Galukhin Andrey, Kachmarzhik Alexander, Rodionov Alexander, Mamin Georgy, Gafurov Marat, Vyazovkin Sergey
Alexander Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlevskaya Street, 420008 Kazan, Russia.
Institute of Physics, Kazan Federal University, 18 Kremlevskaya Street, 420008 Kazan, Russia.
Polymers (Basel). 2023 Dec 19;16(1):7. doi: 10.3390/polym16010007.
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 -toluenesulfonate group and the formation of -toluenesulfonic acid and a polymeric product of markedly different chemical and phase composition.
采用量热法（DSC）和光谱法（原位EPR）热分析技术对二乙炔的液态聚合进行了详细研究。量热数据的等转化率动力学分析表明，液态聚合受明确的限速步骤控制，这一点从几乎恒定的等转化率活化能可以看出。相比之下，固态聚合表现出的等转化率活化能变化很大，这表明存在多步动力学行为。与表现出自催化行为的固态反应不同，液态聚合遵循由DSC和EPR数据确立的相当不寻常的零级反应模型。两种技术还确定了液态聚合的Arrhenius参数惊人地相似。相对于固态过程，液态聚合导致对甲苯磺酸酯基团定量消除，并形成对甲苯磺酸和化学及相组成明显不同的聚合物产物。
