本實驗分成兩部分，第一部分為單體合成，利用矽氫加成反應將聚二甲基矽氧烷 (Polydimethylsiloxane，PDMS)與5-Norbornene-2,3-dicarboxylic anhydride (Nadic anhydride，ND)合成二酐類單體，接著分別與4,4'-Oxydianiline (ODA)、p-Phenylenediamine (PPD)反應形成具有醯亞胺官能基的二胺類單體(PDMS-ND-ODA與PDMS-ND-PPD)。透過FTIR及1H NMR分析鑑定其化學結構，確認合成成功。第二部分則將此兩種二胺單體各別與Pyromellitic dianhydride (PMDA)聚合成聚醯胺酸(Polyamic acid，PAA)後，再以熱醯亞胺化(thermal imidization)方式經過高溫環化脫水形成聚醯亞胺薄膜(PDMS-PI、PDMS-PI(P))。利用FTIR分析鑑定，確認製備成功。接著分別經由DSC及TGA檢測得知，PDMS-PI的玻璃轉移溫度(Tg)為173.72 ℃，重量損失5%與10%的裂解溫度(Td5、Td10)為470.76 ℃與491.54 ℃，殘留灰燼率(char yield)則為36.81 w.t%；而PDMS-PI(P)的Tg為296.73 ℃，Td5與Td10為446.48 ℃與480.18 ℃，char yield則為45.54 w.t%，皆說明具有良好的熱性質。而典型的PI薄膜由於主鏈不具有PDMS的結構，其熱性質表現較為優異；如PI的Td5、Td10與char yield為540.37 ℃、577.29 ℃與53.62 w.t%，PI(P)的則為484.88 ℃、570.77 ℃與57.62 w.t%。然而也因為具有低表面能和低極化率的PDMS結構的關係，PDMS-PI的水接觸角可從51.0 °明顯提升至109.3 °，而PDMS-PI(P)可從57.9 °增加到106.2 °，皆指出優異的疏水性。

In this study, we synthesized the dianhydride monomer (PDMS-ND) from polydimethylsiloxane (PDMS) prepared with 5-Norbornene-2,3-dicarboxylic anhydride (nadic anhydride) by hydrosilylation reaction; and PDMS-ND was synthesized with 4,4'-Oxydianiline (ODA) and p-Phenylenediamine (PPD), respectively, to obtain the PDMS-ND-ODA and PDMS-ND-PPD diamines with the imide groups. We have successfully synthesized them based on FTIR and 1H NMR spectroscopy analyses. Furthermore, they were polymerized with Pyromellitic dianhydride (PMDA) to obtain the polyamic acid (PAA), which is then subjected to form into the polyimide films by the thermal imidization. We have successfully prepared PDMS-PI and PDMS-PI(P) films based on FTIR analyses. Based on DSC and TGA analyses, the Tg, Td5, Td10, and the char yield values of PDMS-PI are 173.72 ℃, 470.76 ℃, 491.54 ℃ and 36.81 w.t%, respectively; and that of PDMS-PI(P) are 296.73 ℃, 446.48 ℃, 480.18 ℃ and 45.54 w.t%, respectively, indicating the good thermal properties. The typical PI film could exhibit better due to the absence of PDMS units on the main chain, which the Td5, Td10, and the char yield values of PI are 540.37 ℃, 577.29 ℃ and 53.62 w.t%, respectively; and that of PI(P) are 484.88 ℃, 570.77 ℃ and 57.62 w.t%, respectively. However, the water contact angles could be significantly enhanced from 51.0 ° to 109.3 ° for PDMS-PI and from 57.9 ° to 106.2 ° for PDMS-PI(P), respectively, due to the flexible PDMS structure with the low surface energy and low polarizability, revealing the excellent hydrophobicity.

論文審定書 i
致謝 iii
摘要 iv
Abstract v
Content vi
Figure Captions viii
Table Captions ix
Scheme Captions x
Chapter 1 Introduction and Literature Review 1
1-1 Polyimide 3
1-1.1 The reaction mechanism of polyimide 4
1-1.2 The preparation of polyimide 4
1-1.3 The imidization method of polyamic acid 4
1-1.4 The type of polyimide 5
1-1.5 The factors affecting the molecular weight of polyimide 5
1-1.6 The properties of polyimide 6
1-1.7 The application of polyimide 7
1-2 Polydimethylsiloxane (PDMS) 8
Chapter 2 Motivation and Objectives 10
Chapter 3 Experimental Section 11
3-1 Materials 11
3-2 Characterization 11
3-3 Syntheses 11
3-3.1 Synthesis of PDMS-ND 11
3-3.2 Synthesis of PDMS-ND-ODA 12
3-3.3 Synthesis of PDMS-ND-PPD 12
3-3.4 Synthesis of PDMS-PI-PAA 12
3-3.5 Synthesis of PDMS-PI(P)-PAA 13
3-3.6 Preparation of PDMS-PI Film 13
3-3.7 Preparation of PDMS-PI(P) Film 13
3-3.8 Synthesis of PI-PAA 14
3-3.9 Synthesis of PI(P)-PAA 14
3-3.10 Preparation of PI Film 14
3-3.11 Preparation of PI(P) Film 14
Chapter 4 Results and Discussion 16
4-1 Synthesis of PDMS-ND-ODA 16
4-2 Synthesis of PDMS-ND-PPD 19
4-3 Preparation of PDMS-PI Film 22
4-4 Preparation of PDMS-PI(P) Film 25
4-5 Thermal transitions analysis 28
4-6 Thermogravimetric analysis 33
4-7 Hydrophobicity analysis 37
Chapter 5 Conclusions 39
Chapter 6 Future Works 40
Chapter 7 References 41

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