臺灣博碩士論文加值系統

在軟性電子產業中產品的開發已逐步朝向可撓曲且高透明的方向進展，像是軟性印刷電路板(flexible printed circuit, FPC)、可撓式顯示器(flexible display)以及軟性太陽能電池(flexible solar cell)基板等，因此軟質塑膠基板材料的使用漸趨普遍，然而材料本身也需具備足夠的熱穩定性與機械強度，以便於後續的製程加工，聚醯亞胺(polyimides, PI)高分子材料其本身擁有優越的耐熱性和機電性能，因此可運用於軟質塑膠基板的製作材料。
然而聚醯亞胺高分子材料因分子中含共軛苯環結構使其形成電荷轉移錯合體 (charge transfer complex)，影響其薄膜產生黃色或是紅棕色的色澤，降低其透明性也限制了在工業上的應用，此外，聚醯亞胺高分子材料因剛硬的分子鏈結構使其溶解度有限，減低了可加工性，因此為改進聚醯亞胺高分子材料於應用上的不足與缺陷，目前已有相當多的文獻研究致力於提出改良方法並且開發出不同種類的透明無色聚醯亞胺高分子材料。
隨著環保意識的抬頭以及環保法規的訂定，軟質塑膠基板材料朝向無鹵素族的方向設計和開發已是不可避免的趨勢，傳統的透明無色聚醯亞胺高分子材料多以含氟二酸酐單體或二胺單體進行合成，其本身具有高含氟量的特性，除了生產成本較為昂貴之外，在元件加工過程中易發生溶劑阻抗(solvent resistance)不佳的情形而影響到元件製作，且經由燃燒後所釋放出的氫氟酸對於人體與環境有立即性的危害和汙染，因此，降低含氟量可使得透明無色聚醯亞胺高分子材料在未來軟質塑膠基板材料的選用上仍保有一定的競爭力。
本研究將以兩種二酸酐單體3,3',4,4'-Biphenyltetracarboxylic dianhydride (BPDA)、 Bicyclooctanete- tracarboxylic dianhydride (BODA) 與兩種不同的二胺單體3,3'-Diaminodiphenyl sulfone (DDS)、2,2'-Bistrifluoromethyl benzidine (TFMB) 在無水極性非質子溶劑NMP下進行一步驟熱溶液環化法聚縮合反應，其中以BODA脂肪族二酸酐單體取代含氟二酸酐單體以及添加DDS二胺單體以降低其含氟量，透過改變二酸酐單體的比例，合成出不同莫耳比例的低氟透明無色聚醯亞胺高分子並製備成薄膜，再將所合成出的聚醯亞胺高分子及其薄膜進行結構鑑定與性質分析。

In the application of flexible electronic products, such as flexible printed circuits and solar
cells, the trend is moving toward the development of more flexible, highly transparent
designs. Polyimides are a class of high temperature polymers with good mechanical
properties. However, limited solubility and colored film features of polyimides are their
central drawbacks. In order to reach the goal of flexible electronic products in the future,
polyimides have to be soluble and highly transparent.
Taking environmental protection in account, research on halo-free colorless polyimides has
become popular. Conventional colorless polyimides contain a high fluorine content. This not
only increases manufacturing costs, but also leads to the production of hydrofluoric acid,
which is harmful to both the human body and the environment. Therefore, the goal of the
present research is to synthesize low fluoro-containing, transparent, colorless polyimide that
have good solubility and high transparency.
In our research, a series of low fluoro-containing polyimides were synthesized from 3,3',4,4'-
Biphenyltetracarboxylic dianhydride (BPDA) and Bicyclooctanete- tracarboxylic
dianhydride (BODA) used as dianhydride monomers, 3,3'-Diaminodiphenyl sulfone (DDS)
and 2,2'-Bistrifluoromethyl benzidine (TFMB) used as diamine monomers. They were
synthesized using a one-step chemical solution polycondensation method in NMP with a
catalyst (isoquinoline) at 200oC for 24 h. The solubility, thermal properties, mechanical
properties, and optical properties of the polyimides were systematically studied. In this study,
both the transparency and solubility increased with increases in the amount of the BODA
dianhydride monomer.

總目錄
摘要……………………………………………………………………………i
誌謝…………………………………………………………………………..ix
圖目錄………………………………………………………………………xiii
表目錄………………………………………………………………………xiv
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 2
1.3 研究架構 4
第二章 文獻回顧 5
2.1 聚醯亞胺之介紹 5
2.1.1 加成型聚醯亞胺高分子 8
2.1.2 縮合型聚醯亞胺高分子 11
2.1.3 改質型聚醯亞胺高分子 13
2.1.4 透明無色聚醯亞胺高分子材料 14
2.2 聚醯亞胺高分子的合成 16
第三章 實驗方法與步驟 20
3.1 實驗藥品 20
3.2 實驗儀器 21
3.3 實驗步驟 22
3.3.1 二酸酐單體純化 22
3.3.2 二胺單體純化 22
3.3.3 BPDA+BODA+TFMB+DDS 聚醯亞胺高分子合成 22
3.3.4 聚醯亞胺高分子薄膜之製備 24
3.4 儀器分析與原理 25
3.4.1 傅立葉轉換紅外線光譜(FTIR)分析 25
3.4.2 核磁共振光譜(1H-NMR)分析 25
3.4.3 元素分析(Elemental Analysis, EA) 25
3.4.4 聚醯亞胺高分子固有黏度(Inherent viscosity, ηinh)測定 26
3.4.5 聚醯亞胺高分子溶解度與耐化學性測試 27
3.4.6 熱重損失分析(TGA) 27
3.4.7 熱差掃描分析(DSC) 28
3.4.8 熱機械分析(TMA) 28
3.4.9 紫外線可見光光譜分析(UV-vis) 29
3.4.10 機械性質分析 29
第四章 結果與討論 31
4.1 聚醯亞胺高分子的合成和化學結構之鑑定 31
4.1.1 聚醯亞胺高分子的結構設計 31
4.1.2聚醯亞胺高分子的合成 32
4.1.3 傅立葉轉換紅外線光譜分析 (FTIR) 32
4.1.4 核磁共振光譜分析(1H-NMR) 33
4.1.5 元素分析(Elemental analysis, EA) 36
4.2 聚醯亞胺高分子之固有黏度(Inherent viscosity, ηinh) 37
4.3聚醯亞胺高分子之熱重損失分析(TGA) 38
4.4 聚醯亞胺高分子之熱差掃描分析(DSC) 39
4.5 聚醯亞胺高分子之熱機械分析(TMA) 40
4.6 聚醯亞胺高分子之溶解度與耐化學性測試 42
4.7 聚醯亞胺高分子薄膜之紫外線可見光光譜分析(UV-vis) 44
4.8 聚醯亞胺高分子薄膜之機械性質分析 46
4.9 聚醯亞胺高分子薄膜之泛黃指數(Yellow index, YI)測量 47
第五章 結論 48
參考文獻 49

圖目錄
圖1-1透明無色聚醯亞胺高分子材料之應用……………………………….2
圖2-1聚醯亞胺高分子材料工業產品應用………………………………….7
圖2-2聚醯胺酸脫水閉環為聚醯亞胺……………………………………...11
圖2-3化學環化法反應機制………………………………………………...12
圖2-4熱溶液環化法反應機制……………………………………………...13
圖2-5透明無色聚醯亞胺高分子結構例…………………………………...15
圖2-6聚醯亞胺高分子之合成反應過程…………………………………...17
圖2-7聚醯胺酸前驅物聚合之可逆反應…………………………………...17
圖2-8醯胺酸/NMP之熱重損失分析圖譜…………………………………18
圖2-9醯胺酸之醯亞胺化反應及其可能產生之逆反應其反應機制……...19
圖3-1 BPDA+BODA+TFMB+DDS聚醯亞胺高分子合成………………..23
圖3-2聚醯亞胺高分子之合成流程圖……………………………………...24
圖4-1三組低氟透明無色聚醯亞胺高分子之FTIR圖譜………………….33
圖4-2 PI (50/50) 低氟透明無色聚醯亞胺高分子的1H-NMR圖譜……….34
圖4-3 PI (40/60) 低氟透明無色聚醯亞胺高分子的1H-NMR圖譜……….34
圖4-4 PI (30/70) 低氟透明無色聚醯亞胺高分子的1H-NMR圖譜……….35
圖4-5 三組低氟透明無色聚醯亞胺高分子之熱重損失分析結果……….39
圖4-6 三組低氟透明無色聚醯亞胺高分子之熱差掃描分析結果……….40
圖4-7 三組低氟透明無色聚醯亞胺高分子之熱機械分析結果………….42
圖4-8 三組低氟透明無色聚醯亞胺高分子之耐化學性測試結果……….44
圖4-9 三組低氟透明無色聚醯亞胺高分子薄膜之UV-vis光譜分析結果.45
圖4-10三組低氟透明無色聚醯亞胺高分子薄膜圖片…………………….45

表目錄
表1 各不同莫耳比例的低氟透明無色聚醯亞胺高分子代號…………….31表2三組低氟透明無色聚醯亞胺高分子之(BPDA:BODA)積分比值之理論
值與實驗值比較…………………………………………………….....35
表3 三組低氟透明無色聚醯亞胺高分子之元素分析結果……………….36
表4 三組低氟透明無色聚醯亞胺高分子之固有黏度…………………….37
表5 三組低氟透明無色聚醯亞胺高分子之熱重損失分析結果………….38
表6 三組低氟透明無色聚醯亞胺高分子之熱機械分析結果…………….41
表7 三組低氟透明無色聚醯亞胺高分子固體粉末之溶解度…………….43
表8 三組低氟透明無色聚醯亞胺高分子薄膜之機械性質分析結果…….46
表9 三組低氟透明無色聚醯亞胺高分子薄膜泛黃指數之測量結果…….47

[1] H.-J. Ni, J.-G. Liu, Z.-H. Wang, and S.-Y. Yang, A review on colorless and optically transparent polyimide films: chemistry, process and engineering applications, Journal of Industrial and Engineering Chemistry, vol. 28, pp. 16–27, 2015.
[2]H.-C. Yu, S.-V. Kumar, J.-H. Lee, S.-Y. Oh, and C.-M. Chung, Preparation of robust, flexible, transparent films from partially aliphatic copolyimides, Macromolecular Research, vol. 23, pp. 566–573, 2015.
[3] 陳泓翔,透明無色聚醯亞胺合成與性質之研究,成功大學材料科學及工程學系學位論文, pp. 1-63, 2014.
[4]C.-L. Tsai, H.-J. Yen, and G.-S. Liou, Highly transparent polyimide hybrids for optoelectronic applications, Reactive and Functional Polymers journal, vol. 108, pp. 2–30, 2016.
[5] P.-K. Tapaswi and C.-S. Ha, Recent trends on transparent colorless polyimides with balanced thermal and optical properties: design and synthesis, Macromolecular Chemistry and Physics, vol. 220, pp. 1–33, 2019.
[6]M. Mrsevic, D. Düsselberg, and C. Staudt, Synthesis and characterization of a novel carboxyl group containing (co)polyimide with sulfur in the polymer backbone, Beilstein Journal of Organic Chemistry, vol. 8, pp. 776–786, 2012.
[7]D.-J. Liaw et al., Synthesis and characterization of new soluble polyimides from 3,3′,4,4′-Benzhydrol tetracarboxylic dianhydride and various diamines, Chemistry of Materials, vol. 10, pp. 734–739, 1998.
[8]L. Tao, H. Yang, J. Liu, L. Fan, and S. Yang, Synthesis and characterization of highly optical transparent and low dielectric constant fluorinated polyimides, Polymer, vol. 50, pp. 6009–6018, 2009.
[9]J. Ishii, N. Yokoyama, and M. Hasegawa, Solution-processable CF3-substituted ductile polyimides with low coefficients of thermal expansion as novel coating-type protective layers in flexible printed circuit boards, Progress in Organic Coatings, vol. 99, pp. 125–133, 2016.
[10]H.-C. Yu, J.-W. Jung, J.-Y. Choi, S.-Y. Oh, and C.-M. Chung, Structure-property relationship study of partially aliphatic copolyimides for preparation of flexible and transparent polyimide films, Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, vol. 54, pp. 97–104, 2017.
[11]E. Schab-Balcerzak, D. Sek, A. Volozhin, T. Chamenko, and B. Jarzbek, Synthesis and characterization of organosoluble aliphatic-aromatic copolyimides based on cycloaliphatic dianhydride, European Polymer Journal, vol. 38, pp. 423–430, 2002.
[12]J.-G. Liu, H.-J. Ni, Z.-H. Wang, S.-Y. Yang, and W.-F. Zhou, Colorless and transparent high temperature resistant polymer optical films – current status and potential applications in optoelectronic fabrications, Optoelectronics - Materials and Devices, 2015.
[13]M. Hasegawa, Development of solution-processable, optically transparent polyimides with ultra-low linear coefficients of thermal expansion, Polymers, vol. 9, 2017.
[14]H. Liu et al., Synthesis and characterization of optically transparent semi-aromatic polyimide films with low fluorine content, Polymer, vol. 163. pp. 106–114, 2019.
[15]C.-P. Yang and Y.-Y. Su, Colorless polyimides from 2,3,3′,4′-biphenyltetracarboxylic dianhydride (α-BPDA) and various aromatic bis(ether amine)s bearing pendent trifluoromethyl groups, Polymer, vol. 46, pp. 5797–5807, 2005.
[16]T. Matsumoto and T. Kurosaki, Soluble and Colorless Polyimides from Bicyclo[2.2.2]octane-2, 3, 5, 6-tetracarboxylic 2, 3 : 5, 6-Dianhydrides1, Macromolecules, vol. 30, pp. 993–1000, 2002.
[17]M. Hasegawa, Y. Watanabe, S. Tsukuda, and J. Ishii, Solution-processable colorless polyimides with ultralow coefficients of thermal expansion for optoelectronic applications, Polymer International, vol. 65, pp. 1063–1073, 2016.
[18]I.-C. Kim and T.-M. Tak, Synthesis and characterization of soluble random copolyimides, Journal of Applied Polymer Science, vol. 74, pp. 272–277, 2002.
[19]Y.-H. Lu, W.-J. Kang, Z.-Z. Hu, Y.-F. Wang, and Q.-X. Fang, Synthesis and properties of fluorinated polyimide films based on 1,2,3,4-Cyclobutanetetracarboxylic dianhydride, Advanced Materials Research, vol. 150–151, pp. 1758–1763, 2010.
[20]L. Zhai, S.-Y. Yang, and L. Fan, Preparation and characterization of highly transparent and colorless semi-aromatic polyimide films derived from alicyclic dianhydride and aromatic diamines, Polymer, vol. 53, pp. 3529–3539, 2012.
[21]E. Pinel et al., Copolyimides containing alicyclic and fluorinated groups: characterization of the film microstructure, Journal of Polymer Science, Part B: Polymer Physics, vol. 41, pp. 2998–3010, 2003.
[22]M.-T. Bogert and R.-R. Renshaw, 4-Amino-o-phthalic acid and some of its derivatives, Journal of the American Chemical Society, vol. 30, pp. 1135–1144, 1908.
[23] 陳憶明,由雜環型二胺衍生的聚醯亞胺之合成與鑑定,中山大學材料科學研究所學位論文, pp. 1-74, 2002.
[24] D.-J. Liaw, K.-L. Wang, Y.-C. Huang, K.-R. Lee, J.-Y. Lai, and C.-S.Ha, Advanced polyimide materials: syntheses, physical properties and applications, Progress in Polymer Science, vol. 37, pp. 907–974, 2012.
[25] T. Takekoshi , Polyimides, Advances in Polymer Science, vol. 94, pp. 1-25, 1990.
[26]G.-D. Roberts and R.-W. Lauver, Quantitative analysis of PMR‐15 polyimide resin by HPLC, Journal of Applied Polymer Science, vol. 33, pp. 2893–2913, 1987.
[27]J.-V. Crivello, Polyaspartimides: condensation of aromatic diamines and bismaleimide compounds, Journal of Polymer Science Part A: Polymer Chemistry, vol. 11, pp. 1185–1200, 1973.
[28]N. Bilow, A.-L. Landis, L.-J. Miller, and C. Park, Acetylene substituted polyamide oligomers, ed: Google Patents, 1974.
[29]M.-H. Tsai, I.-H. Tseng, S.-L. Huang, and C.-W. Hsieh, Enhancement of dimensional stability and optical transparency of colorless organo-soluble polyimide by incorporation of silica and cosolvent, International Journal of Polymeric Materials and Polymeric Biomaterials, vol. 63, pp. 48–56, 2014.
[30]T.-L. Li and S.L.-C. Hsu, Preparation and properties of a high temperature, flexible and colorless ITO coated polyimide substrate, European Polymer Journal, vol. 43, pp. 3368–3373, 2007.
[31]C.-P. Yang, Y.-Y. Su, S.-J. Wen, and S.-H. Hsiao, Highly optically transparent/low color polyimide films prepared from hydroquinone- or resorcinol-based bis(ether anhydride) and trifluoromethyl-containing bis(ether amine)s, Polymer, vol. 47, pp. 7021–7033, 2006.
[32]K.-I. Fukukawa, and M. Ueda, Chemically amplified photosensitive polylmides and polybenzoxazoles, Journal of Photopolymer Science and Technology, vol. 22, pp. 761-771, 2009.
[33]S. Matsuno, Evaluation of processing method and mechanical properties in polyimide thin film diaphragm, pp. 2–3, 2009.
[34]J.-M. Dodda, T. Kovářík, J. Kadlec, and L. Kullová, Preparation, characterization and thermal degradation study of poly(amide imide)s based on tri-component mixture of PMDA/BTDA, diamines and acid chloride, Polymer Degradation and Stability, vol. 98, pp. 2306–2316, 2013.
[35]R.-O. Johnson and H.-S. Burlhis, Polyetherimide: a new high-performance thermoplastic resin, Journal of Polymer Science: Polymer Symposia, vol. 70, pp. 129–143, 2010.
[36]S. Maiti and S. Das, Synthesis and properties of a new polyesterimide, Journal of Die Angewandte Makromolekulare Chemie, vol. 86, pp. 181–191, 1980.
[37] K.-A. Watson, F.-L. Palmieri, and J.-W. Connell, Space environmentally stable polyimides and copolyimides derived from [2,4-bis(3-aminophenoxy)phenyl] diphenylphosphine oxide, Macromolecules, vol. 35, pp. 4968–4974, 2002.
[38]H. Seino, A. Mochizuki, and M. Ueda, Synthesis of aliphatic polyimides containing adamantyl units, Journal of Polymer Science Part A: Polymer Chemistry, vol. 37, pp. 3584–3590, 1999.
[39]M. Hasegawa and S. Horii, Low-CTE polyimides derived from 2,3,6,7-Naphthalenetetracarboxylic dianhydride, Polymer Journal, vol. 39, pp. 610–621, 2007.
[40]M. Hasegawa, M. Fujii, and Y. Wada, Approaches to improve the film ductility of colorless cycloaliphatic polyimides, Polymers for Advanced Technologies, vol. 29, pp. 921–933, 2018.
[41] M. Hasegawa, Y. Watanabe, S. Tsukuda and J. Ishii, Solution-processable colorless polyimides with ultralow coefficients of thermal expansion for optoelectronic applications, Polymer International, vol. 65, pp. 1063-1073, 2016.
[42] Y.-J. Tong, X.-D. Huang, and T.-S. Chung, A new strategy to prepare rodlike/flexible polyimide blends through poly(amic acid) amine salt precursors, Macromolecules, vol. 34, pp. 5748–5751, 2001.
[43]M. ‐J. Brekner and C. Feger, Curing studies of a polyimide precursor, Journal of Polymer Science Part A: Polymer Chemistry, vol. 25, pp. 2005–2020, 1987.
[44] T.-J. Hsu and Z. Liu, Solvent effect on the curing, Journal of Applied Polymer Science, vol. 46, pp. 1821–1833, 1992.
[45]Y.-J. Kim, I.-S. Chung, I. In, and S.-Y. Kim, Soluble rigid rod-like polyimides and polyamides containing curable pendent groups, Polymer, vol. 46, pp. 3992–4004, 2005.
[46]F. Hasanain and Z.-Y. Wang, New one-step synthesis of polyimides in salicylic acid, Polymer, vol. 49, pp. 831–835, 2008.
[47]S.-U. Kim, C. Lee, S. Sundar, W. Jang, S.-J. Yang, and H. Han, Synthesis and characterization of soluble polyimides containing trifluoromethyl groups in their backbone, Journal of Polymer Science, Part B: Polymer Physics, vol. 42, pp. 4303–4312, 2004.
[48]S.-V. Kumar, H.-C. Yu, J. Choi, K. Kudo, Y.-H. Jang, and C.-M. Chung, Structure-property relationships for partially aliphatic polyimides, Journal of Polymer Research, vol. 18, pp. 1111–1117, 2011.
[49]W. Volksen, H.-J. Cha, M.-I. Sanchez, and D.-Y. Yoon, Polyimides derived from nonaromatic monomers: synthesis, characterization and potential applications, Reactive and Functional Polymers, vol. 30, pp. 61–69, 2002.
[50]Q. Zhang, S. Li, W. Li, and S. Zhang, Synthesis and properties of novel organosoluble polyimides derived from 1,4–bis[4-(3,4-dicarboxylphenoxy)] triptycene dianhydride and various aromatic diamines, Polymer, vol. 48, pp. 6246–6253, 2007.
[51]S. Numata, S. Oohara, K. Fujisaki, J. Imaizumi, and N. Kinjo, Thermal expansion behavior of various aromatic polyimides, Journal of Applied Polymer Science, vol. 31, pp. 101–110, 1986.
[52]T. Matsumoto, E. Ishiguro, and S. Komatsu, Low temperature film-fabrication of hardly soluble alicyclic polyimides with high Tg by a combined chemical and thermal imidization method, Journal of Photopolymer Science and Technology, vol. 27, pp. 167–171, 2014.
[53]G.-S. Liou, H.-J. Yen, Y.-T. Su, and H.-Y. Lin, Synthesis and properties of wholly aromatic polymers bearing cardo fluorene moieties, Journal of Polymer Science Part A: Polymer Chemistry, vol. 47, pp. 2304–2317, 2009.
[54] A.-I. Volozhin, N.-P Prokopchuk, E.-T. Krut'ko, L.-N. Korzhavin and S.-V. Bronnikov, Synthesis and study of properties of soluble cyclo-aliphatic polyimides, Polymer Science, vol. 21, pp. 2085-2090, 1978.
[55]R. Hariharan and M. Sarojadevi, Synthesis and properties of organosoluble polyimides derived from bis(4-amino-3, 5-dimethyl phenyl) halo phenyl methane and various dianhydrides, Journal of Applied Polymer Science, vol. 102, pp. 4127–4135, 2006.
[56] T. Matsumoto, E. Ishiguro, S. Nakagawa and R. Kimura, Alicyclic polyimides derived from alkanone bis-spironorbornanetetracarboxylic dianhydrides, Journal of Photopolymer Science and Technology, vol. 26, pp. 361 –365, 2013.
[57] X.-F. Hu, J.-L. Yan, Y.-X. Wang, H.-L. Mu, Z.-K. Wang, H.-Y. Cheng, F.-Y. Zhao and Z. Wang, Colorless polyimides derived from 2R,5R,7 S,10S-naphthanetetracarboxylic dianhydride, Polymer Chemistry, vol. 8, pp. 6165-6172, 2017.