Interfacial polymerization of cyanuric chloride and monomeric amines: pH resistant thin film composite polyamine nanofiltration membranes
Interfacial polymerization of cyanuric chloride and monomeric amines: pH resistant thin film composite polyamine nanofiltration membranes
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DOI：
10.1016/j.memsci.2016.10.012
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发表时间：
2017-02-01
影响因子：
9.5
通讯作者：
Benes, Nieck E.
中科院分区：
文献类型：
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作者：
Lee, Kah P.;Bargeman, Gerrald;Benes, Nieck E.
聚胺纳滤膜在极端pH条件下具有高稳定性。与聚酰胺相反，多胺不含对亲核攻击敏感的羰基。先前的研究已经表明，聚胺膜可以由聚乙烯亚胺和氰尿酰氯的界面聚合反应制备，并且这些膜确实具有高的耐水解性。在本研究中，潜在的各种其他多功能胺/氰尿酰氯组合筛选形成稳定的聚胺纳滤膜。对于几种传统的胺前体，发现氰尿酰氯的适度反应性阻碍了薄的选择性膜的形成。对于两个线性胺单体，这两者都是聚乙烯亚胺的前体，观察到良好定义的，薄的，稳定的，和选择性的多胺膜的形成。特别地，二亚乙基三胺被确定为用于界面反应的合适单体。与先前研究的基于聚乙烯亚胺的膜相比，衍生自该胺的膜具有更高的盐截留率和水渗透率，并且在极端pH条件下显示出极高的稳定性。不同的盐和中性溶质在不同的pH值的交叉流过滤表明，空间效应以及多尔曼排斥效应是相关的溶质的排斥。膜皮层在中性pH（约200 Da的MWCO）下非常致密，并且在极端碱性条件下变得稍微更开放。
Polyamine nanofiltration membranes have a high stability at extreme pH conditions. In contrast to polyamides, polyamines do not contain the carbonyl group that is susceptible to nucleophilic attack. A previous study has shown that polyamine membranes can be prepared from the interfacial polymerization reaction of polyethylenimine and cyanuric chloride, and that indeed these membranes have a high resistance towards hydrolysis. In the present study, the potential of a variety of other multifunctional amine / cyanuric chloride combinations is screened for the formation of stable polyamine nanofiltration membranes. For several traditional amine precursors it is found that the moderate reactivity of the cyanuric chloride hampers the formation of thin selective membrane films. For two linear amine monomers, both of which are precursors to polyethylenimine, the formation of well-defined, thin, stable, and selective polyamine films is observed. In particular, diethylene triamine is identified as a suitable monomer for the interfacial reaction. The membranes derived from this amine have a higher salt rejection and water permeability as compared to the previously studied polyethylenimine based membranes, and show a comparably high stability at extreme pH conditions. Cross-flow filtration of different salts and neutral solutes at different pH indicates that both steric effects as well as Dorman exclusion effects are relevant for the rejection of solutes. The membrane skin layer is very dense at neutral pH (MWCO of about 200 Da), and becomes slightly more open at extreme alkaline conditions.