The design of new dual-function inhibitors simultaneously preventing hydrate formation and corrosion is a relevant issue for the oil and gas industry. The structure-property relationship for a promising class of hybrid inhibitors based on waterborne polyurethanes (WPU) was studied in this work. Variation of diethanolamines differing in the size and branching of N-substituents (methyl, n-butyl, and tert-butyl), as well as the amount of these groups, allowed the structure of polymer molecules to be preset during their synthesis. To assess the hydrate and corrosion inhibition efficiency of developed reagents pressurized rocking cells, electrochemistry and weight-loss techniques were used. A distinct effect of these variables altering the hydrophobicity of obtained compounds on their target properties was revealed. Polymers with increased content of diethanolamine fragments with n- or tert-butyl as N-substituent (WPU-6 and WPU-7, respectively) worked as dual-function inhibitors, showing nearly the same efficiency as commercial ones at low concentration (0.25 wt%), with the branched one (tert-butyl; WPU-7) turning out to be more effective as a corrosion inhibitor. Commercial kinetic hydrate inhibitor Luvicap 55 W and corrosion inhibitor Armohib CI-28 were taken as reference samples. Preliminary study reveals that WPU-6 and WPU-7 polyurethanes as well as Luvicap 55 W are all poorly biodegradable compounds; BODt/CODcr (ratio of Biochemical oxygen demand and Chemical oxygen demand) value is 0.234 and 0.294 for WPU-6 and WPU-7, respectively, compared to 0.251 for commercial kinetic hydrate inhibitor Luvicap 55 W. Since the obtained polyurethanes have a bifunctional effect and operate at low enough concentrations, their employment is expected to reduce both operating costs and environmental impact.

The efficiency of corrosion inhibition for waterborne polyurethane based on N-tert-butyl diethanolamine (tB-WPU) is investigated using different techniques. Corrosion weight loss, open circuit potential experiments, electrochemical impedance spectroscopy, and potentiodynamic polarization measurements show that both a commercial reagent and a polyurethane-based inhibitor prevent corrosion at increasing temperature to 50 °C. At 75 °C, the activity of both reagents is reduced. In stirring conditions, the effectiveness of acid corrosion inhibition (25 °C, 500 ppm) drops abruptly from 89.5% to 60.7%, which is related presumably to the complexity of binding the polymer molecules to the metal surface. As follows from thermodynamic calculations, the adsorption of tB-WPU on the metal surface in 2M HCl can be treated as a physisorption. Model quantum–chemical calculations support the experimental studies and elucidate the nature of steel surface–inhibitor molecule chemical bond, which is realized mainly by carboxyl and amino groups. It is concluded that WPUs can be considered as a perspective alternative to commercial oilfield reagents due to their versatility.