Anionic polymerization of exo‐3,4,5‐trithiatetracyclo[5.5.1.O2,6.O8,12]tridec‐10‐ene (dicyclopentadiene trisulfide)

The anionic polymerization of exo‐3,4,5‐trithiatetracyclo[5.5.1.O2,6.O8,12]tridec‐10‐ene (1) in bulk and/or in aromatic solvents (benzene, toluene) was studied. The polymerization was initiated with sodium benzenethiolate (sodium cation complexed with dibenzo‐18‐crown‐6). Polymers with high‐molecular weights were obtained (Mn ≈ 105, osmometrically). The polymerization was found to be living and reversible; the equilibrium monomer concentration increases with the temperature. The ceilling temperature was estimated as 167°C. The thermodynamic data of the polymerization in toluene was determined and compared with those of the polymerization of exo‐3,4,5‐trithiatricyclo[5.2.O2,6]decane. The standard enthalpy ΔH = −(6,6 ± 0,6)kJ · mol 1 and entropy ΔS = −(29,3 ± 2,1)J · mol 1 · K 1 of the polymerization of 1 were evaluated from the temperature dependence of the equilibrium monomer concentration, determined dilatometrically.