Abstract
AbstractFree radical copolymerization of SO2 with 1‐alkynes (AY) was studied by evaluation of the copolymerization rate under controlled conditions of copolymerization temperature and monomer concentration product ([AY][SO2]). The poly(alkyne sulfone)s always contained equimolar units of SO2 and alkyne, regardless of the copolymerization conditions. Using 1‐hexyne (HY) and 1‐octyne (OY) as comonomers of SO2, the values of ceiling temperature (Tc) were determined: when [HY][SO2] = [OY][SO2] = 0.25 mol2/L2, the values of Tc were 90.5 and 84.5°C, respectively. Tc increases with increasing monomer concentration product. The activation energies for propagation (Ep) and depropagation (Ed) of the SO2‐alkynes copolymerization system were investigated, using the SO2OY copolymerization system, and estimated to be 12.2 and 26.7 kcal/mol, respectively. The value of Ed is high compared with that of the copolymerization of SO2 and 1‐butene (20.3 kcal/mol), demonstrating that the free radical endings (∼ OYSO2 and ∼ SO2OY) are difficult to depropagate, compared with those formed from the copolymerizaton of SO2 and 1‐butene. ΔS and ΔHp, calculated from experiments, were found to be −37.7 cal/mol K and −14.3 kcal/mol, respectively
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