Syntheses and properties of novel fluorinated polyamides based on a bis(ether‐carboxylic acid) or a bis(ether amine) extended from bis(4‐hydroxyphenyl)phenyl‐2,2,2‐trifluoroethane

Two series of novel fluorinated aromatic polyamides were prepared from 1,1‐bis[4‐(4‐carboxyphenoxy)phenyl]‐1‐phenyl‐2,2,2‐trifluoroethane with various aromatic diamines or from 1,1‐bis[4‐(4‐aminophenoxy)phenyl]‐1‐phenyl‐2,2,2‐trifluoroethane with various aromatic dicarboxylic acids with the phosphorylation polyamidation technique. These polyamides had inherent viscosities ranging from 0.51 to 1.54 dL/g that corresponded to weight‐average and number‐average molecular weights (by gel permeation chromatography) of 36,200–80,000 and 17,200–64,300, respectively. All polymers were highly soluble in aprotic polar solvents, such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylacetamide, and some could even be dissolved in less‐polar solvents like tetrahydrofuran. The flexible and tough films cast from the polymer solutions possessed tensile strengths of 76–94 MPa and initial moduli of 1.70–2.22 GPa. Glass‐transition temperatures (T_g's) and softening temperatures of these polyamides were observed in the range of 185–268 °C by differential scanning calorimetry or thermomechanical analysis. Decomposition temperatures (T_d's) for 10% weight loss all occurred above 500 °C in both nitrogen and air atmospheres. Almost all the fluorinated polyamides displayed relatively higher T_g and T_d values than the corresponding nonfluorinated analogues. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 420–431, 2003     

Preparation and properties of new polyimides and polyamides based on 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)naphthalene

A novel, trifluoromethyl‐substituted, bis(ether amine) monomer, 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)naphthalene, was synthesized through the nucleophilic displacement of 2‐chloro‐5‐nitrobenzotrifluoride with 1,4‐dihydroxynaphthalene in the presence of potassium carbonate in dimethyl sulfoxide, followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of new fluorine‐containing polyimides with inherent viscosities of 0.57–0.91 dL/g were prepared by reacting the diamine with six commercially available aromatic dianhydrides via a conventional, two‐step thermal or chemical imidization method. Most of the resulting polyimides were soluble in strong polar solvents such as N‐methylpyrrolidone and N,N‐dimethylacetamide (DMAc). All the polyimides afforded transparent, flexible, and strong films with good tensile properties. These polyimides exhibited glass‐transition temperatures (T_g's) (by DSC) and softening temperatures (by thermomechanical analysis) in the ranges of 252–315 and 254–301 °C, respectively. Decomposition temperatures for 5% weight loss all occurred above 500 °C in both air and nitrogen atmospheres. The dielectric constants of these polyimides ranged from 3.03 to 3.71 at 1 MHz. In addition, a series of new, fluorinated polyamides with inherent viscosities of 0.32–0.62 dL/g were prepared by the direct polycondensation reaction the diamine with various aromatic dicarboxylic acids by means of triphenyl phosphite and pyridine. All the polyamides were soluble in polar solvents such as DMAc and could be solution‐cast into tough and flexible films. These polyamides had T_g's between 228 and 256 °C and 10% weight‐loss temperatures above 400 °C in nitrogen or air. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2377–2394, 2004     

Synthesis,photoluminescence, and electrochromism of novel aromatic poly(amine‐1,3,4‐oxadiazole)s bearing anthrylamine chromophores

Two novel poly(amine‐hydrazide)s were prepared from the polycondensation reactions of the dicarboxylic acid, 9‐[N,N‐di(4‐carboxyphenyl)amino]anthracene ( 1 ), with terephthalic dihydrazide ( TPH ) and isophthalic dihydrazide ( IPH ) via the Yamazaki phosphorylation reaction, respectively. The poly(amine‐hydrazide)s were readily soluble in many common organic solvents and could be solution cast into transparent films. Differential scanning calorimetry (DSC) indicated that these hydrazide polymers had glass‐transition temperatures (T_g) in the range of 182–230 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300–400 °C. The resulting poly(amine‐1,3,4‐oxadiazole)s had useful levels of thermal stability associated with high T_g (263–318 °C), 10% weight‐loss temperatures in excess of 500 °C, and char yield at 800 °C in nitrogen higher than 55%. These organo‐soluble anthrylamine‐based poly(amine‐hydrazide)s and poly (amine‐1,3,4‐oxadiazole)s exhibited maximum UV‐vis absorption at 346–349 and 379–388 nm in N‐methyl‐2‐pyrrolidone (NMP) solution, respectively. Their photoluminescence spectra in NMP solution showed maximum bands around 490–497 nm in the green region. The poly(amine‐hydrazide) I ‐ IPH showed a green photoluminescence at 490 nm with PL quantum yield of 29.9% and 17.0% in NMP solution and film state, respectively. The anthrylamine‐based poly(amine‐1,3,4‐oxadiazole)s revealed a electrochromic characteristics with changing color from the pale yellow neutral form to the red reduced form when scanning potentials negatively from 0.00 to ?2.20 V. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1584–1594, 2009     

Highly stable electrochromic polyamides based on N,N‐bis(4‐aminophenyl)‐N′,N′‐bis(4‐tert‐butylphenyl)‐1,4‐phenylenediamine

A new triphenylamine‐containing aromatic diamine monomer, N,N‐bis(4‐aminophenyl)‐N′,N′‐bis(4‐tert‐butylphenyl)‐1,4‐phenylenediamine, was synthesized by an established synthetic procedure from readily available reagents. A novel family of electroactive polyamides with di‐tert‐butyl‐substituted N,N,N′,N′‐tetraphenyl‐1,4‐phenylenediamine units were prepared via the phosphorylation polyamidation reactions of the newly synthesized diamine monomer with various aromatic or aliphatic dicarboxylic acids. All the polymers were amorphous with good solubility in many organic solvents, such as N‐methyl‐2‐pyrrolidinone (NMP) and N,N‐dimethylacetamide, and could be solution‐cast into tough and flexible polymer films. The polyamides derived from aromatic dicarboxylic acids had useful levels of thermal stability, with glass‐transition temperatures of 269–296 °C, 10% weight‐loss temperatures in excess of 544 °C, and char yields at 800 °C in nitrogen higher than 62%. The dilute solutions of these polyamides in NMP exhibited strong absorption bands centered at 316–342 nm and photoluminescence maxima around 362–465 nm in the violet‐blue region. The polyamides derived from aliphatic dicarboxylic acids were optically transparent in the visible region and fluoresced with a higher quantum yield compared with those derived from aromatic dicarboxylic acids. The hole‐transporting and electrochromic properties were examined by electrochemical and spectro‐electrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium‐tin oxide‐coated glass substrate exhibited two reversible oxidation redox couples at 0.57–0.60 V and 0.95–0.98 V versus Ag/AgCl in acetonitrile solution. The polyamide films revealed excellent elcterochemical and electrochromic stability, with a color change from a colorless or pale yellowish neutral form to green and blue oxidized forms at applied potentials ranging from 0.0 to 1.2 V. These anodically coloring polymeric materials showed interesting electrochromic properties, such as high coloration efficiency (CE = 216 cm²/C for the green coloring) and high contrast ratio of optical transmittance change (ΔT%) up to 64% at 424 nm and 59% at 983 nm for the green coloration, and 90% at 778 nm for the blue coloration. The electroactivity of the polymer remains intact even after cycling 500 times between its neutral and fully oxidized states. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2330–2343, 2009     

Synthesis and properties of new aromatic polyamides with redox‐active 2,4‐dimethoxytriphenylamine moieties

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. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3392–3401, 2010     

New electroactive and electrochromic aromatic polyamides with ether‐linked bis(triphenylamine) units

A new class of electroactive polyamides with ether‐linked bis(triphenylamine) [O(TPA)₂] units were prepared through the direct phosphorylation polycondensation from N,N‐di(4‐aminophenyl)‐N′,N′‐diphenyl‐4,4′‐oxydianiline and aromatic dicarboxylic acids. These polyamides were amorphous with good solubility in many organic solvents, such as NMP and DMAc, and could be solution‐cast into strong and flexible polymer films. Their decomposition temperatures (T_d) at a 10% weight‐loss in nitrogen and air were recorded at 556–568 °C and 537–555 °C, respectively. The glass‐transition temperatures (T_g) of all the polyamides were observed in the range of 218?253 °C by DSC. Cyclic voltammograms of the polyamide films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited two reversible oxidation redox couples at 0.80–0.82 V and 0.96–0.98 V versus Ag/AgCl in an electrolyte containing acetonitrile solution. The polyamide films showed excellent electrochemical and electrochromic stability, with a color change from a colorless or pale yellowish neutral form to green and purple oxidized forms at applied potentials ranging from 0 to 1.2 V. These polymers can also be used to fabricate electrochromic devices, and they showed high coloration efficiency, high redox stability, and fast response time. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 496–510     

Pyrenylamine‐functionalized aromatic polyamides as efficient blue‐emitters and multicolored electrochromic materials

A series of novel aromatic polyamides with pyrenylamine in the backbone were prepared from a newly synthesized dicarboxylic acid monomer, N,N‐di(4‐carboxyphenyl)‐1‐aminopyrene, and various aromatic diamines 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 276–342 °C and 10% weight loss temperatures in excess of 500 °C. The dilute N‐methyl‐2‐pyrrolidone (NMP) solutions of these polymers exhibited fluorescence maxima around 455–540 nm with quantum yields up to 56.9%. The polyamides also showed remarkable solvatochromism of the emission spectra. Their 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 4g containing the pyrenylamine units in both diacid and diamine sides exhibited easily accessible p‐ and n‐doped states, together with multicolored electrochromic behaviors. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and characterization of novel soluble triphenylamine‐containing aromatic polyamides based on N,N′‐bis(4‐aminophenyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine

A new triphenylamine‐containing aromatic diamine, N, N′‐bis(4‐aminophenyl)‐N, N′‐diphenyl‐1,4‐phenylenediamine, was prepared by the condensation of N,N′‐diphenyl‐1,4‐phenylenediamine with 4‐fluoronitrobenzene, followed by catalytic reduction. A series of novel aromatic polyamides with triphenylamine units were prepared from the diamine and various aromatic dicarboxylic acids or their diacid chlorides via the direct phosphorylation polycondensation or low‐temperature solution polycondensation. All the polyamides were amorphous and readily soluble in many organic solvents such as N, N‐dimethylacetamide and N‐methyl‐2‐pyrrolidone. These polymers could be solution cast into transparent, tough, and flexible films with good mechanical properties. They had useful levels of thermal stability associated with relatively high glass‐transition temperatures (257–287 °C), 10% weight‐loss temperatures in excess of 550 °C, and char yields at 800 °C in nitrogen higher than 72%. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2810–2818, 2002     

Green and rapid preparation of thermally stable and highly organosoluble polyamides containing L‐phenylalanine‐9,10‐dihydro‐9,10‐ethanoanthracene‐11,12‐dicarboximido moieties

A chiral diacid monomer containing L ‐phenylalanine‐9,10‐dihydro‐9,10‐ethanoanthracene‐11,12‐dicarboximido unit was successfully synthesized in four steps and used in the preparation of a series of novel optically active polyamides by direct polycondensation with diverse aromatic diamines using 1,3‐dipropylimidazolium bromide under microwave dielectric heating. Ionic liquids (ILs) efficiently absorb microwave energy and thus are employed as solvent. By controlling the concentration of 1,3‐dipropylimidazolium bromide, reaction time and power level, high yield and moderate inherent viscosity polymers could be achieved in a very short period of time. All the resulting polymers exhibited excellent solubility in various organic solvents. The polyamides were found to have inherent viscosities in the range of 0.54–0.85 dL g^?1. These polyamides had glass‐transition temperatures (T_g) above 180°C, and a 10% weight‐loss temperatures in excess of 340°C with char yield at 800°C in nitrogen higher than 40%. A comparative study on effects exerted by microwave technique with conventional method is also presented. Copyright © 2009 John Wiley & Sons, Ltd.     

Rigid‐rod polyamides and polyimides prepared from 4,3″‐diamino‐2′,6′‐di(2‐naphthyl)‐p‐terphenyl and 2′,6′,3‴,5‴‐tetra(2‐naphthyl)‐4,4″‐diamino‐p‐quinquephenyl

A series of rigid‐rod polyamides and polyimides containing p‐terphenyl or p‐quinquephenyl moieties in backbone as well as naphthyl pendent groups were synthesized from two new aromatic diamines. The polymers were characterized by inherent viscosity, elemental analysis, FT‐IR, ¹H‐NMR, ¹³C‐NMR, X‐ray, differential scanning calorimetry (DSC), thermomechanical analysis (TMA), thermal gravimetric analysis (TGA), isothermal gravimetric analysis, and moisture absorption. All polymers were amorphous and displayed T_g values at 304–337°C. Polyamides dissolved upon heating in polar aprotic solvents containing LiCl as well as CCl₃COOH, whereas polyimides were partially soluble in these solvents. No weight loss was observed up to 377–422°C in N₂ and 355–397°C in air. The anaerobic char yields were 57–69% at 800°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 15–24, 1999     

Synthesis and properties of new polyamides derived from 2,2‐bis[4‐[2‐(4‐aminophenoxy)ethoxy]phenyl]sulfone by direct polycondensation

A series of new polyamides containing both sulfone and oxyethylene moieties in the polymer chain was prepared by the direct polycondensation of the diamine monomer 2,2‐bis[4‐[2‐(4‐aminophenoxy)ethoxy]phenyl]sulfone (BAEPS) and various aromatic dicarboxylic acids in N‐methyl‐2‐pyrrolidinone (NMP) using triphenyl phosphite and pyridine as condensing agents. Polymers were produced with inherent viscosities of 0.30–0.60 dl/g and identified by elemental analysis, and infrared and nuclear magnetic resonance spectra. Most of the polymers were readily dissolved in polar solvents such as NMP, dimethylsulfoxide, N,N‐dimethylacetamide, N,N‐dimethylformamide and m‐cresol at room temperature. Polymers containing rigid and symmetric p‐phenylene, naphthalene and p‐biphenylene moieties revealed a crystalline nature and showed no solubility in organic solvents. These polyamides had 10% weight loss temperatures ranging between 423 and 465 °C in nitrogen atmosphere and glass transition temperatures between 170 and 305 °C. The polymers with crystallinity nature exhibited melting endotherms (T_m) below 386 °C in differential scanning calorimetry trace. Copyright © 1999 John Wiley & Sons, Ltd.     

Synthesis and properties of new soluble aromatic polyamides and polyimides on the basis of N,N′‐bis(3‐aminobenzoyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine

A new N‐phenylated amide (N‐phenylamide) unit containing aromatic diamine, N,N′‐bis(3‐aminobenzoyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine, was prepared by the condensation of N,N′‐diphenyl‐1,4‐phenylenediamine with 3‐nitrobenzoyl chloride, followed by catalytic reduction. Two series of organosoluble aromatic poly(N‐phenylamide‐imide)s and poly(N‐phenylamide‐amide)s with inherent viscosities of 0.58–0.82 and 0.56–1.21 dL/g were prepared by a conventional two‐stage method and the direct phosphorylation polycondensation, respectively, from the diamine with various aromatic dianhydrides and aromatic dicarboxylic acids. All polyimides and polyamides are amorphous and readily soluble in many organic solvents such as N,N‐dimethylacetamide and N‐methyl‐2‐pyrrolidone. These polymers could be solution cast into transparent, tough, and flexible films with high tensile strengths. These polyimides and polyamides had glass‐transition temperatures in the ranges of 230–258 and 196–229 °C, respectively. Decomposition temperatures of the polyimides for 10% weight loss all occurred above 500 °C in both nitrogen and air atmospheres. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2564–2574, 2002     

High Tg,ambipolar, and near‐infrared electrochromic anthraquinone‐based aramids with intervalence charge‐transfer behavior

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     

Fluorene‐rich high performance polyesters: Synthesis and characterization of 9,9‐fluorenylidene and 2,7‐fluorenylene‐based polyesters with excellent optical property

Polyesters PEs containing high content of fluorene units in their backbones were synthesized from 9,9‐diarene‐substituted fluorene diols ( 1 ) and fluorene‐based diacid chlorides ( 2 ) by high temperature polycondensation at 185 °C in diphenyl ether. The molecular weights of the polyesters PE1‐PE5 were in a range of M_w 25,000–165,000. The polyesters displayed their high thermostability: the glass transition temperatures (T_g) by differential scanning calorimetry analysis ranged from 109 to 217 °C, while the 10% weight loss temperatures (T_d10) measured by thermogravimetric analysis were over 400 °C in nitrogen and 395 °C in air. The polyesters had good solubility in most common organic solvents such as chloroform and toluene and gave tough, transparent and flexible cast films. The transmittance of the films was over 80% in the wavelength range from 450 to 700 nm in any PEs . The PEs exhibited high refractive index values around 1.65, while they had very low degree of birefringence. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2549–2556, 2008     

Novel aromatic polyamides and polyimides functionalized with 4‐tert‐butyltriphenylamine groups

A new triphenylamine‐containing diamine monomer, 4,4′‐diamino‐4″‐tert‐butyltriphenylamine, was successfully synthesized by the cesium fluoride‐mediated N,N‐diarylation of 4‐tert‐butylaniline with 4‐fluoronitrobenzene, followed by the reduction of the nitro group. The obtained diamine monomer was reacted with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides to produce two series of novel triphenylamine‐based polyamides and polyimides with pendent tert‐butyl substituents. Most of the polymers were readily soluble in polar organic solvents, such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylacetamide (DMAc), and could be solution cast into tough and flexible polymer films. These polymers showed high glass transition temperatures between 282 and 320 °C, and they were fairly stable up to a temperature above 450 °C (for polyamides) or 500 °C (for polyimides). These polymers exhibited UV absorption maxima around 308 to 361 nm. The photoluminescence spectra of the polyamides in DMAc exhibited a peak emission wavelength in the blue at 421–433 nm. Cyclic voltammograms of polyamides and polyimides showed an oxidation wave at 1.0–1.1 V versus Ag/AgCl in an acetonitrile solution. All the polyamides and polyimides exhibited excellent reversibility of electrochromic characteristics by continuous several cyclic scans between 0.0 and 1.1–1.3 V, with a color change from the original pale yellowish neutral form to the green or blue oxidized forms. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4579–4592, 2006     

Synthesis and characterization of new soluble cardo polyesters derived from 1,1‐bis‐[4‐(4‐chlorocarboxyphenoxy)phenyl]‐4‐tert‐butylcyclohexane with various bisphenols by solution polycondensation

A new cardo diacid chloride, 1,1‐bis‐[4‐(4‐chlorocarboxyphenoxy)phenyl]‐4‐tert‐butylcyclohexane ( 4 ), was synthesized from 1,1‐bis‐[4‐(4‐carboxyphenoxy)phenyl]‐4‐tert‐butylcyclohexane in refluxing thionyl chloride. Subsequently, various new polyesters were prepared from 4 with various bisphenols by solution polycondensation in nitrobenzene using pyridine as a hydrogen chloride quencher at 150 °C. These polyesters were produced with inherent viscosities of 0.32–0.50 dL · g^?1. Most of these polyesters exhibited excellent solubility in a variety of solvents such as N,N‐dimethylformamide, tetrahydrofuran, tetrachloroethane, dimethyl sulfoxide, N,N‐dimethylacetamide, N‐methyl‐2‐pyrrolidinone, m‐cresol, o‐chlorophenol, and chloroform. These polymers showed glass‐transition temperatures (T_g's) between 144 and 197 °C. The polymer containing the adamantane group exhibited the highest T_g value. The 10% weight loss temperatures of the polyesters, measured by thermogravimetric analysis, were found to be in the range of 426–451 °C in nitrogen. These cardo polyesters exhibited higher T_g's and better solubility than bisphenol A‐based polyesters. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2951–2956, 2001     

Novel aromatic polyamides containing 2‐diphenylamino‐(9,9‐dimethylamine) units as multicolored electrochromic and high‐contrast electrofluorescent materials

A series of electrochromic and photoluminescence‐active polyamides 4a‐4e were prepared from a novel dicarboxylic acid, N,N‐di(4‐carboxyphenyl)‐2‐amino‐9,9‐dimethylfluorene, and five diamines via a condensation polymerization. These polyamides were amorphous and readily soluble in many solvents. The glass transition temperatures were in the range of 281–339 °C and the 10% weight loss temperatures in nitrogen were in excess of 490 °C. The polyamides exhibited strong fluorescence in either solution or solid states. The polyamides 4a‐4d showed reversible electrochemical redox with color changing from colorless to grey‐green. Specially, the polyamide 4e with 2‐diphenylamino‐(9,9‐dimethylamine) group in both diamine and dicarboxylic acid residues exhibited multicolored electrochromic behaviors. Furthermore, the fluorescence of these polyamides could be reversibly electroswitched with a high contrast up to 221.4, enabling their potential applications in dual‐switching electrochromic/electrofluorescent materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 213–222     

Synthesis and characterization of new soluble aromatic polyamides based on 4‐(1‐adamantyl)‐1, 3‐bis(4‐aminophenoxy)benzene

A set of new aromatic polyamides were synthesized by the direct phosphorylation condensation of 4‐(1‐adamantyl)‐1,3‐bis‐(4‐aminophenoxy)benzene with various diacids. The polymers were produced with high yields and moderate to high inherent viscosities (0.43–1.03 dL/g), and the weight‐average molecular weights and number‐average molecular weights, determined by gel permeation chromatography, were in the range of 37,000–93,000 and 12,000–59,000, respectively. The polyamides were essentially amorphous and soluble in a variety of solvents such as N,N‐dimethylacetamide (DMAc), cyclohexanone, and tetrahydrofuran. They showed glass‐transition temperatures in the range of 240–300 °C (differential scanning calorimetry) and 10% weight‐loss temperatures over 450 °C, as revealed by thermogravimetric analysis in nitrogen. All the polymers gave strong films via casting from DMAc solutions, and these films exhibited good mechanical properties, with tensile strengths in the range of 77–92 MPa and tensile moduli between 1.5 and 2.5 GPa. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1014–1023, 2000     

Synthesis and characterization of new soluble aromatic polyamides derived from 1,4‐Bis(4‐carboxyphenoxy)‐2, 5‐di‐tert‐butylbenzene

Aromatic polyamides based on a novel bis(ether‐carboxylic acid) were synthesized by the direct phosphorylation condensation method. 1,4‐Bis(4‐carboxyphenoxy)‐2,5‐di‐tert‐butylbenzene was combined with various diamines containing flexible linkages and side substituents to render a set of eight novel aromatic polyamides. The polymers were produced with high yields and moderate to high inherent viscosities (0.49–1.32 dL/g) that corresponded to weight‐average and number‐average molecular weights (by gel permeation chromatography) of 31,000–80,000 and 19,000–50,000, respectively. Except for a single example, the polyamides were essentially amorphous and soluble in a variety of common solvents such as cyclohexanone, dioxane, and tetrahydrofuran. They showed glass‐transition temperatures of 250–295 °C (by differential scanning calorimetry) and 10% weight loss temperatures above 460 °C, as revealed by thermogravimetric analysis in nitrogen. Polymer films, obtained by casting from N,N‐dimethylacetamide solutions, exhibited good mechanical properties, with tensile strengths of 83–111 MPa and tensile moduli of 2.0–2.2 GPa. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 475–485, 2001     

Synthesis and properties of new soluble N-phenyl–substituted aromatic-aliphatic and all aromatic polyamides derived from 4,4′-dianilinobiphenyl

New N-phenylated aromatic-aliphatic and all aromatic polyamides were prepared by the high-temperature solution polycondensation of 4,4′-dianilinobiphenyl with both aliphatic (methylene chain lengths of 6–11) and aromatic dicarboxylic acid chlorides. All of the aromatic-aliphatic polyamides and the wholly aromatic polyamides exhibited an amorphous nature and good solubility in amide-type and chlorinated hydrocarbon solvents, except for those aromatic polyamides containing p-oriented phenylene or biphenylylene linkages in the backbone; the latter were crystalline and insoluble in organic solvents except m-cresol. The N-phenylated aromatic-aliphatic polyamides and aromatic polyamides had glass transition temperatures in the range of 79–116°C and 207–255°C, respectively, and all the polymers were thermally stable with decomposition temperatures above 400°C in air. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2193–2200, 1998