Fudan University models thermogelling polymer synthesis from atoms to reactor

Researchers from Fudan University have established a multiscale modeling methodology to design and synthesize complex polymers from the molecular scale up to chemical reactor operations, according to a study published in 中国科学通报：英文版 sciencedirect.com中国科学通报：英文版sciencedirect.comOpen source ↗. The team demonstrated the approach on amphiphilic poly(lactide-co-glycolide)-b-poly(ethylene glycol)-b-poly(lactide-co-glycolide) (PLGA-PEG-PLGA), a polymer system capable of forming physical hydrogels upon heating. All calculations and workflow simulations were executed on a standard personal computer.

Polymer properties in solution depend on molecular weight, chain sequence distribution, and self-assembly behavior, which are typically challenging to predict simultaneously from first principles. The proposed "4+1" strategy combines four numerical methods—density functional theory, kinetic Monte Carlo simulation, dynamic Monte Carlo simulation, and flowsheet synthesis—coupled through a single experimental mapping step. This feedback-loop experiment connects calculated quantum activation energy barriers to empirical polymerization rate constants, while a coarse-grained model simplifies polymer chains for dynamic assembly simulations.

Multiscale kinetics

The synthesis of PLGA-PEG-PLGA was tracked across 24 elementary reactions, consisting of 12 ring-opening polymerizations and 12 ester exchange reactions. The framework covered 19 temporal and 12 spatial scales, capturing distinct kinetic regimes during the process. The simulations demonstrated that monomer conversion, molar mass dispersity, and macromolecular chain sequence reach equilibrium at sequentially different stages of the reaction.

Condensed state control

Simulations and physical experiments confirmed that sampling the synthesis mixture at different time intervals yields products with markedly different behavior in aqueous solutions sciencedirect.com中国科学通报：英文版sciencedirect.comOpen source ↗. Even when polymers possessed similar number-average molecular weights, varying chain distributions produced either liquid sols, macroscopic precipitates, or reversible physical thermogels upon heating. The authors reported that the overall workflow provides a systematic route for predicting condensed states and scaling up functional block copolymers for industrial-scale manufacturing.