臺灣博碩士論文加值系統

第一部份: 一系列新型含氟之芳香族聚醚醯亞胺是由1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl]cyclohexane dianhydride (I) 與各種含三氟取代之芳香族二醚二胺 (IIa-g) 經二步驟先在DMAc中開環聚加成生成聚醯胺酸 (IIIa-g) 再以熱烤 (H) 或化學閉環法 (C) 合成聚醚醯亞胺PEIs (IVa-g)，其固有黏度介於0.70-1.08 dL/g之間，經由GPC之量測得其數量平均分子量( )及重量平均分子量( )分別介於3.80-6.47×10¬4及4.42-7.45×10¬4之間，分子量分佈指數( / )為1.14-1.16之間。IV系列具有極佳溶解性，於所測試的溶劑下包括amide型極性溶劑、氯化溶劑、醚類溶劑和鹼性溶劑等皆具有良好之溶解性。且為一接近無色透明之薄膜，經由UV-visible光譜之透光率及色度計之參數測得其截止波長在375-380 nm，黃色指數(b*)在5.5-7.3之間。熱性質由示差熱掃描分析儀(DSC)測得玻璃轉移溫度在207-269 ℃之間，由熱重分析儀(TGA)之分析在氮氣中與空氣中之10% 重量損失皆在474 ℃以上，且氮氣中800 ℃之焦炭殘餘率在53-62% 之間。這些薄膜具有良好之機械性質，其斷裂點抗張強度在80-113 MPa，斷裂點伸長率介於7-18% 及起始模數在1.5-1.9 GPa之間。IV系列與相應不含CF3之V系列比較，具有高可溶性、低著色與低的介電常數等特色。
第二部份: 一系列色淡且具高有機易溶性之聚醚醯亞胺 (4a-g) 由
3,6-bis(3,4-dicarboxyphenoxy)benzonorbornane dianhydride (1)
與各種含氟之芳香族二胺 (2a-g) 經標準二步驟法先開環聚加成生成聚醯胺酸 (PAA) 再以化學(C)或熱烤閉環法(H)生成。4 系列其固有黏度介於1.19-1.78 dL/g 之間，且經由GPC之量測得其數量平均分子量( )及重量平均分子量( )介於1.53-3.89 × 10¬4及2.96-6.13 × 10¬4之間，分子量分佈指數( / )則介於1.56-2.34之間。於大部份的有機溶劑測試中皆呈現良好的溶解性，且可鑄成之薄膜具有高的穿透度、柔韌性與優異的機械性質。UV-Visible光譜之截止波長 (λ0) 在 372-379 nm 及色度計之 b* 參數值 (黃色指數) 在 10.8-14.15 之間。測得之機械性質其斷裂點抗張強度除介於104-130 MPa之間，斷裂點伸長率介於7-38%及起始模數在1.9-2.5 GPa之間。本系列之玻璃轉移溫度 (Tg) 及軟化點溫度 (Tg) 分別介於 216-292 °C 及 209-285 °C 之間，在氮氣及空氣中之 10%重量損失在 479 °C 與 467 °C 之上，於氮氣中800 °C 之熱重殘餘率在 51% 以上，其介電常數在2.84-3.58 (1 MHz) 及吸濕率範圍在 0.05-0.19% 之間。4系列與相應不含CF3之5系列比較，具有高可溶性、低著色與低的介電常數等特色。


第三部份: 一系列含有酞基及柔軟醚鏈之有機可溶性聚醚萘醯亞胺(PNI) 是經由 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) 與3,3-bis[4-(4-aminophenoxy)-3-methylphenyl]phthalide (BAMP) (6a) 及等當量的芳香族二醚二胺 (6b-g) 於 m-cresol 中，使用一步驟高溫聚縮合法合成共聚合物。PNIs 具有高度適當的固有黏度 1.24-2.25 dL/g，經由m-cresol 可鑄成一柔韌且具有良好機械性質的薄膜，其斷裂點抗張強度在97-138 MPa。本系列顯示出優良的熱性質，玻璃轉移溫度介於 291-321 ℃，10 % 熱重量損失都在 542 ℃ 之上，及氮氣中800 ℃ 之熱重殘餘率皆高於 56%。亦與由不含 BAMP之 PNI 7系列比較，發現經BAMP的改質PNI 8共聚合物具有較佳溶解性及成膜性。

Part 1: A series of novel fluorinated poly(ether imide)s (IV) having inherent viscosities of 0.70-1.08 dL/g were prepared from 1,1-bis[4-(3,4-dicarboxyphenoxy)phenyl]cyclohexane dianhydride (I) and various trifluoromethyl (CF3)-substituted aromatic bis(ether amine)s II¬¬a-g by a standard two-step process with thermal and chemical imidization of poly(amic acid) precursors. These poly(ether imide)s showed excellent solubility in many organic solvents and could be solution-cast into transparent, flexible, and tough films. These films were essentially colorless, with an ultraviolet-visible absorption edge of 375-380 nm and a very low b* value (a yellowness index) of 5.5 to 7.3. They also showed good thermal stability with glass-transition temperatures of 207-269 oC, 10% weight loss temperatures in excess of 474 oC, and char yields at 800 oC in nitrogen more than 62%. In comparison with analogous V series poly(ether imide)s without the -CF3 substituents, the IV series polymers showed better solubility, lower color intensity, and lower dielectric constants.
Part 2: A series of organosoluble and colorless fluorinated poly(ether imide)s (4a-g) were prepared from 3,6-bis(3,4-dicarboxyphenoxy) benzonorbornane dianhydride (1) and various trifluoromethyl (CF3)-substituted aromatic bis(ether amine)s 2a-g by a standard two-step process with thermal and chemical imidization of poly(amic acid) precursors. These poly(ether imide)s had inherent viscosities of 1.19-1.78 dL/g and showed excellent solubility in many organic solvents. They could be solution-cast into transparent, flexible, and tough films with good mechanical properties. These films were virtually colorless, with an ultraviolet-visible absorption edge of 372-379 nm and a very low b* value (a yellowness index) of 10.8 to 14.1. The glass-transition temperatures (Tg) and softening temperatures (Ts) were recorded between 216-292 oC and 209-285oC, respectively. The decomposition temperature for 10% weight loss all occurred above 479 oC in nitrogen and 467 oC in air, and the char yields at 800 oC in nitrogen were more than 51%. They also showed low dielectric constants of 2.84-3.58 (1 MHz) and moisture absorptions in the range of 0.05-0.19%. In comparison with analogous 5 series poly(ether imide)s without the -CF3 substituents, the 4 series ones showed better solubility, lower color intensity, and lower dielectric constants.
Part 3: A series of organic-soluble polynaphthalimides (PNI) bearing flexible ether links and phthalide cardo group were synthesized from 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) with 3,3-bis[4-(4-aminophenoxy)-3-methylphenyl]phthalide (BAMP) and its mixtures with other dietheramines (6b-g) by high-temperature solution polycondensation in m-cresol. The PNIs had moderate to high inherent viscosities in the range of 1.24-2.25 dL/g and could afford flexible and tough films with tensile strengths of 97-138 MPa by casting their m-cresol solutions. These PNIs exhibited high thermal stability, with glass-transition temperature of 291-321 °C, 10% weight-loss temperatures above 542 °C, and char yields at 800 °C in nitrogen higher than 56%. In comparison with PNIs without the BAMP component, these BAMP-modified PNIs revealed an enhanced solubility and film-forming capability.

ABSTRACT IN ENGLISH v
ABSTRACT IN CHINESE viii
LIST OF TABLES xiii
LIST OF FIGURES xiv
LIST OF SCHEMES .xvi
CHAPTER 1 INTRODUCTION 1
CHAPTER 2 EXPERIMENTAL 6
2.1 Materials 6
2.2 Synthesis of Monomers 7
2.2.1 Synthesis of 1,1-Bis[4-(3,4-dicarboxyphenoxy)phenyl]-
cyclohexane dianhydride 7
2.2.2 Synthesis of 3,6-bis(3,4-dicarboxyphenoxy)-
benzonorbornane dianhydride 9
2.2.3 Synthesis of 3,3-bis[4-(4-aminophenoxy)-
3-methylphenyl] phthalide 10
2.3 Synthesis of Polyimides 12
2.3.1 Synthesis of Poly(ether imide)s IVa-g 12
2.3.2 Synthesis of Poly(ether imide)s 5a-g 14
2.3.3 Synthesis of Polynaphthalimides 8a-h 15
2.4 Measurements 16
CHAPTER 3 RESULTS AND DISCUSSION 19
3.1 Synthesis and Properties of Novel organosoluble and
Colorless Poly(ether imide)s Based on 1,1-Bis[4-(3,4-
dicarboxyphenoxy)phenyl]cyclohexane Dianhydride
and Trifluoromethyl-substituted Aromatic
Bis(ether-amine)s 19
3.2 Soluble and Colorless Poly(ether imide)s Based on a Benzonorbornane Bis(ether anhydride) and Trifluoromethyl- Substituted Aromatic Bis(ether amine)s ...............................36
3.3 Synthesis and Properties of Organosoluble Polynaphthal- imides Based on 1,4,5,8-Naphthalenetetracarboxylic Dianhydride, and 3,3-bis[4-(4-aminophenoxy)-3-methyl- phenyl]phthalide, and other Aromatic Diamines 56
CHAPTER 4 CONCLUSIONS 70
CHAPTER 5 REFERENCES 72

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