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The rheological characteristics of anionic colloidal unimolecular polymer (CUP) particles in water were investigated. The intrinsic viscosities were determined for CUPs with different molecular weights as a function of volume fraction. The specific viscosities were measured and fit with models considering hydrodynamic interaction and electroviscous effects. The rheological characteristics were consistent with a surface layer of water which increases with the particle size or molecular weight of CUPs. The effective charges on the surface of particle were calculated and correlated with the rheological behavior of the CUP particles from the dilute to semidilute range, a volume fraction of 0.0001–0.08.

For convenience in handling this volatile diene, it was converted to dimethyl phthalate by Diels-Alder reaction with dimethyl acetylenedicarboxylate as described in this reference before deuterium analysis. (12) E.

Colloidal Unimolecular Polymer (CUP) particles are spheroidal, 3–9 nm with charged groups on the surface and a hydrophobic core, which offer a larger surface water fraction to improve the analysis of its characteristics. Differential scanning calorimetry (DSC) was performed to determine the characteristics of surface water. These properties include the amount of surface water, the layer thickness, density, specific heat of the surface water above and below the freezing point of water, melting point depression of free water, effect of charge density and particle size. The charge density on the CUP surface was varied as well as the molecular weight which controls the particle diameter. The surface water is proportional to the weight fraction of CUP <20%. Analogous to recrystallization the CUP particles were trapped in the ice when rapidly cooled but slow cooling excluded the CUP, causing inter-molecular counterion condensation and less surface water. The density of surface water was calculated to be 1.023 g/mL to 1.056 g/mL depending on the surface charge density. The thickness of surface water increased with surface charge density. The specific heat of surface water was found to be 3.04 to 3.07 J/g·K at 253.15 K and 3.07 to 3.09 J/g·K at 293.15 K. The average area occupied by carboxylate and ester groups on the CUP surface were determined.