(385p) Sustainable Synthesis of Functional Polymers from Cellulose

The unprecedented surge in waste plastics and carbon dioxide emissions, resulting from our dependence on petroleum-based fuels and plastics, stands as the gravest energy and environmental crisis in the annals of human history. One of the most promising solutions regarding this issue is the utilization of biopolymers in replace of petroleum-based resources, in order to produce value-added polymers and plastics. Among various biopolymers, cellulose is the most attractive resource due to the abundance and unique physicochemical properties. In principle, the chemical modification of cellulose to obtain value-added products is straightforward by leveraging –OH groups at the cellulose chain. However, the difficulty of chemical modification is quite high due to the insolubility of cellulose in most common solvents. Moreover, conventional cellulose modification is used to use petroleum-based toxic and hazardous reactants as an electrophile. Cellulose derivatization still needs to be more advanced toward a green and sustainable process. In this work, we aim to obtain cellulose derivatives in a sustainable and environmentally benign manner. Moreover, we extensively characterize our cellulose-derived products to understand structure-property relationship.

One of the most significant achievements has been the cellulose etherification using glycidol (1,2-epoxy-3-hydroxypropane) under heterogeneous slurry conditions [1]. Glycidol was selected as the electrophile because it enables the synthesis of water-soluble 2,3-dihydroxypropyl cellulose (DHPC) and is potentially bio-derived and less hazardous than ethylene oxide or methyl chloride, owing to its higher boiling point. We explored a wide range of etherification conditions with glycidol in a conventional heterogeneous slurry phase. The reaction composition, temperature, time, mixing procedure, and the hydrophobicity of the organic solvent were systematically varied to optimize the cellulose etherification. These efforts resulted in high glycidol utilization, even with a very low concentration of sodium hydroxide. Extensive polymer characterization using NMR, turbidimetry, and viscometry provided deeper insights into the structure–property relationships of the resulting DHPC.

Another notable achievement was the development of degradable cellulose-based thermosets via UV curing [2]. Cellulose was first converted to cellulose acetate allyl carbonate using a CO₂/DBU/DMSO solvent system. This cellulose acetate allyl carbonate was then crosslinked with a trithiol crosslinker under UV irradiation. The resulting thermosets were thoroughly evaluated through mechanical and thermal analyses and exhibited rapid degradability under alkaline conditions. Moreover, by tuning the hydrophilic/hydrophobic balance, the swelling behavior of the thermosets could be precisely controlled across a range of solvents, from water to hydrophobic media.

[1] Jaeheon Kim et al., “Cellulose Etherification with Glycidol for Aqueous Rheology Modification”, ACS Appl. Polym. Mater., 6, 11, 6714 – 6725 (2024).

[2] Jaeheon Kim et al., “Degradable Cross-Linked Cellulose Acetate Allyl Carbonate Synthesized Using CO₂/DBU/DMSO Solvent", Green Chem. advance article (2025).

Research Interests

My research focuses on developing sustainable polymeric materials using renewable resources like biomass compounds. Systematic synthesis will uncover structure-property relationships, guiding further development. Formulation studies will maximize the application of new polymers.