Preparation of supramolecular viscoelastic polymers with shear, temperature, and salt resistance/sensitivity by amphiphilic functional monomer modification

Abstract

To develop high-salinity, high-temperature reservoirs, a novel supramolecular viscoelastic polymer-based fracturing fluid modified with an amphiphilic functional monomer was developed. Investigation of the thickening ability, solubility, and rheology revealed that the as-developed gel system with a rigid hydrophobically associating space network structure and linear entanglement can improve the thickening ability, solubility, temperature adaptation range, and chemical environment resistance sensitivity of supramolecular polymers. The surface/interfacial tension test revealed that the modified polymers exhibit surface and interface activity. At an MHAP-15 concentration of 1500 mg/L, the surface tension was 39.29 Nm/m. At an MHAP-15 concentration of 800 mg/L, a minimum interfacial tension of 0.86 Nm/m was observed. The shear sensitivity test revealed that the copolymer fluid exhibits a high creep recovery performance and elastic response as well as a 100% viscosity recovery rate. In addition, the viscoelasticity and thixotropy of the copolymer solution were investigated. The results revealed that the higher the number of the oxyethylene groups in amphiphilic functional monomers, the higher the increase in the viscous modulus of the copolymer solution. In the modified polymer, the highest energy was required for the destruction of the MHAP-15 solution, reaching 66.5 Pa; this result confirmed the best synergistic effect of hydrophobic association and linear entanglement of the MHAP-15 solution molecules, as well as the best temperature and salt resistance. The viscosity of 0.6 wt% MHAP-15 was 120 mPa s after shearing for 50 min at 120 °C and at 170 s−1. At 160 °C and 100 s−1, the viscosity of the 0.8 wt% MHAP-15 polymer solution reached 153 mPa s after shearing for 50 min. At a NaCl concentration of 25 × 104 mg/L, the viscosities of the 0.6 wt% and 0.8 wt% MHAP-15 solutions were 203 and 245 mPa s, respectively, indicative of the stimulation response of salt thickening. At a CaCl2 concentration of 2 × 104 mg/L, the viscosity of 0.6 wt% MHAP-15 was 87 mPa s, and the viscosity retention rate was 47.9%. Finally, by X-ray diffraction, the particle size test in solution, and scanning electron microscopy, the higher the number of oxyethylene groups in the amphiphilic functional monomers, the higher the mixing entropy of copolymers, and the particle size in solution and multi-peak distribution were higher, as well as more clear linear entanglement between copolymers; all of these factors were conducive to the formation of large-scale supramolecular structures of super-bridged copolymers.