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論文名稱 Title |
仿去氧核醣酸多重氫鍵作用力提升聚氧代氮代苯并環己烷/聚氧乙烯混摻系統互溶性 Miscibility Behavior Enhancement of Polybenzoxazine/ Poly(ethylene oxide) Blend through DNA-Like Multiple Hydrogen Bonding Interaction |
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系所名稱 Department |
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畢業學年期 Year, semester |
語文別 Language |
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學位類別 Degree |
頁數 Number of pages |
105 |
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研究生 Author |
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指導教授 Advisor |
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召集委員 Convenor |
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口試委員 Advisory Committee |
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口試日期 Date of Exam |
2012-06-25 |
繳交日期 Date of Submission |
2012-07-24 |
關鍵字 Keywords |
相溶性、氫鍵、混摻、聚氧代氮代苯并環己烷 Blend, Benzoxazine, Hydrogen Bonding, Miscibility |
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統計 Statistics |
本論文已被瀏覽 5686 次,被下載 501 次 The thesis/dissertation has been browsed 5686 times, has been downloaded 501 times. |
中文摘要 |
本研究於聚氧代氮代苯并環己烷(Polybenzoxazine, PBz)混摻系統中導入DNA的多點氫鍵,利用氫鍵作用力製備出有機/無機的聚氧代氮代苯并環己烷複合材料。我們成功合成出帶有胸腺嘧啶(Thymine, T)的氧代氮代苯并環己烷(Benzoxazine-thymine, Bz-T)以及末端帶有腺嘌呤(Adenine, A)的聚氧乙烯(Poly(ethylene oxide)-adenine, PEO-A)與多面體矽氧烷寡聚物(Polyhedral Oligomeric Silsesquioxanes-adenine, POSS-A),利用液態核磁共振氫譜(1H NMR), 液態核磁共振碳譜(13C NMR)與傅立葉轉換紅外線光譜 (FT-IR)進行化學結構分析。接著利用示差掃描量熱儀(DSC)、熱重分析儀(TGA)、傅立葉轉換紅外線光譜(FT-IR) 以及穿透式電子顯微鏡(TEM),發現thymine(T)的導入,會使得Bz的交聯溫度降低同時形成線性的PBz結構,並在系統中造成強大的氫鍵作用力,使得PBz-T發生排列的現象。 在混摻系統的研究上,我們分別將PEO-A、POSS-A混入Bz-T中並交聯。在PEO-A/PBz-T系統中,透過NMR與FT-IR觀察在氧代氮代苯并環己烷系統發生交聯的同時,A-T氫鍵作用還是存在。再利用DSC、小角度X光散射(SAXS)、廣角度X光散射(WAXD)、TEM與原子力顯微鏡(AFM),發現PEO因為反應導致相分離(Reaction induced phase separation)發生相分離,當導入A-T氫鍵的作用力之後,相分離尺度有明顯的變小,同時PEO被限制在PBz基地中,使相容性有明顯的提升;也發現在PEO與PBz-T的邊界上有A-T官能基的聚集,因此形成一種新型態的相分離界面。最後我們利用SAXS、WAXD、DSC與TEM探討POSS-A自組裝結構,並發現POSS-A/Bz-T會因為氫鍵作用力在交聯後會有自組裝結構的產生,同時透過奈米壓痕試驗(Nanoindenter analyser)分析其表面機械性質,發現POSS的導入,對POSS/PBz的奈米薄膜機械性質有所提升。 |
Abstract |
We have prepared a new class of polybenzoxazine based nanocomposites through DNA-like self-complementary multiple hydrogen bonding. At first, benzoxazine containing thymine (Bz-T), PEO containing adenine (PEO-A) group and POSS containing adenine (POSS-A) have been successfully synthesized, respectively. Those chemical structures were confirmed by 1H and 13C NMR and FT-IR spectroscopies. DSC and TGA analyses showed that the Bz-T had lower cross-link temperature and higher thermostability than benzoxazine containing methyl acrylate (BZ-ac) group. Moreover, TEM and WAXD provided a new evidence for linearly structure and self-assembly polybenzoxaine through self-complementary multiple hydrogen bonding of its T units. Then, PEO-A/PBz-T and POSS-A/PBz-T hybrid materials were prepared. SAX, WAXD, TEM and AFM analyses indicated that the size of PEO domain in PBz-T matrix was significantly decreased and the new type phase separation boundary (discrete domain through non-convent bonds) was obtained. Finally, we were using WAXD, TEM, DSC and nanoindenter to study properties of POSS-A/PBz-T nanocomposite. The presence of self-assembly nano-lamellate structure and enhance the mechanical properties on thin film, because of well-dispersion of POSS in PBz-T matrix through strong hydrogen bonding between A-T interactions. |
目次 Table of Contents |
摘要 i Abstract ii 圖目錄 v 示意圖目錄 viii 表目錄 ix 第一章 緒論 1 1.1. 前言 1 1.2. 研究動機 2 第二章 文獻回顧 4 2.1. 氧代氮代苯并環己烷之聚合反應 (Polymerization of Benzoxazine) 4 2.2. 反應導致相分離 (Reaction induced phase separation, R.I.P.) 5 2-3. 多重氫鍵作用力 7 2-4. Adenine與Thymine自組裝行為 8 2-5. 聚氧化乙烯 (Poly ethylene oxide, PEO) 10 2-6. 多面體矽氧烷寡聚物(Polyhedral Oligomeric Silsesquioxanes , POSS) 10 第三章 實驗方法與步驟 12 3.1實驗藥品: 13 3.2合成方法: 14 3.2.1製備(3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)methyl thymine (Bz-T) 14 a. 合成 (3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)methanol (Bz-a) 14 b. 合成 (3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)methyl acrylate (Bz-ac) 14 c. 合成 (3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)methyl thymine (Bz-T) 15 3.2.2 製備 PEO-Adenine (PEO-A) 15 3.2.3 製備 POSS-Adenine (POSS-A) 16 3.3實驗儀器: 20 3.3-1氫核磁共振分析儀(Nuclear Magnetic Resonance, NMR) 20 3.3-2傅立葉紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR) 21 3.3-3微差掃瞄熱卡儀(Differential Scanning Calorimeter, DSC) 21 3.3-4熱重分析儀(Thermal Gravimetric Analyzer, TGA) 22 3.3-5小角度X光散射儀(Small Angle X-ray Scattering, SAXS) 22 3.3-7廣角度X光散射儀(wide Angle X-ray Scattering, WAXD) 23 3.3-8奈米壓痕試驗機(Nanoindentater) 23 3.3-9流變儀 (Rheology analyzer) 24 3.3-10原子力顯微鏡 (Atomic Force Microscope, AFM) 25 第四章 結果與討論 26 4-1 Benzoxazine containing Thymine (Bz-T)分析研究 26 4-1.1 Benzoxazine-thymine (Bz-T)合成鑑定分析: 27 4-1.2 Bz-T交聯性質與熱穩定性研究: 31 4-1.3 Bz-T/Bz 混摻之交聯性質與氫鍵作用力研究: 35 4-1.4氫鍵導致自組裝結構 41 4-2 Benzoxazine-thymine (Bz-T)與PEO-adenine (PEO-A)混摻性質分析研究 45 4-2.1 PEO-Adenine (PEO-A)合成鑑定分析 46 4-2.2 A-T氫鍵作用力探討 50 4-2.3 PBz-T與PEO-A相分離行為之研究 52 4-3. Benzoxazine-thymine (Bz-T)與POSS-adenine (POSS-A)混摻性質分析研究 58 4-3.1. POSS-Adenine (POSS-A)合成鑑定分析 58 4-3.2. POSS-A自組裝結構分析 63 4-3.3 氫鍵作用力之研究 68 4-3.4. 超分子自組裝研究 74 4-3-5. 奈米機械性質分析與熱重分析: 81 第五章 結論 86 第六章 參考文獻 87 |
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