臺灣博碩士論文加值系統

本研究經由1,6-Bis[4-(3,4-dicarboxyphenoxy)phenyl]diamantane dianhydride 及4,9-Bis[4-(3,4-dicarboxyphenoxy)phenyl]diamantane dianhydride 與不同二胺單體，採用傳統二階段方式，合成含鑽石烷基團在主鏈上之新型聚醯亞胺，包括加成開環成聚醯胺酸，再環化脫水成聚醯亞胺，並分析所製備之聚醯亞胺的固有黏度、溶解度、動態機械性質、介電性質、吸濕性、及熱性質，並討論引進鑽石烷到聚醯亞胺對它物性的影響。
在1,6系列方面，所得之聚醯胺酸(polyamic acid)之固有黏度在0.63-0.85 dL/g 之間，由 GPC測得可溶型聚醯亞胺之分子量範圍在36,000-95,000之間，其固有黏度在0.44-0.86 dL/g，其中VXa、VXb、VXg均可溶於NMP、DMAc、o-Chlorophenol、 m-cresol 及Chloroform等溶劑，而聚合物的抗張強度範圍在77.5-127.6 MPa之間，斷裂伸長率在6.8-12.5 %之間，介電常數介於2.75-2.85之間，吸濕率範圍為0.27-0.66 %，由DMA分析結果得知，除VXb外，其餘聚醯亞胺之玻璃轉移溫度均大於330℃，且經由DMA分析上發現VXa在285℃附近，有一個明顯的次玻璃轉移溫度(β-transition)，在耐熱性上，由TGA 測試結果得其10%重量損失之溫度，在氮氣下，為526-545℃，在空氣下為526-545℃，而其在氮氣下700℃之燃燒殘餘率為51-69 %。
在4,9系列方面，所得之聚醯胺酸(polyamic acid)之固有黏度在0.61-0.82 dL/g 之間，由 GPC測得可溶型聚醯亞胺之分子量範圍在35,000-64,000之間，其固有黏度在0.55-0.78 dL/g，其中IVXa、IVXb、IVXg，均可溶於NMP、 o-Chlorophenol、 m-cresol、Chloroform等溶劑，而聚合物的抗張強度範圍在53.3-99.8 MPa之間，斷裂伸長率在6.5-16.6 %之間，介電常數介於2.73-2.86之間，吸濕率範圍為0.25-0.67 %，由DMA分析結果得知，除VXb外，其餘聚醯亞胺之玻璃轉移溫度均大於310℃，且經由DMA分析上亦發現VXa在286℃附近，有一個明顯的次玻璃轉移溫度(β-transition);在耐熱性上，由TGA 測試結果得知其10%重量損失之溫度，在氮氣下，為530-553℃，在空氣下為511-534℃，而其在氮氣下700℃之燃燒殘餘率為59-64 %。

The study synthesized new diamantane-based polyimides by reacting of 1,6-Bis[4-(3,4-dicarboxyphenoxy)phenyl]diamantane dianhydride and 4,9-Bis[4-(3,4-dicarboxyphenoxy)phenyl]diamantane dianhydride with various aromatic diamines. A series new polyimides were synthesized by the usual two-step procedure that included ring-opening polyaddition to give poly(amic acid)s, followed by cyclodehydration to polyimides. The inherent viscosities, solubility, dynamic mechanical properties, dielectric properties, absorbed moisture,
and the thermal properties of the polyimides were investigated. A comparison of physical properties of the polyimides studies here with the corresponding aromatic polyimides were discussed.
First, the poly(amic acid)s derived from 1,6-Bis[4-(3,4-dicarboxyphenoxy)phenyl]diamantane dianhydride, had inherent viscosities of 0.63-0.85 dL/g. The range of the number-average molecular weights (Mn) and the inherent viscosities of the polyimide are 36,000-95,000 and 0.44-0.86 dL/g, respectively. VXa, VXb and VXg were soluble in NMP, DMAc, o-chlorophenol, m-cresol, and chloroform. These films had tensile strengeths of 77.5-127.6 MPa, and elongation to breakage values of 6.8-12.5%. The films had low dielectric constants of 2.75-2.85, and low moisture absorption of 0.27-0.66%. The glass transition temperatures of polyimides, expect VXb, exceed 330℃. In addition, according to the DMA curve of VXa, we discovered that there is a subglass transition of VXa nearby 285℃. In addition, the temperatures of the 10% weight loss in nitrogen and the air ranged on 526-545℃. Their char yield ranged from 51% to 69% in the nitrogen.
Second, the poly(amic acid)s derived from 4,9-Bis[4-(3,4-dicarboxyphenoxy)phenyl]diamantane dianhydride, had inherent viscosities of 0.61-0.82 dL/g. The Mn and the inherent viscosities of the soluble polyimides are 35,000-64,000 and 0.55-0.78 dL/g, respectively. The solubility of IVXa, IVXb and IVXg is the same as that of VXa, VXb and VXg. The films had tensile strengeths of 53.3-99.8 MPa, and elongation to breakage values of 6.5-16.6%. The films also had low dielectric constants of 2.73-2.86, and low moisture absorptions of 0.25-0.67%. The DMA analysis reveals the glass transition temperatures of polyimides, expect IVXb, exceed 310℃. We also found a subglass tansition of IVXa appear 286℃. The temperatures of 10% weight loss in nitrogen and air ranged on 530-553℃ and 511-534℃, respectively. The char yield ranged from 59 % to 64 %.

中文摘要 ………………………………………………………… I
Abstract ………………………………………………………… III
目錄 ………………………………………………………….V
圖表索引 ………………………………………………………….VII
第一章 緒論 …………………………………………………... 1
1-1 前言 …………………………………………………… 1
1-2 聚醯亞胺的合成方法 …………………………………… 2
1-3 聚醯亞胺的改質 ……………………………………….. 5
1-4 聚醯亞胺在電子相關產業之應用 ……………………… 6
1-5 擬進行之研究 ………………………………………….. 8
第二章 實驗 ………………………………………………….. 10
2-1 實驗藥品 ……………………………………….……….. 10
2-2 實驗程序 …………………………………….………….. 13
2-2-1 單體製備 …………………………………….…….. 13
2-2-2 聚醯亞胺之合成 ………………….……………….. 19
2-3 單體鑑定及聚合物之物性與化性分析 …….…………. 21
第三章 結果與討論 …………………………………….……… 25
3-1 1,6-Bis[4-(3,4-dicarboxyphenoxy)phenyl]diamantane
dianhydride …………………………………………. 25
3-1-1 單體之製備 ………………………………………. 25
3-1-2 聚醯亞胺之合成 …………………………………. 26
3-1-3 聚醯亞胺的物性分析 ……………………………. 28
3-2 4,9-Bis[4-(3,4-dicarboxyphenoxy)phenyl]diamantane
dianhydride ………………………………….………. 34
3-2-1 單體之製備 ………………………………………..34
3-2-2 聚醯亞胺之合成 …………………………………. 35
3-2-3 聚醯亞胺的物性分析 ……………………………. 37
第四章 結論 ………………………………………………… 42
參考文獻 ……………………………………………………..… 44
圖表索引
Table 1. Inherent Viscosities and GPC Molecular Weights of Poly(amic
acid)s and Soluble Polyimides(VX)…………….. 27
Table 2. Solubility of Polyimides (VX)………………………………... 29
Table 3. Physical Properties of Polyimides Films(VX)……………….. 30
Table 4. Thermal Properties of Polymers(VX) ……………………….. 31
Table 5. Inherent Viscosities and GPC Molecular Weight of Poly(amic
acid)s and Soluble Polyimides (IVX)…………………………36
Table 6. Solubility of Polyimides (IVX)………………………………. 38
Table 7. Physical Properties of Polyimides Films(IVX)………………. 38
Table 8. Thermal Properties of Polymers(IVX) ……. .……………….. 40
Figure 1a. FTIR spectrum of 1,6-Bis[4-(3,4-dicyanophenoxy)phenyl]
Diamantane..………………………………………………… 46
Figure 1b. FTIR spectrum of 1,6-Bis[4-(3,4-dicarboxyphenoxy)phenyl]
diamantane dianhydride…………………………………..…47
Figure 2a. MASS spectrum of 1,6-Bis[4-(3,4-dicyanophenoxy)phenyl]
Diamantane………………………………………………….48
Figure 2b. MASS spectrum of 1,6-Bis[4-(3,4-dicarboxyphenoxy)phenyl]
diamantane dianhydride…………………………………..…49
Figure 3. Crystal Structure of 1,6-Bis[4-(3,4-dicarboxyphenoxy) phenyl]
diamantane dianhydride………………………………………50
Figure 4. Crystal Structure of 4,9-Bis[4-(3,4-dicarboxyphenoxy) phenyl]
diamantane dianhydride………………………………………51
Figure 5a. FTIR spectrum of 4,9-Bis[4-(3,4-dicyanophenoxy)phenyl]
Diamantane..………………………………………………….52
Figure 5b. FTIR spectrum of 4,9-Bis[4-(3,4-dicarboxyphenoxy)phenyl]
diamantane dianhydride…………………………………..…53
Figure 6a. MASS spectrum of 4,9-Bis[4-(3,4-dicyanophenoxy)phenyl]
Diamantane…………………………….……………………54
Figure 6b. MASS spectrum of 4,9-Bis[4-(3,4-dicarboxyphenoxy)phenyl]
diamantane dianhydride………………………………..……55

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