Hydrophobically modified associative polymer solutions: Rheology and microstructure in the presence of nonionic surfactants

We report on the rheology and morphology of a hydrophobically modified alkali-swellable emulsion (HASE) polymer solubilized in alkaline media containing nonionic surfactants. The HASE polymer consists of complex alkylaryl hydrophobes composed of oligomeric nonylphenol condensates attached to a poly(ethyl acrylate-co-methacrylic acid) backbone. The complex linear viscoelastic response of the polymer in alkaline solution suggests an unentangled network with an appreciable fraction of microgel. The concentration and hydrophile-lipophile balance (HLB) of nonionic surfactants profoundly affect the solution rheology. A surfactant of high HLB inhibits the dynamic network connectivity of the HASE polymer, as demonstrated by reductions of both the steady-shear viscosity and the dynamic storage modulus. The shear-induced structuring previously reported for this polymer is also progressively diminished as the surfactant concentration is increased. In contrast, the addition of a low-HLB surfactant promotes system structuring, as evidenced by (i) increases in the shear viscosity and the high-frequency plateau modulus and (ii) retention of the ability to undergo shear-induced structuring. We also employ cryofracture-replication transmission electron microscopy for the first time with regard to HASE associative polymers to examine the morphological characteristics of selected systems. The morphology of the HASE polymer in both latex and solubilized form appears more complex than previously anticipated, and a reasonable interpretation of these new data is provided.