Size-exclusion chromatography (SEC) of branched polymers and polysaccharides.

Size-exclusion chromatography (SEC) of branched polymers and polysaccharides.
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DOI:
10.1007/s00216-010-4221-7
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发表时间:
2011-02
影响因子:
4.3
通讯作者:
Castignolles, Patrice
Castignolles, Patrice
中科院分区:
化学2区
文献类型:
--
作者:
Gaborieau, Marianne;Castignolles, Patrice

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支化聚合物是最重要的聚合物之一,范围从聚烯烃到多糖。分支在链动力学中起着关键作用。因此,它对应用性能如机械和粘合性能以及消化率非常重要。它还在粘性中起着关键作用,因此在尺寸排阻色谱法(SEC)中分离这些聚合物的机制中也起着关键作用。批判性地回顾文献,特别是SEC的聚烯烃,聚丙烯酸酯和淀粉,我们讨论了常见的陷阱,但也强调了一些未探索的可能性,以表征支化聚合物。一些长链分支的存在已被证明会导致SEC中的差分离,如通过多重检测SEC或多维液相色谱所证明的。在这种情况下,局部分散性可能很大,并且通过当前方法实现的分子量测定的准确性很差,尽管流体动力学体积分布提供了替代方案。相比之下,高度支化的聚合物在分子量方面不会遭受这种广泛的不完全分离。表示(a)线性聚合物链和具有(B)长链分支(直链淀粉样)、(c)短链分支(支链淀粉样)、(d)短链和长链分支(聚丙烯酸酯样或聚乙烯样)的各种支化聚合物结构。
Branched polymers are among the most important polymers, ranging from polyolefins to polysaccharides. Branching plays a key role in the chain dynamics. It is thus very important for application properties such as mechanical and adhesive properties and digestibility. It also plays a key role in viscous properties, and thus in the mechanism of the separation of these polymers in size-exclusion chromatography (SEC). Critically reviewing the literature, particularly on SEC of polyolefins, polyacrylates and starch, we discuss common pitfalls but also highlight some unexplored possibilities to characterize branched polymers. The presence of a few long-chain branches has been shown to lead to a poor separation in SEC, as evidenced by multiple-detection SEC or multidimensional liquid chromatography. The local dispersity can be large in that case, and the accuracy of molecular weight determination achieved by current methods is poor, although hydrodynamic volume distributions offer alternatives. In contrast, highly branched polymers do not suffer from this extensive incomplete separation in terms of molecular weight. Representation of (a) a linear polymer chain and various branched polymer structures with (b) longchain branches (amylose-like), (c) short-chain branches (amylopectin-like), (d) both short-chain and long-chain branches (polyacrylate- or polyethylene-like).
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发表时间: 2009-12-01
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