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Title page for etd-0828108-162319


URN etd-0828108-162319 Statistics This thesis had been viewed 1506 times. Download 5 times.
Author Ying-Hsiu Hsiao
Author's Email Address No Public.
Department Chemical Engineering
Year 2007 Semester 2
Degree Master Type of Document Master's Thesis
Language English Page Count 137
Title Synthesis and Characterization of Polyamides and Polyimides with Main-chain Triphenylamine Units and Pendent Alkylamine Groups
Keyword
  • polyamine
  • polyimine
  • polyimine
  • polyamine
  • Abstract This thesis consists of two parts. The first part deals with the syntheses and characterization of novel aromatic poly(amine-amide)s and poly(amine-imide)s with 4-piperidinotriphenylamine [(Pi)TPA] units in the backbone from a newly synthesized diamine monomer, 4,4’-diamino-4”-piperidinotriphenylamine, which was synthesized via the cesium fluoride-mediated N,N-diarylation of 4-piperidinoaniline with 4-fluoronitrobenzene, followed by palladium-catalyzed hydrazine reduction of the intermediate dinitro compound. Amorphous and organosoluble poly(amine-amide)s were prepared by the phosphorylation polyamidation of the newly synthesized diamine monomer with various aromatic or aliphatic dicarboxylic acids. Poly(amine-imide)s were prepared from the diamine monomer with various aromatic dianhydrides via a conventional two-step procedure that included a ring-opening polyaddition to form poly(amic acid)s, followed by thermal or chemical cyclodehydration. All poly(amine-amide)s were readily soluble in polar organic solvents and could be solution cast into tough and flexible films. All the polymers showed high glass-transition temperatures (Tg) between 252-318 °C, and they were fairly stable up to a temperature above 400 °C [for poly(amine-amide)s] or 500 °C [for poly(amine-imide)s]. These polymers exhibited UV absorption maxima around 296-366 nm. The photoluminescence spectra of these polymers in N-methyl-2-pyrrolidone (NMP) solution (10-5 M) exhibited a blue light emission at 387-449 nm with a fluorescence quantum yield (ΦF) up to 3.57 %. The hole-transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the poly(amine-amide) films cast onto an indium-tin oxide (ITO) coated glass substrate exhibited two reversible oxidation redox couples at 0.44-0.49 and 0.80-0.88 V versus Ag/AgCl in acetonitrile solution. Most of these poly(amine-amide) films revealed excellent stability of electrochromic characteristics, with a color change from colorless or pale yellowish neutral form to green and blue oxidized forms at applied potentials ranging from 0.00 to 1.20 V. The polymer films showed reversible electrochemical oxidation accompanied by strong color changes with high coloration efficiency, high contrast ratio, and rapid switching time. The optical transmittance change (Δ%T) at 636 nm between the neutral state and the fully oxidized state is up to 83 %. The polymers also displayed low ionization potentials as a result of their (Pi)TPA moieties. Cyclic voltammograms of the poly(amine-amide) films on the indium-tin oxide (ITO)-coated glass substrate exhibited a pair of reversible oxidation waves with very low onset potential of 0.27 V (vs. Ag/AgCl) in acetonitrile solution.
    The second part deals with the syntheses and characterization of novel aromatic poly(amine-amide)s and poly(amine-imide)s with 4-morpholinotriphenylamine [(Mo)TPA] units in the backbone from another newly synthesized diamine monomer, 4,4’-diamino-4”-morpholinotriphenylamine, which was synthesized via the cesium fluoride-mediated N,N-diarylation of 4-morpholinoaniline with 4-fluoronitrobenzene, followed by palladium-catalyzed hydrazine reduction of the dinitro intermediate. All poly(amine-amide)s were readily soluble in polar organic solvents and could be solution cast into tough and flexible films. All the polymers showed high glass-transition temperatures (Tg) between 260-313 °C, and they were fairly stable up to a temperature above 450 °C [for poly(amine-amide)s] or 550 °C [for poly(amine-imide)s]. These polymers exhibited UV absorption maxima around 295-372 nm. The photoluminescence spectra of these polymers in N-methyl-2-pyrrolidone (NMP) solution (10-5 M) exhibited a blue light emission at 376-452 nm with a fluorescence quantum yield (ΦF) up to 4.85 %. The hole-transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the poly(amine-amide) films cast onto an indium-tin oxide (ITO) coated glass substrate exhibited two reversible oxidation redox couples at 0.50-0.56 and 0.87-0.93 V vs. Ag/AgCl in acetonitrile solution. Most of the poly(amine-amide) films revealed excellent stability of electrochromic characteristics, with a color change from colorless or pale yellowish neutral form to green and blue oxidized form at applied potentials ranging from 0.00 to 1.20 V. The polymer films showed reversible electrochemical oxidation accompanied by strong color changes with high coloration efficiency, high contrast ratio, and rapid switching time. The optical transmittance change (Δ%T) at 650 nm between the neutral state and the fully oxidized state is up to 90 %. The polymers also displayed low ionization potentials as a result of their (Mo)TPA moieties. Cyclic voltammograms of the poly(amine-amid)e films on the indium-tin oxide (ITO)-coated glass substrate exhibited a pair of reversible oxidation waves with very low onset potential of 0.36 V (vs. Ag/AgCl) in acetonitrile solution.
    Advisor Committee
  • Sheng-Huei Hsiao - advisor
  • Guey-Sheng Liou - co-chair
  • Kun-Li Wang - co-chair
  • Files indicate in-campus access at 3 years and off-campus not accessible
    Date of Defense 2008-07-22 Date of Submission 2008-08-29


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