Preparation And Application Of Pyrene-based Porous Polymers

The rapid developments of modern industrial,agricultural production and medical technology have intensified the use of nitroaromatic compounds,metal ions,and antibiotic drugs.Irregular operations and abuse have caused pollutants to invade water and resulted in serious harm to ecosystems.Therefore,it is particularly urgent to seek a material with excellent performance to detect and remove pollutants in water.Fluorescent porous polymers constructed through covalent bonds have shown great potential in the fields of gas storage and separation,chemical detection and pollutants removal.Pyrene(Py)plays an important role in the preparation of fluorescent porous polymers due to its excellent optical properties and rigid structure.While the nano-scale octavinylsilsesquioxane with organic-inorganic hybrid property is regarded as an ideal building block for covalently-linked organic-inorganic hybrid porous polymers.In this thesis,Pyrene(Py)and octavinylsilsesquioxane(OVS)are used as two building blocks to construct porous polymers.Two types of porous polymers are prepared by Scholl coupling reaction and Friedel-Crafts reaction,respectively,and applied to the detection and adsorption of pollutants in water as follows:1.Py-OCP was prepared by Scholl coupling reaction with pyrene(Py)as a single building unit.The surface area and pore size distribution of Py-OCP was determined by N2 adsorption-desorption experiment The optical property of Py-OCP was characterized by fluorescence spectrometer.And the order of porous polymer was investigated by PXRD.2.A series of pyrene-functionalized POSS-based hybrid porous polymers Py-HPPs(Py-HPP-1?Py-HPP-3)were successfully prepared by Friedel-Crafts reaction using octavinylsilsesquioxane(OVS)and pyrene(Py)as starting materials,The structure of Py-HPPs were characterized by FT-IR and solid NMR.The N2 adsorption-desorption experiments showed that Py-HPPs have multi-stage pore structures with the specific surface areas of 338-1300 m2g-1.It was found that the porous polymers showed stable fluorescence emission through the fluorescence performance test.Finally,we took Py-HPP-3 as an example to study the removal effect on three antibiotics with different molecular sizes(berberine hydrochloride(BCH),tetracycline hydrochloride(TH),mafenide hydrochloride(MH)).The results showed that the adsorption capacity of Py-HPP-3 for BCH,TH and MH were 330,195 and 165 mg g-1,respectively.The removal efficiency retained 95%after 5 cycles.We also performed fluorescence detection on antibiotic molecules,nitroaromatic compounds and metal ions,and found that Py-HPP-3 showed good response to TH,2,4-dinitrophenol(DNP)and Ru3+,the fluorescence quenching constants(Ksv)were 2.79 × 104,2.07×104 and 1.29 ×104 M-1,respectively.