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研究生: 莊詠涵
Chuang, Yung-Han
論文名稱: 聚(苯乙烯-乙烯-丙烯-苯乙烯)(SEPS)和聚丙烯(PP)共混物磺酸化之分析鑑定與血袋材料上之應用
Sulfonation and characterization of poly(styrene-ethylene-propylene-styrene)(SEPS) and polypropylene (PP) blends for blood bag applications
指導教授: 林睿哲
Lin, Jui-Che
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2019
畢業學年度: 107
語文別: 中文
論文頁數: 107
中文關鍵詞: 陰離子聚合氫化磺酸化熱塑性彈性體聚丙烯苯乙烯異戊二烯血液相容性
外文關鍵詞: Anionic polymerization, Hydrogenation, Sulfonation, Thermoelastomer, Hemocompatibility
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  • 現有的血袋材料多為聚氯乙烯為主,然而其中卻含有高達45%的塑化劑,對於新生兒或是長期需要換液的病患,可能會有影響生長與生殖的風險。因此目前仍然在找尋可替代材料。
    本研究利用陰離子聚合法,成功聚合出聚苯乙烯-異戊二烯-苯乙烯三嵌段共聚物(Poly(Styrene-Isoprene-Styrene),SIS),其中苯乙烯鏈段中含有不同比例的苯乙烯和叔丁基苯乙烯(4-tert-butylstyrene)。藉由金屬觸媒的催化,成功氫化SIS中未飽和的雙鍵,得到聚苯乙烯-乙烯-丙烯-苯乙烯(Poly(Styrene-Ethylene-Propylene-Styrene),SEPS)。之後,將SEPS和聚丙烯(Polypropylene,PP)依不同比例混參。由於SEPS結構與PP相似,這可能提供兩者良好的相容性,並且改善PP的機械性質。最後,利用醋酸酐(Acetic anhydride)與硫酸(Sulfuric acid)將SEPS磺酸化,預計以含有不同比例的叔丁基苯乙烯,獲得不同磺酸化程度的SEPS/PP (sulfonated SEPS/PP,s-SEPS)。
    因帶有負電的磺酸根,改善材料的疏水性質;部分磺酸化也保留SEPS的熱彈性質;實驗結果亦顯示此材料無細胞毒性,且有效減少血小板貼附量和變形。具有發展成血袋材料的潛能。本研究將利用各種儀器與方法探討材料的結構、機械性質、親疏水性等物理特性。

    Most of modern blood bag is mainly made of polyvinyl chloride (PVC) and plasticizers. However, for newborns or patients who need transfusion for a long time or a huge volume, exposure to plasticizers would be a potential problem of fertility and development. Therefore, these years, experts are still looking for alternative materials for blood bag.
    In this study, we successfully synthesized poly(styrene-isoprene-styrene) (SIS) triblock copolymer whose styrene segments contain different ratio of 4-tert-butylstyrene (tBS) with anionic polymerization. Through hydrogenating unsaturated double bonds in SIS, poly(styrene-ethylene-propylene-styrene) (SEPS) was obtained. SEPS was then blended with polypropylene (PP) in different proportions. Since the structure of SEPS is similar to that of PP, this provide a good compatibility and, resulting, an improvement in mechanical properties of PP. Subsequently, the surface of blends was sulfonated with acetic anhydride and sulfuric acid. We expected that we could obtain different degrees of sulfonation of blends (s-SEPS/PP) with controlling different ratio of tBS, and this partial sulfonation could retain the thermoelastic properties of SEPS. Based on various analyses methods, the results would be reported to explore the physical properties and chemical characteristics, such as the chemical configuration, mechanical properties, surface hydrophobicity, and hemocompatibility of different materials prepared.
    Finally, after sulfonation treatment, we could get a hemocompatibility material without cytotoxicity. With the negative surface, platelet adhesion and activation could be reduced by s-SEPS/PP blends. Nonetheless, due to little consideration of sulfonated PP and the effect of molecular weight, tuning degree of sulfonated SEPS/PP with different tBS ratio still poses challenges.

    中文摘要 II Extended Abstract III 誌謝 XXVII 目錄 XXVIII 表目錄 XXXII 圖目錄 XXXIII 第一章 緒論 1 第二章 文獻回顧 2 2-1 血袋材料 2 2-1-1血袋歷史 2 2-1-2血袋的訴求 4 2-1-3現存問題 4 2-1-4影響與商機 5 2-2 血袋的替代材料 6 2-2-1 聚丙烯(Polypropylene, PP) 6 2-2-2 聚(苯乙烯-乙烯-丙烯-苯乙烯)(Polystyrene-ethylene-propylene-styrene, SEPS) 7 2-2-3 PP與SEPS之共混參(Blending) 9 2-3 陰離子聚合法 10 2-3-1起始劑種類與起始反應 (Initiation reaction) 11 2-3-2鏈成長反應 (Propagation reaction) 14 2-3-3鏈終止反應 (Termination reaction) 15 2-4 血液相容性[28] 16 2-4-1 血液的組成 16 2-4-2 血小板的組成 17 2-4-3 血小板的功能 19 2-4-4 凝血機制 21 2-4-5 具有血液相容性的材料表面特性 23 2-5 研究目的與動機 24 第三章 實驗藥品與儀器介紹 26 3-1 實驗藥品 26 3-1-1 Poly(Styrene-Isoprene-Styrene) (SIS)三嵌段共聚物之聚合 26 3-1-2 Poly(Styrene-Isoprene-Styrene) (SIS)三嵌段共聚物之氫化 26 3-1-3 Poly(Styrene-Ethylene-Propylene-Styrene) (SEPS)與Polypropylene (PP)之混參 27 3-1-4 Poly(Styrene-Ethylene-Propylene-Styrene) (SEPS) 與PP共混物之磺酸化 27 3-1-5 血小板貼附實驗 27 3-1-6 細胞毒性實驗 28 3-1-7 蛋白質貼附實驗 28 3-2 實驗設備與儀器 29 3-3 儀器原理與介紹 30 3-3-1 高解析核磁共振光譜儀 (Nuclear Magnetic Resonance, NMR) 30 3-3-2 膠體滲透層析儀 (Gel Permeation Chromatography, GPC) 32 3-3-3 熱重分析儀 (Thermo Gravimetric Analyzer) 34 3-3-4熱示差掃描熱分析儀 (Differential Scanning Carlorimetry) 34 3-3-5 機械性質試驗機 (Mechanical Testing System) 35 3-3-6 衰弱式全反射-霍氏轉換紅外線光譜儀 (Attenuated total reflection-Fourier transform infrared spectroscopy, ATR-FTIR) 36 3-3-7 場發射掃描式電子顯微鏡 (Field emission Scanning electron microscope, FESEM) 37 3-3-8 靜態接觸角(Static Water Contact Angle) 38 3-3-9化學分析電子能譜儀 (Electron Spectroscopy for Chemical Analysis, ESCA)[44, 45] 39 第四章 實驗步驟 41 4-1 實驗流程圖 41 4-2 SIS三嵌段共聚物之聚合 42 4-2-1 實驗藥品前處理 42 4-2-2 聚合SIS三嵌段共聚物 43 4-3 SIS三嵌段共聚物之氫化 45 4-3-1 氫化步驟 45 4-3-2 去除SEPS中殘餘觸媒 46 4-4 SEPS與PP之混參 47 4-5 材料性質鑑定 49 4-5-1 以NMR檢測SIS與SEPS之化學組成 49 4-5-2 以GPC檢測SIS與SEPS之分子量與分子量分佈 49 4-5-3 以TGA檢測高分子之熱穩定性 49 4-5-4 以DSC檢測高分子之熱彈性質 50 4-5-5 以MTS檢測高分子之拉伸強度與延展率 50 4-6 SEPS/PP共混物之磺酸化 51 4-7 磺酸化之鑑定與材料效果評估 52 4-7-1 以ATR-FTIR對磺酸化程度定性檢測 52 4-7-2 以ESCA對磺酸化程度定量檢測 52 4-7-3 以WCA檢測高分子表面親疏水性質 52 4-7-4 材料吸水性 (Water uptake, WU) 52 4-7-5 細胞毒性測試 (Cytotoxicity) 53 4-7-6 血小板貼附實驗 (In vitro platelet adhesion) 54 4-7-7 蛋白質貼附實驗 56 第五章 結果與討論 57 5-1 聚合SIS三嵌段共聚物 57 5-1-1聚合SIS三嵌段共聚物之1H-NMR結構鑑定 57 5-1-2 SIS三嵌段共聚物之分子量鑑定 64 5-2 氫化SIS三嵌段共聚物(SEPS) 66 5-2-1 氫化SIS三嵌段共聚物(SEPS)之1H-NMR結構鑑定 66 5-2-2 氫化SIS三嵌段共聚物(SEPS)之分子量鑑定 70 5-3 磺酸化SEPS/PP共混物 71 5-3-1 ATR-FTIR定性分析 71 5-3-2 ESCA 定性與定量分析 73 5-3-3 表面親疏水性質與型態 82 5-3-4 細胞毒性 85 5-3-5 血小板貼附 86 5-3-6 蛋白質貼附 89 5-4 材料性能比較與鑑定 91 5-4-1 材料熱穩定性 (TGA) 91 5-4-2 熱效應性質 (DSC) 94 5-4-3 機械性質 94 第六章 結論 98 參考文獻 99

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