- 學位論文
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
SYNTHESIS AND PROPERTIES OF NOVEL POLYIMIDES CONTAINING CYCLIC CARDO OR 2,5-DI-TERT-BUTYLBENZENE GROUP
摘要
第一部份中，一種新穎含CF3基團之二醚二胺5,5-Bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]-4,7-methanohexa- hydroindan (2)是由5,5-bis(4-hydroxylhpenyl)-4,7-methanohexahydroindan和2-Chloro-5-nitrobenzotrifluoride之親核置換反應成二硝基化合物後，再以聯胺與Pd/C催化還原而成。2與各種二酐(3a-f)經常溫開環聚加成得PAA後，以化學或熱烤閉環法合成一系列之Polyimides 5a-f。此系列測得之固有黏度在0.64-0.86 dL/g之間，且所有PIs在amide型溶劑達10%以上可溶。測得5系列鑄膜之抗張強度介於93-117 MPa，斷裂伸長率介於7-17%，起始模數在2.0-2.8 GPa之間。5系列之玻璃轉移溫度介於255-307℃之間，而在氮氣與空氣中之10%重量損失皆在464℃以上及氮氣中800℃之熱重殘餘率皆在46%以上。5系列與未含氟之6系列比較，前者具有較低之介電常數(2.92-3.28 at 1 MHz)與吸濕率(0.15-0.43 wt%)以及薄膜色澤亦較色淡。第二部份中，一系列色淡兼具良好物性之poly(ether imide)s (PEIs)是由1,4-Bis(3,4-dicarboxyphenoxy)-2,5-di-tert- butylbenzene dianhydride (3’)與各種芳香族二胺 (4’a-k)經二步驟先在DMAc中開環聚加成polyamic acid (PAA)，然後以熱烤法合成PEIs，此系列測得其PAA之固有黏度在1.00-1.53 dL/g之間，大部分之PEI較易溶於含氯溶劑如CHCl3、CH2Cl2等溶劑中，亦可溶於m-cresol，但對DMSO及amide型極性溶劑的溶解性較差。測得6’系列鑄膜之抗張強度介於93-118 MPa，斷裂伸長率介於7-18%，起始模數在2.0-2.5 GPa之間。6’系列之軟化點(Ts)及玻璃轉移溫度(Tg)介於216-279 ℃及232-285 ℃之間，在氮氣及空氣之10%重量損失皆在487 ℃以上。6’系列之介電常數與吸濕率分別在2.71-3.54 (1 MHz)與0.18-0.66%之間。6’系列之UV-visible光譜之Cutoff wavelength皆低於 385 nm及Colorimeter 之b*參數介於7.3-14.8之間，顯示出特別低著色性。第三部份中，一系列無色高透明易溶性及良好機械性質之聚醚醯亞胺是由1’4-Bis(3,4-dicarboxyphenoxy)-2,5-tert-butylbenzene dianhydride (3”)與各種含CF3基之芳香族二胺(4”a–h)經聚加成反應後，再以化學閉環法直接鑄膜而成，其固有黏度介於0.43-1.25 dL/g之間。6”系列較一般認為色淡之2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) PI-8”系列及近年來新穎之側鏈含CF3基團之二胺與6FDA所合成之PI-9”系列更為淡色，且經由UV-visible光譜之透光率及Colorimeter 之參數測得6”之Cutoff wavelength在 371-380 nm之間，b*參數值在3.7-6.6之間。6”系列具有極佳之溶解性，在N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, pyridine, tetrahydrofuran及dichloromethane 與 chloroform中皆達5-10%之可溶性。6”系列測得其機械性質之斷裂點抗張強度介於100-116 MPa，斷裂點伸長率介於8-20%，起始模數在2.0-2.2 GPa之間。其軟化溫度(Ts)與玻璃轉移溫度(Tg)介於219-284 ℃及230-305 ℃之間，在氮氣與空氣中10%重量損失在478 ℃以上。而介電常數在2.72-3.28 (1 MHz)間，及吸濕率範圍在0.15-0.46 wt% 之間。6”系列與未含氟之7”系列比較，前者具有較佳溶解性及色澤較淡。
並列摘要
First, a novel fluorinated bis(ether amine) monomer, 5,5-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]-4,7-methanohexahy-droindan (2), was prepared through the nucleophilic aromatic substitution reaction of 5,5-bis-(4-hydroxylhpenyl)-4,7-methanohexahydroindan with 2-chloro-5-nitrobenzotrifluoride to yield the intermediate dinitro compound, followed by catalytic reduction with hydrazine and Pd/C. Polyimides (PIs, 5a-f) were synthesized from 2 and various aromatic dianhydrides (3a-f) using a standard two-stage process with chemical or thermal imidization of poly(amic acid). PI 5a-f had inherent viscosities ranging from 0.64 to 0.86 dL/g. All of PIs were soluble in amide-type solvents above 10% wt/V. These PI films had tensile strengths of 93-117 MPa, elongations to break of 7-17%, and initial moduli of 2.0-2.8 GPa. The glass transition temperatures of 5 were 255-307 ℃, and the 10% weight loss temperature was above 464 ℃, with their residues more than 46% at 800 ℃ in nitrogen. Compared with the nonfluorinated PI-6, 5 series was observed to have lower dielectric constants (2.92-3.28 at 1 MHz), lower moisture absorptions (0.15-0.43 wt%), and lower color intensity. Second, a series of poly(ether imide)s (PEIs) 6’a-k with light color and good physical properties were prepared from 1,4-bis(3,4-dicarboxypheoxy)-2,5-di-tert-butylbenzene dianhydride (3’) with various aromatic diamines (4’a-k) via a conventional two-stage procedure that included a ring-opening polyaddition to give poly(amic acid)s (PAAs), followed by thermal imidization to the PEI. The intermediate PAA had inherent viscosities in the range of 1.00-1.53 dL/g. Most of PEIs showed excellent solubility in chloroinated solvents such like dichloromethane and chloroform and m-cresol, but not easily dissolved in dimethylsulfoxide and amide-type polar solvents. 6’ series had tensile strengths of 93-118 MPa, elongation at break of 7-18%, and initial moduli of 2.0-2.5 GPa. The softening temperatures (Ts) and the glass transition temperatures (Tg) of the 6’ series were recorded between 216-279 ℃ and 232-285 ℃, respectively. The decomposition temperatures for 10% weight loss all occurred above 487 ℃ in nitrogen or air. The 6’ series showed low dielectric constants (2.71-3.54 at 1 MHz), low moisture absorption (0.18-0.66 wt%), light-colored, with an cutoff wavelength below 385 nm and low yellow index (b*) values of 7.3-14.8. Third, a series of poly(ether imide)s (PEIs) 6”a-h characterized by colorlessness, high transparency, high solubility, and good mechanical properties, were synthesized from the aromatic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)-2,5-di-tert-butylbenzene dianhydride (3”) and various aromatic diamines 4”a-h with pendent trifluoromethyl group via polyaddition, chemical imidization, and direct casted films. The PEI had inherent viscoseties in the range of 0.43-1.25 dL/g. The PEI of 6” series showed more colorless than the PIs of 2,2-bis(3,4-dicarboxyphenyl)hexa- fluoropropane dianhydride (6FDA)-derived 8” and 9” series, the latter being synthesized from the CF3-containing diamines with 6FDA. The films of 6” had cutoff wavelengths (λo) between 371 and 380 nm, as well as b* value (a yellowness index) ranging from 3.7 to 6.6. All of PEIs showed excellent solubility in organic solvents. They were soluble in N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, pyridine, tetrahydrofuran, even dichloromethane and chloroform at 5-10% wt/V. These PEI films showed tensile strengths of 100-116 MPa, elongations at break of 8-20%, initial moduli of 2.0-2.2 GPa. The softening temperatures and the glass transition temperatures of the 6” series were recorded between 219-284 ℃ and 230-305 ℃, respectively. The decomposition temperatures for 10% weight loss all occurred above 478℃. When compared with the corresponding nonfluorinated 7”, the 6” series showed better solubility and lighter color than the 7” series.