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Analysis of the substituent distribution in the glucosyl units and along the polymer chain of hydroxypropylmethyl celluloses and statistical evaluation

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Abstract

Three hydroxypropylmethyl celluloses (HPMC 1, 2, 3; DSMe=2.06, 1.99, 2.04; MSHP=0.21, 0.19, 0.21) have been analyzed with respect to their methyl and hydroxypropyl pattern in the glucosyl units and along the polymer chain. The determination of the methyl pattern in the glycosyl unit was performed by GLC/MS after hydrolysis, reduction, and acetylation, while the distribution of hydroxypropyl residues in the monomers could be analyzed with higher sensitivity including a permethylation step prior to hydrolysis. To determine the distribution of the substituents along the polymer chain, a method developed for hydroxyethylmethyl cellulose (HEMC) was applied. This method comprises random partial acid hydrolysis after perdeuteromethylation and reductive amination with propylamine, followed by N- and O-alkylation, yielding completely alkylated and permanently charged oligosaccharide derivatives. These compounds could be quantitatively analyzed by means of matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), since all discrimination effects related to the hydroxyalkyl groups are leveled off by the sample preparation procedure in combination with the choice of a MALDI-TOF instrument. Methyl data deviate to some extent from the random distribution calculated from the monomer composition, but in contrast to methyl cellulose (MC) or HEMC, it is not heterogeneous, but more regular. The distribution of HP groups is random within experimental error as has been found for HEMC as well.

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Acknowledgements

We are grateful to Dr. M. Nimtz, GBF Braunschweig, Germany, for recording the MALDI-TOF mass spectra. Financial support of Wolff Cellulosics GmbH & Co. KG, Walsrode, Germany, is gratefully acknowledged.

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Authors and Affiliations

  1. Institut für Lebensmittelchemie, TU Braunschweig, Schleinitzstr. 20, D-38106, Braunschweig, Germany

    Roland Adden, Romy Müller & Petra Mischnick

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  1. Roland Adden
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  2. Romy Müller
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  3. Petra Mischnick
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Correspondence to Petra Mischnick.

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Adden, R., Müller, R. & Mischnick, P. Analysis of the substituent distribution in the glucosyl units and along the polymer chain of hydroxypropylmethyl celluloses and statistical evaluation. Cellulose 13, 459–476 (2006). https://doi.org/10.1007/s10570-005-9028-x

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  • DOI: https://doi.org/10.1007/s10570-005-9028-x

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