双膦Cu及不对称Pd催化剂的结构及其对烯烃-一氧化碳完全交替共聚的催化性能

 配体及配合物的结构对催化烯烃-CO完全交替共聚反应活性及稳定性具有重要的影响. IR和XPS实验结果表明,5-硝基-1,10-菲咯啉的钯配合物催化苯乙烯-CO共聚的高活性与其结构的不对称性有关; 揭示了廉价的Cu金属双膦螯合物作为新型乙烯-CO交替共聚催化剂具有一定的可行性,探讨了配合物结构对烯烃-CO共聚反应活性及稳定性的影响,同时通过IR,1H NMR和13C NMR确认了所得交替共聚物聚酮的结构.

Structure of Pd and Cu Complexes and Their Catalytic Performance for Perfectly Alternating Copolymerization of Olefin with Carbon Monoxide

The alternating copolymerization of olefin with CO is of great theoretical and practical interest, for it utilizes the plentiful and inexpensive carbon monoxide as one of the monomers to give a kind of plastics with environment-protective function. The bidentate ligands (N-N) with N and P atoms were prepared. Their corresponding Pd and Cu complexes were synthesized and used as catalysts in the copolymerization of styrene-CO and ethylene-CO, respectively. The effects of structure of the catalysts on their catalytic activity and stability were investigated. The IR absorption peaks of the CO 2 in [(N-N)Pd(CH 3CO 2) 2] and [(N-N)Pd(CF 3CO 2) 2] confirmed the coordinating state of the anions. The XPS results suggested the strength of N-Pd coordinating bond. The asymmetrical substitution of 1,10-phenanthroline (phen) could make [(NO 2-phen)Pd(CF 3CO 2) 2] more active. In the copolymerization of ethylene-CO, it was suggested that the six-coordinated Cu complex could be formed with Ph 2P(CH 2) 3PPh 2, which was relatively stable as the catalyst active species. The relative molecular mass of both copolymerization products was determined, and the structure of the polyketone was confirmed by IR, 1H NMR and 13C NMR results.