Tailoring HASE rheology through polymer design: Effects of hydrophobe size, acid content, and molecular weight

Abstract

Hydrophobically modified alkali-soluble emulsion (HASE) polymers are an important class of rheology modifiers for waterborne coatings applications. They are typically prepared as terpolymers by emulsion polymerization of ethyl acrylate (EA), methacrylic acid (MAA), and an associative macromonomer. The viscosity development and shear responses of HASE solutions depend on a number of factors. This article presents rheological data reflecting the impacts of three key variables: hydrophobe size, acid content, and molecular weight, on model HASE thickening and rheological performance. The relative contributions of hydrophobic association, chain expansion, and polymer chain length are discussed. In steady shear flow, all thickener solutions approached some constant low-shear viscosity at small deformation rates. At the same molar composition, larger hydrophobe size resulted in higher viscosity development and greater shear thinning behavior. The amount of acid monomer in HASE polymers can influence the balance between hydrophobic attraction and electrostatic repulsion forces. It was found that a minimum of 15 wt% MAA was required to effect dissolution and thickening of the model HASE polymers. Increasing the MAA level yielded higher zero-shear viscosity and storage modulus G’ with maximal values being obtained at 40% MAA. The molecular weight of the model thickeners was controlled by the amount of chain transfer agent (CTA) added during polymerization. When the CTA level was below 0.1 wt% based on total monomers, the polymer solutions displayed shear-thinning behavior. A small increase in CTA concentration beyond 0.1% resulted in a dramatic change to Newtonian flow, and the solution viscosity was nearly two orders of magnitude lower. The model thickeners were also tested in a vinyl acrylic architectural paint formulation. The effects of each individual factor on paint thickener efficiency, high-shear, and low-shear properties are discussed and compared with solution rheology for predictive relationships.