本論文分成兩部份。第一部份探討具扭曲基團且含三氟甲基之二胺單體所衍生之有機可溶性聚醯胺其合成與物性研究。第二部份探討由此二胺單體與偏苯三酸酐反應所得二醯亞胺-二羧酸單體所衍生之有機可溶性聚醯胺醯亞胺之合成與物性研究。一種具扭曲基團且含三氟甲基之二胺單體[雙4-(2-三氟甲基-4-胺基苯氧基)苯]二苯亞甲基[2,2’-dimethyl-4,4’-bis(2-trifluoromethyl-4-amino-phenoxy)biphenyl]是經由雙二苯亞甲基之二酚類單體[bis(4-hydroxyphenyl) diphenylmethane]與2-氯-5-三氟硝基苯於碳酸鉀之存在下，以N,N-二甲基甲醯胺為溶劑進行親核取代反應合成出二硝類化合物，再將此二硝類化合物經聯胺(H2NNH2•H2O)及Pd/C以乙醇為溶劑還原成二胺單體。使用此二胺單體與二羧酸經過聚縮合，可製備一系列之有機可溶性、固有黏度在0.65－0.89 dL．g-1之聚醯胺。另外，以此二胺單體與偏苯三酸酐(TMA)經縮合反應可製得二醯亞胺-二羧酸單體，使用不同之芳香族二胺單體與二醯亞胺-二羧酸單體，經直接聚縮合可製得一系列之有機可溶性、固有黏度在0.63－0.89 dL．g-1的聚醯胺醯亞胺。
本論文利用元素分析、紅外線光譜儀及核磁共振儀等來鑑定單體及聚合物的結構，並且探討各種聚合物的物性，包括溶解性、固有黏度、介電常數、光學性質、機械性質(如抗拉強度、變形量、抗張模數及動態機械性質)、熱性質(包括玻璃轉移溫度及熱裂解溫度等)。實驗結果發現在聚合物的結構中導入三氟甲基，可提高溶解度，並有效的改善聚合物的加工性，亦可保持其熱安定性及機械性質，不失高性能材料之特性。且這些聚合物大多可溶於極性溶劑，可利用溶劑N,N-二甲基乙醯胺塗佈成強韌、透明且具撓曲性的薄膜。
在聚醯胺方面，這些薄膜具有76－94 MPa之抗張強度，斷裂點伸長率為6－15 %，而抗張模數在1.8－2.2 GPa之間。這些聚合物有較中等的熱膨脹係數(56－84 ppm/℃)，玻璃轉移溫度範圍在187－252℃，且於氮氣中之10%重量損失溫度都超過470℃以上。這些含氟的聚合物具有優異光學穿透性(紫外光/可見光光譜切斷點低於362nm)，其介電常數介於3.58和4.15 (1 KHz)之間。
在聚醯胺醯亞胺方面，其玻璃轉移溫度範圍在229－254℃，且於氮氣中之10%重量損失溫度介於455和500℃之間。這些薄膜具有74－102 MPa之抗張強度，斷裂點伸長率為6－10 %，而抗張模數在1.7－2.1 GPa之間。其紫外光/可見光光譜切斷點(穿透率< 1%)範圍在331－400 nm且在1 KHz頻率下之介電常數介於3.46－3.92之間。

This thesis had been divided into two parts. Part I deals with the synthesis and properties of organosoluble polyamides based on kink and trifluoromethyl group. Part II deals with the synthesis and properties of poly(amide-imide)s based on diimide-dicarboxylic acid. A fluoro containing diamine with kink linkage, bis[4-(2-trifluoromethyl- 4-aminophenoxy)phenyl] diphenylmethane (BTFAPDM) was prepared through a nucleophilic substitution reaction of corresponding bisphenol and 2-chloro-5-nitrobenzotrifluoride in the presence of potassium carbonate in N,N-dimethylformamide, followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of polyamides with inherent viscosities of 0.65－0.89 dL．g-1 were prepared from this diamine with dicarboxylic diacids by polycondensation. In addition, a new diimide-dicarboxylic acid was synthesized from the diamine and trimellitic anhydride by the condensation reaction. A series of poly(amide-imide)s with inherent viscosities of 0.63－0.89 dL．g-1 were prepared from diimide-diacid with various aromatic diamides by the direct polycondensation.
The structure of monomers and polymers were characterized by using elemental analysis, FTIR and NMR spectroscopic methods. The physical properties of polymers, such as solubility, inherent viscosity, dielectric constant, transparency, mechanical properties (tensile strength, elongation, tensile modulus and dynamic mechanical analysis), thermal properties (glass transition temperature and thermal decomposition temperature) were determined. The incorporation of trifluoromethyl and kink linkage into the polymer backbone improved the solubility of these polymers without sacrificing their high-performance characteristic. These polymers were soluble in solvents and formed a tough, transparent, and flexible film by casting form DMAc solution.
The polyamides had a tensile strength in the range of 76－94 MPa, elongation at break from 6 to 15 (%), and initial modulus from 1.8 to 2.2 GPa. These polymers possessed a moderate coefficient of thermal expansion between 56 and 84 ppm/℃, the glass transition temperatures were between 187 and 252 ℃ (by DSC) and 10 % weight loss temperatures were higher than 475 ℃ in the atmosphere of nitrogen. Transmittance of the films was high and the cutoff wavelength was lower than 362 nm and dielectric constants of polyamides were in the range between 3.58 and 4.15 at 1 KHz.
The poly(amide-imide)s possessed the glass transition temperatures were between 229 and 254 ℃(by DSC) and 10 % weight lose in the range of 455－500 ℃ in the atmosphere of nitrogen. The polymer films had a tensile strength in the range of 74－102 MPa, elongation at break was between 6 and 10 (%) and an initial modulus in the range of 1.7－2.1 GPa. Transmittance of the films was high and their cutoff wavelengths were between 331－400 nm and dielectric constants of polyamides were in the range between 3.46 and 3.92 at 1 KHz.

CHAPTER 1-----------------------------------------------------1
Light Color and High Transparency of Organosoluble Polyamides Containing Trifluoromethyl and Diphenylmethylene Linkage
1.1 ABSTRACT ------------------------------------------------2
1.2 INTRODUCTION --------------------------------------------4
1.3 EXPERIMENTAL --------------------------------------------7
1.3.1 Materials ---------------------------------------------7
1.3.2 Measurements ------------------------------------------7
1.3.3 Monomer synthesis -------------------------------------9
1.3.4 Polymer synthesis -----------------------------------12
1.4 RESULTS AND DISCUSSION ---------------------------------15
1.4.1 Monomer synthesis -----------------------------------15
1.4.2 Polymer synthesis ------------------------------------16
1.4.3 Polymer characterization------------------------------20
1.5 CONCLUSIONS---------------------------------------------28
1.6 REFERENCES----------------------------------------------29
1.7 FIGURE CAPTIONS-----------------------------------------32
CHAPTER 2----------------------------------------------------47
Highly Transparent and Organoslouble Poly(amide-imide)s Based on Diimide-dicarboxylic Acid with Kink and Trifluoro Substitution
2.1 ABSTRACT------------------------------------------------48
2.2 INTRODUCTION--------------------------------------------49
2.3 EXPERIMENTAL--------------------------------------------51
2.3.1 Materials --------------------------------------------51
2.3.2 Measurements - ---------------------------------------51
2.3.3 Monomer Synthesis-------------------------------------52
2.3.4 Polymer Synthesis-------------------------------------54
2.4 RESULTS AND DISCUSSION----------------------------------57
2.4.1 Monomer synthesis-------------------------------------57
2.4.2 Polymer synthesis-------------------------------------59
2.4.3 Polymer Characterization------------------------------62
2.5 CONCLUSIONS---------------------------------------------68
2.6 REFERENCES----------------------------------------------69
2.7 FIGURE CAPTIONS-----------------------------------------72

CHAPTER 1
1. Cassidy, P. E. " Thermally Stable Polymer", Dekker, New York, 1980
2. Frazer, A. H. " High Temperature Resistant Polymers", Wiely, New York, 1968
3. Avella, N.; Maglio, G.; Palumbo, R.; Russo, F. and Vignola, M. C. Macromol. Chem. Rapid Commun., 14, 545 (1993)
4. Negi, Y. S.; Suzuki, Y. I.; Kawamura, I.; Kakimoto, M. A. and Imai, Y. J. Polym. Sci. Part A: Polym. Chem., 34, 1663 (1996)
5. Weber, N. J. " In Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.", Wiely, New York, 19, 509 (1996)
6. Varma, I. K.; Kumar, R. and Bhattacharyya, A. B. J Appl. Polym. Sci., 40, 531 (1990)
7. Chiriac, C. and Stille, J. K. Macromolecules, 10, 712 (1977)
8. Liaw, D. J. and Wang, K. L. J. Polym. Sci. Part A: Polym. Chem., 34, 1029 (1996)
9. Sava, I.; Iosip, M. D.; Bruma, M.; Hamciuc, C.; Robison, J.; Okrasa, L. and Pakula, T. Eur. Polym. J., 39, 725 (2003)
10. Lee, C. J.; Park, S. K.; Kim, S. Y.; Lee, Y. J.; Min, B. G.; Son, T. W. and Kim, B. C. Polym. Int., 36, 203 (1995)
11. Liaw, D. J. and Liaw, B. Y. Macromol. Symp., 122, 343 (1997)
12. Liaw, D. J. and Liaw, B. Y. J. Polym. Sci., Part A: Polym. Chem., 36, 1069 (1998)
13. Jeong, H. J.; Oishi, Y.; Kakimoto, M. A. and Imai, Y. J. Polym. Sci., Part A: Polym. Chem., 28, 3293 (1990)
14. Sakaguchi, Y. and Harris, F. W. Polym. J., 24, 1147 (1992)
15. Spiliopoulos, I. K. and Mikroyannidis, J. Macromolecules, 31, 515 (1998)
16. Yamashita, M.; Kakimoto, M. A. and Imai, Y. J. Polym. Sci., Part A: Polym. Chem., 31, 1513 (1993)
17. Lucas, M.; Brock, P. and Hedrich, J. L. J. Polym. Sci., Part A: Polym. Chem., 31, 2179 (1993)
18. Bellomo, M. R.; Pasquale, G. D.; Rosa, A. L.; Pollicino, A. and Siracusa, G. Polymer, 37, 2877 (1996)
19. Liaw, D. J.; Liaw, B. Y. and Tsai, M. Y. Polym. J., 29, 474 (1997)
20. Liaw, D. J. and Liaw, B. Y. J. Polym. Sci., Part A: Polym. Chem., 36, 1075 (1998)
21. Negi, Y. S.; Suzuki, Y.; Hagiwara, T.; Kawamura, I.; Yamamoto, N.; Mori, K.; Yammada, Y.; Kakimoto, M. and Imai, Y. Am. Chem. Soc. Polym. Prepr. Div. Polym. Chem., 32, 112 (1991)
22. Xie, K.; Liu, J. G.; Zhou, H. W.; Zhang, S. Y.; He, M. H. and Yang, S. Y. Polymer, 42, 7267 (2001)
23. Liaw, D. J.; Liaw, B. Y. and Yang, C. M. Macromolecules, 32, 1248 (1999)
24. Yamazaki, N.; Matsumoto, M. and Higashi, F. J. Polym. Sci., Polym. Chem. Ed. 13, 1373 (1975)
25. Hougham, G.; Tesoro, G. and Shaw, J. Macromolecules, 27, 3642 (1994)
26. Gutch, P. K.; Banerjee, S. and Jaiswal, D. K. J. Appl. Polym. Sci., 89, 691 (2003)
27. Kim, S. I.; Shin, T. J.; Pyo, S. M.; Moon, J. M. and Ree, M. Polymer 40, 1603 (1999)
28. Matsuura, T.; Hasuda, Y.; Nishi, S. and Yamada, N. Macromolecules, 24, 5001 (1991)
29. Cassidy, P. E.; Thaemlitz, C. J. and Brewer, K. W. Am. Chem. Soc. Polym. Prepr. Div. Polym. Chem., 31, 582 (1990)
30. Chuang, K. C.; Kinder, J. D.; Hull, D. L.; McConville, D. B. and youngs, W. J. Macromolecules, 30, 7183 (1997)
31. Maier, G. Prog. Polym. Sci., 26, 3 (2001)
32. Feiring, A. E.; Auman, B. C, and Wonchoba, E. R. Macromolecules, 26, 2779 (1993)
33. Devasahayam, S.; Hill, D. J. T. and Connell, J. W. Radiation Physics and Chemistry, 62, 189 (2001)
34. Sroog, C. Prog. Polym. Sci., 16, 561 (1991)
35. Liaw, D. J.; Liaw, B. Y.; Li, L. J.; Sillion, B.; Mercier, R.; Thiria, R. and Sekiguchi, H. Chem. Mater., 10, 734 (1998)
36. Hari, S. N. " Handbook of Low and High Dielectric Constant Materials and Their Applications", Elsevier Science & Technology Books, (1999)
37. Hamciuc, E.; Bruma, M.; Mercer, F. W. and Simionescu, C. I. Angew. Makromol. Chem., 210, 143 (1993)
38. Bruma, M.; Mercer, F.; Fitch, J. and Cassidy, P. J. Appl. Polym. Sci., 56, 527 (1995)
39. St. Clair, T. L. " Structure-property relationships in linear aromatic polyimide. In: Wilson, D., Stenzenberger, H. D., Hergenrother, P. M. (Eds.), Polyimides", Blackie, New York, pp58-78. (1990)
40. Matsuura, T.; Hasuda, Y.; Nishi, S. and Yamada, N. Macromolecules, 24, 5001 (1991)
41. Qian, Z. G.; Ge, Z. Y.; Li, Z. X.; He, M. H.; Liu, J. G.; Pang, Z. Z.; Fan, L. and Yang, S. Y. Polymer, 43, 6057 (2002)
42. Liaw, D. J.; Liaw, B. Y. and Tsai, M. Y. Eur. Polym. J., 33, 997 (1997)
43. Bottino, F. A.; Pasquale, G. D.; Leonardi, N. and Pollicino, A. J. Polym. Sci., Part A: Polym. Chem., 34, 1305 (1996)
CHAPTER 2
1. Cassidy, P. E. " Thermally Stable Polymers", Marcel Dekker, New York, (1980)
2. Liaw, D. J.; Liaw, B. Y. and Yang, C. M. Macromolecules, 32, 1248 (1999)
3. Yang, H. H. " Aromatic High-strength Fibers", Wiley, New York, (1989)
4. Abadie, M. J. M. and Sillion, B. in Polyimide and Other High-temperature Polymers, New York, pp. 255-282 (1991)
5. Feger, C.; Khojastech, M. M. and McGrath, J. E. " Polyimides: Materials, Chemistry and Characterization", Elsevier, New York, pp. 453-478 (1989)
6. Liaw, D. J.; Hsu, P. N. and Liaw, B. Y. J. Polym. Sci. Polym. Chem. Ed., 39, 775 (2001)
7. Mallakpour, S. E.; Hajipour, A. R. and Faghihi, K. Eur. Polym. J., 36, 2455 (2000)
8. Hougham, G.; Tesoro, G.; Shaw, J. Macromolecules, 27, 3642 (1994)
9. Takekoshi, T.; Kochanowski, J. E.; Manello, J. S.; Webber, M. J. J Polym. Sci. Polym. Symp., 74, 93 (1986)
10. Imai, Y.; Maldar, N. N.; Kakimoto, M. J. J. Polym. Sci. Polym. Chem. Ed., 23, 2077 (1985)
11. Liaw, D. J.; Hsu, P. N.; Chen, W. H.; Liaw, B. Y. J. Polym. Sci. Part A: Polym. Chem., 39, 3498 (2001)
12. Hasegawa, M. and Horie, K. Prog. Polym. Sci., 26, 259 (2001)
13. Matsuura, T.; Hasuda, Y.; Nishi, S. and Yamada, N. Macromolecules, 24, 5001 (1991)
14. Malay, K. G. and Mittal, K. L. " Polyimides: Fundamentals and Applications", Marcel Dekker, New York, Chapter 2, pp. 47—70, (2003)
15. Yamazaki, N.; Matsumoto, M. and Higashi, F. J. Polym. Sci. Polym. Chem. Ed., 13, 1373 (1975)
16. Kurita, K.; Itoh, H. and Iwakura, Y. J. Polym. Sci. Polym. Chem. Ed., 16, 779 (1978)
17. Liaw, D. J. and Wang, K. L. J Polym Sci, Part A, Polym. Chem., 34, 1029 (1996)
18. Park, J. W.; Lee, M.; Lee, M. H.; Liu, J. W.; Kim, S. D. and Chang, J. Y. Macromolecules, 27, 3459 (1994)
19. Ghasemi, H. and Hay, A. S. Macromolecules, 27, 3116 (1994)
20. Irvin, D. J.; Cassidy, P. E.; Meurer, D. L.; Fitch III, J. W,; Taylor, D. A,; St Clair, A. and Stoakley, D. Polymer, 37, 2227 (1996)
21. Cassidy, P. E.; Thaemlitz, C. J. and Brewer, K. W. Am. Chem. Soc. Polym. Prepr. Div. Polym. Chem., 31, 1582 (1990)
22. St Clair, T. L., " Structure-property relationships in linear aromatic polyimide. In: Wilson, D., Stenzenberger, H. D., Hergenrother, P. M. (Eds.), Polyimides", Blackie, New York, pp. 58-78, (1990)
23. Devasahayam, S.; Hill, D. J. T. and Connell, J. W. Radiation Physics and Chemistry, 62, 189 (2001)
24. Qian, Z. G.; Ge, Z. Y.; Li, Z. X.; He, M. H.; Liu, J. G.; Pang, Z. Z.; Fan, L. and Yang, S. Y. Polymer, 43, 6057 (2002)
25. Chung, I. S. and Kim, S. Y. Macromolecules, 33, 3190 (2000).
26. Hougham, G.; Tesoro, G. and Shaw, J. Macromolecules, 27, 3642 (1994)
27. Maier, G. Prog. Polym. Sci., 26, 3 (2001)
28. Matsuura, T.; Hasuda, Y.; Nishi, S. and Yamada, N. Macromolecules 24, 5001 (1991)
29. Xie, K.; Zhang, S. Y.; Liu, J. G.; He, M. H. and Yang, S. Y. J. Polym. Sci., Part A: Polym. Chem., 39, 2581 (2001)
30. Myung, B. Y.; Kim, J. J. and Yoon, T. H. J. Polym. Sci., Part A: Polym. Chem., 40, 4217 (2002)
31. Banerjee, S.; Madhra, M. K.; Salunke, A. K. and Maier, G. J. Polym. Sci., Part A: Polym. Chem., 40, 10 (2002)
32. Liaw, D. J.; Liaw, B. Y.; Sillion, B.; Mercier, R.; Thiria, R. and Sekiguchi, H. Polym. Int., 48, 473 (1999)
33. Liaw, D. J.; Liaw, B. Y. and Kang, E. T. Macromol. Chem. Phys., 200, 2402 (1999)
34. Li, Z. X.; Fan, L.; Ge, Z. Y.; Wu, J. T. and Yang, S. Y. J. Polym. Sci., Part A: Polym. Chem., 41, 1831 (2003)
35. Yamazaki, N.; Matsumoto, M. and Higashi, F. J. Polym. Sci., Polym. Chem. Ed., 13, 1373 (1975)
36. Yamazaki, N. and Higashi, F. Tetrahedron, 30, 1323 (1974)
37. Liaw, D. J. and Liaw, B. Y. J. Polym. Sci., Part A: Polym. Chem., 36, 2301 (1998)
38. Liaw, D. J. and Liaw, B. Y. Macromol. Symp., 122, 343 (1997)
39. Matsuura, T.; Hasuda, Y.; Nishi, S. and Yamada, N. Macromolecules, 24, 5001 (1991)
40. Chuang, K. C.; Kinder, J. D.; Hull, D. L.; McConville, D. B. and Youngs, W. J. Macromolecules, 30, 7183 (1997)
41. Liaw, D. J., Hsu, P. N.; Chen, W. H. and Liaw, B. Y. Macromol. Chem. Phys., 202, 1483 (2001)
42. Negi, Y. S.; Suzuki, Y. I.; Kawamura, I. M.; Kakimoto, A. and Imai, Y. J. Polym. Sci., Part A: Polym. Chem., 34, 1663 (1996)
43. Matsumoto, T. Macromolecules, 32, 4933 (1999)
44. Sava, I.; Bruma, M.; Hamcicu, C.; Hamciuc, E.; Timpu, D. and Mercer, F. J. Appl. Polym. Sci., 80, 650 (2001)