含多芽苯並三唑苯酚氧配位基之鋅、鈷、鎳、銅與鈀錯合物之合成、結構鑑定以及應用於二氧化碳和環氧環己烷共聚合反應的催化研究

本論文主要利用Duff reaction將苯並三唑苯酚(benzotriazole phenol，BTP-H)合成含有醛官能基的C8AldBTP-H再與1,3-Diaminopropane的一級胺成功利用Imination得到Salen-type Schiff-base的配位基C83CBiIBTP-H2，將上述配位基與醋酸銅、鈀、鋅、鎳、鈷在不同比例條件下可得到單核及雙核的錯合物(1)-(5)，並經由1H NMR光譜、13C NMR光譜、元素分析儀、APCI-MS、IR吸收光譜以及單晶X-ray繞射儀鑑定證明其結構。將錯合物(3)、(4)、(5)應用於二氧化碳/環氧環己烷(cyclohexene oxide, CHO)進行共聚合催化反應，發現錯合物(4)對於此反應的活性及選擇性極佳，只需要0.03125mol%的低催化劑含量(72hr、300psi、120oC、con:82%、Mn: 62300/28900)，>99%的Carbonate linkage且產物皆為聚碳酸酯(Poly cyclohexene carbonate)，無任何的環碳酸酯(Cyclic carbonate)的產生。又在0.0625mol%、6hr、300psi、120oC時TOF值可達到80。然而錯合物(5)的催化活性與(4)一樣，但是在高分子選擇性(Copolymer selectivity)還是錯合物(4)較好，沒有任何環碳酸酯的產生。也優於錯合物(3)的催化活性及高分子選擇性。

關鍵字

共聚合反應催化；環氧環己烷；二氧化碳

並列摘要

Several novel metal complexes incorporated by salen type which bearing BTP ligands (BTP = N,O-bidentate benzotriazole phenoxide), [(C83CBiIBTP)Cu] (1) , [(C83CBiIBTP)Pd] (2) , [(C83CBiIBTP)Zn2(OAc)2] (3) , [(C83CBiIBTP)Ni2(OAc)2] (4) , [(C83CBiIBTP)Co2(OAc)2] (5) were synthesized and structurally characterized. Their catalytic activities of carbon dioxide/cyclohexene oxide copolymerization were systematic studied. [(C83CBiIBTP)Ni2(OAc)2] (4) was active for the copolymerization of carbon dioxide/cyclohexene oxide in controlled manner, yielding poly(cyclohexene carbonate) with the highly molecular weights and narrow PDIs (Mn: 62300/28900 , PDI:1.06/1.05). Additionally, There were no evidence of cyclic carbonate being formed only when complex (4) as catalyst, and it showed good productivity (TON:2784) and activity (TOF:80). Although complex (5) and (3) were also a active catalyst for the copolymerization of carbon dioxide/cyclohexene oxide, its can not compared with the well defined (4). Therefore, the copolymerization activity is (4) > (5) > (3).

並列關鍵字

CHO ； CO2 ； Catalysis for Copolymerization

參考文獻

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含多芽苯並三唑苯酚氧配位基之鋅、鈷、鎳、銅與鈀錯合物之合成、結構鑑定以及應用於二氧化碳和環氧環己烷共聚合反應的催化研究

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