pH-/Temperature-Triggered Gel Transition of Hyperbranched PEI-g-PDMAEMA as a Dual-Responsive Inhibitor for Clay Hydration Control

To mitigate clay hydration and wellbore instability during deepwater drilling, a pH/temperature dual-responsive graft copolymer, hyperbranched polyethylenimine-g-poly(2-(dimethylamino)ethyl methacrylate) (HPEI-g-PDMAEMA), was designed and synthesized via free radical polymerization. Optimized synthesis at an HPEI/DMAEMA mass ratio of 1:2 with 2.4% AIBN at 70 °C for 10 h yielded a grafting ratio of 35.2% and a molecular weight of 84.3 kDa. The copolymer exhibits a tunable lower critical solution temperature (LCST) of approximately 48 °C at pH 8, decreasing with increasing pH due to tertiary amine deprotonation. Zeta potential measurements confirm that the polymer retains a positive charge (+5 mV at pH 8) under weakly alkaline conditions, enabling strong electrostatic anchoring onto negatively charged clay surfaces. Above the LCST, dynamic light scattering reveals a sharp increase in hydrodynamic diameter from ~30 nm to >200 nm, confirming a hydrophilic-to-hydrophobic transition of PDMAEMA segments that drives the formation of a hydrophobically associated gel barrier. This thermally triggered gelation is fully reversible, as evidenced by repeated heating–cooling cycles with almost complete transmittance recovery. The gel barrier drastically reduces water uptake, with inhibition performance against clay swelling at 60 °C being 18.5 percentage points higher than that at 25 °C. Hot-rolling tests demonstrate that with only 1.5 wt% inhibitor, shale recovery reaches 94.1% at 150 °C (8.8 percentage points higher than unmodified HPEI) and remains above 60% even in 20 wt% CaCl2 or MgCl2 brines, highlighting exceptional resistance to divalent cations. Water contact angle on treated clay surfaces increases from 18.5° to 52.6°, confirming effective surface hydrophobization. This work provides a molecular-level gel-engineering strategy where pH governs electrostatic anchoring and temperature triggers reversible hydrophobic gelation, enabling on-demand switching of clay wettability and hydration resistance under high-temperature, high-salinity conditions.