Red,green, and blue electrochromism in ambipolar poly(amine–amide–imide)s based on electroactive tetraphenyl‐p‐phenylenediamine units

A series of novel poly(amine–amide–imide)s (PAAIs) based on tetraphenyl‐p‐phenylenediamine (TPPA) units showing anodically/cathodically electrochromic characteristic with three primary colors [red, green, and blue (RGB)] were prepared from the direct polycondensation of the TPPA‐based diamine monomer with various aromatic bis(trimellitimide)s. These multicolored electrochromic polymers were readily soluble in polar organic solvents and showed excellent thermal stability associated with high glass‐transition temperatures (288–314 °C) and high‐char yield (higher than 60% at 800 °C in nitrogen). The PAAI films revealed electrochemical oxidation and reduction accompanied with high contrast of optical transmittance color changes from the pale yellow neutral state to the green/blue oxidized state and red reduced state, respectively. The electrochromic films had high‐coloration efficiency (CE = 178 and 242 cm²/C at the first and the second stages, respectively), low‐switching time, and good redox stability, which still retained a high electroactivity after long‐term redox cycles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Novel high‐performance polymer memory devices containing (OMe)2tetraphenyl‐p‐phenylenediamine moieties

The functional polyimide (OMe)₂TPPA‐6FPI ( PI ) and the polyamide (OMe)₂TPPA‐6FPA ( PA ) consisting of electron‐donating N,N′‐bis(4‐aminophenyl)‐N,N′‐di(4‐methoxylphenyl)1,4‐phenylenediamine [(OMe)₂TPPA‐diamine] for memory application were prepared in this study. These polyimide and polyamide memory devices were fabricated with the sandwich configuration of indium tin oxide (ITO)/polymer/Al, and could be switched from the initial low‐conductivity (OFF) state to the high‐conductivity (ON) state with high ON/OFF current ratios of 10⁷ and 10⁹, respectively. PI exhibited dynamic random access memory (DRAM) performance, whereas PA showed static random access memory (SRAM) behavior. To get more insight into the memory behaviors of these two different types of polymer memory devices, molecular simulation on the basic unit was carried out. Furthermore, the differences of highest occupied molecular orbital (HOMO) energy level, lowest unoccupied molecular orbital (LUMO) charge density isosurfaces, dipole moment, and linkage conformation between PI and PA were found to affect the volatile memory behavior. Both polymer memory devices revealed excellent stability with long operation time of 10⁴ s at continuous applied voltage of ‐2 V. The effect of polymer thickness on the volatile memory behavior of PA was also investigated in this study. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of a new class of triphenylamine‐containing poly(ether‐imide)s for electrochromic applications

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     

Synthesis and properties of poly(ether imide)s based on a benzonorbornane bis(ether anhydride)

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. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1712–1725, 2002     

Synthesis,characterization, and investigation of structure‐thermal cycloimidization relationship of novel poly(amide amic acid)s to poly(amide imide)s by thermogravimetric analysis

Novel diamic acids (DAAs) and poly(amide amic acid)s (PAAs) were prepared and their thermal cycloimidization to the corresponding imide form was investigated by thermogravimetric analysis under isothermal conditions at four different temperatures, that is, at 175, 200, 225, and 260 °C for 75 min. A general equation, 18NW/R_MW, where, the numerical 18 corresponds to the molecular weight of water, N is the number of water molecules, which would be eliminated per repeat unit of the PAA upon cycloimidization, W is the weight of PAA taken for TGA, and R is the molecular weight of the repeat unit of PAA, has been derived for the calculation of theoretical amount of weight loss of PAA upon complete cycloimidization. The degree of cycloimidization (DCI%) of PAAs to poly(amide imide)s (PAI) has been calculated from their isothermal TGA curves. The variation in DCI on temperature, time, and the structures of diamine and acid chloride, especially, with respect to meta‐ and para‐linkages and the presence of electron withdrawing groups has been discussed. Cycloimidization occurs at faster rate in the initial stages of about 20 min, curing and then proceeds in a gradual manner and reaches almost a plateau within an hour. The DCI was more at higher temperatures, and the final values were 22?60% at 175 °C, 34?78% at 200 °C, 50?96% at 225 °C, and 85?99% at 260 °C after 75 min of heating, depending on the nature of diamine and acid chloride in the PAA. The DCI of PAAs with meta‐linkages in either of diamine or diacid chloride was somewhat lower than those having para‐linkages. The DCI of PAAs containing electron withdrawing group like sulfone in the diamine is somewhat higher compared with those of others. The final DCI (%) values obtained from FT‐IR spectra and isothermal TGA curves were very close to each other. Further, the thermal and thermooxidative stabilities of the PAIs were discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2937–2947, 2007     

Aromatic poly(sulfone sulfide amide imide)s as new types of soluble thermally stable polymers

A new diamine monomer containing flexible sulfone, sulfide, and amide units was prepared via three steps. Nucleophilic chloro displacement reaction of 4‐aminothiophenol with 4‐nitrobenzoyl chloride in the presence of propylene oxide afforded N‐(4‐mercapto‐phenyl)‐4‐nitrobenzamide and subsequent reduction of the nitro intermediate led to 4‐amino‐N‐(4‐mercapto‐phenyl)benzamide. Two moles of this amino thiophenol compound was reacted with bis‐(4‐chloro phenyl)sulfone to provide a novel diamine monomer. The diamine was reacted with aromatic dianhydrides to form polyimides via a two‐step polycondensation method, formation of poly(amic acid)s, followed by chemical imidization. The resulting polymers were characterized and their physical properties including thermal behavior, thermal stability, solubility and inherent viscosity were studied. Copyright © 2007 John Wiley & Sons, Ltd.     

New hyperbranched second‐order nonlinear optical poly(arylene‐ethynylene)s containing pentafluoroaromatic rings as isolation group: Facile synthesis and enhanced optical nonlinearity through Ar‐ArF self‐assembly effect

In this article, a facile route was designed to prepare four new hyperbranched poly(arylene‐ethynylene)s containing azo‐chromophore moieties through one‐pot “A₂+B₃” approach via simple Sonogashira coupling reaction. The polymers were all soluble in organic solvents and demonstrated good nonlinear optical (NLO) properties, because of the three‐dimensional spatial isolation effect of these hyperbranched polymers. Due to the different B₃‐type comonomer, the self‐assembly effect of pentafluoroaromatic in the interior of these polymers were different, leading to the different trends of the NLO activities. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Metal‐ and solvent‐free,clickable synthesis and postpolymerization functionalization of poly(triazole)s

In this study, a series of linear poly(triazole)s (PTAs) were successfully synthesized by the metal‐ and solvent‐free, thermal click polymerization of diazide and dialkyne (A₂ + B₂) monomers. All click polymerizations proceeded smoothly at 80 °C in an open atmosphere without protection from oxygen and moisture. After being polymerized for 36 h, the crude polymer was further fractionated into three fractions using a multistep precipitation method. By selectively choosing precipitating agents, this process produced poly(triazole) fractions with low polydispersity index (<1.30). The resulting PTAs are soluble in common organic solvents and stable at a temperature up to 320 °C. Furthermore, the methyl benzoate moieties in the main chain can serve as useful building blocks for further postpolymerization functionalization, yielding 1,2,4‐triazole derivatives. This functionalization strategy offers potential for the development of novel triazole‐based materials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Thermal and optical properties of some phosphorus‐containing poly(1,3,4‐oxadiazole‐ester‐imide)s

A series of phosphorus‐containing poly(1,3,4‐oxadiazole‐ester‐imide)s was prepared by polycondensation reaction of an aromatic dianhydride, namely 1,4‐[2‐(6‐oxido‐6H‐dibenz<c,e><1,2>oxaphosphorin‐6‐yl)]‐naphthalene‐bis(trimellitate)dianhydride, with different aromatic diamines containing 1,3,4‐oxadiazole ring. A solution imidization procedure was used to convert quantitatively the poly(amic acid) intermediates to the corresponding polyimides. The chemical structures of the monomers and polymers were confirmed by Fourier transform infrared, ¹H NMR and ³¹P NMR spectroscopy. The polymers were easily soluble in polar solvents such as N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethylformamide and tetrahydrofuran. They exhibited good thermal properties having the decomposition temperature above 380°C and the glass transition temperature in the range of 201–232°C. Due to the presence of phosphorus the polymers gave high char yield in termogravimetric analysis, hence good flame retardant properties. Optical properties were analyzed in solution by using UV–vis and photoluminescence spectroscopy. Solutions of the polymers in NMP exhibited photoluminescence in the blue region. Copyright © 2010 John Wiley & Sons, Ltd.     

Poly(ether imide)s derived from phthalazinone‐containing dianhydrides

An unsymmetrical and noncoplanar heterocyclic dianhydride was synthesized from a bisphenol‐like phthalazinone, 4‐(4‐hydroxylphenyl)‐2,3‐phthalazin‐1‐one, and a series of novel poly(ether imide)s based on it, with intrinsic viscosities of 0.67–1.42 dL/g, were obtained by one‐step solution polymerization in m‐cresol at 200 °C for 20 h. The polymers were readily soluble in N‐methyl‐2‐pyrrolidinone and m‐cresol. The poly(ether imide)s derived from 4,4′‐oxydianiline and 4,4′‐methylenedianiline were also very soluble in chloroform, 1,1′,2,2′‐tetrachloroethane, and N,N‐dimethylacetamide. The glass‐transition temperatures were 289–326 °C, as determined by differential scanning calorimetry. All the degradation temperatures for 5% weight loss occurred above 482 °C in nitrogen. The tensile strength of thin films of some of the polymers varied from 103.1 to 121.4 MPa. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6089–6097, 2004     

Oxidation and epoxidation of poly(1,3‐cyclohexadiene)

Poly(1,3‐cyclohexadiene) (PCHD) derivatives were synthesized via facile chemical modification reactions of the residual double bond in the repeat unit. The oxidation and degradation of PCHD was investigated to enable subsequent controlled epoxidation reactions. PCHD exhibited a 15% weight loss at 110 °C in the presence of oxygen. The oxidative degradation, demonstrated by gel permeation chromatography (GPC) and ¹H NMR spectroscopy, was attributed to main‐chain scission. Aldehyde and ether functional groups were introduced into the polymer during the oxidation process. PCHD was quantitatively epoxidized in the absence of deleterious oxidation with meta‐chloroperoxybenzoic acid. ¹H and ¹³C NMR spectroscopy confirmed that polymers with controlled degrees of epoxidation were reproducibly obtained. Epoxidized PCHD exhibited a glass‐transition temperature at 154 °C, which was slightly higher than that of a PCHD precursor of a nearly equivalent molecular weight. Moreover, GPC indicated the absence of undesirable crosslinking or degradation, and the molecular weight distributions remained narrow. The thermooxidative stability of the fully epoxidized polymer was compared to that of the PCHD precursor, and the epoxidized PCHD exhibited an initial weight loss at 250 °C in oxygen, which was 140 °C higher than the temperature for PCHD. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 84–93, 2003     

Thermally stable,light‐emitting,triphenylamine‐containing poly(amine hydrazide)s and poly(amine‐1,3,4‐oxadiazole)s bearing pendent carbazolyl groups

A series of new organosoluble poly(amine hydrazide)s were synthesized via the Yamazaki phosphorylation reaction and were solution‐cast into transparent films. Differential scanning calorimetry indicated that the hydrazide polymers 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 exhibited glass‐transition temperatures in the range of 276–297 °C, 10% weight loss temperatures in excess of 520 °C, and char yields at 800 °C in nitrogen higher than 67%. The hole‐transporting and electrochromic properties were examined with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of these polymers prepared by the casting of polymer solutions onto an indium tin oxide coated glass substrate exhibited two reversible oxidative redox couples at 1.10–1.19 and 1.35–1.60 V versus Ag/AgCl in an acetonitrile solution, respectively. The poly(amine hydrazide)s revealed excellent stability of the electrochromic characteristics, changing color from the original pale yellow to green and then to blue. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 48–58, 2007     

One‐pot synthesis of linear and branched poly(amide aspartimide)s with good solubility in organic solvents

Linear and branched poly(amide aspartimide)s were prepared through the reaction of 4,4′‐diaminodiphenylmethane with 4‐maleimidobenzoic acid and 5‐maleimidoisophthalic acid, respectively. The synthesis was performed through a one‐pot operation by means of the Michael addition reaction between amine and maleimide groups and the dehydration condensation reaction between amine and carboxylic acid groups. The obtained polymers exhibited fairly good solubility in aprotic polar solvents at room temperature and in pyridine, tetrahydrofuran, acetone, and chloroform upon heating. High glass‐transition temperatures (≥225 °C) and thermal stability above 360 °C were found for the polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1923–1929, 2005     

Highly soluble and optically transparent poly (ether imide)s based on 2,6‐ or 2,7‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride and aromatic bis(ether amine)s bearing trifluoromethyl groups

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     

Fluorinated poly(benzoxazole–imide)s

New poly(benzoxazole–imide)s have been prepared by polycondensation of bis(o-aminophenol)s, such as 3,3′ dihydroxybenzidine or 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, with diacid chlorides containing both imide and hexafluoroisopropylidene groups. The soluble polymer precursor resulting from the first step of polycondensation in N-methylpyrrolidinone (NMP) at low temperature was processed into thin flexible films, which were then thermally treated to reach the fully cyclized structure of poly(benzoxazole–imide)s, as observed by infrared spectra. An alternative way to produce the cyclization was by heating at reflux the solution of polymer precursor in NMP. Thermal stability, glass transition temperature, dielectric constant and its dependence on relative humidity have been studied and compared with those of related polybenzoxazoles and other heterocyclic Polymers.     

Scalable ambient synthesis of water‐soluble poly(β‐hydroxythio‐ether)s

Proton transfer polymerization through thiol‐epoxy “click” reaction between commercially available and hydrophilic di‐thiol and di‐epoxide monomers is carried out under ambient conditions to furnish water‐soluble polymers. The hydrophilicity of monomers permitted use of aqueous tetrahydrofuran as the reaction medium. A high polarity of this solvent system in turn allowed for using a mild catalyst such as triethylamine for a successful polymerization process. The overall simplicity of the system translated into a simple mixing of monomers and isolation of the reactive polymers in an effortless manner and on any scale required. The structure of the resulting polymers and the extent of di‐sulfide defects are studied with the help of 13C‐ and ¹H‐NMR spectroscopy. Finally, reactivity of the synthesized polymers is examined through post‐polymerization modification reaction at the backbone sulfur atoms through oxidation reaction. The practicality, modularity, further functionalizability, and water solubility aspects of the described family of new poly(β‐hydroxythio‐ether)s is anticipated to accelerate investigations into their potential utility in bio‐relevant applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3381–3386     

Pt‐catalyzed chemical modification of α,ω‐bis(hydrido)polydimethylsiloxanes and copoly(methylhydridosiloxane/dimethylsiloxane) with vinylheptaphenylcyclotetrasiloxane

Pt‐catalyzed hydrosilylation between vinylheptaphenylcyclotetrasiloxane and a series of α,ω‐bis(hydrido)polydimethylsiloxanes and copoly(methylhydridosiloxane/dimethylsiloxane) was used to prepare chemically modified materials. These modified polymers were characterized by IR, UV, and ¹H, ¹³C, and ²⁹Si NMR spectroscopy and gel permeation chromatography (GPC). The molecular weights, determined by GPC, UV, and NMR end‐group analysis, showed the anticipated increases. The thermal properties of the polymers were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The crystallinity, determined by DSC, was either reduced or completely eliminated for the modified polymers. The thermal stabilities, measured in both air and nitrogen by TGA, were slightly higher than the thermal stability of α,ω‐bis(trimethylsiloxy)polydimethylsiloxane. Significantly increased bulk viscosities were observed for all the modified polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3007‐3017, 2005     

Glycoconjugated polymer: Synthesis and characterization of poly(vinyl saccharide)‐block‐polystyrene‐block‐poly(vinyl saccharide) as an amphiphilic ABA triblock copolymer

Styrene (St) was polymerized with α,α′‐bis(2′,2′,6′,6′‐tetramethyl‐1′‐piperidinyloxy)‐1,4‐diethylbenzene ( 1 ) as an initiator (bulk, [St]/] 1 ] = 570) at 120 °C for 5.0 h to obtain polystyrene having 2,2,6,6‐tetramethylpiperidiloxy moieties on both sides of the chain ends ( 2 ) with a number‐average molecular weight (M_n) of 14,300 and a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.14. 4‐Vinylbenzyl glucoside peracetate ( 3a ) was polymerized with 2 as a macromolecular initiator and dicumyl peroxide (DCP) as an accelerator in chlorobenzene at 120 °C. The polymerization with the [ 3a ]/[ 2 ]/[DCP] ratio of 30/1/1.2 for 5 h afforded a product in a yield of 73%; it was followed by purification with preparative size exclusion chromatography to provide the ABA triblock copolymer containing the pendant acetyl glucose on both sides of the chain ends ( 4a ; M_n = 21,000, M_w/M_n = 1.16). Similarly, the polymerization of 4‐vinylbenzyl maltohexaoside peracetate produced the ABA triblock copolymer containing the pendant acetyl maltohexaose on both side of the chain end ( 4b ; M_n = 31,800, M_w/M_n = 1.11). Polymers 4a and 4b were modified by deacetylation into amphiphilic ABA triblock copolymers containing the pendant glucose and maltohexaose as hydrophilic segment, 5a and 5b , respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3978–3985, 2006     

End‐group functionalization and postpolymerization modification of helical poly(isocyanide)s

This contribution presents the synthesis of helical alkyne‐terminated polymers using a functionalized Nickel complex to initiate the polymerization of menthylphenyl isocyanides. The resulting polymers display low dispersities and controlled molecular weights. Copper‐catalyzed azide/alkyne cycloadditions (CuAAC) are performed to attach various azide‐containing compounds to the polymer termini. After azido‐phosphonate moiety attachment the polymer displays a signal at 25.4 ppm in the ³¹P NMR spectrum demonstrating successful end‐group functionalization. End‐group functionalization of a fluorescent dye allows to determine the functionalization yield as 89% (±8). Successful ligation of an azide‐functionalized peptide sequence (M_KLA = 1547 g/mol) increases the M_n from 5100 for the parent polymer to 6700 for the bioconjugate as visualized by GPC chromatography. Analysis by CD spectroscopy confirms that the helical conformation of the poly(isocyanide) block in the peptide–polymer conjugate is maintained after postpolymerization modification. These results demonstrate an easy, generalizable, and versatile strategy toward mono‐telechelic helical polymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2766–2773