Study On The Preparation And Catalytic Oxidation Performance Of Binuclear Metallophthalocyanine Derivatives

The plane binuclear phthalocyanines possess extended?-electron system in molecular structure, which have received considerable attentions in recent years since they exhibit unique photoelectric and catalytic properties. The application of metallophthalocyanines has been restricted in many fields because of its insolubility in water. Hydrophilic groups such as carboxyl, amide were introduced into phthalocyanine molecular, which can not only improve its solubility in the water or other polar solvents, but also improve its catalytic activity.In view of their insolubility in water, binuclear metallophthalocyanines and bimetallophthalocyanines derivatives were synthesized. At the same time, their catalytic performance in oxidizing cyclohexane and removing mercaptans was studied under mild conditions.Using Pyromellitic dianhydride as reactant, binuclear metallophthalocyanine (Co?Cu?Fe) derivatives were synthesized by solid-phase method. The optimum synthesis and hydrolysis conditions of intermediate products have been sought out on the basis of process optimizing. Furthermore, binuclear bimetallophthalocyanine(CoCu?FeCu?FeCo) derivatives were synthesized. For the first time, binuclear bimetallophthalocyanine(FeCu?FeCo) derivatives of different metal proportion were synthesized through changing dosage of metal salt in raw materials. The results showed that in the binuclear bimetallophathalocyanines like the intermediate products and hudrolysis products, the proportions of Fe to Cu and Fe to Co (mole ratio) increase with the increasing amount of iron salt in raw materials while controlling the amount of copper salt or cobalt salt in raw materials within the theoreotic amount.In the process of exploring optimum hydrolysis conditions, due to the problems of tedious purification process and easy loss of products, a simple method of determination optimum hydrolysis time was rapidly established by detecting the UV-Vis spectrum of hydrolysis solution under different time. The optimum hydrolysis time of the products, such as binuclear metallophthalocyanine(Fe, Co), binuclear bimetallophthalocyanine (FeCo, FeCu, CoCu) and FePc derivatives, was determined.The structures of the binuclear single metal and bimetal phthalocyanines derivatives synthesized were confirmed by characterization methods including UV-Vis, IR, 1H-NMR, time-of-flight mass spectrometry, elemental analysis, TGA, et al. The structures of CoBPcC, CuBPcC, and FeBPcC were determined. The solubility of binuclear metallophthalocyanine derivatives was determined in many solvents such as alkaline solution, DMSO, DMF, pyridine with UV-Vis spectrometry. It revealed that the solubility of hydrolysis products was more excellent than that of intermediate products; the solubility of hydrolysis products was in consistent with the polarity of solvents, so hydrolysis products can be easily dissolved in 2%NaOH and DMSO; The solubility of carboxyl substituted binuclear metallophthalocyanine derivatives containing different metal was different in the same solvent.For the first time, the determination method of metal content in binuclear metallophthalocyanine derivatives was established through colorimetry combining with chemical treatment. Metal contents in binuclear metallophthalocyanine derivatives were determined. The results showed that: (1) the determination of content of Co?Cu was affected by temperature. It was conducted under constant temperature because absorbance was in consistent with increasing temperature. When determining Co and Cu content, the solution should be heated to navy blue and/or green respectively during decomposition stage. (2) The determination of Cu content was affected by time, the precision was improved significantly when prolonging time from 10min to 30min. (3) The affect of Cu and Fe to Co can be eliminated by bubbling up when Co content of FeCoBPc and CuCoBPc derivatives was investigated.The catalytic activity of binuclear metallophthalocyanines and bimetallophthalocyanines derivatives in cyclohexane oxidation was detected with t-BHP as oxidant. Binuclear iron phthalocyanine represented the highest activity among the binuclear metallophthalocyanines derivatives, and the optimum reaction conditions were sought out. Binuclear iron copper phthalocyanine behaved the highest activity among binuclear bimetallophthalocyanines derivatives, and the catalytic activity was increased with Fe content. The catalytic activity and selectivity of binuclear iron phthalocyanine in the oxidation of cyclohexane were corresponding to that of iron porphyrin or iron phthalocyanine, and binuclear iron phthalocyanine took on the advantage of being recycled.The catalytic activity of binuclear cobalt phthalocyanine derivatives in removal of mercaptans was also studied. The results showed that the catalytic activity of intermediate product of binuclear cobalt phthalocyanine in removal of tert-butyl mercaptan was better than that of CoSPc or CoPPc significantly. The catalytic activity of supported catalyst in removal of mercaptan in catalytic cracking gasoline was showed as follows: CoBPcC-AC>CoSPc-AC>CoPPc-AC. Further more, the catalytic activity of supported catalyst of CoBPcC in removal mercaptan in catalytic cracking gasoline was better than that of CoSPc while its life was equal to that of CoSPc. The superior supported catalyst in removal of mercaptan in catalytic cracking gasoline was selected.