Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16801
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dc.contributor高漢謀zh_TW
dc.contributor葉玉堂zh_TW
dc.contributor.advisor陳繼添zh_TW
dc.contributor.author張又仁zh_TW
dc.contributor.authorChang, Yu-Jenen_US
dc.contributor.other中興大學zh_TW
dc.date2011zh_TW
dc.date.accessioned2014-06-06T06:56:21Z-
dc.date.available2014-06-06T06:56:21Z-
dc.identifierU0005-1307201011200900zh_TW
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dc.identifier.urihttp://hdl.handle.net/11455/16801-
dc.description.abstract我們成功製備吡唑酚基前驅物52-59,並利用配位基前驅物52-59和1.05當量的三甲基鋁試劑反應,可以成功合成錯合物60-67,並利用核磁共振光譜以及元素分析數據進行鑑定。經由X-光單晶繞射儀之數據確認了錯合物60-63以及65-66的分子結構。在苯甲醇的存在下,錯合物60-67對於左旋乳酸交酯以及環己內酯的開環聚合反應,皆有良好的活性以及狹窄的PDIs數值,並具有Living以及Immortal的性質。由錯合物63催化合成之聚酯類,其氫光譜末端鑑定顯示,在聚合反應中是以苯甲氧基作為起始基進行反應。zh_TW
dc.description.abstractThe pyrazolyl-phenolate ligand precursors 52-59 have been prepared. Treatment of ligand precursors with 1.05 equiv. of AlMe3 affords aluminum complexes 60-67。All these compounds were characterized by NMR spectroscopy and elemental analysis. The molecular structures of complexes 60-63 and 65-66 were determined by single-crystal X-ray diffraction techniques. All of these aluminum complexes show catalytic activities for the ring opening polymerization of L-lactide and ε-caprolactone in the presence of benzyl alcohol with narrow PDIs. They also exhibit both “living” and “immortal” characters. Based on the 1H NMR spectrum for end group analysis of the polymer produced from complex 63 and cyclic esters, polymerization could be initiated by the benzyl alkoxide group in this system.zh_TW
dc.description.tableofcontents第一章 序論......................................1 1-1 對環境及生物友善的聚合物........................1 1-2 開環聚合反應的種類..............................4 1-3 常見開環聚合反應的機制及應用....................5 1-4 金屬錯合物的設計................................8 1-5 應用於開環聚合反應常見的催化劑..................10 1-5-1 具酚基的金屬錯合物............................10 1-5-1-1 胺三酚基金屬錯合物..........................10 1-5-1-2 雙酚基金屬錯合物............................13 1-5-1-2-1 N2O2形式的雙胺雙酚基金屬錯合物............13 1-5-1-2-2 氮原子架橋的胺雙酚基金屬錯合物............16 1-5-1-3 NO形式的酚基金屬錯合物......................18 1-5-1-3-1胺酚基金屬錯合物...........................18 1-5-1-3-2亞胺酚基金屬錯合物.........................19 1-5-2具吡唑架構的金屬錯合物.........................20 1-5-2-1 Tris(pyrazolyl)borate之金屬錯合物...........20 1-5-2-2 Amino-bis(pyrazolyl)之金屬錯合物............21 1-5-2-3 Bis(pyrazolyl)-aminophenolate之金屬錯合物...22 1-5-2-4 Bis(pyrazolyl)-phenolate之金屬錯合物........23 1-5-2-5 Pyrazolyl-iminophenolate之金屬錯合物........24 1-6 研究方向........................................26 第二章 實驗部份.....................................27 2-1 一般操作........................................27 2-2 溶劑處理........................................28 2-3 藥品處理........................................29 2-4 鑑定儀器........................................30 2-4-1 核磁共振儀(NMR)...............................30 2-4-2 元素分析儀(EA)................................30 2-4-3 X-ray單晶繞射儀(X-ray diffractometer)........30 2-4-4 凝膠滲透層析儀(GPC)..........................31 2-5 養晶方式........................................32 2-5-1 單一溶劑......................................32 2-6 吡唑酚配位基之合成與鑑定........................33 2-6-1 吡唑酚配位基52之合成與鑑定....................33 2-6-2 吡唑酚配位基53之合成與鑑定....................33 2-6-3 吡唑酚配位基54之合成與鑑定....................33 2-6-4 吡唑酚配位基55之合成與鑑定....................35 2-6-5 吡唑酚配位基56之合成與鑑定....................36 2-6-6 吡唑酚配位基57之合成與鑑定....................37 2-6-7 吡唑酚配位基58之合成與鑑定....................38 2-6-8 吡唑酚配位基前驅物59之合成與鑑定..............39 2-7 吡唑酚基鋁錯合物之合成與鑑定....................40 2-7-1 吡唑酚基鋁錯合物60之合成與鑑定................40 2-7-2 吡唑酚基鋁錯合物61之合成與鑑定................41 2-7-3 吡唑酚基鋁錯合物62之合成與鑑定................43 2-7-4 吡唑酚基鋁錯合物63之合成與鑑定................44 2-7-5 吡唑酚基鋁錯合物64之合成與鑑定................45 2-7-6 吡唑酚基鋁錯合物65之合成與鑑定................46 2-7-7 吡唑酚基鋁錯合物66之合成與鑑定................48 2-7-8 吡唑酚基鋁錯合物67之合成與鑑定................49 2-7-9 吡唑酚基鋁錯合物68之合成與鑑定................50 2-7-10 吡唑酚基鋁錯合物69之合成與鑑定...............51 2-8 聚合物的合成..................................53 2-8-1 合成末端具有苯甲氧基之聚己內酯 (PCL)..........53 2-8-2 合成末端具有苯甲氧基之聚乳酸交酯 (PLA)........54 第三章 結果與討論...................................55 3-1 吡唑酚配位基前驅物之合成........................55 3-2 吡唑酚基鋁錯合物之合成..........................56 3-3 吡唑酚基鋁錯合物之光譜鑑定......................57 3-4 吡唑酚基鋁錯合物之晶體架構及探討................58 3-4-1 錯合物60之晶體架構及探討......................58 3-4-2 錯合物61之晶體架構及探討......................60 3-4-3 錯合物62之晶體架構及探討......................61 3-4-4 錯合物63之晶體架構及探討......................63 3-4-5 錯合物65之晶體架構及探討......................64 3-4-6 錯合物66之晶體架構及探討......................65 3-4-7 錯合物68之晶體架構及探討......................67 3-4-8 錯合物69之晶體架構及探討......................68 3-5 環酯類的開環聚合反應............................70 3-5-1 催化系統......................................70 3-5-2 鋁錯合物63對環己內酯進行開環聚合反應之條件優選.70 3-5-3 鋁錯合物60-67對環己內酯進行開環聚合反應之比較..72 3-5-4 鋁錯合物63對環己內酯進行開環聚合反應...........74 3-5-5 鋁錯合物63對乳酸交酯進行開環聚合反應...........76 3-5-6 鋁錯合物63對環己內酯開環聚合產物之光譜鑑定.....78 3-5-7 鋁錯合物63對乳酸交酯開環聚合產物之光譜鑑定.....79 3-6 開環聚合反應之機制探討...........................80 3-6-1 鋁錯合物60和苯甲醇反應的光譜分析...............80 3-6-2 鋁錯合物63和苯甲醇反應的光譜分析...............83 3-6-3 鋁錯合物對於開環聚合反應的活性差異探討.........84 3-6-4 鋁錯合物對於開環聚合反應的機制推導.............85 第四章 結論..........................................87 參考文獻.............................................88 附錄.................................................91zh_TW
dc.language.isoen_USzh_TW
dc.publisher化學系所zh_TW
dc.subjectring-opening polymerizationen_US
dc.subject開環聚合反應zh_TW
dc.subjectPLAen_US
dc.subjectAl complexen_US
dc.subjectPCLen_US
dc.subjectBiodegradableen_US
dc.subjectpolymeren_US
dc.subject聚乳酸交酯zh_TW
dc.subject鋁錯合物zh_TW
dc.subject聚己內酯zh_TW
dc.subject生物可分解性zh_TW
dc.subject聚合物zh_TW
dc.title具吡唑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.titleSynthesis and Characterization of Aluminum Complexes Bearing Pyrazolyl-phenolate Ligands and their Application in Ring Opening Polymerization of Cyclic Estersen_US
dc.typeThesis and Dissertationzh_TW
dc.date.paperformatopenaccess2019.07.18-
dc.date.openaccess2019.07.18-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.cerifentitytypePublications-
item.languageiso639-1en_US-
item.openairetypeThesis and Dissertation-
item.fulltextno fulltext-
item.grantfulltextnone-
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