臺灣博碩士論文加值系統

本論文主要在合成新型高性能高分子材料，包括聚醯胺、聚醯亞胺、及聚醯胺-醯亞胺等聚合物。先利用各種二酚化合物分別與對-氯硝基苯及對-氟苯基月青 反應，合成各種二硝及二月青化合物，再分別進行氫化及水解的步驟，得到各種新型二胺單體及二羧酸單體。二酚化合物亦可與4-硝基磷苯二月青 反應，再經過水解及脫水閉環等步驟製得新型二酸酐單體。另外，以新型的二胺單體與偏苯三酸酐反應可製得各種新型二醯亞胺-二羧酸單體。利用合成出來的二羧酸單體及二酸酐分別與二胺類經過聚縮合，可製備聚醯胺及聚醯亞胺。此外,利用自行合成的二醯亞胺-二羧酸單體與不同二胺化合物，經直接聚縮合可製得不同的聚醯胺-醯亞胺。本論文在聚合物中導入各種不同的基團來改善聚合物之加工性，這些基團包括柔軟基團(如醚基、異丙烷基、六氟異丙烷基、石風基、乙氧烷基等)、非共平面聯苯基、龐大取代基(如第三丁基)以及龐大側鏈基團(如:環十二烷、鑽石烷、原冰片烷、三環十烷、第三丁基環六烷、苯基環六烷及二甲基苯等)。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各種新型單體及聚合物的結構，接著再測定並探討各種聚合物的物性，包括溶解性、固有黏度、分子量、結晶性、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，熔點及熱裂解溫度等)以及其他特性 (如光學性質及電化學性質)等。另外也探討不同基團對聚合物各種物性的影響。
研究結果發現在聚合物(包括聚醯亞胺、聚醯胺及聚醯胺-醯亞胺) 結構中導入柔軟基、非共平面基、龐大取代基及側鏈基等基團後，可降低聚合物的結晶性並提高溶解度、有效改善聚合物的加工性。在這同時，聚合物仍具有優異的熱安定性及機械性質，不失高性能材料的特性。這些聚合物大多可溶於極性溶劑如N-甲基-2-口比 口各 酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲亞石風、間位-甲基酚，γ-丁內酯，四氫口夫口南 及口比 啶等溶劑，部份含醚基的聚醯亞胺甚至可溶於劑氯仿。這些聚合物可利用溶劑塗佈的方法製得強韌的薄膜，這些薄膜的抗張強度大多超過 80 MPa，抗張模數大多超過 2.0 GPa。這些聚合物的玻璃轉移溫度大多分佈在 250至300℃之間。熱重分析儀的測量發現這些材料大多安定至 450 ℃以上才開始裂解。在比較各種基團對聚合物之物性的影響後可發現，導入醚基及龐大側鏈基團 (如鑽石烷等) 最能有效增加聚合物的溶解性並保有良好的熱安定性。

A variety of diamines, dicarboxylic acids and diimido-diacids with various structural modifications such as flexible bridging linkages, bulky substituents, noncoplanar biphenylene units, and bulky pendent groups have been synthesized and used to prepare various new soluble and processable
polyamides,polyimides and poly(amide-imide)s. The incorporation of flexible units, such as aryl ether,hexafluoroisopropylidene, sulfonyl, isopropylidene, oxyethylene and diphenylmethylene units and bulky tert-butyl substituents, and noncoplanar 2,2'-dimethyl-4,4'-biphenyl, as well as of pendent groups such as cyclododecylidene, adamantane, tricyclodecane, norbornane, tert-butylcyclohexane and phenylcyclohexane groups into the polymer backbone of polyamides, polyimides and poly(amide-imide)s lowered the crystallinity and enhanced the solubility of these polymers. Most of these polymers were soluble in solvents including N-methyl-2-pyrrolidinone(NMP),N,N-dimethylacetamide(DMAc),N,N-dimethylformamide(DMF), dimethyl sulfoxide(DMSO), pyridine, cyclohexanone, and also in tetrahydrofuran(THF). These polymer films were obtained by solution-casting and showed tough and flexible behavior. All of these polyamides, polyimides and poly(amide-imide)s exhibited good thermal stability and mechanical properties. These polymers had glass transition temperatures higher than 250 ℃ and 10 % weight loss temperatures higher than 450 ℃. Most of these polymer films exhibited tensile strength above 90 MPa and tensile modulus above 2.0 GPa. The effects of various structures on the polymer properties such as solubility and thermal stability were investigated. In comparison with the effect of various structural modifications on the polymer properties, the incorporation of rigid and bulky pendent groups such as adamantane as well as diphenylmethylene units led to the most success.

中文摘要--------------------------------------------------------------------------------I
英文摘要--------------------------------------------------------------------------------III
誌謝--------------------------------------------------------------------------------V
圖表索引--------------------------------------------------------------------------------VI
第一章Synthesis and Characterization of New Soluble Polyamides Containing Phthalimide Pendent Group1
1.1INTRODUCTION-----------------------------------------------1
1.2EXPERIMENTAL-----------------------------------------------3
1.3RESULTS AND DISCUSSION--------------------6
1.4CONCLUSIONS--------------------------------------------------20
1.5REFERENCES----------------------------------------------------21
第二章Synthesis and Characterization of New Organosoluble Polyamides Derived from Bis[4-(4-carboxyphenoxy)phenyl]diphenylmethane23
2.1INTRODUCTION-----------------------------------------------23
2.2EXPERIMENTAL-----------------------------------------------25
2.3RESULTS AND DISCUSSION--------------------28
2.4CONCLUSIONS--------------------------------------------------36
2.5REFERENCES----------------------------------------------------37
第三章Synthesis and Characterization of Novel Polyamide-imides Containing Noncoplanar 2,2'-Dimethyl-4,4'-biphenylene Unit39
3.1INTRODUCTION-----------------------------------------------39
3.2EXPERIMENTAL-----------------------------------------------41
3.3RESULTS AND DISCUSSION--------------------44
3.4CONCLUSIONS--------------------------------------------------57
3.5REFERENCES----------------------------------------------------58
第四章Synthesis and Characterization of Novel Polyamide-imides Containing Noncoplanar 2,2'-Dimethyl-4,4'-biphenylene Unit60
4.1INTRODUCTION-----------------------------------------------60
4.2EXPERIMENTAL-----------------------------------------------62
4.3RESULTS AND DISCUSSION--------------------65
4.4CONCLUSIONS--------------------------------------------------74
4.5REFERENCES----------------------------------------------------75
第五章Synthesis and Characterization of Highly Soluble Polyamide-imides Derived from α,α’-Bis[3,5-dimethyl-4-(4-trimellitimidophenoxy)phenyl]-1,4-diisopropylbenzene 77
5.1INTRODUCTION-----------------------------------------------77
5.2EXPERIMENTAL-----------------------------------------------79
5.3RESULTS AND DISCUSSION--------------------82
5.4CONCLUSIONS--------------------------------------------------92
5.5REFERENCES----------------------------------------------------93
第六章Synthesis and Characterization of New Soluble Cardo Polyamide-imides Derived from 2,2-bis[4-(4-trimellitimidophenoxy)phenyl]norbornane 95
6.1INTRODUCTION-----------------------------------------------95
6.2EXPERIMENTAL-----------------------------------------------97
6.3RESULTS AND DISCUSSION--------------------100
6.4CONCLUSIONS--------------------------------------------------110
6.5REFERENCES----------------------------------------------------111
第七章Synthesis and Characterization of Novel Polyamide-imides Containing Noncoplanar 2,2'-Dimethyl-4,4'-biphenylene Unit113
7.1INTRODUCTION-----------------------------------------------113
7.2EXPERIMENTAL-----------------------------------------------115
7.3RESULTS AND DISCUSSION--------------------120
7.4CONCLUSIONS--------------------------------------------------133
7.5REFERENCES----------------------------------------------------134
第八章Synthesis and Characterization of New Soluble Polyamide-imides Derived from 2,2-Bis[4-(4-trimellitimidophenoxy) phenyl]hexafluoropropane136
8.1INTRODUCTION-----------------------------------------------136
8.2EXPERIMENTAL-----------------------------------------------138
8.3RESULTS AND DISCUSSION--------------------141
8.4CONCLUSIONS--------------------------------------------------150
8.5REFERENCES----------------------------------------------------151
第九章Highly Organosoluble Polyimides With Pendent Cyclododecane Group: Synthesis and Characterization153
9.1INTRODUCTION-----------------------------------------------153
9.2EXPERIMENTAL-----------------------------------------------156
9.3RESULTS AND DISCUSSION--------------------162
9.4CONCLUSIONS--------------------------------------------------173
9.5REFERENCES----------------------------------------------------174
第十章Synthesis and Characterization of New Highly Organosoluble Poly(ether imide)s Based on 3,3',5,5'-Tetramethyl-2,2-Bis[4-(4-dicarboxyphenoxy)phenyl]Propane Dianhydride176
10.1INTRODUCTION---------------------------------------------176
10.2EXPERIMENTAL---------------------------------------------178
10.3RESULTS AND DISCUSSION------------------183
10.4CONCLUSIONS-----------------------------------------------193
10.5REFERENCES--------------------------------------------------194
結論--------------------------------------------------------------------------------196
附 錄 (著作目錄)---------------------------------------------------------------------------------198
作者簡介----------------------------------------------------------------------------------202

1.M. K. Ghosh and K. L. Mittal, "Polyimides:Fundamentals and Applications", Marcel Dekker, New York, 1996, pp.49-70
2.Y. Imai, N. N. Maldar, and M. Kakimoto, J. Polym, Sci., Part A: Polym. Chem., 23, 2077 (1985)
3.A. Ray, Y. V. Rao, V. K. Bhattacharya, and S. Maiti, Polym. J., 15, 169 (1983)
4.S. Das and S. Maiti, Macromol. Chem. Rapid Commun., 1, 403 (1980)
5.A. Ray, S. Das, and S. Mait, Macromol. Chem. Rapid Commun., 2, 333 (1981)
6.J. L. Nieto, J.G. la Campa, and J. de Abajo, Macromol. Chem., 183, 557 (1982)
7.J. G. de la Campa, J. de Abajo, and J. L. Nieto, Macromol. Chem., 183, 571 (1982)
8.Y. Oishi, M. Kakimoto, and Y. Imai, J. Polym. Sci., Part A: Polym. Chem., 29, 1925 (1991)
9.R. J. Perry, S. R. Turner, and R. W. Blevins, Macromoleules, 27 4058 (1994)
10.(a) N. Yamazaki, M. Matsumoto, and F. Higashi, J. Polym. Sci., Polym. Chem. Ed., 13, 1373 (1975); (b) N. Yamazaki and F. Higashi, Tetrahedron, 30, 1323 (1974)
11.(a) D. J. Liaw and B. Y. Liaw, J. Polym. Sci., Part A: Polym. Chem., 36, 2301 (1998); (b) D. J. Liaw, B. Y. Liaw and Y. S. Chen, Polymer, 40, 4041 (1999)
12.D. J. Liaw, B. Y. Liaw, B. Sillion, R. Mercier, R. Thiria and H. Sekiguchi, Polym. Inter., 48, 473 (1999)
13.D. J. Liaw, B. Y. Liaw and E. T. Kang, Macromol. Chem. Phys., 200, 2402 (1999)
14.D. J. Liaw, B. Y. Liaw and J. M. Tseng, J. Polym. Sci., Part A: Polym. Chem., 37, 14, 2629 (1999)
15.M. I. Bessonov and N. P. Kuznetsov, "Polyimides: Synthesis, Characterization and Applications", K. L. Mittal, Ed., Plenum Press, NY, p. 385 (1984)
16.P. Kannan, S. Sudhakar, C. S. Swaminathan, and S. C. Murugavel, J. Polym. Sci., Part A: Polym. Chem., 34, 3559 (1996)
17.F. P. Glatz and R. Mulhaupt, Polym. Bull. 31, 137 (1993)
18.P. M. Hergenrother and S. J. Havens, J. Polym. Sci., Part A: Polym. Chem., 27, 1161 (1989)
19.S. Tjugito and W. A. Feld, J. Polym. Sci., Part A: Polym. Chem., 27, 963 (1989)
20.D. J. Liaw and B. Y. Liaw, Macromol. Chem. Phys., 199, 1473 (1998)
21.Y. S. Negi, Y. Suzui, I. Kawamura, T. Hagiwara, Y. Takahashi, M. Iijima, M. Kakimoto, and Y. Imai, J. Polym. Sci., Part A: Polym. Chem., 30, 2281 (1992)
22.P. R. Sundararajan, Macromolecules, 23, 2600 (1999)
23.A. C. Misra, G. Tesoro, G. Hougham, and S. M. Pendharkar, Polymer, 33, 1078 (1992)
24.J. W. Park, M. Lee, M. H. Lee, J. W. Liu, S. D. Kim, J. Y. Chang, and S. B. Rhee, Macromolecules, 27, 3459 (1994)
25.Y. S. Negi, Y. I. Suzuki, I. Kawamur, M. A. Kakimoto, Y. Imai, J. Polym. Sci., Part A: Polym. Sci., 34, 1663 (1996)
26.D. J. Liaw, K. L. Wang, J. Polym. Sci., Part A: Polym. Chem. 34, 1209 (1996)
27.D. J. Liaw, B. Y. Liaw and C. M. Yang, Macromolecules, 32, 7248 (1999)
28.D. J. Liaw, B. Y. Liaw and C. Y. Chung, Acta Polym., 50, 135 (1999)
29.D. Wilson, H. D. Stenzenberger, P. M. Hergenrother, Eds., Polyimdes; Chapman and Hall; New York, 1990.
30.P. M. Hergenrother, N. T. Wakelyn, S. J. Havens, J. Polym. Sci., Part A: Polym. Chem., 25, 1093 (1987).
31.T. Asanuma, H. Oikawa, Y. Okawa, W. Yamasita, M. Matsuo, A.Yamaguchi, J. Polym. Sci., Part A: Polym. Chem., 32, 2111 (1994).
32.S. Matsuo and K. Mitsuhashi, J. Polym. Sci., Part A: Polym. Chem., 32, 1969 (1994).
33.Y. Imai, N. N. Malder, M. Kakimoto, J. Polym. Sci., Part A: Polym. Chem., 22, 2189 (1984)
34.D. J. Liaw, B. Y. Liaw, L. J. Li, B. Sillion, R. Mercier, R. Thiria and H. Sekiguchi, Chem. Mater., 10, 734 (1998)
35.X. Sun, Y. K. Yang, and F. Lu, Macromolecules, 31, 4291 (1998)
36.I. K. Spiliopoulos and J. A. Mikroyannidis, Macromolecules, 31, 515 (1998)
37.M. H. Yi, W. Huang, M. Y. Jin, and K. Y. Choi, Macromolecules, 30, 5606 (1997)
38.D. J. Liaw and B. Y. Liaw, Polymer, 40, 3183 (1999)
39.Wirth, J. G., in Discovery and Development of Polyetherimides In High Performance Polymers: Their Origin and Development; Seymour, R. B; Kirshenbaum, G. S, Eds., Elsevier, Amsterdam, 1986.
40.D. K. Mohanty, Y. Sachdeva, J. L. Hedrick, J. F. Wolfe and J. E. McGrath, Polym. Prepr., 25 (2), 19 (1984)
41.D. J. Liaw and B. Y. Liaw, Macromol. Chem. Phys., 199, 1473 (1998)
42.D. J. Liaw, B. Y. Liaw and Y. S. Chen, Polymer, 40, 4041 (1999)
43.J. March, "Advanced Organic Chemistry ", John Wiley & Sons, 4th ed., New York, pp.887-888 (1992)
44.T. Matsuura, Y. Hasuda, S. Nishi, and N. Yamada, Macromolecules, 24, 5001 (1991)
45.W. Hatke, H. W. Schmidt, and W. Heitz, J. Polym. Sci., Part A: Polym. Chem., 29, 1387 (1991)
46.V. V. Korshak, S. V. Vinogradova, Y. S. Vygodski, J. Macromol. Sci., Rev. Macromol. Chem., C11, 45 (1974)
47.J. W. Park, M. Lee, M. H. Lee, J. W. Liu, S. D. Kim, J. Y. Chang, S. B. Rhee, Macromolecules, 27, 3459 (1994)
48.D. J. Liaw, B. Y. Liaw and C. M. Yang, Macromolecules, 32, 7248 (1999)
49.W. Heitz and N. Niessner, Makromol. Chem., 191, 225 (1990)