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研究生:蘇育央
研究生(外文):Su Yu-Yang
論文名稱:由4,4’-二羥基二苯甲酮及3-硝基苯酚經由二胺合成含氟聚醯亞胺及其性質
論文名稱(外文):Synthesis and Properties of Fluorinated Polyimides Based onFluorine-Containing Diamines Extended from 4,4'-Dihydroxybenzophenone and 3-Nitrophenol
指導教授:楊金平楊金平引用關係
指導教授(外文):Yang Chin-Ping
學位類別:碩士
校院名稱:大同大學
系所名稱:化學工程研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2003
畢業學年度:91
語文別:英文
論文頁數:78
中文關鍵詞:44’-二羥基二苯甲酮3-硝基苯酚含氟聚醯亞胺
外文關鍵詞:44’-Dihydroxybenzophenone3-NitrophenolFluorinatedPolyimide
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第一部份中,一新型含CF3基與醚酮基之芳香族二胺4,4’-Bis(4-amino-2-trifluoromethy-phenoxy)benzophenone (2)是由2-chloro-5-nitrobenzotrifluoride 與4,4’-Dihydroxybenzophenone在無水K2CO3共存之DMAc下親核置換縮合成二硝基化合物後,以聯胺-Pd/C還原而成。2與各種市售二酐﹝PMDA、BTDA、BPDA、DSDA、ODPA及6FDA (3a-f)﹞以熱烤法及化學閉環法聚縮合成一系列之Polyimides 5(H)a-f與5(C)a-f及其Copolyimides 5c/a-f。測得5系列之固有黏度在0.72-1.22之間,其中化學法除5c外幾乎皆可溶於NMP、DMAc、DMF、DMSO、m-cresol、Py、Dioxane、THF等溶劑,但熱烤法之PI卻呈難溶性。測得鑄膜之機械性質:抗張強度介於92-112 MPa,斷裂伸長率介於8-15 %,起始模數在2.0-2.1 GPa之間,且5(H)與5(C)差異不大。5之熱性質由DSC測定之玻璃轉移溫度在232-278 ℃之間,由TGA之分析,在氮氣及空氣中之10%重量損失在535 ℃以上及氮氣中800 ℃之熱重殘餘率在50-55%。Polyimide 5系列與相對不含CF3之4,4’-Bis(4-aminophenoxy)benzophenone合成之 6系列比較,5以溶解性較佳,薄膜之色澤較淡介電常數及吸濕性較低為特色。經由UV-visible光譜之透光率及Colorimeter 之參數測得5之Cutoff wavelength在 370-410 nm之間,b*參數值在9.6-58.3之間,而介電常數在3.05-3.64 (1 MHz)間,及吸濕率範圍在0.08-0.38 wt % 之間。第二部份中,一種含CF3基之色淡二胺3’-trifluoromethyl-3,4’-oxydianiline (3’-CF3-3,4’-ODA) (2’) 是由2-chloro-5-nitrobenzotrifluoride與3-nitrophenol在無水K2CO3共存下親核置換縮合成二硝基化合物後,以聯胺-Pd/C還原而成。2’與各種市售二酐3’a-f以熱烤法及化學閉環法聚縮合成一系列之Polyimides 5’a-f。此系列測得5’之固有黏度在0.88-1.12之間。比較5’系列與相應不含氟6’系列及對應之同分異構物3-CF3-4,4’-ODA (7’)及4,4’-ODA (8’)比較生成PI之顏色。發現meta結構與含CF3之para結構苯醚胺皆有減少著色作用。顏色之色淡依序為3’-CF3-3,4’-ODA (5’) > 3-CF3-4,4’-ODA (7’) > 3,4’-ODA (6’) > 4,4’-ODA (8’)。5’系列之溶解性亦優於6’、7’及8’系列。5’系列測得鑄膜之機械性質:抗張強度介於124-147 MPa,斷裂伸長率介於9-65%,起始模數在2.3-2.8 GPa之間。5’系列之熱性質由DSC測定之玻璃轉移溫度在234-313 ℃之間,由TGA之分析,氮氣與空氣中10%重量損失在515 ℃以上及氮氣中800 ℃之熱重殘餘率在50-60 %。Polyimide 5’與由3,4’-oxydianiline(3,4’-ODA)合成之不含氟Polyimide 6’比較,5’除具易溶性外,薄膜之色澤較淡且低介電常數在2.80~3.50 (40 MHz)間及低吸濕率範圍在0.44-1.02 wt% 之間較低為特色。

Part I, A novel fluorinated diamime monomer with ether-ketone group, 4,4’-Bis(4-amino-2-trifluoromethyphenoxy)benzophenone (2) was prepared through the nucleophilic substitution reaction of 2-chloro-5-nitrobenzotrifluoride and 4,4’-Dihydroxybenzophenone in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C. Polyimides 5a-f and copolyimides 5c/a-f were synthesized from 2 and various commercial aromatic dianhydrides ﹝PMDA, BTDA, BPDA, DSDA, ODPA and 6FDA (3a-f)﹞ via the thermal or chemical imidization. The 5 series had inherent viscosities ranging from 0.72 to 1.22 dL/g. Beside the chemical imidization of 5c(C), 5(C) series were soluble in amide-type solvents and even in less polar solvents, but 5a-f via thermal imidization showed insoluble. Polyimide films 5a-f show tensile strength ranging from 92 to 112 MPa, elongations to break from 8 to 15%, and initial moduli in 2.0-2.1 GPa. The glass transition temperature of 5 series were in the range of 232-278 ℃, and the 10% weight loss temperature were above 535 ℃, and they left more than a 50% char yield at 800 ℃ in nitrogen. Compared 5 series with analogous nonfluorinated polyimides 6 series based on 4,4’-Bis(4-aminophenoxy)benzophenone, 5 series revealed better solubility, lower color intensity, dielectric constant, and moisture absorption. Their films had cutoff wavelengths between 370-410 nm, b* values ranging from 9.6 to 58.3, dielectric constants of 3.05-3.64 (1 MHz), and moisture absorption in the range of 0.08-0.38 wt%. Part II, A colorless fluorinated diamine, 3’-trifluoromethy-3,4’-oxydianiline (3’-CF3-3,4’-ODA) (2’) was prepared through the nucleophilic substitution reaction of 3-nitrophenol and 2-chloro-5-nitrobenzotrifluoride, followed by catalytic reduction with hydrazine and Pd/C. A series of Polyimides 5’ were synthesized from the diamine 2’ with various aromatic dianhydrides 3’a-f via the thermal and chemical imidization. These polyimides had inherent viscosities ranging from 0.88 to 1.12 dL/g. A comparison of 5’, 6’ to analogous polyimides 7’, 8’, which 6’, 7’ and 8’ were based on 3’4-ODA, 3-CF3-4,4’-ODA, 4,4’-ODA, respectively. In terms of the colorness of PI revealed that the color intensity of phenoxy-containing amine of the meta-structure and the para-structure with the CF3 group would fell off color intensity. The color intensity of the four polyimide series was lessened in the following order: 5’ > 7’ > 6’ > 8’. The solubility of 5’ is better than 6’, 7’ and 8’. The polyimide 5’ films had a tensile strength ranging from 124 to 147 MPa, elongation at break from 9 to 65%, and initial modulus from 2.3 to 2.8 GPa. The glass transition temperature of polymers was recorded at 234—313 ℃. They had 10% weight loss at a temperature above 515 ℃ and left more than 50% residue even at 800 ℃ in nitrogen. Compared with polyimides 6’, 5’ showed the lower dielectric constants of 2.80—3.50 (40 MHz), and moisture absorptions in the range of 0.44—1.02 wt%.

ACKNOWLEDGEMENTS v
ABSTRACT (in English) vi
ABSTRACT (in Chinese) ix
LIST OF TABLES xiii
LIST OF FIGURES xiv
LIST OF SCHEMES xvi
CHAPTER 1 INTRODUCTION 1
CHAPTER 2 EXPERIMENTAL 5
2.1 Materials 5
2.2 Synthesis of Monomers 6
2.2.1 Synthesis of 4,4’-Bis(4-amino-2- Trifluoromethylphenoxy)benzophenone 6
2.2.2 Synthesis of 3’-Trifluoromethyl-3,4’-oxydianiline 8
2.3 Synthesis of Polyimides 11
2.3.1 Synthesis of Polyimides 5a-f 11
2.3.2 Synthesis of Polyimides 5’a-f 13
2.4 Measurement 15
CHAPTER 3 RESULTS AND DISCUSSION 17
3.1 Synthesis and Properties of Organosoluble Polyimides Based on 4,4'-Bis(4-amino-2-trifluoromethylphenoxy)benzophenone 17
3.2 Properties of Organosoluble Aromatic Polyimides from 3’- Trifluoromethyl-3,4’-oxydianiline 45
CHAPTER 4 CONCLUSIONS 74
CHAPTER 5 REFERENCES 76
LIST OF TABLES
Table 3.1.1 Inherent Viscosity of Poly(amic acid)s 4 and polyimides 5(C), and Elemental Analysis of the polyimides 5 29
Table 3.1.2 Inherent Viscosity and GPC Data of Polyimides 5 31
Table 3.1.3 Solubility Behavior of Polyimides 32
Table 3.1.4 Color Coordinates and the Cut-off Wavelength from
UV-Visible Spectra for both 5 and 6 Series
Polyimide Films 34
Table 3.1.5 Tensile Properties of Polyimide Films 39
Table 3.1.6 Thermal Behavior Data of Polyimides 41
Table 3.1.7 Moisture Absorption and Dielectric Constants of
polyimides 44
Table 3.2.1 Elemental Analysis of the polyimides 56
Table 3.2.2 Inherent Viscosity and GPC Data of Polyimides 58
Table 3.2.3 Color Coordinates and the Cut-off Wavelength (λ0)
from UV-Visible Spectra for Polyimide Films 59
Table 3.2.4 Solubility Behavior of Polyimides 66
Table 3.2.5 Tensile Properties of Polyimide Films 68
Table 3.2.6 Thermal properties of Polyimides 70
Table 3.2.7 Moisture Absorption and Dielectric Constants of
polyimides 72
LIST OF FIGURES
Figure 3.1.1 FT-IR spectra of 3F-dinitro compound 1, 3F-
diamine 2 and Polyimide 5d. 20
Figure 3.1.2 The 1H and 13C NMR spectrum of 3F-dinitro compound
1 in DMSO-d6. 21
Figure 3.1.3 The 1H and 13C NMR spectrum of 3F-diamine 2 in
DMSO-d6. 22
Figure 3.1.4 Viscosity change of poly(amic acid)s prepared in
DMAc at 12% solid content at root temperature. 25
Figure 3.1.5 The 1H and 13C NMR spectrum of polyimide 5d in
DMSO-d6. 28
Figure 3.1.6 Comparison of the yellowness index ( b* value )
between polyimides 5 and 6. 36
Figure 3.1.7 UV-visible spectra of polyimide films. 37
Figure 3.2.1 FT-IR spectra of dinitro compound 1’, CF3-diamine
2’and Polyimide 5’f. 47
Figure 3.2.2 The 1H and 13C NMR spectrum of dinitro compound 1'
in DMSO-d6. 49
Figure 3.2.3 The 1H and 13C NMR spectrum of CF3-diamine 2’ in
DMSO-d6. 50
Figure 3.2.4 Viscosity change of poly(amic acid)s prepared in
DMAc at 10% solid content at room temperature. 53
Figure 3.2.5 The 1H and 13C NMR spectra of polyimide 5’f in
DMSO-d6. 55
Figure 3.2.6 Comparison of the yellowness index ( b* value )
between Polyimides 5’ and 6’. 60
Figure 3.2.7 UV-visible spectra of polyimide films prepared
via thermal cyclization. 61
Figure 3.2.8 Comparison of the yellowness index ( b* value )
between polyimides 5’(H), 5’(C) and 7’. 63
Figure 3.2.9 Comparison of the yellowness index ( b* value )
between polyimides 5’, 6’, 7’, 8’. 65
LIST OF SCHEMES
Scheme 3.1.1 Synthesis of 3F-diamine 2. 18
Scheme 3.1.2 Synthesis of polyimides. 18
Scheme 3.2.1 Synthesis of 3F-diamine 2’. 46
Scheme 3.2.2 Synthesis of polyimides. 46

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1. 由4,4’-二羥基二苯甲酮及2,5-雙特丁基對苯二酚經由二醚二胺合成聚醯亞胺及其性質
2. 由含三氟甲基之芳香族二醚二胺衍生之無色含氟聚醯亞胺、可溶性聚萘醯亞胺、及聚醯亞胺/二氧化矽混成材料之合成及其性質之研究
3. 由1,1-雙(4-羥基苯)-1-苯乙烷及苯基對苯二酚經由二胺合成含氟聚醯亞胺及其性質
4. 由2,3-雙(3,4-二羧基苯氧)萘二酐、1,4-雙(4-胺基-2-三氟甲基苯氧)-2,5-雙特丁基苯及1,4,5,8-萘二酐衍生之聚醚醯亞胺、醯胺醯亞胺及萘醯亞胺等聚合物及其性質研究
5. 新型聚醚醯亞胺及聯苯型各種聚醯亞胺/二氧化矽混合材之合成與性質
6. 含cardo複脂環及2,5-雙特丁基苯之新型聚醯亞胺之合成及性質研究
7. 含1,4-或1,5-萘二氧及三氟甲基之芳香族聚醯亞胺及聚醯胺之合成與特性研究
8. 含側接對位三聯苯結構及三氟甲基之可溶性聚醯亞胺及聚醯胺之合成與特性研究
9. 有機可溶性聚醯亞胺及色淡聚醯胺醯亞胺之合成與性質
10. 由鄰苯二酚與酚酉太經由二醚二胺合成含氟聚醯亞胺及其性質
11. 新型含三氟甲基取代之萘環結構的芳香族二醚二胺所衍生之有機可溶性及低介電常數之聚醯亞胺之合成與性質
12. 由丙二酚-A與六氟丙二酚-A經由二醚二胺合成含氟聚醯亞胺及其性質
13. 高耐熱透明聚醚醯亞胺之合成及其應用於可撓式元件界面接著性探討
14. 應用於無接著劑型軟性銅箔基板之新型聚亞醯胺
15. 具有三氟甲基或甲基取代之三苯胺成分的新型芳香族聚醯胺及聚醯亞胺之合成與光電性質研究
 
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