New Polymers Possessing a Disulfide Bond in a Unique Environment

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.