Synthesis and properties of phosphorus containing aromatic polyimides

以 DOPO、4-Methylacetophenone 與 phenol 在酸觸媒催化下進行親 核性加成反應製得磷系單酚(1)，再與 2,4-二硝基氯苯進行芳香親核取 代反應生成二硝化合物(2)後，經由氫氣與 Pd/C 催化還原反應得到含磷 不對稱巨大懸掛基團之二胺單體(3)。由於單體(3)導入不對稱結構提升其溶解性，使聚合過程不易析出不溶物，因而可成功獲得均聚物，同時所得聚醯亞胺皆具有高分子量、低分子量分佈以及優異的成膜性。所得共聚物皆具有好的有機溶解性及撓曲性。經由 DMA 測定的玻璃轉移溫度表現出優於文獻中相似結構對稱型的 polyimide (B-9-50)。均聚物仍具有優異的可撓性，並可於室溫溶於 THF、CH2Cl2、CHCl3等有機溶劑，表現出十分優異的溶解性，其玻璃轉移溫度相較於共聚物亦有更加優異的表現。Phenyl phosphorus monomer (1) are generally prepared by the nucleophilic addition reaction of DOPO、4-methylacetophenone and phenol in the presence of acid as catalyst. Dinitromonomer (2) will be prepared by thenucleophilic aromatic substitution reaction of monomer (1) and 2,4-Dinitrochlorobenzene. Monomer (3) with bulky pendant phosphorus group will also be prepared by the reduction reaction of dinitro compound (2) in the presence of hydrogen and Pd/C as catalyst. The monomer (3) containing an asymmetric structure to improve solubility in organic. The polymerization process has excellent solubility, Which can be successfully obtained homopolymer, The obtained polyimide has a high molecular weight, Low polydispersity index and excellent film formability. Polyimiedes copolymer had good organic solubility and flexibility. The glass transition temperature of asymmetric structure polyimides is batter than symmetric structure polyimide (B-9-5025) by DMA analysis. Polyimide homopolymer still has good flexibility, and soluble in THF, CH2Cl2, CHCl3 and other organic solvents at room temperature, has excellent solubility, compared with copolyimides the glass transition temperature is more excellent performance.第一章緒論 ............................................ 1 第二章文獻回顧 ........................................ 2 2-1 聚醯亞胺的合成方式 ...............................2 2-2 聚醯亞胺的改質 ................................ 4 2-3 導入含磷系材料 ....................................6 2-4 研究動機 .............................................8 第三章實驗 ........................................... 9 3-1 藥品 .............................. 9 3-2 測試儀器 .......................................... 10 3-3 實驗規劃 ............................................13 3-3-1 實驗簡介 .......................................13 3-3-2 實驗設計 ......................................14 3-4 實驗步驟 ............................................17 3-4-1 製備 DOPO 含酚單體(1) ..............................17 3-4-2 製備含有二硝基官能基單體(2) .........................18 3-4-3 製備含有二胺基官能基單體(3) ........................19 3-5 聚醯亞胺的合成 ...............................20 3-5-1 製備聚醯亞胺 ................................... 20 3-5-2 共聚型聚醯亞胺(Copolyimide)之製備................................................... 21 3-5-3 均聚型聚醯亞胺(Homopolyimide)之製備 ............................................. 22 3-6 聚醯亞胺薄膜製備 ........................................23 第四章結構鑑定與分析 ........................................24 4-1 單體(1)結構鑑定與分析 ...............................24 4-2 單體(2)結構鑑定與分析 ...........................28 4-3 單體(3)結構鑑定與分析 .......................32 第五章聚醯亞胺薄膜性質分析 ........................36 5-1 聚醯亞胺合成性質分析 ........................ 36 5-2 聚醯亞胺 FTIR 鑑定 ...............................36 5-3 聚醯亞胺 GPC 分子量鑑定 ..........................39 5-4 聚醯亞胺溶解度測試 ................................40 5-5 聚醯亞胺熱性質分析 ...............................42 5-5-1 DMA 分析.................................... 42 5-5-2 TMA 分析 ......................................42 5-5-3 TGA 分析 ......................................46 5-6 聚醯亞胺機械性質測試 .................................49 5-7 接觸角(contact angle)測試 ............................52 5-8 薄膜性質與呈色分析 ..............................53 第六章結論 ..............................................54 參考文獻 ........................................... 55 附錄 ...................................5