Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16890
標題: 含NNO三牙配基之鋅、鎂金屬錯化合物之合成與鑑定及其在環酯類開環聚合反應之應用與探討
Synthesis and Characterization of Zinc and Magnesium Complexes Bearing NNO-Tridentate Ligands: Their Application in Ring-Opening Polymerization of Cyclic Ester
作者: 陳祖韻
Chen, Zu-Yun
關鍵字: NNO-tridentate ligands
NNO三牙配位基
ring-opening polymerization
cyclic ester
開環聚合
環酯類
出版社: 化學系所
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摘要: 本論文主要利用含NNO之三牙配基搭配鋅、鎂金屬與苯甲醇合成出一系列帶有芐氧基之錯化合物,且對其作一系列的鑑定工作,並探討其在環酯類 (乳酸交酯與環己內酯) 的開環聚合反應。由結果可知,此系列錯化合物在開環聚合上有優異的表現,良好的活性及分子量分佈度與分子量控制性都有一定的水準,在外消旋乳酸交酯的選擇性上也有良好的結果,Pr值可達0.81。根據之前研究中相似結構錯化合物之變溫1H NMR實驗與錯化合物4a的凝固點下降之實驗推論錯合物4a在溶液中之構型為雙核結構,並搭配錯合物6a與左旋乳酸交酯之動力學實驗研究推知其速率反應式為-d[LA]/dt = kapp [LA]2 [6a]1,屬於單體為二級反應而對錯合物為一級反應,並藉由上述之實驗推導其可能之反應機制。
A series of metal benzylalkoxides, [LM(μ-OBn)]2 (L= L1-H~L6-H, M = Mg or Zn) based on NNO-tridentate ligands have been synthesized and characterized. Studies of reveal, 1a-6a and 3b-4b, are dinuclear species with pentacoordinated metal centers through the bridging of the benzylalkoxy oxygen atoms in the solid state. In contrast, X-ray structure studies of 4a is a dinuclear species and the geometry around the metal center is pentacoordinated. The activities of 1a-6a and 3b-4b toward the ring-opening polymerization of L-lactide have been investigated. The stereoselectivity of 1a-6a toward of rac-lactide are also examined. Experimental results show that these complexes efficiently catalyze the polymerization of cyclic ester in a controlled fashion, yielding polymers with narrow polydispersity indexes. Complexes 1a-6a exhibit medium to high stereoselectivity with Pr above the 0.81. The polymerization kinetics using complex 6a results reveal that reaction rate: -d[LA]/dt = kapp [LA]2 [6a]1.
URI: http://hdl.handle.net/11455/16890
其他識別: U0005-2206201115563400
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-2206201115563400
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