Relaxation and charge transport in mixtures of zwitterionic polymers and inorganic salts

Dielectric spectroscopy is employed to analyze the molecular dynamics and the charge transport in mixtures of zwitterionic polymers of the type poly{3 [N(ω-methacryloyloxyalkyl)] N, [N-dimethylammonio propanesulfonate] with sodium iodide in the frequency range of 10²Hz–10⁷ Hz and in the temperature range of 110 K-400 K. The amount of inorganic salt added varies from 0–200 mol-% relative to the number of zwitterionic groups present in the polymer, contributing strongly to the conductivity. One relaxation process is observed whose relaxation rate depends strongly on the length of the aliphatic spacer between the polymethacrylate main chain and the zwitterionic group. Exhibiting an Arrhenius-like temperature depence with activation energy E_A = 47 KJ/mol, this relaxation process is assigned to fluctuation of the quaternary ammonium groups in the side chains. At higher temperatures, the dielectric properties and the conductivity are primarily dominated by the mobile inorganic ions: conductivity strongly depends on the salt concentration, showing a pronounced electrode polarization effect. The frequency and salt concentration, dependences of the conductivity can be quantitatively described as hopping of charge carriers being subject to spatially randomly varying energy barriers. For the low-frequency regime and for the critical frequency marking the onset of the conductivity's dispersion, the Barton-Nakajima-Namikawa (BNN) relationship is fulfilled.     

Effect of dilution during network formation on the sol fraction and elasticity of polyurethane networks

The effect of dilution at network formation (polymer volume fraction v⁽⁰⁾ = 1 ? 0,4) on the fraction and equilibrium photoelastic behaviour of polyurethane networks was investigated. The networks were prepared from poly(oxypropylene)triol and 4,4′-methylenedi(phenyl isocyanate) with various mole ratios of reactive groups 1 ≤ r_H = [OH]/[NCO] ≤ 1,5. From a comparison between the experiments and the theory of branching processes we find that: (a) with both increasing ratio r_H and increasing dilution the fraction of bonds lost in elastically inactive cycles increases from 0,02 to 0,06; (b) the experimental reduced equilibrium moduli G_r of the predominant majority of samples are higher than those theoretically predicted by the Flory junction-fluctuation theory for the front factor A = 1. Also the decrease of G_r with dilution (expressed as volume fraction of diluent during network formation v⁽⁰⁾) is very steep, thus supporting the contribution of permanent interchain constraints to the overall G_r value.     

Viscosity of aqueous and alkaline solutions of poly(ethylene oxide)

Viscosity measurements over a wide range of temperature were made on aqueous solutions of poly(ethylene oxide) samples of different molar mass and of low polydispersity. Above ca. 308 K the Mark-Houwink exponent decreases and tends to a value of 0,50 at a lower critical solution temperature of 376 ± 2 K. The same value for this θ-temperature is derived also as that at which the slope of Stockmayer-Fixman plots tends to zero. At 298 K the unperturbed dimensions [〈r²〉₀/M]^1/2 = 0,089 nm · g^?1/2 · mol^1/2 and their temperature coefficient d ln 〈r²〉₀/dT ≈ ? 1,5 (±0,5) · 10^?3 K^?1. In aq. KOH the intrinsic viscosity [η] is virtually uninfluenced by pH at low-medium pH, but at high pH, [η] falls sharply. Viscosity and phase separation measurements yield θ-conditions in 1,24 M aq. KOH at 298 K. The derived polymer-water interaction parameters χ increase from 0,449 at 276 K to 0,493 at 358 K, but the enthaplic component χ_H is incapable of yielding a meaningful value for the solubility parameter δ₂ of the polymer in such a hydrogen-bonding system. The calculated value of χ₂ was 18,9 (kJ · dm^?3)^1/2.     

Polylactones, 11. Cationic copolymerization of glycolide with L,L-dilactide

Copolymerizations of glycolide with L ,L -dilactide were conducted in chloroform, 1,2-dichloroethane and nitrobenzene. Chlorosulfonic acid, triflic acid, boron trifluoride, triethyloxonium tetrafluoroborate, but mainly methyl triflate, were used as initiators. 50°C was found to be an optimum reaction temperature, because higher temperatures resulted in dark coloured products of low viscosities. The composition of the copolyesters was determined by ¹H NMR spectroscopy and the sequences by ¹³C NMR spectroscopy. Dyad splitting of the carbonyl signals allowed an accurate calculation of average block lengths. Under all circumstances glycolide showed a higher rate of incorporation, and truely random sequences were never obtained. However, the relative reactivities of both monomers largely depend on the nature of the initiator. The best results with regard to random sequences were obtained in 1,2-dichloroethane with methyl triflate (r_G = 10,5 and r_L = 0,9) and with triflic acid (r_G = 14,0 and r_L = 0,5). DSC measurements revealed that most samples possess crystalline domains of polyglycolide blocks. Nonetheless, many samples are soluble in hexafluoro-2-propanol and the amorphous samples also in dichloromethane or chloroform.     

Copolymerization of olefins with SiO2-, Al2O3-, and MgCl2-supported metallocene catalysts activated by trialkylaluminiums

Copolymerizations of ethylene with propene, of ethylene with 1-hexene and of propene with 1-hexene were carried out at 40°C under atmospheric pressure with SiO₂-, Al₂O₃- and MgCl₂-supported metallocene catalysts using common alkylaluminiums as cocatalyst. From a detailed analysis of copolymers by ¹³C NMR, all the copolymers obtained were found to be random (r₁·r₂ ≤ 1). When ethylene was used as a base monomer, the polymer yield markedly increased with increasing comonomer concentration. The molecular weight of the copolymers obtained in this study were found to be much higher than those obtained with homogeneous Kaminsky-Sinn catalysts. Whereas, the polydispersity (M _w/M _n) of the copolymer is dependent on the combination of monomers as well as on the inorganic compounds used as carrier.     

Syntheses of N-(4-substituted phenyl)isocitraconimides and reactivities in their radical copolymerizations with styrene

Radical copolymerizations of isomeric N-(4-substituted phenyl)isocitraconimides 7a–f and 9a–f (M₁) with styrene (ST) (M₂) were performed at 60°C, using 2,2′-azoisobutyronitrile as initiator in tetrahydrofuran, in order to study the substitutent effect on the copolymerization parameters. From the results, the monomer reactivity rations were determined as r₁ = 0,0,81 ≤ r₂ = 1,76 in the 7/ST systems, and r₁ = 0, 0,27 ≤ r₂ ≤ 0,42 in the system 9 /ST. It was found that the relative reactivities (1/r₂) of 7 toward the polystyrly radical cannot be correlated by the polar-substituent constant (σ) but by the resonance-substituent constant (E_R) in the modified Hammett equation: log(1/r₂) = ρσ + γE_R. Furthermore, the monomer reactivity ratios considering the influence of the penultimate effect were also determined, and the substituent effect of 7 and 9 was studied according to the above equation.     

Molecular dynamics in liquid crystalline N-acylated oligoethylenimines as studied by broadband dielectric spectroscopy

The molecular dynamics and the charge transport in six liquid crystalline N-acylated oligoethylenimines were investigated by dielectric spectroscopy. The dielectric spectra in the temperature range from 125 K up to 400 K and in the frequency range between 10⁻² Hz and 10⁷ Hz could be described by a conductivity contribution and three relaxation processes. The molecular assignment of the α-process is a relaxation of the rigid benzamide unit. Its mean relaxation time is influenced by the length of the alkoxy side chains, the spacer length (ethylene or propylene groups) and the neighboring repeating units. In the columnar mesophase this process is cooperative due to sterical hindrance. A normalized g-factor expressing the intermolecular cooperativity was calculated. The cooperativity increases when approaching the glass transition temperature. The γ-process is assigned to local librational motions of the alkoxy side chain involving the ether linkage. It has an Arrhenius-like temperature dependence (activation energy ΔE_a = 22–32 kJ/mol). The β-process is presumably a libration at the end of the alkyl chains. The conductivity contribution to the imaginary part of the dielectric function ε″ is frequency independent except for very low frequencies where electrode polarization causes a decrease in the measured conductivity. The charge transport is strongly influenced by the phase transitions isotropic to columnar and columnar to crystalline, but not by the glass transition.     

The stability of polyelectrolyte complexes of Calf-Thymus DNA and synthetic polycations: Theoretical and experimental investigations

Complexes of Calf-Thymus DNA and some polycations such as PDADMAC, IONEN, and P4VP were formed and investigated with respect to their stoichiometry and stability. The central part of the study are two theoretical models, the E-model and the T-model. It is assumed that a complex molecule consists of two linear polyion strands connected by electrostatic forces. One strand is a DNA molecule and the other is built by the polycations. Both strands carry equal number of charges, so that the complex molecule is electrically neutral. In the E-model the complex binding distance, r₁, is a constant, while in the T-model r₁ depends on the system parameters, such as the concentration, C_S, of added salt or the dielectric constant, ε, of the solvent. Both theories predict a critical salt concentration, C_S,d where a complex molecule becomes instable and dissociates in its single strands. According to the E-model C_S,d is 0.6 mol/1 for a 1 : 1 salt if the solvent is water and the temperature 298.16 K. This value agrees quite well with those obtained experimentally, which are 0.5 mol/1 for LiCl, 0.6 mol/1 for NaCl, 0.56 mol/l for KCl, and 0.68mol/1 for CsCl. If the dielectric constant of the solvent decreases, C_S,d should decrease. This is also confirmed by the experiment. The T-model predicts that the complex binding distance, r_l,d, at which a complex molecule dissociates, is correlated with C_S,d r_1,d is large at low C_S,d and vice versa. Using the experimental data of C_S,d the T-model predicts that r₁ increases from r₁ ≈ 3.8 · 10^?10 m when the complex is built to r₁ = r_1,d ≈ 8 · 10^?10m when the complex dissociates. This value is nearly as large as the average distance of a counterion bound territorial to a DNA molecule. However, for the divalent cations, Ca²⁺ and Sr²⁺, r_1,d is only 4 · 10^?10 m. This may be unrealistic.     

Interstitial Fluid Pressurization During Confined Compression Cyclical Loading of Articular Cartilage

The objective of this study was to experimentally verify the well-accepted but untested hypothesis that cartilage interstitial fluid pressurizes variously under the action of an applied cyclical stress in confined compression over a range of loading frequencies, contributing significantly to the cartilage dynamic stiffness. Eighteen bovine cartilage cylindrical samples were tested under load control using a porous indenter in a confined compression chamber fitted with a microchip pressure transducer at its bottom. Over a static stress of 130 kPa, a cyclical stress of amplitude 33 kPa was applied with the indenter at frequencies ranging from 0.0001 to 0.1 Hz. The cartilage interstitial fluid pressure and deformation were measured simultaneously as a function of time. The displacement response at the lowest tested frequency was curvefitted in the time domain to determine the linear biphasic material properties, H_A=0.70±0.10 MPa and k ₀=2.4 × 10^-16±0.64 × 10^-16m⁴/Ns. These properties were employed in the biphasic theory to predict the interstitial fluid pressure response and compare it to experiment, resulting in nonlinear coefficients of determination ranging from r²=0.89 ± 0.15 to 0.96±0.03 depending on frequency. It was found for the samples of this study that above a characteristic frequency of 0.00044 Hz, the magnitude and phase of fluid pressurization matched the applied stress, reducing the tissue strain at the impermeable bottom surface to nearly zero. The findings of this study verify the hypothesis that cartilage dynamic stiffness derives primarily from flow-dependent viscoelasticity as predicted by the linear biphasic theory; they demonstrate experimentally the significance of interstitial fluid pressurization as the fundamental mechanism of cartilage load support over a wide range of frequencies. © 2000 Biomedical Engineering Society. PAC00: 8719Rr     

Linear-lumped-parameter modeling of pulmonary impedance in monkeys

Pulmonary impedance, Z_L, measured from 2 to 32 Hz in anesthetized, intubated and paralyzed bonnet monkeys (Macaca radiata) was fitted to a variety of linearlumped parameter mechanical networks. Parameter values for each network were obtained by minimizing the average of the percent distance, D_r, between the computed network impedance and measured Z_L at all frequencies. Measured resistance, R_L, decreased from 2 to 8 Hz and increased from 8 to 32 Hz indicating that a single series resistance-inertance-compliance (RIC) network was not optimal (D_r∼19%). Networks consisting of two series RIC pathways in parallel resulted in a lower D_r (∼14%), but parameter values were difficult to interpret. Despite not modeling the decrease in R_L with frequency below 8 Hz, an airway wall compliance, C _aw , network in which the airways were separated into central and peripheral components resulted in an even lower D_r (∼11%). In addition, parameter values were easy to interpret, consistent among our “normal” monkeys and changed consistently and explainably with change in lung mechanics induced by decrease in lung volume. We conclude that (1) networks containing both parallel pathways and C _aw are necessary to model Z_L over the entire frequency range (2–32 Hz), (2) the effect of C _aw is an important determinant of Z_L above 8 Hz, and (3) a six-parameter C _aw network with the ratio of C _aw to parenchymal compliance, C_p, fixed may prove useful in interpreting changes in Z_L induced by alterations in lung mechanics in monkeys.     

Interaction between polynucleotides in aqueous NaCl solution, 5. Temperature dependence of the heat of formation of poly(I) · poly(C) duplex

The heat of mixing of equimolar solutions of poly(I) and poly(C) containing various NaCl concentrations was measured at 288 and 308 K, and the heat of formation of Poly(I) · poly(C) duplex from the randomly coiled constituents, poly(I) and poly(C), was estimated from the heat of mixing with the aid of CD measurements. The temperature dependence of this heat of formation, ΔH, differs at lower and higher NaCl concentrations: In the region of NaCl concentration less than 0,5 mol · dm^-3, ΔH increases with temperature, while in the region of NaCl concentrations higher than 0,5 mol · dm^-3, ΔH decreases with temperature. The free energy change, ΔG, of the formation of poly(I) · poly(C) duplex decreases as the NaCl concentration increases, that is, the stability of poly(I) · poly(C) duplex increases with NaCl concentration. Moreover, the conformation of poly(I) · poly(C) duplex seems to differ at lower and higher NaCl concentration as derived from the CD spectra and the thermodynamic quantities.     

Influence of lateral substituents in the mesogens on the properties of liquid-crystalline side group copolymethacrylates: dielectric relaxation spectroscopy on homopolymers

Broad-band dielectric spectroscopy in the frequency range from 10^-2 Hz to 10⁶ Hz and in a temperature range from 170 K to 430 K was employed to study the molecular dynamics in polymethacrylates with novel calamitic side groups. As mesogenic units, derivatives of p-methoxyphenyl benzoate were used where the hydrogen in the meta position of the benzoate ring is substituted by a methoxy group or by bromine. The substituted samples do not show any mesophases. The following results were obtained: (i) The β-relaxation which corresponds to a rotational fluctuation of the mesogen around its long axis is drastically suppressed by the lateral substitution. Moreover the activation parameter of this process depends strongly on the actual mesophase structure of the material under study. (ii) The β-relaxation is related to the dynamic glass transition of the system. It is shown that the value of the glass transition temperature of the liquid-crystalline polymethacrylate can be understood as competition of internal plasticization and molecular ordering. (iii) The α-relaxation corresponds to a rotational fluctuation of the side group around its short axis. From comparison of the relaxation rates of the α- and δ-relaxation, the temperature dependence of the order parameter of the liquid-crystalline polymethacrylate is estimated by dielectric spectroscopy.     

Temperature and Pressure Dependence of the Free Volume in Polyisobutylene from Positron Lifetime and Pressure‐Volume‐Temperature Experiments

Summary: The microstructure of the free volume and its temperature and pressure dependence in PIB were studied by PVT experiments and PALS. Employing the Simha–Somcynsky equation of state, the hole‐free volume fraction h and the specific free and occupied volumes, V_f = hV and V_occ = (1 ? h)V, respectively, and their expansivity and compressibility were calculated. From the PALS spectra analyzed using the LT9.0 software, the hole size distribution, the mean hole size 〈v_h〉 and mean dispersion σ_h were calculated. From a comparison of 〈v_h〉 with V_f, the hole density was obtained. It was found that PIB shows an unusual thermal expansion with glass‐like transitions at 210 K and 290 K (at 0 MPa). A similar behavior is observed for tan δ. It was found that at 296 K, 〈v_h〉 decreases exponentially from 80 ų at 0.1 MPa to the extremely low value of 10 ų at 1 300 MPa. Starting from a fluctuation approach, the free‐volume fluctuations and the characteristic length scale (ξ) of dynamic heterogeneity of structural relaxation were estimated from σ_h. It was found that ξ increases from ≈1.5 nm to ≈1.9 nm when the temperature decreases from 293 K to the glass transition temperature T_g = 207 K (at 0 MPa) or the pressure increases from 0.1 MPa to 200 MPa (at 296 K).

Fractional free volume and its mean fluctuation in PIB as determined from positron lifetime spectroscopy and PVT experiments analyzed with the Simha‐Somcynsky equation of state.     

Viscoelastic properties of poly(dibutyl itaconate) melts

Complex dynamic viscosities η^* of poly(dibutyl itaconate) melts were determined for nonuniform polymers with viscosity-average molecular weights varying from 8000 to 327000 in the temperature range from 323 to 463 K and the frequency range from 0,1 to 100 rad/s. By applying the time and temperature superposition principle, master curves for the selected reference temperature T₀ = 383 K were obtained, permitting the estimation of the Newtonian viscosity in terms of molecular weights. The temperature dependence of viscous flow was analysed by verification of the linearity of the a_T shift factor, interpreted via the Williams-Landel-Ferry equation. Deviations from linearity were observed only for very low molecular weights M and at the highest temperatures. The activation energy of viscous flow was calculated by applying the concept of absolute reaction rates and the concept of free volume. Good agreement was observed. The linearized η^* vs. M dependence changes slope at a critical molar mass M_c = 69000 with exponents of M α = 1,05 below and β = 2,92 above the M_c value in the function η^* = f(M). The rheological properties of poly(dibutyl itaconate) are discussed in terms of substituent size and compared to those of other related vinyl polymers.     

Terpolymerization of ethene,acrylonitrile and vinyl acetate

The free-radical terpolymerization of ethene, acrylonitrile and vinyl acetate was studied at 2000 bar in the temperature range from 170°C to 240°C in a continuously operated tubular-type reactor. Polymerization was induced either thermally or chemically by di-tert-butyl peroxide as the initiator. Addition of vinyl acetate to ethene and acrylonitrile substantially enlarges the range for polymerization in the homogeneous fluid phase as compared to the binary copolymerization of ethene with acrylonitrile; a terpolymer with a high content of nitrile functional groups can be obtained from a single-phase reaction. The six reactivity ratios of this terpolymerization, r_EA, r_EV, r_AE, r_AV, r_VE and r_VA are derived by applying first-order Markov-chain simulations. As ethene is the major component in the monomer mixtures, r_EA and r_EV are obtained with higher accuracy. For r_EA the Arrhenius expression r_EA = 2,6 · exp(?2,1 · 10³ · (T/K)^?1) is found (for 2000 bar). r_EV = 0,9 ± 0,2 appears to be independent of temperature. The accuracy of the reactivity ratios r_VE, r_AV, r_VA and r_AE is not sufficient to detect a temperature dependence. The terpolymerization is also treated as a quasi binary copolymerization of ethene/vinyl acetate and acrylonitrile.     

The relative influence of physical fitness,acclimatization state,anthropometric measures and gender on individual reactions to heat stress

Summary An experiment was set up to quantify the relative influence of fitness, acclimatization, gender and anthropometric measures on physiological responses to heat stress. For this purpose, 12 male and 12 female subjects were exposed to a neutral [ambient temperature (T _a) 21°C, relative humidity (r.h. 50%)], a warm, humid (T _a 34°C, r.h. 80%) and a hot, dry (T _a 45°C, r.h. 20%) climate at rest and at two exercise intensities [25%, and 45% maximal O₂ intake (VO_2max)], seated seminude in a net chair behind a cycle ergometer. Their physiological responses were recorded and the data submitted to a multiple regression analysis. It was shown that for the variance in heat storage, the percentage of body fat and the surface to mass ratio had relatively the largest influence of all the individual parameters, followed by VO_2max and the sweat rate versus increase in core temperature (total r ²=92%). For the skin temperature variation, the relative influence of individual parameters (sweat gain, VO_2max) was small. For body core temperatures, individual parameters had a large influence. The largest effect was due to the percentage of fat and the surface to mass ratio, followed by the sweating setpoint and, finally, VO_2max (total r ² = 54%–70%). For the variance in heart rate the VO_2max was the most relevant parameter, followed by the setpoint of the sweat rate:rectal temperature relationship (total r ²=88%). Blood pressure and skin blood flow predictions were also shown to improve by the addition of individual characteristics to the model. Body surface area, VO_2max and the sweating setpoint were shown to have a large influence but the proportion of the variance explained by these variables was too small (r ² < 70%) to use them as strain predictors, however. For all the predicted variables, it was shown that gender lost its influence, once VO_2max or anthropometric data were introduced into the prediction equation.     

The resonant step frequency in human running

 At running speeds less than about 13 km h^–1 the freely chosen step frequency (f _free) is lower than the frequency at which the mechanical power is minimized (f _min). This dissociation between f _free and f _min was investigated by measuring mechanical power, metabolic energy expenditure and apparent natural frequency of the body’s bouncing system (f _sist) during running at three given speeds with different step frequencies. The f _free requires a mechanical power greater than that at f _min mainly due to a larger vertical oscillation of the body at each step. Energy expenditure is minimal and the mechanical efficiency is maximal at f _free. At a given speed, an increase in step frequency above f _free results in an increase in energy expenditure despite a decrease in mechanical power. On the other hand, a decrease in step frequency below f _free results in a larger increase in energy expenditure associated with an increase in mechanical power. When the step frequency is forced to values above or below f _free, f _sist is forced to change similarly by adjusting the stiffness of the bouncing system. However the best match between f _sist and step frequency takes place only in proximity of f _free (2.6–2.8 Hz). It is concluded that during running at speeds less than 13 km h^–1 energy is saved by tuning step frequency to f _sist, even if this requires a mechanical power larger than necessary. Received: 13 January 1997 / Received after revision: 7 April 1997 / Accepted: 28 May 1997     

High-pressure free-radical copolymerization of ethene-methacrylic acid and of ethene-acrylic acid, 1. (Meth)acrylic acid reactivity ratios

Free-radical copolymerizations of ethene (E)-methacrylic acid (MAA) and of E-acrylic acid (AA) have been carried out in a continuously operated device at 2 000 bar and at temperatures between 240 and 280°C. Even at low degrees of overall monomer conversion, below 1%, and at small (M)AA contents of the copolymerizing mixtures, below 0.5 mol-%, the resulting copolymer is not soluble in the reaction mixture at contents of acid units well above 6 mol-%. At such low (M)AA contents, the classical procedure of deriving both reactivity ratios, r_E and r_(M)AA, from fitting monomer and copolymer compositions to the differential copolymerization equation is not applicable. r_E may be estimated by this procedure, but the composition range is too small to derive r_(M)AA. Data for r_(M)AA may, however, be deduced from relative amounts of (M)AA-centered triad sequences that are available from quantitative ¹³C NMR spectroscopy of the copolymer. Because of assignment problems for the E-(M)AA copolymers, the ¹³C NMR studies have been carried out on product samples after complete methyl-esterification to yield E-methyl(meth)acrylate copolymeric material. The resulting r_MAA data are slightly above the r_AA values. The numbers, e. g., for 240°C and 2 000 bar, are: r_MAA = 11 ± 3 and r_AA = 8 ± 2. The r_MAA and r_AA values are compared with (meth)acrylate reactivity ratio data of several ethene-(meth)acrylate high-pressure copolymerizations.     

Unvernetzte epoxide-amin-additionspolymere, 32. Hochmolekulare polykationen vom michler-hydrolblau-typ und ihre dielektrische charakterisierung

A high-molecular-weight poly(leuco base) (M _n = 11000–18000) was obtained by addition polymerization of N,N′-dibenzyl-4,4′-methylenedianiline ( 2 ) and 2,2-bis[4-(2,3-epoxypropoxy)-phenyl]propane (diglycidyl ether of Bisphenol A) ( 1 ). The oxidation of this addition polymer with chloroanil, iodine, bromine, chlorine or antimony pentachloride results in polymeric dyes (absorption at λ = 620 nm) containing units of the “Michler Hydrolblau” type. The dielectric behavior in the frequency range 10² Hz up to 10⁷ Hz shows a dependence of the conductivity on the temperature. Polymer 4c exhibits a conductivity of σ = 6 · 10^?6 S/cm at 134,3°C and 10⁶ Hz.     

Ionic conduction in polyphosphazene containing oligo(oxyethylene) side chains with cyclic carbonate as terminal groups

Novel comb-type polyphosphazene derivatives with cyclic carbonate groups as the terminal function of oligo(oxyethylene) side chains [CEP] were prepared for the achievement of high ionic conductivity, when they were hybridized with LiCIO₄, in accordance with increase of permittivity. The relative permittivity of CEP turned out to be extraordinarily high, i.e. 24,6, whereas that of a similar comb-type polyphosphazene with methyl ether terminal function of side chains was less than 10 at 25°C. The [LiCIO₄(5)/CEP (95 wt.-%)] hybrid showed relatively high ionic conductivity of 7,3 · 10^?6 at 25°C and 9,6 · 10^?5 S · cm^?1 at 60°C, respectively. From the observation of the temperature dependence of ionic conductivity at 10–60°C, it was revealed that the ionic conduction obeys the Vogel-Tamman-Fulcher and Williams-Landel-Ferry equations based on the free volume theory.