臺灣博碩士論文加值系統

本論文分為兩部分。第一部分主要是開發出對環酯類的開環聚合反應具有催化活性及立體選擇性的有機金屬錯合物。本實驗室修飾了配基上的官能基，在中心金屬附近增加具有立體阻礙的異丁基(tert-butyl)，成功的提升對於乳酸交酯(rac-lactide)的催化活性，反應時間只需要5小時即可使單體轉換率(Conversion)達到99%，並且改善分子量與理論分子量的誤差，也有最高的Pr值為0.64。
第二部份中，主要是將兩種不同的聚合反應機構結合在一起，第一種為活性自由基聚合反應(Living radical polymerization)，所選擇的單體為苯乙烯(Styrene)，第二種為開環聚合反應(Ring-opening polymerization)，使用的單體為己內酯(ε-Caprolactone)，而成功的利用二氯二茂鈦(Cp2Ti Cl2)當作催化劑及對甲氧基苯甲醛當作起始劑將兩種反應機制結合，合成出聚苯乙烯及聚己內酯的嵌端共聚物。

In part 1, we have developed the complexes that can mediate the polymerization of lactone with stereoselectivity. The bulky group, tert-butyl, was including to the position close to enhance the steric effect, which increased the catalytic activity and stereoselectivity in ring opening polymerization of rac-lactide. BTPIP2-tBuZnEt led to a ring opening polymerization of rac-lactide to 99% monomer conversion in 5 hours at 30oC with PDI equal to 1.05 and Pr = 0.64.
In part 2, we synthesized the block copolymer via different mechanisms. First, the styrene was polymerized by living radical polymerization. Second, the polycaprolactone was polymerized by ring opening polymerization. We also used the Cp2Ti Cl2 as catalyst and anisaldehyde as initiator to synthesize the block copolymer of polystyrene and polycaprolactone through chain extension and one-pot recation.

摘要 I
Abstract II
謝誌 III
目錄 IV
表目錄 VII
圖目錄 VIII
式目錄 XV
第一章 緒論 1
1-1 開環聚合反應(Ring-Opening Polymerization, ROP) 2
1-2 傳統的自由基聚合反應 6
1-3 活性聚合反應 7
1-4 鈦錯合物的聚合反應 11
1-5 研究目的及動機 16
第二章 鋅與鋁的有機金屬錯合物在開環聚合反應之應用 Applied of Ring Opening Polymerization by Zn and Al complexes 17
2-1 前言 18
2-2 鋅與鋁的有機金屬錯合物的合成 19
2-3 己內酯的開環聚合反應 24
2-4 乳酸交酯的開環聚合反應 28
2-5 有機金屬錯合物與起始劑的反應 34
2-6 苯乙烯和己內酯及乳酸交酯的嵌端共聚物的合成 40
2-7 結論 44
2-8 實驗方法 45
第三章 結合活性自由基聚合及開環聚合以合成嵌段共聚物 Block Copolymers Sythesized by Ring Opening Polymerization and Living Radical Polymerzation. 60
3-1 前言 61
3-2 以苯甲醛為起始劑進行苯乙烯的聚合 62
3-3 以苯甲醛為起始劑進行環酯類的開環聚合 65
3-4 以苯甲醛為起始劑進行苯乙烯及環己酯的嵌端共聚物的合成 70
3-5 以對甲氧基苯甲醛為起始劑進行聚苯乙烯的合成 76
3-6 以苯甲醛為起始劑進行苯乙烯及己內酯的嵌端共聚物的合成 81
3-7 結論 83
3-8 實驗方法 84
第四章 附錄 87
4-1 NMR光譜儀圖譜 88
4-2 X-ray晶體數據 100
第五章 參考文獻 166

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