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含二羟基的季铵官能团的烷基取代的阴离子交换剂的制备与表征。

Preparation and characterisation of anion exchangers with dihydroxy-containing alkyl substitutes in the quaternary ammonium functional groups.

机构信息

Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1/3, GSP-1, Moscow 119991, Russia.

Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1/3, GSP-1, Moscow 119991, Russia.

出版信息

J Chromatogr A. 2014 Jan 3;1323:104-14. doi: 10.1016/j.chroma.2013.11.013. Epub 2013 Nov 14.

DOI:10.1016/j.chroma.2013.11.013
PMID:24309716
Abstract

Novel poly(styrene-divinylbenzene) (PS-DVB) based anion exchangers having one and two (2,3-dihydroxypropyl) substitutes in the quaternary ammonium functional groups are prepared and characterised by ion chromatography (IC). The introduction of bulky and hydrophilic substitutes to the anion-exchange groups allows the elimination of non-ionic interactions between the polarisable anions and the aromatic rings from the matrix and the improvement of separation selectivity as compared with the traditional trimethylammonium (TMA) functionalised ion exchangers. The synthesis of the ion exchangers includes acylation of PS-DVB particles with acetic anhydride followed by reductive amination either with methylamine hydrochloride or dimethylamine and further alkylation with oxiranes under varied conditions. The ion exchange selectivity and separation efficiency of nine adsorbents having different structure of bonded groups, ion exchange capacity (9-98μequiv.g(-1)) or particle size is studied for model mixture of inorganic anions (F(-), Cl(-), NO2(-), Br(-), NO3(-), HPO4(2-) and SO4(2-)) using carbonate and hydroxide eluents. The adsorbents with more hydrophilic substitutes provided superior columns efficiencies and better peak symmetry as compared with analogues having hydrophobic functional groups. The calculated values of column efficiencies for polarisable NO3(-) and HPO4(2-) are 18,500 and 29,000N/m, respectively, for anion-exchanger, having N-methyl-N',N″-di-(2,3-dihydroxypropyl)ammonium groups which is significantly higher than 1800 and 12,000N/m obtained for these anions with anion exchanger bearing TMA functional groups.

摘要

新型聚苯乙烯-二乙烯基苯(PS-DVB)基阴离子交换剂,在季铵官能团中具有一个和两个(2,3-二羟丙基)取代基,通过离子色谱(IC)进行了表征。将大体积和亲水取代基引入阴离子交换基团可以消除可极化阴离子与基质中的芳环之间的非离子相互作用,并与传统的三甲基铵(TMA)官能化离子交换剂相比提高分离选择性。离子交换剂的合成包括用乙酸酐酰化 PS-DVB 颗粒,然后用盐酸甲胺或二甲胺进行还原胺化,然后在不同条件下用环氧化物进行烷基化。研究了具有不同键合基团结构、离子交换容量(9-98μequiv.g(-1))或粒径的九种吸附剂对模型混合无机阴离子(F(-)、Cl(-)、NO2(-)、Br(-)、NO3(-)、HPO4(2-)和 SO4(2-))的离子交换选择性和分离效率,使用碳酸盐和氢氧化物洗脱剂。与具有疏水性官能团的类似物相比,具有更亲水取代基的吸附剂提供了更高的柱效和更好的峰对称性。对于具有 N-甲基-N',N″-二-(2,3-二羟丙基)铵基团的阴离子交换剂,可极化的 NO3(-)和 HPO4(2-)的计算柱效值分别为 18,500 和 29,000N/m,这明显高于具有 TMA 官能团的阴离子交换剂对这些阴离子的 1800 和 12,000N/m。

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