Controlled Allocation of Aromatic/Aliphatic Substituents to Polysaccharides and Lignin in Sugarcane Bagasse via Successive Homogeneous Transesterification Using Ionic Liquid.

Lignocellulosic agricultural waste is an abundant renewable feedstock that can be utilized as a sustainable source of biomass-based plastics. Ideally, it is used without discarding any components, including cellulose, hemicellulose, and lignin. However, their utilization as lignocellulose-based plastics has been limited because of the low compatibility between the polysaccharides and lignin derivatives and the resulting poor mechanical properties of the final products. Here, we demonstrate a facile but highly controllable conversion of sugarcane bagasse into valuable thermoplastics by utilizing the excellent solubility and unique organocatalytic abilities of an ionic liquid, 1-ethyl-3-methylimidazolium acetate. In a homogeneous and one-pot chemical modification reaction system, the substitution ratio of an aromatic benzoyl group to an aliphatic hexanoyl group in the bagasse derivative was adjusted by the ratio of acyl reagents used. Moreover, the allocation of these two acyl groups to polysaccharide and lignin components in bagasse was successfully controlled only by exchanging the order of the acyl reagents introduced into the reaction system. The controlled introduction of the acyl groups into bagasse achieved a homogeneous polymer phase in the resultant multicomponent hot-pressed film, resulting in enhanced mechanical properties such as sufficient tensile strength (∼20 MPa) and excellent ductility with a high strain energy density (∼5 MJ m