Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16778
標題: 合成與鑑定具NNO三牙配位基之鎂和鋅烷氧錯化合物及其在乳酸交酯開環聚合反應之探討
Zinc and Magnesium Complexes Bearing NNO-Tridentate Ligands: Synthesis, Characterization, and Their Highly Activity for Controlled Ring-Opening Polymerization of Lactide
作者: 廖姿婷
Liao, Tzu-Ting
關鍵字: polylactide;開環聚合反應;lactide;racemic lactide;magnesium;zinc;selectivity;ring-opening polymerization;左旋乳酸交酯;外消旋乳酸交酯;鎂;鋅;聚乳酸交酯;選擇性
出版社: 化學系所
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摘要: 
合成四個具有NNO-三牙酮胺之配位基(L1-H~L4-H),並利用這些配位基與二正丁基鎂或二乙基鋅搭配苯甲醇(Benzyl Alcohol)反應形成錯合物[LMg(μ-OBn)]2 (1a-4a)及[LZn(μ-OBn)]2 (1b-4b)共8個錯合物。其中1a、2a、2b與3b由X-光單晶繞射儀證實其結構為五配位雙核錯合物。所有錯合物對於左旋乳酸交酯開環聚合反應均具良好催化活性並有效控制分子量與狹窄的分子量分佈度。而對於外消旋乳酸交酯之開環聚合反應,鎂錯合物(1a,2a)具有較高選擇性,其Pr值可高達89 %。錯合物[L1Zn(μ-OBn)]2 (1b)可經由錯合物[(L2)2Zn] (1c)與Zn(OBn)2反應得到。由動力學研究推測每次以一當量催化劑與二當量的單體進行配位-插入機制。且經由[L-LA]0/[1a]0 = 2:1之Tube實驗可知,在進行開環聚合反應時,會以Mg-N鍵斷裂而使金屬中心多一配位,因此單體即可配位而進行開環聚合反應。

A series of metal benzylalkoxides, [LM(μ-OBn)]2 (L= L1-H~L4-H, M = Mg or Zn), based on N,N,O-tridentate ketiminate ligands were synthesized and characterized. X-ray crystal structural studies of [L1Mg(μ-OBn)]2 (1a) (L1-H = (Z)-4-((2-(Dimethylamino)ethylamino) (4-methoxyphenyl)methyl-ene)-3-methyl-1-phenyl-pyrazolin-5-one), [L2Mg(μ-OBn)]2 (2a) ( L2-H = (Z)-4-((4-Chlorophenyl)(2-(dimethylamino) ethylamino)methylene)-3-methyl-1-phenyl-pyrazolin-5-one ), [L2Zn(μ-OBn)]2 (2b) and [L3Zn(μ-OBn)]2 (3b) (L3-H = (Z)-4-((4- Methoxyphenyl)(pyridin-2-ylmethylamino)methylene)-3-methyl-1-phenyl-pyrazol-5-one) show that they are dinuclear species with the geometry around the metal centers are penta-coordinated bridging through the benzylalkoxy oxygen atoms in the solid state. The activities and selectivities of these complexes toward the ring-opening polymerization of L-lactide and rac-lactide have been investigated. Experimental results show that all complexes proceed the polymerization rapidly and efficiently in a controlled manner, yielding polymers with controlled molecular weight and narrow molecular weight distribution. In addition, 1a and 2a exhibit highly selectivities toward rac-lactide with Pr up to 0.89. The kinetic studies for 1a and L-lactide show first order with complex 1a and second order with the L-lactide. It is interesting to note that complex 1a can derived from complex 1c in the presence of Zn(OBn)2 at room temperature.
URI: http://hdl.handle.net/11455/16778
其他識別: U0005-0406201016190000
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