Kinetics and Mechanism of Liquid-State Polymerization of 2,4-Hexadiyne-1,6-diyl bis -( p -toluenesulfonate) as Studied by Thermal Analysis.

A detailed investigation of the liquid-state polymerization of diacetylenes by calorimetric (DSC) and spectroscopic (in situ EPR) thermal analysis techniques is performed. Isoconversional kinetic analysis of the calorimetric data reveals that liquid-state polymerization is governed by a well-defined rate-limiting step as evidenced by a nearly constant isoconversional activation energy. By comparison, solid-state polymerization demonstrates isoconversional activation energy that varies widely, signifying multistep kinetics behavior. Unlike the solid-state reaction that demonstrates an autocatalytic behavior, liquid-state polymerization follows a rather unusual zero-order reaction model as established by both DSC and EPR data. Both techniques have also determined strikingly similar Arrhenius parameters for liquid-state polymerization. Relative to the solid-state process, liquid-state polymerization results in quantitative elimination of the p -toluenesulfonate group and the formation of p -toluenesulfonic acid and a polymeric product of markedly different chemical and phase composition.