Synthesis, Structural Characterization and CatalyticStudies for Carbon Dioxide/Epoxides Copolymerization of Novel Multinuclear Nickel Complexes Containing Diamine-Bis(Benzotriazole Phenolate)/Bis(Benzotriazole Iminophenolate)and Nitrophenolate Ligands

• Main Authors: Hsin-Wei Wu, 伍薪維
• Other Authors: Bao-Tsan Ko
• Format: Others
• Language: zh-TW
• Published: 2017
• Online Access: http://ndltd.ncl.edu.tw/handle/15777711930781491374

碩士 === 國立中興大學 === 化學系所 === 105 === Seven novel di-nuclear and one tri-nuclear nikel-metal complexes bearing diamine-bis(benzotriazole phenolate), bis(benzotriazole iminophenolate) and nitrophenolate ligands (NP, DNP, TNP), [(C8MEADiBTP)Ni2(NP)2] (1), [(C8MEADiBTP)Ni2(TNP)2] (2), [(C8BEADiBTP)Ni3(NP)4(H2O)2] (3), [(C8BEADiBTP)Ni2(TNP)2] (4), [(C83CBiIBTP)Ni2(NP)(MeOH)2][ClO4] (5), [(C83CBiIBTP)Ni2(NP)(MeOH)2] [NP] (6), [(C83CBiIBTP)Ni2(DNP)2(MeOH)2] (7), [(C83CBiIBTP)Ni2(DNP)(H2O)3][DNP] (8) have been synthesized and structurally characterized. Their catalytic performances of carbon dioxide/epoxides copolymerization were systematic studied. In the first part of this study, we apply complex 1~4 to catalyze the copolymerization of cyclohexene oxide (CHO) with CO2. Among these complex, di-nickel complex 1 is the most effective catalyst .It was found that high activity(TOF=752h-1), excellent copolymer/copolymerization selectivity, and high molecular weight could be achieved under the appropriate reaction conditions. In the second part , di-nickel complex 6 and 7 were used to test the catalytic performance of CO2/CHO copolymerization. Both of them are effective catalyst for the alternating copolymerization of CHO with CO2, giving good activity (complex 6, TOf = 500h-1; complex 7, TOF = 640h-1) and PCHCs with high molecular weights (complex 6, Mn = 22,400 g/mol; complex 7, Mn= 23,500 g/mol) with high carbonate linkages. In addition, adjusting different temperatures of copolymerization for complexes 1/6/7 to optimize reaction conditions and to compare activity of them. Finally, we chose complex 1 to copolymerize cyclopentene oxide (CPO) with CO2 because it reveals the most excellent performance among them. According to the results of catalysis experiments, the highest-molecular-weight copolymer (PCPC) with a large amount of carbonate linkages and narrow PDIs ( Mn = 16,900 g/mol, PDI = 1.21) was obtained.