Application of the solvation parameter model to poly(methylcyanopropylsiloxane) stationary phases

The solvation parameter model has been applied to the specific retention volumes of 65 solutes of varied polarity on glass capillary columns coated with commercial and synthesized poly(methylcyanopropyl)siloxanes (CNPXX) with eight different percentages of cyanopropyl group (CNP). Their system constants were determined at 75, 90, 105 and 120 °C. The polymers examined do not either show any acidity (b = 0) or interact with solute π/n electrons (e = 0); the prominent constants, dipolarity/polarizability and hydrogen-bond basicity, are of the same order (s ≈ a), and the cavity formation/dispersive forces have normal values. Constants s, l and a decrease linearly with temperature for each cyanopropyl percentage. At each temperature, the constants s and a increase with polarity of polymer according to a curve, while the constant l decreases slightly. Cluster analysis shows that six CNPXX with medium to high cyanopropyl substitution integrate into a group with other high-polarity cyano-containing stationary phases taken from the literature, while the other three CNPXX with low CNP percentage form a group with other low-polarity stationary phases of different chemical nature. These clusters are supported by the dendrogram of 52 stationary phases made with the nine polymers presented here and other 43 taken from the literature.