Uncharged Lewis bases yield polydimethylsiloxane ionomers with amidinium alkyldithiocarbamate side chains

Abstract Ionomers exhibiting good thermal stability have been prepared by mixing three uncharged components—a poly(dimethyl)siloxane (PDMS) with randomly substituted amidine side chains, an alkylamine, and carbon disulfide. In essence, the three uncharged components produce charged materials, polyelectrolytes with amidinium dithiocarbamate ion pairs . The preparation, structures, and properties of the ionomers at the microscopic and macroscopic levels are reported as a function of PDMS chain length, degree of amidine substitution, and length of the alky group of the amine component. Whereas ionomers with hexyldithiocarbamate anions are viscous liquids at room temperature, those with octadecyldithiocarbamate groups are semi‐crystalline solids, exhibiting multiple thermal transitions between 0 °C and the temperature at which they become isotropic phases. The structural natures of those transitions have been characterized from analyses of data from differential scanning calorimetry, X‐ray diffraction, and rheology measurements. Among the interesting properties exhibited by the ionomers are strong adhesion to different surfaces, and high ultimate shear stress considering their relatively low amidinium contents.