Abstract
Pure, well soluble p-toluenesulfonyl (tosyl) starch samples with a DSTos range from 0.4 to 2.0 were prepared by reacting starch with tosyl chloride in the presence of triethylamine dissolved in the solvent N,N-dimethyl acetamide in combination with LiCl. The thermal degradation starts at a temperature of 166 °C for a sample with DSTos of 0.61 which is sufficiently high for subsequent modifications of the remaining OH groups, for instance by acylation reactions. The total DSTos can be determined using the signal of the methyl protons of the tosyl, acetyl or propionyl moieties of peracylated samples. Moreover, the NMR characterisation reveals that a predominant functionalisation at position 2 occurs. On the other hand, 6-O-tosyl starch products can be synthesised via 2-O-acetyl starch which is accessible by a new acylation procedure. The functionalisation patterns of new synthesised polymers with an unusual distribution of functional groups and high DS values were unambiguously characterised by various NMR techniques.
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References
Heinze, Th., Glasser, W.G., 1998, The role of novel solvents and solution complexes for the preparation of highly engineered cellulose derivatives. In Cellulose derivatives: modification, characterization, and nanostructures, (Thomas J. Heinze, Wolfgang G. Glasser, eds.) ACS Symposium Series 688. Washington, DC: American Chemical Society
Wurzburg, O.W., 1986, Modified starches: properties and uses. Boca Raton, USA: CRC Press
Clode, D.M., Horton, D., 1971, Preparation and characterization of the 6-aldehydo derivatives of amylose and whole starch. Carbohydr. Res.; 17: 365–373.
Horton, D., Meshreki, M.H., 1975, Syntheses of 2,3-unsaturated polysaccharides from amylose and xylan. Carbohydr. Res. 40: 345–352.
Teshirogi, T., Yamamoto, H., Sakamoto, M., Tonami, H., 1978, Syntheses and reactions of Aminodeoxycelluloses. Sen-i Gakkaishi 34: T510-T515.
Teshirogi, T., Yamamoto, H., Sakamoto, M., Tonami, H., 1979, Synthesis of mono- and diaminated starches. Sen-i Gakkaishi 35: T479-T485.
Weill, C.E., Kaminsky, M., Hardenbergh, J., 1980, Random substitution of amylose. Carbohydr. Res. 84: 307–313.
Mahoney, J.F., Purves, C.B., New methods for investigating the distribution of ethoxyl groups in a technical ethylcellulose. J. Amer. Chem. Soc. 1942; 64: 9–15.
Horton, D., Luetzow, A.E., Theander, O., 1973, Preparation of 6-chloro-6-deoxyamylose of various degrees of substitution; an alternative route to 6-aldehydoamylose. Carbohydr. Res. 27: 268–272.
Heinze, Th., Schaller, J., 2000, New water soluble cellulose esters synthesized by an effective acylation procedure. Macromol. Chem. Phys. 201: 1214–1218.
Klemm, D., Stein, A., 1995, Silylated cellulose materials in design of supramolecular structures of ultrathin cellulose films. J.M.S.-Pure Appl. Chem. A32: 899–904.
Matulova, M., Toffanin, R., Navarini, L., Gilli, R., Paoletti, S., Cesaro, A., 1994, NMR analysis of succinoglycans from different microbial sources: partial assignment of their 1H and 13C NMR spectra and location of the succinate and the acetate groups. Carbohydr. Res. 65: 167–179.
Deus, C., Friebolin, H., Siefert, E., 1991, Partiell acetylierte Cellulose-Synthese und Bestimmung der Substituentenverteilung. Makromol. Chem. 192: 75–83.
Dicke, R., 1999, Ph.D. Thesis, Friedrich Schiller University of Jena, Germany.
Hall, D.M., Horne, J.R., 1973, Model compounds of cellulose: trityl ethers substituted exclusively at C-6 primary hydroxyls. J. Appl. Polym. Sci. 17: 2891–2896.
Takahashi, S.-I., Fujimoto, T., Bama, B.M., Miyamoto, T., Inogaki, H., 1986, 13C-NMR spectral studies on the distribution of substituents in some cellulose derivative. J. Polym. Sci., Part A: Polym. Chem. 24: 2981–2993.
Rahn, K., Diamantoglou, M., Klemm, D., Bergmans, H., Heinze, T., 1996, Homogeneous synthesis of cellulose p-toluenesulfonates in N,N-dimethyl acetamide/LiC1 solvent system. Angew. Makromol. Chem. 238: 143–163.
Dicke, R., Rahn, K., Haack, V., Heinze, T., Starch derivatives of high degree of functionalization 2. Determination of the functionalization pattern of p-toluenesulfonyl starch by peracylation and NMR spectroscopy. Carbohydr. Polym., in press.
Heinze, T., 1998, Ionische Funktionspolymere aus Cellulose: Neue Synthesekonzepte, Strukturaufklärung und Eigenschaften. Shaker Verlag, Aachen
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Heinze, U., Haack, V., Heinze, T. (2001). New Highly Functionalised Starch Derivatives. In: Chiellini, E., Gil, H., Braunegg, G., Buchert, J., Gatenholm, P., van der Zee, M. (eds) Biorelated Polymers. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-3374-7_18
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DOI: https://doi.org/10.1007/978-1-4757-3374-7_18
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