A Comprehensive Monte Carlo Model of the Grafting of Maleic Anhydride onto Polypropylene with Experimental Validation

Abstract

A Monte Carlo model is employed to investigate the grafting of maleic anhydride onto polypropylene using a peroxide initiator. The study aimed to develop a comprehensive model that considered a very detailed kinetic mechanism, including chain transfer to polymer, homopolymerization as well as several copolymer reactions. The relative importance of these reactions is evaluated using a sensitivity analysis, which identified homopolymerization, β‐scission, chain grafting, and termination by disproportionation as the most influential reactions. The kinetic constants of these reactions are tuned to fit reported experimental data using the Surface Response Method. The model considers a pseudo‐homogeneous reaction medium and predicts average molecular weights, degree of grafting, molecular weight distribution, and grafting distribution. Furthermore, model simulations provided useful information about the impact of initial concentrations of reactants and reaction time on the molecular properties of the grafted polymer.

Functionalization of Polyolefins with Maleic Anhydride by Flash Reactive Extrusion: Processing and Applications

“…Despite extensive research, the degradation mechanism of polyolefins such as polyethylene is still not fully understood and remains scarcely unclear due to the complexity of the involved radical reactions. , The generation of free radicals during the degradation of polyolefins can be exploited for chemical recycling when new reactive molecules are added in the reaction media to functionalize the polyolefins by radical addition reactions. This has been demonstrated through the free radical addition of polar comonomers such as maleic anhydride, − glycidyl methacrylate, acrylic acid, and other vinyl molecules. − Polyolefins grafted with maleic anhydride, i.e. polyethylene grafted with maleic anhydride (PE- g -MA) as a polar comonomer, are commercially available products that improve adhesion and miscibility between polar and nonpolar components .…”