I Furosemide Base -Zn (Ⅱ) -Ln (Ⅲ) And Asymmetric Seats Furosemide Base -Zn (Ⅱ) And Its Catalytic Oxidation Of Cyclohexene With Maleic Anhydride Copolymers Research Ring Opening

To solve environmental pollution by barely biodegradable polyolefin wastes, unsaturated aliphatic polyesters, as one of biodegradable polymers, are of universal interest because of their good biocompatibility and easy post-polymerization modification with unsaturated carbon-carbon bond. However, the needed catalytic systems often play a crucial role in copolymerization of epoxides and anhydrides. Herein, new catalysts are designed and used for the ring-opening copolymerization of epoxides and anhydrides, aiming at developing new route and technology to get unsaturated aliphatic polyester products.In this thesis, two series of symmetric Schiff-base-Zn(Ⅱ)-Ln(Ⅲ) and asymmetric Schiff-base-Zn(Ⅱ) catalysts are synthesized and characterized by EA, FT-IR,1H NMR and XRD, from which symmetric Schiff base-Zn(Ⅱ)-Ln(Ⅲ) hetero-binuclear catalysts [L-Zn-Ln, Ln=La, Nd, Eu, Gd, Tb, Er, Yb] with different active metal ions and the asymmetric Schiff base-Zn(Ⅱ) catalysts [Ln-Zn, n=1～5] with different electronic and steric effects are used for ring-opening copolymerization of cyclohexene oxide (CHO) with maleic anhydride (MA). Specific results are as follows:(1) Unsaturated aliphatic polyesters Poly[CHO-MA] are obtained, their number-average molecular weights (Mn, g/mol) are in the range of103～104and their polydispersity distribution indexes (PDI) are about1.5.(2) With rare earth metal ions of [L-Zn-Ln] catalysts varying by the sequence of Nd, Eu, Gd, Tb, Er, Yb, Mn of the copolymers successively reduce (12636-6065g/mol) from the solution copolymerization of CHO with MA. Solution copolymerization of CHO and MA catalyzed by L-Zn-Nd in presence of co-catalyst of DMAP gives the better catalytic behaviors, where the catalytic activity is1960g/mol-1h-1; Mn is15544g/mol and the PDI is1.51on the optimum conditions of polymerization time of300min, polymerization temperature of110℃and the molar ratio [CHO:MA:L-Zn-Nd:DMAP] of250:250:1:1.(3) The catalytic activity sequence of [Ln-Zn] in the ring-opening copolymerization of CHO with MA is:①l1-Zn <L4-Zn <L5-Zn;②L2-Zn <L3-Zn. Copolymerization of CHO with MA catalyzed by [Ln-Zn] also show the favorable results with the catalytic activity of5360g/mol-1h-1; Mn of11284g/mol and PDI of1.60on the optimum conditions, such as solution polymerization, L5-Zn/DMAP, toluene; polymerization time of150min, polymerization temperature of110℃and the molar ratio [CHO:MA:L5-Zn:DMAP:CTA (benzyl alcohol)] of250:250:1:1:8.