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

SYNTHESIS AND PROPERTIES OF FLUORINATED POLYIMIDES BASED ON FLUORINE-CONTAINING DIAMINES EXTENDED FROM 1,1-BIS(4- HYDROXYPHENYL)-1-PHENYLETHANE AND PHENYLHYDROQUINONE

陳永忠(Yung-Chung Chen)

指導教授 ： 楊金平

大同大學/工程學院/化學工程學系所/碩士(2004年)

摘要

第一部份中: 為探討CF3基團對於Polyimides (PI)之顏色與溶解性之影響，由1,1-bis(4-hydroxyphenyl)-1-phenylethane與2-chloro-5-nitrobenzotrifluoride合成含CF3側鏈基之新型二胺1,1-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]-1-phenylethane (2)。一系列色淡、易溶性PI 5系列是由2 與市售六種二酐﹝PMDA、BTDA、BPDA、DSDA、ODPA及6FDA (3a-f)﹞經由開環聚加成反應生成poly(amic acid)後再以熱烤化學閉環法聚縮合而成一系列之polyimides。5a-f(H)與5a-f(C)所測得固有黏度在0.60-0.98 dL/g及0.55-0.78 dL/g之間。在溶解性方面，熱烤法除了5b外其餘均可溶於NMP、DMAc、DMF、DMSO等極性溶劑，甚至在低極性溶劑如m-Cresol、Py、Dioxane、THF、CH2Cl2等溶劑也呈現可溶或部分溶的現象，化學法則是呈現皆溶的情形。5a-f(C)之分子量由GPC測定其數量平均分子量(Mn)與重量平均分子量(Mw)介於5.5-8.7×104及8.5-10.6×104之間，polydispersity index (Mw/Mn)介於1.2-1.5之間。測得鑄膜之機械性質：抗張強度介於82-134 MPa，斷裂伸長率介於10-21%，起始模數在1.7-2.8 GPa之間。其熱性質由DSC測定之玻璃轉移溫度在232-276 °C之間，由TGA之分析，在氮氣中之10%重量損失在505-548 °C而空氣中之10%重量損失在508-532 °C及氮氣中800 °C之熱重殘餘率在56以上。經由UV-visible光譜之透光率及Colorimeter 之參數測得5系列之截止波長在 356.5-411.5 nm之間，b*參數值在5.0-71.1之間，而介電常數在3.11-3.43 (1 MHz)間，及吸濕率範圍在0.11-0.40% 之間。5系列亦與由1,1-Bis[4-(4-aminophenoxy)phenyl]-1-phenylethane合成之不含氟Polyimides 6系列比較性質，實驗證明含CF3側鏈基團的5系列有較色淡，較低介電常數和有機溶解性較佳之性質。
第二部份中: 一系列色淡含氟之新型polyimides (Va-f)是由新型二胺2,5-bis(4-amino-2-trifluoromethylphenoxy)biphenyl (II)與六種市售芳香族二酐(IIIa-f)經開環聚加成反應成poly(amic acid)後，以熱烤(H)或化學醯亞胺化法(C)合成。其中II是由phenyl-hydroquinone 與2-chloro-5-nitrobenzotrifluoride在無水K2CO3共存下親核置換反應成二硝基化合物後，以聯胺與Pd/C還原而成。V系列中，Vd-Vf及Vb(C)於大部份的測試溶劑中皆呈現良好的溶解性，而Vc因其聯苯結構而呈現難溶性。因此，為了改善Vc之溶解性，本篇亦合成IIIc/a-f等莫耳比之共聚合物(Vc/a-f)。測得V系列之機械性質為抗張強度介於73-112 MPa，斷裂伸長率介於9-23%，起始模數在1.6-2.0 GPa之間。V系列之熱性質由DSC測定之玻璃轉移溫度在220-267 °C之間，由TGA之分析，在氮氣及空氣中之10%重量損失在516-588 °C與533-572 °C之間，在氮氣中800 °C之熱重殘餘率在52%以上。V系列亦與由2,5-bis(4-aminophenoxy)biphenyl (II’)合成結構類似不含氟之PI-VI系列比較性質，前者除有較佳有機溶解性外且有較色淡，較低介電常數和低吸濕性等性質，包括UV-Visible光譜之截止波長(λ0)在 364.0-423.0 nm及Colorimeter 之b*參數值在8.3-72.5，以及介電常數在3.14-3.48 (1 MHz)及吸濕率範圍在0.13-0.40 % 之間。

關鍵字

苯基對苯二酚 ； 1-雙(4-羥基苯)-1-苯乙烷 ； 1 ； 聚醯亞胺

並列摘要

Part 1: To investigate the CF3 group affecting the coloration and solubility of polyimides (PI), a novel fluorinated diamine 1,1-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]-1-phenylethane (2) was prepared starting 1,1-bis(4-hydroxyphenyl)-1-phenylethane and 2-chloro-5-nitrobenzotrifluoride to yield the intermediate dinitro compound, followed by catalytic reduction with hydrazine and Pd/C. A series of light-colored and soluble polyimides (PIs) 5 series were synthesized from 2 with various commercially available aromatic dianhydrides 3a-f via the thermal (H) or chemical (C) imidization of poly(amic acid) films. 5a-f(H) and 5a-f(C) had inherent viscosities ranging from 0.60 to 0.98 dL/g and 0.55 to 0.78 dL/g. In solubility, except for the polymer 5b(H), 5(H) series was soluble in amide-type solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF) and even in less polar solvents such as m-cresol、pyridine、dioxane、tetrahydrofuran (THF)、dichloromethane (CH2Cl2), and 5(C) was soluble in all solvents. The GPC data of 5a-f(C) indicated that the Mn and Mw values were in the range of 5.5-8.7×104 and 8.5-10.6×104, the polydispersity index (PDI) Mw/Mn values were 1.2-1.5. These films had tensile strengths of 82-134 MPa, elongations to break of 10-21% and initial moduli of 1.7-2.8 GPa. The glass transition temperatures (Tg) of 5 series were in the range of 232-276 °C, and the 10% weight loss temperatures were above 500 °C, respectively, and they left more than 56% char yield at 800 °C. Compared 5 with the analogous nonfluorinated PI 6 series based on 1,1-bis[4-(4-aminophenoxy)phenyl]-1-phenylethane (BAPPE), the 5 series revealed lower color intensity, dielectric constants and better solubility. These films had cutoff wavelengths between 356.5 and 411.5 nm, the b* values ranging from 5.0-71.1, dielectric constants of 3.11-3.43 (1MHz) and moisture absorptions in the range of 011-0.40%. Part 2: A novel fluorinated diamine monomer, 2,5-bis(4-amino-2-trifluoromethylphenoxy)biphenyl (II), was prepared through the nucleophilic substitution reaction of 2-chloro-5-nitrobenzotrifluoride and phenylhydroquinone in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C. A series of light-colored fluorine-containing PIs were synthesized from II with six commercially available aromatic dianhydrides (IIIa-f) using a standard two-stage process with thermal or chemical imidization of poly(amic acid) films. The PIs Vd-f and Vb(C) were highly soluble in a variety of organic solvents; however, the PI Vc exhibited poor solubility in all the tested solvents. For improving the solubility of Vc based on 3,3,4,4-biphenyltetracarboxylic dianhydride, copolyimides (Vc/a-f) were prepared from II and a pair of dianhydrides (IIIc/a-f), which were mixed at 1:1 molar ratios. The PI films had a tensile strength in the range from 73-112 MPa, an elongation at break within a range of 9-23%, and initial moduli in the range from 1.6-2.0 GPa. These PIs exhibited Tg of 220-267 °C and showed no significant decomposition below 500 °C under either nitrogen or air atmosphere. In comparison of PI V series with the analogous non-fluorinated PI VI series based on 2,5-bis(4-aminophenoxy)biphenyl (II'), the V series revealed better solubility, lower color intensity, dielectric constant, and moisture absorption. These PI films had cutoff wavelengths between 364 and 423 nm, b* values ranging from 8.3 to 72.5, dielectric constants of 3.14-3.48 (1 MHz), with moisture absorption in the range of 0.13-0.40 wt%.

並列關鍵字

1 ； 1-BIS(4-HYDROXYPHENYL)-1-PHENYLETHANE ； PHENYLHYDROQUINONE ； POLYIMIDES

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