应用化学

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酚醛基质苯并咪唑螯合树脂的合成及配位性能

曹宇,束怡,洪春雪,娄杰,束家有*   

  1. (武汉大学药学院 武汉 430072)
  • 收稿日期:2011-03-24 修回日期:2011-05-31 出版日期:2012-02-10 发布日期:2012-02-10
  • 通讯作者: 束家有,教授; Tel:027-68759996; Fax:027-68759850; E-mail:314630359@qq.com; 研究方向:药物新剂型研究
  • 基金资助:
    科技部科技人员服务企业项目([2009] 2009GJD10040)

Synthesis, Characterization and Adsorption toward Divalent-ions of Bisbenzimidazole Supported on Phenolformaldehyde

CAO Yu, SHU Yi, HONG Chunxue, LOU Jie, SHU Jiayou*   

  1. (College of Pharmacy,Wuhan University,Wuhan 430072)
  • Received:2011-03-24 Revised:2011-05-31 Published:2012-02-10 Online:2012-02-10

摘要: 通过1,4-对苯二酚二缩水甘油醚和2,2′-二苯并咪唑二乙胺反应合成四苯并咪唑单体(TBMZ),经甲醛等缩合生成酚醛聚合物为基质的苯并咪唑螯合树脂(PTBMZs)。 新型螯合树脂配基含量达2.1~3.02 mmol/g。新树脂及其单体结构经13C核磁共振谱、FT-IR红外光谱、元素分析和DSC分析确证。 测定了Cu2+、Ni2+、Zn2+、Cd2+和Co2+氯化物在pH值为1.0~6.0的缓冲溶液中的配位容量。 实验结果表明,该类螯合树脂对Cu2+有高度的选择性,KCuX≥4.3非竞争条件下,PTBMZ-1的最大配位容量为1.15 mmol/g(pH=5.0,Cu2+),PTBMZ-2的最大配位容量为0.97 mmol/g(pH=5.0,Cu2+),配基占有率分别为35.9%,33.4%。 PTBMZ-1树脂对Cu2+吸附较快,t1/2=21 min。 电子顺磁共振谱和FT-IR光谱分析结果表明,形成n(金属离子)∶n(配基)=1∶2的螯合物为主。

关键词: 螯合树脂, 酚醛基质, 二苯并咪唑二乙胺, 金属离子吸附

Abstract: A couple of new benzimidazole chelating resins, bisbenzimidazole supported on phenol-formaldehyde(PTBMZs), were synthesized by phenolformaldehyde condensation of tetrabenzimidazole ligand. The PTBMZs have a 2.06~3.02 mmol of ligand content per gram of the resin. Their structures were characterized by solid-state 13C crossing-polarization and magic-angle spinning(CP MAS) NMR, FT-IR spectroscopy. Batch adsorption capacities were determined for the chloride of some divalent metal cations in buffer solutions in the pH rang of 1.0 to 6.0. The adsorption capacities of the PTBMZ-1 under non-competitive condition are 1.15 mmol/g for Cu2+ at pH=5 and the ligand occupations are 35.7%. Elemental analysis and electron paramagnetic resonance(EPR) studies suggested that complexes with the metal cation to ligand ratio of mainly 1∶2 were formed on the BBEAH modified resins via tridentate chalete structure.

Key words: Chelating resin, Matrix of Bakelite-type, 1,3-bis(benzimidazol-2yl)propylamine, Metal adsorption.

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