Synthesis and ionic conductivity of hyperbranched poly(glycidol)

A novel hyperbranched poly(glycidol) (HPG) was prepared and characterized. The synthesized HPG was used as a substrate of a polymer electrolyte. The ionic conductivity of a blend of HPG, polyurethane (PU), and salt was studied. The ionic conductivity of HPG/PU/LiClO₄ was about 6.6 × 10^?6 S · cm^?1 at 20 °C and 6.3 × 10^?4 S · cm^?1 at 60 °C. The results indicated that HPG showed higher solubility for salt than linear polyether when both had the same [O]/[Li⁺] molar ratio. The main reason was that more cavities and a lower degree of chain entanglement in HPG resulted in a lower glass‐transition temperature and were beneficial for decreasing the aggregation of salt or enhancing the ionic conductivity. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2225–2230, 2001     

Low glass transition temperature polymer electrolyte prepared from ionic liquid grafted polyethylene oxide

In this contribution, we report a new type of poly (ionic liquids) prepared by imidazolium ionic liquids directly grafting onto polyethylene oxide backbone. Different molecular weights of poly (ionic liquids) are obtained with a low glass transition temperature up to ?14 °C. The materials as polymer electrolyte achieve a high conductivity around 10^?5 S cm^?1 at 30 °C and close to 10^?3 S cm^?1 at 90 °C. High viscosity up to 4000 Pa s at room temperature would minimize the electrolytes leaking in electrochemical devices. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2104–2110     

Intrinsic viscosities of polyelectrolytes: determination and modeling of the effects of extra salt

Based on early measurements of J. J. Hermans and co-workers (D. T. F. Pals, J. J. Hermans, Recl. Trav. Chim. Pays-Bas 1952, 71, 513-520; D. T. F. Pals, J. J. Hermans, J. Polym. Sci. 1950, 5, 733-734; D. T. F. Pals, J. J. Hermans, J. Polym. Sci. 1948, 3, 897-898), the present contribution demonstrates how primary data should be evaluated in order to obtain reliable intrinsic viscosities. This procedure yields detailed information on the changes of the intrinsic viscosities and of the corresponding viscometric interaction parameters caused by an increasing salinity of water. Both quantities decline from a maximum value in the pure solvent to a minimum value, which is approached in the limit of sufficiently high salt concentrations, and can be modeled quantitatively by means of a Boltzmann sigmoid. Particular attention is paid to the significance of results obtained by means of the method of isoionic dilution, proposed by J. J. Hermans and co-workers.     

The effect of ionic strength on the diffusion of 125I in Gaomiaozi bentonite

The diffusion of ¹²⁵I^? in compacted Gaomiaozi (GMZ) bentonite was investigated by capillary in-diffusion method. Apparent and effective diffusion coefficients and accessible porosity of iodide in GMZ bentonite were obtained, and the effect of ionic strength on diffusion parameters was studied. The apparent diffusion coefficients of iodide in compacted GMZ bentonite are in the range of 1.0–6.0 × 10^?10 m² s^?1 under the conditions of dry bulk density 1,500 kg m^?3 and temperature 298 K, and increase with increasing ionic strength. This effect was explained through the analysis of microscopic structure of compacted bentonite. The iodide can only diffuse in unbound interparticle pore solution of compacted bentonite. The apparent diffusion coefficient is a function of accessible porosity which is decided by the thickness of diffusion double layer, and the thickness is in turn controlled by ionic strength.     

Preparation of a solution‐processable,nanostructured ionic polyacetylene

Polymerization of a self‐assembled 1‐dodecyl‐3‐propargylimidazolium bromide ionic liquid (IL) yields a nanostructured ionic polyacetylene. A 1:1 aqueous mixture of the amphiphilic IL produces an ordered lyotropic mesophase that adopts a hexagonal perforated lamellar structure. Rh (I)‐mediated polymerization of the assembled mixture yields a hexagonal modulated lamellar structured polymer. FTIR spectroscopy reveals that the polymer was self n‐doped. The polymer was fractioned into three components with the majority product, possessing an intermediate molecular weight that is soluble in polar organic solvents. In methanol, the optical band gap of the main fraction was determined to be 2.38 eV and was nonemissive. The solution‐processable polymer was airbrush sprayed onto glass substrates to give a liquid‐crystalline, lamellar structured semiconductive film (7.02 × 10^?5 S cm^?1). The polymer resisted oxidation (degradation) upon storage in air as monitored by vibrational spectroscopy. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1215–1227     

Synthesis and properties of polymeric analogs of ionic liquids

A number of methacrylate ionic monomers with different structures and mobilities of ionic centers were synthesized. The free-radical polymerization of these monomers in solution affords high-molecular-mass (M _sD = 0.5 to 2.5 × 10⁶) thermally stable (T _dec > 170°C) polyelectrolytes or cationic or anionic “polymeric ionic liquids.” The conductivities of polycation- and polyanion-derived coatings are (7.4 × 10^?10)?(7.6 × 10^?7) and (4.9 × 10^?10)-(1.6 × 10^?7) S/cm (25°C), respectively. As exemplified by poly(1-[3-(methacryloyloxy)propyl]-3-methylimidazolium bis[(trifluoromethanesulfonyl)imide]), the molecular mass and glasstransition temperature of the polymer affect the ionic conductivity of the film coating. The transition from linear polyelectrolytes to crosslinked systems based on ionic monomers and poly(ethylene glycol dimethacrylate) 750 leads to the formation of elastic films featuring satisfactory strength, reduced glass-transition temperatures (?8 to +15°C), and increased ionic conductivity (up to 3.2 × 10^?6 S/cm (25°C)).     

Potentiometric measurements of the first hydrolysis quotient of magnesium(II) to 250°C and 5 molal ionic strength (NaCl)

The first molal hydrolysis quotient, Q_1.1, of Mg²⁺ was measured potentiometrically from 1 to 250°C at ionic strengths of 0.11, 0.31, 1.01, and 5.0 mol-kg^-1 in an aqueous NaCl medium using a hydrogen-electrode, concentration cell. Only hydrolysis of the first four percent of the magnesium in solution could be followed before precipitation of brucite, Mg(OH)₂(cr), occurred. The log Q_1.1 values were fitted as a function of temperature and ionic strength using four adjustable parameters. The resulting constants are compared with the limited existing low temperature data. At infinite dilution and 25°C the following quantities are reported: logK _1.1 = -11.68±0.05, †H_so = 70.1±1.2 kJ-mol^-1, †S^o = 11±4 J-K^-1-mol^-1, and †C _p ^o = 0 J-K^-1-mor^-1. At each ionic strength, including the values extrapolated to infinite dilution, the heat capacity change for the hydrolysis reaction was zero,i.e., logQ _1.1 was found to be a linear function of the reciprocal temperature in Kelvin, at least over the measured range of l-250°C. The hydrolysis constants at infinite dilution were modeled to 550°C and two kbar pressure with a function incorporating solvent density using published results obtained at these extreme conditions.     

Effects of polyethylene spacer length in polymeric electrolytes on gelation of ionic liquids and ionogel properties

Polymer electrolytes containing N,N′-(trans-cyclohexane-1,4-diyl)dibenzamide linkages, polyethylene ((CH₂)_m, m = 2, 4, 10) spacers, and bis(trifluoromethanesulfonyl)amide (TFSA) or bis(fluorosulfonyl)amide (FSA) counteranions (polymer abbreviation: CDBAm•X; m = 2, 4, 10; X = TFSA, FSA) have been synthesized, adding to our previous report (m = 6). In addition, their ability to effect the gelation of six ionic liquids and the properties of the resulting ionogels have been examined. The polymers, except for CDBA10•TFSA, effect the gelation for all ionic liquids used in this study at fairly low concentrations (0.9–50 g/L). Ionogel ionic conductivity is not dependent on the spacer length, but does decrease slightly as increasing amounts of the gelatinizer are introduced. In contrast to ionic conductivity, the temperatures at which these ionogels transition into isotropic fluids is dependent on the spacer length; the gel composed of [EMI][FSA] and 100 g/L of CDBA6•FSA transforms at 120 °C, while the gel composed of [EMI][FSA] and 5 g/L of CDBA2•FSA does not transform into a sol even when temperatures become 155 °C. In brief, ionogel heat resistance can be improved by changing the spacer length of the polyelectrolyte. Finally, it has been determined using cyclic voltammetry that the potential window of the polyelectrolytes is particularly wide, ranging from −1.6 to 2.5 V. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 249–255     

Imidazolium‐based poly(ionic liquid)s with poly(ethylene oxide) main chains: Effects of spacer and tail structures on ionic conductivity

Ten types of cationic glycidyl triazole polymers (GTPs) are prepared from combinations of five alkyl‐imidazolium units (methyl‐, ethyl‐, n‐propyl‐, iso‐propyl‐, and n‐butyl‐imidazoliums) and two spacers [di‐ and tri(ethylene glycol)s]. Since these poly(ionic liquid)s are prepared from the same sample of glycidyl azide polymer by postfunctionalization method, they have the same degree of polymerization. Therefore, the structure–property relationship can be discussed without influence of molecular weight difference. The samples are characterized by NMR, differential scanning calorimetry, and thermogravimetric analysis. The ionic conductivity data are obtained by impedance measurements. The GTPs with the tri(ethylene glycol) spacer and ethyl‐ and n‐butyl‐imidazolium units afford the highest anhydrous conductivity of 1.5 × 10^?5 S cm^?1 at 30 °C. Based on electrode polarization (EP) analysis, we calculate the conducting ion (carrier) concentration and mobility. We discuss the effect of the spacer and N‐alkyl tail structures on the ionic conductivity using the data obtained by EP analysis and X‐ray diffraction. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2896–2906     

Preparation and characterization of conductive chitosan–ionic liquid composite membranes

Anhydrous conductive membranes composing of a composite of chitosan (CS) and ionic liquids with symmetrical carboxyl groups were explored. Scanning electron microscope images revealed that porous composite membranes could be obtained by combining CS with different amounts of 1,4‐bis(3‐carboxymethyl‐imidazolium)‐1‐yl butane chloride ([CBIm]Cl). Fourier transform infrared and proton nuclear magnetic resonance confirmed that the formation of ammonium salts after CS was combined with [CBIm]Cl. The thermal property of CS–ionic liquid composite membranes was studied through thermogravimetric analysis. The anhydrous ionic conductivities of CS–[CBIm]X (X = Cl, Ac, BF₄, and I) composite membranes were measured using ac impedance spectroscopy at room temperature in N₂ atmosphere. The conductivities (0.4–0.7 × 10^?4 Scm^?1), found to be in the same range as semiconductors, were significantly higher than those of pure CS membrane (<10^?8 Scm^?1). In addition, the anhydrous conductivity of composite membrane based on CS–[CBIm]I at room temperature reached a level as high as 0.91 × 10^?2 Scm^?1 when iodine was doped. Copyright © 2011 John Wiley & Sons, Ltd.     

Preparation and ionic conductivity of poly(ethylene oxide) oligomers having thiolate groups on the chain ends

Poly(ethylene oxide) (PEO) oligomers having alkali metal thiolate groups on the chain ends (PEO _m -S⁻M⁺) were prepared as an ion conductive matrix. The molecular weight of the PEO part (m) and the content of the thiolate groups in the molecule were changed to analyze the effect of carrier ion concentration in the bulk. In a series of potassium salt derivatives, PEO₃₅₀-SK showed the highest ionic conductivity of 6.42 × 10⁻⁵ S/cm at 50 °C. In spite of a poor degree of dissociation which was derived from the acidity of the thiolate groups, PEO _m -SM showed quite high ionic conductivity among other PEO/salt hybrids. PEO _m -SM had glass transition temperatures (T _g) 20 °C lower than other PEO/salt hybrids. Lowering the T _g was concluded to be effective in providing higher ionic conductivity for PEO-based polymer electrolytes. Received: 30 April 1999 / Accepted: 20 June 1999     

Polymerization of the new double‐charged monomer bis‐1,3(N,N,N‐trimethylammonium dicyanamide)‐2‐propylmethacrylate and ionic conductivity of the novel polyelectrolytes

The achievement of high ionic conductivity in single‐ion conducting polymer electrolytes is one of the important aims for various electrochemical devices including modern lithium batteries. One way to enhance the ionic conductivity in polyelectrolyte systems is to increase the quantity of charge carriers in each monomer unit. Highly charged poly(bis‐1,3(N,N,N‐trimethylammonium)‐2‐propylmethacrylate) with one of the most conducting anions, namely dicyanamide, was prepared via free radical bulk polymerization or using ionic liquids as reaction medium. The cationic polymers of the double‐charged monomer have molar masses up to = 1,830,000 g/mol and the ionic conductivity equal to 5.51 × 10^?5 S / cm at 25°C. The film forming ability, crystallinity, thermal stability, and glass transition temperatures of the new polymeric ionic liquids obtained from detailed studies are presented. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide on the properties of poly(glycidyl methacrylate) based solid polymer electrolytes

A free standing polymer electrolytes films, containing poly(glycidyl methacrylate) (PGMA) as the polymer host, lithium perchlorate (LiClO₄), and ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide [Bmim][TFSI] as a plasticizer was successfully prepared via the solution casting method. The XRD analysis revealed the amorphous nature of the electrolyte. ATR-FTIR and thermal studies confirmed the interaction and complexation between the polymer host and the ionic liquid. The maximum ionic conductivity of the solid polymer electrolyte was found at 2.56 × 10^–5 S cm^–1 by the addition of 60 wt % [Bmim][TFSI] at room temperature and increased up to 3.19 × 10^–4 S cm^–1 at 373 K, as well as exhibited a transition of temperature dependence of conductivity: Arrhenius-like behavior at low and high temperatures.     

Synthesis and ionic conductivity of polymer ionic liquids

Four vinyl monomers containing a covalently bonded cation ethylimidazolium and various anions—Br^?, (CF₃SO₂)₂N^?, (CN)₂N^?, and CF₃SO ₃ ^? —have been synthesized. High-molecular-mass polymers (M _w up to 1.84 × 10⁶) having the structure of ionic liquids have been prepared via the free-radical polymerization of 1-vinyl-3-ethylimidazolium in bulk and molecular and ionic solvents. The thermal stability and heat resistance of the resulting polymer salts have been estimated. It has been demonstrated that the thermal characteristics of these salts significantly depend on the nature of anions. The glass-transition temperatures of the polymers range from 19 to 235°C. The ionic conductivity of the polymer salts and their compositions with individual ionic liquids has been studied in the frequency range 50–10⁶ Hz. The highest conductivity (1.5 × 10^?5 S/cm) is exhibited by the polymer containing the (CN)₂N^? anion.     

Study of solvent effects on the stability constant and ionic mobility of the dibenzo‐18‐crown‐6 complex with potassium ion by affinity capillary electrophoresis

The effect of solvent on the strength of noncovalent interactions and ionic mobility of the dibenzo‐18‐crown‐6 complex with K⁺ in water/organic solvents was investigated by using affinity capillary electrophoresis. The proportion of organic solvent (methanol, ethanol, propan‐2‐ol, and acetonitrile) in the mixtures ranged from 0 to 100 vol.%. The stability constant, K_KL, and actual ionic mobility of the dibenzo‐18‐crown‐6‐K⁺ complex were determined by the nonlinear regression analysis of the dependence of the effective electrophoretic mobility of dibenzo‐18‐crown‐6 on the concentration of K⁺ (added as KCl) in the background electrolyte (25 mM lithium acetate, pH 5.5, in the above mixed hydro–organic solvents). Competitive interaction of the dibenzo‐18‐crown‐6 with Li⁺ was observed and quantified in mixtures containing more than 60 vol.% of the organic solvent. However, the stability constant of the dibenzo‐18‐crown‐6‐Li⁺ complex was in all cases lower than 0.5 % of K_KL. The log K_KL increased approximately linearly in the range 1.62–4.98 with the increasing molar fraction of organic solvent in the above mixed solvents and with similar slopes for all four organic solvents used in this study. The ionic mobilities of the dibenzo‐18‐crown‐6‐K⁺ complex were in the range (6.1–43.4) × 10^?9 m² V^?1 s^?1.     

Dilute solution properties of a polyurethane. I. Linear polymers

A linear polyurethane of high molecular weight was prepared in solution by the polyaddition of equimolar amounts of ethylene glycol and methylene bis(4-phenyl isocyanate). The polymer was fractionated by using a direct sequential extraction procedure, with a solvent–nonsolvent system consisting of N,N′-dimethylformamide (DMF) and acetone (A). The resulting fractions were characterized by viscosity and lightscattering measurements. The relationship between the intrinsic viscosity and molecular weight was found in DMF at 25°C. to be [η] = 3.64 × 10^?4M^0.71. The unperturbed polymer chain dimensions were determined from intrinsic viscosity measurements carried out under experimentally determined theta conditions.     

Rheological Behavior of Dope Solutions of Poly(acrylonitrile‐co‐itaconic acid) in N,N‐dimethylformamide: Effect of Polymer Molar Mass

The rheological behavior of dope solutions of poly(acrylonitrile‐co‐itaconic acid) or poly(AN‐co‐IA) is important from the point of view of deriving the spinning conditions for good quality special acrylic fibers. The viscosity of the resin dope is dictated by the polymer concentration, molar mass, temperature and shear force. The dynamic shear rheology of concentrated poly(AN‐co‐IA) polymer dope solutions in N, N‐dimethylformamide, in the molar mass (M¯_v) range of 1×10⁵ to 1×10⁶ g/mol, was investigated in the shear rate (γ′) range of 1×10¹ to 5×10⁴ min^?1. An empirical relation between η and M¯_v was found to exist at constant shear rate. The dope viscosity was dependent on the molar mass and the shear rate at a given temperature (T) and concentration. The polymer molar mass index of dope viscosity (m) was calculated as functions of concentration (c), shear rate and temperature. The m values increased with shear rate and temperature. A master equation relating m, with shear rate and temperature was derived for a given dope concentration. At higher shear rates, m tends to the value of 3.4, which is close to the molar mass index of viscosity reported for molten thermoplastics. m increased significantly with shear rate and nominally with temperature, while an increase in concentration decreased it. The onset of shear thinning of the dope shifted to a lower shear rate regime with an increase in polymer concentration and the molar mass. For a given value of molar mass, the increase in viscosity of the dope solution with polymer concentration was dependent on the shear rate.     

Interfacial adsorption characteristics of ionic polymeric amphiphiles with comb‐like structures: Effect of dodecyl and poly(ethylene oxide) side chains

Two sets of terpolymers, polymer A and polymer B consisting of almost same level of 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) component at 0.635 ± 0.005 m and varying dodecyl methacrylate (DoDMAc) and monomethoxy poly(ethylene glycol) acrylate (PEGAc) components have been designed. Polymer A, consisting of less C₁₂ component, has been shown to promote intermolecular aggregated structures wherein C₁₂ domains exhibit compact packing characteristics. It is demonstrated that in polymer B, AMPS segments are predominantly present as ionic clusters contributing to a high pKa at about 9.50 for a low α of 0.20. From the results of interfacial adsorption estimations at air/solution and water/hexane interface, it is shown that open coil structures provided under high pH (>9.0) conditions promote efficiency of adsorption. This is shown from higher surface excess concentration (Γ) and lower interfacial area (a) estimated using Gibbs adsorption isotherm equation. For example, at water/hexane interface, polymer A exhibits Γ of 1.20 × 10^?3 moles/1000 m² at pH 3.2 and 1.97 × 10^?3 moles/1000 m² at pH 10.0. Significantly, in case of polymer B consisting of ionic clusters of AMPS, adsorption at the liquid/liquid interface is more efficient in comparison to polymer A at all pH. © 2008 Wiley Periodicals, Inc. JPolym Sci Part A: Polym Chem 46: 3257–3271, 2008     

Fabrication and characterization of electrochemical double layer capacitors using ionic liquid-based gel polymer electrolyte with chemically treated activated charcoal electrodes

The present investigation deals with electrochemical double layer capacitors (EDLCs) made up of ionic liquid (IL)-based gel polymer electrolytes with chemically treated activated charcoal electrodes. The gel polymer electrolyte comprising of poly(vinylidine fluoride-co-hexafluropropylene) (PVdF-HFP)–1-ethyl-2,3-dimethyl-imidazolium-tetrafluroborate [EDiMIM][BF₄]–propylene carbonate (PC)–magnesium perchlorate (Mg(ClO₄)₂) exhibits the highest ionic conductivity of ~8.4?×?10^?3?S?cm^?1 at room temperature (~20 °C), showing good mechanical and dimensional stability, suitable for their application in EDLCs. Activation of charcoal was done by impregnation method using potassium hydroxide (KOH) as activating agent. Brunauer–Emmett–Teller (BET) studies reveal that the effective surface area of treated activated charcoal powder (1,515 m²?g^?1) increases by more than double-fold compared to the untreated one (721 m²?g^?1). Performance of EDLCs has been tested using cyclic voltammetry, impedance spectroscopy, and charge–discharge techniques. Analysis shows that chemically treated activated charcoal electrodes have almost triple times more capacitance values as compared to the untreated one.     

Hydrophobic ionic liquid modified thermoresponsive molecularly imprinted monolith for the selective recognition and separation of tanshinones

A hydrophobic ionic liquid modified thermoresponsive molecularly imprinted monolith was synthesized using N‐isopropylacrylamide as a thermoresponsive monomer and a long‐chain hydrophobic ionic liquid as an auxiliary modification monomer. The ionic‐liquid‐modified thermoresponsive molecularly imprinted polymer was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. When the column temperature was 50°C, the synthesized monolithic column was successfully applied to the selective separation of homologue tanshinones within 7 min and eluted only by water (mobile phase) (theoretical plates more than 1.00 × 10⁵ per meter). The negative Gibbs free energy (≤–2.37) values showed that the transfer of the tanshinones from the mobile phase to the stationary phase on this monolithic column was a thermodynamically spontaneous process. Good linearity of the five tanshinones by thermoresponsive monolith was obtained in the range of 0.100–25.0 μg/mL. The limit of detection (S/N = 3) and limit of quantitation (S/N = 10) were less than 0.0390 and 0.0630 μg/mL, respectively, with a relative standard deviation of <4.8%. In this proposed thermoresponsive chromatography method, the separation of homologue analytes can be achieved by changing the column temperature, and the use of water as the mobile phase would decrease the economic cost and organic pollution.