Kitahara Kei-Ichi, Okuya Shuji, Yoshihama Isao, Hanada Takako, Nagashima Kunio, Arai Sadao
Department of Chemistry, Tokyo Medical University, 6-1-1 Shinjuku, Shinjuku-ku, Tokyo 160-8402, Japan.
J Chromatogr A. 2009 Oct 30;1216(44):7409-14. doi: 10.1016/j.chroma.2009.04.067. Epub 2009 May 4.
For the separation of aromatic amines, two types of monodispersed porous polymer resins were prepared by the copolymerization of 2-vinylpyridine and 4-vinylpyridine with divinylbenzene in the presence of template silica gel particles (particle size 5 microm), followed by dissolution of the template silica gel in an alkaline solution. The transmission electron micrographs and the scanning electron micrograph revealed that these templated polymer resins have a spherical morphology with a good monodispersity and porous structure. Using these monodispersed polymer resins, the high-performance liquid chromatographic separation of aromatic amines in the mobile phases of pHs 2.0, 2.9, 4.1, 7.2 and 11.7 were carried out. The 2-vinylpyridine-divinylbenzene copolymer resins showed slightly stronger retentions for aromatic amines than the 4-vinylpyridine-divinylbenzene copolymer resins. Under acidic conditions (around pH 2.0), aniline and the toluidines showed no retention on these copolymer resins due to the repulsion between the cationic forms of these amines and pyridinium cations in the stationary phase, whereas less basic aromatic amines or non-basic acetanilide showed slight retentions. Above pH 4.1, the separation of aromatic amines with these polymer resins showed a typical reversed-phase mode separation. Therefore, the separation patterns of aromatic amines are effectively tunable by changing the pH value of the mobile phases. A good separation of eight aromatic amines was achieved at pH 2.9 using the 2-vinylpyridine-divinylbenzene copolymer resins.
为了分离芳香胺,通过在模板硅胶颗粒(粒径5微米)存在下使2-乙烯基吡啶和4-乙烯基吡啶与二乙烯基苯共聚,然后将模板硅胶溶解在碱性溶液中,制备了两种类型的单分散多孔聚合物树脂。透射电子显微镜照片和扫描电子显微镜照片显示,这些模板聚合物树脂具有球形形态,具有良好的单分散性和多孔结构。使用这些单分散聚合物树脂,在pH值为2.0、2.9、4.1、7.2和11.7的流动相中对芳香胺进行了高效液相色谱分离。2-乙烯基吡啶-二乙烯基苯共聚物树脂对芳香胺的保留力略强于4-乙烯基吡啶-二乙烯基苯共聚物树脂。在酸性条件下(pH约为2.0),由于这些胺的阳离子形式与固定相中的吡啶鎓阳离子之间的排斥作用,苯胺和甲苯胺在这些共聚物树脂上没有保留,而碱性较弱的芳香胺或非碱性乙酰苯胺则有轻微保留。在pH 4.1以上,用这些聚合物树脂分离芳香胺呈现典型的反相模式分离。因此,通过改变流动相的pH值可以有效地调节芳香胺的分离模式。使用2-乙烯基吡啶-二乙烯基苯共聚物树脂在pH 2.9时实现了八种芳香胺的良好分离。