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博碩士論文 etd-0724112-121413 詳細資訊
Title page for etd-0724112-121413
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
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
105
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
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
統計
Statistics
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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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