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URN etd-0809107-142648 Statistics This thesis had been viewed 2965 times. Download 901 times. Author Yi-Fen Huang Author's Email Address No Public. Department Chemical Engineering Year 2006 Semester 2 Degree Master Type of Document Master's Thesis Language English Page Count 132 Title Synthesis, Photoluminescence and Electrochromism of Novel
Aromatic Polymers with N-indolyltriphenylamine Moiety
Keyword Electrochromism Electrochromism Abstract This thesis consists of three parts. The first part deals with the syntheses and characterization of novel aromatic poly(amine amide)s and poly(amine imide)s bearing a N-indolyltriphenylamine unit on the main chian. A new triphenylamine-based diamine monomer, 4-(N-indolyl)-4’,4”-diaminotriphenylamine (4) was synthesized via the cesium fluoride-mediated N,N-diarylation of N-(4-aminophenyl)indole with 4-fluoronitrobenzene, followed by palladium-on-charcoal-catalyzed hydrazine reduction of the dinitro intermediate. Amorphous and organosoluble poly(amine-amide)s were prepared by the phosphorylation polyamidation of the newly synthesized diamine monomer (4) with various aromatic dicarboxylic acids. Poly(amine imide)s were prepared in conventional two-step method by the reaction of diamine 4 with various aromatic dianhydrides to form poly(amic acid)s, followed by thermal or chemical cyclodehydration. Basic properties of these poly(amine amide)s and poly(amine imide)s, such as inherent viscosity, molecular weights, film-forming ability, mechanical properties, crystallinity, solubility, thermal properties, optical and electrochemical properties were investigated and compared with those of parent poly(amine amide)s and poly(amine imide)s derived from 4,4’-diaminotriphenylamine with the same aromatic diacids and dianhydrides.
The second part of this thesis describes the synthesis and properties of novel poly(amine-amide)s on the basis of 4,4'-dicarboxy-4"-(N-indolyl)triphenylamine (7). The
new triphenylamine-containing dicarboxylic acid monomer 8, was synthesized via the double N-arylation of 4-fluoroaniline with N-(4-aminophenyl)indole, followed by alkaline hydrolysis of the dinitrile intermediate. A new family of poly(amine amide)s with inherent viscosities of 0.75-1.28 dL/g were prepared by the direct phosphorylation polycondensation from the diacid monomer 7 with various aromatic diamines. All of the poly(amine amide)s were readily soluble in a variety of organic solvents and formed strong and tough films via solution casting. The wholly aromatic poly(amine-amide)s have useful levels of thermal stability associated with moderately high glass transtion temperatures (254–305 ℃) and 10 % weight loss temperatures in excess of 516 ℃ in nitrogen. The photoluminescence (PL) spectra of these polymers in N-methyl-2-pyrrolidone (NMP) solution (10-5M) exhibited a strong emission in the blue region at 449-465 nm.
The final part of this thesis reports the synthesis and properties of novel N-indoly poly(amine-hydrazide)s and poly(amine-1,3,4-oxadiazole)s based on 4,4'-dicarboxy-4"-(N-indolyl)triphenylamin. Novel wholly aromatic poly(amine -hydrazide)s were synthesized via the Yamazaki phosphorylation reaction from the diacid and various commercially available aromatic dihydrazides, followed by thermal cyclodehydration to poly(amine-1,3,4-oxadiazole)s. All aromatic polymers exhibited strong UV-Vis absorption bands at 302-375 nm in NMP solution. The photoluminescence spectra showed maximum bands around 453-490 nm in the blue and green region. The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. For a comparative study, analogous poly(amine-hydrazide)s and poly(amine-1,3,4-oxadiazole)s based on 4,4’-dicarboxytriphenylamine were also prepared and characterized.
Advisor Committee Sheng-Huei Hsiao - advisor
none - co-chair
none - co-chair
Files Date of Defense 2007-07-24 Date of Submission 2007-08-09