The synthesis and some of the physical properties of
the first poly(disulfidediamines) are reported. The disulfidediamine
functional group (R2NSSNR2) possesses a disulfide
bond in a unique environment that leads to a low bond dissociation
energy (calculated BDE of 43.1 kcal mol–1). These
polymers were synthesized in high yields and with conversions up to
>98% by reactions between secondary diamines and a new disulfide
monomer. The disulfide monomer was synthesized in two steps without
the need for column chromatography. The polymerizations were robust
and completed at room temperature, under ambient atmospheric conditions,
and in solvents that were used as purchased. These polymers were stable,
but they rapidly decomposed under acidic, aqueous conditions or by
heating to 175 °C as shown by thermal gravimetric analysis. The
first fully conjugated poly(disulfidediamine) was synthesized, and
its electrical conductivity was characterized in the solid state.