Preparation of chiral polystyrene monoliths by utilizing W/O emulsion polymerization and their optical resolution ability
Preparation of chiral polystyrene monoliths by utilizing W/O emulsion polymerization and their optical resolution ability
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DOI：
10.1002/pola.20645
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发表时间：
2005-06
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影响因子：
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通讯作者：
M. Teraguchi;M. Ohtake;H. Inoue;A. Yoshida;T. Aoki;T. Kaneko;K. Yamanaka
中科院分区：
文献类型：
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作者：
M. Teraguchi;M. Ohtake;H. Inoue;A. Yoshida;T. Aoki;T. Kaneko;K. Yamanaka
我们合成了两种手性聚苯乙烯基整体柱，它们是具有连续开孔结构的大孔凝胶。因此，合成了两种手性苯乙烯单体：(-)-对-[二甲基(10-蒎基)硅基]苯乙烯((-)-Psst)和(-)-对-(薄荷氧羰基)苯乙烯((-)-MTST)，并在二乙烯基苯和AIBN存在下进行了油包水乳液聚合。通过扫描电子显微镜观察，直接证实了所得整体的大孔结构。得到的整体具有光学分辨能力。也就是说，在对映体选择性吸附中，聚[(-)-Psst]整体柱和聚[(-)-MTST]整体柱优先吸附(S，S)-异构体[聚[(-)-]-Psst]整体柱：α(S，S)=1.49(0.25wt%丙酮溶液)；聚[(-)-MTST]整体柱：α(S，S)=1.39(0.25wt%甲苯溶液)。聚[(-)-Psst]整体柱的硅烷化和薄荷基的去除分别是通过酸催化的硅碳键断裂和碱催化的水解法实现的。此外，脱聚[(-)-Psst]和脱聚[(-)-MTST]在吸附反式氧化二苯乙烯时表现出对映体选择性((S，S)-异构体优先被吸附)，尽管整体中没有手性取代基。
We synthesized two kinds of chiral polystyrene-based monoliths, which are macroporous gel with continuous open-celled monolith structure. Thus, two chiral styrene monomers, (-)-p-[dimethyl(10-pinanyl)silyl]styrene ((-)-PSSt) and (-)-p-(menthoxycarbonyl)styrene ((-)-MtSt]), were prepared and subjected to water-in-oil emulsion polymerization in the presence of divinylbenzene and AIBN. The macroporous structure of the obtained monoliths was directly confirmed by SEM observation. The obtained monoliths showed an optical resolution ability. That is, in the enantioselective adsorption using trans-stilbene oxide, poly[(-)-PSSt] monolith and poly[(-)-MtSt] monoliths preferentially adsorbed (S,S)-isomer [poly[(-)-PSSt] monolith: α (S,S) = 1.49 (0.25 wt % acetone solution); poly[(-)-MtSt] monolith: α (S,S) = 1.39 (0.25 wt % toluene solution)]. Depinanylsilylation of the poly[(-)-PSSt] monolith and removal of menthyl groups from the poly[(-)-MtSt] monolith were achieved by acid-catalyzed scission of the Si-C bond and base-catalyzed hydrolysis, respectively. In addition, de-poly[(-)-PSSt] and de-poly[(-)-MtSt] showed enantioselectivity ((S,S)-isomer preferentially absorbed) in adsorption using trans-stilbene oxide in spite of the absence of chiral substituents in the monoliths.