臺灣博碩士論文加值系統

本論文利用咪唑甲基甲醛苯酚與雙甲醛甲基苯酚，藉由三種不同從醛基合成咪唑的配方，合成出一系列甲基咪唑苯酚R1-R3及2R1-2R3，[R1 = HOPhMeImph；R2 = HOPhMeImH；R3 = HOPhMeImMe與甲基雙咪唑苯酚2R1 = HOPhMebis-Imph ；2R2 = HOPhMebis-ImH；2R3 = HOPhMebis-ImMe]。以1當量的甲基咪唑苯酚配位基前驅物R1-R3與2R2-2R3和1當量的三甲基鋁試劑反應可以成功合成出鋁錯合物14-18。鋁錯合物14及16-18對環己內酯的開環聚合反應在外加9-蒽甲醇的條件下，皆表現出良好的催化活性與狹窄的PDI值分佈，其中鋁錯合物16在100倍與200倍的單體開環聚合反應有良好的控制，但在300倍單體的反應不佳，而鋁錯合物16及17 在不外加醇類的情形下對環己內酯的開環聚合反應有良好的活性，但其做出聚合物呈黏稠狀其分子量與PDI的分佈都偏高。

A series of imidazole-phenolate and bis-imidazole-phenolate ligand
precursors R1-R3 and 2R1-2R3，[R1 = HOPhMeImph；R2 = HOPhMeImH；R3 = HOPhMeImMe ；2R1 = HOPhMebis-Imph ；2R2 = HOPhMebis-ImH；2R3 = HOPhMebis-ImMe] have been discovered. These ligand precursors can react with trimethyl aluminum to make complexes 14-18. Complexes 14-18 show good activity and low PDI toward ε-caprolactone ring-opening polymerization with 9-AnOH. The complex 16 shows good activity toward 100 and 200-fold concentrationε-caprolactone，but it shows less control when the concentration of ε-caprolactone reaches 300-fold. The complex 16 and 17 show activity towardε-caprolactone ring-opening polymerization without adding alcohol，while the molecular weight and PDI are much higher than respect.

摘要....................................................i
Abstract...............................................ii
目錄...................................................iii
圖目錄..................................................iv
式目錄...................................................x
表目錄...................................................xi
第一章 緒論..............................................1
1.1生物可降解之高分子聚合物................................1
1.1.1 簡介...............................................1
1.1.2環酯類單體介紹.......................................2
1.2 各種不同類型的開環聚合反應.............................4
1.2.1金屬試劑在開環聚合反應的應用..........................4
1.2.2金屬開環聚合反應的機制................................5
1.3早期的金屬催化劑.......................................7
1.4金屬催化劑的設計.......................................9
1.5 O O形式的輔助配位基..................................10
1.6 N O 形式的輔助配位基.................................11
1.6.1 ketiminate輔助配位基..............................11
1.6.2 aminophenolate輔助配位基..........................12
1.6.3 iminophenolate輔助配位基..........................13
1.6.4 Salen輔助配位基...................................14
1.6.5 含咪唑的輔助配位基.................................16
1.7研究方向.............................................17
第二部 實驗部份........................................19
2.1 一般操作............................................19
2.2 溶劑處理............................................20
2.3 藥品處理............................................21
2.4 鑑定儀器............................................22
2.4.1 核磁共振光譜儀(NMR).............................22
2.4.2 元素分析儀(EA)..................................22
2.4.3 X-ray 單晶繞射儀(X-ray diffractmeter) .........22
2.4.4 凝膠滲透層析儀 (GPC)............................23
2.5 養晶方式...........................................24
2.5.1 單一溶劑.......................................24
2.5.2 兩種溶劑.......................................24
2.6 咪唑苯酚配位基前驅物之合成及鑑定......................25
2.6.1 咪唑苯酚配位基前驅物HOPhMeImPh (R1)............25
2.6.2 咪唑苯酚配位基前驅物HOPhMeImH (R2).............26
2.6.3 咪唑苯酚配位基前驅物HOPhMeImMe (R3)............27
2.6.4 雙咪唑苯酚配位基前驅物HOPhMebis-ImPh (2R1)......28
2.6.5 雙咪唑苯酚配位基前驅物HOPhMebis-ImH (2R2).......29
2.6.6 雙咪唑苯酚配位基前驅物HOPhMebis-ImMe (2R3)......30
2.7 咪唑苯酚鋁錯合物之合成及鑑定..........................31
2.7.1 咪唑苯酚鋁錯合物(PhMeImPh)AlMe2 (14).............31
2.7.2 咪唑苯酚鋁錯合物(PhMeImH)AlMe2 (15).............32
2.7.3 咪唑苯酚鋁錯合物(PhMeImMe)AlMe2 (16)............33
2.7.4雙咪唑苯酚鋁錯合物HOPhMe-bis-ImPhAlMe2 (17).......34
2.7.5雙咪唑苯酚鋁錯合物HOPhMe-bis-ImMeAlMe2 (18).......35
2.8 開環聚合之反應步驟...................................36
2.8.1 外加9-蒽甲醇對環己內酯之開環聚合反應步驟...........36
第三章 結果與討論........................................37
3.1咪唑苯酚前驅物的合成及鑑定.............................37
3.1.1 咪唑苯酚配位基前驅物之合成........................37
3.1.2 咪唑苯酚醛及不對稱雙咪唑苯酚之合成......... .......38
3.1.3 對稱雙咪唑苯酚合成...............................39
3.1.4 咪唑苯酚的鑑定...................................40
3.2.咪唑苯酚甲基鋁錯合物之合成及鑑定.......................41
3.2.1 單咪唑苯酚甲基鋁錯合物之合成及鑑定.................41
3.2.2雙咪唑苯酚甲基鋁錯合物之合成及鑑定..................42
3.4環酯類之開環聚合催化反應...............................44
3.4.1 催化系統之設計...................................44
3.4.2 鋁錯合物14-18對環己內酯進行開環聚合反應之催化劑優選
.......................................................44
3.4.3 鋁錯合物16 對環己內酯進行開環聚合反應之條件優選.....46
3.4.4 鋁錯合物16 對不同倍數環己內酯進行開環聚合反應.......47
3.4.5 鋁錯合物16 對環己內酯進行開環聚合產物之光譜鑑定....48
第四章 結論............................................49
參考文獻...............................................51
附錄...................................................53

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