The acidolysis kinetics of the initial stage in the bulk polymerization of aromatic diacids (AA-type monomers) with aromatic diacetates (BB-type monomers) were investigated by a newly developed gas chromatography (GC) method. The model reactions of p-tert-butylbenzoic acid (ptBuBA) with either hydroquinone diacetate (HQD) or p-acetylaminophenol (APAP) follow second-order kinetics in these homogeneous conditions. HQD and APAP have approximately equal reactivity. The polycondensation of terephthalic acid (TA) with HQD, TA with 2-phenylhydroquinone diacetate (PhHQD), and TA with HQD and with 2,6-naphthalenedicarboxylic acid (NDA), follow pseudo-first-order kinetics. These reactions are heterogeneous. The polymerization of TA/PhHQD is the fastest, whereas the polymerization of TA/HQD is slower than that of TA/HQD/NDA. We propose that the solubility of the 1:1 dimer plays a crucial role in determining the polymerization rate, and that the mechanism changes from acidolysis to a dehydration esterification in the later stage of the AA/BB polymerization. The reaction rate constants and activation energies were obtained for all model reactions and polymerizations.

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芳族二酸和二乙酸酯的本体聚合动力学

通过新开发的气相色谱（GC）方法研究了芳族二酸（AA型单体）与芳族二乙酸酯（BB型单体）本体聚合的初始阶段的酸解动力学。的模型反应p -叔-butylbenzoic酸（ptBuBA）与任一对苯二酚双乙酸酯（HQD）或p-乙酰氨基酚（APAP）在这些均相条件下遵循二级动力学。HQD和APAP具有近似相等的反应性。对苯二甲酸（TA）与HQD，TA与2-苯基氢醌二乙酸酯（PhHQD）以及TA与HQD和2,6-萘二甲酸（NDA）的缩聚反应遵循拟一级动力学。这些反应是异质的。TA / PhHQD的聚合最快，而TA / HQD的聚合慢于TA / HQD / NDA的聚合。我们认为1：1二聚体的溶解度在决定聚合速率中起着至关重要的作用，并且该机理在AA / BB聚合的后期从酸解转变为脱水酯化。获得了所有模型反应和聚合反应的反应速率常数和活化能。