Synthesis And Adsorption Property Of Zero-dimensional Supramolecular Monomers-based Metallopolymers

Zero-dimensional supramolecules not only have unique solubility but also excellent physical and chemical properties.With the concept of polymer monomers,the zero-dimensional supramolecular monomers and polymer monomers are combined to prepare metal-organic polymers with both supramolecular and polymer properties,realizing the control of material structures and properties,and broadening the functions and applications of both.In this thesis,starting from the strategy of constructing zero-dimensional supramolecules,carbon-carbon double bond active functional groups were grafted to the organic building units which were used to assemble supramolecules,and then further coordinated with metal ions through supramolecular coordination to synthesize zero-dimensional supramolecular monomers with potential polymerization reactivity,and then copolymerized with polymer monomers through free radical reaction to prepare metal-organic polymers.On the basis of characterizing the structures,the adsorption property of pollutants in water as an adsorption material were studied.The main research works of this thesis are as follows:（1）Organic building units（L¹and L²）were designed and synthesized with polymerizable functional groups（-CH=CH₂）,and then were assembled into grid-like supramolecular monomers（G¹and G²）with metal ions,and finally copolymerized with Butyl methacrylate（BMA）to prepare a series of metal-organic polymers.The experimental results showed that different contents and structures of grid-like supramolecular monomers had different effects on the adsorption performance of Cr（Ⅵ）and the stability of materials.And metal-organic polymers Poly（60G¹-BMA）with 60.0 wt.%supramolecular monomers G¹not only had a better adsorption capacity(30.26 mg·g^-1),but also exhibited excellent stability in different simulated environments.（2）Based on the construction method of zero-dimensional cage-like supramolecules,a series of cage-like supramolecular monomers(C^a-f)with polymerizable functional groups（-CH=CH₂）were synthesized,and finally copolymerized with the polymer monomers BMA to synthesize metal-organic polymers.The research structure showed that metal-organic polymers with cage-like cavities exhibited excellent adsorption properties for picric acid,which were affected by the structure of cage-like supramolecular monomers.The maximum adsorption capacity was 118.92 mg·g^-1,and the adsorption processes were best fitted with the pseudo-second-order kinetic model.By copolymerization and adsorption of picric acid,the mechanical sensitivity of cage-like supramolecular monomers decreased obviously.