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URN etd-0205107-194047 Statistics This thesis had been viewed 2764 times. Download 739 times. Author Chia-Sheng Chiang Author's Email Address No Public. Department Chemical Engineering Year 2006 Semester 1 Degree Master Type of Document Master's Thesis Language English Page Count 72 Title Synthesis, Electrochemistry and Photoluminescence of High-Performance Polymers Bearing Pyrrole-substituted Triphenylamino Groups Keyword Triphenylamine Pyrrole Photoluminescence Polyamide Polyamide Photoluminescence Pyrrole Triphenylamine Abstract This thesis consists of two parts. The first part describes the synthesis and properties of novel aromatic poly(amine-amide)s containing 4-(N-pyrrolyl)triphenylamine moieties. A new pyrrole-derived triphenylamine-containing dicarboxylic acid monomer, 4,4'-dicarboxy-4"-(N-pyrrolyl)triphenylamine, was synthesized via the aromatic nucleophilic fluoro-displacement reaction of 4-fluorobenzonitrile with 4-(N-pyrrolyl)aniline using sodium hydride as the base, followed by alkaline hydrolysis of the dinitrile intermediate. One series of poly(amine-amide)s with inherent viscosities of 0.52-0.88 dL/g were prepared by the direct phosphorylation polycondensation from the synthesized diacid monomer with various aromatic diamines. The resultant poly(amine-amide)s were readily soluble in a variety of organic solvents and could afford strong and tough films via solution casting. These aromatic poly(amine-amide)s have useful levels of thermal stability associated with high glass transtion temperatures (Tg＝275-326 ℃) and 10 % weight loss temperatures in excess of 450 ℃ in nitrogen. In dilute NMP solution, these polymers exhibited a medium to strong photoluminescence in the blue region at 446~455 nm with quantum yield up to 38 %.
The second part of this thesis investigates the synthesis and properties of novel poly(amine-hydrazide)s and poly(amine-1,3,4-oxadiazole)s containing pyrrolyl-substituted triphenylamine units. Two novel poly(amine-hydrazide)s were synthesized from 4,4'-dicarboxy-4"-(N-pyrrolyl)triphenylamine with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH) via the Yamazaki phosphorylation reation. The obtained poly(amine-hydrazide)s were easily soluble in polar organic solvents such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc) and could be solution-cast into free-standing or strong films. The poly(amine-hydrazide) derived from IPH exhibited strong blue photoluminescence at 478 nm in NMP with 33 % quantum yield. Differential scanning calorimetry (DSC) indicated that these two hydrazide polymers had Tg values of 252℃ (from TPH) and 235℃ (from IPH), respectively, and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300-400℃. The resulting poly(amine-1,3,4-oxadiazole)s exhibited Tg around 266-268℃, 10 % weight-loss temperature in excess of 543℃, and char yield at 800℃ in nitrogen higher than 70 %. In comparison with the parent triphenylamine-based analogs without the pyrrole pendent group, the newly synthesized poly(amine-amide)s and poly(amine-hydrazide)s containing the 4-(N-pyrrolyl)triphenylamine unit revealed a relatively decreased electrochemical stability.
Advisor Committee Sheng-Huei Hsiao - advisor
Guey-Sheng Liou - co-chair
Wen-Fu Lee - co-chair
Files Date of Defense 2007-01-26 Date of Submission 2007-02-05