A series of highly branched random copolymers of acrylamide (AM) and N-isopropylacrylamide (NIPAM) have been prepared from a waxy potato starch-based macroinitiator by aqueous Cu 0 -mediated living radical polymerization (Cu 0 -mediated LRP). The NIPAM intake in the copolymer was varied between 0% and 50 mol % to evaluate the influence of chain composition on the aqueous rheological properties as well as their low critical solution temperature (LCST). The viscosity of the copolymer was found to increase with the NIPAM intake and an LCST can be observed when the NIPAM content is high enough (e.g., 50 mol %). In addition, thermo-thickening behavior was observed at a low shear rate (γ ≤ 10 s −1 ) and higher NIPAM content was found to shift the onset of thermo-thickening behavior to a lower temperature. However, the absolute increase in viscosity values is reduced with the NIPAM intake. Besides this, an interesting significant thermo-thickening behavior was also observed on highly branched starch-g-polyacrylamide at high temperatures (>80 • C), which has not been previously reported. Rheology tests also revealed a good salt-resistant property in copolymers with low NIPAM content (e.g., <25 mol %). Considering the viscosity profile in saline as compared to that in pure water, this NIPAM intake seems to represent an optimum balance of viscosity and salt-resistance performance.

In the present study, three different block copolymers based on styrene, tert‐butyl methacrylate, and glycidyl methacrylate (GMA) were synthesized via sequential atom transfer radical polymerization. The addition of the GMA block was found to be best performed at 60°C. The polymers were then hydrolyzed and neutralized, to afford amphiphilic block copolymers, and the rheological properties of their aqueous solutions were measured, in order to investigate solution properties relevant for enhanced oil recovery, as a function of the polymer structure. It was observed that these polymers behave as thickening agents with shear thinning behavior. As expected, the polymers were sensitive to the presence of salt, as lower viscosities were recorded in saline water. However, the viscosity is less affected by high salinity, when compared to previously studied analogous diblock systems. In the best case, the viscosity only decreased by a factor of 1.8 upon salt addition whereas it decreased by a factor of 10 in previously reported non‐GMA containing polymers. Finally, thermo‐responsive behavior was found for one of the synthesized polymers. In particular, a hydrolyzed triblock poly[styrene‐b‐tert‐butyl methacrylate‐b‐glycidyl methacrylate], which synthesis is reported here for the first time, showed a thermothickening behavior, promising for the intended application in oil recovery.