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博碩士論文 etd-0528116-114942 詳細資訊
Title page for etd-0528116-114942
論文名稱
Title
研究可光交聯香豆素分子與芘分子之雙官能化聚氧代氮代苯并環己烷及混摻奈米碳管複合材料
Bifunctional polybenzoxazine nanocomposites contain photo-crosslinkable coumarin units and pyrene units are capable of dispersing single-walled carbon nanotubes
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
72
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
2016-06-16
繳交日期
Date of Submission
2016-07-12
關鍵字
Keywords
芘、氧代氮代苯并環己烷、π–π 作用力、單壁奈米碳管、玻璃轉換溫度
π–π stacking, Glass transition temperature, Polybenzoxazine, Single-walled carbon nanotube, Pyrene
統計
Statistics
本論文已被瀏覽 5671 次,被下載 427
The thesis/dissertation has been browsed 5671 times, has been downloaded 427 times.
中文摘要
本研究是合成含芘(Pyrene)和Coumarin的雙官能化新型氧代氮代苯并環己烷(Benzoxazine),利用傅立葉轉換紅外光光譜儀(FTIR)和核磁共振儀(NMR)做結構鑑定,並使用示差掃描量熱儀(DSC)、熱重分析儀(TGA)和傅立葉轉換紅外光光譜儀(FTIR)來觀察此Coumarin-Py BZ單體做熱交聯(Curing)成Poly(Coumarin-Py BZ)後的分析,由於此新型的BZ單體帶有可光交聯的分子(Coumarin),因此進行UV光照射形成BZ二聚體單體後,再進一步做結構鑑定與熱性質分析。從DSC分析結果得知,行UV光交聯後的BZ二聚體單體做熱交聯而成Poly(di-Coumarin-Py BZ)因為交聯密度提高,因此其玻璃轉換溫度(Tg)高於Poly(Coumarin-Py BZ),此外,本新型BZ單體的另一端分子(Pyrene)可以與單壁奈米碳管(SWCNT)以π–π stacking作用,並且均勻分散奈米碳管在有機溶劑(THF)中。從DSC和TGA結果得知,當進行UV光交聯完並與單壁奈米碳管結合的Polybenzoxazine,其熱性質(熱穩定性、高殘餘量)明顯提升。
Abstract
In this study, we have synthesized a new bifunctional benzoxazine monomer (Coumarin–Py BZ) possessing both coumarin and pyrene groups through the reaction of 4-methyl-7-hydroxycoumarin (coumarin–OH), paraformaldehyde, and amino-pyrene (Py–NH2) in 1,4-dioxane. Fourier transform infrared (FTIR) and 1H and 13C nuclear magnetic resonance spectroscopy confirmed the structure of this new coumarin–Py BZ monomer. We used differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and FTIR spectroscopy to monitor the curing behavior of coumarin–Py BZ to form poly (Coumarin–Py BZ), both before and after photodimerization of the coumarin moiety. DSC profiles revealed that the glass transition temperature of poly (Di-coumarin–Py BZ) was higher than that of its corresponding polymer, and consistent with an increase in crosslinking density after UV irradiation. The pyrene moiety of coumarin–Py BZ enhanced the dispersibility of single-walled carbon nanotubes (SWCNTs) in THF, leading to the formation of highly dispersible coumarin–Py BZ/SWCNT nanocomposites stabilized through π–π stacking between the pyrene and SWCNT units, as detected by Photoluminescence (PL). The combination of photo-crosslinkable coumarin groups and SWCNT nanohybrids enhanced the thermal stability, and char yield of the polybenzoxazine matrix, based on DSC and TGA analyses.
目次 Table of Contents
論文審定書 i
致謝 ii
摘要 iii
Abstract iv
目錄 vi
圖目錄 ix
表目錄 xii
第一章 緒論 1
1-1 酚醛樹酯 1
1-2 氧代氮代苯并環己烷 (Benzoxazine) 1
1-3 奈米複合材料 2
第二章 理論與文獻回顧 4
2-1 氧代氮代苯并環己烷 (Benzoxazine) 4
2-2 簡介Benzoxazine與Polybenzoxazine 6
2-3 光誘導交聯特性分子 7
2-4 非共價鍵結 8
2-5 奈米碳管 10
2-6 材料表面疏水特性 14
2-7 研究動機 15
第三章 實驗方法 16
3-1 實驗內容與流程 16
3-2 實驗藥品 17
3-3 實驗合成 18
3-3.1合成1-nitropyrene 18
3-3.2合成1-aminopyrene 18
3-3.3合成Coumarin-OH 18
3-3.4合成Coumarin-Py BZ 19
3-3.5紫外光誘導Coumarin分子產生Di-Coumarin-Py BZ 19
3-3.6 合成B-ala BZ 20
3-3.7 塗佈溶液之製備 20
3-4 實驗儀器 21
3-4.1傅立葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer, FTIR) 型號:Bruker Tensor-27 21
3-4.2核磁共振光譜儀(Nuclear Magnetic Resonance, NMR) 型號:Varian Unity Inova-500 21
3-4.3示差掃描量熱儀(Differential Scanning Calorimeter, DSC) 型號:TA Q-20 22
3-4.4熱重分析儀(Thermal Gravimetric Analyzer, TGA) 型號:TA Q-50 23
3-4.5紫外光/可見光吸收光譜儀(Ultraviolet/Visible Spectrophotometer) 型號:BWTEK/BDS130 23
3-4.6螢光光譜儀(Photoluminescence, PL) 型號:LabGuide X350 24
3-4.7穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 型號:JEOL-2100 24
3-4.8接觸角( Dataphysics, OCA-20) 24
第四章 結果討論 25
4-1 Coumarin-Py BZ之合成 25
4-1.1 Coumarin-Py BZ結構鑑定分析 25
4-1.2 Coumarin-Py BZ聚合之熱性質分析 29
4-2 UV光誘導Coumarin分子行環加成反應 31
4-2.1 光致Coumarin分子交聯成二聚體 31
4-2.2 Di-Coumarin-Py BZ結構鑑定 33
4-2.3 Di-Coumarin-Py BZ聚合之熱性質分析 35
4-3 Coumarin-Py BZ以π-π interaction貼合單壁奈米碳管 37
4-3.1 Coumarin-Py BZ混摻單壁奈米碳管之螢光光譜儀分析 37
4-3.2 Coumarin-Py BZ混摻單壁奈米碳管 38
4-3.3 Coumarin-Py BZ混摻單壁奈米碳管之熱性質研究 39
4-4 Di-Coumarin-Py BZ以π-π interaction貼合單壁奈米碳管 43
4-4.1 Di-Coumarin-Py BZ混摻單壁奈米碳管之熱性質研究 44
4-4.2 紫外光誘導交聯與混摻奈米碳管對玻璃轉移溫度之影響 46
4-4.3 光誘導交聯及混摻奈米碳管對Coumarin-Py BZ熱穩定性影響 48
4-5 Poly (Coumarin-Py BZ)之表面親疏水接觸角分析 49
4-5.1 熱交聯時間對Poly (Coumarin-Py BZ)之水滴接觸角影響 49
4-5.2 Coumarin-Py BZ混摻B-ala塗佈於不鏽鋼表面分析 50
4-5.3 Coumarin-Py BZ/B-ala對於不鏽鋼抗指紋測試 54
第五章 結論 57
第六章 參考文獻 58
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