磺化聚醯亞胺之質子交換膜的合成與性質研究

Synthesis and Properties of Sulfonated Polyimides as Proton Exchange Membranes

10.6841/NTUT.2014.00475

許元繼

磺化聚醯亞胺 ； 質子交換膜 ； sulfonated polyimide ； proton exchange membranes

臺北科技大學化學工程研究所學位論文

2014年

碩士

汪昆立

繁體中文

本實驗成功合成一系列聚醯亞胺共聚物，首先合成新型雙胺單體4,4'-(diphenylmethylene)bis(2,6-dimethylaniline) 後與各種二酐聚合成聚醯胺酸，並利用傳統化學閉環法進行脫水反應合成聚醯亞胺 ( PI )，再利用氯磺酸磺化聚醯亞胺 ( SPI )，並探討其熱性質、光電性質以及溶解性。 聚醯亞胺在氮氣下的玻璃轉移溫度 ( Tg ) 介於309~327℃之間；聚醯亞胺和磺化聚醯亞胺在氮氣下的5%重量損失分別在405 ~ 451℃和292~308℃，而10%重量損失498~514℃和339~360℃。固有黏度分別為0.31~0.48 dL/g和0.37~0.49 dL/g。在DMF/CHCl3 (1：1) 混合溶液中，於250~360 nm有UV-Vis吸收峰。電化學性質由循環伏安法 ( CV ) 所檢測，聚醯亞胺與磺化聚醯亞胺的HOMO與LUMO值可藉由氧化電位和吸收光譜的起始波長計算而得，聚醯亞胺的HOMO與LUMO值分別為 -7.06 eV ~ -6.79 eV與 -3.52 eV ~ -3.35 eV，而磺化聚醯亞胺為 -7.69 eV ~ -7.55 eV與 -4.16 eV ~ -4.11 eV。磺化聚醯亞胺的磺化率 ( DS ) 在43~61.5%間。

A series of novel polyimides were successfully synthesized. First, 4,4'-(diphenylmethylene)bis(2,6-dimethylaniline) was prepared and polymerized with various tetracarboxylic dianhydrides. The polyimides (PIs) were synthesized using chemical cyclodehydration reaction, then sulfonated with chlorosulfonic acid to obtain sulfonated polyimides (SPIs). The thermal properties, optical properties, electrochemical properties and solubility of the polymers were investigated and discussed. The glass transition temperatures of polyimides ranged from 309 to 327℃. Polyimides and sulfonated polyimides showed 5% weight loss temperatures under nitrogen at 405~451℃ and 292~308℃, respectively, and 10% weight loss temperatures at 498~514℃ and 339~360℃. The inherent viscosity of polyimides and sulfonated polyimides were 0.31~0.48 dL/g and 0.37~0.49 dL/g, respectively. The UV-Vis absorption spectrum of polyimides and sulfonated polyimides in DMF/CHCl3 (1:1) solution exhibits in the range of 250~360 nm. Electrochemical properties of polyimides and sulfonated polyimides were investigated by cyclic voltammetry. The energy levels of the HOMO and LUMO were calculated from the oxidation potentials and onset absorption wavelengths of the UV-Vis spectra. HOMO and LUMO values of polyimides obtained from -7.06 eV to -6.79 eV and -3.52 eV to -3.35 eV, respectively, and sulfonated polyimides showed in the range of -7.69 eV ~ -7.55 eV and -4.16 eV ~ -4.11 eV. Sulfonated polyimides has degree of sulfation (DS) values of 43~61.5%.