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標題: NNO三牙配位基之鋁、鎂與鋅錯合物之製備及其在左旋乳酸交酯與環己內酯開環聚合之應用
Preparation of Aluminum、Magnesium and Zinc Complexes Containing NNO-Tridentate Ketiminate Ligands: Their Application in the Ring-Opening Polymerization of Lactides and ε-Caprolactone
作者: 黃佩玲
Huang, Pei-Lin
關鍵字: 開環聚合;ROP;左旋乳酸交酯;環己內酯;LA;CL
出版社: 化學系所
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本篇論文主要利用NNO三牙配位基配位鋁、鎂和鋅金屬合成一系列錯合物,並對鋁、鎂和鋅錯合物分析其晶體結構。研究改變錯合物之電子環境,對於開環聚合左乳酸交酯和環己內酯錯合物催化活性的影響,其中鎂、鋅錯合物對於聚合物分子量有良好的控制性,且分子量分佈在一狹窄範圍內。在立體選擇性方面,鎂金屬錯合物具有優良之選擇性。根據錯合物2a之變溫1H NMR實驗與凝固點下降之實驗推論錯合物2a在溶液態之構型,並搭配錯合物2a與左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 [2a]1,屬於單體為二級反應而對錯合物為一級反應,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= L1H-L2H, M = Mg or Zn) and LM(Me2) (L= L1H-L2H, M = Al) based on N,N,O-tridentate ketiminate ligands are synthesized and characterized. Studies of 1a,1b, 2a and 2b reveal 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 1c discloses mononuclear species with the geometry around the metal center is penta-coordinated in the solid state. Their activities and stereoselectivities toward the ring-opening polymerization of L-Lactide and rac-lactide have been investigated. Experimental results show that complexes efficiently catalyze the polymerization of cyclicester in a controlled fashion, yielding polymers with narrow polydispersity indexes . Complexes 1a, 2a exhibit high stereoselectivity with Pr above the 80 % and complex 2a possesses the highest activity and stereoselectivity. The polymerization kinetics using complex 2a was also studied, and the experimental results reveal that the rate of reaction is second-order dependence on monomer and first-order dependency on catalyst 2a concentration.
其他識別: U0005-2706201021594300
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