Synthesis and characterization of chitosan-based graft copolymers with temperature-switchable and self-adaptive plugging performance for drilling in microporous formation

Abstract

The increasing oil–gas explorations in microporous formations and the intensified environmental requirements necessitate the development of high-performance, environmentally friendly and sustainable plugging materials to maintain wellbore stability in drilling engineering. In this work, a series of graft copolymers of carboxymethyl chitosan-g-poly(oligo(ethylene glycol) methyl ether methacrylate-co-acrylic acid) (GCOA) is synthesized through free-radical graft-from polymerization. The oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and acrylic acid (AA) can be well copolymerized in the grafts as confirmed by structural characterizations, and the incorporation of AA improves the grafting ratio and grafting efficiency. All obtained GCOAs possess the temperature-responsive aggregation behavior, which causes the formation of aggregated meso-assemblies from original nano-micelles when heating above their lower critical solution temperature (LCST), accompanied by the phase separation. Meanwhile, the presence of AA segments increases the LCST due to the resistance of enhanced polymer–polymer electrostatic repulsion to the hydrophobic attraction. By the delicate control of AA molar ratio from 0 to 50 mol%, the LCST values of GCOAs can be adjusted from 90 °C to 110 °C. Furthermore, the GCOAs are formulated as smart plugging fluids and the intelligent plugging evaluation method is established based on core flow test with continuous temperature control. The results indicate that the GCOAs can form effective plugging in both low- and median-permeability cores when temperature reaches above a switching point and the formed plugging can be partially removed after cooling, showing the temperature-switchable and self-adaptive plugging capacity as a consequence of reversible retention of GCOA aggregates and thermo-thickening behavior in pore-throat spaces. These features enable the implementation and removal of in-situ plugging in the specific temperature sections during drilling, and provide a new insight into the design of novel smart plugging materials with sustainable and recycling values.