本論文探討以環戊二烯鈦系統 (Cp2TiCl2) 可達成以一鍋化的合成方式製備聚苯乙烯與環己內酯的嵌段共聚物。先以環戊二烯鈦系統調控的聚苯乙烯自由基聚合反應為基礎，探討反應物苯甲醛 (benzaldehyde)、環戊二烯鈦及奈米鋅 (nano-size) 對於苯乙烯自由基聚合反應的影響。當聚合反應中的苯甲醛濃度過高時聚合反應的整體控制明顯下降。而奈米鋅在反應中扮演還原劑的角色同時其含量也會影響聚合反應的控制。環戊二烯鈦的濃度主要影響苯乙烯的分子量，當濃度上升會獲得分子量較小的聚苯乙烯。延續苯乙烯聚合反應所獲得的聚合條件，我們成功合成出聚苯乙烯與聚環己內酯的嵌段共聚物，也發現降低苯乙烯與環己內酯的濃度可改善共聚合反應，分子量隨轉換率成線性成長且 GPC peak 也隨時間規律地往高分子量移動。我們也嘗試探討鈷錯合物的氧化還原能力與鈷催化的自由基聚合反應 (Cobalt-mediated radical polymerization, CMRP) 之間的關聯，調查了 CoII(TMP)、 CoII(acac)2、 CoII(etsalen)、 CoII(etsalentBu)、 CoII(Salen*)、 CoII (Salophen) ，在循環伏安法中發現氧化還原能力較弱的 CoII(Salophen) 在丙烯酸甲酯 (Methylacrylate, MA) 自由基聚合反應中的表現較差，氧化還原能力較佳的 CoII(TMP) 可提供控制較佳的丙烯酸甲酯自由基聚合。

We demonstrated one-pot synthesis of polystyrene-b-polycaprolactone (PSt-b-PCL) mediated by Cp2TiCl2. First we optimized styrene radical polymerization mediated by Cp2TiCl2 and tuned many factors of polymerization such as benzaldehyde, Cp¬2TiCl2, nano-sized zinc. We observed lower concentration benzaldehyde led to better polymerization control, nano-sized zinc not only acted a role of reducing agent, but had relationship with polymerization control, more Cp¬2TiCl2 afforded lower polymer molecule weight. Based on optimized styrene polymerization, we successfully synthesized blockcopolymer of styrene (St) and-caprolactone (CL). According the GPC results, the polymerization was initiated with good living characteristics demonstrated by linear increasing in molecular weight with time. In second part, we used cyclic voltammetry (CV) and polymerization results to discuss the relationship between redox ability of various cobalt complexes (CoII(TMP), CoII(acac)2, CoII(etsalen), CoII(etsalentBu), CoII(Salen*) and CoII (Salophen)) and cobalt-mediated radical polymerization (CMRP) of methyacrylate MA. We found CoII(Salophen) had low redox ability and also proivded worse MA polymerization, in addition, CoII(TMP) had high redox ability and showed better polymerization. It seems that cobalt complexes having high redox bility can afford better MA polymerization.

中文摘要 I
Abstract II
謝誌 III
圖目錄 VI
表目錄 VII
式目錄 VII
第一章 緒論 1
1-1 高分子聚合物的發展 1
1-2 傳統自由基聚合反應 3
1-3活性聚合反應 5
1-3-1 活性聚合反應的原理 5
1-3-2 活性/可控自由基聚合反應 (Living / controlled radical polymerization) 5
1-3-3 氮氧穩定自由基聚合反應 (Nitroxide-mediated radical polymerization, NMP) 6
1-3-4 原子轉移自由基聚合反應 (Atom transfer radical polymerization, ATRP) 7
1-3-5 可逆加成斷裂鏈轉移聚合 (Reversible addition-fragmentation chain transfer, RAFT) 8
1-3-6 鈷催化自由基聚合 (Cobalt-mediated radical polymerization, CMRP) 9
1-4 開環聚合反應 (Ring-opening polymerization) 12
1-4-1 反應機制 12
1-4-2 發展與趨勢 14
1-5 鈦錯合物調控活性聚合反應 16
1-5-1 配位聚合與 Ziegler-Natta catalyst 16
1-5-2 鈦錯合物控制開環聚合 17
1-5-3 鈦錯合物控制自由基聚合 19
1-6 結合自由基聚合與開環聚合之合成嵌段共聚物 (Block copolymer) 21
1-6-1 聚苯乙烯與具環己內酯之嵌段共聚物 (Polystyrene-b-polycaprolactone) 21
1-6-2 聚丙烯酸甲酯與聚內酯之嵌段共聚物 (Polyacrylate-b-polyester) 26
第二章 實驗方法 27
2-1 化學藥品 27
2-2儀器設備與鑑定方法 29
2-2-1核磁共振光譜儀 (Nuclear Magnetic Resonance, NMR) 29
2-2-2紫外光/可見光光譜儀 (UV-vis spectroscopy) 29
2-2-3 THF凝膠滲透層析儀 (Gel Permeation Chromatography) 30
第三章 結合可控自由基聚合與開環聚合合成polystyrene-b-polycaprolactone 之嵌段共聚物 31
3-1實驗動機與目的 31
3-2 實驗步驟 33
3-3 不同濃度之苯甲醛對於苯乙烯自由基聚合之影響 34
3-4 不同濃度之環戊二烯鈦對於苯乙烯自由基聚合之影響 38
3-5不同當量之奈米鋅對於苯乙烯自由基聚合之影響 41
3-6 不同濃度之苯乙烯對於合成嵌段共聚物之影響 44
3-7 不同溶劑對於合成嵌段共聚物之影響 49
3-8 結論與展望 50
第四章 探討鈷錯合物在可控自由基聚合中的行為物與其氧化還原電位之關係 51
4-1 實驗動機與目的 51
4-2 鈷錯合物之氧化還原電位與可控自由基聚合行為之間的關聯 52
4-3 結論與展望 59
第五章 參考文獻 60

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