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使用新型非交联聚(3-(三丁氧基硅基)三环壬烯-7)作为模型固定相评估聚合物气相色谱固定相老化的色谱方法。

Chromatographic Method for Evaluation of Polymeric GC Stationary Phases Ageing Using the Novel Non-Cross-Linked Poly(3-(Tributoxysilyl)Tricyclononene-7) as the Model Stationary Phase.

作者信息

Kanateva Anastasiia, Bermeshev Maxim, Alentiev Dmitrii, Korolev Alexander A, Kurganov Alexander

机构信息

A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Science, 119991 Moscow, Russia.

出版信息

Polymers (Basel). 2021 Jun 7;13(11):1899. doi: 10.3390/polym13111899.

Abstract

The chromatographic properties and thermal stability are investigated for the polymeric stationary phase based on the norbornene polymer. It was shown that without additional cross-linking, poly(3-(tributoxysilyl)tricyclononene-7) demonstrates properties similar to liquid chromatographic stationary phases. It was also found to be more thermally stable than previously studied trimethylsilyl- and trimethoxysilyl- derivatives. The long-term heating at 170 °C resulted in an increase of mass transfer rate between stationary and mobile phases which could be observed as a decrease of parameter C of Van Deemter equation. This effect is rather unusual, as the polymeric stationary phases tend in decrease of the layer volume and porosity while ageing. Additionally, the values of thermodynamic parameters of sorption are calculated for the polymeric stationary phase: enthalpy of sorption varied -28 to -37 kJ/mol, entropy change was -41 to -51 J/mol K. The compensation curves were plotted for the alkanes, arenes, and alcohols, and the parameters of compensation plot were calculated, demonstrating the different sorption mechanisms both for hydrocarbons and oxygen-containing compounds, and different classes of organic compounds.

摘要

对基于降冰片烯聚合物的聚合物固定相的色谱性能和热稳定性进行了研究。结果表明,在没有额外交联的情况下,聚(3-(三丁氧基甲硅烷基)三环壬烯-7)表现出与液相色谱固定相相似的性能。还发现它比先前研究的三甲基甲硅烷基和三甲氧基甲硅烷基衍生物具有更高的热稳定性。在170°C下长期加热导致固定相和流动相之间的传质速率增加,这可以通过范德姆特方程参数C的降低来观察到。这种效应相当不寻常,因为聚合物固定相在老化时往往会减小层体积和孔隙率。此外,还计算了聚合物固定相的吸附热力学参数值:吸附焓在-28至-37 kJ/mol之间变化,熵变为-41至-51 J/mol K。绘制了烷烃、芳烃和醇类的补偿曲线,并计算了补偿图的参数,表明烃类和含氧化合物以及不同类别的有机化合物具有不同的吸附机制。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a9d0/8201275/79cc497934e3/polymers-13-01899-g001.jpg

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