Sutton Adam T, Read Emmanuelle, Maniego Alison R, Thevarajah Joel J, Marty Jean-Daniel, Destarac Mathias, Gaborieau Marianne, Castignolles Patrice
University of Western Sydney (UWS), Australian Centre for Research on Separation Science (ACROSS), School of Science and Health, Locked Bag 1797, Penrith 2751, NSW, Australia; University of Western Sydney (UWS), Molecular Medicine Research Group, School of Science and Health, Locked Bag 1797, Penrith 2751, NSW, Australia.
University Paul Sabatier, IMRCP, CNRS UMR 5623, 118 route de Narbonne, 31062 Toulouse, France.
J Chromatogr A. 2014 Dec 12;1372C:187-195. doi: 10.1016/j.chroma.2014.10.105. Epub 2014 Nov 6.
Block copolymers enable combining properties of different polymers; double hydrophilic block copolymers are innovative examples. Size-exclusion chromatography (SEC or GPC) has a quasi-monopoly in separation-based characterization methods for polymers, including block copolymers. However, in terms of purity determination (unintended homopolymers present in the copolymers), SEC resolution proves insufficient except for the extreme compositions for which the second block is much larger than the first one. The free solution capillary electrophoresis (capillary zone electrophoresis) technique does not separate charged homopolymers by their molar mass and we thus named the corresponding method capillary electrophoresis in the critical condition (CE-CC). CE-CC provides a means to assess the purity of poly(acrylic acid-b-acrylamide) - P(AA-b-AM) - copolymers, as well as of the more challenging cationic poly(acrylamido-N-propyltrimethylammonium chloride-b-N-isopropylacrylamide)-P(APTAC-b-NIPAM). In addition it can identify that a block copolymer has been produced. It is to be noted that P(APTAC-b-NIPAM) block copolymers cannot be eluted in SEC due to their exceptional ability to adsorb onto surfaces, while some information is obtained from CE-CC. Both possible parent homopolymers can be detected and their quantity estimated in a single injection by CE-CC. In both cases, one of the parent homopolymers is neutral and comes with the electro-osmotic flow. If the electro-osmotic flow is weak (conditions used for the cationic copolymer) then pressure assisted CE-CC is used to detect this homopolymer.
嵌段共聚物能够结合不同聚合物的特性;双亲水嵌段共聚物就是创新的例子。尺寸排阻色谱法(SEC或GPC)在聚合物(包括嵌段共聚物)基于分离的表征方法中具有近乎垄断的地位。然而,就纯度测定(共聚物中存在的非预期均聚物)而言,除了第二种嵌段比第一种大得多的极端组成情况外,SEC的分辨率被证明是不够的。自由溶液毛细管电泳(毛细管区带电泳)技术不会根据摩尔质量分离带电均聚物,因此我们将相应的方法命名为临界条件下的毛细管电泳(CE-CC)。CE-CC提供了一种评估聚(丙烯酸-b-丙烯酰胺)-P(AA-b-AM)-共聚物以及更具挑战性的阳离子聚(丙烯酰胺基-N-丙基三甲基氯化铵-b-N-异丙基丙烯酰胺)-P(APTAC-b-NIPAM)纯度的方法。此外,它还可以确定是否已经制备出嵌段共聚物。需要注意的是,P(APTAC-b-NIPAM)嵌段共聚物由于其在表面吸附的特殊能力而无法在SEC中洗脱,而从CE-CC中可以获得一些信息。通过CE-CC单次进样就可以检测到两种可能的母体均聚物并估计其数量。在这两种情况下,母体均聚物之一是中性的,并伴随着电渗流。如果电渗流较弱(用于阳离子共聚物的条件),则使用压力辅助CE-CC来检测这种均聚物。