This paper describes the rheological behavior of a HEUR (hydrophobic ethoxylated urethane) associative polymer with C16H33 end groups at 2.0 wt % concentration in aqueous solution. Under normal steady shear, this solution exhibits Newtonian behavior at low shear rates and, as the shear rate is increased, passes through a shear-thickening region before exhibiting a sharp decrease in viscosity. Here we report superposition-of-oscillation experiments on steady-shear flows to examine the state of the network structure under different shear conditions. The technique involves applying a steady shear deformation to the fluid, and once the steady state is achieved, a small amplitude oscillation is imposed on the sample to measure the linear viscoelastic properties. We observe that within the shear-thickening region, the plateau modulus is larger than in the Newtonian region, suggesting that shear-thickening is the result of a shear-induced increase in the density of mechanically active chains, which may be due to incorporation of free micelles or higher aggregates into the network structure. In the shear-thinning region, the Maxwell relaxation time decreases with increasing shear stress or shear rate. Thus shear thinning is a consequence of a shear-enhanced exit rate of the hydrophobic end groups from the micellar junctions of the network. This is the first experimental evidence for shear enhancement of the relaxation rate of an associative polymer network.

The rheological properties of 1 wt % aqueous solutions (at pH between 8.7 and 9.5) of model associative (HASE) polymers are presented. These polymers are the polymerization product of methacrylic acid, ethyl acrylate, and macromonomers which contain hydrophobes with the alkyl chain ranging in length from C12 to C20. At high pH, the polymers form a network of temporarily associating hydrophobic junctions, resulting in an enhancement of the shear viscosity which increases with the hydrophobe chain length. Strain amplitude sweep results show that the strength of the hydrophobic association increases with the length of the hydrophobe. This is also reflected in the increase in the ratio of the elastic to viscous components of the linear viscoelastic properties. When sheared beyond its equilibrium state, the associative polymers display a terminal (second-order) viscoelastic behavior at higher frequencies as the network is increasingly being disrupted by higher applied stresses. The general behavior of the polymers changes from Zimm-like to Rouse-like, and to reptation-type with a crossover between the storage and loss moduli curves, as the alkyl chain of the hydrophobes increases from 12 to 16, and to 20, carbon atoms. It is believed that in the unstressed state, other relaxation processes with much longer times are involved, and it is these long relaxation times which are greatly curtailed as the network is disrupted by an applied stress.

The viscoelastic properties over a range of steady shear conditions of an alkali-swellable associative polymer have been determined using the technique of superposition of oscillations upon steady shear flow, thus enabling the structure of the polymer to be investigated. The associative polymer studied consists of a backbone of methacrylic acid and ethyl acrylate to which is attached macromolecules containing C20 hydrophobes via an ethylene oxide−isocyanate linkage. A 1 wt % solution with its pH adjusted to 9.5 was used. At high pHs, the polymer solubilizes to form a network of both intra- and intermolecular associating hydrophobic junctions. The solution shows a non-power-law shear-thinning behavior:  the viscosity flow curve, when plotted against shear stress, shows two distinct regions where network rupture is prominent, at stress of 2 Pa and between 40 and 50 Pa. By superimposing small amplitude oscillations on to shear flow at constant stresses, the network structure of the polymer is unperturbed and linear viscoelastic properties of the polymer under the applied stress conditions can be obtained. At an applied stress of 2 Pa and above, both the storage and loss moduli of the polymer are greatly reduced at low frequencies, with the G‘ approaching second-order behavior and η‘ tending toward constant values. By analogy to Maxwell relaxation time, an estimate of the relaxation time of the associative polymer at different stress conditions can be made. The results show that the relaxation time is reduced by up to 4 orders of magnitude as the stress is increased from 1 to 60 Pa, while a much smaller decrease in viscosity is observed. At sufficiently high frequencies, both the storage and loss moduli show an increase above their linear viscoelastic values as the strain amplitude is increased. This behavior is believed to be dependent on the relaxation time of the polymer which is a function of the state of network disruption. Thus the technique may prove to be a powerful tool for probing the structure of network polymer in solution.

Rheological and photophysical data are presented for a hydrophobically modified alkali-soluble copolymer, of a constitution similar to materials currently employed as rheology modifiers in water-borne coatings. The copolymer comprises a polyelectrolyte backbone bearing ethoxylate side chains capped with complex alkylaryl groups of a high molar volume. In aqueous alkaline media, the hydrophobes associate dynamically, the topology of the network so formed being dependent on the polymer concentration. Photophysical studies, employing pyrene as a hydrophobic fluorescent probe, indicate the presence of hydrophobic associations. At concentrations below the coil overlap concentration, c*, these associations are predominantly intramolecular. At higher polymer concentrations, intermolecular interactions become more probable. This change in network topology is in qualitative agreement with previous theoretical considerations of associative polymer systems and is reflected in an unusually high concentration dependence of the zero shear viscosity, with η0∼c8. Evidence for shear-induced structuring in steady shear, large amplitude oscillatory shear, and parallel superposed steady and dynamic shear is presented. Such structuring is more pronounced at lower polymer concentrations, consistent with the formation of intermolecular associations at the expense of intramolecular. In contrast to the simple linear telechelic associative polymers considered in a number of previous studies, the network dynamics of the polymer are no longer represented by a single characteristic time. This deviation from a classical Maxwellian response in oscillatory shear is interpreted as a broadening of the relaxation spectrum, arising from the coexistence of both hydrophobic associations and topological entanglements. Mechanistically, stress relaxation is better envisaged in terms of “hindered reptation” [Liebler et al. (1991)] of the chains, rather than Rouse-like behavior moderated purely by the hydrophobe disengagement rate [Annable et al. (1993)].