臺灣博碩士論文加值系統

中文摘要
二種新型含氟的二醚胺2,2’-bis(4-amino-2-trifluoromethyl- phenoxy)biphenyl (3F-BPDA)和 2,2’-bis(4-amino-2-trifluoromethyl- phenoxy)-1,1’-binaphthyl (3F-BNDA) 是分別以2,2’-biphenol及2,2’-dihydroxy-1,1’-binaphthyl為起始原料與 2-chloro-5-nitrobenzo- trifluoride經由取代及還原二個反應合成而成。本論文分成兩個部分。第一部份在探討二種含氟結構之雙苯環及雙萘環所衍生的新型芳香族聚醯胺之合成與性質，這些聚醯胺是由含氟之2,2’-biphenyl 和2,2’-binaphthyl的二胺單體與芳香族二羧酸經由磷酸化聚醯胺反應而成。這二系列聚醯胺可以容易的溶在極性有機溶劑中，而且能經由溶液鑄膜法塗製成強韌且具可撓曲性的薄膜。這些聚醯胺的玻璃轉化溫度介於190到255℃之間，並可耐熱至420℃以上。第二部分論及了以含氟二胺3F-BNDA為主體的新型聚醯亞胺的合成及性質。此系列含氟結構之聚醯亞胺，是由含氟的二胺單體3F-BNDA和市售六種的芳香族二酐，經由常用的二步法合成。這些聚醯亞胺對有機溶劑有良好的溶解性，並具有低吸濕性(0.2-0.5%)、低介電常數(2.84-3.49 at 10 kHz)及良好光學穿透特性(cutoff wavelength 356-434 nm)。其玻璃轉化溫度介於250到265℃之間，在空氣或氮氣中分解掉10﹪減少重量的溫度皆在520℃以上，顯示這些聚醯亞胺具有良好的熱穩定性。

ABSTRACT
Two novel fluorine-containing diamines, 2,2’-bis(4-amino-2- trifluoromethylphenoxy)biphenyl (3F-BPDA) and 2,2’-bis(4-amino-2- trifluoromethylphenoxy)-1,1’-binaphthyl (3F-BNDA), were prepared in two steps synthesizing from 2,2’-biphenol and 2,2’-dihydroxy-1,1’-binaphthyl with 2-chloro-5-nitrobenzotrifluoride by the aromatic nucleophilic displacement using potassium carbonate and sodium hydride, respectively, followed by hydrazine catalytic reduction of the intermediate dinitro compounds. This study has been separated into two parts. Part Ⅰ deals with the synthesis and properties of two series of new aromatic polyamides based on two fluorine-containing 2,2’-biphenyl and 2,2’-binaphthyl diamines by the direct phosphorylation polycondensation. All two series polyamides were readily dissolved in polar organic solvents and afforded transparent, flexible and tough films by solution casting. These polyamides had glass-transition temperatures in the range of 190-255 ℃, and thermal stability above 420 ℃. Part Ⅱ reports the synthesis and properties of new aromatic polyimides based on 3F-BNDA. A set of fluorinated polyimides were prepared from the diamine 3F-BNDA with various aromatic dianhydrides via a conventional two-stage technique. All polyimides showed good solubility in polar organic solvents, low moisture absorption (0.2-0.5%), low dielectric constant (2.84-3.49 at 10 kHz), and high optical transparency (cutoff wavelength 356-434 nm). These polyimides showed glass-transition temperatures in the range of 250-265℃, and high thermal stability with decomposition temperature for 10% weight loss above 520℃ in both nitrogen and air atmospheres.

TABLE OF CONTENTS
ACKNOWLEDGEMENTS……………………………………………… v
ABSTRACT (in English)………………………...………………………. vi
ABSTRACT (in Chinese)……………………………………...………… viii
TABLES OF CONTENTS……………………………………………….. ix
LIST OF TABLES……………………………………………………….. xiii
LIST OF FIGURE………………………………………………………... xv
PART Ⅰ
Syntheses and Properties of Novel Fluorinated Polyamides Based on 2,2’-Bis(4-amino-2-trifluoromethylphenoxy)biphenyl and 2,2’-Bis(4-amino-2-trifluoromethylphenoxy)-1,1’-binaphthyl
ABSTRCT OF PART Ⅰ……………………………………………………2
CHAPTER 1 INTRODUCTION……………………………………………3
CHAPTER 2 EXPERIMENTAL……………………………………………6
2.1. Materials…………………………………………………...6
2.2. Monomer Synthesis………………………………………..7
2.2.1. 2,2’-Bis(4-nitro-2-trifluoromethylphenoxy)biphenyl (1)……………………………………………………….7
2.2.2. 2,2’-Bis(4-amino-2-trifluoromethylphenoxy)biphenyl (2)……………………………………………………….8
2.2.3. 2,2’-Bis(4-nitro-2-trifluoromethylphenoxy)-1,1’- binaphthyl (3)…………………...………………………9
2.2.4 2,2’-Bis(4-amino-2-trifluoromethylphenoxy)-1,1’- binaphthyl (4)………………………………………….11
2.3 Polymer Synthesis………………………………..………12
2.4 Preparation of the Polyamide Films…….………………..13
2.5 Measurements…………………………………………….13
CHAPTER 3 RESULTS AND DISCUSSION……………………………..16
3.1. Mononer Synthesis……………………………………….16
3.2. Polymer Synthesis………………………………………..25
3.3. Polymer Properties……………………………………….31
CHAPTER 4 CONCLUSIONS………………………..…………………...42
REFERENCES………………………………………………………...…...43
PART Ⅱ
Syntheses and Properties of Novel Fluorinated Polyimides Based on 2,2’-Bis(4-amino-2-trifluoromethylphenoxy)-1,1’-binaphthyl
ABSTRCT OF PART Ⅱ.………………………………………………….47
CHAPTER 1 INTRODUCTION…………………………………………..48
CHAPTER 2 EXPERIMENT…………………………………………..….52
2.1. Materials………………………………………………....52
2.2. Polymer Synthesis………………………………………..53
2.2.1. Homopolymer Synthesis……………………………….53
2.2.2. Copolymer Synthesis…………………………………54
2.3 Measurements……………………………………………55
CHAPTER 3 RESULTS AND DISCUSSION………………………….…57
3.1. Polymer Synthesis……………………………………….57
3.2. Polymer Properties……………………………………….63
3.2.1. Organo-solubility………………………………………63
3.2.2. Tensile properties………………………………………64
3.3.3. X-ray diffraction data…………………………………..67
3.3.4. Optical transparency…………………………………...70
3.3.5. Thermal properties……………………………………..72
3.3.6. Dielectric constants and moisture absorption……...…..75
CHAPTER 4 CONCLUSIONS…………………………………………….78
REFERENCE……………………………………………………………....79
LIST OF TABLES
PART Ⅰ
1.1. Inherent Viscosity and Elemental Analysis of Polyamides………….27
1.2. Solubility Behavior of Polyamides………………………………….34
1.3. Mechanical Properties and optical transparency of Polyamide Films ……...………….……………………………………………..35
1.4. Thermal Behavior Data of Polyamides………….…………….…….39
PART Ⅱ
2.1. Inherent Viscosity and optical transparency of Polyimides, Copolyimides and Elemental Analysis of Polyimides………….…...60
2.2. Solubility Behavior of Polyimides and Copolyimides Prepared Via Chemical Imidization………………………………………….…….65
2.3. Solubility Behavior of Polyimides and Copolyimides Prepared Via Thermal Imidization…………………………………………..……..66
2.4. Mechanical Properties of Copolyimide Films……………………….68
2.5. Thermal Behavior Data of Polyimides and Copolyimides…………….73
2.6. Moisture Absorption and Dielectric Constants of Polyimides………...77
LIST OF FIGURES
PART Ⅰ
1.1. IR spectra of (a) 3F-dinitro compound 1 and (b) 3F-diamine 2…….19
1.2. IR spectra of (a) 3F-dinitro compound 3 and (b) 3F-diamine 4…….20
1.3. The proton nuclear magnetic resonance from the 300 MHz 1H NMR spectra of (a) 3F-dinitro compound 1 and (b) 3F-amino compound 2 in DMSO-d6…………………………………………………………21
1.4. The proton nuclear magnetic resonance from the 300 MHz 1H NMR spectra of (a) 3F-dinitro compound 3 and (b) 3F-amino compound 4 in DMSO-d6…………………………………………………………22
1.5. The carbon nuclear magnetic resonance from the 300 MHz 1H NMR spectra of (a) 3F-dinitro compound 1 and (b) 3F-amino compound 2 in DMSO-d6…………………………………………………………23
1.6. The carbon nuclear magnetic resonance from the 300 MHz 1H NMR spectra of (a) 3F-dinitro compound 3 and (b) 3F-amino compound 4 in DMSO-d6…………………………………………………………24
1.7. IR spectra (film) of polyamides 6d and 7d………………………….28
1.8. The 1H NMR and 13 C NMR spectra of polyamide 6e in DMSO-d6……………………………………………………………29
1.9. The 1H NMR and 13C NMR spectra of polyamide 7e in DMSO-d6……………………………………………………………30
1.10. Wide-angle X-ray diffractograms of polyamides 6 and 6’ series (see ref. 5)………………………………………………………………..32
1.11. Transmission UV-visible absorption spectra of some polyamide films…………………………………………………………………36
1.12. Typical TMA thermograms for polyamides 6e and 7e (heating rate = 10 ℃/min; applied force = 10 mN)……………...………………….40
1.13. TGA curves of polyamides 6g and 7g (Heating rate = 20℃/min)…..41
PART Ⅱ
2.1. IR spectrum (film) of polyimide Ⅲe………………………………..61
2.2. The 1H NMR and 13C NMR spectra of polyimide Ⅲe in DMSO-d6…………………………………………………………....62
2.3. Wide-angle X-ray diffractograms of polyimides Ⅲ and Ⅲ’ (see ref. 18) series…………………………………………………………….69
2.4. Transmission UV-visible absorption spectra of some polyimide and copolyimides Films…………………………..……………………...71
2.5. Typical TMA thermogram for polyimide Ⅲf (heating rate = 10 ℃/min; applied force = 10 mN)………………………………………..74
2.6. TGA curves of polyimides Ⅲf (Heating rate = 20 ℃/min)……….74

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