The Synthesis Of Terpyridine-Copper Complexes And Their Catalytic Properties To Oxidative Carbonylation Of Methanol

The thesis mainly focused on the synthesis of a series of monohydroxy or polyhydroxy terpyridines and their copper complexes, including a derivative from chloromethylated bead. These complexes were applied to catalyze the reaction of liquid phase oxidative carbonylation of methanol to synthesis dimethyl carbonate. The catalytic activities of such complexes were collected from gas chromatograph.The literature review was presented in the first chapter. The physical and chemical properties of dimethyl carbonate, including application and preparation methods, were briefly introduced.The research progress of catalytic application of terpyridine-metal complexes was also summarized. On the basis of the literatures and laboratory research achievements, we put forward the researching idea of the topic.The synthesis and characterization of terpyridine-matal complexes were discribed in the second chapter. Some of the complexes were characterized by IR spectrometry. The data of those complexes were analyzed.The synthesis and characterization of terpyridine-matal polymer were reported in the third chapter. We have successfully grafted4’-(4-anilino)-2,2’:6’,2"-terpyridine onto chloromethylated crosslinked polystyrene microspheres. Then polymer-CuCl complex is prepared by coordination reaction. The structure of this complex was characterized.The fourth chapter is about the testing results and discussion of catalytic performance. In this part, the testing methods for synthesis of dimethyl carbonate by the liquid phase reaction of oxidative carbonylation of methanol were described, including the control of high pressure reaction kettle, the test conditions of gas chromatography and the processing method of the catalytic data. According to the experimental results, the performance of each catalyst was evaluated respectively, including the methanol conversion, selectivity and space-time conversion of dimethyl carbonate, corrosion rate. Furthermore, factors on the catalytic performance were discussed, such as the effects of ligand structure, negative or positive ions, reaction time and feeding methods. Under the condition of the reaction temperature120℃, total reaction pressure2.4MPa (PCO:P02=2:1), the catalyst concentration0.05mol/L, the reaction time up to3h,4’-(4-hydroxylethoxyphenyl)-2,2’:6’,2"-terpyridine/CuI complex exhibited the best experimental results in all complexes.The conversion rate of methanol reached1.73%, the selectivity of dimethyl carbonate was98.98%, the space-time conversion was0.01083mol-DMC/(mol·cat·h), corrosion rate was0.77g/h.(m2) to Q235stainless steel.