Title

比較N,S和N,O希夫鹼鋁錯合物 對環己內酯以及乳酸交酯進行開環聚合反應

Translated Titles

Comparative Study of Aluminum Complexes Bearing N,O and N,S-Schiff Base in Ring-opening Polymerization of -Caprolactone and L- Lactide

Authors

張夢芝

Key Words

希夫鹼 ; 開環聚合 ; 鋁錯合物 ; 環己內酯 ; 乳酸交酯 ; Ring-opening Polymerization ; Aluminum Complexes ; -Caprolactone ; Schiff- base ; L- Lactide

PublicationName

中山大學化學系研究所學位論文

Volume or Term/Year and Month of Publication

2014年

Academic Degree Category

碩士

Advisor

蔣燕南

Content Language

繁體中文

Chinese Abstract

我們成功的利用 N,O 以及 N,S-希夫鹼配位基合成出下列能催化環己內酯 (-caprolactone, CL) 以及乳酸內酯 (L-lactide, LA) 進行開環聚合反應的鋁金屬錯合物:(1) LOtBuAlMe2 (2) LOPh2AlMe2 (3) LStBuAlMe2 (4) LSPh2AlMe2 (5) LSPh2AlEt2 (6) LSPh2AlClMe,並且藉由動力學的研究分析發現:1.當亞胺上的取代基立障越大時會提升整體的反應活性;2. N,S-希夫鹼的鋁金屬錯合物比N,O-希夫鹼的鋁金屬錯合物要具有更良好的催化活性,其中錯合物 LSPh2AlEt2 ,可在 25 ℃的條件下, 80 分鐘內環己內酯轉化率達 97 %,且 PDI 為 1.04 ; 同時我們也深入研究了 LSPh2AlMe2 催化環己內酯進行開環聚合反應並考察了不同聚合條件對產物分子量以及分子量分布的影響,結果表明,該聚合反應速率為一級,且聚合反應具有好的可控性。 此外,透過理論計算我們了解到,N,S-希夫鹼配位基之配位化合物上的鋁金屬帶有較少正電荷且 N,S 和 N,O-希夫鹼鋁錯合物兩者之單晶結構在空間位阻上的差異而導致 N,S-希夫鹼配位基的鋁錯合物比N,O-希夫鹼的鋁金屬錯合物在催化活性上明顯優異。 關鍵字:希夫鹼、鋁錯合物、開環聚合、環己內酯、乳酸交酯

English Abstract

We successfully used N,O and N,S-schiff base ligands to synthesize the aluminum complexes which can catalyze the ring opening polymerization of -caprolactone and L-lactide. These complexes are LOtBuAlMe2, LOPh2AlMe2, LStBuAlMe2, LSPh2AlMe2, LSPh2AlEt2, LSPh2AlClMe. Meanwhile, from kinetic analysis, we have found that the bulkier substituent on the imino group is associated with higher overall reactivity. In addition, we also concluded that N, S-schiff base aluminum complexes are more reactive than N,O-schiff base aluminum complexes. For example, LSPh2AlMe2 reaches a conversion rate of 92% with a PDI of 1.05 within 80 minutes under 25 ℃. The data of X-ray crystallography and theoretical calculations revealed that the different electronic density in the aluminum metal may be responsible for the differences in their catalytic activities. Otherwise, experimental results showed that LSPh2AlMe2 efficiently catalyzes the ROP of -caprolactone in a controlled fashion yielding polymers with very narrow PDIs in a wide range of monomer-to-initiator ratios. Keywords: Schiff- base, Aluminum Complexes, Ring-opening Polymerization, -Caprolactone, L- Lactide

Topic Category 基礎與應用科學 > 化學
理學院 > 化學系研究所
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