The Dow Chemical Company, Core R&D Analytical Sciences, Shanghai, 201203, China.
The Dow Chemical Company, Core R&D Analytical Sciences, Midland, MI, 48674, USA.
J Chromatogr A. 2018 Aug 17;1563:28-36. doi: 10.1016/j.chroma.2018.04.050. Epub 2018 Apr 24.
Accurate measurement of molecular weight averages (M¯M¯M¯) and molecular weight distributions (MWD) of polyether polyols by conventional SEC (size exclusion chromatography) is not as straightforward as it would appear. Conventional calibration with polystyrene (PS) standards can only provide PS apparent molecular weights which do not provide accurate estimates of polyol molecular weights. Using polyethylene oxide/polyethylene glycol (PEO/PEG) for molecular weight calibration could improve the accuracy, but the retention behavior of PEO/PEG is not stable in THF-based (tetrahydrofuran) SEC systems. In this work, two approaches for calibration curve conversion with narrow PS and polyol molecular weight standards were developed. Equations to convert PS-apparent molecular weight to polyol-apparent molecular weight were developed using both a rigorous mathematical analysis and graphical plot regression method. The conversion equations obtained by the two approaches were in good agreement. Factors influencing the conversion equation were investigated. It was concluded that the separation conditions such as column batch and operating temperature did not have significant impact on the conversion coefficients and a universal conversion equation could be obtained. With this conversion equation, more accurate estimates of molecular weight averages and MWDs for polyether polyols can be achieved from conventional PS-THF SEC calibration. Moreover, no additional experimentation is required to convert historical PS equivalent data to reasonably accurate molecular weight results.
通过常规 SEC(尺寸排阻色谱法)准确测量聚醚多元醇的重均分子量(M¯M¯M¯)和分子量分布(MWD)并不像看起来那么简单。使用聚苯乙烯(PS)标准进行常规校准只能提供 PS 表观分子量,而不能准确估计多元醇的分子量。使用聚氧化乙烯/聚乙二醇(PEO/PEG)进行分子量校准可以提高准确性,但 PEO/PEG 的保留行为在基于四氢呋喃(THF)的 SEC 系统中不稳定。在这项工作中,开发了两种使用窄 PS 和多元醇分子量标准的校准曲线转换方法。使用严格的数学分析和图形绘图回归方法开发了将 PS-表观分子量转换为多元醇-表观分子量的方程。两种方法得到的转换方程非常吻合。研究了影响转换方程的因素。得出的结论是,分离条件(如柱批次和操作温度)对转换系数没有显著影响,可以获得通用的转换方程。使用该转换方程,可以从常规 PS-THF SEC 校准获得更准确的聚醚多元醇重均分子量和 MWD 的估计值。此外,无需进行额外的实验即可将历史 PS 等效数据转换为合理准确的分子量结果。