Anionic polymerization of exo-3,4,5-trithiatetracyclo[5.5.1.O2,6.O8,12]tridec-10-ene (dicyclopentadiene trisulfide) |
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Authors: | Teresa Baran Andrzej Duda Stanistaw Penczek |
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Abstract: | The anionic polymerization of exo-3,4,5-trithiatetracyclo5.5.1.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 (M n ≈ 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-trithiatricyclo5.2.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. |
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