Phenolation of cyclodextrin polymers controls their lead and organic micropollutant adsorption†,Chemical Science

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Phenolation of cyclodextrin polymers controls their lead and organic micropollutant adsorption†
Chemical Science ( IF 7.6 ) Pub Date : 2018-09-24 00:00:00 , DOI: 10.1039/c8sc03267j
Max J Klemes ₁ , Yuhan Ling ₂ , Marta Chiapasco ₁ , Alaaeddin Alsbaiee ₃ , Damian E Helbling ₂ , William R Dichtel ₁

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Porous β-cyclodextrin polymers linked with tetrafluoroterephthalonitrile (TFN-CDPs) have shown promise for adsorbing organic micropollutants (MPs) more quickly and effectively than conventional adsorbents. Prior to their discovery, the nucleophilic aromatic substitution (S_NAr) reaction used to prepare TFN-CDP was nearly unknown for the aliphatic alcohol nucleophiles, and the low isolated yields of TFN-CDP motivated model studies of the reaction between TFN and n-butanol. These experiments reveal a previously undescribed substitution reaction of TFN in which a fluorine is substituted by a hydroxyl group. This process is responsible for the low yields of the polymerization and incorporates phenolate groups into the polymer network. Phenolation and polymerization (etherification) are competing processes, and the level of phenolate incorporation was controlled by varying the rate of base addition and initial monomer concentrations. TFN-CDPs with varying phenolate content were prepared and evaluated as adsorbents for both Pb²⁺ ions and 83 MPs. More heavily phenolated polymers showed increased capacity to bind Pb²⁺ ions. Phenolation was also correlated with increased binding affinity for almost all of the 83 MPs tested, including neutral, cationic, and anionic substances. These results leverage a newly discovered side reaction during S_NAr reactions of electron-poor aryl fluorides to improve both the yield and the uptake affinity for both lead and organic MPs of TFN-CDPs.

中文翻译：

环糊精聚合物的酚化控制其铅和有机微污染物的吸附†

与四氟对苯二甲腈连接的多孔 β-环糊精聚合物 (TFN-CDP) 已显示出比传统吸附剂更快、更有效地吸附有机微污染物 (MP) 的前景。在他们发现之前，用于制备 TFN-CDP 的亲核芳香取代 (S _N Ar) 反应对于脂肪醇亲核试剂来说几乎是未知的，并且 TFN-CDP 的低分离产率激发了对 TFN 与n - 之间反应的模型研究。丁醇。这些实验揭示了先前未描述的 TFN 取代反应，其中氟被羟基取代。该过程导致聚合反应产率低，并将酚盐基团引入聚合物网络中。酚化和聚合（醚化）是竞争过程，酚盐掺入水平通过改变碱添加速率和初始单体浓度来控制。制备了具有不同酚盐含量的 TFN-CDP，并作为 Pb ²⁺离子和 83 MP 的吸附剂进行了评估。酚化程度更高的聚合物显示出结合 Pb ²⁺离子的能力增强。酚化还与几乎所有测试的 83 种 MP（包括中性、阳离子和阴离子物质）的结合亲和力增加相关。这些结果利用缺电子芳基氟化物的 S _N Ar 反应期间新发现的副反应来提高 TFN-CDP 的铅和有机 MP 的产率和吸收亲和力。

更新日期：2018-09-24

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