Dipole moments of styrene/4-vinylpyridine copolymers—II: Relation to microstructure

Mean-square dipole moment values of styrene/4-vinylpyridine (S4VP) copolymers determined at 25–60°C in 1,4-dioxane solutions were related to the microstructure of the chains. Data on the synthesis and dipole moments of S4VP copolymers were used to calculate the distribution of triad fractions and effective dipole moments of styrene, S-centred, and 4-vinylpyridine, V-centred, fractions in the copolymer chains. The relative magnitudes of the effective dipole moment values calculated for each type of triad reflect the effect of dipole–dipole interactions on these values.     

Synthesis,properties, and functions of thermosensitive copolymers having pyridyl and/or pyridinium groups

Thermosensitive copolymers with pyridyl and/or pyridinium groups were prepared by copolymerization of 4-vinylpyridine (4VP) and N-isopropylacrylamide (NIPAAm) followed by the reaction of 4VP–NIPAAm copolymers with benzyl chloride.The copolymer 4VP–NIPAAm was soluble in dilute HCl below 32 °C, but the quaternized 4VP–NIPAAm copolymer was soluble even in aqueous solutions of pH 6.5 below 28 °C. The thermosensitivity of both 4VP–NIPAAm and the quaternized 4VP–NIPAAm copolymer was observed. The quaternized 4VP–NIPAAm copolymer could adsorb food dyes dissolved in water and the copolymer–dye complexes became water-insoluble. The quaternized 4VP–NIPAAm copolymer also exhibited high antibacterial activity against bacteria such as Escherichia coli.     

Polyelectrolyte complex–surfactant interactions: effect of neutralization degree on viscometric behaviour in aqueous solution

The interaction between polyelectrolytes and ionic surfactants has attracted significant interest in recent years in different areas of research. In this study, the effect of the neutralization degree α on the viscosimetric behaviour of (hydrolyzed polyacrylamide, AD37–poly(4-vinylpyridine), P4VP) complex in aqueous solution and in the presence of sodium dodecyl sulphate (SDS) at T = 25 °C was studied. Physicochemical results show that neutralization degree has an important effect on reduced viscosities values of (AD37–P4VP–SDS) system that reveals the electrostatic and hydrophobic interactions. Indeed, these values increase with α, and this influence is even greater for low P4VP—high AD37 concentrations systems.     

The compatibilizing effect of poly(styrene-co-4-vinylpyridine) copolymers on the polystyrene–polyethylene-based ionomer blends

The compatibilizing effect of styrene-co-4-vinylpyridine (SVP) random copolymers on the immiscible polystyrene (PS)–polyethylene-based ionomer (Surlyn) blends was examined by means of scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and tensile test. For the binary SVP–Surlyn and ternary PS–Surlyn–SVP blends, the domain size of dispersed phase decreases dramatically with the increase in the vinyl pyridine (VP) content of the SVP copolymers. The mechanical properties are improved with increasing the VP content in copolymers. FTIR results suggest that the compatibilization in this blend system is attributed to the ion–dipole interaction between the polar VP groups of SVP copolymer and ionic groups of Surlyn. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 807–816, 1998     

Synthesis, Characterization, and Some Properties of 4-Vinylpyridine-Cr(CO)5 Containing Polymers

The polymerization of 4-vinylpyridine (4VP) and 4-vinylpyridine chromium pentacarbonyl [(4VP)Cr(CO)₅] was performed under N₂ atmosphere at 60–80°C temperature range. Different percent of feed (%PF) of Cr(CO)₅ groups were anchored into poly(4-vinylpyridine) (P4VP) by addition of the intermediate Cr(CO)₅THF, which was generated photochemically from Cr(CO)₆ in THF, to the polymer at ambient temperature. The determined percent of anchoring (%PA) has shown that the maximum anchored Cr(CO)₅ groups was 40% (w/w) with respect to P4VP, and the optimum percent of anchoring was 20% (w/w). The rate of polymerization (R _p ) and the activation energy (E _a ) of 4VP in the absence and in the presence of 16.7% Cr(CO)₅(4VP) were determined. Thermal analysis has shown various changes in the properties of the 4VP polymers after modification of the polymer by Cr(CO)₅ groups. The X-ray diffraction and the melting enthalpy derived from the DSC thermogram revealed that the synthesized poly[(CO)₅Cr(4VP)] has a crystallinity of about 40%, whereas no crystallinity was observed for pure P4VP.     

Solution behavior of Na sulfonated polystyrene: Dipole moment determinations

Solution behavior of Na sulfonated polystyrene (NaSPS) ionomers with different percentages of sulfonate was studied by viscosity and dipole moment measurements. Two solvents of different character were chosen, i.e. dioxane (? = 2.22) and dimethyl formamide (DMF, ? = 36) and their mixtures. The reduced viscosity as a function of concentration in polar solvents reflects the ‘polyelectrolyte’ behaviour of the ionomers. Mean-squared dipole moment (<μ²>/x) values were calculated over a temperature range of 20–100°C, in dioxane and in a mixture of 4% DMF in dioxane. The results confirm the ‘polyelectrolyte’ behavior of ionomers by the addition of a small amount of polar cosolvent. The effect of increasing temperature on <μ²>/x in the DMF-dioxane mixture is attributed to the formation of a coordination complex.     

Dielectric properties of poly(vinyl chloride) in tetrahydrofuran and cyclohexanone

The dielectric absorption and dispersion of poly(vinyl chloride), M M_v = 49 000, in THF and in cyclohexanone have been studied over a frequency range of 120 kHz to 11·0 MHz, at temperatures from ?22·5 to 35°C, and at concentrations ranging from 4 to 12·0(w/v)% PVC/THF and from 2 to 8·0(w/v)% PVC/cyclohexanone. The viscosities of the two systems have also been measured at temperatures from 20 to 50°C. A single relaxation time was found (β = 0·8–1·0), which indicates that relaxation occurs by segmental rotation. The dielectric and viscous activation energies have been calculated. The dipole moment associated with the relaxation process has also been calculated. The relaxation time, dielectric and viscous activation energies and the dipole moment were found to be dependent on the type of solvent. The dipole moment also showed a molecular weight dependence. The influence of the concentration and temperature on the apparent dipole moment and on the relaxation time is discussed.     

Temperature‐dependent permeability of polyelectrolyte complex capsule membranes having N‐isopropylacrylamide domains

As a microcapsule with temperature sensitivity, poly(methacrylic acid)–polyethylenimine complex capsules containing N‐isopropylacrylamide units were designed. Two kinds of copolymers of methacrylic acid and N‐isopropylacrylamide were synthesized by free‐radical copolymerization. Partly crosslinked poly(methacrylic acid)–polyethylenimine complex capsules containing the methacrylic acid–N‐isopropylacrylamide copolymers were prepared at 40 or 25°C. The permeation of phenylethylene glycol through the capsule membranes was investigated. Permeability of the capsules prepared at 25°C increased monotonously with increasing temperature from 10 to 50°C. Permeability of the capsules prepared at 40°C also increased with increasing temperature up to 25°C but decreased above 30°C. Also, the degree of swelling of the membranes prepared at 40°C decreased above 30°C. Differential scanning calorimetry measurement showed that N‐isopropylacrylamide units underwent more efficient transition in the capsule membranes prepared at 40°C than in the membranes prepared at 25°C. The capsule membranes prepared at 40°C might have domains in which N‐isopropylacrylamide units are concentrated, whereas these units should distribute uniformly in the capsule membranes made at 25°C. Such a difference in distribution of N‐isopropylacrylamide units might result in the different permeation property of the capsule membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2703–2710, 2000     

Water Free Operated Phosphoric Acid Doped Radiation‐Grafted Proton Conducting Membranes for High Temperature Polymer Electrolyte Membrane Fuel Cells

The present study uses the radiation‐induced grafting method and applies it onto poly(ethylene‐alt‐tetrafluoroethylene) (ETFE) for the synthesis of proton‐exchange membranes by using monomers 4‐vinyl pyridine (4VP), 2‐vinyl pyridine (2VP), N‐vinyl‐2‐pyrrolidone (NVP) followed by phosphoric acid doping. Phosphoric acid that provides Grotthuss mechanism in proton mobilization is used to transform the graft copolymers to a high temperature membrane state. Resultant proton‐exchange membranes are verified with their proton conductivity, water uptake, mechanical and thermal properties, and phosphorous distribution as ex situ characterization. Our most important finding as a novelty in literature is that ETFE‐g‐P4VP phosphoric acid doped proton‐exchange membranes exhibit proton conductivities as 66 mS cm^–1 at 130 °C, 53 mS cm^–1 at 120 °C, 45 mS cm^–1 at 80 °C at RH 100% and 55 mS cm^–1 at 130 °C, 40 mS cm^–1 at 120 °C, 35 mS cm^–1 at 80 °C at dry conditions. Moreover, ETFE‐g‐P4VP membranes still conserves the mechanical properties, i.e., tensile strength up to 48 MPa. ETFE‐g‐P4VP membranes were tested in PEMFC at 80, 100, and 120 °C and RH <2% and exhibit promising performance as an alternative to commercial Nafion® membranes. The single cell testing performance of ETFE‐g‐P4VP membranes is presented for the first time in literature in our study.     

Dipole moments of poly(allyl methacrylate) prepared by group transfer polymerization

Dipole moments of poly(allyl methacrylate) prepared by group transfer polymerization and of allyl methacrylate were determined from dielectric constant, refractive index increment and density measurements performed on their dilute benzene and carbon tetrachloride solutions within a temperature range of 25–60°C. Dipole moments ratios and temperature coefficient, d ln〈μ²〉/dT, where 〈μ²〉 is the mean-square dipole moment of the chain, were calculated. These results are compared with earlier results.     

Dielectric properties of copolymers based on cyano monomers and methyl α‐acetoxyacrylate

With the aim of developing dielectric polymers containing CN groups with strong dipole moment, alternating and statistical copolymers of the cyano monomers vinylidene cyanide (VCN), acrylonitrile and methacrylonitrile with methyl α‐acetoxyacrylate (MAA) were synthesized and characterized. The copolymer's composition and microstructure were analysed by NMR spectroscopy, SEC and elemental analysis. The reactivity ratios calculated from the Q–e Alfrey–Price parameters for these copolymers indicated the alternating and statistical structures confirmed by NMR analysis. The copolymers have glass transition temperatures T_g in the range 83–146 °C and are stable up to 230 °C. The thermal stability of the copolymers depends on the nature of the cyano monomers. Their molecular dynamics were investigated by dielectric relaxation spectroscopy. We revealed a weak relaxation β at sub‐T_g temperature for poly(VCN‐co‐MAA) usually originating from molecular motions that are restricted to the scale of a few bond lengths. Strong α‐relaxation processes occurred above T_g for these copolymers. This primary relaxation was associated with cooperative movements of the polar groups (CN) at the time of mobility of the principal chains. The activation energy of the α‐relaxation process was also calculated. The values of the dielectric increment Δε for these copolymers were determined by Cole–Cole plots and indicated that the copolymers exhibit interesting dielectric properties compared with similar cyano materials. The polarity–permittivity relationship was also established. © 2012 Society of Chemical Industry     

Comonomer effect: Switching the lower critical solution temperature to upper critical solution temperature in thermo-pH sensitive binary graft copolymers

Hydrophilic biocompatible surfaces can be obtained by grafting stimuli-sensitive polymers onto commercially available medical devices. Thermo and pH-responsive polymers are two of the most studied materials due to their potential application as drug delivery systems. Poly(N-vinylcaprolactam) has a lower critical solution temperature (LCST) near to physiological temperature. However, when it is grafted with pH-sensitive moieties its LCST it is affected undergoing remarkable displacements. We studied the effect of acrylic acid (AAc), 4-vinylpyridine (4VP), and 1-vinylimidazole (Vim) on the LCST of N-vinylcaprolactam (NVCL) grafted onto silicone rubber (SR), and SR-g-NVCL (32.5 °C). The binary graft copolymers were obtained by ionizing grafting radiation using the simultaneous technique; the samples were characterized by Fourier transform infrared attenuated total reflectance (FTIR-ATR), cross-polarization magic angle spinning nuclear magnetic resonance (CP/MAS ¹³C-NMR), and thermogravimetrical analysis (TGA). LCST value was dramatically affected by the comonomer content; even it was observed the switching from LCST to upper critical solution temperature (UCST) for (SR-g-NVCL)-g-AAc and (SR-g-NVCL)-g-4VP samples. The observed behavior is rarely reported for binary graft copolymers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48170.     

Open- and short-circuit thermally stimulated currents in ethyl cellulose

Thermally stimulated currents (TSCs) in short-circuit and open-circuit configuration for ethyl cellulose samples (≈40 µm thick) have been studied as a function of polarizing field (25–100kV/cm) and polarizing temperature (323–353K). The thermograms have been found to be characterized by two prominent peaks located around 70 ± 10°C and 140 ± 10°C and the appearance of anomalous current in the high temperature region of the short-circuit TSC thermograms. The observed behaviour has been explained in terms of the existence of heterocharge due to dipole orientation and ionic homocharge drift, together with the injection of charge carriers from electrodes and their subsequent localization in surface and bulk traps.     

Thermorheological and mechanical behavior of polylactide and its enantiomeric diblock copolymers and blends

In this study, different compositions of nearly monodispersed diblock copolymers of dl-lactide or d-lactide and l-lactide were synthesized by living ring-opening polymerization with a dinuclear indium catalyst. The effects of molecular weight and block length ratio on the rheological behavior of dl and l-lactide diblock copolymers in the disordered state were investigated. For comparison, blends of PDLLA and PLLA homopolymers of equivalent molecular weights to the diblock copolymers were prepared. We found that the time–temperature (t–T) superposition principle is applicable to the diblock copolymers PLLA-b-PDLLA and blends in the disordered state. However, the t–T superposition failed at low temperatures close to the temperature of crystallization. In contrast, diblock copolymers PLLA-b-PDLA formed stereocomplex crystallites of high melting point (slightly above 200 °C) that causes a viscosity enhancement. The failure of t–T superposition was found due to existing of micro homo or stereocomplex crystallites. The non-isothermal crystallization behavior was investigated using differential scanning calorimetry (DSC). The DSC thermograms of blends exhibited a single glass transition at 50–60 °C followed by melting point of PLLA at 177 °C. With decreasing of the PLLA content in the blends, the intensity of the melting peak decreased. In addition, different crystallization behavior was observed for diblock copolymers compared to their equivalent blends. Specifically, low temperatures and enthalpies of melting peaks were observed for diblock copolymers. These also show improvement in elongation at break and tensile strength as compared to their counterpart homopolymer blends.     

pH- and temperature-responsive amphiphilic diblock copolymers of 4-vinylpyridine and oligoethyleneglycol methacrylate synthesized by RAFT polymerization

Diblock copolymers of 4-vinylpyridine (4VP) and oligoethyleneglycol methyl ether methacrylate (OEGMA) were synthesized for the first time using RAFT polymerization technique as potential drug delivery systems. Effects of the number of ethylene glycol units in OEGMA, chain length of hydrophobic P4VP block, pH, concentration and temperature on the solution behavior of the copolymers were investigated comprehensively. Copolymer chains formed micelles at pH values higher than 5 whereas unimeric polymers were observed to exist below pH 5, owing to the repulsion between positively charged P4VP blocks. The size of the micelles was dependent on the relative length of blocks, P4VP and POEGMA. Thermo-responsive properties of copolymers were investigated depending on the pH and length of P4VP block. The increase in the length of P4VP block decreased the LCST substantially at pH 7. At pH 3, LCST of copolymers shifted to higher temperatures due to the increased interaction of copolymers with water through positively charged P4VP block.     

Nonlinear viscoelastic behavior of butadiene–acrylonitrile copolymers filled with carbon black

Various viscoelastic measurements including dynamic mechanical measurements in tension at 110 Hz from ?60° to 160°C, tensile stress relaxation measurements with 100% elongation at 25°, 54°, and 98°C, capillary flow measurements at 70°, 100°, and 125°C, and high-speed tensile stress–strain measurements carried to break at 25°, 56°, and 98°C were performed on four samples of carbon black-filled butadiene–acrylonitrile copolymers. All the data were treated with the same equation for time–temperature conversion. The capillary viscosity–shear rate curves were significantly lower than the complex viscosity–angular frequency curves, indicating “strain softening” with extrusion. The viscosity was estimated from the stress–strain relationship at the yield point. The viscosity as a function of the strain rate is significantly higher than the complex viscosity as a function of angular frequency, indicating “strain hardening” with extension. The strain softening and strain hardening are attributable to the structural changes upon deformation of the carbon black-filled elastomers. With the unfilled elastomers, neither strain softening nor strain hardening were observed in similar measurements.     

Copolymers derived from bismaleimide oligomer with active solvent

An oligomer from 4, 4′‐bis(maleimido)diphenyl methane and methylenedianiline were dissolved in active solvent N,N‐dimethyl acrylamide in a solid content up to 50–70%; the solution was poured in a sheet‐shaped module and irradiated by ⁶⁰Co with the dose from 20 to 350 kGy at room temperature. The polymerized sheet was postcured at 180°C to obtain a transparent red‐orange sheet with tensile strength above 100 MPa. The glass transition temperature before and after postcuring was around 100°C and 150–180°C, respectively. Styrene was used along with DMAA to decrease the water absorption for the copolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2879–2882, 2004     

Concentration effect of <Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide on viscoelastic properties of hydrosoluble thermo-thickening copolymers

In this work, we described the preparation of hydrosolubles thermosensitive copolymers obtained via free radical polymerization in aqueous media. The reactions were carried out under different molar ratio of acrylamide and N-isopropylacrylamide (NIPAM) and are considered [80]/[20], [60]/[40], [50]/[50], [40]/[60] and [20]/[80], respectively. The initial concentration of monomer mixture was kept at 3% (weight) based on the water volume. The polymerizations were performed at 70 °C under mechanical agitation during 7 h and the molar ratio between monomer and initiator (4,4′-azobis cyano pentanoic acid) was kept at 0.07%. The copolymers were characterized and results demonstrated that the monomer concentrations were closed to previously feed to the reaction. The turbidity point rises according to the quantity of poly(acrylamide), PAM, incorporated into the copolymers (composition value). Also, it was observed that the molecular weight of each copolymer decreases when the amount of NIPAM increases. On the other hand, the viscosity of all copolymers growth compared to the increase in the temperature from 25 to 70 °C is observed. Notwithstanding, in the case of copolymer with highest NIPAM concentration (CP5), the viscosity decreases in the temperature range from 60 to 70 °C.     

Radiation-initiated graft copolymerization of 4-vinylpyridine onto polyethylene and polytetrafluoroethylene films and anion-exchange membranes therefrom

Radiation-initiated graft copolymerization of 4-vinylpyridine (4VP) onto low-density polyethylene (LDPE) and polytetrafluoroethylene (PTFE) films was carried out by γ-rays from ⁶⁰Co source in nitrogen atmosphere. The direct method of multiple grafting was used, connected with posteffect taking place at irradiation doses from 1 to 35 kGy. Thus the monomer diffused into the polymer matrix together with the stepwise generation of free radicals to reduce the thickness of the nongrafted layer. The grafting proceeds in the amorphous phase of the polymers which is further amorphized by the irradiation. Copolymers with grafting degree (P) from 17 to 75% for LDPE and from 0.7 to 13% for PTFE were obtained. The dependence of the degree of grafting of 4VP on irradiation dose was established. The spectral and thermodynamic properties of the synthesized copolymers were studied. The degree of crystallinity was found to decrease and a two-stage mechanism of thermooxidative destruction was observed. The synthesized copolymers contain pyridine groups determining their anion-exchange properties. The initial pyridine groups in the grafted copolymers were quaternized. Some of the basic characteristics, such as water content and specific electric resistance of anion-exchange membranes (AEM) were studied depending on the grafting degree of 4VP. The ionomers studied possess high transport number (t_- ∼ 0.8–0.9), good diffusion characteristics (9.2 × 10⁻⁸−1.7 × 10⁻⁷ cm²/s), and suitable tensile properties. The AEM obtained, combined with the cation exchange membranes we have synthesized earlier on the same polymeric basis, can be used successfully in various electrodialysis processes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1469–1475, 1997     

Formation of thermosensitive water‐soluble copolymers with phosphinic acid groups and the thermosensitivity of the copolymers and copolymer/metal complexes

Thermosensitive and water‐soluble copolymers were prepared through the copolymerization of acryloyloxypropyl phosphinic acid (APPA) and N‐isopropyl acrylamide (NIPAAm). The thermosensitivity of the copolymers and copolymer/metal complexes was studied. The APPA–NIPAAm copolymers with less than 11 mol % APPA moiety had a lower critical solution temperature (LCST) of approximately 45°C, but the APPA–NIPAAm copolymers with greater than 21 mol % APPA moiety had no LCST from 25 to 55°C. The APPA–NIPAAm copolymers had a higher adsorption capacity for Sm³⁺, Nd³⁺, and La³⁺ than for Cu²⁺, Ni²⁺ and Co²⁺. The APPA–NIPAAm (10:90) copolymer/metal (Sm³⁺, Nd³⁺, or La³⁺) complexes became water‐insoluble above 45°C at pH 6–7, but the APPA–NIPAAm (10:90) copolymer/metal (Cu²⁺,Ni²⁺, or Co²⁺) complexes were water‐soluble from 25 to 55°C at pH 6–7. The temperature at which both the APPA–NIPAAm copolymers and the copolymer/metal complexes became water‐insoluble increased as the pH values of the solutions increased. The APPA–NIPAAm copolymers were able to separate metal ions from their mixed solutions when the temperature of the solutions was changed; this was followed by centrifugation of the copolymer/metal complexes after the copolymers were added to the metal solutions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 116–125, 2004