臺灣博碩士論文加值系統

第一部份中：二醯亞胺二羧酸(DIDA I)是由trimellitic anhydride (TMA)和3,4’-oxydianiline (3,4’-ODA)以2:1之比例；四醯亞胺二羧酸(TIDA II)是由4,4’-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)， TMA和3,4’-ODA 以1:2:2之比例縮合而得，然後再與各種芳香族二胺以Yamazaki磷酸化反應法直接聚縮合成二系列聚醯胺醯亞胺(PAIs；IVa�{k)和聚醯胺醯亞胺醯亞胺(PAIIs；Va�{k)。大部份的PAIs和所有的PAIIs皆具有良好的溶解性且皆可鑄成透明強韌之薄膜，具優異之機械性質。熱性質測試結果顯示，PAIs IVa�{k和PAIIs Va�{k之玻璃轉移溫度(Tg)分別介於242-274 ℃與264-295 ℃之間，它們在氮氣與空氣中10%重量損失溫度皆在500 ℃以上。
第二部份中：以四種組成合成PI / SiO2 hybrids，並以BPDA/BAPP為PI成份在DMAc中生成PAA後，加入Si(OCH3)4/H2O進行sol-gel反應後鑄膜醯亞胺化生成。前三種hybrids(IV、V及VI)是使用APrTMOS為coupling agent：其中IV系列是改變PI之鏈段長，V系列是改變SiO2含量。並以IR、UV-vis、掃描式電子顯微鏡(SEM)、DSC、TGA及萬能拉力機等測定光學、熱性質與機械等物性之變化。結果顯示使用APrTMOS為耦合劑之PI/SiO2(IV和VI系列)，SiO2含量達30wt%的混成膜仍具有良好的透明性及機械強度，而不加耦合劑之VI’皆呈霧狀不透明之薄膜。含耦合劑合成之IV和VI兩系列和不加耦合劑之VI’ 系列比較性質，實驗證明含耦合劑可有效明顯改善薄膜光學透明度。在實驗中，所有的PI/SiO2混成薄膜皆具優異之熱穩定性，熱性質經由DSC測得玻璃轉移溫度(Tg)在237-266 ℃之間，由TGA之分析在氮氣與空氣中10%重量損失皆在554 ℃以上，在氮氣中800 ℃測得之熱重殘餘率皆在56% 以上。

Part 1: A diimides-dicarboxylic acid (DIDA) (I) was synthesized from the condensation reaction of trimellitic anhydride (TMA) and 3,4’-oxydianiline (3,4’-ODA) in a 2:1 molar ratio, and a tetraimide-dicarboxylic acid (TIDA) (II) was prepared from 4,4’-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), TMA, and 3,4’-ODA in a 1:2:2 molar ratio. Several poly(amide-imide)s (PAIs) (IVa�{k) and poly(amide-imide-imide)s (PAIIs) (Va�{k) were synthesized by Yamazaki phosphorylation polyamidation reactions of DIDA I and TIDA II, respectively, with various aromatic diamines. Due to a highly random segmental sequence in the polymer chain (for both series) and the incorporation of 6FDA moieties (for the V series), most of the IV series PAIs and all the V series PAIIs were readily soluble in many organic solvents and could be solution-cast into transparent, flexible, and tough films with good mechanical properties. Glass-transition temperature (Tgs) of the IV series PAIs and the V series PAIIs were recorded in the range of 242-274℃ and 264-295℃. Almost all these amide-imide polymers showed 10% weight loss temperatures higher than 500℃ under a nitrogen or an air atmosphere. Part 2 : Four series (IV, V, VI, and VI’) of polyimide-silica hybrid (PI/SiO2) were prepared by the sol-gel reaction and characterized in this study. They were synthesized from 3,3’,4,4’-biphenyltetracarboxylic dianhydride (BPDA) and 2,2-bis-[4-(4-aminophenoxy)pheny]propane (BAPP) to obtain viscous poly(amic acid)s, then the hybrid composite films were obtained by the hydrolysis and polycondensation of tetramethylorthosilicate (TMOS) and H2O in N,N-dimethylacetamide (DMAc), following by spin coating and multistep heating. The former three series hybrids were prepared using 3-aminopropyltrimethoxysilane (APrTMOS) as coupling agent. The IV series had dufferent chain length in PI segment; the V series was designed with various contents of silica. The optical, thermal and mechanical properties of the PI/SiO2 hybrids were investigated. All the APrTMOS-modified hybrid films (V and VI series) containing up to 30 wt% silica were mechanically robust and optically transparent. The V and VI series hybrid films showed a higher optical transparency than the VI’ series (without APrTMOS as the coupling agent). All the hybrid films showed excellent thermal stability, including moderately high Tgs of 237-266℃, 10% weight loss temperatures higher than 554 oC, and high char yields at 800oC in nitrogen (＞56%).

TABLE OF CONTENTS

ACKNOWLEDGEMENTS i
ABSTRACT IN ENGLISH ii
ABSTRACT IN CHINESE iv
TABLE OF CONTENTS vi
LIST OF SCHEMES viii
LIST OF TABLES ix
LIST OF FIGURES x
CHAPTER 1 INTRODUCTION 1
CHAPTER 2 EXPERIMENTAL 6
2.1 Materials 6
2.2 Synthesis of Monomers 7
2.2.1 Synthesis of Diimide-Dicarboxylic Acid (I) 7
2.2.2 Synthesis of Tetraimide-Dicarboxylic Acid (II) 8
2.3 Synthesis of Polymers 10
2.3.1 Synthesis of PAIs 10
2.3.2 Synthesis of PAIIs .10
2.3.3 Synthesis of polyimide/silica hybrid films 11
2.4 Measurements 13
CHAPTER 3 RESULTS AND DISCUSSION 15
3.1 Synthesis and Characterization of New Poly(amide-imide)s and Poly(amide-imide-imide)s Containing the 3,4’-Oxydianiline moiety 15
3.2 Synthesis and Characterization of Polyimide-Silica Hybrids by the Sol-Gel Process 30
CHAPTER 4 CONCLUSIONS 50
REFERENCES 52

LIST OF SCHEMES

Scheme 3.1.1. Synthesis of PAI and PAIIs 17
Scheme 3.2.1. PI (BPDA-BAPP)/silica block copolymer 31
Scheme 3.2.2. PI (BPDA-BAPP)/silica hybrid with coupling agent 32
Scheme 3.2.3. PI (BPDA-BAPP)/silica hybrid without coupling agent 33

LIST OF TABLES

Table 3.1.1. Elemental Analysis of the PAIs and PAIIs 23
Table 3.1.2. Solubility Behavior of the PAIs and PAIIs 26
Table 3.1.3. Thin-Film Tensile Properties of the PAIs and PAIIs 27
Table 3.1.4. Thermal Behavior Data of the PAIs and PAIIs 29
Table 3.2.1. Experimental Conditions of Poly(imide-Silica) Hybrid Materials 35
Table 3.2.2. Tensile Properties of Poly(imide-Silica) Hybrid Films 42
Table 3.2.3. Thermal Behavior of Poly(imide-Silica) Hybrid Materials
47

LIST OF FIGURES

Figure 3.1.1. FT-IR spectra of diimide diacid I and PAI IVb 18
Figure 3.1.2. FT-IR spectra of tetraimide diacids II and PAII Vb 19
Figure 3.1.3. 1H NMR spectra of diacids I and II in DMSO-d6 20
Figure 3.2.1. FT-IR spectra of representative PI/SiO2 films 36
Figure 3.2.2. UV-visible spectra of PI/SiO2 hybrid films (V, VI and VI’ series) 38
Figure 3.2.3. SEM photographs of VI’ PI/SiO2 hybrid films (without APrTMOS as the coupling agent). 39
Figure 3.2.4. SEM photographs of VI PI/SiO2 hybrid films (with APrTMOS as the coupling agent) 41
Figure 3.2.5. Tensile strengths and moduli of VI series PI/SiO2 films 43
Figure 3.2.6. Effect of the Silica content on the modulus of PI/SiO2 hybrid films 44
Figure 3.2.7. Effect of the Silica content on the tensile strength of the PI/SiO2 hybrid films 45
Figure 3.2.8. TGA thermograms of polyimide-silica hybrid nanocomposites in air 48

1.Wilson, D.; Stenzenberger, H.-D.; Hergenrother, P.-M. Eds. Polyimides; Blackie: New York, 1990.
2.Ghosh, M.-K.; Mittal K.-L. Eds. Polyimides: Fundamentals and Applications; Marcel Dekker: New York, 1996.
3.Huang, S.-J.; Hoyt, A.-E. TRIP 1995, 3, 262.
4.de Abajo, J.; de la Campa, J.-G. Adv Polym Sci 1999, 140, 23.
5.Yang, C.-P.; Lin, J.-H.; Hsiao, S.-H. J Polym Sci Part A: Polym Chem 1991, 29, 1175
6.Yang, C.-P.; Lin, J.-H.; Hsiao, S.-H. J Polym Sci Part A: Polym Chem 1992, 30, 1865
7.Yang, C.-P.; Hsiao, S.-H.; Chen, C.-D. J. Polym. Res., 1994, 1, 43.
8.Yang, C.-P.; Hsiao, S.-H.; Lin, J.-H. J Polym Sci Part A: Polym Chem 1993, 31, 2995.
9.Yang, C.-P.; Lin, J.-H. J Polym Sci Part A: Polym Chem 1994, 32, 2653.
10.Yamazaki, N.; Matsumato, M.; Higashi, F. J Polym Sci Polym Chem Ed 1975, 13, 1373.
11.Yang, C.-P.; Hsiao, S.-H. Makromol Chem 1989, 190, 2119.
12.Hsiao, S.-H.; Yang, C.-P. J Polym Sci Part A: Polym Chem 1990, 28, 1149.
13.Hsiao, S.-H.; Yang, C.-P. Makromol Chem 1990, 28, 1149.
14.Wrasidlo, W.; Augl A.-M. J Polym Sci Polym Chem Ed 1969, 7, 321.
15.Nieto, J.-L.; de la Campa, J.-G.; de Abajo, J. Makromol Chem 1982, 183, 557.
16.de la Campa, J.-G.; de Abajo, J.; Nieto, J.-L. Makromol Chem 1982, 183, 551.
17.Li, Z.-X.; Fan, L.; Ge, Z.-Y.; Wu, J.-T.; Yang, S.-Y. J Polym Sci A: Polym Chem 2003, 41, 1831.
18.Liaw, D.-J.; Hsu, P.-N.; Chen W.-H.; Liaw, B.-Y. Macromol Chem Phys 2001, 202, 1483.
19.Liaw, D.-J.; Hsu, P.-N.; Liaw B.-Y. J Polym Sci Part A: Polym Chem 2001, 39, 63.
20.Banishashemi, H.; Behniafar, H. Polym Int 2003, 52, 1136.
21.Behniafar, H.; Banishashemi, H. Eur Polym J 2004, 40, 1409.
22.Yang, C.-P.; Chern, J.-J. J Polym Sci Part A: Polym Chem 33, 2209 (1995).
23.Wen, J.; Mark, J.-E. Polym J 1995, 27, 492.
24.Clarson, S.-J; Mark, J.-E. Polym Commun 1987, 28, 249.
25.Navak, B.-M.; Auerbach, D.; Verruer, C. Chem Mater 1994, 6, 282.
26.Huang, H.-H.; Wilkes, G.-L.; Carlson, J.-G. Polymer 1989, 30, 2001.
27.Morikawa, A.; Iyoku, Y.; Kakimoto, M.; Imai, Y. Polym J 1992, 24, 107.
28.Wang, S.; Ahmad, Z.; Mark, J.-E. Chem Mater l994, 6, 943.
29.Morikawa, A; Iyoku, Y.; Kakimoto, M.; Imai, Y. Chem Mater 1994, 6, 913.
30.Jenekhe, S.-A.; Osaheni, J.-A. Chem Mater 1994, 6, 1906.
31.Shao, P.-L; Mauritz, K.-A; Moore, R.-B. Chem Mater 1995, 7, 192.
32.Chen, Y.; Iroh, J.-O. Chem Mater 1999, 11, 1218.
33.Stefanithis, I.-D.; Mauritz, K.-A. Macromolecules 1990, 23, 2397.
34.Wilson, D.; Stenzenberger, H.-D.; Hergenrother, P.-M.; editors. Polyimides. Glasgow: Blackie, 1990.
35.Ghosh, M.-K; Mittal, K.-L.; editors. Polyimides: fundamentals and applications. New York: Marcel Dekker, 1996.
36.Chen, B.-K.; Chiu, T.-M.; Tsay, S.-Y. J App Polym Sci 2004, 94, 382.
37.Okada, A.; Usuki, A.; Kurauchi, T.; Kamogaito, O. ACS symposium series. vol. 585. Washington, DC: American Chemical Society; 1995. p. 55–7.
38.Ozin, G.-A. Adv Mater 1992, 4, 613.
39.Komerneni, S.-J. Mater Chem 1992, 2, 1219.
40.Ahmad, Z.; Mark, J.-E. Chem Mater 2001, 13, 3320.
41.Chang, C.-C; Chen W.-C. Chem Mater 2002, 14, 4242.