Design, Synthesis And Characterization Of Novel Porous Organic Frameworks Based On Cyanuric Chloride

Recently, porous organic framework, a new class of porous materials, becomes research hotspot because its high surface area, low framework density and excellent adsorption properties. Micro-and mesoporous polymers are relevant, classical materials, with application as sorption materials or in chromatography. Their interest has been revamped by the upcoming technological problems of the new energy cycles, thus stimulating research on "energy materials/polymers" necessary for the production of energy (e.g., novel catalysts and catalyst supports, fuel cell membranes), its storage (hydrogen, lithium, etc.), but also for green processes (wastewater treatment, detoxification, etc.). Alternatively, the search for "all organic" porous materials made by polymerization processes of organic monomers can not only lead to enhanced performances (shapeability and simplified synthesis and processing) but also introduce new opportunities relying on functional properties, such as electronic conductivity or complex, converging functionalities. It is also the hope that these polymer-like materials may overpass the limitations of their counterparts in terms of pore size and connectivity. Therefore, it is no wonder that since a few years, more and more research groups became interested in the development of porous organic materials, and several different types of porous polymer networks have been synthesized. Most of these examples introduced the chemical tools required to build such materials, through cross-linking strategies, reversible polymerization systems for crystalline materials, and precise building blocks allowing the appearance of a stable porosity. On the other side, some studies already proved that porous polymeric materials can feature novel intrinsic structural properties. All these materials were prepared following conventional synthetic approaches, i.e., by using well-known organic reactions in an organic solvent at low temperatures. However, very high porosities (surface area 2000-3000 m2 g-1, pore volume cm3 g-1) are still the domain of MOFs and amorphous activated carbons. In our opinion, this is caused by the effects of cold flow and ductility of polymers, which close a majority of the very fine pores of those networks. This work focuses on design, synthesis and characterization of novel organic frameworks which bases on cyanuric chloride with rigid construction and high reaction active.In the second part of the issue, we report a new covalently-linked porous organic framework, PAF-6. PAF-6 was prepared in the A3 (Cyanuric chloride)+B2 (piperazine) reaction system via the one-step polymerization method. The PXRD, MS simulation and calculation, TEM, N2 sorption results implied that PAF-6 possess a 2D ordered structure with C2/m space group and a uniform pore size of 11.8(?). For the first time, we conduct an investigation into POFs in biomedical applications. No toxicity of PAF-6 architecture was observed using MTT assay. As a novel drug carrier, PAF-6 have been employed to control Ibuprofen drug delivery under in vitro conditions, the release behavior of PAF-6 is close to or even better than the drug release performance of MCM-41 which is one of the most widely studied inorganic compounds for drug delivery.In the third section, we present the preparation of a novel 3D porous organic framework by linking (4-amino-tetraphenyl)-methane and Cyanuric chloride. FTIR XRD,NMR,TEM and CO2 adsorption are employed to confirm the chemical structure (contain a high density of-NH-) and the supermicroporous structure of the framework. The characterization of gas adsorption shows that this novel porous materials suitable for gas adsorption and separation, especially for CO2/N2 separation (carbon capture). CO2 isotherm indicates that the uptake of TC-1 is 104.2 mg/g at 273 K and 68.7 mg/g at 298 K. and a high enthalpy towards CO2 up to 37 kJ/mol. TC-1 is a excellent candidate for CO2 capture and storage.And 4'4-bipyridyl and 1,2-bis (4-pyridyl) ethylene were employed to form two novel organic frameworks with quaternary ammonium function group which named CPy-1 and CPy-2. According to the vapor adsorption of vary organic molecules, we found that these two compounds can not sorb nitrogen benzene, cyclohexane and thiophene, but have excellent capability of adsorption for amines such as pyridine, piperidine, triethylamine and N, N'-diisopropyl ethylamine etc. Unexpected, the uptake of pyridine is very high,859 wt.% and 442.4 wt.% , respectively., both the two compounds show the capability of enrichment of pyridine, and can increase the molar ratio of pyridine and toluene from 1:1 to 4:1 through selective adsortption.