基于季铵化烯丙基缩水甘油醚改性的阴离子交换固定相的制备  

Preparation of an anion stationary phase modified by quaternary ammoniated allyl glycidyl ether

作　　者：李宗英 陈新 章飞芳[1] 杨丙成[1] LI Zongying;CHEN Xin;ZHANG Feifang;YANG Bingcheng(School of Pharmacy, East China University of Science and Technology, Shanghai 200237, China)

机构地区：[1]华东理工大学药学院,上海200237

出　　处：《色谱》2022年第8期730-735,共6页Chinese Journal of Chromatography

基　　金：国家重点研发计划(2018YFC1603500).

摘　　要：制备了一种季铵化烯丙基缩水甘油醚(allyl glycidyl ether,AGE)改性聚合物基质的阴离子固定相应用于离子色谱系统。它是利用AGE与水解的聚甲基丙烯酸缩水甘油酯-二乙烯基苯poly(glycidylmethacrylate-divinylbenzene,GMA-DVB)微球表面残留双键通过表面自由基共聚,再通过N,N-二甲基乙醇胺(一种叔胺)进行开环反应制备得到的。通过考察有机叔胺类型、微球水解、单体和引发剂用量、反应温度和时间对7种阴离子分离性能的影响,优化了制备条件。采用扫描电镜、元素分析对所得阴离子固定相进行了表征。结果表明,采用预先水解的GMA-DVB微球(水解过程中微球表面丰富的环氧基团转化为羟基)相对于直接采用GMA-DVB微球有助于降低固定相的交换容量和微球自身的非离子吸附作用;通过淋洗液浓度和目标离子保留因子的拟合结果证实了该固定相保留机理为典型的离子交换作用。使用碳酸根淋洗液,在优化的色谱条件下,该固定相可在13 min内实现常见7种无机阴离子的基线分离,并表现出较高的柱效(Cl-理论塔板数为49000块/m)。该色谱柱实用性通过分析自来水实际样品进行了验证。A polymer-based strong anion stationary phase modified by quaternary ammoniated allyl glycidyl ether(AGE)for ion chromatography(IC)was developed.It was prepared by surface copolymerization between AGE and the pedant double bonds associated with hydrolyzed poly(glycidylmethacrylate-divinylbenzene)(GMA-DVB)substrate,followed by quaternization with N,N-methyldiethanolamine(a tertiary amine,MDEA).The synthesis conditions were optimized,including the type of organic tertiary amines(MDEA,N,N-dimethylethanolamine,trimethylamine),substrate hydrolysis,the amount of monomer and initiator,reaction temperature and reaction time.The obtained anion stationary phase was characterized by scanning electron microscope and elemental analysis.MDEA was observed to be the best quaternization reagent since the anion exchanger obtained by such reagent showed good separation and suitable retention time towards model inorganic anions.The resulting reason probably lies in higher hydrophilicity of MDEA relative the other two ones.The use of rich epoxy groups of GMA-DVB to introduce the functional groups was commonly used in many previous reports.Here the epoxy groups were firstly hydrolyzed to be diol groups and the pendant double bonds onto the surface of GMA-DVB particles were used to graft AGE.The data achieved indicated that the use of hydrolyzed GMA-DVB substrate would be helpful to reduce anion exchange capacity and unwanted non-ion exchange interaction,in which the rich epoxy groups were converted to hydroxy groups.More important,the obtained anion exchanger after hydrolytic treatment could offer a significantly reduction of retention time(~68%)and a~1.67-fold higher plate count(take Br-as an example).The apparent capacity of the phase was computed to be 264μmol/g by content of N data and its effective capacity was measured to be 98.5μmol/column by the breakthrough curve method.Under the optimal chromatographic conditions,the obtained stationary phase showed baseline separation of seven common inorganic anions in less than 13 min u

关 键 词：离子色谱 聚甲基丙烯酸缩水甘油酯-二乙烯基苯 残留双键 固定相 

分 类 号：O658[理学—分析化学]