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Local Polydispersity Detection in Size Exclusion Chromatography:Method Assessment

机译:尺寸排阻色谱中的局部多分散性检测:方法评估

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摘要

Local polydispersity is the term describing the variety of molecules present at the same retention volume in size exclusion chromatography (SEC) analysis.In the analysis of a linear homopolymer,local polydispersity is generally attributed to the effect of axial dispersion:it can cause molecular size variety (i.e.,imperfect resolution) at each retention volume and thus local polydispersity in the molecular weight.In the analysis of polymer blends (copolymers and branched polymers),it is possible to have local polydispersity,even when the resolution is perfect,because molecules of different compositions (or degrees of branching) can have the same molecular size in solution.Conventional SEC interpretation assumes no local polydispersity if the axial dispersion effects are negligible.Three methods are currently available for detecting local polydispersity by using a combination of differential refractive index,light scattering,and viscometer detectors: the chromatogram comparison method,the conventional calibration curve comparison method,and the universal calibration comparison method.Here we experimentally assess these three methods using polymer blends and emphasize the chromatogram comparison method.All three are shown to be useful for assessing triple detector systems,but they are capable of detecting local polydispersity due to molecular heterogeneity only for very large differences in specific refractive index increments in the blend components.
机译:局部多分散性是描述尺寸排阻色谱法(SEC)分析中在相同保留体积上存在的各种分子的术语。在线性均聚物的分析中,局部多分散性通常归因于轴向分散的影响:它可以引起分子尺寸在每个保留体积上的分子量分布(即不完美的分离度),从而导致分子量的局部多分散性。在聚合物共混物(共聚物和支链聚合物)的分析中,即使是理想的分离度,由于分子,也可能具有局部多分散性组分的不同组成(或支化度)在溶液中可以具有相同的分子大小。传统的SEC解释假设轴向分散效应可忽略不存在局部多分散性。目前有三种方法可通过结合差分折射率来检测局部多分散性,光散射和粘度计检测器:色谱图比较法常规的校准曲线比较方法和通用的校准比较方法。在这里,我们使用聚合物共混物对这三种方法进行了实验评估,并着重于色谱图的比较方法。所有这三种方法都可用于评估三重检测器系统,但它们能够检测由于分子异质性而导致的局部多分散性仅适用于共混组分中特定折射率增量的很大差异。

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