Synthesis, Characterization and Catalysis for Carbon Dioxide/Epoxides Copolymerization of Novel Di-nuclear Nickel and Cobalt Complexes Bearing Asymmetric Diamine-Bis(Benzotriazole Phenolate) Ligands

• Main Authors: Siao-Ting Huang, 黃筱婷
• Other Authors: Bao-Tsan Ko
• Format: Others
• Language: zh-TW
• Published: 2019
• Online Access: http://ndltd.ncl.edu.tw/handle/bep946

碩士 === 國立中興大學 === 化學系所 === 107 === The treatment of the metal prcursors and carboxylic acid derivatives with the ligand precursors (C8EtBiIBTP-H2 and C1EtBiIBTP-H2) afforded bimetallic complexes 1-13. [(C8EtHDiBTP)Ni2(OAc)2(MeOH)] , [(C1EtHDiBTP)Ni2(OAc)2(MeOH)], [(C8EtHDiBTP)Ni2(O2CCF3)2(H2O)], [(C1EtHDiBTP)Ni2(O2CCF3)2(H2O)], [(C8EtHDiBTP)Ni2(O2CC6F5)2(H2O)], [(C1EtHDiBTP)Ni2(O2CC6F5)2(H2O)], [(C8EtHDiBTP)Ni2(NP)2], [(C8EtHDiBTP)Ni2(DNP)2], [(C8EtHDiBTP)Ni2(TNP)2], [(C1EtHDiBTP)Ni2(DNP)2], [(C1EtHDiBTP)Ni2(TNP)2], [(C8EtHDiBTP)Co2(OAc)2MeOH ], [(C1EtHDiBTP)Co2(OAc)2MeOH]. Compexes 1-13 were isolated as air-stable crystalline solids and fully characterized by elemental analysis and electrospray ionization mass spectrometry (ESI-MS) and X-ray crystallography. Experimental results showed that all metal complexes were active for the copolymerization of CHO/CO2, giving highly alernating PCHC products. The CHO/CO2 copolymerizations catalyzed by those complexes were systematically studied, and complex 1 revealed the highest catalytic and enabled the formation of poly(cyclopentene carbonate)s with large molecular weitht ( Mn = 34,700 g/mol) and great copolymerization selectivity (>99%) among them. In addition, using various chain transfer agents (CTA) provided polymer chains with chain extended architecture, and the polymer chains could be initiated from the diol dervatives for prepration of polycarbonate polyols. A series of different diols were use as the chain transfer agents, such as 1,2-cyclohexanediol (CHD), 1,3-butanediol (BDO), 2,2-dimethyl-1,3-propanediol (NPG) and H2O were performed to afford the corresponding PCHC polyols. The result have successfully demonstrated that complex 1 was a new high potential catalyst for copolymerization of cyclohexene oxide with caron dioxide with the “controllable” and “immortal” character.