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Tailoring Pore Size and Chemical Interior of near 1 nm Sized Pores in a Nanoporous Polymer Based on a Discotic Liquid Crystal
Macromolecules ( IF 5.1 ) Pub Date : 2017-03-23 00:00:00 , DOI: 10.1021/acs.macromol.7b00013 Subham Bhattacharjee 1 , Jody A M Lugger 1 , Rint P Sijbesma 1
Macromolecules ( IF 5.1 ) Pub Date : 2017-03-23 00:00:00 , DOI: 10.1021/acs.macromol.7b00013 Subham Bhattacharjee 1 , Jody A M Lugger 1 , Rint P Sijbesma 1
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A triazine based disc shaped molecule with two hydrolyzable units, imine and ester groups, was polymerized via acyclic diene metathesis in the columnar hexagonal (Colhex) LC phase. Fabrication of a cationic nanoporous polymer (pore diameter ∼1.3 nm) lined with ammonium groups at the pore surface was achieved by hydrolysis of the imine linkage. Size selective aldehyde uptake by the cationic porous polymer was demonstrated. The anilinium groups in the pores were converted to azide as well as phenyl groups by further chemical treatment, leading to porous polymers with neutral functional groups in the pores. The pores were enlarged by further hydrolysis of the ester groups to create ∼2.6 nm pores lined with −COONa surface groups. The same pores could be obtained in a single step without first hydrolyzing the imine linkage. XRD studies demonstrated that the Colhex order of the monomer was preserved after polymerization as well as in both the nanoporous polymers. The porous anionic polymer lined with −COOH groups was further converted to the −COOLi, −COONa, −COOK, −COOCs, and −COONH4 salts. The porous polymer lined with −COONa groups selectively adsorbs a cationic dye, methylene blue, over an anionic dye.
中文翻译：
基于盘状液晶的纳米多孔聚合物中近 1 nm 尺寸孔的孔径和化学内部的定制
具有两个可水解单元（亚胺和酯基团）的三嗪基盘形分子通过无环二烯复分解在柱状六角形（Col hex ）液晶相中聚合。通过亚胺键的水解制备了孔表面排列有铵基的阳离子纳米多孔聚合物（孔径~1.3 nm）。证明了阳离子多孔聚合物对醛的尺寸选择性吸收。通过进一步的化学处理，孔中的苯胺基团转化为叠氮基和苯基，从而形成孔中具有中性官能团的多孔聚合物。通过酯基团的进一步水解，孔扩大，形成 2.6 nm 的孔，孔内衬有 -COONa 表面基团。无需首先水解亚胺键，即可一步获得相同的孔。 XRD 研究表明，单体的 Col六角有序性在聚合后以及在两种纳米多孔聚合物中均得以保留。衬有-COOH基团的多孔阴离子聚合物进一步转化为-COOLi、-COONa、-COOK、-COOCs和-COONH 4盐。衬有-COONa基团的多孔聚合物选择性地吸附阳离子染料（亚甲基蓝）而不是阴离子染料。
更新日期：2017-03-23
中文翻译：
基于盘状液晶的纳米多孔聚合物中近 1 nm 尺寸孔的孔径和化学内部的定制
具有两个可水解单元（亚胺和酯基团）的三嗪基盘形分子通过无环二烯复分解在柱状六角形（Col hex ）液晶相中聚合。通过亚胺键的水解制备了孔表面排列有铵基的阳离子纳米多孔聚合物（孔径~1.3 nm）。证明了阳离子多孔聚合物对醛的尺寸选择性吸收。通过进一步的化学处理，孔中的苯胺基团转化为叠氮基和苯基，从而形成孔中具有中性官能团的多孔聚合物。通过酯基团的进一步水解，孔扩大，形成 2.6 nm 的孔，孔内衬有 -COONa 表面基团。无需首先水解亚胺键，即可一步获得相同的孔。 XRD 研究表明，单体的 Col六角有序性在聚合后以及在两种纳米多孔聚合物中均得以保留。衬有-COOH基团的多孔阴离子聚合物进一步转化为-COOLi、-COONa、-COOK、-COOCs和-COONH 4盐。衬有-COONa基团的多孔聚合物选择性地吸附阳离子染料（亚甲基蓝）而不是阴离子染料。
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