I. 雙酚配位基鋁金屬錯合物之合成及其對ε-環己內酯開環聚合之催化應用 II. 雙酚配位基鈦金屬錯合物之合成及其對ε-環己內酯及L-乳酸交酯開環聚合之催化應用

I. Synthesis of Aluminum Complexes with Diphenolate and Their Application in Ring Opening Polymerization of ε-Caprolactone. II. Synthesis of Titanium Complexes with Diphenolate and Their Application in Ring Opening Polymerization of ε-Caprolactone and L-Lactide.

李盈嫻(Ying-Hsien Li)

指導教授 ： 陳喧應

高雄醫學大學/生命科學院/醫藥暨應用化學研究所/碩士(2014年)

摘要

雙酚配位基鋁金屬錯合物之合成及其對ε-環己內酯
開環聚合之催化應用:
以一系列不同取代基的雙酚配位基搭配鋁金屬，合成鋁錯合物，用它們對ε-環己內酯進行開環聚合反應的應用。以1莫耳的雙酚配位基搭配1.1莫耳的三甲基鋁，在室溫下反應可以得到鋁錯合物。不同取代基的配位影響催化活性的結果。透過晶體的分析，發現到在進行開環聚合時，催化劑是以雙核的結構所呈現的。有鄰位取代基的配位基，會促使錯合物在對ε-環己內酯進行催化時，苄氧基由架橋的形式變為非架橋的形式，如同參考文獻中所說非架橋形式催化速率會比較快。

雙酚配位基鈦金屬錯合物之合成及其對ε-環己內酯及
L-乳酸交酯開環聚合之催化應用:
以一系列不同取代基的雙酚配位基搭配鈦金屬，合成鈦錯合物，用它們對ε-環己內酯及乳酸交酯進行開環聚合反應的應用。以1莫耳的雙酚配位基搭配1莫耳的Ti(OiPr)4，在室溫下反應可以得到鈦錯合物。不同取代基的配位影響催化活性的結果。在過去相關鈦金屬錯合物文獻中提到配位基會降低開環聚合反應的速率，實驗結果顯示與文獻相符，與前篇論文鋁錯合物的結論相反，原因我們還需要進一步做實驗探討。

關鍵字

鋁錯合物 ； 鈦錯合物

並列摘要

Synthesis of Aluminum Complexes with Diphenolate and
Their Application in Ring Opening Polymerization of ε-Caprolactone:
A series of aluminum complexes bearing different diphenolate ligands was synthesized and their application for the ring-opening polymerization of ε-caprolactone was studied. The synthesis of aluminum complexes was reacted with 1.0 molar eqivalents of bulky diphenolate ligand and 1.1 molar equivalent of trimethyl aluminum at ambient temperature. The resulting catalysis was affected through different coordinations of the ligands. Through the crystal analysis, dimeric Al structure should be the possible intermediate during the catalytic process. Ligand with o-substituents would coordinate to aluminum in order to influence the benzyl alkoxide from bridging type to terminal type and increase the initiation rate of benzyl alkoxide to ε-caprolactone.

Synthesis of Titanium Complexes with Diphenolate and
Their Application in Ring Opening Polymerization of ε-Caprolactone and L-Lactide:
A series of titanium complexes bearing different diphenolate ligands was synthesized and their application for the ring-opening polymerization of ε-caprolactone and L-lactide was studied. The synthesis of titanium complexes was reacted with 1.0 molar eqivalents of bulky diphenolate ligand and 1.0 molar equivalent of titanium (Ⅳ) isopropoxide at ambient temperature. The catalysis was affected through different coordinations of the ligands. In the past, the papers showed the coordinate group will decrease the catalytic activities. The resulting situation is the same as the papers but different from the aluminum. We need to explore experiments in the future.

並列關鍵字

aluminum complex ； titanium complex

參考文獻

參考文獻

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2. http://newstar.superlife.ca/2012/05/17/%E5%A4%9A%E5%B8%82%E5%A1%91%E8%83%B6%E8%A2%8B%E6%94%B6%E8%B4.

3. http://green21.tw/org/?p=207.

4. Zhang, W. J.; Wang, Y. H.; Sun, W. H.; Lin W. G.; Carl, R. S. Dalton Trans., 2012, 41, 11587-11596.