Electrochromic properties and electrochromic device application of copolymer of N‐(4‐(3‐thienyl methylene)‐oxycarbonylphenyl)maleimide with thiophene

A new copolymer of N‐(4‐(3‐thienyl methylene)‐oxycarbonylphenyl)maleimide (MBThi) with thiophene [P(MBThi‐co‐Th)] was synthesized electrochemically in the presence of tetrabutylammonium tetrafluoroborate as the supporting electrolyte, in acetonitrile/borontrifluoride ethylether solvent mixture (80 : 20, v/v). Spectroelectrochemical analysis of the resulting copolymer reflected electronic transitions at 440, 730, and ～1000 nm, revealing π–π* transition, polaron, and bipolaron band formation, respectively. Switching ability was evaluated by a kinetic study via measuring the transmittance (%T) at the maximum contrast. Dual‐type polymer electrochromic devices (ECDs) based on P(MBThi‐co‐Th) and poly(ethylene dioxythiophene) (PEDOT) were constructed. Spectroelectrochemistry, switching ability, and stability of the devices were investigated by UV–vis spectroscopy and cyclic voltammetry. These devices exhibit low switching voltages (between 0.0 and +2.0 V) and short switching times with reasonable switching stability under atmospheric conditions. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 4500–4505, 2006     

Synthesis and characterization of poly(thiophen‐3‐yl acetic acid 4‐pyrrol‐1‐yl phenyl ester‐co‐N‐methylpyrrole) and its application in an electrochromic device

Copolymer of thiophen‐3‐yl acetic acid 4‐pyrrol‐1‐yl phenyl ester (TAPE) with N‐methylpyrrole (NMPy) was synthesized by potentiostatic electrochemical polymerization in acetonitrile–tetrabutylammonium tetrafluoroborate solvent–electrolyte couple. The chemical structures were confirmed via Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), and UV–vis spectroscopy. Electrochromic and spectroelectrochemical properties of poly(TAPE‐co‐NMPy) [P(TAPE‐co‐NMPy)] were investigated. Results showed that the copolymer revealed color change between light yellow and green upon doping and dedoping of the copolymer, with a moderate switching time. Furthermore, as an application, dual‐type absorptive/transmissive polymer electrochromic device (ECD) based on poly(TAPE‐co‐NMPy) and poly(3,4‐ethylene dioxythiophene) (PEDOT) have been assembled, where spectroelectrochemistry, switching ability, stability, and optical memory of the ECD were investigated. Results showed that the device exhibited good optical memory and stability with moderate switching time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1988–1994, 2006     

Synthesis and characterization of thiophene functionalized polystyrene copolymers and their electrochemical properties

Thiophene functionalized polystyrene samples (TFPS) were synthesized by atom transfer radical polymerization (ATRP) of styrene, followed by Suzuki coupling with 3‐thiophene (Th) boronic acid. Conducting graft polymer of TFPS with thiophene was achieved at 1.5 V in tetrabutylammonium tetrafluoroborate/dichloromethane (TBAFB/DM) by electrochemical methods. Spectroelectrochemical analysis of the resulting copolymers [P(TFPS‐co‐Th)] reflected electronic transitions at 449, 721 and 880 nm, revealing π ? π* transition, polaron and bipolaron band formation, respectively. We also successfully established the utilization of dual type complementary colored polymer electrochromic devices using P(TFPS‐co‐Th)/poly(3,4‐ethylenedioxythiophene (PEDOT) in sandwich configuration. The switching ability, stability and optical memory of the electrochromic device were investigated by UV–visible spectrophotometry and cyclic voltammetry. Device switches between brown and blue color with a switching time of 1.3 s were prepared with optical contrast (%ΔT) of 25 %. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of novel polythiophenes containing poly(ethylene oxide) side chains

Thiophene copolymers and their derivatives with poly(ethylene oxide) side chains were synthesized. The starting monomers were 3‐hexylthiophene and 2‐(3‐thienyl) ethanol with poly(ethylene oxide) grafted to the side chains. New functionalized polythiophenes were prepared by both chemical oxidation with FeCl₃ and electropolymerization. The conjugating polymers were characterized. The structures of the polythiophene derivatives agreed with the design. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1803–1808, 2006     

Ionic conductivity and morphology of semi‐interpenetrating‐type polymer electrolyte entrapping poly(siloxane‐g‐allyl cyanide)

We prepared a semi‐IPN (interpenetrating network)‐type solid polymer electrolyte (SPE) using poly (ethylene glycol)dimethacrylate (PEGDMA) as a polymer matrix containing a monocomb‐type poly(siloxane‐g‐allyl cyanide) and poly(ethylene glycol)dimethylether (PEGDME) for the lithium secondary battery. The poly(siloxane‐g‐allyl cyanide)s were prepared by a hydrosilation reaction of poly (methyl hydrosiloxane) with allyl cyanide and characterized by ¹H NMR and FTIR. The semi‐IPN‐type electrolyte was prepared by thermal curing, and conductivities of samples were measured by impedance spectroscopy using an indium tin oxide (ITO) electrode. The ionic conductivity of the semi‐IPN‐polymer electrolyte was about 1.05 × 10^?5 S cm^?1 with 60 wt % of the poly(siloxane‐g‐allyl cyanide) and 6.96 × 10^?4 S cm^?1 with 50 wt % of the PEGDME and 10 wt % of the poly(siloxane‐g‐allyl cyanide) at 30°C. The SEM morphology of the cross section of the semi‐IPN‐polymer electrolyte film was changed from discontinuous network to continuous network as increasing the PEGDME content and decreasing the poly(siloxane‐g‐allyl cyanide) content. The mechanical stability was also enhanced when increasing the PEGDME content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of ionic liquid fragment on the performance of polymer electrolytes

An ionic liquid 1‐methyl‐3‐[2‐(methacryloyloxy)ethyl]imidazolium bis(trifluoromethane sulfonylimide) (MMEIm‐TFSI) was synthesized and polymerized. Composite polymer electrolytes based on polymeric MMEIm‐TFSI (PMMEIm‐TFSI) and poly[(methyl methacrylate)‐co‐(vinyl acetate)] (P(MMA‐VAc)) were prepared, with lithium bis(trifluoromethane sulfonylimide) (LiTFSI) as target ions (Li⁺). DSC/TGA analysis showed good flexibility and thermal stability of the composite electrolyte membranes. The AC impedance showed that the ionic conductivity of the electrolytes increased with PMMEIm‐TFSI up to a maximum value of 1.78 × 10^?4 S cm^?1 when the composition was 25 wt% P(MMA‐VAc)/75 wt% PMMEIm‐TFSI/30 wt% LiTFSI at 30 °C. The composite electrolyte membrane (transmittance ≥ 90%) can also be used as the ion‐conductive layer material for electrochromic devices, and revealed excellent colorization performance. Copyright © 2011 Society of Chemical Industry     

Aggregation phenomena of amphiphilic UVB absorptive oligoesters containing p‐alkoxycinnamate and poly(ethylene oxide) blocks

The synthesis of new amphiphilic oligoesters containing a hydrophobic block based on p‐alkoxycinnamate and hydrophilic poly(ethylene oxide) is reported. Two hydrophobic monomers, 1,2‐(bis(4‐(2‐carboxyvinyl)phenoxy))ethane ( M2 ) and 1,12‐(bis(4‐(2‐carboxyvinyl) phenoxy))dodecane ( M12 ), were synthesized. Four oligoesters, poly((1,2‐(bis(4‐(2‐carboxyvinyl)phenoxy))ethane) ‐co‐(poly(ethylene oxide)200)) ( P2‐200 ), poly((1,2‐(bis(4‐(2‐carboxyvinyl)phenoxy))ethane)‐co‐(poly(ethylene oxide) 400)) ( P2‐400 ), poly((1,12‐(bis(4‐(2‐carboxyvinyl)phenoxy)) dodecane)‐co‐(poly(ethylene oxide)400)) ( P12‐400 ), and poly((1,12‐(bis(4‐(2‐carboxyvinyl)phenoxy))dodecane)‐co‐ (poly(ethylene oxide)1000)) ( P12‐1000 ) were then constructed by reacting the M2 or M12 with poly(ethylene oxide) (PEO) with lengths of ～ 4 (PEO 200), ～ 10 (PEO 400), or ～ 23 (PEO1000) units using multiple esterifications. These oligoesters possess UVB absorption properties and show good solubility in various organic solvents. Self‐assembly of the oligoesters into aqueous spherical colloids could be induced through an acetone to water solvent displacement technique. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Solid-state electrochromic devices using pTMC/PEO blends as polymer electrolytes

Flexible, transparent and self-supporting electrolyte films based on poly(trimethylene carbonate)/poly(ethylene oxide) (p(TMC)/PEO) interpenetrating networks doped with LiClO₄ were prepared by the solvent casting technique. These novel solid polymer electrolyte (SPE) systems were characterized by measurements of conductivity, cyclic voltammetry, differential scanning calorimetry and thermogravimetry.The incorporation of solid electrolytes as components of electrochromic devices can offer certain operational advantages in real-world applications. In this study, all-solid-state electrochromic cells were characterized, using Prussian blue (PB) and poly-(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT) as complementary electrochromic compounds on poly(ethyleneterphthalate) (PET) coated with indium tin oxide (ITO) as flexible electrodes. Assembled devices with PET/ITO/PB/SPE/PEDOT/ITO/PET “sandwich-like” structure were assembled and successfully cycled between light and dark blue, corresponding to the additive optical transitions for PB and PEDOT electrochromic layers. The cells required long cycle times (>600 s) to reach full color switch and have modest stability towards prolonged cycling tests. The use of short duration cycling permitted the observation of changes in the coloration-bleaching performance in cells with different electrolyte compositions.     

Surface modification of LDPE with PE‐PEO graft copolymer

Films of LDPE containing 1–10 wt % of various polymeric additives were prepared by different techniques. Three poly(ethylene‐graft‐ethylene oxide)s synthesized by grafting poly(ethylene‐co‐acrylic acid) with poly(ethylene oxide) monomethyl ether (MPEO), and two pure MPEOs having molecular weights 750 and 2000 were used as additives. The additives were mixed with LDPE both by blending in a common solvent and by melt mixing. The blends were then solvent cast from xylene onto glass Petri dishes or compression molded between glass plates. The film surfaces were studied by water contact angle measurements and by X‐ray photoelectron spectroscopy (XPS), and melting points and heats of melting were recorded by differential scanning calorimetry (DSC). The blends had a two‐phase morphology, with enrichment of the graft copolymers at the glass–polymer interface, as shown by contact angle values and XPS spectra. Large differences in the interface accumulation between the different film samples were observed. Films prepared by compression molding of solution‐mixed blends exhibited much lower surface accumulation of graft copolymer at the glass–polymer interface than did the solvent cast or melt‐mixed/compression‐molded samples. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 316–326, 2000     

Fabrication and characterization of PEO/PPC polymer electrolyte for lithium‐ion battery

A new poly(propylene carbonate)/poly(ethylene oxide) (PEO/PPC) polymer electrolytes (PEs) have been developed by solution‐casting technique using biodegradable PPC and PEO. The morphology, structure, and thermal properties of the PEO/PPC polymer electrolytes were investigated by scanning electron microscopy, X‐ray diffraction, and differential scanning calorimetry methods. The ionic conductivity and the electrochemical stability window of the PEO/PPC polymer electrolytes were also measured. The results showed that the T_g and the crystallinity of PEO decrease, and consequently, the ionic conductivity increases because of the addition of amorphous PPC. The PEO/50%PPC/10%LiClO₄ polymer electrolyte possesses good properties such as 6.83 × 10^?5 S cm^?1 of ionic conductivity at room temperature and 4.5 V of the electrochemical stability window. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

In situ synthesis of iron oxide nanoparticles on poly(ethylene oxide) nanofibers through an electrospinning process

Iron oxide nanoparticle coated poly(ethylene oxide) nanofibers as organic–inorganic hybrids with 200–400‐nm diameters were prepared by the in situ synthesis of iron oxide nanoparticles on poly(ethylene oxide) nanofibers through the electrospinning of a poly(ethylene oxide) solution having Fe²⁺ and Fe³⁺ ions in a gaseous ammonia atmosphere. Transmission electron microscopy analysis proved the presence of iron oxide nanoparticles on the polymer nanofibers. The thermal properties of the nanofiber mat were also studied with differential scanning calorimetry and thermogravimetric analysis techniques. X‐ray diffraction showed that the formed iron oxide nanoparticles were maghemite nanoparticles. The results were compared with those of the electrospinning of a poly(ethylene oxide) solution having Fe²⁺ and Fe³⁺ ions and a pure poly(ethylene oxide) solution in an air atmosphere. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and thermal stability of polystyrene and poly(vinyl chloride) coated with polythiophene and modified with Fe2O3 nanoparticles

In this study, polystyrene and poly(vinyl chloride) particles were coated successfully with polythiophene in aqueous media. These nanocomposites were prepared in situ by polymerization of thiophene in the presence of FeCl₃ as an oxidant and poly(vinyl pyrrolidone) as a surfactant. The effect of Fe₂O₃ nanoparticles on the characteristics of products such as thermal stability and morphology was investigated. The chemical structure, morphology, and thermal stability of these core‐shell nanocomposites were studied by Fourier‐transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, and thermogravimetric analysis. Thermal stability of the nanocomposites was compared and indicated that the thermal stability of polythiophene/polystyrene was better than the polythiophene/poly(vinyl chloride) nanocomposite. Also, the presence of Fe₂O₃ nanoparticles can drastically increase the thermal stability of polythiophene nanocomposites. J. VINYL ADDIT. TECHNOL. 20:212–217, 2014. © 2014 Society of Plastics Engineers     

Influence of LiClO4 on the thermal,mechanical, and morphological properties of P(DMS‐co‐EO)/ P(EPI‐co‐EO) blends

The UV‐vis absorption, thermal analysis, ionic conductivity, mechanical properties, and morphology of a blend of poly(dimethylsiloxane‐co‐ethylene oxide) [P(DMS‐co‐EO)] and poly(epichlorohydrin‐co‐ethylene oxide) [P(EPI‐co‐EO)] (P(DMS‐co‐EO)/P(EPI‐co‐EO) ratio of 15/85 wt %) with different concentrations of LiClO₄ were studied. The maximum ionic conductivity (σ = 1.2 × 10^?4 S cm^?1) for the blend was obtained in the presence of 6% wt LiClO₄. The crystalline phase of the blend disappeared with increasing salt concentration, whereas the glass transition temperature (T_g) progressively increased. UV‐vis absorption spectra for the blends with LiClO₄ showed a transparent polymer electrolyte in the visible region. The addition of lithium salt decreased the tensile strength and elongation at break and increased Young's modulus of the blends. Scanning electron microscopy showed separation of the phases between P(DMS‐co‐EO) and P(EPI‐co‐EO), and the presence of LiClO₄ made the blends more susceptible to cracking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1230–1235, 2004     

Cylinder‐to‐rod‐to‐sphere evolution of complex micelles in solution and their corresponding solvent‐induced crystallization process

In a previous paper, we investigated the solvent‐induced crystallization of films made up of spherical micelles, which were prepared by mixing polystyrene‐block‐poly(acrylic acid) and polystyrene‐block‐poly(2‐vinylpyridine)‐block‐poly(ethylene oxide) in the neutral solvent N,N‐dimethylformamide (DMF). In the work reported in the present paper, we further studied the cylinder‐to‐rod‐to‐sphere evolution of complex micelles in solution and their corresponding solvent‐induced crystallization process. The initial morphology of the micelles in the solution was cylindrical due to a rapid growth of micelles with high unimer concentration, and spheres became the dominant form after storage at room temperature for a longer time. Regular square platelets can form after a certain period of treatment for all micelles in DMF vapor for sufficient time. However, the kinetics of their solvent‐induced crystallization process is quite different. The aggregation and subsequent nucleation of poly(ethylene oxide) blocks are determined by the distribution of crystallizable poly(ethylene oxide) blocks in the films. Copyright © 2010 Society of Chemical Industry     

Memory functions in polymer modified asphalts

The viscoelastic nonlinear behavior of several base and polymer modified asphalts (PMA) has been studied in step‐strain experiments. The polymers were poly(styrene‐b‐butadiene‐b‐styrene), poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene), poly(ethylene‐r‐vinylacetate) copolymers, and a linear low density poly(ethylene), which were chosen as representatives of the main categories of asphalt modifiers. Because of the complexity of the morphological structure of these materials, the relaxation modulus has only partial and qualitative similarities with that of melt or high concentrated solutions of entangled polymeric liquids. No time strain separability can be applied, and the relaxation experiments are conveniently described by means of the memory functions. These have been calculated both via a parametric fitting procedure and by interpolation algorithms. Results are presented, and a correlation between the PMA structure and the corresponding memory function is proposed for the investigated materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2330–2340, 2007     

Fabrication and properties of solution processed all polymer thin‐film ferroelectric device

A ferroelectric device, making use of a flexible plastic, polyethylenterephtalate (PET), as a substrate was fabricated by all solution processes. PET was globally coated by a conducting polymer, poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) acid (PEDOT/PSSH), which is used as bottom electrode. The ferroelectric copolymer, poly(vinylidenefluoride–trifluoroethylene) (PVDF–TrFE), thin film was deposited by spin‐coating process from solution. The top electrode, polyaniline, was coated by solution process as well. The ferroelectric properties were measured on this all solution processed all polymer ferroelectric thin‐film devices. A square and symmetric hysteresis loop was observed with high‐polarization level at 15‐V drive voltage on a all polymer device with 700 Å (PVDF–TrFE) film. The relatively inexpensive conducting polyaniline electrode is functional well and therefore is a good candidate as electrode material for ferroelectric polymer thin‐film device. The remnant polarization P_r was 8.5 μC/cm² before the fatigue. The ferroelectric degradation starts after 1 × 10³ times of switching and decreases to 4.9 μC/cm² after 1 × 10⁵ times of switching. The pulse polarization test shows switching take places as fast as a few micro seconds to reach 90% of the saturated polarization. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of nanofiller concentration on conductivity and dielectric properties of poly(ethylene oxide)–poly(methyl methacrylate) polymer electrolytes

This paper reports the effect of nanofiller concentration on the conductivity and dielectric properties of the poly(ethylene oxide)–poly(methyl methacrylate)–poly(ethylene glycol)–AgNO₃–Al₂O₃ polymer electrolyte system. The preparation of polymer films was done using the solution‐casting technique and characterization of the films was carried out using scanning electron microscopy, differential scanning calorimetry and ionic transport techniques. The ionic conductivity, investigated using impedance spectroscopy, was expected to show interesting behaviour at below and above the melting temperature of poly(ethylene oxide) in the polymer blend films. Complex impedance data were analysed in an alternating current conductivity and dielectric permittivity formalism in order to throw light on the transport mechanism. The effect of nanofiller concentration on conduction and relaxation processes at various temperatures was studied. © 2013 Society of Chemical Industry     

Polythiophene‐based materials for nonvolatile polymeric memory devices

Polymeric materials used in memory devices have attracted significant scientific interest due to their several advantages, such as low cost, solution processability, and possible development of three‐dimensional stacking devices. Polythiophenes, including tethered alkyl substituted polythiophenes and block copolymers, poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and composites, are one of the most attractive polymeric systems for memory applications because of their commercial availability, high conductivity, and mechanical strength. In this article, recent studies of functional polythiophene for memory applications are reviewed, mostly focusing on the role of the materials in the memory functionality, optimizing the chemical structure of the polythiophene and the component of each layer in memory device. A critical summary of the proposed mechanisms, including filament formation, electric field‐induced charge transfer and reduction‐oxidation (redox) driven, is given to explain the resistive switching phenomena in the polythiophene system. In addition, the challenges facing the research and development in the field of polythiophene electronic memories are summarized. POLYM. ENG. SCI., 54:2470–2488, 2014. © 2013 Society of Plastics Engineers     

Preparation and characterization of amphiphilic block copolymer of polyacrylonitrile‐block‐poly(ethylene oxide)

The synthesis of polyacrylonitrile‐block‐poly(ethylene oxide) (PAN‐b‐PEO) diblock copolymers is conducted by sequential initiation and Ce(IV) redox polymerization using amino‐alcohol as the parent compound. In the first step, amino‐alcohol potassium with a protected amine group initiates the polymerization of ethylene oxide (EO) to yield poly(ethylene oxide) (PEO) with an amine end group (PEO‐NH₂), which is used to synthesize a PAN‐b‐PEO diblock copolymer with Ce(IV) that takes place in the redox initiation system. A PAN‐poly(ethylene glycol)‐PAN (PAN‐PEG‐PAN) triblock copolymer is prepared by the same redox system consisting of ceric ions and PEG in an aqueous medium. The structure of the copolymer is characterized in detail by GPC, IR, ¹H‐NMR, DSC, and X‐ray diffraction. The propagation of the PAN chain is dependent on the molecular weight and concentration of the PEO prepolymer. The crystallization of the PAN and PEO block is discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1753–1759, 2003     

Porous polymer monolith templated by small polymer molecules

Porous poly(ethylene glycol) diacrylate (PEGDA) monoliths have been prepared by UV‐initiated polymerization of PEGDA oligomer (M_n = 700 g/mol). In the mean time, the addition of hydrophobic poly(propylene oxide) (PPO, M_n = 725 g/mol) as porogen into an ethanol solution of PEGDA oligomer to form a homogenous mixture, causes a phase separation between PPO and PEGDA following removal of ethanol by UV heating. Porous PEGDA monolith was prepared by immediate heating at 300°C to remove PPO molecules from the as‐synthesized PEGDA/PPO hybrid. The micrometer pores of the PEGDA monolith have relatively concentrated pore size distribution according to the mercury intrusion porosimetry results and field emission scanning electron microscopy (FE‐SEM).