Synthesis and Properties of Phosphorus-containing Aromatic Polyamides the Study

以磷系阻燃劑 DOPO 當原料，和 4-Methylacetophenone 與 Phenol 在酸性環境下合成不對稱含磷單體(1)，再藉由一系列硝基化、氧化、還等反應，逐步合成出具有羧酸官能基及胺官能基單體(4)，再於Triphenyl phisphite 和 Pyridine 的縮合劑存在下進行自身縮合反應，製備一種新的 AB 型含磷芳香族聚醯胺。藉由導入龐大側鏈 DOPO 基團與主鏈柔軟醚鍵結構，來改善聚醯胺對有機溶劑的溶解性，及降低玻 璃轉移溫度，增加加工的範圍；另藉 DOPO 是磷系阻燃劑，使合成 出來的聚醯胺，在高溫下提高熱穩定性和阻燃性。 最終得到聚醯胺具有十分優異的有機溶解性，可溶如 NMP、DMAc、DMF、DMSO 等高極性溶劑中；粘度為 0.76 dL/g 及重量平均分子量 Mw=88,677，玻璃轉移溫度 Tg=317℃ 獲得改善，5%的熱重損失溫度為 279℃，焦炭產率在 800℃氮氣下超過 50%以上，有不錯的高溫熱穩定性，並且在 UL-94 耐燃測試中 ， 具備最高等級的VTM-0 特性。When DOPO phosphorus flame retardant material, the 4-Methylacetophenone Phenol in an acidic environment with asymmetric synthesis of phosphorus-containing monomer (a), and then through a series of nitration, oxidation and other reactions also gradually synthesized having carboxylic acid functional groups and amine functional groups of the monomer (4), then the self-condensation reaction to prepare a new type of phosphorus-containing aromatic polyamide AB in the presence of a condensing agent of Triphenyl phisphite and Pyridine. By introducing a large group of the side chain and main chain DOPO ether bond soft structure to improve the solubility of the organic solvent polyamides, and lower the glass transition temperature, increasing the range of machining; DOPO by other phosphorus-based flame retardant, out of synthetic polyamides to improve the thermal stability and flame resistance at elevated temperatures. Finally obtained polyamide has very excellent organic solubility, such as soluble NMP, DMAc, DMF, DMSO highly polar solvent; viscosity of 0.76 dL / g and a weight average molecular weight Mw = 88,677, a glass transition temperature Tg = 317℃ improvement of 5% weight loss temperature of heat 279 ℃, coke yield at 800 ℃ for more than 55% nitrogen, have good thermal stability, and UL-94 flame test, with the highest level of VTM -0 characteristics..摘要............................................................................................... i Abstract ........................................................................................ ii 第一章緒論.................................................................................. 1 第二章 原理與文獻回顧 ........................................................... 3 2.1.Polyamide(PA)發展 ........................................................................................................ 3 2.2.可溶性 Polyamide(PA)聚縮合文獻回顧 ....................................................................... 5 2.3.含磷化合物之難燃原理 ............................................................................................... 10 2.4.研究動機 ...................................................................................................... 12 第三章 實驗.............................................................................. 13 3.1 實驗藥品 .................................................................................................. 13 3.2 儀器設備 ............................................................................................ 14 3.3 實驗規劃 ........................................................................................... 17 3.3.1 實驗簡介 ........................................................................................... 17 3.4 實驗步驟.............................................................................................. 19 3.4.1 不對稱含磷單體(1) 的合成................................................................................. 20 3.4.2 單體(2) 的合成 .................................................................................................... 21 3.4.3 單體(3) 的合成 .................................................................................................... 22 3.4.4 單體(4) 的合成 .................................................................................................... 23 3.4.5 薄膜的製備 ....................................................................................... 24 第四章結構鑑定與分析 ........................................................... 25 4.1 單體(1)結構鑑定與分析 ............................................. 25 4.1.1 1H NMR 鑑定....................................................................................... 25 4.1.2. 13C NMR 鑑定....................................................................................................... 27 4.1.3 傅立葉轉換紅外線光譜(FTIR)鑑定.................................................................... 30 4.1.4 質譜儀(MASS)分析............................................................................................... 31 4.1.5 微差掃描熱卡計(DSC)分析 ................................................................................... 32 4.2 單體(2)結構鑑定與分析 ............................................. 33 4.2.1 1H NMR 鑑定......................................................................................................... 33 4.2.2. 13C NMR 鑑定....................................................................................................... 35 4.2.3 傅立葉轉換紅外線光譜(FTIR)鑑定.................................................................... 38 4.2.4 質譜儀(MASS)分析............................................................................................... 39 4.2.5 微差掃描熱卡計(DSC)分析 ................................................................................... 40 4.3 單體(3)結構鑑定與分析 ............................................. 41 4.3.1 1H NMR 鑑定......................................................................................................... 41 4.3.2 13C NMR 鑑定........................................................................................................ 43 4.3.3 傅立葉轉換紅外線光譜(FTIR)鑑定.................................................................... 46 4.3.4 質譜儀(MASS)分析............................................................................................... 47 4.3.3 微差掃描熱卡計(DSC)分析 ................................................................................... 48 4.4 單體(4)結構鑑定與分析 ............................................. 49 4.4.1 1H NMR 鑑定......................................................................................................... 49 4.4.2 13C NMR 鑑定........................................................................................................ 51 4.4.3 傅立葉轉換紅外線光譜(FTIR)鑑定.................................................................... 54 4.4.4 質譜儀(MASS)分析............................................................................................... 55 4.4.5 微差掃描熱卡計(DSC)分析 ................................................................................... 56 4.5 Polyamide 結構鑑定與分析 ........................................... 57 4.5.1 NMR 鑑定 .............................................................................................................. 57 4.5.2 傅立葉轉換紅外線光譜(FTIR)鑑定.................................................................... 58 4.5.3 微差掃描熱卡計(DSC)分析 ................................................................................... 59 4.5.4 聚醯胺粘度測試及分子量鑑定 ....................................................................... 60 第五章結果與討論 ................................................................... 61 5.1 單體(1)合成探討 ................................................... 61 5.2 單體(2)合成探討 ................................................... 62 5.3 單體(3)合成探討 ................................................... 63 5.4 單體(4)合成探討 ................................................... 64 5.5 Polyamide 合成探討 ................................................. 65 5.5.1 聚醯胺熱性質探討 ............................................................................................... 66 5.5.2 溶解度測試&耐燃測試 ........................................................................................ 69 第六章結論................................................................................ 70 參考文獻.................................................................................... 7