The Synthesis Of Terpyridines Derivatives With Muti-hydroxyl Groups And The Catalytic Properties Of Terpy-CuCl Complexes To Oxidative Carbonylation Of Methanol

The synthetic methods of a variety of4’-substituted-2,2’:6’,2"-terpyridine derivatives were investigated in this thesis. A series of terpyridine-cuprous complexes were prepared and the catalytic properties of these complexes were tested in oxidative carbonylation of methanol to synthesize dimethyl carbonate in small reactors.The first part is the introduction. In this section, the basic concepts such as coordination chemistry and coordination polymers were given and the potential development of the terpyridine ligands was briefly introduced. The synthetic methods and the applications of terpyridine derivatives and their corresponding complexes in the recent reports were summarized. At last, the ideas and the topic of this thesis were proposed.The preparation and characterization of terpyridine ligands and their corresponding complexes were discussed in the second part.4’-Substituted-2,2’:6’,2"-terpyridine derivatives with multiple hydroxyl groups were synthesized and characterized by NMR and infrared spectral. Furthermore, several ligands were tried to synthesize in different approaches. Detailed analysis and discussion about synthetic method were described, including unfinished ligands.The catalytic properties of terpyridine complexes for oxidative carbonylation of methanol were described in the third part. Terpyridine ligands and cuprous chloride were reacted to prepare corresponding complexes. Simulating factorial productive conditions, catalytic properties were tested in a small reactor under the condition of120℃,2.4MPa (Pco:Po2=2:1) with0.05mol/L catalyst in3h. The results showed that the complex formed by4,4"-dioctyloxy-4’-hydroxy-2,2’:6’,2"-terpyridine and CuCl exhibited the best catalytic activity. The conversion rate of methanol achieved2.313%, the selectivity of DMC up to97.89%, space-time yield up to0.0143mol-DMC/(mol-cat-h), the corrosion rate was2.08g/(m2-h)。...