2018 (3) 4

https://doi.org/10.15407/polymerj.40.03.166

Dextran-silica hybrid materials: production, adsorption, thermal transformations and structure of the adsorption layer

T.V. Kulik

O.O. Chuiko Institute of Surface Chemistry NAS of Ukraine

17, General Naumov str., Kyiv, 03164, Ukraine; tanyakulyk@i.ua

Polym. J., 2018, 40, no. 3: 166-178

Section: Structure and properties.

Language: Ukrainian.

Abstract:

The paper is devoted to the studying of the interaction of biocompatible carbohydrate polymer – dextran with the nanosilica surface, investigation of adsorbed polymer layer structure and influence of the adsorption on the dextran thermochemical properties using adsorption methods of analysis, IR-spectroscopy, analysis of P/T-curves and temperature-programmed desorption mass spectrometry (TPD MS). The adsorption/desorption processes of dextran on the nanosilica surface was investigated. The main products formed during pyrolysis of dextran in the condensed state are the compounds of consecutive elimination of one, two and three water molecules from the monomeric unit (glucose): levoglucosan, dianhydro derivatives and levoglucosenone. The corresponding ions in the mass spectra of volatile pyrolysis products – m/z 162, 144, 126, can be considered as key markers in the pyrolysis of natural polysaccharides based on the monomeric units of glucose. In addition to derivatives of the pyran series, derivatives of the furan series are observed: methylfurfural, hydroxymethylfurfural, furfural, etc. Pyrolysis on the silica surface does not lead to the formation of levoglucosan and dianhydro derivatives. This is due to the formation of adsorption complexes of dextran then their chemisorption upon heating with the formation of grafted ether groups and their subsequent thermal degradation at Tmax~380 °C. That is why there are two stages of pyrolysis of adsorbed dextran (Stage I – Tmax~300 °C and Stage II – Tmax ~380 °C) which relate to the pyrolysis of non-connected segments of adsorbed dextran (loops, trains) and segments directly connected to the nanosilica surface. Approach for the estimation of p parameter value based on TPD MS data was suggested. The correlation of adsorbed dextran amount and p parameter value was obtained. It was revealed that with the increasing of dextran amount the p parameter decreases from ~1 to ~0,6.

Keywords: pyrolysis, levoglucosenone, levoglucosan, methylfurfural, thermo-programmed desorption mass spectrometry.

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