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The impact of band broadening on molar-mass determination of narrow-distribution polymer by size-exclusion chromatography

机译:谱带扩宽对尺寸排阻色谱法测定窄分布聚合物摩尔质量的影响

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摘要

A systematic study of the effects of band broadening (BB) in size-exclusion chromatography (SEC) on Poisson molar-mass distributions (MMDs) is carried out. Such distributions apply for polymer standards used for SEC calibration, and they are a good model for the MMD from any quasi-living polymerization, including reversible-deactivation radical polymerization (RDRP). BB is simulated using the exponentially modified Gaussian model, which is shown to work excellently for actual polymer standards. A series of simulations with this model revealed how BB parameter values affect number-average degree of polymerization and polydispersity index from SEC. It is shown that the skewness parameter is particularly important in these considerations. Many of the obtained trends echo ones from RDRP, suggesting that BB has been making a hitherto unsuspected - indeed uninvestigated - contribution to deviations from ideal behavior in such systems.
机译:系统地研究了尺寸排阻色谱法(SEC)中的谱带展宽(BB)对泊松摩尔质量分布(MMD)的影响。这样的分布适用于用于SEC校准的聚合物标准品,并且对于任何准活性聚合(包括可逆失活自由基聚合(RDRP))的MMD都是很好的模型。使用指数修正的高斯模型对BB进行了仿真,结果表明该模型对于实际的聚合物标准品具有出色的性能。用该模型进行的一系列模拟揭示了BB参数值如何影响SEC的数均聚合度和多分散指数。结果表明,在这些考虑中,偏度参数特别重要。许多获得的趋势与RDRP的趋势相呼应,这表明BB迄今从未对这种系统中的理想行为做出过令人怀疑的(实际上是未经调查的)贡献。

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