本研究利用矽氫加成反應及合環反應成功製備出兩種具有雙官能基矽氧烷寡聚體(Double-Decker Silsesquioxanes, DDSQ)之聚氧代氮代苯并環己烷(Polybenzoxazine, PBz)，為Bz-DDSQ與PDMS- Bz-DDSQ。首先，透過傅立葉紅外線光譜儀(FTIR)、核磁共振分析儀(NMR)與質輔助雷射脫附游離飛行時間質譜儀(MALDI-TOF MS) 進行結構上的鑑定，接著，藉由微差掃描熱卡儀(DSC)、熱重分析儀(TGA)與動態黏彈機械分析儀(DMA)探討每個結構之熱性質以及機械性質，以上的分析結果顯示，目前仍未商業化之DDSQ小分子接於Poly(Bz-DDSQ)主鏈上後，確實提供更優異的熱穩定性與表面疏水特性，另外，於拉伸試驗以及紫外線/可見光光譜儀結果可知，在接上聚二甲基矽氧烷(Poly(dimethylsiloxane), PDMS) 後的Poly(PDMS-Bz-DDSQ)相較前者展現出更好的韌性以及穿透度。最後，我們成功改善了原先Poly(Bz) 質地脆、顏色深的缺點，並成功製備出具有高熱穩性且可撓的Poly(PDMS-Bz-DDSQ)薄膜。

In this study, two kinds of benzoxazine containing double-decker silsesquioxanes (DDSQ), Bz-DDSQ and PDMS-Bz-DDSQ were successfully synthesized by a combination of cycloaddition and hydrosilylation condensation. First of all, we employed Fourier transform infrared spectrometer (FTIR), nuclear magnetic resonance (NMR), and matrix-asssisted laser desorption/ionization time of flight mass spectrometer (MALDI-TOF MS) to determined the purity of chemical structure for all compounds. Next, We discussed thermal properties and mechanical properties by differential scanning calorimeter (DSC) ,thermogravimetric analysis (TGA) and dynamic mechanical analyzer (DMA), the results showed that incorporation of the DDSQ unit on the main chain of the Poly(DDSQ-Bz) moiety enhanced the thermal properties and hydrophobicity. In addition, the attachment of PDMS into the main chain of Poly(PDMS-Bz-DDSQ) could increase toughness and transparenty in bulk state, compared with pure Poly(DDSQ-Bz) by ultraviolet-visible spectrophotometry (UV-vis), universal testing machine and scanning electron microscope(SEM) analyses. Finally, we improved the shortcomings of Poly(Bz), such as deep brown color, brittleness, and synthesized the Poly(PDMS-Bz-DDSQ) films, which have high thermal stability and flexibility.

論文審定書 i
謝誌 ii
摘要 iv
Abstract v
目錄 vi
圖目錄 ix
表目錄 xi

第一章 緒論 1
1-1 前言 1
1-2 聚氧代氮代苯并環己烷(Polybenzoxazine) 2
1-2-1 Benzoxazine 單體及Polybenzoxazine 之製備 2
1-2-2 官能基對於Benzoxazine 單體及Polybenzoxazine 之熱性質影響 4
1-2-3 Polybenzoxazine/Polysiloxane 複合材料 4
1-3 無機/有機的奈米複合材料 5
1-4多面體矽氧烷寡聚體(Polyhedral Oligomeric Silsesquioxanes, POSS) 7
1-4-1多面體矽氧烷寡聚體的製備 9
1-4-2 多面體矽氧烷寡聚體與高分子共聚方式 9
1-4-3 水解縮合 11
1-5 研究動機 13
第二章 實驗方法及步驟 14
2-1實驗內容及流程 14
2-2實驗藥品 15
2-3實驗步驟 16
2-3-1合成Double-Deckered Silsesquioxanes-Na(DDNa) 16
2-3-3合成1-4 vinyl acetate-DDSQ(AS-DDSQ) 16
2-3-4合成Phenol-DDSQ 16
2-3-2合成Double-Deckered Silsesquioxanes(DDSQ) 16
2-3-5合成Benzoxazine-DDSQ(Bz-DDSQ) 17
2-3-6合成PDMS-Benzoxazine-DDSQ(PDMS-Bz-DDSQ) 17
2-4儀器介紹 20
2-4-1 基質輔助雷射脫附游離飛行時間質譜儀(Matrix-Assisted Laser Desorption/Ionization Tima of Flight Mass Spectrometer,MALDI-TOF MS)型號 :Bruker Autoflex III TOF/TOF 20
2-4-2 X光粉末繞射儀(X-ray diffractometer,XRD) 型號 :Siemens D5000 system 21
2-4-3 掃描式電子顯微鏡(Scanning Electron Microscopr,SEM) 型號 : JEOL JSM-6380 21
2-4-4 核磁共振光譜儀(Nuclear Magnetic Resonance, NMR)型號: Varian® Unity Inova-500 22
2-4-5 傅利葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR)型號﹕Bruker Tensor-27 23
2-4-6 微差掃瞄卡計(Differential Scanning Calorimeter, DSC)型號：TAQ-20 23
2-4-7熱重分析儀 (Thermogravimetry Analysis,TGA)型號：TAQ-50 24
2-4-8 接觸角分析儀(Contact Angle Analyzer,CA) 型號﹕Data Physics OCA20 24
2-4-9 動態黏彈機械分析儀(Dynamic Mechanical Analyzer, DMA)型號: Perkin Elmer DMA8000 25
第三章 結果與討論 26
3-1 DDSQ及其衍生物之分子結構鑑定 26
3-1-1 Double-Deckered Silsesquioxanes (DDSQ)之鑑定分析 26
3-1-2 1-4 vinyl acetate-DDSQ (AS-DDSQ)之鑑定分析 27
3-1-3 Phenol-DDSQ之鑑定分析 27
3-1-4 Benzoxazine-DDSQ (Bz-DDSQ)之鑑定分析 27
3-1-5 PDMS-Benzoxazine-DDSQ (PDMS-Bz-DDSQ)之鑑定分析 28
3-1-6 DDSQ、AS-DDSQ、Phenol-DDSQ之熱分析 33
3-2 Bz-DDSQ之性質探討 37
3-2-1 Bz-DDSQ之熱性質分析 37
3-2-2 Bz-DDSQ之光學性質分析 42
3-2-3 Bz-DDSQ之機械性質分析 43
3-2-4 Bz-DDSQ之表面性質分析 45
3-3 PDMS-Bz-DDSQ之性質探討 47
3-3-1 PDMS-Bz-DDSQ之熱性質分析 47
3-3-2 PDMS-Bz-DDSQ之光學性質分析 50
3-3-3 PDMS-Bz-DDSQ之機械性質分析 51
3-3-4 PDMS-Bz-DDSQ之表面性質分析 53
第四章 結論 55
第五章 參考文獻 56

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