Towards Chiral Microporous Soluble Polymers—Binaphthalene‐Based Polyimides

Abstract

Recently, intrinsically microporous polymers have received increased interest in research. Contrary to currently commercially used microporous materials, e.g., zeolithes or polymer networks, they can be dissolved, processed and further functionalized. Microporous poly(imide)s are especially interesting, as they are chemically and thermally resistant to decomposition up to high temperatures. In this paper, we report for the first time on a chiral poly(imide) which is intrinsically microporous and soluble in common solvents. After analysing the structure of the polymer, its pore system is characterised via its ability to adsorb nitrogen, argon, hydrogen and carbon dioxide. Furthermore, the chiral polymer is compared with its racemic counterpart, illustrating the special role of an organised superstructure.

Polycyclotrimers of 1,4‐Diethynylbenzene, 2,6‐Diethynylnaphthalene, and 2,6‐Diethynylanthracene: Preparation and Gas Adsorption Properties

“…Nitrogen isotherms on Pc(1,4-DEB) and Pc(2,6-DEN) in Figure 1 and 2 are characterized by a hysteresis loop typical for many organic polymers. As frequently observed for these materials, [ 45,47 ] desorption branches of the isotherms do not show a low pressure limit of adsorption/desorption irreversibility which is for inorganic mesoporous materials close relative pressure p / p 0 ≈ 0.4 (Lowell et al [ 57 ] ). In contrast to Pc(1,4-DEB) and Pc(2,6-DEN), nitrogen isotherm on the sample Pc(2,6-DEA) ( Figure 3 ) is reminiscent of nitrogen benzene-1,2,4-triyl linkers are most probably present in the structure of polycyclotrimers as branching and/ or cross-linking points.…”

“…Generally, adsorption properties of MOPs are still not completely understood. The structure-porosity-adsorption properties relationship of MOPs was studied by using either single nitrogen adsorption at 77 K [42][43][44] or a combination of isotherms of various adsorptives, such as nitrogen, argon and hydrogen at 77 K, and carbon dioxide at 273-333 K. [45][46][47][48] Gas adsorption was also combined with small-angle X-ray scattering analysis [ 48 ] or 129 Xe NMR spectroscopy. [ 49 ] The use of small-angle X-ray scattering has confi rmed that besides adsorption in micropores, pronounced elastic deformations of analyzed MOPs took place during increasing gas pressures.…”

“…Irreversibility of gas adsorption on polymers represents phenomenon, which raises doubts about the applicability of standard procedures for the analysis of porous fl exible materials. [ 47 ] The BET, BJH, or t -plot methods were suggested for inert solid adsorbents. If they are applied on MOPs, the meaning of obtained porosity characteristics may be problematic.…”

Twisted Morphologies and Novel Chiral Macroporous Films from the Self‐Assembly of Optically Active Helical Polyphosphazene Block Copolymers

“…To our knowledge, this is the first example of a chiral macroporous film. [28] The easy methodology used (direct drop-casting) and the particularly interesting formation of chiral-rich pores, combined with the tunability of the phosphazene block arising from the versatility of the macromolecular substitution step from the chlorinated precursor 6, should facilitate the development of a variety of uses in, for example, catalysis.…”

Microporous Organic Polymers for Carbon Dioxide Capture

“…More importantly, they obtained the first chiral PIMs by reaction of R(+)-2,2′-diamino-1,1′-binaphthalene [(+)BINAM] (Fig. 5.15, A3) and PMDA [120]. The resulting chiral polyimide (+)BINAM-PMDA shows the BET surface area about 500 m 2 g −1 and can adsorb 8.3 wt% of CO 2 at 273 K/1 bar.…”