Synthesis, Structural Determination and Catalysis for Carbon Dioxide/Epoxides and Cyclic Anhydrides/Epoxides Copolymerization of Bimetallic Nickel and Cobalt Complexes Incorporated by Nitrogen Heterocycle-Containing Bis(Phenolate) Ligands

• Main Authors: Chi-Hang Chang, 張際航
• Other Authors: 柯寶燦
• Format: Others
• Language: zh-TW
• Published: 2016
• Online Access: http://ndltd.ncl.edu.tw/handle/50339984429823036522

碩士 === 國立中興大學 === 化學系所 === 104 === Six novel di-nuclear metal complexes incorporated by nitrogen heterocycle-containing salen-type ligands, [(C8EtBiIBTP)Ni2(OAc)2] (1), [(C1EtBiIBTP)Ni2(OAc)2] (2), [(C8EtBiIBTP)Co2(OAc)2] (3), [(C1EtBiIBTP)Co2(OAc)2] (4), [(C1EtBiIBThP)Ni2(OAc)2] (5) and [(C1EtBiIBThP)Co2(OAc)2] (6), have been synthesized and structurally characterized. Their catalytic performances of carbon dioxide/epoxides and cyclic anhydride/epoxides copolymerization were systematic studied. Nickel(II) complexes 1, 2 and 5 are effective catalysts for the alternating copolymerization of cyclohexene oxide (CHO) with CO2; di-nickel complex 1 is shown to be the most active and selective, leading to obtain poly(cyclohexene carbonate) with the highest molecular weight. Additionally, complex 1 was able to behave an active catalyst for the alternating copolymerization of different epoxides with CO2 to provide the corresponding polycarbonates. Cobalt(II) complexes 3, 4 and 6 are efficient catalysts for the alternating copolymerization of CHO and phthalic anhydride (PA) under mild conditions. According to the results of catalysis experiments, complex 3 is demonserated to be the most active and selective in CHO/PA copolymerization, producing the polymeric products in a “controlled” manner with the expected molecular weights and narrow PDIs. In addition, complex 3 is an effective catalyst for the alternating copolymerization of different epoxides with PA to give the corresponding polyesters.