Diels–Alder modification of poly(ethylene terephthalate‐co‐anthracene‐2,6‐carboxylate) with N‐substituted maleimides

Dimethyl 2,6‐anthracene dicarboxylate is used as a comonomer in the synthesis of functional copolymers that are subject to modification with Diels–Alder reactions. The formation of poly(ethylene terephthalate‐co‐2,6‐anthracenate), containing less than 20 mol % of the anthracene‐2,6‐dicarboxylate structural units, provides materials that are tractable and soluble. The anthracene units of the copolymers undergo Diels–Alder reactions with N‐substituted maleimides. The grafting of N‐alkylmaleimides affords soluble, hydrophobic polymers, whereas grafting with maleimide‐terminated poly(ethylene glycol) affords hydrophilic polymers. Because this reaction proceeds below the melting point of the copolymers, the procedure can be applied to thin films, whereby the surface properties are modified. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3256–3263, 2002     

Aliphatic poly(ester‐carbonate)s bearing amino groups and its RGD peptide grafting

This article deals with (1) synthesis of novel cyclic carbonate monomer (2‐oxo [1,3]dioxan‐5‐yl)carbamic acid benzyl ester (CAB) containing protected amino groups; (2) ring‐opening copolymerization of the cyclic monomer with L ‐lactide (LA) to provide novel degradable poly(ester‐carbonate)s with functional groups; (3) removal of the protective benzyloxycarbonyl (Cbz) groups by catalytic hydrogenation to afford the corresponding poly(ester‐co‐carbonate)s with free amino groups; (4) grafting of oligopeptide Gly‐Arg‐Gly‐Asp‐Ser‐Tyr (GRGDSY, abbreviated as RGD) onto the copolymer pendant amino groups in the presence of 1,1′‐carbonyldiimidazole (CDI). The structures of P(LA‐co‐CA/RGD) and its precursor were confirmed by ¹H NMR analysis. Cell experiments showed that P(LA‐co‐CA/RGD) had improved adhesion and proliferation behavior. Therefore, the novel RGD‐grafted block copolymer is promising for cell or tissue engineering applications. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7022–7032, 2008     

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     

Dendronized polymers via Diels–Alder “click” reaction

A modular approach toward the synthesis of polymers containing dendron groups as side chains is developed using the Diels–Alder “click” reaction. For this purpose, a styrene‐based polymer appended with anthracene groups as reactive side chains was synthesized. First through third‐generation polyester dendrons containing furan‐protected maleimide groups at their focal point were synthesized. Facile, reagent‐free, thermal Diels–Alder cycloaddition between the anthracene‐containing polymer and latent‐reactive dendrons leads to quantitative functionalization of the polymer chains to afford dendronized polymers. The efficiency of this functionalization step was monitored using ¹H and ¹³C NMR spectroscopy and FTIR and UV–vis spectrometry. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 410–416, 2010     

Synthesis and nonlinear optical properties of methacrylate polymers based on 2‐[4‐(N‐methyl,N‐hydroxyethylamino)phenylazo]‐phenyl‐6‐nitrobenzoxazole chromophore

Methacrylate polymers containing different molar contents of nonlinear optical (NLO) active molecular segments based on 2‐[4‐(N‐methyl,N‐hydroxyethylamino)phenylazo]‐phenyl‐6‐nitrobenzoxazole chromophores were synthesized, and their phase behavior and second‐order NLO properties were investigated. Polymers containing 6–17 mol % chromophore segments allowed the preparation of amorphous and optically clear thin films. Some mesomorphic structuration was exhibited by a polymer with 33 mol % chromophoric units. However, this feature did not prevent the possibility of investigating the NLO properties. Nonlinear resonance‐enhanced d₃₃ coefficients were determined by second harmonic generation experiments on spin‐coated, corona‐poled thin films at λ = 1064 nm. Values ranging from 40 to 60 pm/V were measured with increasing chromophore molar contents. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1841–1847, 2003     

Cyclic peptide–polymer conjugates: Grafting‐to vs grafting‐from

A systematic comparison between the grafting‐to (convergent) and grafting‐from (divergent) synthetic routes leading to cyclic peptide–polymer conjugates is described. The reversible addition–fragmentation chain transfer (RAFT) process was used to control the polymerizations and the couplings between cyclic peptide and polymer or RAFT agent were performed using N‐hydroxysuccinimide (NHS) active ester ligation. The kinetics of polymerization and polymer conjugation to cyclic peptides were studied for both grafting‐to and grafting‐from synthetic routes, using N‐acryloyl morpholine as a model monomer. The cyclic peptide chain transfer agent was able to mediate polymerization as efficiently as a traditional RAFT agent, reaching high conversion in the same time scale while maintaining excellent control over the molecular weight distribution. The conjugation of polymers to cyclic peptides proceeded to high conversion, and the nature of the carbon at the α‐position to the NHS group was found to play a crucial role in the reaction kinetics. The study was extended to a wider range of monomers, including hydrophilic and temperature responsive acrylamides, hydrophilic and hydrophobic acrylates, and hydrophobic and pH responsive methacrylates. Both approaches lead to similar peptide–polymer conjugates in most cases, while some exceptions highlight the advantages of one or the other method, thereby demonstrating their complementarity. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1003–1011     

Unsaturated alkoxy‐substituted poly(p‐phenylene 1,3,4‐oxadiazole)s: Synthesis and chemical–physical characterization

A new series of alkoxy‐substituted poly(p‐phenylene 1,3,4‐oxadiazole)s modified by the insertion of small percentages of various comonomers were synthesized through the precursor polyhydrazides. The comonomers used contained trans double bonds or meta‐alkoxy‐substituted aromatic rings to improve the solubility of the final polymers. The synthesized copolymers were chemically characterized by ¹H NMR and Fourier transform infrared spectroscopy. In some cases, the copolymers really showed improved solubility in organic solvents. The ¹⁵N solid‐state NMR technique was applied to examine the degree of conversion from the precursor polyhydrazides to the final polymers, which determined the effective conjugated length in the target polyoxadiazoles. Thermal stability and structural characteristics of all the polymers as well as a preliminary investigation on the optical properties of polyoxadiazoles are also reported. The copolymers retained high absorbance in the UV region and high transmission in the whole telecommunication range. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3916–3928, 2003     

Remarkably stable amphiphilic random copolymer assemblies: A structure–property relationship study

Synthesis of a library of amphiphilic random copolymers from a single reactive pre‐polymer and their self‐assembly is reported. Post‐polymerization modifications of the parent polymer containing pendant N‐hydroxy succinimide (NHS) ester groups with various oligooxyethylene (OE) amines produce amphiphilic random copolymers with same degree of polymerization and equal extent of randomness. ¹H‐NMR and FT‐IR data indicate quantitative substitution in all cases. The critical aggregation concentration (CAC) for all the polymers is estimated to be in the range of 10^?5 M. Stability of these nano‐aggregates is studied by photoluminescence using time dependent F—rster Resonance Energy Transfer (FRET) between co‐encapsulated lipophilic dyes namely DiO and DiI in the hydrophobic pocket of the aggregates. These studies suggest remarkably high stability for all systems. However those with shorter hydrophilic pendant chains are found to be even more robust. Morphology is examined by high resolution transmission electron microscopy (HRTEM) which reveals multi‐micellar clusters and vesicles for polymers containing short and longer OE segments, respectively. Encapsulation efficacy is tested with both hydrophobic and hydrophilic guest molecules. All of them can encapsulate hydrophobic guest pyrene while a hydrophilic dye Calcein can be sequestered only in vesicle forming polymers. Lower critical solution temperature (LCST) is exhibited by only one polymer that contains the shortest OE chains. All polymers exhibit excellent cell viability as determined by MTT assay. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4932–4943     

A New Approach for the Synthesis of Miktoarm Star Polymers Through a Combination of Thiol–Epoxy “Click” Chemistry and ATRP/Ring‐Opening Polymerization Techniques

A new approach was developed for synthesis of certain A₃B₃‐type of double hydrophilic or amphiphilic miktoarm star polymers using a combination of “grafting onto” and “grafting from” methods. To achieve the synthesis of desired miktoarm star polymers, acetyl protected poly(ethylene glycol) (PEG) thiols (M_n = 550 and 2000 g mol^?1) were utilized to generate A₃‐type of homoarm star polymers through an in situ protective group removal and a subsequent thiol–epoxy “click” reaction with a tris‐epoxide core viz. 1,1,1‐tris(4‐hydroxyphenyl)ethane triglycidyl ether. The secondary hydroxyl groups generated adjacent to the core upon the thiol–epoxy reaction were esterified with α‐bromoisobutyryl bromide to install atom transfer radical polymerization (ATRP) initiating sites. ATRP of N‐isopropylacrylamide (NIPAM) using the three‐arm star PEG polymer fitted with ATRP initiating sites adjacent to the core afforded A₃B₃‐type of double hydrophilic (PEG)₃[poly(N‐isopropylacrylamide)] (PNIPAM)₃ miktoarm star polymers. Furthermore, the generated hydroxyl groups were directly used as initiator for ring‐opening polymerization of ε‐caprolactone to prepare A₃B₃‐type of amphiphilic (PEG)₃[poly(ε‐caprolactone)]₃ miktoarm star polymers. The double hydrophilic (PEG)₃(PNIPAM)₃ miktoarm star polymers showed lower critical solution temperature around 34 °C. The preliminary transmission electron microscopy analysis indicated formation of self‐assembly of (PEG)₃(PNIPAM)₃ miktoarm star polymer in aqueous solution. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 146–156     

Arborescent polypeptides from γ‐benzyl l‐glutamic acid

The synthesis of arborescent polymers with poly(γ‐benzyl L‐glutamate) (PBG) side chains was achieved through successive grafting reactions. The linear PBG building blocks were produced by the ring‐opening polymerization of γ‐benzyl L‐glutamic acid N‐carboxyanhydride initiated with n‐hexylamine. The polymerization conditions were optimized to minimize the loss of amino chain termini in the reaction. Acidolysis of a fraction of the benzyl groups on a linear PBG substrate and coupling with linear PBG using a carbodiimide/hydroxybenzotriazole promoter system yielded a comb‐branched or generation zero (G0) arborescent PBG. Further partial deprotection and grafting cycles led to arborescent PBG of generations G1 to G3. The solvent used in the coupling reaction had a dramatic influence on the yield of graft polymers of generations G1 and above, dimethylsulfoxide being preferable to N,N‐dimethylformamide. This grafting onto scheme yielded well‐defined (M_w/M_n ≤ 1.06), high molecular weight arborescent PBG in a few reaction cycles, with number‐average molecular weights and branching functionalities reaching over 10⁶ and 290, respectively, for the G3 polymer. α‐Helix to coiled conformation transitions were observed from N,N‐dimethylformamide to dimethyl sulfoxide solutions, even for the highly branched polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5270–5279     

Poly(DCAQI): Synthesis and characterization of a new redox‐active polymer

Redox‐active anthraquinone based polymers are synthesized by the introduction of a polymerizable vinyl and ethynyl group, respectively, resulting in redox‐active monomers, which electrochemical behaviors are tailored by the modification of the keto groups to N‐cyanoimine moieties. These monomers can be polymerized by free radical polymerization and Rh‐catalyzed polymerization methods, respectively. The resulting polymers are obtained in molar masses (M_n) of 4,400 to 16,800 g mol^?1 as well as high yields of up to 97%. The monomers and polymers are furthermore electrochemically characterized by cyclic voltammetry. The monomers exhibit two one‐electron redox reactions at about ?0.6 and ?1.0 V versus Fc⁺/Fc. The N‐cyanoimine units are, however, partially hydrolyzed during the polymerization step or during the electrochemical measurements and degenerate to carbonyl groups, resulting in a new reduction signal at ?1.26 V versus Fc⁺/Fc. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1998–2003     

Small‐angle neutron scattering analysis of bottlebrush backbone and side chain flexibility

Bottlebrush polymers have densely tethered side chains grafted to a linear polymer backbone, resulting in stretching of both the side chains and backbone. Prior studies have reported that the side chains are only weakly stretched while the backbone is highly elongated. Here, scaling laws for the bottlebrush backbone and side chains are determined through small‐angle neutron scattering analysis of a systematic series of poly(lactic acid) bottlebrush polymers synthesized via a “grafting‐through” ring‐opening polymerization. Scattering profiles are modeled with the empirical Guinier–Porod, rigid cylinder, and flexible cylinder models. Side chains are found to be only weakly stretched, with an end‐to‐end distance proportional to N^0.55, while the overall bottlebrush increases in size proportional to N^0.77. These results demonstrate that the bottlebrush backbone is not fully extended and that both side chains and backbone have significant conformational flexibility in solution. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 104–111     

Synthesis and properties of novel sulfonated polyimides containing 1,5‐naphthylene moieties

A series of novel sulfonated polyimides (equivalent weight per sulfonic acid = 310–744 g/equiv) containing 10–70 mol % 1,5‐naphthylene moieties were synthesized as potential electrolyte materials for high‐temperature polymer electrolyte fuel cells. The polycondensation of 1,4,5,8‐naphthalene tetracarboxylic dianhydride, 4,4′‐diamino‐2,2′‐biphenyldisulfonic acid, and 1,5‐diaminonaphthalene gave the title polymer electrolytes. The polyimide electrolytes were high‐molecular‐weight (number‐average molecular weight = 36.0–350.7 × 10³ and weight‐average molecular weight = 70.4–598.5 × 10³) and formed flexible and tough films. The thermal properties (decomposition temperature > 260 °C, no glass‐transition temperature), stability to oxidation, and water absorption were analyzed and compared with those of perfluorosulfonic acid polymers. The polyimide containing 20 mol % 1,5‐naphthylene moieties showed higher proton conductivity (0.3 S cm^?1) at 120 °C and 100% relative humidity than perfluorosulfonic acid polymers. The temperature and humidity dependence of the proton conductivity was examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3901–3907, 2003     

New P‐type of poly(4‐methoxy‐triphenylamine)s derived by coupling reactions: Synthesis,electrochromic behaviors,and hole mobility

Methoxy‐substituted poly(triphenylamine)s, poly‐4‐methoxytriphenylamine ( PMOTPA ), and poly‐N,N‐bis(4‐methoxyphenyl)‐N′,N′‐diphenyl‐p‐phenylenediamine ( PMOPD ), were synthesized from the nickel‐catalyzed Yamamoto and oxidative coupling reaction with FeCl₃. All synthesized polymers could be well characterized by ¹H and ¹³C NMR spectroscopy. These polymers possess good solubility in common organic solvent, thermal stability with relatively high glass‐transition temperatures (T_gs) in the range of 152–273 °C, 10% weight‐loss temperature in excess of 480 °C, and char yield at 800 °C higher than 79% under a nitrogen atmosphere. They were amorphous and showed bluish green light (430–487 nm) fluorescence with quantum efficiency up to 45–62% in NMP solution. The hole‐transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. All polymers exhibited reversible oxidation redox peaks and E_onset around 0.44–0.69 V versus Ag/AgCl and electrochromic characteristics with a color change under various applied potentials. The series of PMOTPA and PMOPD also showed p‐type characteristics, and the estimated hole mobility of O ‐ PMOTPA and Y ‐ PMOPD were up to 1.5 × 10^?4 and 5.6 × 10^?5 cm² V^?1 s^?1, respectively. The FET results indicate that the molecular weight, annealing temperature, and polymer structure could crucially affect the charge transporting ability. This study suggests that triphenylamine‐containing conjugated polymer is a multifunctional material for various optoelectronic device applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4037–4050, 2009     

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     

Dehydrocoupling and Diels–Alder reactions on siloxane polymers

Dehydrocoupling reactions between linear poly(methylhydrosiloxane) {Me₃SiO–[MeSi(H)O]_n–SiMe₃} and alcohols such as cholesterol, anthracene‐9‐carbinol, (12‐crown‐4)‐2‐carbinol, pyrene‐1‐carbinol, 4‐methyl‐5‐thiazoleethanol, and 4‐pyridilpropanol were introduced under catalytically mild conditions. The degrees of conversion of Si? H bonds in polysiloxane were monitored with ¹H NMR spectra. The reaction of the 9‐methoxyanthracene adduct on siloxane polymers and maleimide derivatives (maleimide, N‐ethylmaleimide, and maleic acid anhydride) produced [2+4]‐cycloadducts in very high yields. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4013–4019, 2002     

Donor–acceptor semiconducting polymers based on pyromellitic diimide

Three donor–acceptor copolymers P1 , P2 , and P3 with N,N′‐dodecylpyromellitic diimide as the electron‐acceptor unit with three diethynyl‐substituted donor monomers: 1,4‐diethynyl‐2,5‐bis(octyloxy)benzene, 2,7‐diethynyl‐9,9‐dioctyl‐9H‐fluorene, and 3,3′‐didodecyl‐5,5′‐diethynyl‐2,2′‐bithiophene have been synthesized by Sonogashira crosscoupling polymerization. The synthesized polymers showed deep highest occupied molecular orbital energy levels and larger band gaps (>2.5 eV). Polymers P1 , P2 , and P3 underwent fluorescence quenching with [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM), indicating the intermolecular photo‐induced charge transfer between the donor polymers and the PCBM acceptor. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1617–1622     

Antimicrobial anilinium polymers: The properties of poly(N,N‐dimethylaminophenylene methacrylamide) in solution and as coatings

Antimicrobial polymers have been widely reported to exert strong biocidal effects against bacteria. In contrast with antimicrobial polymers with aliphatic ammonium groups, polymers with anilinium groups have been rarely studied and applied as biocidal materials. In this study, a representative polymer with aniline side functional groups, poly(N,N‐dimethylaminophenylene methacrylamide) (PDMAPMA), was explored as a novel antimicrobial polymer. PDMAPMA was synthesized and its physicochemical properties evaluated. The methyl iodide‐quaternized polymer was tested against the Gram‐positive Staphylococcus aureus, with a minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of 16–32 and 64–128 μg mL^?1, respectively. Against the Gram‐negative Escherichia coli, the MIC and MBC were both 64–128 μg mL^?1. To broaden the range of applications, PDMAPMA was coated on substrates via crosslinking to endow the surface with contact‐kill functionality. The effect of charge density of the coatings on the antimicrobial behavior was then investigated, and stronger biocidal performance was observed for films with higher charge density. This study of the biocidal behavior of PDMAPMA both in solution and as coatings is expected to broaden the application of polymers containing aniline side groups and provide more information on the antimicrobial behavior of such materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1908–1921     

Poly(ethyleneimine)/arginine–glycine–aspartic acid conjugates prepared with N‐succinimidyl 3‐(2‐pyridyldithio)propionate: An investigation of peptide coupling and conjugate stability

Poly(ethylene imine) (PEI), a highly cationic polymer, is being used for deoxyribonucleic acid (DNA) complexation and delivery into cells. To enhance the cellular uptake of polymer/DNA complexes, arginine–glycine–aspartic acid (RGD) peptides have been conjugated to PEI with N‐succinimidyl 3‐(2‐pyridyldithio)propionate (SPDP). This coupling scheme creates a disulfide‐linked conjugate, the stability of which in the presence of thiols is uncertain. We have investigated the conjugation of an RGD peptide, glycine–arginine–glycine–aspartic acid–serine–proline–cysteine (GRGDSPC), to PEI with SPDP and subsequently assessed the stability of the conjugates in the presence of two thiol compounds, mercaptoethanol and cysteine. SPDP effectively controls the extent of GRGDSPC substitution on PEI. The conjugates, however, are readily cleaved in the presence of the thiols; the cleavage is rapid (～50% cleavage in 2–4 h) and inversely related to the degree of peptide substitution on the polymers. The peptide coupling is stable in the absence of thiols, and its cleavage is strongly dependent on the pH of the medium but not on the ionic strength of the medium. We conclude that RGD peptides coupled to PEI are labile in the presence of physiological concentrations of thiols, and this should be taken into account when such polymer–peptide conjugates are used for DNA delivery. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6143–6156, 2004     

Near‐infrared electrochromic poly(aryl ether)s based on isolated electroactive tetraphenyl‐p‐phenylenediamine moieties

A series of near‐infrared (NIR) electrochromic aromatic poly(aryl ether)s containing N,N,N′,N′‐tetraphenyl‐p‐phenylenediamine (TPPA) moieties in the backbone were prepared from the high‐temperature polycondensation reactions of a biphenol monomer, 2,5‐bis(diphenylamino)hydroquinone, with difluoro compounds. The obtained polymers were readily soluble in many organic solvents and showed useful levels of thermal stability associated with high glass‐transition temperatures (182–205 °C) and high char yields (higher than 40% at 800 °C in nitrogen). The polymer films showed reversible electrochemical oxidation with high contrast ratio both in the visible range and NIR region, and also exhibited high coloration efficiency (CE), low switching time, and stability for electrochromic operation. The polyether TPPA‐a thin film revealed good CE in visible (CE = 217 cm²/C) and NIR (CE = 192 cm²/C) region with reversible electroactive stability (over 500 times within 5% loss relative to its initial injected charge). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5378–5385, 2009