Abstract
Thermal properties of industrial hydrolysis lignin (HL) obtained from bio-ethanol production plants were investigated by thermogravimetry and differential scanning calorimetry. Thermal decomposition of HL was observed in two stages suggesting coexisting carbohydrates. Glass transition temperature (T g) was observed in a temperature range from 248 to 363 K. T g values were lower than that of other industrial lignins, such as kraft lignin or lignosulfate. Enthalpy relaxation was observed as sub-T g, which is not as prominent as other industrial or laboratory scale isolated lignins. T g of HL decreased in the presence of water and saturated at water content (W c) of 0.18 (mass of water/mass of dry HL). The amount of bound water calculated from melting enthalpy of water and W c was ca. 0.18. Thermal decomposition and molecular motion of as obtained industrial HL are affected by coexisting carbohydrates.
Similar content being viewed by others
References
Cholkin UI. The hydrolysis manufacture technology. Moscow: Forest Industry; 1989.
Lin SY, Dence CW. Methods in lignin chemistry. Berlin: Springer-Verlag; 1992.
Zarubin MJa, Alekseev SR, Krutov SM. Hydrolysed lignin, structure and perspectives of transformation into low molecular products. In: Kennedy JF, Phillips GO, Williams PA, Hatakeyama H, editors. Recent advances in environmentally compatible polymers. Chichester: Woodhead; 2001. p. 155–60.
Hatakeyema H. Thermal analysis of environmentally compatible polymers containing plant components in the main chain. J Therm Anal Calorim. 2002;70:755–955.
Hatakayama H, Asano Y, Hatakeyama T. Biobased polymeric materials. In: Chiellini E, Solaro R, editors. Biodegradable polymers and plastic. New York: Kluwer Academic/Plenum; 2003. p. 103–19.
Hatakeyama T, Hatakeyama H. Thermal properties of green polymers and biocomposites. Dordrecht: Kluwer Academic; 2004.
Saraf VP, Glasser WG, Wilkes G. Engineering plastics from lignin. VII. Structure property relationships of polybutadiene glycol-containing polyurethane networks. J Appl Polym Sci. 1985;30:3809–23.
Rials TG, Glasser WG. Enginnering plastics from lignin IV. Effect of crosslink density on polyurethane film properties- variation in NCO:OH ratio. Hotzforschung. 1984;38:191–9.
Gandini A, Naceur BM, Guo ZX, Montanari S. Lignins as macromonomers for polyesters and polyurethanes. In: Hu TQ, editor. Chemical modification, properties, and usage of lignin. New York: Academic/Plenum; 2002. p. 57–80.
Yoshida H, Mörck R, Kringstad KP, Hatakeyama H. Kraft lignin in polyurethanes. II. Effects of the molecular weight of kraft lignin on the properties of polyurethanes from a kraft ligni-polyether triol-polymeric MDI system. J Appl Polym Sci. 1990;40:1819–32.
Nakamura K, Hatakeyama T, Hatakeyama H. Thermal properties of solvolysis lignin-derived polyurethanes. Polym Adv Technol. 1992;3:151–5.
Hatakeyama T, Quinn FX. Thermal analysis, fundamentals and applications to polymer science. 2nd ed. Chichester: John Wiley; 1999.
Hatakeyama T, Liu Z. Handbook of thermal analysis. Chichester: John Wiley; 1999.
Nguyen T, Zavarin E, Barrell II EM. Thermal analysis of lignocellulosic materials. Part I. Unmodified materials. J Macromol Sci Rev Macromol Chem. 1981;C20:1–65.
Hirose S, Hatakeyama H. A kinetic study on lignin pyloysis using integral method. Mokuzai Gakkishi. 1986;32:621–5.
Baumberger S, Dole P, Lapierre C. Using transgenic poplars to elcidate the relationship between the structure and the thermal properties of lingins. J Agric Food Chem. 2002;50:2450–3.
Hirose S, Kobashigawa K, Izuta Y, Hatakeyama H. Thermal degradation of polyurethanes containing lignin studied by TG-FTIR. Polym Int. 1998;47:247–56.
Goring DAI. Thermal softening of lignin, hemicellulose and cellulose. Pulp Paper Mag Can. 1963;64:T517–27.
Goring DAI. Polymer properties. In: Sarkanen KV, Ludwig CH, editors. Lignins. New York: Wiley Interscience; 1971. p. 695–768.
Ramiah VM, Goring DAI. The thermal expansion of cellulose, hemicellulose and lignin. J Polym Sci. 1965;C11:27–48.
Hatakeyama H, Kubota K, Nakano J. Thermal analysis of lignin by differential scanning calorimetry. Cell Chem Technol. 1972;6:521–9.
Hatakeyama T, Nakamura K, Hatakeyama H. Studies on heat capacity of cellulose and lignin by differential scanning calorimetry. Polymer. 1982;23:1801–4.
Hatakeyama H. Thermal analysis. In: Lin SY, Dence CW, editors. Methods in lignin chemistry. Berlin: Springer; 1992. p. 200–14.
Salmén L. Viscoelastic properties of in situ lignin under water-saturated conditions. J Mater Sci. 1984;19:3090–6.
Wunderlich B. Study of the change in specific heat of monomeric and polymeric glasses during the glass transition. J Phys Chem. 1960;64:1052–6.
Hatakeyama T, Hatakeyama H. Effect of chemical structure of amorphous polymers on heat capacity difference at glass transition temperature. Thermochim Acta. 1995;267:249–57.
Marshall AS, Petrie SEB. Physical aging of glassy polymers: effects of subsidiary relaxation processes. In: Eby RH, editor. Durability of macromoelcular materials. ACS Symposium, Series 95, Washington DC, Am Chem Soc; 1979. p. 245–59.
Hodge IM, Berens AR. Effects of annealing and prior history on enthalpy relaxation in galssy polymers. 2. Mathermatical modeling. Macromolecules. 1982;15:762–70.
Åkernholm M, Salmén L. The oriented structure of lignin and its viscoelstic properties studied by static and dynamic FT-IR spectroscopy. Hotzhorshung. 2003;57:459–65.
Åkernholm M, Salmén L. Softening of wood polymers induced by moisture studied by dynamic FTIR spectroscopy. J Appl Polym Sci. 2004;94:2032–40.
Hatakeyama T, Hirose S, Hatakeyama H. Differential scanning calorimetric studies on bound water in 1.4-dioxane acidolysis lignin. Thermochim Acta Makromol Chem. 1983;184:1265–74.
Hatakeyama H, Hatakeyama T. Interaction between water and hydrophilic polymers. Thermochim Acta. 1998;308:3–22.
Hatakeyama T, Kasuga H, Tanaka M, Hatakeyama H. Cold crystallization of poly(ethylene glycol)-water systems. Thermochim Acta. 2007;465:59–66.
Tanaka M, Mochizuki A, Motomura T, Hatakeyama T. Study of blood compatibility with poly(2-methoyehtyl acrylate). Relationship between water structure and platelet compatibility in poly(methoxyethylacrylate-co-2- hydroxythylmethacrylate. Biomacromolecules. 2002;3:36–41.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Hatakeyama, H., Tsujimoto, Y., Zarubin, M.J. et al. Thermal decomposition and glass transition of industrial hydrolysis lignin. J Therm Anal Calorim 101, 289–295 (2010). https://doi.org/10.1007/s10973-010-0698-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-010-0698-8