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Title page for etd-0215111-154153


URN etd-0215111-154153 Statistics This thesis had been viewed 2271 times. Download 367 times.
Author Yi-Chun Kung
Author's Email Address No Public.
Department Chemical Engineering
Year 2010 Semester 1
Degree Ph.D. Type of Document Doctoral Dissertation
Language English Page Count 343
Title SYNTHESIS AND OPTOELETRONIC PROPERTIES OF HIGH PERFORMANCE POLYMERS BEARING PYRENYLAMINE CHROMOPHORE
Keyword
  • electrochromic devices
  • electrochromism
  • fluorescene
  • pyrenylamine
  • polyimides
  • polyamides
  • High performacne polymes
  • High performacne polymes
  • polyamides
  • polyimides
  • pyrenylamine
  • fluorescene
  • electrochromism
  • electrochromic devices
  • Abstract This dissertation deals with the synthesis and characterization of two new
    pyrenylamine-containing monomers, named as N,N-di(4-aminophenyl)-1-aminopyrene
    and N,N-di(4-carboxyphenyl)-1-aminopyrene, and their derived high performance
    polymers that include polyamides, polyimides, polyhydrazides, and poly(1,3,4-
    oxadiazole)s. Optoelectronic properties such as absorption, photoluminescent,
    electrochemical, and electrochromic properties of these pyrenylamine-based polymers
    were investigated.
    First, a series of novel polyamides with diphenylpyrenylamine chromophore in the
    backbone were prepared from the newly synthesized diamine monomer,
    N,N-di(4-aminophenyl)-1-aminopyrene, and aromatic or aliphatic dicarboxylic acids via
    the phophorylation polyamidation technique. These polyamides were readily soluble in
    many organic solvents and could be solution-cast into tough and amorphous films. They
    had useful levels of thermal stability with glass-transition temperatures in the range of
    246-326 oC and 10 % weight loss temperatures in excess of 500 oC. The dilute NMP
    solutions of these polyamides exhibited fluorescence maxima around 522-544 nm with
    quantum yields up to 30.2%. These polyamides also showed remarkable fluorescence
    solvatochromism in various solvents. The polymer films showed reversible
    electrochemical oxidation and reduction accompanied by strong color changes from
    yellow neutral state to purple oxidized state and to orange reduced state. The anodically
    electrochromic films had high coloration efficiency (up to 172 cm2/C at 834 nm) and
    good redox stability, which still retained a high electroactivity after long-term redox
    cycles.
    Second, a new family of polyimides based on N,N-di(4-aminophenyl)-1-
    aminopyrene and aromatic or alicyclic tetracarboxylic dianhydrides were synthesized.
    These polyimides exhibited good solubility in many polar organic solvents and could
    afford robust films via solution casting. The polyimides derived from aromatic
    dianhydrides exhibited high thermal stability and high glass transition temperatures
    (333-364 oC). Cyclic voltammetry studies of the polymer films showed that these
    polyimides are both p and n dopable and have multicolored electrochromic states. For the
    polyimides derived from alicyclic dianhydrides, they revealed a strong blue-light
    emission with high fluorescence quantum yields (ΦFL > 45%) and a marked
    solvatochromic behavior.
    Thirdly, another series of novel polyamides with diphenylpyrenylamine segments in
    the backbone were prepared from the newly synthesized dicarboxylic acid monomer,
    N,N-di(4-carboxyphenyl)-1-aminopyrene, and various aromatic diamines via the
    phophorylation polyamidation technique. These polyamides were readily soluble in many
    organic solvents and could be solution-cast into tough and amorphous films. They had
    useful levels of thermal stability with glass-transition temperatures in the range of
    276-342 oC and 10 % weight loss temperatures in excess of 500 oC. The dilute NMP
    solutions of these polyamides exhibited fluorescence maxima around 455-540 nm with
    quantum yields up to 56.9%. These polyamides also showed remarkable fluorescence
    solvatochromism in various solvents. The polymer films showed reversible
    electrochemical oxidation and reduction accompanied by strong color changes from
    colorless neutral state to purple oxidized state and to yellow reduced state. The polyamide
    bearing diphenylpyrenylamino unit in both diacid and diamine components exhibited both
    p- and n-doping electrochemical processes, and showed a multicolored electrochromic
    behavior with color change from pale yellow neutral state to greenish gray then purplish
    gray fully oxidized state and to dark yellow semi-reduced state then reddish orange fully
    reduced state.
    Finally, two new polyhydrazides bearing redox-active diphenylpyrenylamine unit
    were prepared from the phosphorylation polycondensation reaction of N,N-di(4-carboxyphenyl)-
    1-aminopyrene with terephthalic dihydrazide and isophthalic dihydrazide,
    respectively. These two polyhydrazide prepolymers could be further thermally
    cyclodehydrated into the corresponding poly(1,3,4-oxadiazole)s in the solid state. The
    resulting poly(1,3,4-oxdiazole)s had high glass-transition temperatures and high thermal
    stability. The dilute solutions of all the hydrazide and oxadiazole polymers showed a
    medium to strong fluorescence in the blue to yellow region. Additionally, cyclic
    voltammetry studies of the oxadiazole polymers also showed reduction processes
    accompanied by strong color changes from pale yellow to orange, orange-red or deep
    blue due to the formation of radical anions of the oxadiazole and pyrene units.
    Advisor Committee
  • Sheng-Huei Hsiao - advisor
  • Ching-Hsuan Lin - co-chair
  • Eamor M. Woo - co-chair
  • Guey-Sheng Liou - co-chair
  • Jyh-Chien Chen - co-chair
  • Wen-Fu - co-chair
  • Yaw-Terng Chern - co-chair
  • Files indicate in-campus access at 1 years and off-campus access at 1 years
    Date of Defense 2011-01-28 Date of Submission 2011-02-15


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