Rheological and small-angle neutron scattering studies of aqueous solutions of branched PEO-PPO-PEO copolymers

Tetronic® 908 is a four-branched copolymer comprised of polyethylene oxide (PEO) and polypropylene oxide (PPO) blocks fixed on an aliphatic diamine. In aqueous solution, this polymer has an amphiphilic character due to the difference in PEO and PPO solubilities with increase in temperature. This system presents interesting rheological properties depending on the polymer concentration in solution and temperature. At low temperatures and/or concentrations, the solution behaves as a Newtonian fluid. For a weight percentage p comprised between 2% and 22%, the viscosity of the solution goes through a maximum. Small-angle neutron scattering experiments show that the increase in viscosity is due to progressive aggregation of chains. For weight percentages higher than $p=22\%,$ the viscosity of the system diverges and the mixture becomes gel-like. In fact, spectromechanical measurements show that the solution behaves as an entangled polymer with a high relaxation time in the flow zone. Small-angle neutron scattering (SANS) studies of the same solution reveal the presence of several peaks indicating that the micelles are organized in a cubic structure. We have developed a model that suitably describes the SANS curves of this system in the region where micelles are formed. Our model considers that micelles are trilayered spherical entities that coexist with unimers by obeying an equilibrium reaction. Moreover, it allows the calculation of several parameters such as the volume fraction of micelles, their size, and composition. The evolution of these parameters with temperature and polymer concentration is detailed. Comparisons with literature models are presented and discussed. This compilation of results has permitted the establishment of precise relations between the structure of this polymer in solution and its rheological properties.