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

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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.

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Acknowledgments

Funding from the Natural Sciences and Engineering Council (NSERC) of Canada and Xerox Canada is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemical Engineering, Queen’s University, Dupuis Hall, 19 Division St., Kingston, ON, K7L 3N6, Canada

    Manoj Nerkar, Juliana A. Ramsay, Marianna Kontopoulou & Robin A. Hutchinson

  2. Polyferm Canada Inc., 4530 CamdenE-Portland Bdry Rd. RR1 Harrowsmith, Ontario, K0H 1V0, Canada

    Bruce A. Ramsay

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  1. Manoj Nerkar
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  2. Juliana A. Ramsay
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  3. Bruce A. Ramsay
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  4. Marianna Kontopoulou
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  5. Robin A. Hutchinson
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Correspondence to Robin A. Hutchinson.

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Nerkar, M., Ramsay, J.A., Ramsay, B.A. et al. Determination of Mark-Houwink Parameters and Absolute Molecular Weight of Medium-Chain-Length Poly(3-Hydroxyalkanoates). J Polym Environ 21, 24–29 (2013). https://doi.org/10.1007/s10924-012-0525-3

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  • DOI: https://doi.org/10.1007/s10924-012-0525-3

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