Challenges in the mechanistic and kinetic study on the polymerization with multiple functional monomers hinder the scale-up for the controllable reaction process. Herein, poly (isosorbide carbonate) synthesized from isosorbide (ISB) was employed to investigate the reaction behavior of functional monomers during polymerization. DFT calculations not only determined the energetically preferable pathways but also provided explanations for the significant differences between terminal groups at the molecular level. Subsequently, the characteristic absorption bands were detected from 1000 to 1100 cm⁻¹ for hydroxyls on ISB, providing a quantitative measure for asymmetric hydroxyls. The reaction network indicated that the reactivity was dominated by the types of terminal groups instead of the chain length. Thereafter, a functional group model with six kinetic parameters was built, acting a crucial role in reaction control and reactor design. This method can be promoted to other functional monomers, conducing to the industrialization of high-performance polymers.

中文翻译：

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异山梨醇合成聚碳酸酯的机理和动力学：端基反应性的鉴定


多官能单体聚合的机理和动力学研究中的挑战阻碍了可控反应过程的放大。在此，采用由异山梨醇（ISB）合成的聚（异山梨醇碳酸酯）来研究聚合过程中功能单体的反应行为。 DFT 计算不仅确定了能量上优选的途径，而且还为分子水平上端基之间的显着差异提供了解释。随后，在ISB上从1000至1100cm ^-1检测到羟基的特征吸收带，从而提供不对称羟基的定量测量。反应网络表明，反应活性受端基类型而非链长的影响。此后，建立了具有六个动力学参数的官能团模型，在反应控制和反应器设计中发挥着至关重要的作用。该方法可推广到其他功能单体，有助于高性能聚合物的产业化。