Impedance spectroscopy of polymer electrolytes based on epoxidized natural rubber with 50 mol% epoxide content

Polymer electrolytes of epoxidized natural rubber with 50 mol% epoxide content (ENR‐50) and lithium perchlorate (LiClO₄) were studied with respect to variation of thermal and electric properties with salt content. Below salt content of 5% and above 12%, glass transition temperature stays constant. A steep increase is observed in between. Frequency dependence of impedance was studied over a wide range of salt concentration. Complex impedance plots exhibit one semicircle. Location of semicircles above 12% clearly points towards phase heterogeneity. Analysis of resistivity leads to the result that one phase's resistivity corresponds to salt content of 12%, whereas the second phase exceeds this resistivity by one order of magnitude. Imaginary part of impedance supports this behavior with respect to resistivity. Polarization relaxation time, however, does not change with salt content. It demonstrates that the phase with the excess resistivity does not contribute to polarization relaxation. Therefore, universal dielectric behavior can be observed also in the heterogeneous system. POLYM. ENG. SCI., 55:2250–2255, 2015. © 2015 Society of Plastics Engineers     

Synthesis and thermal,mechanical and gas permeation properties of aromatic polyimides containing different linkage groups

Two series of aromatic polyimides containing various linkage groups based on 2,7‐bis(4‐aminophenoxy)naphthalene or 3,3′‐dimethyl‐4,4′‐diaminodiphenylmethane and different aromatic dianhydrides, namely 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride), 4,4′‐(hexafluoroisopropylidene)bis(phthalic anhydride), 3,3′,4,4′ benzophenonetetracarboxylic dianhydride, 9,9‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]fluorene dianhydride and 4,4′‐(4,4′‐hexafluoroisopropylidenediphenoxy)bis(phthalic anhydride), were synthesized and compared with regard to their thermal, mechanical and gas permeation properties. All these polymers showed high thermal stability with initial decomposition temperature in the range 475–525 °C and glass transition temperature between 208 and 286 °C. Also, the polymer films presented good mechanical characteristics with tensile strength in the range 60–91 MPa and storage modulus in the range 1700–2375 MPa. The macromolecular chain packing induced by dianhydride and diamine segments was investigated by examining gas permeation through the polymer films. The relationships between chain mobility and interchain distance and the obtained values for gas permeability are discussed. © 2014 Society of Chemical Industry     

Strain‐induced deformation mechanisms of polylactide plasticized with acrylated poly(ethylene glycol) obtained by reactive extrusion

This work aimed at identifying the tensile deformation mechanisms of an original grade of plasticized polylactide (pPLA) obtained by reactive extrusion. This material had a glass transition temperature of 32.6 °C and consisted of a polylactide (PLA) matrix grafted with poly(acryl‐poly(ethylene glycol)) (poly(Acryl‐PEG)) inclusions. pPLA behaved like a rubber‐toughened amorphous polymer at 20 °C, and its tensile behavior evolved toward a rubbery semicrystalline polymer with increasing temperature. The drawing of pPLA involved orientation of amorphous and crystalline chains, crystallization, and destruction of crystals. It was found that crystal formation and crystal destruction were in competition below 50 °C, resulting in a constant or slightly decreasing crystallinity with strain. Increasing temperature enhanced crystal formation and limited crystal destruction, resulting in an increased crystallinity with the strain level. Drawing yielded a transformation of the initial spherical poly(Acryl‐PEG) inclusions into ellipsoids oriented in the tensile direction. This mechanism may engender the formation of nanovoids within the inclusions due to a decreased density, assumed to be responsible for the whitening of the specimen. © 2015 Society of Chemical Industry     

Kinetics of reversible addition–fragmentation transfer (RAFT) miniemulsion polymerization of styrene using dibenzyl trithiocarbonate as RAFT reagent and costabilizer

The roles of dibenzyl trithiocarbonate (DBTTC) as both costabilizer and reversible addition–fragmentation transfer (RAFT) reagent in RAFT miniemulsion polymerizations of styrene were investigated. The effectiveness of DBTTC costabilizer in retarding Ostwald ripening involved in the storage stability of miniemulsion is comparable to that of conventional low‐molecular‐weight costabilizers such as cetyl alcohol, but inferior to that of hexadecane. The major variables chosen for studying kinetics of RAFT miniemulsion polymerizations include the type of initiators and levels of DBTTC and surfactant. At a constant level of DBTTC, the rate of polymerization for benzoyl peroxide (BPO)‐initiated polymerization is slower than that for sodium persulfate (SPS)‐initiated polymerization. Furthermore, the polymerization rate decreases with increasing level of DBTTC for polymerizations initiated by BPO (or SPS). It is the monomer droplet nucleation that governs BPO‐initiated polymerizations. In contrast, for SPS‐initiated polymerizations, the probability for homogeneous nucleation to take place is greatly increased, especially for polymerizations with lower levels of DBTTC and higher levels of surfactant. © 2015 Society of Chemical Industry     

Intensity enhancement of photoluminescent polyesters by photocrosslinking

A series of polyesters with alkylated triazole heterocyclic rings at the branches were designed and synthesized via the polycondensation reaction. The synthesized polyesters were examined with various spectroscopic methods such as Fourier transform IR, ¹H NMR and ¹³C NMR. The alkyl chain length at the branch was found to affect the thermal stability of the polyesters, which decreased with longer alkyl chain. These polyesters possessed an aggregation‐induced emission enhancement characteristic evidenced by the transformation of the clear solutions in tetrahydrofuran with weak greenish blue emission to cloudy solutions with enhanced blue emission when water was added to promote aggregation. Furthermore, enhancement in the photoluminescence intensity was observed when the polyesters underwent photocrosslinking upon UV irradiation and appeared as self‐assembled aggregates. The formation of aggregates in the water ? tetrahydrofuran solutions and after photocrosslinking was confirmed via TEM analysis. The SEM images showed that the photocrosslinked polyesters were highly porous which may enhance the π ? π stacking interaction that improved the photoluminescence intensity. © 2015 Society of Chemical Industry     

Extensive N‐methylation of chitosan: evaluating the effects of the reaction conditions by using response surface methodology

The effects of reaction time, concentration of aqueous sodium hydroxide and molar ratio iodomethane/chitosan on the yield of the reaction of chitosan with iodomethane in N‐methyl‐2‐pyrrolidone (NMP) at 25.0 ± 0.1 °C, as well as on the characteristics of the resulting N,N,N‐trimethylchitosan (TMCh), were evaluated by using full‐factorial 2³ design analysis and response surface methodology. This study also aimed to determine the reaction conditions allowing the production of water‐soluble TMCh presenting a high average degree of quaternization and intrinsic viscosity at high reaction yield. ¹H NMR spectroscopy was employed for structural characterization, including the determination of average degrees of acetylation () and quaternization (), while capillary viscometry was used to determine intrinsic viscosity [η]. The results show that when the extensive N‐methylation is carried out for 24 h in NMP/15% NaOH (w/v) employing a lower excess of iodomethane (CH₃I/Ch = 9), water‐soluble highly substituted ( = 46.0%) TMCh ([η] = 213.0 mL g^?1) can be produced in high yield (81.8%). The highly significant mathematical models resulting from this study describe the dependence of the experimental responses on the reaction conditions and allow the characteristics and properties of the resulting TMCh to be defined by properly choosing the reaction conditions. © 2015 Society of Chemical Industry     

Poly(4‐vinyl pyridine)‐grafted graphene oxide for drug delivery and antimicrobial applications

Graphene oxide (GO) was covalently functionalized with poly(4‐vinyl pyridine) (P4VP) by atom transfer radical polymerization for drug delivery and antimicrobial applications. The physiochemical properties, chemical structure, composition and morphology of the P4VP‐functionalized GO (GO‐P4VP) were studied. Simple physisorption of a cancer drug, camptothecin (CPT), via π ? π stacking and/or hydrophobic interactions on the GO‐P4VP was tested for drug loading and its release by altering the pH. The GO‐P4VP has low cytotoxicity, and the CPT‐loaded GO‐P4VP exhibited a high potency for killing cancer cells in vitro. Prominent antimicrobial properties against Escherichia coli and Staphylococcus aureus were also observed. Thus, the GO‐P4VP can be utilized as a drug delivery vector with high biocompatibility, solubility and stability in physiological solutions, a suitable payload capacity and excellent bacterial toxicity. Owing to its small size, low cost, large specific area, ready scalability and useful non‐covalent interactions, GO‐P4VP is a novel material for biomedical, industrial and environmental applications. © 2015 Society of Chemical Industry     

Thermal,morphological, and physicomechanical properties of (chlorinated polyethylene rubber)/(chloroprene rubber) blends

The effect of the blend ratio on the thermal, morphological, and physicomechanical properties of (chlorinated polyethylene rubber)/(chloroprene rubber) (CPE/CR) blends was studied. Two distinct glass transition temperatures (T_g) of all blends were observed in differential scanning calorimetry curves, falling between the T_g of the two pure rubbers. Analysis of the blends by scanning electron microscopy showed both dispersed and continuous phase morphology that depended on the blend composition. Thermogravimetric analysis showed that all the compounds underwent two stages of thermal degradation. The Mooney viscosity and optimum cure times increased with the increase in CPE contents, whereas the scorch times decreased. The tensile strength and elongation at break decreased, whereas the 100% modulus, hardness, and compression set increased with the increase of CPE content; the tear strength had the lowest value for the 50/50 CPE/CR blend because of the poor miscibility. The results from thermal aging and oil resistance tests showed that pure CPE possessed better thermal aging property and oil resistance than those of pure CR. Thus, considerable improvement in oil resistance of the blend compounds was achieved with the increase of CPE content. J. VINYL ADDIT. TECHNOL., 21:18–23, 2015. © 2014 Society of Plastics Engineers     

Complexation of Surfactant/β‐Cyclodextrin to Inhibit Surfactant Adsorption onto Sand,Kaolin, and Shale for Applications in Enhanced Oil Recovery Processes. Part I: Static Adsorption Analysis

Surfactant adsorption onto solid surfaces is a major issue during surfactant flooding in enhanced oil recovery applications; it decreases the effectiveness of the chemical injection making the process uneconomical. Therefore, it was hypothesized that the adsorption of surfactant onto solid surfaces could be inhibited using a surfactant delivery system based on the complexation between the hydrophobic tail of anionic surfactants and β‐cyclodextrin (β‐CD). Proton nuclear magnetic resonance spectroscopy was used to confirm the complexation of sodium dodecyl sulfate (SDS)/β‐CD. Surface tension analysis was used to establish the stoichiometry of the complexation and the binding constant (K_a). Static adsorption testing was applied to determine the adsorption of surfactant onto different solids (sandstone, shale, and kaolinite). The release of the surfactant from the β‐CD cavity was qualitatively evaluated through bottle testing. The formation of the inclusion complex SDS/β‐CD with a 1:1 stoichiometry was confirmed. The K_a of the complexations increases as salinity and hardness concentration increases. The encapsulation of the surfactant into the β‐CD cavity decreases the adsorption of surfactant onto solid surfaces up to 79 %. Qualitative observations indicate that in the presence of solid adsorbents partially saturated with crude oil, the β‐CD cavity releases surfactant molecules, which migrate towards the oil–water interface.     

Revisiting tetranitrophenolsulfonephthalein

Among the vast series of phenolsulfonephthalein dyes, the nitro derivatives and especially 3,3′,5,5′‐tetranitrophenolsulfonephthalein (nitrophenol crimson) remain practically unexplored, whereas the halogen and alkyl derivatives have been studied comprehensively. This striking difference is probably due to the enormous influence of the four NO₂ groups on the properties of the dye. As a result, the protolytic behaviour is unlike even that of tetrabromo phenolsulfonephthalein, and the recognised scheme of acid–base and tautomeric equilibrium of the sulfonephthaleins is unable to explain it. The molecular form H₂R was isolated as a sultonic tautomer, and an X‐ray crystal structure analysis was carried out. Our studies of the UV‐vis absorption spectra in water, methanol, dimethyl sulfoxide, acetonitrile, acetone, and dichloromethane, as well as in aqueous micellar solutions of surfactants, allowed us to evaluate the true molar absorptivity of the dianion R^2?, and to elucidate the enormous tendency to form yellow trianionic carbinol ROH^3?, even in the presence of traces of H₂O. Nuclear magnetic resonance and electrospray data confirm the proposed scheme of ionisation and tautomerism of nitrophenol crimson.