Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/14159
標題: 吡唑啉酮金屬化合物之製備及其在 環酯類開環聚合反應上之應用
Preparation of Metal Pyrazolonate Complexes: Efficient Initiators for the Ring-Opening Polymerization of Cyclic Esters
作者: 莊惠如
Chuang, Hui-Ju
關鍵字: 
zinc


開環聚合
環酯類
magnesium
aluminum
ROP
cyclic esters
出版社: 化學系所
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摘要: 本論文以N,N,O-pyrazolonate 架構之配位基,合成鋅金屬錯合物1a-12a,鎂金屬錯合物1b-12b及鋁金屬錯合物1c-5c,並對所有錯合物以氫光譜、碳光譜及元素分析儀進行鑑定。錯合物1a, 2a, 5a, 1b, 2b, 4b及5b之晶體結構及 DOSY NMR 實驗顯示在固態與液態下,鋅與鎂金屬化合物皆為雙核構形。錯合物1c由晶體結構證實為單核四配位結構,而4c則為單核五配位結構存在。綜合多數鎂金屬錯合物,重新對動力學公式進行適配,選擇對單體為二級反應進行,並參考先前文獻所發表凝固點下降及變溫NMR實驗結果,推導配位-插入開環聚合之反應機制。 在應用方面,鋅金屬錯合物與鎂金屬錯合物,對於環酯類單體開環聚合皆有良好的催化活性,分子量分佈度與分子量控制性都有一定的水準,而以鋅金屬之活性有優於鎂金屬。討論相同金屬錯合物在配位基上修飾對乳酸單體開環聚合反應之催化活性及現象,以修飾推電子官能基所形成之鋅及鎂錯合物有較好的催化活性,而鋁金屬錯合物則有完全相反的結果。實驗結果發現以雙牙N,O及四牙O,N,N,O配位基鍵結之鋁金屬錯合物在對環己內酯單體開環聚合反應上,相較於N,N,O三牙系統則有較為優異的催化活性。
A series of zinc benzylalkoxide complexes, magnesium benzylalkoxide complexes, and aluminum methyl complexes supported by NNO-tridentate pyrazolonate ligands with various electron withdrawing -donating subsituents have been synthesized and characterized. X-ray crystal structural studies and PGSE experimental revealed that complexes 1a, 2a, 5a, 1b, 2b, 4b and 5b are dinuclear bridging through the benzylalkoxy oxygen atoms with penta-coordinated metal centers. However, the aluminum complex 1c exhibits a monomeric feature with a tetra-coordinated Al center different from the penta-coordinated aluminum complex 4c. Based on kinetic studies, the activity of the magnesium complexes is significantly influenced by the electronic effect of the ancillary ligands with the electron-donating substituents at the phenyl rings enhancing the polymerization rate. All the zinc and magnesium complexes have acted as efficient initiators for the ring-opening polymerization of L-lactide. The ring-opening polymerization (ROP) of caprolactone, decalactone,butyrolactone and their copolymer with complexes 1a and 1b were investigated. It is interesting to note that aluminum complexes bearing O,N,N,O-tetradntate ligand are excellent efficient initiators for the ring-opening polymerization of caprolactone.
URI: http://hdl.handle.net/11455/14159
其他識別: U0005-2801201316024200
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-2801201316024200
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