Physical Chemistry Department, Alexander Butlerov Institute of Chemistry, Kazan Federal University, Kremlevskaya Str. 18, 420008 Kazan, Russia.
Department of Chemistry, University of Alabama at Birmingham, 901 S. 14th Street, Birmingham, AL 35294, USA.
Molecules. 2022 Jun 3;27(11):3605. doi: 10.3390/molecules27113605.
This study highlights the value of nonisothermal kinetic methods in selecting temperature conditions for the isothermal preparation of microporous polymeric materials. A dicyanate ester is synthesized and the kinetics of its polymerization in diphenyl sulfone are studied by calorimetry under nonisothermal conditions. The kinetics are analyzed by a model-based approach, using the Kamal model, as well as by a model-free approach, using an advanced isoconversional method. Both approaches correctly predict the time to completion of polymerization at a given temperature. The material prepared independently at the predicted temperature is characterized by electron microscopy and CO adsorption measurements and is confirmed to possess a microporous structure with a multimodal distribution of micropores with two major maxima at ~0.5 and 0.8 nm.
本研究强调了非等温热力学方法在选择等温制备微孔聚合物材料的温度条件方面的价值。合成了一种二氰酸酯，并通过量热法在非等温条件下研究了其在二苯砜中的聚合动力学。通过基于模型的方法（使用 Kamal 模型）和无模型方法（使用先进的等转化率方法）对动力学进行了分析。两种方法都正确预测了在给定温度下聚合完成所需的时间。在预测的温度下独立制备的材料通过电子显微镜和 CO 吸附测量进行了表征，并证实其具有微孔结构，微孔呈双峰分布，两个主要峰值分别在~0.5nm 和 0.8nm 左右。
