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  • 學位論文

含雙氧配位基Biphen 之鎂、鋁及鋅錯合物之 合成、鑑定及其於開環聚合反應之催化研究

Synthesis, Characterization and Catalytic Studies of Biphen Supported Magnesium, Aluminum and Zinc Complexes : Efficient Catalysis for Ring-Opening Polymerization of Cyclic Esters and Trimethylene Carbonate

指導教授 : 柯寶燦
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摘要


摘要 本論文已成功合成一系列含Biphen雙氧配位基(Biphen-H2 = 3,3’-di-tert-butyl-5,5’,6,6’-tetramethylbiphenyl-2,2’-diol)的金屬錯化合物(1)- (5);其中(1) - (3) 錯合物為使用THF作為溶劑並與鎂、鋁和鋅烷基試劑進行錯合物之合成,其化學結構皆有THF進行配位的雙核[(Biphen)Mg(THF)]2 (1)、單核[(Biphen)Al(THF)] (2)與参核[(Biphen)2Zn3Et2(THF)2] (3)等錯合物。同時我們也利用以上三種錯合物在有9-Anthracenemethanol的存在下,對環己內酯(CL)、環碳酸酯(TMC)及環丁內酯(BBL)進行開環聚合反應。在催化環己內酯聚合反應中,錯合物(1)-(3)皆具有良好的開環聚合活性以及不錯的分子量控制性。特別是錯合物(3)呈現最佳的催化活性,因此選用其再對環碳酸酯及環丁內酯進行開環聚合反應,同時有不錯的催化活性及可控制性的分子量分佈度。 為了符合單一活性中心的設計概念,利用磺酸化反應來改質Biphen配位基使其為帶-1價之配位基(CF3Biphen(OS)-H與OMeBiphen(OS)-H)。利用上述兩個磺酸化後的配位基與鎂烷基試劑進行錯合物之合成,可得到錯合物[(CF3Biphen(OS))2Mg] (4) 和[(OMeBiphen(OS))2Mg] (5) 。利用兩個鎂金屬錯合物對環己內酯進行開環聚合反應皆具有極佳的開環聚合活性以及良好的分子量分佈度;其中又以錯合物 (4) 具有最佳的效果,因此利用(4)對環碳酸酯進行開環聚合亦可得到理想的效果。另外,亦嘗試進行團聯共聚物的合成與研究,利用依序加入不同單體的合成策略可成功的對環己內酯與環碳酸酯進行共聚合。由實驗結果顯示,以錯合物(4)為催化劑所合成的PCL-b-PTMC皆具備有良好的分子量控制性和不錯的分子量分佈度。在CL的開環聚合反應中,錯合物(4)的催化活性高於錯合物(5)。可能原因在於錯合物(4)的配位基上之CF3基團為一拉電子基而造成Mg2+金屬具有較高的路易士酸性,因此錯合物(4)呈現較佳的活性。

並列摘要


Abstract Novel and soluble metal complexes have been synthesized and structurally well-characterized.The reaction of (Biphen-H2 = 3,3’-di-tert-butyl-5,5’,6,6’-tetra methylbiphenyl-2,2’-diol) with alkyl magnesium, aluminum and zinc reagents in THF gives [(Biphen)Mg(THF)]2 (1), [(Biphen)Al(THF)] (2)and [(Biphen)2 Zn3Et2(THF)2](3). Experimental results show that complexes (1) , (2) and (3) are efficient catalysts for ring-opening polymerization of ε-caprolactone (ε-CL), trimethylene carbonate (TMC) and β-Butyrolacton (β-BL) in the presence of 9-anthracenemethanol ; Among them complex (3) catalyzes the polymerization of ε-CL , TMC and β-BL in a controlled manner, yielding polymers with the expected molecular weights and narrow polydispersity indexes (PDIs). In ε-CL polymerization, the activity of complex (3) is higher than that of complex (1) and complex (2) , which is probably due to the complex (3) have higher Lewis acidity of Zn2+. Two novel sulfonate phenol ligands, CF3Biphen(OS)-H and OMeBiphen (OS)-H , have been prepared by the sulfonylation Biphen with one molar equiv. of the corresponding 4-substituted benzenesulfonyl chloride in the presence of excess triethylamine. Magnesium (Mg) complexes supported by sulfonate phenoxide ligands have been synthesized and structurally characterized. Reaction of Mg(nBu)2 with two equivalent amount of RBiphen(OS)-H (R=CF3 or OMe) produces the four-coordinated monomeric complex [(CF3Biphen(OS))2Mg] (4) and [(OMeBiphen(OS))2Mg] (5), respectively. Experimental results show that complexes (4) and (5) are efficient catalysts for ring-opening polymer ization of ε-caprolactone (ε-CL) and trimethylene carbonate (TMC) in the presence of 9-anthracenemethanol ; complex (4) catalyzes the polymerization of ε-CL and TMC in a controlled manner, yielding polymers with the expected molecular weights and narrow PDIs . In ε-CL polymerization, the activity of complex (4) is higher than that of complex (5) , which is probably due to the higher Lewis acidity of Mg2+ metal caused by the electron-withdrawing substitute, trifluoromethyl(-CF3) on the 4-position of the benzenesulfonate group.

參考文獻


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