Inverse Design of Comb-Shaped Polyolefin Elastomers via Deterministic Microstructure Modeling and Optimization

A deterministic modeling and optimization framework is developed for the precise microstructure control of comb-shaped polyolefin elastomers (CPOEs). By incorporating a positional variable into a population balance equation model, the grafting distribution of polyethylene (PE) side chains along copolymer backbones is captured, enabling simultaneous prediction of molecular weight distribution (MWD) and long-chain branching distribution (LCBD). To achieve real-time applicability, the high-dimensional differential-algebraic system is efficiently solved using orthogonal collocation on finite elements, providing a ∼3077-fold speedup over kinetic Monte Carlo methods. Microstructure-oriented multiobjective optimization is formulated for both batch and continuous processes to maximize monomer conversion while minimizing residual macromonomers. The optimization follows the principle of inverse design, where desired MWD and LCBD profiles guide the identification of optimal operating strategies. The proposed approach successfully identifies optimal reactor configurations, catalyst feed strategies, and operating conditions, enabling coordinated regulation of MWD and LCBD in CPOE synthesis.