Understanding and Controlling the Multistep Crystallization of Fatty Acid Cellulose Esters

• Published in: Biomacromolecules Vol. 26; no. 8; pp. 4872 - 4885
• Main Authors: Breuer, Carina, Sprandl, Linus, Soltwedel, Olaf, von Klitzing, Regine, Geissler, Andreas, Biesalski, Markus
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 11.08.2025
• Subjects: Calorimetry, Differential Scanning; Cellulose - chemistry; Crystallization; Esters - chemistry; Fatty Acids - chemistry; Rheology; X-Ray Diffraction
• ISSN: 1525-7797; 1526-4602; 1526-4602
• DOI: 10.1021/acs.biomac.5c00278

Fatty acid cellulose esters (FACEs) have great potential as biogenic alternatives to petroleum-based plastics. Nevertheless, their thermal property profiles have been the subject of controversial discussion, particularly with respect to their crystallization behavior. A thorough understanding of the crystallization behavior of FACEs is fundamentally important for gaining deep insights into their solid-state characteristics and thermal properties. This systematic study succeeds in elucidating the crystallization behavior of FACEs as bulk materials. Differential scanning calorimetry combined with rheological analysis and X-ray diffraction of cellulose esters bearing side chains with varying numbers of fatty acid residues (C-12–C-20) and degrees of substitution (ranging from partial to full esterification, i.e., 0.1–3.0) revealed that crystallization of FACEs occurs in multiple stages. These stages involve the distinct crystallization of inter and intramolecular side chains and polysaccharide backbones. A quantitative multistep crystallization mechanism is proposed based on the study findings.