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

In this thesis,the synthesis of a series of nitrogen/oxygen-containing terpyridine compounds with single hydroxyl group or polyhydroxy groups were reported.A method for terpyridine being grafted to polyvinyl alcohol(PVA)was also described.Terpyridine-copper complexes were prepared and applied to methanol oxidative carbonylation for the synthesis of dimethyl carbonate(DMC).The catalytic properties of these complexes were tested in a autoclave and the results were collected and discussed.Literature reviewing part was presented in the first chapter.The nature,applications and the latest developments on dimethyl carbonate(DMC)were described,focusing on methanol liquid phase synthesis of dimethyl carbonate by oxidative carbonylation with copper catalyst.At last,the ideas of our research were proposed partly based on previous results in our laboratory.The synthesis and characterization of terpyridine ligands were summarized in the second part.A lot of nitrogen/oxygen-containing terpyridine compounds with single hydroxyl group or polyhydroxy groups were synthesized,which molecular structures were characterized by nuclear magnetic resonance(NMR)and infrared(IR)spectroscopy.In addition,the several experimental results not completed were discussed.The preparation of the catalysts were reported.Different terpyridine ligands coordinated with cuprous chloride to generate catalysts which structures were characterized.The synthesis and analysis of the polymer were reported in the third chapter.Polymers of PVA-terpyridine were synthesized starting from a terpyridine derivative and their structures were characterized.The results and discussion of the catalytic reaction and the experimental method of methanol oxidative carbonylation to synthesize DMC were presented in the fourth chapter.The operating methods of the autoclave and gas chromatography,data collection and calculation were also described in this chapter.Analytic methods on gas chromatography were especially compared.Packed column gas chromatography was replaced by capillary-column gas chromatography.An internal standard method was adopted,instead of an external standard previous used.Testing results were collected and discussed according to conversion of methanol,selectivity of DMC,space-time conversion of catalyst and corrosion rate of stainless steel.Furthermore,influences of catalytic activity of a catalyst were discussed respectively from the structure of a ligand,reaction time,solubility and concentration of a complex,and feeding methods of a catalyst.Experiments proved that the complex formed by L2 and CuCl showed the best catalytic activity under the conditions of 120℃,2.4MPa(Pco:Po2 = 2:1)with 0.05 mol/1 in 5 hours.The conversion rate of methanol achieved 12.27%,the selectivity of DMC up to 97.22%,space-time yield up to 5.2 mol-DMC/(mol·cat·h),the the corrosion rate was 0.89 g/(m2·h)for stainless steel Q235.