含三苯胺結構之芳香族高分子之合成與性質

SYNTHESIS AND PROPERTIES OF AROMATIC POLYMERS BEARING TRIPHENYLAMINE UNITS

陳建瑋(Chien-Wei Chen)

指導教授 ： 蕭勝輝 ； 楊金平 ； 郭文正 ； 劉貴生

大同大學/工程學院/化學工程學系所/碩士(2004年)

摘要

中文摘要

本論文包含三個研究主題，第一部分在描述含有diphenylamino 和 carbazolyl 基團之新穎芳香族之聚醯胺之合成與性質。兩種新型二胺
2,4-diaminotriphenylamine和 N(2,4-diaminophenyl)carbazole是由1-fluoro-2,4-dinitrobenzene 和 diphenylamine 或 carbazole進行CsF-芳香親核置換反應，生成二硝化合物後，再以聯胺和Pd/C催化還原反應而得到。含有diphenylamino 和 carbazolyl 基團之不定型和可溶性之
聚醯胺，藉由芳香族二羧酸和上述之二胺進行磷酸化聚縮合反應可製得
得。這些聚醯胺的基本性質，如固有黏度、分子量、成膜性、機械性質、結晶性與熱性質，和m-phenylenediamine所衍生之另一系列聚醯胺的合成與性質，在本研究中將加以比較探討。
本論文的第二部分描寫含有diphenylamino懸掛基團之新穎芳香族之聚醯胺醯亞胺之合成與性質。2,4-diaminotriphenylamine 和trimellitic anhydride以1：2等莫耳比例進行縮合反應，可合成出一種新型含有醯亞胺環芳香族二羧酸2,4-bis(N-trimellitoyl)triphenylamine。利用上述的二胺單體與多種單邊醯亞胺環與雙邊醯亞胺環之芳香族二羧酸或由新型2,4-bis(N-trimellitoyl)triphenylamine與多種芳香族二胺進行triphenylphosphite-活化劑聚縮合反應，可得到兩系列之聚醯胺醯亞胺，其固有黏度範圍為0.38-0.66 dL/g。所有的聚醯胺醯亞胺易溶於各式各樣的有機溶劑中，且可利用溶液鑄成強韌的薄膜。這些芳香族聚醯胺醯亞胺具有高的玻璃轉移溫度 (238-314 ℃) 和在氮氣或空氣中10 % 熱種損失之溫度皆在490 ℃，顯示具有良好的熱穩定性。
本論文的第三部分探討以4,4’-diamino-3”,5”-bis(trifluoromethyl) triphenylamine為主體之新穎含氟聚醯亞胺之合成與性質。一種新型之二胺4,4’-diamino-3”,5”-bis(trifluoromethyl)triphenylamine 是由3,5-bis(trifluoromethyl)aniline 和 p-fluoronitrobenzene進行CsF-芳香親核置換反應，生成二硝化合物後，再以Pd-C/聯胺催化還原反應而得到。新穎之聚醯亞胺，藉由上述之二胺與市售之芳香族二酐經由熱閉環法或化學閉環法可製得。所有的聚醯亞胺均可製成具撓曲性及強韌的薄膜。它們都具有適當的溶解性、極佳的抗拉性質和合理的介電常數 (3.46-3.86 at 10 kHz)。這些聚醯亞胺，在NMP溶劑中， UV/Vis吸收光譜波長介於311–318 nm 和光激發光光譜最大波長介於522–562 nm。這些聚醯亞胺的軟化溫度介於266-311 oC之間，它們在氮氣或空氣中，10 % 熱重損失皆在550 oC以上才會產生明顯的熱分解。為了性質比較，另一系列由4,4’-diaminotriphenylamine所衍生之聚醯亞胺的合成與性質在本研究中也將加以探討。

關鍵字

含氟聚醯亞胺 ； 三苯胺衍生物 ； 聚醯胺醯亞胺 ； 磷酸化聚縮合

並列摘要

ABSTRACT

This thesis consists of three parts. The first part deals with the syntheses and properties of novel aromatic polyamides bearing pendent diphenylamino or carbazolyl groups. Two new diamines, 2,4- diaminotriphenylamine and N-(2,4-diaminophenyl)carbazole, were synthesized via the cesium fluoride-mediated aromatic substitution reactions of 1-fluoro-2,4-dinitrobenzene with diphenylamine and carbazole, followed by palladium-on-charcoal-catalyzed hydrazine reduction. Amorphous and soluble polyamides having pendent diphenylamino and carbazolyl groups were prepared by the phosphorylation polycondensation of aromatic dicarboxylic acids with the prepared diamines. Basic properties of these polyamides, such as inherent viscosity, molecular weights, film-forming ability, mechanical properties, crystallinity, solubility, and thermal properties, are investigated and compared with those of parent polyamides derived from m-phenylenediamine and the same aromatic diacids.
The second part of this theses describes the synthesis and properties of novel poly(amide-imide)s having pendent diphenylamino groups. A new dicarboxylic acid, 2,4-bis(N-trimellitoyl)triphenylamine, bearing two preformed imide rings was synthesized from the condensation of 2,4-diaminotriphenylamine and trimellitic anhydride at 1 : 2 molar ratio. Two series of poly(amide imide)s with inherent viscosities of 0.38-0.66 dL/g were prepared by triphenylphosphite-activated polycondensation from the diamine monomer with various monoimide- and diimide-dicarboxylic acids or from 2,4-bis(N-trimellitoyl)triphenylamine with various aromatic diamines. All of the poly(amide imide)s were readily soluble in a variety of organic solvents and formed strong and tough films via solution casting. The wholly aromatic poly(amide imide)s have useful levels of thermal stability associated with moderately high glass transtion temperatures (238-314 ℃) and 10 % weight loss temperatures in excess of 490 ℃ in nitrogen or in air.
The third part of this thesis investigates the synthesis and properties of novel fluorinated polyimides on the basis of 4,4’-diamino-3”,5”- bis(trifluoromethyl)triphenylamine. A new trifluoromethyl-substituted monomer, 4,4’-diamino-3”,5”-bis(trifluoromethyl)triphenylamine, was prepared via the CsF-mediated aromatic substitution reactions of 3,5-bis(trifluoromethyl)aniline with p-fluoronitrobenzene, followed by Pd-C/hydrazine catalytic reduction. Novel polyimides were synthesized with the diamine and various commercially available aromatic dianhydrides by thermal or chemical imidization routes. All the polyimides could afford transparent, flexible, and strong films with favorable solubility, excellent tensile properties and reasonable dielectric constants of 3.46-3.86 at 10 kHz. These polyimides exhibited appreciate UV-Vis absorption bands at 311–318 nm in NMP solution. The photoluminescence spectra showed maximum bands around 522–562 nm. The softening temperatures of the polyimides were in the range 266-311 ℃, and the 10 % weight-loss temperatures were higher than 550 oC. For a comparative study, a series of analogous polyimides based on 4,4’-diaminotriphenylamine were also prepared and characterized.

並列關鍵字

Fluorinated polyimides ； Phosphorylation polycondensation ； poly(amide imide)s ； Triphenylamine derivatives

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