Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/14190
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dc.contributor陳繼添zh_TW
dc.contributor.author張祐誠zh_TW
dc.contributor.authorChang, Yu-Chengen_US
dc.contributor.other化學系所zh_TW
dc.date2013en_US
dc.date.accessioned2014-06-06T06:51:52Z-
dc.date.available2014-06-06T06:51:52Z-
dc.identifierU0005-1706201317113000en_US
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dc.identifier.urihttp://hdl.handle.net/11455/14190-
dc.description.abstract本論文利用具不同立體障礙修飾的溴苯酚與吡唑,經由銅催化之碳-氮偶合反應可得一系列的吡唑苯酚配位基前驅物L1H-L6H,[L1H = HOPhHPzH; L2H = HOPhMePzH; L3H = HOPhtBuPzH; L4H = HOPhHPzMe; L5H = HOPhMePzMe; L6H = HOPhtBuPzMe]。以1.0當量的吡唑苯酚配位基前驅物L1H-L6H與1.2當量的三甲基鋁試劑反應,可以成功合成鋁錯合物36-41。其中鋁錯合物41與苯甲醇進一步反應,可以合成帶烷氧基的鋁錯合物47。合成之鋁錯合物,皆以核磁共振光譜以及元素分析數據進行鑑定,並經由 X-ray 單晶繞射儀之數據鑑定鋁錯合物36與47的分子結構。於外加苯甲醇的條件下,將鋁錯合物36-41對於環己內酯及左旋乳酸交酯進行開環聚合反應,皆具有良好的催化活性以及狹窄的 PDI 數值,且鋁錯合物38具有Living以及Immortal的性質。以鋁錯合物47進行動力學研究,得知單體及催化劑濃度對反應速率之影響皆為一級反應。催化合成之高分子聚合物,可經由核磁共振氫光譜以及基質輔助雷射脫附游離飛行時間質譜儀進行鑑定。zh_TW
dc.description.abstractA series of pyrazolyl-phenolate ligand precursors L1H-L6H, [L1H = HOPhHPzH; L2H = HOPhMePzH; L3H = HOPhtBuPzH; L4H = HOPhHPzMe; L5H = HOPhMePzMe; L6H = HOPhtBuPzMe] was synthesized via copper- catalyzed N-arylation in good yields. The reactions of L1H-L6H with 1.2 equivalent of AlMe3 yielded aluminum alkyl complexes 36-41. Furthermore, reaction of aluminum alkyl complex 41 with benzyl alcohol afforded aluminum benzyl alkoxide complex 47. All these compounds were characterized by NMR spectroscopy and elemental analysis. The molecular structures of complexes 36 and 47 were determined by single-crystal X-ray diffraction techniques. Complexes 36-41 demonstrated catalytic activities towards the ring-opening polymerization of e-caprolactone and L-lactide in the presence of BnOH with narrow PDIs. Complex 38 exhibited both “ living ” and “ immortal ” characters. Nevertheless, the kinetics using complex 47 as an initiator was also studied, and the experimental results revealed that the rate of reaction was first-order dependence on monomer and catalyst concentration. End group analysis of the polymer was characterized by 1H NMR spectrum and MALDI-TOF mass spectrum .en_US
dc.description.tableofcontents目錄 摘要 I Abstract II 目錄 III 圖目錄 VIII 式目錄 XIII 表目錄 XIV 第一章 緒論 1 1.1 生物可分解之高分子聚合物 1 1.1.1 簡介 1 1.1.2 環酯類單體之介紹 3 1.2 開環聚合催化反應 4 1.2.1 開環聚合反應之分類 4 1.2.2 金屬催化開環聚合反應機制 6 1.3 早期金屬催化劑之應用及其缺點 8 1.4 金屬催化劑之設計 11 1.5 應用於開環聚合反應之催化劑 12 1.5.1 O-donor形式的輔助配位基 13 1.5.2 N-donor形式的輔助配位基 14 1.5.3 N/O-donor形式的輔助配位基 16 1.5.3.1 Salen輔助配位基 16 1.5.3.2 Amino phenolate輔助配位基 17 1.5.3.3 Imino phenolate輔助配位基 19 1.5.4 含吡唑的輔助配位基 20 1.6 研究方向 25 第二章 實驗部分 28 2.1 一般操作 28 2.2 溶劑處理 29 2.3 藥品處理 30 2.4 鑑定儀器 32 2.4.1 核磁共振光譜儀(NMR) 32 2.4.2 元素分析儀(EA) 32 2.4.3 X-ray 單晶繞射儀(X-ray diffractmeter) 32 2.4.4 凝膠滲透層析儀(GPC) 33 2.4.5 基質輔助雷射脫附游離飛行時間質譜儀(MALDI-TOF) 34 2.5 養晶方式 35 2.5.1 單一溶劑 35 2.5.2 兩種溶劑 35 2.6 吡唑苯酚配位基前驅物之合成及鑑定 36 2.6.1 起始物2-bromo-4,6-dimethylphenol 25,26 36 2.6.2 起始物2-bromo-4,6-ditertbutylphenol 27 37 2.6.3 吡唑苯酚配位基前驅物HOPhMePzH 38 2.6.4 吡唑苯酚配位基前驅物HOPhtBuPzH 28 39 2.6.5 吡唑苯酚配位基前驅物HOPhHPzH 28 40 2.6.6 吡唑苯酚配位基前驅物HOPhMePzMe 41 2.6.7 吡唑苯酚配位基前驅物HOPhtBuPzMe 28 42 2.6.8 吡唑苯酚配位基前驅物HOPhHPzMe 28 43 2.7 吡唑苯酚配位基前驅物之合成及鑑定 44 2.7.1 吡唑苯酚基鋁錯合物(PhHPzH)AlMe2 (36) 44 2.7.2 吡唑苯酚基鋁錯合物(PhMePzH)AlMe2 (37) 46 2.7.3 吡唑苯酚基鋁錯合物(PhtBuPzH)AlMe2 (38) 48 2.7.4 吡唑苯酚基鋁錯合物(PhHPzMe)AlMe2 (39) 50 2.7.5 吡唑苯酚基鋁錯合物(PhMePzMe)AlMe2 (40) 52 2.7.6 吡唑苯酚基鋁錯合物(PhtBuPzMe)AlMe2 (41) 54 2.7.7 吡唑苯酚基鋁錯合物[(PhtBuPzMe)Al(OBn)2]2 (47) 56 2.8 開環聚合之反應步驟 58 2.8.1 外加苯甲醇對環己內酯之開環聚合反應步驟 58 2.8.2 外加苯甲醇對左旋乳酸交酯之開環聚合反應步驟 59 2.9 環己內酯開環聚合反應之動力學反應步驟 60 第三章 結果與討論 61 3.1 吡唑苯酚配位基前驅物之合成及鑑定 61 3.2 吡唑苯酚基鋁錯合物之合成及鑑定 63 3.2.1 雙核雙取代吡唑苯酚基鋁錯合物 63 3.2.2 雙核吡唑苯酚基鋁苯甲氧基錯合物 65 3.3 吡唑苯酚基鋁錯合物之晶體資料及探討 66 3.3.1 雙核雙取代吡唑苯酚基鋁錯合物 66 3.3.2 雙核吡唑苯酚基鋁苯甲氧基錯合物 67 3.4 環酯類之開環聚合催化反應 69 3.4.1 催化系統之設計 69 3.4.2 鋁錯合物36-41對環己內酯進行開環聚合反應之催化劑優選 70 3.4.3 鋁錯合物38對環己內酯進行開環聚合反應之條件優選 72 3.4.4 鋁錯合物38對不同倍數環己內酯進行開環聚合反應 74 3.4.5 鋁錯合物38對環己內酯進行開環聚合產物之光譜鑑定 77 3.4.6 鋁錯合物38對環己內酯進行開環聚合產物之基質輔助雷射脫附游離飛行時間質譜鑑定 78 3.4.7 鋁錯合物47對環己內酯進行開環聚合反應之動力學探討 79 3.4.8 鋁錯合物36-41對左旋乳酸交酯進行開環聚合反應之催化劑優選 83 3.4.9 鋁錯合物38對左旋乳酸交酯進行開環聚合反應之條件優選 85 3.4.10 鋁錯合物38對不同倍數左旋乳酸交酯進行開環聚合反應 87 3.4.11 鋁錯合物38對左旋乳酸交酯進行開環聚合產物之光譜鑑定 90 3.4.12 鋁錯合物41與47於開環聚合反應活性探討 91 第四章 結論 94 參考文獻 96 附錄 100zh_TW
dc.language.isozh_TWen_US
dc.publisher化學系所zh_TW
dc.relation.urihttp://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-1706201317113000en_US
dc.subject鋁金屬zh_TW
dc.subjectring-opening polymerizationen_US
dc.subject吡唑zh_TW
dc.subjectAluminumen_US
dc.subjectPyrazoleen_US
dc.title吡唑苯酚基鋁錯合物之合成、鑑定及其對環酯類開環聚合反應之應用zh_TW
dc.titleAluminum Complexes Containing Pyrazolyl-phenolate Ligands: Synthesis, Characterization and Application in Ring-Opening Polymerization of Cyclic Estersen_US
dc.typeThesis and Dissertationzh_TW
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