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Direct synthesis of cellulose adipate derivatives using adipic anhydride

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Abstract

The poor aqueous solubility of many drugs can be overcome by formulation as amorphous solid dispersions (ASD) in cellulosic-based polymer matrices. Cellulose esters containing adipates and other ester groups have shown great promise as new ASD polymers. Previous attempts to synthesize these cellulose adipate esters by direct reaction of cellulose derivatives with adipic anhydride failed due to crosslinking and gelation, caused by formation of poly(adipic anhydride) and subsequent reaction of the poly(anhydride) with cellulosic hydroxyls. In order to develop direct, efficient syntheses of these pH-sensitive cellulose adipate derivatives, we have developed new synthetic procedures that cleanly afford soluble ester products by direct condensation with adipic anhydride, that show no evidence of crosslinking. A series of cellulose ester adipates has been synthesized by this direct route, containing substantial adipate DS (up to 0.53). This new method requires no complex solvents or protective groups, and is an effective and versatile route to these useful materials.

Graphical Abstract

Reaction of cellulose acetate propionate (CAP-504-0.2) with adipic anhydride

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Acknowledgments

This project was supported primarily by a grant from the National Science Foundation (NSF, grant number DMR-0804501). The authors would like to thank the Eastman Chemical Company for their kind donation of the cellulose esters used in this work. We would also like to thank the Macromolecules and Interfaces Institute and the Institute for Critical Technologies and Applied Science at Virginia Tech for their support, and Tianyu Wu for running the SEC analyses.

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Authors and Affiliations

  1. Virginia Tech, Blacksburg, VA, USA

    Haoyu Liu, Nilanjana Kar & Kevin J. Edgar

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  1. Haoyu Liu
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  2. Nilanjana Kar
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  3. Kevin J. Edgar
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Correspondence to Kevin J. Edgar.

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10570_2012_9724_MOESM1_ESM.doc

Supplementary information available for this paper includes 1H NMR spectra of pure adipic anhydride, CAAdP samples 1 and 3 prior to hot water washing, CAAdP samples 2, 3, and 10, CAAdB samples 13 and 16, and CAAd sample 19. FTIR spectra of CAAdB sample 13 and CAAd sample 17. 13C NMR spectra of CAAdB sample 16 and CAAd sample 17. (DOC 1001 kb)

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Liu, H., Kar, N. & Edgar, K.J. Direct synthesis of cellulose adipate derivatives using adipic anhydride. Cellulose 19, 1279–1293 (2012). https://doi.org/10.1007/s10570-012-9724-2

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  • DOI: https://doi.org/10.1007/s10570-012-9724-2

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