Preparation And Application Of Hypercrosslinked Polymers Based On Friedel-Crafts Reaction

Hypercrosslinked polymers（HCPs）are porous polymers with permanent pores obtained by crosslinking aromatic ring compounds or polymers containing aromatic rings through the Friedel-Crafts reaction.The covalent bonds formed by cross-linking hold up the polymer chains and prevent them from compacting and forming pore structures.Thus HCPs have high specific surface area and abundant pore structures.In addition,HCPs have a lot of advantages such as simple synthesis method,easy functionalization and low cost of raw materials.So they are widely used in catalysis,optoelectronics,gas storage and separation,wastewater treatment and supercapacitors.In this thesis,three novel kinds of HCPs have been synthesized by Friedel-Crafts reaction and applied to iodine adsorption,supercapacitor and dye adsorption according to their structural characteristics.And their performance in these applications has been studied.1.Novel phenothiazine-based HCPs（PZ-HCPs）:PZ-HCPs were synthesized using phenothiazine containing N and S double-rich electrons as monomers and dimethoxymethane as crosslinker by the conditions of Friedel-Crafts reaction.The experimental results show that the specific surface area and pore size distribution of PZ-HCPs could be influenced by changing the amount of monomer and crosslinker.Besides,PZ-HCP-1:4 has a high iodine vapor adsorption capacity of 3.33 g g^-1.FTIR and Raman spectra showed that aromatic rings and electron-rich atoms are iodine adsorption sites,which can polarize I₂ into I₃^-and I₅^-to make them adsorb on the material.The adsorption amount of iodine by PZ-HCP-1:4 in hexane solution was 1537 mg g^-1 and the removal rate of iodine in aqueous solution reached 96.5%.2.Novel polysulfone based supercrosslinked polymers（PSF-HCPs）:PSF-HCPs were obtained using polysulfone with a large number of benzene rings in the main chain as the monomer and dimethoxymethane as the crosslinker by Friedel-Crafts reaction.The specific surface area of PSF-HCPs ranged from 100 to 292 m² g^-1,and the specific surface area and pore size distribution of PSF-HCPs were influenced by the ratio of polysulfone to cross-linking agent.Then,the supercapacitors were prepared after their carbonization and activation at different temperatures and the electrical properties of the supercapacitors were tested.The results showed that the maximum specific capacitance of C-PSF-HCP-1:5-700,C-PSF-HCP-1:5-750 and C-PSF-HCP-1:5-800 were 164.4 F g^-1,98.8 F g^-1 and304.8 F g^-1 at a current density of 0.5 A g^-1,respectively.And the capacitance gradually decreased when the current density increased.The CV curves show that the capacitance characteristics are controlled by the Faraday redox reaction and EDLC,which both help to improve the storage performance of the supercapacitor.C-PSF-HCP-1:5-800 also has good cycling stability,maintaining a specific capacitance of 136 F g^-1 for 5000 cycles at a current density of 5A g^-1.3.Novel silicone resin-based supercrosslinked polymers（HCPs-603 and HCPs-604）:All-phenyl silicone resin（603）and methylphenyl silicone resin（604）as monomers and dimethoxymethane as the crosslinking agent were used to synthesize HCPs-603 and HCPs-604 by Friedel-Crafts reaction.The specific surface area and pore size distribution of HCPs-603 and HCPs-604 were affected by changing the ratio of cross-linking agent and silicone resin.The specific surface area of HCPs-603 ranged from 741～889 m²g^-1and that of HCPs-604 ranged from 583～829 m² g^-1.The results of the dye adsorption experiments showed that HCP-603-1:5 showed fast adsorption rates and large adsorption amounts for three dyes:CR,MG and Rh B.The maximum adsorption amounts were 1278mg g^-1,1900 mg g^-1 and 1418 mg g^-1,respectively.