Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3722
標題: 新型聚醚碸與多官能環氧樹脂硬化劑之合成與特性
Synthesis and Characterization of New Poly(ether sulfone)s and Multifunctional Epoxy Curing Agents.
作者: 魏采珮
Wei, Tsai-Pei
關鍵字: poly(ether sulfone)s
聚醚碸環氧樹脂硬化劑
epoxy curing agent
出版社: 化學工程學系所
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摘要: 第一部分實驗是由反應物DOPO、4-hydroxyacetophenone (或4-hydroxybenzaldehyde) 與phenol (或2,6-dimethyl phenol) 在簡單的一步法中合成一系列的含磷雙酚單體(1-3)。並由三種單體藉由親核性取代反應縮合聚合成poly(ether sulfone)s (P1-P3)。然而在P3的合成結果由NMR圖譜看到在鹼性環境下發生磷基側鏈斷裂現象,顯示高分子P3還是不容易聚合。在薄膜的性質上,本實驗合成出來的薄膜P1-P2皆具極佳的可撓曲與可折疊特性,且由UV-Vis量測下其截止波長分別為327nm與328nm,顯示高分子薄膜具極高的穿透性質。在熱性質上的分析是與雙酚A型的poly(ether sulfone)s (P0) 作比較,由動態機械分析儀結果顯示,其玻璃轉移溫度分別高達258℃與274℃。此外,由熱機械分析儀顯示,P1-P2 (48 ppm/℃ by TMA) 比P0 (57 ppm/℃ by TMA)具較低的熱膨脹係數。 第二部分藉由低成本反應物DOPO、4-hydroxyacetophenone與resorcinol(或catechol、o-phenylenediamine)利用簡單的一步反應合成三種低成本的難燃型環氧樹脂硬化劑(m-DMP3、o-DMP3、o-DMPA2),由光譜鑑定結果看到反應產物m-DMP3為一混合物;而另外o-DMP3與o-DMPA2為單一產物。將三種硬化劑分別與環氧樹脂DGEBA、CNE進行硬化反應。測試其固化物的玻璃轉移溫度、熱裂解溫度、難燃特性等。在DGEBA硬化系統中Tg範圍為158-203℃,CNE系統為207-237℃;由熱重分析儀顯示在氮氣下Td為378-413℃,相較於PN/DGEBA系統有稍微降低的情況,但是在空氣下測試固化物的殘留率(17-18%)遠高於PN系統(1.04%)。另外在UL-94難燃測試下皆達V-0難燃等級。
[Part I] Biphenols (1-3) with bulky biphenylene phosphinate pendant were prepared by an efficient one-pot procedure. Base on these three biphenols (1-3), three poly(ether sulfone)s (P1-P3) were prepared. P1 and P2 were successfully prepared via a general procedure for poly(ether sulfone). However, P3, according to NMR analysis, was difficult to prepare under various conditions due to the cleavage of biphenylene phosphinate pendant (C-P bond) under alkaline condition. The thermal properties of P1 and P2 were studied and compared with a bisphenol A-based poly(ether sulfone), P0. P1 and P2 are flexible, creasable, and highly transparent with a cut-off wavelength around 327 and 328 nm, respectively. They display high glass transition temperatures (258 and 274℃ by DMA, respectively), lower coefficient of thermal expansion (48 ppm/oC by TMA) than those of P0 (208℃and 57 ppm/℃). [Part II] Three flame-retardant epoxy curing agents, m-DMP3, o-DMP3 and o-DMPA2, were prepared by an economic one-pot procedure. 1H NMR spectra indicate that only one compound in product when synthesizing curing agents (o-DMP3 and o-DMPA2). The resorcinol tends to react with electrophiles at ortho- and para- sites and leads to a mixture product (m-DMP3). These compounds served as curing agents for diglycidyl ether of bisphenol A (DGEBA) and cresol novolac epoxy (CNE). Properties such as glass transition temperature, coefficient of thermal expansion, thermal decomposition temperature, and flame retardancy of the resulting epoxy thermosets were evaluated. The range of Tg in DGEBA curing system is 158-203℃. The resulting epoxy thermosets show high Tg and excellent flame retardancy.
URI: http://hdl.handle.net/11455/3722
其他識別: U0005-0608200916175300
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-0608200916175300
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