臺灣博碩士論文加值系統

　　酚醛樹脂因為有著獨特良好的性質，所以到今天在高技術應用上仍然是不可取代的材料。然而酚醛樹脂卻很少運用在奈米複合材料上面，這是因為酚醛樹脂是三維的結構，所以要插入矽酸鹽層間是一件很困難的事。通常解決這個問題，可由酚醛樹脂種類或複合材料聚合方法做進一步發展。酚醛樹脂種類可使用線性的novolac型酚醛樹脂ヽresol型低分子量酚醛樹脂或resol型酚醛樹脂。而複合材料聚合方法則有In-situ聚合法ヽ溶液中之高分子插層法以及熔融態高分子直接插層法。此外，易脆性和交聯收縮性是阻礙酚醛樹脂應用的兩大缺點，使其在應用上受到限制。故在酚醛樹酯的應用上，增韌為相當重要的一環。
　　本研究是將resol型酚醛樹脂與數種改質蒙脫土2M2HTMMTヽC18MMTヽ2C18MMTヽB2MPMMTヽB2MHMMT和B3EMMT利用in-suit聚合法分別合成酚醛樹脂/改質蒙脫土奈米複合材料。利用XRD與TEM分別觀察蒙脫土改質程度以及複合材料的結構，得到2M2HTMMT-PF與2C18MMT-PF為插層型複合材料(intercalated nanocomposites)以及C18MMT-PFヽB3EMMT-PFヽB2MPMMT-PF與B2MHMMT-PF為脫層型複合材料(exfoliated nanocomposites)。而從TGA測量得知，B3EMMT-PFヽB2MPMMT-PF與B2MHMMT-PF之改質劑因含有benzyl ring，改質劑與酚醛樹脂有著相似的結構，造成良好的化學相容性，所以跟其他改質劑比起來有良好的熱穩定性。總而言之，改質劑對於熱穩定性(thermal stability)與奈米複合材料最終型態(morphology)上扮演著重要的腳色。另外，本研究藉由導入NBR橡膠來增加酚醛樹酯材料的韌性，摻混後利用拉力機測量發現機械性質能夠提升，但是從TGA與DMA得知，對於熱穩定性的影響不大。

　　Phenolic resins today are indeed irreplaceable materials for selective high- technology applications, because of their excellent ablative properties. However, phenolic resin has been abandoned in the nanocomposite field. The reason is that general phenolic resin has a threedimensional structure that makes phenolic resin very difficult to intercalate in the layered silicate gallery
　　In this work, phenolic　resin/modified-montmorillonite nanocomposites were synthesized by in-situ polymerization with resol type phenolic resins and organoclays such as 2M2HTMMT, C18MMT, 2C18MMT, B2MPMMT, B2MHMMT, and B3EMMT. XRD measurements and TEM observations showed that clay platelets were exfoliated or intercalated. It is found that 2M2HTMMT-PF and 2C18MMT-PF were intercalated nanocomposites and C18MMT-PF, B3EMMT-PF, B2MPMMT-PF and B2MHMMT-PF were exfoliated nanocomposites. TGA showed the thermal stability of B3EMMT- PF, B2MBMMT-PF, and B2MHMMT-PF were higher than that of C18MMT -PF, 2M2HTMMT-PF and 2C18MMT-PF due to chemical affinity derived from the favorable interaction between the phenolic resin and intercalant containing benzene ring. Conclusively, the modification of layered silicate and the resulting interaction between organic modifier and phenolic resin played an important role in determining the thermal stability and the final morphology of phenolic resin-layered silicate nanocomposite. Phenolic resins were also blended with NBR and the measurements of stress-strain properties, TGA, DMA and TEM. It was observed that the mechanical properties of the blend enhanced on incorporation of NBR into the phenolic resin.

中文摘要.......................................................................Ⅰ
英文摘要.......................................................................Ⅱ
誌　　謝.......................................................................Ⅲ
目　　錄.......................................................................Ⅳ
表 目 錄.......................................................................Ⅶ
圖 目 錄.......................................................................Ⅹ


第一章 緒論
1-1　前言.......................................................................1
1-2　理論基礎...................................................................2
　1-2-1　奈米無機層材的種類與結構...............................................2
　1-2-2　改質劑的種類...........................................................5
　1-2-3　有機╱無機混成材料之製程...............................................7
1-3　高分子奈米複合材料之優勢...................................................9
1-4　奈米無機層狀材料的新機能與應用............................................11
1-5　奈米高分子複合材料世界發展趨勢............................................13


第二章 文獻回顧
2-1　Resole type酚醛樹酯的製備與特性...........................................15
2-2　奈米複合材料製備法........................................................17
　2-2-1　In-situ 聚合法........................................................17
　2-2-2　溶液中之高分子插層法..................................................18
　2-2-3　熔融態高分子直接插層法................................................18
2-3　黏土╱高分子奈米複合材料之型態............................................20
2-4　酚醛樹脂奈米複合材料之發展................................................22
2-5　酚醛樹酯與NBR摻混的相關研究...............................................29
2-6　研究動機..................................................................30


第三章 實驗內容
3-1　實驗裝置與設備............................................................32
3-2　操作及鑑定測量儀器........................................................32
3-3　藥品及材料................................................................35
3-4　實驗步驟與結果............................................................36
　3-4-1　改質蒙脫土的製備......................................................36
　3-4-2　酚醛樹脂╱改質蒙脫土奈米複合材料的製備................................40
3-5　聚合原理..................................................................42
3-6　酚醛樹脂╱蒙脫土奈米複合材料之Curing......................................43
3-7　TEM試片...................................................................44
　3-7-1　試片製作..............................................................44
　3-7-2　試片切片..............................................................44
3-8　酚醛樹酯與NBR摻混.........................................................45


第四章 結果與討論
4-1　X-ray繞射光譜圖分析.......................................................47
　4-1-1　蒙脫土改質之X-ray繞射光譜圖分析.......................................47
　4-1-2　複合材料之X-ray繞射光譜圖分析.........................................52
4-2　TEM分析...................................................................54
4-3　複合材料熱性質分析........................................................55
4-4　酚醛樹脂與NBR摻混部分.....................................................58
　4-4-1　酚醛樹脂與NBR的相溶性.................................................58
　4-4-2　酚醛樹脂與NBR的混合黏度測定...........................................60
　4-4-3　酚醛樹脂與NBR硬化後的熱性質...........................................61
　4-4-4　酚醛樹脂與NBR硬化後的微相分離情形.....................................63
　4-4-5　酚醛樹脂與NBR硬化後的機械性質.........................................63


第五章 結論
5-1　酚醛樹脂╱改質蒙脫土複合材料..............................................64
5-2　酚醛樹脂╱NBR之摻混.......................................................66


參考文獻......................................................................104


自述..........................................................................110

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