新型多孔有机聚合物分离材料的表面修饰、合成研究进展
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摘要
多孔有机聚合物(Porous Organic Polymers,POPs)是分离科学领域重要的分离材料之一,已广泛应用于从天然产物中分离制备有效成分。鉴于目前多孔有机聚合物选择性较差的现状,定向设计、合成对天然产物中目标化合物具有高度选择性、专一性的多孔有机聚合物是分离科学和功能高分子科学领域研究热点之一。本文综述了近年来作者在大孔吸附树脂(Macroporous Adsorption Resins,MARs)改性方面的研究进展,主要内容包括:1.MARs表面修饰:通过在MARs表面键合功能基,如氯甲基、氨基、羧基、酰胺基、聚乙二醇等功能基,引入氢键等作用力,以天然产物中有效成分的分离制备为研究对象,研究结果表明:可增强对目标化合物的分离选择性和分离效率。2.新型功能化超交联吸附树脂合成:利用低交联度氯球,通过后交联反应形成超高比表面积的吸附树脂,然后引入离子液体功能基(咪唑、N-甲基咪唑、咔唑、苯并咪唑),通过增强功能化超交联吸附树脂与有效成分之间的多重相互作用及比表面积对吸附过程的贡献,定向设计、合成对目标化合物具有高选择性的新型功能化超交联吸附树脂,以天然产物中有效成分的分离制备为研究对象,研究结果表明:同表面修饰的MARs相比,新型功能化超交联吸附树脂表现出更好的分离选择性和分离效率。
Due to the high specific surface area and unique porous structure, porous organic polymers(POPs) have received a great deal of attention as separation materials for separation and preparation of effective components from natural products. However, the main issues currently facing is the poor selectivity of porous organic polymers. Therefore, design and synthesis of high selectivity and specificity of porous organic polymers is one of hot spots in the separation of science and functional polymer science. This paper covers recent advances in the field of macroporous adsorption resins(MARs) modification in our team. First, a series of MARs with novel structures are synthesized based on the Friedel–Crafts reaction, for instance modification with chloromethyl, amino, carboxyl, amide groups, and polyethylene glycol groups. And then corresponding adsorption properties are determined with active ingredients of natural products as target analytes. These introduced functional groups can interact with active ingredients via hydrogen bonding. The results indicated that MARs with a variety of functional groups being developed in our laboratory can enhance the adsorption selectivity and separation efficiency for active ingredients. Second, by enhancing multiple adsorption interactions and the contribution of specific surface area, hypercrosslinked adsorbents functionalized with ionic liquids are prepared from poly(styrene-co-divinylbenzene) with low degree of crosslinking using Friedel–Crafts and post-crosslink reaction. It has large surface area, polar groups, and bimodal distribution of pore sizes for separation and purification of active ingredients from natural product. Compared with the functional MARs, the experimental results suggested that the possibility of enhancing the adsorption selectivity and separation efficiency for active ingredients from natural product using ionic liquids modified hypercrosslinked polystyrene resins. Analysis of the adsorption mechanism suggested that specific surface area, molecular sieving effect, and multiple adsorption interactions were the driving forces of the adsorption. These factors acted synergistically in the adsorption process.
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