Solvent-free modification of lignocellulosic wood pulp into a melt-flowable thermoplastic
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ORIGINAL RESEARCH
Solvent-free modification of lignocellulosic wood pulp into a melt-flowable thermoplastic Jinlei Li . Hongfeng Zhang . Guerino G. Sacripante . David J. W. Lawton . Heera S. Marway . Michael R. Thompson
Received: 15 June 2020 / Accepted: 12 November 2020 Ó Springer Nature B.V. 2020
Abstract This paper reports on a flowable lignocellulosic thermoplastic prepared from forestry biomass by solvent-free acetylation. The non-solvent approach relies upon a functionalizing agent derived from benzethonium chloride (hyamine) and sulfuric acid, which was chose for its similar wetting attributes to an ionic liquid for the lignocellulose but was much less expensive to use. Besides acetylation, this functionalizing agent became chemically bonded to the lignocellulose by the sulfate group formed in situ, as demonstrated by 13C NMR, infrared and elemental analysis. This attached species appeared to contribute strongly to the flowable nature of the product. The modified material showed good melt flowability by compression molding, as demonstrated in this study by the production of semi-transparent films and was characterized by differential scanning calorimetry and dynamic mechanical analysis. An experimental investigation of reaction parameters was included in the study, exploring the mechanism by which the cationic
J. Li H. Zhang G. G. Sacripante H. S. Marway M. R. Thompson (&) Department of Chemical Engineering, McMaster University, 1280 Main Street West, Hamilton, ON L8S 4L7, Canada e-mail: [email protected] D. J. W. Lawton Xerox Research Centre of Canada, 2660 Speakman Drive, Mississauga, ON L5K 2L1, Canada
functionalizing agent modified the structure of lignocellulose. Keywords Biomass Lignocellulose Solvent-free Chemical modification Thermoplastic
Introduction The decline in fossil fuel reserves will soon impact the supply chain of the polymer industry. Cellulosic thermoplastics constitute one group of many promising replacements to synthetic plastics. Cellulose is a macromolecule that is insoluble in most solvents and has no innate thermoplasticity, which is attributed to its crystallinity and intra- and inter hydrogen bonds. Chemical modifications can interfere with these hydrogen bonds and simultaneously introduce side groups along the cellulose backbones, which improve chain flexibility and thus afford thermoplasticity (Yan et al. 2009; Toyama et al. 2015; Larsson and Wa˚gberg 2016; Huang et al. 2016a; Chen et al. 2018). However, the manufacturing of current cellulose thermoplastics like cellulose acetate, cellulose acetate propionate or cellulose acetate butyrate is costly, especially as compared with competitive petroleum-based thermoplastics (Edgar et al. 2001). The production of cellulose thermoplastics currently relies on using a large excess of acetic acid to
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Cellulose
swell and disperse the insoluble fibrillar mass for chemical modifications (Hummel 2004). Using such a high amount of reactants leads to high costs in the
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