Daniela E. Ortega

Understanding the catalytic behavior of heterogeneous systems for the copolymerization of ethylene with polar monomers is essential for developing advanced functional polyolefins. In this study, we conducted a quantum chemical investigation of the SiO₂-supported Ni–allyl–α-imine ketone catalyst (Ni-OH@SiO₂) to uncover the factors governing monomer insertion, selectivity, and reactivity. Using DFT calculations and energy decomposition analysis (ALMO-EDA), we evaluated the coordination and insertion of six industrially relevant polar monomers, comparing their behavior to ethylene homopolymerization. Our results show that special polar monomers (SPMs) with aliphatic spacers, such as vinyltrimethoxysilane (vTMS) and 5-hexenyl acetate (AMA), exhibit favorable insertion profiles due to enhanced electrostatic and orbital interactions with minimal steric hindrance. In contrast, fundamental polar monomers (FPMs), including methyl acrylate (MA) and vinyl chloride (vCl), show higher activation barriers and increased Pauli repulsion due to strong electron-withdrawing effects and conjugation with the vinyl group. AMA displayed the lowest activation barrier (7.4 kcal/mol) and highest insertion thermodynamic stability (−17.6 kcal/mol). These findings provide molecular-level insight into insertion mechanisms and comonomer selectivity in Ni–allyl catalysts supported on silica, extending experimental understanding. This work establishes key structure–reactivity relationships and offers design principles for developing efficient Ni-based heterogeneous catalysts for polar monomer copolymerization.

Furan/maleimide dynamic covalent chemistry has been extensively used to fabricate re-workable and self-healing thermosets. Understanding the relationship between crosslinker structure, network dynamics, and material final properties, however, remains a challenge. This study introduces self-healing and shape-memory thermosets derived from furan-functionalized polyketones (PKFU) crosslinked with aromatic bis-maleimides, i.e., 1,1′-(methylenedi-4,1-phenylene)bis-maleimide (BISM1) and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BISM2), via a thermally reversible Diels-Alder reaction. Polyketones were chemically modified with furfurylamine through the Paal-Knorr reaction, achieving varying furan grafting ratios. The resulting networks, characterized by ATR-FTIR, ¹H-NMR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and rheology, demonstrated tunable thermomechanical properties. BISM2-based thermosets exhibited enhanced thermal stability and reversibility over a broad temperature range (20–120 °C), with a shape recovery ratio of up to 89% and complete self-healing at 120 °C within 5 min. These findings highlight the potential of polyketone-based thermosets for applications requiring adaptive thermomechanical properties, efficient self-repair, and sustainability.

Context This study investigates the ethylene insertion reaction mechanism for polymerization catalysis, aiming to discern differences between Ni-α-imine ketone–type catalyst and their SiO₂-supported counterpart. The reaction force analysis unveils a more intricate mechanism with SiO₂ support, shedding light on unexplored factors and elucidating the observed lower catalytic activity. Furthermore, reactivity indexes suggest earlier ethylene activation in the supported catalyst, potentially enhancing overall selectivity. Finally, the reaction electronic flux analysis provides detailed insights into the electronic activity at each step of the reaction mechanism. In sum, this study offers a comprehensive understanding of the ethylene insertion reaction mechanism in both molecular and supported catalysts, underscoring the pivotal role of structural and electronic factors in catalytic processes. Methods Density functional theory (DFT) calculations were conducted using the ωB97XD functional and the 6–31 + G(d,p) basis sets with Gaussian16 software. Computational techniques utilized in this study encompassed the IRC method, reaction force analysis, and evaluation of electronic descriptors such as electronic chemical potential, molecular hardness, and electrophilicity reactivity indexes. Additionally, reaction electronic flux analysis was employed to investigate electronic activity along the reaction coordinate.