| Summary: | 博士 === 大同大學 === 化學工程學系(所) === 99 === 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.
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