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Demulsifiers provide an important means of breaking water‐in‐crude oil, which are formed during crude oil exploitation. In present work, twenty polyether copolymers based on polyethyleneimine (PEI) were synthesized. The interfacial properties of the PEI polyethers at the water‐crude oil interface were described by interfacial tension (IFT) and interfacial dilational modulus. The effects of position isomerism, size of intermediate and ratio of ethylene oxide (EO)/propylene oxide (PO) on the demulsification efficiency of these polyethers were studied. The results show that different positions of the EO and PO in copolymers lead to huge difference in both interfacial properties and demulsification performance. Polymers with hydrophilic core and hydrophobic tails (Ex‐mn series) are not efficient on demulsification of water‐in‐oil emulsion whereas polymers with hydrophobic core and hydrophilic tails (Px‐mn series) are. Meanwhile, Px‐mn series show higher IFT and lower interfacial dilational modulus than Ex‐mn series. In the same series, the IFT and interfacial dilational modulus decrease with decreasing EO/PO ratio. In the series with best demulsification performance (P199‐mn series), 60 min water removal rates of the polymers increase with decreasing EO/PO ratio at 65°C. In other words, the longer the hydrophobic blocks of polymers, the stronger the demulsification capacity. The effect of concentration of demulsifier on the demulsification efficiency was also investigated. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

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