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Being an important class of water-soluble synthetic polymers, polyacrylamide (PAM) and its derivatives have found a wide range of applications in the oil and gas industry. Due to the increasingly active exploration of deep and ultra-deep wells, PAM-based polymers are more and more frequently applied under hostile subterranean conditions, particularly high temperature. Therefore, it becomes an imminent research topic to elucidate the thermal degradation pathways of PAM-based polymers in order to upgrade these chemicals for more challenging scenarios. Neighboring groups attached to the same polyvinyl backbone have been suggested to exert an effect to the degradation of the PAM-based polymers. Herein we report a combined theoretical and experimental study on the energetics of such neighboring group effect. Taking advantage of a computational method based on density functional theory, we have identified two competing degradation pathways in neutral medium and have calculated their respective activation energies. These results enable us to predict the relative thermal stabilities of a series of PAM-based polymers, and we have also used temperature-variant rheology measurements to verify these predictions. This work will guide the design of better heat-resistant PAM-based products.

Traditional Shilov reactions (performed in aqueous solution with a PtCl2catalyst) for methane conversion suffer from catalyst deactivation at high temperatures (> 100 °C), therefore only very low conversion rates have been achieved. In this paper, we show that Shilov-type C–H activations are achievable at much higher temperatures (∼200 °C) by addition of concentrated aqueous solutions of Cl−to inhibit Pt catalyst precipitation. Various chloride-based ionic liquids also stabilized the Pt catalyst at mild reaction temperatures (∼140 °C). Under high-pressure conditions (> 25.5 MPa), achieved using a specially designed sealed gold-tube reactor, very high methane conversion rates (> 90%) were obtained; this is attributed to the improved methane solubility in aqueous solution. Deuterium isotope (H/D) exchange between methane and water was used to examine the reaction reactivity and selectivity. Multiply D-substituted products were observed, indicating that multiple C–H activations occurred. A comprehensive network reaction that included all the chain reactions was set up to clarify the reactivities and product selectivities of the methane activation reactions. The reaction network consisted of a series of parallel first-order reactions, which can be described by the Arrhenius equation. The kinetic parameters such as the frequency factor, activation energies, and stoichiometric coefficients were obtained by fitting the experimental data. Because all four C–H bonds in a methane molecule are equivalent, multiple substitutions during methane conversion cannot be avoided. Our studies indicate that mono-substituted and di-substituted methane isotopologue generations have similar activation energies, suggesting that the highest mono-substitution selectivity cannot be greater than 50%.