Effects of Ring Opening and Chemical Modification on the Properties of Dry and Moist Cellulose─Predictions with Molecular Dynamics Simulations

Biomacromolecules. 2024 Dec 9;25(12):7581-7593. doi: 10.1021/acs.biomac.4c00735. Epub 2024 Nov 25.

Abstract

Thermoplastic properties in cellulosic materials can be achieved by opening the glucose rings in cellulose and introducing new functional groups. Using molecular dynamics, we simulated amorphous cellulose and eight modified versions under dry and moist conditions. Modifications included ring openings and functionalization with hydroxy, aldehyde, hydroxylamine, and carboxyl groups. These modifications were analyzed for density, glass transition temperature, thermal expansivity, hydrogen bond features, changes in energy term contributions during deformation, diffusivity, free volume, and tensile properties. All ring-opened systems exhibited higher molecular mobility, which, consequently, improved thermoplasticity (processability) compared to that of the unmodified amorphous cellulose. Dialcohol cellulose and hydroxylamine-functionalized cellulose were identified as particularly interesting due to their combination of high molecular mobility at processing temperatures (425 K) and high stiffness and strength at room temperature (300 K). Water and smaller side groups improved processability, indicating that both steric effects and electrostatics have a key role in determining the processability of polymers.

MeSH terms

  • Cellulose* / chemistry
  • Hydrogen Bonding
  • Molecular Dynamics Simulation*
  • Temperature
  • Tensile Strength
  • Water / chemistry

Substances

  • Cellulose
  • Water