Effect of cosolvent on the rheological properties and self-assembled structures from telechelic polyampholytes

A triblock copolymer with hydrophobic end blocks and a polyampholytic middle block is investigated in a mixture of water and acetone with a focus on the dependence of the rheological properties and of the micellar structure and correlation on the content of acetone. The polymer under study is PMMA₈₆-b-P(DEA₁₉₀-co-MAA₉₆)-b-PMMA₈₆, where PMMA stands for poly(methyl methacrylate) and P(DEA-co-MAA) for poly(2-(diethylamino) ethyl methacrylate-co-methacrylic acid). The pH is chosen at 3. Rheological measurements reveal a transition from a viscoelastic solid over a viscoelastic liquid to a freely flowing liquid upon addition of 5 or 10 wt% of acetone to a 3 wt% aqueous polymer solution, respectively. Using small-angle neutron scattering on 0.5 wt% polymer solutions in water/acetone with the content of the latter ranging between 0 and 30 wt%, significant structural changes are observed as well, such as a decrease of the distance between the PMMA cross-links and of the size of the network clusters upon increasing acetone constant. These changes are attributed to the reduction of the dielectric constant by the addition of the cosolvent acetone, enhancing the flexibility of the middle blocks and their tendency to backfolding, as well as to the decrease of the solvent selectivity, inducing significant exchange rate enhancement of the core-forming PMMA blocks.