具有芳香氧取代基之三苯胺結構之芳香族聚醯胺及聚醯亞胺之合成與光電性質研究

SYNTHESIS AND OPTOELECTRONIC PROPERTIES OF AROMATIC POLYAMIDES AND POLYIMIDES WITH ARYLOXY-SUBSTITUTED TRIPHENYLAMINO GROUPS

曾怡潔(Yi-Chieh Tseng)

指導教授 ： 蕭勝輝

大同大學/工程學院/化學工程學系所/碩士(2006年)

摘要

第ㄧ部份 : 4-Chloronitrobenzene 與 4-phenylphenol進行芳香親核置換反應，再用鈀催化聯胺還原法合成出 4-(Biphenylyl-4-oxy)aniline。以氟化銫(CsF)為媒介將此苯胺與 4-fluoronitrobenzene 進行芳香族親核取代反應，隨後再進行dinitro中間體的還原反應，製得ㄧ種新型具有三苯胺結構的芳香族二胺單體4,4’-diamino-4”-(biphenylyl-4-oxy)triphenylamine。然後利用此二胺單體和ㄧ系列的芳香族二羧酸進行磷酸化直接聚縮合反應，製備一系列新型、具有對位聯苯氧基取代的三苯胺結構之芳香族聚醯胺。這些聚醯胺的固有黏度範圍在0.46~0.82 dL/g。由4,4’-oxydibenzoic acid 衍生的聚醯胺具有結晶性，且用溶液製得的薄膜會脆裂。其他的聚合物是無定型的，並可溶於極性有機溶劑中鑄成具可撓曲性且強韌的薄膜。這些聚合物的玻璃轉移溫度在230~251 ℃ 之間和軟化點溫度範圍在230~250 ℃ 之間，在氮氣下或空氣下的10 % 重量損失皆在488 ℃ 以上，在氮氣下加熱至800 ℃ 時的焦炭殘餘率超過61 %，顯示具有良好的熱安定性。此外，再利用上述製得的二胺單體和一系列芳香族二酐用二步驟熱烤或化學閉環法進行縮合反應得到一系列新型具有對位聯苯氧基取代之三苯胺結構的芳香族聚醯亞胺。其聚醯胺酸前驅物的固有黏度範圍在0.78~1.06 dL/g，所有的聚醯胺酸可以用熱烤法鑄成具可撓曲性及強韌的聚醯亞胺薄膜。大部分的聚醯亞胺都可溶解在如NMP、DMAc 和DMF的極性溶劑中。這些聚合物的玻璃轉移溫度在240~295 ℃ 之間，在氮氣或空氣下加熱到500 ℃ 之前都不會產生明顯的熱裂解，在氮氣下加熱到800 ℃ 時的焦炭殘餘率超過60 %。這些聚醯胺和聚醯亞胺溶於NMP的溶液分別在298~355 nm 以及 298~318 nm 之間具有強的UV-Vis吸收，它們在受到紫外光激發時會釋放藍光，最大放光波長範圍在381~473 nm 及　404~483 nm之間。這些聚合物塗佈在ITO玻璃上的薄膜的循環伏安 (CV) 圖皆顯示出ㄧ對可逆的氧化還原峰，施加電壓連續掃瞄數次，仍具有良好的電致變色特性，顏色從中性態的淺黃色變化成氧化態的綠色或藍色。
第二部份 : 4-Chloronitrobenzene 與 4-tert-butylphenol進行芳香親核置換反應，再用鈀催化聯胺還原合成出 4-amino-4’-tert-butyldiphenyl ether，然後利用氟化銫 (CsF) 為媒介將此化合物與 4-fluoronitrobenzene 進行芳香族親核取代反應，隨後再進行二硝化合物的還原反應，製得ㄧ種新型具有三苯胺結構的芳香族二胺單體4,4’-diamino-4”-(4-tert-bubylphenoxy)triphenylamine。此新合成的二胺單體和各種芳香族二羧酸及二酐聚合成兩系列新型具有對位含第三丁基取代之苯氧基及主鏈含三苯胺結構的芳香族聚醯胺和聚醯亞胺。大部分的聚合物可溶於如NMP及DMAc的強極性溶劑中，並可鑄成具可撓曲性及強韌的薄膜。這些聚合物的玻璃轉移溫度在247~308 ℃ 之間，聚醯胺可耐熱到450 ℃ 以上，聚醯亞胺在500 ℃ 之前不會產生明顯的熱裂解。聚醯胺溶於NMP的溶液的光激發光譜的最大放光波長在429~458 nm 之間，屬於藍光區。這些聚合物塗佈在ITO玻璃上的薄膜的循環伏安 (CV) 圖皆顯示出ㄧ對可逆的氧化還原峰，聚醯胺的半波氧化電位約在0.78-0.86 V附近，聚醯亞胺的半波氧化電位約在1.04-1.12 V之間。這些聚合物具有良好的電致變色特性，他們在中性態為淡黃色，在氧化態會呈現綠色或藍綠色。

關鍵字

三苯胺 ； 聚醯亞胺 ； 聚醯胺 ； 電致變色

並列摘要

Part 1 : 4-(Biphenylyl-4-oxy)aniline was synthesized by the nucleophilic chloro-displacement of 4-chloronitrobenzene with the potassium phenolate of 4-phenylphenol, followed by palladium-catalyzed hydrazine reduction. The cesium fluoride (CsF)-mediated N,N-diarylation of 4-(biphenyl-4-oxy)aniline with 4-fluoronitrobenzene and subsequent reduction of the dinitro intermediate led to a new triphenylamine-based diamine monomer, 4,4’-diamino-4”-(biphenylyl-4-oxy)triphenylamine. A series of novel aromatic polyamides containing biphenylyloxy-pendent triphenylamino moieties were synthesized by the direct phosphorylation polycondensation of the diamine with various aromatic dicarboxylic acids. The inherent viscosities of the resulting polyamides were in the range of 0.46~0.82 dL/g. The polyamide derived from 4,4’-oxydibenzoic acid was semicrystalline and formed a highly brittle film upon solution casting. The other polyamides were amorphous and organosoluble and could afford flexible and tough films via solution casting. These polyamides showed glass-transition temperatures between 230~251 oC and softening temperatures between 230~250 oC, 10% weight-loss temperatures in excess of 488 oC in nitrogen and air atmospheres, and char yields higher than 61% at 800 oC in nitrogen. Furthermore, a series of novel aromatic polyimides containing triphenylamine groups with biphenylyl-4-oxy para-substituent on the pendent phenyl ring were prepared from the diamine with various aromatic dianhydrides via a conventional two-step thermal or chemical imidization method. The poly(amic acid) precursors had inherent viscosity of 0.78~1.06 dL/g, and all of them could be cast and thermally converted into transparent, flexible, and tough polyimide films. Most of the polyimides were soluble in polar aprotic solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF). The glass-transition temperatures of these polyimides were recorded between 240~295 oC by differential scanning calorimetery. The polyimides showed no significant decomposition before 500 oC in air or nitrogen atmosphere and char yields higher than 60% at 800 °C in nitrogen. The solutions of the polyamides and polyimides in NMP exhibited strong UV-vis absorption bands at 298~355 nm and 298~318 nm, and they showed photoluminescence maximum at 381~473 nm and 404~483 nm in the blue region. Cyclic voltammetry curves of the polymer films on an indium-tin oxide (ITO)-coated glass substrate showed one pair of reversible redox peak. The polyamide and polyimide films revealed excellent stability of electrochromic characteristics by continuous several cyclic scans, with the color change from the pale yellowish neutral form to the green or blue oxidized form.
Part 2 : 4-Amino-4’-tert-butyldiphenyl ether was first synthesized by the nucleophilic chloro-displacement with the potassium phenolate of 4-tert-butylphenol, followed by palladium-catalyzed hydrazine reduction. A new triphenylamine-containing diamine monomer, 4,4’-diamino- 4”-(4-tert-butylphenoxy)triphenylamine, was synthesized by the cesium fluoride-assisted N,N-diarylation of 4-amino-4’-tert-butyldiphenyl ether with 4-fluoronitrobenzene, followed by the reduction of the nitro group. The newly synthesized diamine monomer was reacted with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides to produce two series of novel triphenylamine-based polyamides and polyimides with pendent tert-butylphenoxy substituents. Most of the polymers were readily soluble in polar organic solvents, such as NMP and DMAc, and could be solution cast into flexible and strong films. These polymers showed glass-transition temperatures between 247~308 oC and they were fairly stable up to a temperature above 450 oC (for polyamides) or 500 oC (for polyimides). The solutions of the polyamides in NMP emitted blue light with a photoluminescence maximum at 429-458 nm. Cyclic voltammetry of the polymer films on an ITO-coated glass substrate showed one pair of reversible redox peak with half-wave oxidation potentials (E1/2) in the range of 0.78-0.86 V (for polyamides) and 1.04-1.12 V (for polyimides) versus Ag/AgCl. The polyamide films revealed good electrochromic properties, with color change from the pale yellowish neutral from to the turquoise oxidized form.

並列關鍵字

triphenylamino ； polyamide ； polyimide ； electrochromic

參考文獻

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