本研究合成含有懸掛苯環和羥基之2,6-二胺基-4-苯基苯酚(DAPP)二胺，再與4,4-二胺基二苯醚(ODA)、苯均四酸二酐(PMDA)經由熱環化法合成數種可繞曲性之共聚醯亞胺，並探討DAPP二胺對共聚醯亞胺的物理性質之影響。
利用FT-IR鑑定各種共聚醯亞胺之結構，再藉由DSC、TGA等分析以探討其熱安定性和玻璃轉移溫度；以及使用拉力機和介電分析儀測定各種共聚醯亞胺之機械性質與介電常數。
結果顯示，DAPP二胺的含量超過40%之共聚醯亞胺可溶解於加熱的NMP、DMAc及DMF等有機溶劑，而且具有高玻璃轉移溫度（351.4~357.5oC）、高起始模數（3.81~3.93 GPa）。共聚醯亞胺在高於420oC之溫度下，會有部分醯亞胺環轉化成苯噁唑環，轉化後的共聚醯亞胺具有較佳的熱穩定性、較低的介電常數和吸濕率，但不溶於有機溶劑。

A series of copolyimides containing phenyl and hydroxyl pendant groups were synthesized from various ratios of two diamines with one aromatic tetracarboxylic dianhydride through thermal imidization process to determine the effect of 2,6-diamino-4-phenylphenol(DAPP) on the physical properties of polymers.
The structures and physical properties of copolyimides were characterized by Ft-IR, DSC, TGA, Instron and dielectric analyzer.
Copolyimides containing more than 40% DAPP were soluble in hot NMP, DMAc and DMF , and possessed high glass transition temperature (351.4~357.5oC), high initial modulus (3.81~3.93GPa).
A segment of imide linkages were converted to benzoxazole linkages by decarboxylation at temperatures higher than 420oC under vacuum.Copolyimides were found to have better thermal stability, lower dielectric constant and lower moisture absorption and were insoluble in organic solvents after decarboxylation.

1.W. M., I. M. Robinsin, British Pat. 570858; U.S. Pat. 2710853 (1955)
2.林金雀, 聚醯亞胺薄膜全球市場及應用狀況,化工資訊月刊, 13, 7, 58-62 (1999)
3.顏慶山, 全芳香族聚醯亞胺的加工與應用, 高分子工業, 77, 73-79 (1998)
4.金進興, 聚醯亞胺在IC元件之應用, 工業材料, 144, 118-125 (1996)
5.W. F. Gresham and M. A. Naylor, U.S. Pat., 2731447 (1956)
6.R. W.Lauver, J. Polym. Sci., A, Polym. Chem., 17, 2529 (1979)
7.謝國煌, 韓錦鈴, 專題計畫成果報告-雙馬來聚醯亞胺改質聚胺酯交聯環氧樹脂之研究, 工程科技通訊, 4, 30-31 (1996)
8.M. Grundschober, British Pat. 1190718 (1978)
9.N. A. Adrova, M. I. Bessonov, L. A. Laius, A. P. Rudakov, Polyimide:A new class of thermally stable polymers (in Russian), Nauka, Leningrad (1968)
10.X. Q. Liu, M. Jikei, M. Kakimoto, Synthesis and properties of AB-type demicrystalline polyimides prepared from poluamic acid ethyl ester precursors, macromolecules, 34, 3146-3154 (2001)
11.T. Takekoshi, J. E. Kochanowski, U.S. Pat., 3905 942, G. E. Co., (1975)
12.G. D. Khune, Preparation and properties of polyimides from diisocyanates, J. Macromol. Sci., Polym. Chem. Ed., 18, 6, 1905-1909 (1980)
13.M. L. Bender, Y-L. Chow, F. Chloupek, Intramolecular catalysis of hydrolytic reactions. II. The hydrolysis of phthalamic acid, J. Am. Chem. Soc., 80,5380-5384 (1958)
14.J. A. Kreuz, A. L. Endrey, F. P. Gay, C. E. Sroog, Studies of thermal cyclizations of polyamic acids and tertiary amine salts, J. Appl. Polym. Sci., A-1, 4, 2607-2616 (1966)
15.Y. J. Kim, T. E. Glass, G. D .Lyle, J. E. Mcgrath, Kinetic and mechanistic investigations of the formation of polyimides under homogeneous conditions, Macromolecules, 26, 1344-1358 (1993)
16.M. K. Ghosh, K.L. Mittal, Polyimides : Fundamentals and Applications, New York : Dekker (1996)
17.A.G.Endry, U.S. Pat., 3179630 (1965)
18.W.R.Hendrix, US Pat., 3179632 (1965)
19.C. P. Yang, S. H. Hsiao, K. L. Wu, Organosoluble and light-colored fluorinated polyimides derived from 2,3-bis (4-amino-2-trifluoromethylphenoxy) naphthalene and aromatic dianhydrides, Polymer, 44, 23, 7067-7078 (2003)
20.C. P. Yang, R. S. Chen, C. S. Wei, Synthesis and properties of new soluble poly(amide–imide–imide)s based on tetraimide- dicarboxylic acid condensed from ODPA,BAPP and p-ABA, and various aromatic diamines, J. Mater. Chem., 77, 226–235 (2002)
21.S. L. C. Hsu, W. C. Chen, A novel positive photosensitive polybenzoxazole precursor for microelectronic applications, Polymer, 43, 6743-6750 (2002)
22.日本東洋紡公司網頁 www.toyobo.co.jp
23.H. Seino., A. Mochizuki, O. Haba, M. Ueda, J. Appl. Polym. Sci., 36, 13, 2261-2267 (1998)
24.G. L. Tullos, L. J. Mathias, Unexpected thermal conversion of hydroxy-containing polyimides to polybenzoxazoles, Polymer, 40, 3463-3468 (1999)
25.G. L. Tullos, J. M. Powers, S. J. Jeskey, and L. J. Mathias, Thermal conversion of hydroxy-containing imides to benzoxazoles: polymer and model compound study, Macromolecules, 32, 3598-3612 (1999)
26.J. H. Chang, K. M. Park, S. M. Lee, J. B. Oh, Two-Step Thermal conversion from poly(amic acid) to polybenzoxazole via polyimide: their thermal and mechanical properties, J. Polym. Sci., B, Polym. Phys., 38, 2537–2545 (2000)
27.Olah, George A., Nitration : Methods and mechanisms, VCH Publishers (1989)
28.Morrison and Boyd, Organic Chemistry, Sixth Edition (1994)
29.K. L. Mittal, Polyimides : Synthesis, Characterization, and Applications, New York and London (1982)
30.S. L. C. Hsu, K. C. Chang, Synthesis and properties of polybenzoxazole-clay nanocomposites, Polymer, 43, 4097-4101 (2002)
31.丁孟賢, 何天白, 聚醯亞胺新型材料, 科學出版社 (1998)
32.D. Ayala, A. E. Lozano, J. D. Abajo, J. G. D. L. Campa, Synthesis and characterization of novel polyimides with bulky pendant group, J. Polym Sic., A. Polym. Chem., 37, 805-814 (1999)
33.Y. Imai, K. Itoya, M. Kanamaru, M. Kakimoto, Synthesis and properties of new hydroxyl-pendant aromatic polyimides derived from trimethylsilylated 4,4-diamino-3,3-dihydroxy biphenyl and aromatic tetracarboxylic dianhydride, J. Polym Sic., A. Polym. Chem., 40, 1790-1795 (2002)
34.D. Ayala, A. E. Lozano, J. D. Abajo, J. G. D. L. Campa, Novel polyimides with p-nitrophenyl pendant groups. Synthesis and characterization, J. Polym Sic., A. Polym. Chem., 37, 3377-3384 (1999)
35.L. K. Spiliopoulos, J. A. Mikroyannidis, Aromatic polyamides and polyimides bearing bulky ether pendent groups derived from 1-aryloxy- 2,4-diaminobenzenes, Polymer, 37, 3331 (1996)
36.L. H. Sperling, Introduction to physical polymer science, Third Edition (2001)
37.美國杜邦公司之網頁 www.dupont.com
38.Fox, T. G. Bull. Am. Phys. Soc. 1, 123 (1956)
39.T. S. Leua, C. S. Wang, Synthesis and properties of copolyimides containing naphthalene group, Polymer, 43, 7069-7074 (2002)
40.Y. L. Liu, C. Y. Hsu, C. S. Wu, Polyimides possessing bulky phosphorus groups : synthesis and characterization, J. Appl. Polym. Sci., 89, 791-796 (2003)
41.S. C. Khatua, 1. S. Matti, High-performance polymer films. III. preparation and characterization, J. Appl. Polym. Sci. 82, 976-988 (2001)
42.T. D. Dang, P. T. Mather, M. D. Alexander, Jr., C. J. Grayson, M. D. Houtz, R. J. Spry, F. E. Arnold, Synthesis and characterization of fluorinated benzoxazole polymers with high Tg and low dielectric constant, J. Polym. Sci., A, Polym. Chem., 38, 1991-2003 (2000)
43.H. Fan, Y. Gu, M. Xie, Self reinforced polyimide for film materials, Polym. Int., 50, 1331-1337 (2001)
44.C. E. Sroog, A. L. Endrey, S. V. Abramo, C. E. Berr, W. M. Edwards, and K. L. Olivier, Aromatic polypyromellitimides from aromatic polyamic acids, J. Polym. Sci., Part A, Gen. Pap., 3, 1373-1390 (1965)