Structure-activity relationships for hydration inhibition and environmental protection with modified branched polyethyleneimine: Experiments and simulations

Inhibiting the surface hydration of clay is the main task for the water-based drilling fluids used in the development of shale gas. Branching polyethyleneimine (BPEI) completely inhibits the clay surface hydration. However, the use of BPEI is limited by its high toxicity. In this paper, BPEI was modified by grafting with hydroxyethyl groups to reduce the toxicities of BPEI hydration inhibitors. The structures and properties of the modified BPEI were characterized by infrared spectroscopy, mass spectrometry, the luminescent bacteria method, isothermal adsorption, X-ray diffraction, thermogravimetric analysis, contact angle measurement, scanning electron microscopy, X-ray photoelectron spectroscopy and molecular simulations. The relative luminescence rate of the modified BPEI inhibitors increased from 14 % to 62 % with increases in the number of grafted hydroxyethyl groups. After hydrated sodium montmorillonite (Na–Mt) contacted the modified BPEI inhibitors, the basal spacings of the Na–Mt decreased from 1.90 nm to a minimum of 1.40 nm, and the DTG curve had only one low-temperature peak. Molecular simulations showed that the energy for adsorption of the inhibitor on the Mt surface increased with increases in the number of grafted hydroxyethyl groups. These results suggested a structure-activity relationship for inhibition and the biological toxicity of the modified BPEI inhibitor. That is, within the range of 20:1 to 5:1 for the molar ratios of amino and hydroxyl groups, increases in the number of grafted hydroxyethyl groups gradually decreased the biological toxicities of BPEI inhibitors, and the inhibition performance was gradually enhanced. BPEI-OH4 (amino:hydroxyl = 5:1) showed the best performance among the modified BPEI inhibitors. This provides an excellent inhibitor and a low-toxicity modification method, which will facilitate the development of environmentally friendly high-performance water-based drilling fluids.