Synthesis And Properties Of Functional Porous Organic Polymers

Recent years,porous organic polymers have attracted tremendous attention owing to their high surface area,controllable porous features,good stability,facile surface functionality and tremendous potential applications like light harvesting,gas separation and storage,catalysis,energy conversion,etc.In this paper,a series of porous organic polymer were designed and synthesized with monomers containing B and N atom by coupling and condensation reactions.The special functionalporous organic polymers were prepared by introducing heteroatom and morphologies controlling.The main finding and results were summarized as follows:1)Two novel B-?-N based conjugated porous polymers have been successfully synthesizedbasedontris?bromoduryl?boranecouplingwith4,4,4-?tri?4,4,5,5-tetramethyl-1,3,2-dioxaborol-an-2-yl??triphenylamineand tris?4-ethynylphenyl?amine via the Suzuki and Sonogashira cross-coupling reaction,respectively.They exhibited high chemical,thermal stabilities and high surface areas(1279 m² g^-1).The Donor-?-Acceptor structure of such new type of porous polymers rendered their rich luminescent properties,solvatochromic emission and electrochemical activities.Further,they showed multifunctions including effective H₂uptake capacity and collection of fluoride anion.2)The B,N-containing rigid cross-linked polymers?PPs-BN?were achieved via transition metal-catalyzed cross coupling by the monomers containing boron and nitrogen elements.These cross-linked polymers exhibit high thermal stabilities,which allow them to be efficiently converted to B/N co-doped porous carbons after pyrolysis at high temperature under inert atmosphere.The porous carbon with high contents boron?³.21%?and nitrogen?⁵.72%?,and large specific surface area(291 m² g^-1).The gas adsorption experiment showed the resulting carbon with high CO₂ caption,rendered such kind of materials applicable for gas separation and purification.3)A series of boron-containing conjugated polymers with hierarchical porous structures have been readily prepared via typical transition metal-catalyzed cross-coupling reactions.The distribution of micro-and mesopores in the networks as well as the specific surface areas are tunable via tailoring the structures of the building blocks.The resulting neutral porous polymers can convert into stable anionic porous polymers balanced with counter-cation.The different metal cations were loaded into the organic frameworks by the ion exchange process.Notably,the cobalt-loaded porous polymers can effectively catalyze stoichiometric homocoupling reactions of aryl Grignard regents with size selectivity depending on the porous features of the networks.4)The nanocube-like Pd loaded porous polymers were synthesized by the palladium-catalyzed cross-coupling of tris?bromoduryl?borane and 1,3,5-triethynylbenzene via a typical Sonogashira cross-coupling by in-situ polymerization.Their morphology and porous structures were confirmed by scanning electron microscopy?SEM?,transmission electron microscopy?TEM?and nitrogen sorption analyses.The obtained materials showed excellent stability,high catalytic activity and shape selectivity for Suzuki-Miyaura and Heck coupling reaction even in aerobic conditions.5)Two-dimensional hyper-cross-linked microporous polymers?2D HCPs?have been readily synthesized by emulsion polymerization using trithiocarbonate functionalized graphene oxide as a template.The resulting HCPs exhibited high specific surface area(1224 m² g^-1)and gas adsorption.In addition,the as-synthesized 2D HCPs were used as carbon precursors to generate 2D porous carbons with a high specific surface areas(871 m² g^-1)and high-performance electrochemical energy storage(144 F g^-11 at 0.5 A g^-1).In summary,based on the functionalization of the porous organic polymer,a series of porous organic polymer were designed and synthesized by introducing heteroatom and morphologies controlling.Their applications in the fields of photoelectric performance,catalytic performance,gas adsorption,etc.