10.
    Berger E, Ramsay BA, Ramsay JA, Chavarie C, Braunegg G (1989) Biotechnol Tech 3:227–232CrossRefGoogle Scholar
  11. 11.
    Ramsay JA, Berger E, Voyer R, Chavarie C, Ramsay BA (1994) Biotechnol Tech 8:589–594CrossRefGoogle Scholar
  12. 12.
    Shozui F, Matsumoto K, Sasaki T, Taguchi S (2009) Appl Microbiol Biotechnol 84:1117–1124CrossRefGoogle Scholar
  13. 13.
    Daly PA, Bruce DA, Melik DH, Harrison GM (2005) J Appl Polym Sci 98:66–74CrossRefGoogle Scholar
  14. 14.
    Jiang X, Sun Z, Marchessault RH, Ramsay JA, Ramsay BA (2012) Biomacromolecules (Accepted). doi:10.1021/bm3009507
  15. 15.
    Sun Z, Ramsay JA, Guay M, Ramsay BA (2009) J Biotechnol 143:262–267CrossRefGoogle Scholar
  16. 16.
    Jiang X, Ramsay JA, Ramsay BA (2006) J Microbiol Methods 67:212–219CrossRefGoogle Scholar
  17. 17.
    Dupont AL, Harrison G (2004) Carbohydr Polym 58:233–243CrossRefGoogle Scholar
  18. 18.
    Beuermann S, Buback M, Davis TP, Gilbert RG, Hutchinson RA, Kajiwara A, Klumperman B, Russell GT (2000) Macromol Chem Phy 201:1355–1364CrossRefGoogle Scholar
  19. 19.
    Marschessault RH, Monasterios CJ, Morin FG, Sundararajan PR (1999) Int J Biol Macromol 12:158–165CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  • Manoj Nerkar
    • 1
  • Juliana A. Ramsay
    • 1
  • Bruce A. Ramsay
    • 2
  • Marianna Kontopoulou
    • 1
  • Robin A. Hutchinson
    • 1
  1. 1.Department of Chemical EngineeringQueen’s UniversityKingstonCanada
  2. 2.Polyferm Canada Inc.OntarioCanada

Personalised recommendations