Synthesis and properties of new aromatic polyamides with redox-active 2,4-dimethoxytriphenylamine moieties Part A Polymer chemistry
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Abstract:
A new triphenylamine-based diamine monomer, 4,4′-diamino-2″,4″-dimethoxytriphenylamine (2), was synthesized from readily available reagents and was reacted with various aromatic dicarboxylic acids to produce a series of aromatic polyamides (4a-h) containing the redox-active 2,4-dimethoxy-substituted triphenylamine (dimethoxyTPA) unit. All the resulting polyamides were readily soluble in polar organic solvents and could be solution cast into tough and flexible films. These polymers exhibited good thermal stability with glass transition temperatures of 243-289 °C and softening temperatures of 238-280 °C, 10% weight loss temperatures in excess of 470 °C in nitrogen, and char yields higher than 60% at 800 °C in nitrogen. The redox behaviors of the polymers were examined using cyclic voltammetry (CV). All these polyamides showed two reversible oxidation processes in the first CV scan. The polymers also displayed low ionization potentials as a result of their dimethoxyTPA moieties. In addition, the polymers displayed excellent stability of electrochromic characteristics with coloration change from a colorless neutral state to green and blue-purple oxidized states. These anodically coloring polyamides showed high green coloration efficiency (CE = 329 cm²/C), high contrast of optical transmittance change (ΔT% = 84% at 829 nm), and long-term redox reversibility.Keywords:
Triphenylamine
Thermal Stability
Diphenylmethane
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A series of solution-processable near-infrared (NIR) electrochromic aromatic polyamides with N,N,N′,N′-tetraphenyl-p-phenylenediamine (TPPA) units in the backbone were prepared from the phosphorylation polyamidation reactions of a newly synthesized diamine monomer, N,N′-bis(4-aminophenyl)-N,N′-di(4-methoxylphenyl)-1,4-phenylenediamine, with various aromatic dicarboxylic acids. These polymers were readily soluble in many organic solvents and showed useful levels of thermal stability associated with high glass-transition temperatures (236−246 °C) and high char yields (higher than 58% at 800 °C in nitrogen). The polymer films showed reversible electrochemical oxidation with high contrast ratio both in the visible range and NIR region, which also exhibited high coloration efficiency (CE), low switching time, and the highest stability for long-term electrochromic operation to date. At the first oxidation stage, the polyamide Ib thin film revealed high coloration efficiency in visible (CE = 388 cm2/C) and NIR (CE = 330 cm2/C) region with reversible electroactive stability (over 10000 times within 0.4% loss relative to its initial injected charge). As the dication form of second oxidation stage, the polymer film still exhibited excellent electrochromic/electroactive stability (more than 3000 cyclic switches) with higher CE of 464 cm2/C.
Thermal Stability
Electrochromic devices
Triphenylamine
Dication
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Two series of polyamides and polyimides containing bulky trityl-substituted triphenylamine units were synthesized from condensation reactions of 4,4'-diamino-4''-trityltriphenylamine with various dicarboxylic acids and tetracarboxylic dianhydrides, respectively. The polymers showed good solubility and film-forming ability. Flexible or robust films could be readily obtained via solution-casting. The use of aliphatic diacid or dianhydride reduces interchain charge transfer complexing and leads to colorless polyamide and polyimide films. These polymers showed glass-transition temperatures in the range of 206⁻336 °C. Cyclic voltammograms of the polyamide and polyimide films displayed reversible electrochemical oxidation processes in the range of 0⁻1.0 or 0⁻1.3 V. Upon oxidation, the color of polymer films changes from colorless to blue-green or blue. As compared to the polyimide counterparts, the polyamides showed lower oxidation potentials and thus a higher electrochromic stability and coloration efficiency. Simple electrochromic devices were also fabricated as a preliminary investigation for electrochromic applications of the prepared polymers.
Triphenylamine
Electrochromic devices
Polyfluorene
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A series of organosoluble, aromatic polyamides were synthesized from a 4- methyl-substituted, triphenylamine-containing, aromatic diacid monomer, 4,4 0 -dicar- boxy-4 00 -methyltriphenylamine, which is a blue-light (454-nm) emitter with a fluorescence quantum efficiency of 46%. These triphenylamine-based, high-performance polymers had strong fluorescence emissions in the blue region with high quantum yields up to 64% and one reversible oxidation redox couple around 1.20 V versus Ag/AgCl in acetonitrile solu- tions. They exhibited good thermal stability, with 10% weight loss temperatures above 480 8C under a nitrogen atmosphere and with relatively high glass-transition tempera- tures (252-309 8C). All the polyamides revealed excellent stability of electrochromic char- acteristics, changing color from the original pale yellow to blue. V C 2006 Wiley Periodicals,
Triphenylamine
Thermal Stability
Chromophore
Quantum Efficiency
Quantum yield
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A series of electroactive aromatic polyamides with 4-(dimethylamino)triphenylamine [(NMe2)TPA] units in the backbone were prepared from a newly synthesized diamine monomer, 4,4′-diamino-4′′-(dimethylamino)triphenylamine, and various aromatic dicarboxylic acids via the phophorylation polyamidation reaction. These polyamides are readily soluble in many organic solvents and can be solution-cast into tough and amorphous films. They had useful levels of thermal stability associated with relatively high glass-transition temperatures (277–298 °C), 10% weight loss temperatures in excess of 500 °C, and char yields at 800 °C in nitrogen higher than 67%. 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 640 nm between the neutral state and the fully oxidized state is up to 88%, and the coloration efficiency is as high as ca. 261 cm2/C with high optical density change (δOD) up to 0.94. The polymers also displayed low ionization potentials as a result of their (NMe2)TPA moieties. Cyclic voltammograms of the polyamide films on the indium−tin oxide (ITO)-coated glass substrate exhibited a pair of reversible oxidation waves with very low onset potential of 0.35 V (vs Ag/AgCl) in acetonitrile solution.
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Thermal Stability
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Triphenylamine
Diphenylamine
Thermal Stability
Electrochromic devices
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A novel triphenylamine (TPA)-containing bis(ether anhydride) monomer, namely 4,4′-bis(3,4-dicarboxyphenoxy)triphenylamine dianhydride, was synthesized and reacted with various aromatic diamines leading to a series of new poly(ether-imide)s (PEI). Most of these PEIs were soluble in organic solvents and could be easily solution cast into flexible and strong films. The polymer films exhibited good thermal stability with glass-transition temperatures in the range 211–299 °C. The polymer films exhibited reversible electrochemical processes and stable color changes (from transparent to navy blue) with high coloration efficiency and contrast ratio upon electro-oxidation. During the electrochemical oxidation process, a crosslinked polymer structure was developed due to the coupling reaction between the TPA radical cation moieties in the polymer chains. These polymers can be used to fabricate electrochromic devices with high coloration efficiency, high redox stability, and fast response time. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 825–838
Triphenylamine
Imide
Thermal Stability
Electrochromic devices
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A series of novel polyamides with a pyrenylamine chromophore in the backbone were prepared from a newly synthesized diamine monomer, N,N-di(4-aminophenyl)-1-aminopyrene, and various dicarboxylic acids via the phosphorylation 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 °C and 10% weight loss temperatures in excess of 500 °C. 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 the yellow neutral state to a purple oxidized state and to an orange reduced state. The anodically electrochromic films had high coloration efficiency (up to 172 cm2 C−1 at 834 nm) and good redox stability, which still retained a high electroactivity after long-term redox cycles.
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Abstract Two novel series of ambipolar and near‐infrared electrochromic aromatic polyamides with electroactive anthraquinone group were synthesized from new aromatic diamines, 2‐(bis(4‐aminophenyl)amino)anthracene‐9,10‐dione and 2‐(4‐(bis(4‐aminophenyl)amino)phenoxy)anthracene‐9,10‐dione, respectively, via low‐temperature solution polycondensation reaction. These polymers were readily soluble in many polar solvents and showed useful levels of thermal stability associated with high glass‐transition temperatures ( T g ) (285–360 °C). Electrochemical studies of these electrochromic polyamides revealed ambipolar behavior with reversible redox couples and high contrast ratio both in the visible range and near‐infrared region. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012
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Anthraquinones
Sulfonium
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A series of solution-processable near-infrared (NIR) electrochromic aromatic polyamides with starburst triarylamine units in the backbone were prepared by the phosphorylation polyamidation from a newly synthesized diamine monomer, N,N-bis[4-(4-methoxyphenyl-4′-aminophenylamino)phenyl]-N′,N′-di(4-methoxyphenyl)-p-phenylenediamine, and two aromatic dicarboxylic acids. These polymers were highly soluble in many organic solvents and showed useful levels of thermal stability associated with high glass-transition temperatures and high char yields (higher than 66% at 800 °C in nitrogen). The polymer films showed reversible electrochemical oxidation and electrochromism with high contrast ratio both in the visible range and NIR region, which also exhibited high coloration efficiency (CE), low switching time, and relatively high stability for long-term electrochromic operation. At the first oxidation stage, the polyamide Ia thin film revealed high coloration efficiency in NIR (CE = 290 cm2/C) region with reversible electroactive stability (more than 10000 times within 0.6% loss relative to its initial injected charge). As the dication radical form of second oxidation stage, the polymer film still exhibited excellent electrochromic/electroactive stability (more than 10 000 cyclic switches) with enhanced CE of 339 cm2/C.
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Triphenylamine
Electrochromic devices
Thermal Stability
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Triphenylamine
Thermal Stability
Dicarboxylic acid
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