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A new 2,7-bis(diphenylamino)naphthalene-based diamine monomer, N,N′-bis(4-aminophenyl)-N,N′-bis(4-methoxyphenyl)-2,7-naphthalenediamine, was synthesized and polymerized with various aromatic dicarboxylic acids via the phosphorylation polyamidation reaction leading to a new series of redox-active and electrochromic aromatic polyamides. The polyamides exhibited high solubility in many polar aprotic solvents, good film-forming ability, and high thermal stability. They also showed stable electrochemical stability and anodically green coloring when oxidized. The two arylamino centers showed a weak electronic interaction via the 2,7-naphthalenediyl bridge, and thus they started to oxidize almost at the same time. No intervalence charge transfer (IVCT) absorption was observed during the oxidation processes of these polyamides. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1409–1421

Two novel electropolymerizable monomers, namely 3,5-bis(4-diphenylaminobenzamido)-N-[4-(carbazol-9-yl)phenyl]benzamide (5) and 3,5-bis(4-diphenylaminobenzamido)-N-[4-(3,6-dimethoxycarbazol-9-yl)phenyl]benzamide (5-MeO), were synthesized, and their electrochemical properties were studied by cyclic voltammetry. The electron-withdrawing amide groups efficiently blocked the radical cations delocalization between the two terminal TPA groups, rendering the electropolymerization of the TPA groups feasible. The polymer electrodeposited from monomer 5 could be further crosslinked through electro-coupling of the carbazole groups, which showed both electrochromic and fluorescent properties (the emission of blue light (460 nm) in solid state). Both of the electro-generated polymer films derived from 5 and 5-MeO showed reversible electrochemical oxidation processes in the range of 0 − 1.4 V with strong color changes and high contrast ratios in the visible and NIR regions upon electro-oxidation. © 2016 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. 2016, 54, 2476–2485

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 (Td) at a 10% weight-loss in nitrogen and air were recorded at 556–568 °C and 537–555 °C, respectively. The glass-transition temperatures (Tg) 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

Three series of aromatic polyimides with 4-(carbazol-9-yl)triphenylamine moieties were prepared from the polycondensation reactions of 4,4′-diamino-4″-(carbazol-9-yl) triphenylamine (1), 4,4′-diamino-4″-(3,6-di-tert-butylcarbazol-9-yl)triphenylamine (t-Bu-1), and 4,4′-diamino-4″-(3,6-dimethoxycarbazol-9-yl)triphenylamine (MeO-1), respectively, with various commercially available tetracarboxylic dianhydrides. In addition to high thermal stability and good film-forming ability, the resulting polyimides exhibited an ambipolar electrochromic behavior. The polyimides based on t-Bu-1 and MeO-1 revealed higher redox-stability and enhanced electrochromic performance than the corresponding ones based on 1 because the active sites of their carbazole units are blocked with bulky t-butyl or electron-donating methoxy groups. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1172–1184

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

New series aromatic polyamides with (carbazol-9-yl)triphenylamine units were synthesized from a newly synthesized diamine monomer, 4,4′-diamino-4″-(3,6-dimethoxycarbazol-9-yl) triphenylamine, and aromatic dicarboxylic acids via the phosphorylation polyamidation technique. These polyamides exhibit good solubility in many organic solvents and can be solution-cast into flexible and strong films with high thermal stability. They show well-defined and reversible redox couples during oxidative scanning, with a strong color change from colorless neutral form to yellowish green and blue oxidized forms at applied potentials scanning from 0.0 to 1.3 V. They show enhanced redox-stability and electrochromic performance as compared to the corresponding analogs without methoxy substituents on the active sites of the carbazole unit. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 272–286

A series of electroactive polyetherimides (PEIs) with triphenylamine (TPA) units were prepared from the polycondensation reactions of 4,4′-bis(p-aminophenoxy)triphenylamine with aromatic tetracarboxylic dianhydrides via a conventional two-step technique. The PEIs showed high thermal stability, with glass-transition temperatures of 234–282 °C and decomposition temperatures in excess of 500 °C. They showed well-defined and reversible redox couples during both p- and n-doping processes, together with multielectrochromic behaviors. These polymers exhibited enhanced redox-stability and electrochromic performance as compared with the corresponding analogs without the phenoxy spacer between the TPA and imide units. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2925–2938

Two new aromatic poly(amide-hydrazide)s (PAHs)-bearing electroactive pyrenylamine units in the backbone were prepared from the phosphorylation polycondensation reactions of N,N-di(4-carboxyphenyl)-1-aminopyrene (1) with p-aminobenzoyl hydrazide (p-ABH) and m-aminobenzoyl hydrazide (m-ABH), respectively. The PAHs could be further cyclodehydrated into the corresponding poly(amide-1,3,4-oxadiazole)s in the range of 300–400 °C in the solid film state. All the hydrazide and oxadiazole polymers were soluble in many polar organic solvents and could afford flexible and strong films via solution casting. The poly(amide-1,3,4-oxdiazole)s had high glass-transition temperatures (294–309 °C) and high thermal stability (10% weight-loss temperature in excess of 520 °C). The dilute solutions of all the hydrazide and oxadiazole polymers showed strong fluorescence with emission maxima around 457–459 nm in the blue region. Copolymers obtained from the polycondensation of equimolar mixture of diacid 1 and 4,4′-oxydibenzoic acid with p-ABH or m-ABH exhibited a significantly increased fluorescence quantum efficiency in comparison with the homopolymers. Cyclic voltammetry results indicated that all the hydrazide and oxadiazole polymers exhibited an ambipolar (n- and p-doping processes) and electrochromic behavior. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.

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

Two new triptycene-containing bis(ether amine)s, 1,4-bis(4-aminophenoxy)triptycene (4) and 1,4-bis(4-amino-2-trifluoromethylphenoxy)triptycene (6), were synthesized, respectively, from the nucleophilic chloro-displacement reactions of p-chloronitrobenzene and 2-chloro-5-nitrobenzotrifluoride with 1,4-dihydroxytriptycene in the presence of potassium carbonate, followed by palladium-catalyzed hydrazine reduction of the dinitro intermediates. The bis(ether amine)s were polymerized with six commercially available aromatic tetracarboxylic dianhydrides to obtain two series of novel triptycene-based polyimides 8a―f and 9a―f by using a conventional two-step synthetic method via thermal and chemical imidizations. All the resulting polyimides exhibited high enough molecular weights to permit the casting of flexible and strong films with good mechanical properties. Incorporation of trifluoromethyl groups in the polyimide backbones improves their solubility and decreases their dielectric constants. The fluorinated polyimides 9d and 9f derived from diamine 6 with 4,4'-oxydiphthalic anhydride and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), respectively, could afford almost colorless thin films.

A series of novel polyimides based on N,N-di(4-ami- nophenyl)-1-aminopyrene and aromatic or alicyclic tetracarbox- ylic dianhydrides were synthesized. The polymers 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 � C). Cyclic vol- tammetry studies of the polymer films showed that these poly- imides 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 (UPL > 45%) and a marked solvatochromic behavior. V C 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2210-2221, 2011

A new bis(triphenylamine)-type dicarboxylic acid monomer, N,N-bis(4-carboxyphenyl)-N′,N′-bis(4-tert-butylphenyl)-1,4-phenylenediamine, was prepared by a well-established procedure and led to a new family of redox-active aromatic polyamides with di-tert-butyl-substituted N,N,N′,N′-tetraphenylphenylenediamine (TPPA) segments. The resulting polyamides were amorphous with good solubility in many organic solvents, and most of them could be solution cast into flexible polymer films. The polyamides exhibited high thermal stability with glass-transition temperatures in the range of 247–293 °C and 10% weight-loss temperatures in excess of 500 °C. They showed well-defined and reversible redox couples during oxidative scanning, with a strong color change from a colorless or pale yellowish neutral form to green and blue oxidized forms. They had enhanced redox stability and electrochromic performance when compared with the corresponding analogs without tert-butyl substituents on the TPPA unit. The polyamide with TPPA units in both the diacid and diamine components shows multicolored electrochromic behavior. A polyamide containing both the cathodic coloring anthraquinone chromophore and the anodic coloring TPPA chromophore has the ability to show red, green, and blue states, toward single-component RGB electrochromics. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

A new carbazole-derived, triphenylamine (TPA)- containing aromatic dicarboxylic acid monomer, 4,4 0 -dicar- boxy-4 00 -(3,6-di-tert-butylcarbazol-9-yl)TPA, was synthesized, and it led to a series of electroactive aromatic polyamides with main-chain TPA and pendent 3,6-bis(tert-butyl)carbazole units by reacting it with various aromatic diamines via the phosphorylation polyamidation technique. The polyamides were amorphous with good solubility in many organic sol- vents and could be solution-cast into flexible and strong films. They showed high glass-transition temperatures (282- 335 � C) and high thermal stability (10% weight loss tempera- tures >480 � C). The electroactive polymer films had

A new triphenylamine-based aromatic dicarboxylic acid monomer, 4-tert-butyl-4 0 ,4 00 -dicarboxytriphenylamine (2), was synthesized from the cesium fluoride mediated N,N-diary- lation reaction of 4-tert-butylaniline with 4-fluorobenzonitrile and subsequent alkaline hydrolysis of the dinitrile intermedi- ate. A series of six aromatic polyamides 4a-4f with tert-butyltri- phenylamine groups was prepared from the newly synthesized dicarboxylic acid and various aromatic diamines. These polya- mides were readily soluble in many organic solvents and could be solution-cast into flexible and strong films. The glass-transi- tion temperatures of these polymers were in the range of 274- 311 � C. These polymers exhibited strong UV-vis absorption bands at 356-366 nm in NMP solution. Their photolumines- cence spectra showed maximum bands around 433-466 nm in the blue region. Cyclic voltammograms of all the polyamides exhibited reversible oxidation redox couples in acetonitrile. The polyamide 4f, with tert-butyltriphenylamine segment in both diacid and diamine residues, exhibited stable electrochro- mic characteristics with a color change from a colorless neutral form, through a green semioxidized form, to a deep purple fully oxidized form. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2798-2809, 2010

A new triphenylamine-based diamine monomer, 4,4 0 -diamino-2 00 ,4 00 -dimethoxytriphenylamine (2), was synthesized from readily available reagents and was reacted with various aro- matic dicarboxylic acids to produce a series of aromatic poly- amides (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 poly- mers exhibited good thermal stability with glass transition temper- atures 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 behav

A new triphenylamine-containing aromatic diamine monomer, N,N-bis (4-aminophenyl)-N 0 ,N 0 -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 0 ,N 0 -tetraphenyl-1,4- phenylenediamine units were prepared via the phosphorylation polyamidation reac- tions 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-dimethylaceta- mide, 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 voltam- mograms 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 elcterochemi- cal 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 ¼ 216 cm 2 /C for the green coloring) and high contrast ratio of optical transmittance change (DT%) 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

A novel structurally asymmetric bis(ether amine) monomer containing trifluoromethyl groups, 1,7-bis(4-amino-2-trifluoromethylphenoxy)naphthalene, was prepared through the nucleophilic substitution reaction of 2-chloro-5-nitrobenzotrifluoride and 1,7-dihydroxynaphthalene in the presence of potassium carbonate in N-methyl-2-pyrrolidone (NMP), followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of new fluorine-containing polyimides were synthesized from the diamine with various commercially available aromatic tetracarboxylic dianhydrides using a two-stage process with thermal or chemical imidization method. The intermediate poly(amic acid)s had inherent viscosities between 0.93 and 1.93 dL/g. Most of the polyimides obtained from both routes were readily soluble in many organic solvents such as NMP and N,N-dimethylacetamide (DMAc). All the polyimides could afford transparent, flexible, and strong films with low moisture absorptions of 0.29-0.69%, low dielectric constants of 2.81-3.23 at 10 kHz, and an ultraviolet-visible absorption cutoff wavelength at 358-423 nm. The glass-transition temperatures (Tgs) (by DSC) and softening temperatures (by thermomechanical analysis) of the polyimides were recorded in the range of 222-271 °C and 210-266 °C, respectively. Decomposition temperatures for 10% weight loss all occurred above 500 °C in both nitrogen and air atmospheres. For a comparative study, some properties of the present polyimides will be compared with those of structurally related ones derived from 1,7-bis(4-aminophenoxy)naphthalene and 1,5-bis(4-amino-2-trifluoromethylphenoxy)naphthalene.

A novel adamantoxytriphenylamine-containing diamine monomer, 4-(1- adamantoxy)-4 0 ,4 00 -diaminotriphenylamine, was synthesized from readily available reagents. Two series of novel electroactive aromatic polyamides and polyimides with bulky 4-(1-adamantoxy)triphenylamine moieties were prepared from the newly syn- thesized diamine monomer with various aromatic dicarboxylic acids and tetracarbox- ylic dianhydrides, respectively. All the resulting polyamides and most of the poly- imides were readily soluble in polar organic solvents and could be solution cast into tough and flexible films. These polymers showed moderate to high glass transition temperatures in the range of 263-311 � C, and they were fairly stable up to a temper- ature above 480 � C (for polyamides) or 500 � C (for polyimides). Cyclic voltammo- grams of the polyamides and polyimides showed one pair of reversible redox waves with oxidation half-wave potentials (E1/2) in the range of 0.78-0.81 and 0.97-1.05 V, respectively, versus Ag/AgCl in an acetonitrile solution. In addition, the polymers were found to display stable electrochromic properties by repeated cyclic scans between 0.0 and 1.1-1.2 V, with coloration change from a colorless or pale yellowish neutral form to a dark blue or bluish green oxidized form. V C 2009 Wiley Periodicals, Inc.

A series of novel aromatic polyarylates with triphenylamine units in the main chain and as the pendent group were prepared from the dicarboxylic acid mono- mer, N,N-bis(4-carboxyphenyl)-N 0 ,N 0 -diphenyl-1,4-phenylenediamine (1), and various bisphenols. These polyarylates were amorphous and readily soluble in common organic solvents. They had excellent levels of thermal stability associated with mod- erately high Tg values (182-263 8C). These polymers exhibited strong UV-vis absorp- tion bands at 357-360 nm in toluene solution and the photoluminescence spectra showed maximum bands around 493-503 nm in the green region. The hole-transport- ing and electrochromic properties were examined by electrochemical and spectro- electrochemical methods. Cyclic voltammograms of the polyarylates exhibited two reversible oxidation redox couples in acetonitrile solution at Eonset 0.77-0.79 V and 1.12-1.14 V, respectively. The typical polymer 3b film revealed good stability of electrochromic characteristics, with color change from colorless to green and blue at applied potentials ranging from 0.00 to 1.24 V. These anodically polymeric electrochromic materials not only showed excellent reversible electrochromic stability with good green coloration efficiency (CE ¼ 159 cm 2 /C) and blue coloration efficiency (CE ¼ 154 cm 2 /C) but also exhibited high contrast of optical transmittance change (DT%), 54% in 895 nm for green color and up to 84% in 595 nm for blue color. After over 100 cyclic switches, the polymer films still exhibited excellent stability of electro- chromic characteristics. V

Two series of novel fluorinated poly(ether imide)s (coded IIIA and IIIB) were prepared from 2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride and 2,7-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride, respectively, with various trifluoromethyl-substituted aromatic bis(ether amine)s by a standard two-step process with thermal or chemical imidization of the poly(amic acid) precursors. These fluorinated poly(ether imide)s showed good solubility in many organic solvents and could be solution-cast into transparent, flexible, and tough films. These films were nearly colorless, with an ultraviolet–visible absorption edge of 364–386 nm. They also showed good thermal stability with glass-transition temperatures of 221–298 °C, 10% weight loss temperatures in excess of 489 °C, and char yields at 800 °C in nitrogen greater than 50%. The 2,7-substituted IIIB series also showed better solubility and higher transparency than the isomeric 2,6-substituted IIIA series. In comparison with nonfluorinated poly (ether imide)s, the fluorinated IIIA and IIIB series showed better solubility, higher transparency, and lower dielectric constants and water absorption. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5909–5922, 2006

A new triphenylamine-containing diamine monomer, 4,4 0 -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 reduc- tion of the nitro group. The obtained diamine monomer was reacted with various aro- matic 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 tempera- tures between 282 and 320 8C, and they were fairly stable up to a temperature above 450 8C (for polyamides) or 500 8C (for polyimides). These polymers exhibited UV absorp- tion 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 vol- tammograms of polyamides and polyimides showed an oxidation wave at 1.0-1.1 V ver- sus 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. V C 2006 Wiley Periodicals, Inc. J Polym Sci

Two new phenyl- and naphthyl-substituted rigid-rod aromatic dicarboxylic acid monomers, 2,2 0 -diphenylbiphenyl-4,4 0 -dicarboxylic acid (4) and 2,2 0 -di(1-naphthyl)- biphenyl-4,4 0 -dicarboxylic acid (5), were synthesized by the Suzuki coupling reaction of 2,2 0 -diiodobiphenyl-4,4 0 -dicarboxylic acid dimethyl ester with benzeneboronic acid and naphthaleneboronic acid, respectively, followed by alkaline hydrolysis of the ester groups. Four new polyhydrazides were prepared from the dicarboxylic acids 4 and 5 with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH), respectively, via the Yamazaki phosphorylation reaction. These polyhydrazides were amorphous and readily soluble in many organic solvents. Differential scanning calorimetry (DSC) indi- cated that these hydrazide polymers had glass transition temperatures in the range of 187-234 8C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300-400 8C. The resulting poly(1,3,4-oxadiazole)s exhibited Tg's in the range of 252-283 8C, 10% weight-loss temperature in excess of 470 8C, and char yield at 800 8C in nitrogen higher than 54%. These organo-soluble polyhydrazides and poly(1,3,4-oxadiazole)s exhibited UV-Vis absorption maximum at 262-296 and 264-342 nm in NMP solution, and their photoluminescence spectra showed maximum bands around 414-445 and 404-453 nm, respectively, with quantum yield up to 38%. The electron-transporting properties were examined by electrochemical methods. Cyclic voltammograms of the poly(1,3,4-oxadiazole) films cast onto an indium-tin oxide (ITO)-coated glass substrate exhibited reversible reduction redox with Eonset at � 1.37 to � 1.57 V versus Ag/AgCl in dry N,N-dimethylformamide solution. V C 2006 Wiley Periodicals

A series of novel aromatic poly(ether imide)s (PEI) containing ortho-catenated phenylene rings and pendant trifluoromethyl group have been prepared from 1,2-bis(3,4-dicarboxyphenoxy)benzene dianhydride (1) with seven trifluoromethyl-substituted aromatic bis(ether amine)s (2a-g) via a conventional two-stage process that included ring-opening polyaddition to form the poly(amic acid)s followed by chemical imidization to the polyimides. These PEIs had inherent viscosities in the range of 0.45–1.17 dL/g that corresponded to weight–average and number–average molecular weights (by gel-permeation chromatography) of 42,000–102,000 and 28,500–67,500, respectively. All the PEIs were readily soluble in many organic solvents and could be solution-cast into transparent, flexible, and strong films. These films were essentially colorless; they had a very low yellowness index of 4.34–6.55 and an UV–vis absorption cut-off wavelength at 361–370 nm. The PEIs exhibited moderate-to-high glass-transition temperatures (Tg) in the range of 185–270 °C, softening temperatures (Ts) in the range of 184–275 °C, and 10% weight loss temperatures higher than 466 °C in nitrogen or in air. They also showed low moisture absorptions of 0.49–0.70% and low dielectric constants of 2.78–3.26 (measured at 10 kHz). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3092–3102, 2006

We describe the preparation, characterization, and luminescence of four novel electrochromic aromatic poly(amine hydrazide)s containing main-chain triphenylamine units with or without a para-substituted N,N-diphenylamino group on the pendent phenyl ring. These polymers were prepared from either 4,4′-dicarboxy-4″-N,N-diphenylaminotriphenylamine or 4,4′-dicarboxytriphenylamine and the respective aromatic dihydrazide monomers via a direct phosphorylation polycondensation reaction. All the poly(amine hydrazide)s were amorphous and readily soluble in many common organic solvents and could be solution-cast into transparent and flexible films with good mechanical properties. These poly(amine hydrazide)s exhibited strong ultraviolet–visible absorption bands at 346–348 nm in N-methyl-2-pyrrolidone (NMP) solutions. Their photoluminescence spectra in NMP solutions or as cast films showed maximum bands around 508–544 and 448–487 nm in the green and blue region for the two series of polymers. The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. All obtained poly(amine hydrazide)s and poly(amine-1,3,4-oxadiazole)s exhibited two reversible oxidation redox couples at 0.8 and 1.24 V vs. Ag/AgCl in acetonitrile solution and revealed excellent stability of electrochromic characteristics, changing color from original pale yellow to green and then to blue at electrode potentials of 0.87 and 1.24 V, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3245–3256, 2005

We report the preparation and characterization of a series of novel electro- chromic, aromatic poly(amine amide)s with pendent triphenylamine units. The synthe- sis proceeded via direct phosphorylation polycondensation between a novel diamine, N,N-bis(4-aminophenyl)-N,N-diphenyl-1,4-phenylenediamine, and various aromatic dicarboxylic acids. All the poly(amine amide)s were amorphous and readily soluble in many common organic solvents and could be solution-cast into transparent, tough, and flexible films with good mechanical properties. They exhibited good thermal stability and 10% weight-loss temperatures above 540 °C. Their glass-transition temperatures were 263-290 °C. These polymers in N-methyl-2-pyrrolidinone solutions exhibited strong ultraviolet-visible absorption peaks at 307-358 nm and photoluminescence peaks around 532-590 nm in the green region. The hole-transporting and electrochro- mic properties were studied with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of poly(amine amide) films prepared by the casting of polymer solutions onto an indium tin oxide coated glass substrate exhibited two reversible oxidation redox couples at 0.65 and 1.03 V versus Ag/AgCl in an acetonitrile solution. All the poly(amine amide)s showed excellent stability with respect to their electrochro- mic characteristics; the color of the films changed from pale yellow to green and then blue at 0.85 and 1.25 V, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2085-2098, 2005

A new fluorinated diamine monomer, 2′,5′-bis(4-amino-2-trifluoromethylphenoxy)-p-terphenyl, was synthesized from the chloro-displacement of 2-chloro-5-nitrobenzotrifluoride with the potassium phenolate of 2,5-diphenylhydroquinone, followed by hydrazine palladium-catalyzed reduction. A series of trifluoromethyl-substituted polyimides containing flexible ether linkages and laterally attached side rods were synthesized from the diamine with various aromatic dianhydrides via a conventional two-step process. The inherent viscosities of the poly(amic acid) precursors were 0.84–1.26 dL/g. All the polyimides afforded flexible and tough films. The use of 4,4′-oxydiphthalic anhydride and 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride produced essentially colorless polyimide films. Most of the polyimides revealed an excellent solubility in many organic solvents. The glass-transition temperatures of these polyimides were recorded between 254 and 299 °C by differential scanning calorimetry, and the softening temperatures of the polymer films stayed in the range of 253–300 °C according to thermomechanical analysis. The polyimides did not show significant decomposition before 500 °C in air or under nitrogen. These polyimides also showed low dielectric constants (2.83–3.34 at 1 MHz) and low moisture absorption (0.4–2.2%). For a comparative study, a series of analogous polyimides based on the nonfluorinated diamine 2′,5′-bis(4-aminophenoxy)-p-terphenyl were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1255–1271, 2004

A novel bis(ether anhydride) monomer, 2′,5′-bis(3,4-dicarboxyphenoxy)-p-terphenyl dianhydride, was synthesized from the nitro displacement of 4-nitrophthalonitrile by the phenoxide ion of 2′,5′-dihydroxy-p-terphenyl, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and cyclodehydration of the resulting bis(ether diacid). A series of new poly(ether imide)s bearing laterally attached p-terphenyl groups were prepared from the bis(ether anhydride) with various aromatic diamines via a conventional two-stage process that included ring-opening polyaddition to form the poly(amic acid)s followed by thermal or chemical imidization to the poly(ether imide)s. The inherent viscosities of the poly(amic acid) precursors were in the range of 0.62–1.26 dL/g. Most of the poly(ether imide)s obtained from both routes were soluble in polar organic solvents, such as N,N-dimethylacetamide. All the poly(ether imide)s could afford transparent, flexible, and strong films with high tensile strengths. The glass-transition temperatures of these poly(ether imide)s were recorded as between 214 and 276 °C by DSC. The softening temperatures of all the poly(ether imide) films stayed in the 207–265 °C range according to thermomechanical analysis. For all the polymers significant decomposition did not occur below 500 °C in nitrogen or air atmosphere. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1008–1017, 2004

A new ether-bridged aromatic dicarboxylic acid, 2',5'-bis(4-carboxyphenoxyl-p-terphenyl (3), was synthesized by the aromatic fluoro-displacement reaction of p-fluorobenzonitrile with 2',5'-dihydroxy-p-terphenyl in the presence of potassium carbonate, followed by alkaline hydrolysis. A set of new aromatic polyamides containing ether and laterally attached p-terphenyl units was synthesized by the direct phosphorylation polycondensation of diacid 3 with various aromatic diamines. The polymers were produced with high yields and moderately high inherent viscosities (0.44-0.79 dL/g). The polyamides derived from 3 and rigid diamines, such as p-phenylenediamine and benzidine, and a structurally analogous diamine, 2',5'-bis(4-aminophenoxy)-p-terphenyl, were semicrystalline and insoluble in organic solvents. The other polyamides were amorphous and organosoluble and could afford flexible and tough films via solution casting. These films exhibited good mechanical properties, with tensile strengths of 91-108 MPa, elongations to break of 6-17%, and initial moduli of 1.95-2.43 GPa. These polyamides showed glass-transition temperatures between 193 and 252 °C. Most of the polymers did not show significant weight loss before 450 °C, as revealed by thermogravimetric analysis in nitrogen or in air.

A new aromatic asymmetrical ether diamine, 5-(4-aminophenoxy)-1-naphthylamine, was synthesized through the nucleophilic displacement of 4-chloronitrobenzene with the potassium phenolate of 5-amino-1-naphthol in dimethylformamide, followed by hydrazine palladium-catalyzed reduction. A series of novel aromatic polyimides containing asymmetrical diaryl ether segments were prepared from the diamine with various aromatic dianhydrides via a conventional two-step thermal or chemical imidization method. The poly(amic acid) precursors had inherent viscosities of 1.21–1.99 dL/g, and all of them could be cast and thermally converted into transparent, flexible, and tough polyimide films. The polyimides derived from less stiff dianhydrides generally displayed higher solubility. The glass-transition temperatures of these polyimides were recorded between 307 and 336 °C by differential scanning calorimetry, and the softening temperatures of the polymer films were 299–344 °C according to thermomechanical analysis. The polyimides showed insignificant decomposition before 520 °C in air or nitrogen. For a comparative study, two series of analogous polyimides based on symmetrical diamines such as 1,5-diaminonaphthalene and 1,5-bis(4-aminophenoxy)naphthalene were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 331–341, 2005

Two new diamines, 2,4-diaminotriphenylamine (3) and N-(2,4-diaminophe- nyl)carbazole (4), were synthesized via the cesium fluoride-mediated aromatic substi- tution reactions of 1-fluoro-2,4-dinitrobenzene with diphenylamine and carbazole, fol- lowed by palladium-catalyzed hydrazine reduction. Amorphous and soluble aramids having pendent diphenylamino and carbazolyl groups were prepared by the phosphor- ylation polycondensation of aromatic dicarboxylic acids with diamines 3 and 4, respec- tively. The aramids derived from diamine 3 had sufficiently high molecular weights to permit the casting of flexible and tough films. They exhibited excellent mechanical properties and moderately high softening temperatures in the 221-298 °C range. However, the reactions of diamine 4 with aromatic diacids gave relatively lower mo- lecular weights products that could not afford flexible films. For a comparative purpose, the parent aramids derived from m-phenylenediamine and aromatic diacids were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3302-3313, 2004

Two series of fluorinated polyimides were prepared from 2,2-bis(4-amino- 2-trifluoromethylphenoxy)biphenyl (2) and 2,2-bis(4-amino-2-trifluoromethylphe- noxy)-1,1-binaphthyl (4) with various aromatic dianhydrides via a conventional, two- step procedure that included a ring-opening polyaddition to give poly(amic acid)s, followed by chemical or thermal cyclodehydration. The inherent viscosities of the polyimides ranged from 0.54 to 0.73 and 0.19 to 0.36 dL/g, respectively. All the fluori- nated polyimides were soluble in many polar organic solvents, such as N,N-dimethyl- acetamide and N-methylpyrrolidone, and afforded transparent and light-colored films via solution-casting. These polyimides showed glass-transition temperatures in the ranges of 222-280 and 257-351 °C by DSC, softening temperatures in the range of 264 -301 °C by thermomechanical analysis, and a decomposition temperature for 10% weight loss above 520 °C both in nitrogen and air atmospheres. The polyimides had low moisture absorptions of 0.23- 0.58%, low dielectric constants of 2.84 -3.61 at 10 kHz, and an ultraviolet-visible absorption cutoff wavelength at 351- 434 nm. Copolyimides derived from the same dianhydrides with an equimolar mixture of 4,4-oxydianiline and diamine 2 or 4 were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2416 -2431, 2004

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 (Tg'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 Tg'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

A new trifluoromethyl-substituted bis(ether amine) monomer, 2,7-bis(4-amino-2-trifluoromethylphenoxy)naphthalene, was synthesized. It led to a series of novel fluorinated polyimides by thermal and chemical imidization routes when reacted with various commercially available aromatic tetracarboxylic dianhydrides. Most of the polyimides obtained from both routes were soluble in many organic solvents, such as N,N-dimethylacetamide. All the polyimides could afford transparent, flexible, and strong films with low moisture absorptions of 0.3-0.6%, low dielectric constants of 2.52-3.27 at 10 kHz, and an ultraviolet-visible absorption cutoff wavelength at 377-436 nm. The glass-transition temperatures of the polyimides were in the range of 244-297 °C, and the 5% weight-loss temperatures were higher than 550 °C. For a comparative study, a series of analogous polyimides based on 2,7-bis(4-aminophenoxy)naphthalene were also prepared and characterized.

Two new bis(ether acyl chloride)s, 1,1-bis[4-(4-chloroformylphenoxy)phenyl]-1-phenylethane and 1,1-bis[4-(4-chloroformylphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane, were prepared from readily available reagents. Aromatic polybenzoxazoles with both ether and phenylethylidene or 1-phenyl-2,2,2-trifluoroethylidene linkages between phenylene units were obtained by a conventional two-step procedure including the low-temperature solution polycondensation of the bis(ether acyl chloride)s with three bis(o-aminophenol)s, yielding poly(o-hydroxyamide) precursors, and subsequent thermal cyclodehydration. The intermediate poly(o-hydroxyamide)s exhibited inherent viscosities of 0.39–0.98 dL/g. All of the poly(o-hydroxyamide)s were amorphous and soluble in polar organic solvents such as N,N-dimethylacetamide, and most of them could afford flexible and tough films via solvent casting. The poly(o-hydroxyamide)s exhibited glass-transition temperatures (Tg's) of 129–194 °C and could be thermally converted into corresponding polybenzoxazoles in the solid state at temperatures higher than 300 °C. All the polybenzoxazoles were amorphous and showed an enhanced Tg but a dramatically decreased solubility with to respect to their poly(o-hydroxyamide) precursors. They exhibited Tg's of 216–236 °C through differential scanning calorimetry and were stable up to 500 °C in nitrogen or air, with 10% weight-loss temperatures being recorded between 538 and 562 °C in nitrogen or air. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 914–921, 2003

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 (Tg'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 (Td's) for 10% weight loss all occurred above 500 °C in both nitrogen and air atmospheres. Almost all the fluorinated polyamides displayed relatively higher Tg and Td values than the corresponding nonfluorinated analogues. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 420–431, 2003

A new triphenylamine-containing aromatic dicarboxylic acid, N,N-bis(4- carboxyphenyl)-N,N-diphenyl-1,4-phenylenediamine, was synthesized by the conden- sation of N,N-diphenyl-1,4-phenylenediamine with 4-fluorobenzonitrile, followed by the alkaline hydrolysis of the intermediate dinitrile compound. A series of novel triphenylamine-based aromatic poly(amine amide)s with inherent viscosities of 0.50 - 1.02 dL/g were prepared from the diacid and various aromatic diamines by direct phosphorylation polycondensation. All the poly(amine amide)s were amorphous in nature, as evidenced by X-ray diffractograms. Most of the poly(amine amide)s were quite soluble in a variety of organic solvents and could be solution-cast into transpar- ent, tough, and flexible films with good mechanical properties. They had useful levels of thermal stability associated with glass-transition temperatures up to 280 °C, 10% weight-loss temperatures in excess of 575 °C, and char yields at 800 °C in nitrogen higher than 60%. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 94 -105

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

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

A novel bis(ether anhydride) monomer, 3,6-bis(3,4-dicarboxyphenoxy)benzonorbornane dianhydride, was synthesized from the nitro displacement of 4-nitrophthalonitrile with 3,6-dihydroxybenzonorbornane in the presence of potassium carbonate, followed by the alkaline hydrolysis of the intermediate bis(ether dinitrile) and the cyclodehydration of the resulting bis(ether diacid). A series of poly(ether imide)s bearing pendant norbornane groups were prepared from the bis(ether anhydride) with various aromatic diamines via a conventional two-stage process that included ring-opening polyaddition to form the poly(amic acid)s followed by thermal imidization to the poly(ether imide)s. The inherent viscosities of the poly(amic acid) precursors were 0.81-1.81 dL/g. The poly(ether imide) with m-phenylenediamine as a diamine showed good organosolubility. Most of the cast poly(ether imide) films have had high tensile strengths and moduli. The glass-transition temperatures of these poly(ether imide)s, except for those from rigid p-phenylenediamine and benzidine, were recorded between 211 and 246°C by differential scanning calorimetry. The softening temperatures of all the poly(ether imide) films stayed within 210-330 °C according to thermomechanical analysis. No polymers showed significant decomposition before 500°C in a nitrogen or air atmosphere. A comparative study of the properties with the corresponding poly(ether imide)s without pendant substituents was also made.

A series of new aromatic polyamides having pendent naphthoxy groups were synthesized by the triphenyl phosphite-activated polycondensation of (2-naphthoxy)terephthalic acid (NOTPA) with various aromatic diamines in a medium consisting of N-methyl-2-pyrrolidone (NMP), pyridine, and calcium chloride. The diacid monomer NOTPA was prepared from the nitro displacement of dimethyl 2-nitroterephthalate with the potassium naphthoxide of β-naphthol, followed by base-induced ester hydrolysis. All the resulting polymers were noncrystalline and readily soluble in aprotic polar solvents such as NMP and N,N-dimethylacetamide. Almost all the polymers could be solution-cast to tough, creasable amorphous films with good mechanical properties, the values of tensile strengths ranging from 90 to 124 MPa with initial moduli ranging from 1.72 to 2.51 GPa. Except for two examples, all the other polyamides displayed discernible glass transitions between 189 and 248 °C in the differential scanning calorimetric traces. These polyamides showed insignificant decomposition below 400 °C in nitrogen or air. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1781–1789, 2002

A set of new aromatic polyamides containing ether and benzonorbornane units were synthesized by the direct phosphorylation polycondensation of 3,6-bis(4-carboxyphenoxy)benzonorbornane with various aromatic diamines. The polymers were produced in high yields and moderate to high inherent viscosities (0.64–1.70 dL/g). The polyamides derived from rigid diamines such as p-phenylenediamine and benzidine were semicrystalline and insoluble in organic solvents. The other polyamides were amorphous and organosoluble and afforded flexible and tough films via solution casting. These films exhibited good mechanical properties, with tensile strengths of 95–101 MPa, elongations at break of 13–25%, and initial moduli of 1.97–2.33 GPa. The amorphous polyamides showed glass-transition temperatures between 176 and 212 °C (by differential scanning calorimetry) and softening temperatures between 194 and 213 °C (by thermomechanical analysis). Most of the polymers did not show significant weight loss before 450 °C in nitrogen or in air. Some properties of these polyamides were also compared with those of homologous counterparts without the pendent norbornane groups. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 947–957, 2002

Two series of phosphorus-containing aromatic poly(ester amide)s with inherent viscosities of 0.46–3.20 dL/g were prepared by low-temperature solution polycondensation from 1,4-bis(3-aminobenzoyloxy)-2-(6-oxido-6H-dibenz〈c,e〉〈1,2〉oxaphosphorin-6-yl)naphthalene and 1,4-bis(4-aminobenzoyloxy)-2-(6-oxido-6H-dibenz〈c,e〉〈1,2〉oxaphosphorin-6-yl)naphthalene with various aromatic diacid chlorides. All the poly(ester amide)s were amorphous and readily soluble in many organic solvents, such as N,N-dimethylformamide, N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP). Transparent, tough, and flexible films of these polymers were cast from DMAc and NMP solutions. Their casting films had tensile strengths of 71–214 MPa, elongations to break of 5–10%, and initial moduli of 2.3–6.0 GPa. These poly(ester amide)s had glass-transition temperatures of 209–239 °C (m-series) and 222–267 °C (p-series). The degradation temperatures at 10% weight loss in nitrogen for these polymers ranged from 462 to 489 °C, and the char yields at 800 °C were 55–63%. Most of the poly(ester amide)s also showed a high char yield of 35–45%, even at 800 °C under a flow of air. The limited oxygen indices of these poly(ester amide)s were 35–46. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 459–470, 2002; DOI 10.1002/pola.10129

A novel fluorinated diamine monomer, 9,9-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]fluorene (II) was prepared via the nucleophilic substitution reaction of 2-chloro-5-nitrobenzotrifluoride with 9,9-bis(4-hydroxyphenyl)fluorene in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C. Polyimides V were synthesized from diamine II and various aromatic dianhydrides IIIa-f via thermal imidization. These polymers had inherent viscosities ranging from 0.84 to 1.03 dL/g and were soluble in a variety of organic solvents such as NMP, DMAc, DMF, and DMSO, and some could even be dissolved in less polar solvents such as m-cresol, pyridine, and dioxane. Polyimide films Va-f had tensile strengths of 85–105 MPa, elongations to break of 7–9%, and initial moduli of 2.13–2.42 GPa. The glass transition temperature of these polymers were in the range of 277–331 °C, their 10% weight loss temperatures were in the range of 539–594 °C in nitrogen and above 544 °C in air, and their char yields at 800 °C in nitrogen ranged between 55–65 wt%. Compared with nonfluorinated polyimides VI, V showed better solubility and lower color intensity. Low dielectric constants (2.68–2.85 at 1 MHz) and low moisture absorptions (0.12–0.24 wt%) were also observed. In particular, Vc-f afforded lightly-colored films, which had cutoff wavelengths lower than 385 nm and b* values ranging from 6 to 22.

Polyhydrazides and poly(amide-hydrazide)s were prepared from two ether-sulfone-dicarboxylic acids, 4,4′-[sulfonylbis(1,4-phenylene)dioxy]dibenzoic acid and 4,4′-[sulfonylbis(2,6-dimethyl-1,4-phenylene)dioxy]dibenzoic acid, or their diacyl chlorides with terephthalic dihydrazide, isophthalic dihydrazide, and p-aminobenzhydrazide via a phosphorylation reaction or a low-temperature solution polycondensation. All the hydrazide polymers were found to be amorphous according to X-ray diffraction analysis. They were readily soluble in polar organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide and could afford colorless, flexible, and tough films with good mechanical strengths via solvent casting. These hydrazide polymers exhibited glass-transition temperatures of 149–207 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the solid state at elevated temperatures. Although the oxadiazole polymers showed a significantly decreased solubility with respect to their hydrazide prepolymers, some oxadiazole polymers were still organosoluble. The thermally converted oxadiazole polymers had glass-transition temperatures of 217–255 °C and softening temperatures of 215–268 °C and did not show significant weight loss before 400 °C in nitrogen or air. For a comparative study, related sulfonyl polymers without the ether groups were also synthesized from 4,4′-sulfonyldibenzoic acid and the hydrazide monomers by the same synthetic routes. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2271–2286, 2001

Three new bis(ether-acyl chloride) monomers, 1,1-bis[4-(4-chloroformylphenoxy)phenyl]cyclohexane (1a), 5,5-bis[4-(4-chloroformylphenoxy)phenyl]-4,7-methanohexahydroindan (1b), and 9,9-bis[4-(4-chloroformylphenoxy)phenyl]fluorene (1c), were synthesized from readily available compounds. Aromatic polybenzoxazoles bearing ether and cardo groups were obtained by the low-temperature solution polycondensation of the bis(ether-acyl chloride)s with three bis(aminophenol)s and the subsequent thermal cyclodehydration of the resultant poly(o-hydroxy amide)s. The intermediate poly(o-hydroxy amide)s exhibited inherent viscosities in the range of 0.35–0.71 dL/g. All of the poly(o-hydroxy amide)s were amorphous and soluble in many organic polar solvents, and most of them could afford flexible and tough films by solvent casting. The poly(o-hydroxy amide)s exhibited glass-transition temperatures (Tg's) in the range of 141–169 °C and could be thermally converted into the corresponding polybenzoxazoles approximately in the region of 240–350 °C, as indicated by the DSC thermograms. Flexible and tough films of polybenzoxazoles could be obtained by thermal cyclodehydration of the poly(o-hydroxy amide) films. All the polybenzoxazoles were amorphous and showed an enhanced Tg but a dramatically decreased solubility as compared with their poly(o-hydroxy amide) precursors. They exhibited Tg's of 215–272 °C by DSC and showed insignificant weight loss before 500 °C in nitrogen or air. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4014–4021, 2001

A series of poly(o-hydroxy amide)s having both ether and sulfone linkages in the main chain were synthesized via the low-temperature solution polycondensation of 4,4'-[sulfonylbis(1,4-phenylene)dioxy]dibenzoyl chloride and 4,4'-[sulfonylbis(2,6-dimethyl-1,4-phenylene)dioxy]dibenzoyl chloride with three bis(o-aminophenol)s including 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl, and 2,2-bis(3-diamino-4-hydroxyphenyl)hexafluoropropane. Subsequent thermal cyclodehydration of the poly(o-hydroxy amide)s afforded polyethersulfone benzoxazoles. Most of the poly(o-hydroxy amide)s were soluble in polar organic solvents such as N-methyl-2-pyrrolidone; however, the polybenzoxazoles without the hexafluoroisopropylidene group were organic-insoluble. The polybenzoxazoles exhibited glass-transition temperatures (T g ) in the range of 219-282 °C by DSC and softening temperatures (T s ) of 242-320 °C by thermomechanical analysis. Thermogravimetric analyses indicated that most polybenzoxazoles were stable up to 450 °C in air or nitrogen. The 10% weight loss temperatures were recorded in the ranges of 474-593 °C in air and 478-643 °C in nitrogen. The methyl-substituted polybenzoxazoles had higher T g 's but lower T s 's and initial decomposition temperatures compared with the corresponding unsubstituted polybenzoxazoles. For a comparative purpose, the synthesis and characterization of a series of sulfonyl polybenzoxazoles without the ether group that derived from 4,4'-sulfonyldibenzoyl chloride and bis(o-aminophenol)s were also reported.

New phosphorus-containing aromatic diesteramines, 1,4-bis(4-aminobenzoyloxy)-2-(6-oxido-6H-dibenz〈c,e〉〈1,2〉oxaphosphorin-6-yl)naphthalene (p-3) and 1,4-bis(3-aminobenzoyloxy)-2-(6-oxido-6H-dibenz〈c,e〉〈1,2〉oxaphosphorin-6-yl)naphthalene (m-3), were synthesized by the reaction of 2-(6-oxido-6H-dibenz〈c,e〉〈1,2〉oxaphosphorin-6-yl)-1,4-naphthalenediol with 4-nitrobenzoyl chloride and 3-nitrobenzoyl chloride, respectively, followed by catalytic reduction. Two series of phosphorus-containing aromatic poly(ester-amide-imide)s with inherent viscosities of 0.94–2.00 and 0.41–0.56 dL/g were prepared via low-temperature solution polycondensation from p-3 and m-3, respectively, with three imide ring-preformed diacid chlorides. All the poly(ester-amide-imide)s were amorphous and readily soluble in many organic solvents such as N,N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP). Transparent, tough, and flexible films of these polymers were cast from DMAc or NMP solutions. Their casting films possessed a tensile strength range of 118–181 MPa, an elongation to break of 5–11%, and an initial modulus range of 2.41–4.46 GPa. They had useful levels of thermal stability associated with relatively high glass-transition temperatures (264–286 °C) and 10% weight-loss temperatures in excess of 450 °C in nitrogen or air. The limiting oxygen indices of these polymers were 41–46. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1786–1799, 2001