Synthesis of chiral helical poly[p‐(oligopinanylsiloxanyl)phenylacetylene]s and enantioselective permeability of their membranes
Synthesis of chiral helical poly[p‐(oligopinanylsiloxanyl)phenylacetylene]s and enantioselective permeability of their membranes
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DOI：
10.1002/pola.20356
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发表时间：
2004-09
期刊：
影响因子：
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通讯作者：
T. Aoki;Tomoyuki Fukuda;K. Shinohara;T. Kaneko;M. Teraguchi;M. Yagi
中科院分区：
文献类型：
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作者：
T. Aoki;Tomoyuki Fukuda;K. Shinohara;T. Kaneko;M. Teraguchi;M. Yagi
为了开发更好的光学拆分膜材料，我们合成了九种含蒎烷基的手性苯乙炔。我们用它们来研究化学结构的影响，包括单体中手性基团的数量和位置，对聚合过程中主链中手性的诱导和聚合物膜渗透中对映选择性的程度。单体包括六个新的手性对-（低聚甲基蒎烷基）苯乙炔。这9种单体与Rh配合物均聚生成高分子量聚合物（分子量= 10 5 ~ 10 6）。的5个聚合物与手性pinanyl基团在1-位置的每个oligopinanyl基团，除了两个聚合物在主链区域的圆二色性光谱中显示出高的摩尔椭圆率。这一发现表明这些聚合物具有手性螺旋主链。除两种聚合物外，由本研究中合成的所有聚合物制成的膜都是高质量的。所有这些膜表现出对映选择性渗透两种氨基酸和醇。具有手性螺旋骨架、高含量的蒎烷基、无低聚二甲基硅氧烷部分或这些的组合的聚合物的膜在渗透中显示出良好的对映选择性（= 1.7-640）。我们认为主链螺旋度的方向决定了选择性。
To develop better polymeric materials for optical-resolution membranes, we synthesized nine chiral phenylacetylenes containing pinanyl groups. We used them to investigate the effects of chemical structures, including the number and position of the chiral groups in the monomers, on the induction of chirality in the main chain during polymerization and on the degree of enantioselectivity in the permeation of the polymeric membranes. The monomers included six new chiral p-(oligomethylpinanylsiloxanyl)phenylacetylenes. The homopolymerizations of these nine monomers with a Rh complex produced high-molecular-weight polymers (molecular weight = 10 5 -10 6 ). Of the five polymers with a chiral pinanyl group at the 1-position of each oligosiloxanyl group, all except for two polymers showed high molar ellipticity in the main-chain region in the circular dichroism spectra. This finding indicated that these polymers had a chiral helical main chain. The membranes fabricated from all the polymers synthesized in this study were high-quality, except for two polymers. All these membranes showed enantioselective permeabilities for two amino acids and an alcohol. The membranes from the polymers with a chiral helical backbone, a high content of pinanyl groups, no oligodimethylsiloxane moieties, or a combination of these showed good enantioselectivities ( = 1.7-640 ) in permeation. We propose that the sense of the main-chain helicity determined the selectivity.