Synthesis Of Functional Polymer Supported Pd Catalyst And Its Application In C-C Coupling Reaction

Over the past 40 years,people were interested in the Suzuki-Miyaura（S-M）coupling reaction and its applications has increased.Especially in the past ten years,various reports have increased exponentially,which fully demonstrates its efficiency and effectiveness.This widely used approach provides a useful synthetic route for directly forming C-C bond,in addition to the full synthesis and the pharmaceutical industry,in the production of polymers,fine chemicals and materials found considerable academic and industrial applications.Although the traditional homogeneous catalyst has high catalytic efficiency,it also has some disadvantages such as high price,trace residues,difficult separation and environmental pollution.In contrast,the supported catalysts can improve these shortcomings.In recent years,the development of new environmentally friendly,stable and efficient supported catalysts has gradually become the main research focus.According to the concept of“green chemistry”,three kinds of Pd catalysts supported by COF,MOF@COF and biomass eggshell membrane were developed in this paper.And their catalytic activities was also investigated in the C-C coupling reaction1.A novel covalent organic framework OC-MA was synthesized by using nitrogen-rich melamine and 4,4-oxydibenzoyl chloride as raw materials in one step.Then,Pd@OC-MA catalyst was successfully prepared by impregnation in acetonitrile solution of palladium acetate.The structures of OC-MA and Pd@OC-MA were confirmed by ICP-AES,IR,XRD,XPS,SEM et al.The Pd@OC-MA catalyst shows effective catalytic activity and selectivity for the Suzuki-Miyaura coupling reaction in water.Especially for the less reactive chlorinated aromatic hydrocarbons,they also have moderate to excellent conversion rates.The catalyst Pd@OC-MA showed excellent stability and recycles 5 times without any activity decrease.2.A novel type of porous hybrid material MOF@COF was successfully synthesized by in-situ growth of COF on the surface of amino-functionalized metal organic framework（NH₂-MOF）,which was employed as support to anchoring palladium particles to obtain heterogeneous catalyst MOF@COF-Pd.The MOF@COF-Pd shows favourable catalytic activity in the C-C coupling reaction of involving pyrimidine sulfonate and aryl boronic acid.It has excellent recyclability and the catalytic activity drops slightly after 5 recycles.3.A stable heterogeneous palladium catalyst ESM-Pd（OAc）₂ was synthesized by using domestic waste eggshell membrane（ESM）as support by a simple and green process.The ESM-Pd（OAC）₂ catalyst can effectively catalyzed the Suzuki coupling reaction without ligands in water.The reaction of various aryl halides and aryl boronic acid can be obtained corresponding coupling products with moderate to excellent yields.The catalyst ESM-Pd（OAc）₂ shows outstanding stability and has broad tolerance to the substrate,and can be recycled for at least 12 times without any activity decrease.