Compositionally Driven Viscometric Behaviors of Poly (Alkyl Methacrylates) in Lubricating Oils

Viscosity index (VI) and shear stability index (SSI) are standard methods used in the lubricant industry to determine temperature-viscosity dependency and resistance to product degradation, respectively. A variety of oil-soluble polymers, including poly(alkyl methacrylates) (PAMAs) are routinely used to control these properties in fully-formulated liquid lubricants. In this report, we use reversible addition-fragmentation chain transfer (RAFT) polymerization to precisely target identical degrees of polymerization in a family of PAMAs with varying lauryl, hexyl, butyl, ethyl, and methyl groups. Then, expanding on previous methodology reported in the literature, we establish structure property relationships for these PAMAs, specifically looking at how intrinsic viscosity [η] and Martin interaction parameters K_M relate to VI and SSI characteristics. While the intrinsic viscosity [η] is associated with the volume of macromolecules at infinite dilution, the parameter K_M reflects the hydrodynamic interactions of polymer chains at actual polymer concentrations in lubricating oils. In this paper, we show that the dependence of VI on the non-dimensional concentration c/c* (or c[η]) can be presented in a form of master curve with shift factors proportional to K_M that decreases with increasing size of alkyl groups. This finding implies that even in the dilute regime, the coil-expansion theory used to explain the effect of macromolecules on VI should be complemented with the idea of hydrodynamic interactions between polymer molecules that can be controlled by the choice