臺灣博碩士論文加值系統

ATRPA源自於原子轉移自由基加成反應(Atom Transfer Radical Addition, ATRA)，以起始劑型單體(Inimer)進行聚合，透過兩種不同活性點的差異進行聚加成。在適當的控制條件下，聚合過程中會產生一具活性的鹵素末端，以及一不具活性的鹵素側鏈端，利用此特性僅讓末端的鹵素帶有活性，重複地進行加成反應。一般典型的原子轉移自由基聚合(ATRP)無法直接聚合出主鏈帶有酯基結構的高分子鏈而ATRPA可以。高分子自組裝後的規則結構應用面廣，具有特殊的物理性質，有不同之應用性。本研究論文的第一部分利用AB型起始劑型單體探討不同種類原子轉移自由基聚加成反應(Atom Transfer Radical Polyaddition, ATRPA)反應，製備出主鏈結構帶有酯基的高分子，接著將高分子主鏈官能基化，合成出具有疊氮官能基之聚酯或透過帶有硫醇基之單體與高分子鏈末端乙烯基進行硫醇-烯(Thiol-ene)加成反應，隨後將疊氮化之聚酯透過點擊化學反應合成雙親性高分子刷並調控其親/疏水比例，經過液態自組裝後探討微胞之性質。論文的第二部分利用AA/BB型單體對透過原子轉移自由基聚加成(Atom Transfer Radical Polyaddition, ATRPA)反應，合成出主鏈帶有其他官能基之聚酯，酯基與雙硫鍵分別在酸鹼環境或還原劑存在下會降解成小分子。

第一章、緒論 1
第二章、文獻回顧 3
2.1 活性自由基聚合(Living Radical Polymerization) 3
2.1.1 可控/活性自由基聚合(Control/Living Radical Polymerization) 5
2.2 原子轉移自由基聚合(Atom Transfer Radical Polymerization) 6
2.2.1 輔助激活與還原原子轉移自由基聚合(Supplemental activators and reducing agents atom transfer radical polymerization(SARA ATRP)) 10
2.2.2 活化電子轉移再生ATRP (Activator Regenerated by Electron 13
2.3 原子轉移自由基聚加成(Atom Transfer Radical Polyaddition) 14
2.3.1 逐步聚合(Step-growth Polymerization) 18
2.4 點擊化學(Click Chemistry) 19
2.5 硫醇與烯烴類的自由基加成反應(Thiol-ene) 21
2.6 藥物載體機制 23
2.6.1 溫度應答 23
2.6.2 酸鹼應答 23
2.6.3 氧化還原應答 24
2.7 研究動機 24
第三章、實驗步驟 25
3.1 藥品 25
3.2 儀器 27
3.3 實驗步驟 29
3.3.1 VBA之合成 29
3.3.2 VBBPA之合成 30
3.3.3 4-Vinylbenzyl 2-bromo-2-phenylacetate(VBBPA)進行原子轉移自由基聚加成(ATRPA)反應 30
3.3.4 PVBHPA之合成 32
3.3.5 PVBAPA之合成 32
3.3.6 alkyl-PVBBPA之合成 33
3.3.7 mPEG550-propargyl之合成 33
3.3.8 PVBPA-mPEG550之合成 34
3.3.9 PVBAPA-mPEG550-Octyne之合成 34
3.3.10 刷狀高分子自組裝 35
3.3.11 臨界微胞濃度測定 35
3.3.12 最低臨界溶解溫度(LCST)測定 35
3.3.13 1,2-bis(4-vinylphenyl)ethane(BVPE)之合成 36
3.3.14 Disulfanediylbis(ethane-2,1-diyl)bis(2-bromo-phenylacetate) (DSBPA)之合成 36
3.3.15 Oxybis(ethane-2,1-diyl)bis(2-bromo-2-phenylacetate)(EG200-BPA)之合成 37
3.3.16 Butane-1,4-diyl bis(2-bromo-2-phenylacetate)(BuBPA)之合成 37
3.3.17 BVPE/DSBPA單體對進行原子轉移自由基聚加成反應 38
3.3.18 BVPE/EG200-BPA單體對進行原子轉移自由基聚加成反應 39
3.3.19 BVPE/BuBPA單體對進行原子轉移自由基聚加成反應 39
3.3.20 聚酯鹼性環境下水解測試 40
3.3.21 含雙硫鍵之聚酯降解測試 40
第四章、結果與討論 41
4.1 單體結構鑑定 41
4.4.1 VBA結構鑑定 41
4.4.2 VBBPA結構鑑定 41
4.4.3 mPEG550-propargyl結構鑑定 43
4.2 VBBPA進行SARA&ICAR&ARGET ATRPA 44
4.2.1 VBBPA在不同配體、觸媒接觸面積下進行SARA ATRPA 44
4.4.2 VBBPA在不同溫度、銅觸媒濃度下進行ICAR ATRPA與ARGET ATRPA 47
4.3 PVBBPA官能基化 51
4.3.1 alkyl-PVBBPA結構鑑定 51
4.3.2 PVBAPA與PVBHPA結構鑑定 52
4.4 微胞性質 55
4.4.1 雙親性高分子刷之臨界微胞濃度 55
4.4.2 微胞粒徑與型態 57
4.4.3 微胞穩定測試 60
4.4.4 最低臨界溶解溫度(LCST) 60
4.5 單體結構鑑定 62
4.5.1 BVPE結構鑑定 62
4.5.2 DSBPA結構鑑定 64
4.5.3 EG200-BPA結構鑑定 65
4.5.4 BuBPA結構鑑定 65
4.6 BVPE/DSBPA單體對進行ATRPA 66
4.7 BVPE/EG200-BPA單體對進行ATRPA 68
4.8 BVPE/BuBPA單體對進行ATRPA 69
4.9 PVPDSBPA降解測試 70
第五章、結論 72
第六章、參考文獻 74

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