Kinetics of Polycycloaddition of Flexible α-Azide-ω-Alkynes Having Different Spacer Length.

Two flexible α-azide-ω-alkynes differing in the length of the hydrocarbon spacers (C vs. C) between functional groups are synthesized. Their bulk polymerization kinetics is studied by differential scanning calorimetry (DSC) and parameterized with the aid of isoconversional methodology.

Probing kinetic and mechanistic features of bulk azide-alkyne cycloaddition.

Bulk azide-alkyne cycloaddition between 1-azidodecane and phenyl propargyl ether is studied in detail under the conditions of linear heating. The reaction mechanism involves two parallel channels that respectively yield isomeric 1,4- and 1,5-adducts. Remarkably, the ratio of the isomer amounts remains practically the same at different heating rates.