博碩士論文 111324017 詳細資訊




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姓名 林柏諺(Po-Yen Lin)  查詢紙本館藏   畢業系所 化學工程與材料工程學系
論文名稱 建立耐氧光聚合連續流反應器
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檔案 [Endnote RIS 格式]    [Bibtex 格式]    [相關文章]   [文章引用]   [完整記錄]   [館藏目錄]   至系統瀏覽論文 (2029-9-1以後開放)
摘要(中) 相較於傳統批次反應器,流動式反應器具備一些明顯的優勢,包括均勻混合、熱量與質量傳送效率高、易於控制停留時間、高再現性等。因此,流動反應器系統可通過選擇合適之反應參數,快速確定其最佳反應條件,並應用於大規模生產以增加生產效率。
因此在本研究中,我們使用聚全氟乙烯丙烯 (Fluorinated Ethylene Propylene) 透明管作為連續反應器,以綠色LED光作為光聚合的光源。此外,我們還利用泵控制器自動調整各種反應參數,如停留時間、單體濃度和光催化劑/單體比例,以及使用自動樣品收集器對產物進行分類。此外,由於其簡單的設計和低成本,這種管狀連續反應器適用於擴大生產和降低合成成本。它還可以用於高通量合成,以快速篩選共聚物組成,從而實現對各種聚合物的快速合成和分析。在本實驗中,丙烯醯胺表現出更好的反應活性和轉化率。因此,我們以磺基甜菜鹼丙烯醯胺(Sulfobetaine Acrylamide) 和丙烯醯甘氨(Acryloylglycine) 為基礎,合成了約為25,000 g/mol的共聚物。磺基甜菜鹼丙烯醯胺提供抗菌和抗污垢的效果。而丙烯酰甘氨則可以通過氫鍵修飾於316不鏽鋼基板上。通過核磁共振氫譜 (Nuclear Magnetic Resonance Spectroscopy) 譜學鑑定共聚物的結構和轉化率,然後使用凝膠滲透層析 (Gel Permeation Chromatography) 確認不同條件下的分子量。最後,我們通過將共聚物接枝到不銹鋼基板上進行表面修飾,並使用水接觸角測量儀確認其親水性。使用X射線光電子能譜儀 (X-ray photoelectron spectroscopy) 和衰減全反射傅立葉變換紅外光譜儀 (Attenuated Total Reflection-Fourier Transform Infrared Spectrometer) 驗證塗層的表面組成。進行細菌和蛋白質附著測試以評估塗層的抗污垢性能。
摘要(英) Compared to traditional batch reactors, flow reactors offer several notable advantages, including uniform mixing, high efficiency of heat and mass transfer, ease of controlling residence time, and high reproducibility. Therefore, flow reactor systems can rapidly determine optimal reaction conditions through appropriate selection of reaction parameters and can be applied to large-scale production to increase production efficiency.
In this study, a fluorinated ethylene propylene (FEP) transparent tubing was utilized as a continuous reactor, with green LED light serving as the light source for photopolymerization. Additionally, we utilized a pump controller to automatically adjust various reaction parameters, such as residence time, monomer concentration, and photocatalyst/monomer ratio, and an automatic sample collector to sort products. Furthermore, this tubular continuous reactor, due to its simple design and low cost, is suitable for scaling up production and reducing synthesis costs. It can also be used for high-throughput synthesis to screen copolymer compositions rapidly, thereby enabling the rapid synthesis and analysis of a wide range of polymers. In this experiment, acrylamide showed better reactivity and conversion. Therefore, we synthesized a copolymer with a molecular weight of approximately 25,000 g/mole based on sulfobetaine acrylamide (SBAA) and acryloylglycine (AG). Sulfobetaine acrylamide has the effect of antibacterial and antifouling. Acryloylglycine can be modified on the 316 stainless steel substrates through hydrogen bonding. The copolymers were identified using proton nuclear magnetic resonance (1H NMR) spectroscopy to determine their structures and conversion rates, followed by gel permeation chromatography (GPC) to confirm molecular weights under different conditions. Finally, we modified stainless steel substrates by grafting the copolymers, and their hydrophilicity was confirmed using a water contact angle measurement instrument. The surface composition of the coatings was verified using X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR). Bacterial and protein attachment tests were conducted to assess the anti-fouling properties of the coatings.
關鍵字(中) ★ 連續式反應器
★ 流動化學
★ 高通量
★ 可見光氧化還原劑
★ 光聚合
關鍵字(英) ★ Continuous Flow reactor
★ Flow chemistry
★ High throughput
★ Photoredox
★ Photopolymerization
論文目次 中文摘要 I
Abstract II
致謝 IV
目錄 V
圖目錄 VIII
表目錄 XI
化學品名詞簡稱 XII
共聚物名詞簡稱 XIII
一、 文獻回顧 1
1-1批次反應器 1
1-2連續式微反應器 2
1-2-1 管式微反應器 2
1-2-2聚全氟乙烯丙烯管 (FEP tube) 4
1-2-3 氧氣對光聚合反應之影響 5
1-2-4自動化控制 6
1-3高通量合成 8
1-3-1 製程分析技術 (Process Analytical Technology, PAT) 9
1-3-2 全因子設計 9
1-4光起始自由基聚合反應 10
1-4-1可逆加成-斷裂鏈轉移 (Reversible Addition-Fragmentation Chain Transfer, RAFT) 10
1-4-2光誘導能量轉移-可逆加成-斷裂鏈轉移 (Photoinduced Energy Transfer-Reversible Addition-Fragmentation Chain Transfer, PET-RAFT) 11
1-5 表面修飾 13
1-5-1 表面接枝 13
1-5-2 羧酸官能基接枝於金屬表面 13
1-6 抗吸附單體 14
1-6-1 雙離子材料 14
1-6-2 磺基甜菜鹼丙烯醯胺 (Sulfobetaine acrylamide, SBAA) 15
二、 研究目的 16
三、 實驗藥品及實驗方法 17
3-1實驗藥品與設備 17
3-1-1實驗藥品清單 17
3-1-2儀器設備清單 19
3-1-3連續式微流道光反應器設計 21
3-2材料製備 24
3-2-1 磺基甜菜鹼甲基丙烯酸 (Sulfobetaine methacrylate, SBMA) 24
3-2-2 磺基甜菜鹼丙烯酸酯 (Sulfobetaine acrylate, SBA) 24
3-2-3磺基甜菜鹼丙烯醯胺 (Sulfobetaine acrylamide, SBAA) 25
3-2-4丙烯醯胺基乙酸 (Acryloylglycine, AG) 25
3-2-5 合成PHEMA 26
3-2-6 合成PHEA 26
3-2-7 合成PSBMA 26
3-2-8 合成PSBA 26
3-2-9 合成PSBAA 27
3-2-10 合成Poly(SBAA-ran-AG)高分子 27
3-2-11 316不鏽鋼基材製備 27
3-3分析方法 28
3-3-1 液態核磁共振氫譜 (1H NMR) 28
3-3-2 凝膠滲透層析儀 (Gel Permeation Chromatogragh, GPC) 28
3-3-3 紫外光/可見光分光光譜儀 (Ultraviolet Visible Spectroscopy, UV-VIS) 29
3-3-4 Poly(SBAA-ran-AG)高分子修飾316不鏽鋼表面 29
3-3-5 衰減式全反射傅立葉轉換紅外線光譜儀 (Attenuated Total Reflectance-Fourier-Transform Infrared Sepectroscopy, ATR-FTIR) 29
3-3-6 薄膜厚度之量測 (Ellipsometry) 30
3-3-7 水接觸角量測 (Water Contact Angle) 30
3-3-8 X射線光電子能譜儀 (X-ray Photoelectron Spectroscopy, XPS)表面元素鑑定 30
3-3-9 細菌貼附測試 (Bacteria Attachment) 31
3-3-10 蛋白質貼附測試 (Protein Adhesion) 31
3-3-11統計學分析 32
四、 結果討論 33
4-1 光聚合反應 33
4-1-1 光聚合反應於聚全氟乙烯丙烯管 (FEP) 33
4-1-2 PET-RAFT光催化劑選擇 34
4-1-3 光反應器設計優化 37
4-2 高通量篩選 40
4-2-1 SBA單體結構鑑定 (1H NMR) 40
4-2-2 SBMA單體結構鑑定 (1H NMR) 41
4-2-3 SBAA單體結構鑑定 (1H NMR) 42
4-2-4 PET-RAFT於不同單體之適用性 43
4-2-5 Poly(SBAA-ran-AG) 高分子結構鑑定 (1H NMR) 46
4-2-6還原劑與光催化劑添加量對轉化率之影響 47
4-2-7 還原劑與光催化劑添加量對分子量之影響 49
4-2-8 單體濃度與滯留時間對轉化率之影響 50
4-2-9 單體濃度與滯留時間對分子量之影響 52
4-2-10 光照強度對轉化率之影響 54
4-2-11 光照強度對分子量之影響 56
4-2-12 分液收集連續圖譜 57
4-3 表面薄膜分析 59
4-3-1 不鏽鋼表面官能基分析 (ATR-FTIR) 59
4-3-2 表面元素鑑定 (XPS) 60
4-2-3 不鏽鋼表面薄膜厚度 (Ellipsometer) 62
4-3-4 不鏽鋼表面親水性能測試 (Water Contact Angle) 63
4-4 不鏽鋼表面抗吸附測試 65
4-4-1 抗細菌貼附測試 65
4-4-2 抗蛋白質沾黏測試 68
五、 結論 69
六、 未來展望 70
參考文獻 71
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指導教授 黃俊仁(Chun-Jen Huang) 審核日期 2024-7-18
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