Synthesis and Charaterization of Zinc Acetate Complexes Supported by Amino-BTP: Their Applications for CO2/Epoxide Copolymerization and Coupling reaction

• Main Authors: Chen-Ruei Wu, 吳晨瑞
• Other Authors: Bao-Tsan Ko
• Format: Others
• Language: zh-TW
• Published: 2012
• Online Access: http://ndltd.ncl.edu.tw/handle/55741978171529957909

碩士 === 中原大學 === 化學研究所 === 100 === The amino-benzotriazole phenol ligands (C1DEABTP-H, C8DEABTP-H, C1PPBTP-H, C8PPBTP-H, C8NNBTP-H) were prepared through the Mannich condensation of 2-(2H-benzotriazol-2-yl)-4-alkyl-phenol (alkyl = CH3 or C8H17) with the mixtures of excess paraformaldehyde and secondary amine under reflux conditions. The reaction of Zn(OAc)2 with RamineBTP-H (RDEABTP-H = 0.5 equiv, RPPBTP-H and RNNBTP-H = 0.67 equiv) produced di- and tri-zinc complexes [(C1DEABTP)Zn2(OAc)¬4] (1), [(C8DEABTP)Zn2(OAc)¬4] (2), [(C1PPBTP)2Zn3(OAc)4] (3), [(C8PPBTP)2Zn3(OAc)¬4] (4) and [(C8NNBTP)2Zn3(OAc)¬4] (5). The novel di- and tri-zinc catalysts incorporated by the BTP ligands are synthesized with variation of the amino group. The catalytic system which have acetate end group were prepared for the copolymerization/coupling of cyclohexene oxide and carbon dioxide in the presence of the quaternary ammonium salts (tetrabutylammonium bromide, TBAB) as cocatalyst. The catalyst selectivity was changed on the scale of cocatalyst to yield perfectly alternating copolymer (PCHC) or cis-isomer of the cyclic carbonate (cis-CHC), herein we report the production of polymer with more than 99% carbonate linkage. In the existence of the TBAB as cocatalyst (1 equiv), the complex show the better active in copolymerization to yield PCHC, molecular weights of 5200 and polydispersity indices 1.42. An increase in the TBAB ratio decreases the rate of PCHC formation and favors the formation of cis-CHC.