Synthesis, Structural Characterization and Catalytic application for Carbon Dioxide/Epoxides Copolymerization of Novel Dinuclear Nickel and Cobalt Complexes Bearing Diamine-Bis(Benzotriazole Phenolate) Ligands

• Main Authors: Pei-Min Lin, 林佩旻
• Other Authors: Bao-Tsan Ko
• Format: Others
• Language: zh-TW
• Published: 2016
• Online Access: http://ndltd.ncl.edu.tw/handle/35417312445863452960

碩士 === 國立中興大學 === 化學系所 === 104 === Eight novel di-nuclear metal complexes bearing diamine-bis(benzotriazole phenolate) ligands, [(C8BEADiBTP)Ni2(OAc)2] (1), [(C8BEADiBTP)Co2(OAc)2] (2), [(C8MEADiBTP)Ni2(OAc)2(H2O)] (3), [(C8MEADiBTP)Co2(OAc)2(H2O)] (4), [(C8BEADiBTP)Ni2(O2CCF3)2] (5), [(C8MEADiBTP)Ni2(O2CCF3)(H2O)2] ClO4 (6), [(C8BEADiBTP)Ni2(DNP)2] (7), [(C8MEADiBTP)Ni2(DNP)2] (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, nickel complex 3 is an effective catalyst for the alternating copolymerization of cyclohexene oxide (CHO) with CO2 to give turnover numbers of up to >4000 and turnover frequencies of up to >400 h-1. Not only controlled CO2/CHO coupling of nickel catalyst 3 has enabled, but also catalyst 3 been applied to catalyze the copolymerization of 4-vinyl-1,2-cyclohexene oxide (VCHO) and CO2 to obtain the corresponding polycarbonate with the vinyl functionality on the side chains. This is the first example of a dinuclear Ni complex that is efficient for both CO2/VCHO copolymerization as well as the formation of a high-molecular-weight copolymer with high carbonate linkages.   In the second part , di-nickel complexes 5 and 8 with different co-ligands are effective catalyst for the alternating copolymerization of cyclohexene oxide (CHO) with CO2 to give good productivity (complex 5, TON = 4800; complex 8, TON = 7100) and poly(cyclohexene carbonate)s with highly molecular weights and narrow PDIs (complex 5, Mn = 55,000 g/mol, PDI = 1.23; complex 8, Mn = 56,100 g/mol, PDI = 1.37). In addition, both complexes 5 and 8 are efficient for CO2/VCHO copolymerization and the formation of a high-molecular-weight copolymer with a large amount of carbonate linkages.