Crosslinked quaternized poly(arylene ether sulfone) copolymer membrane applied in an electric double-layer capacitor for high energy density

The low energy density of supercapacitors, especially supercapacitors based on aqueous electrolytes, is the main factor limiting their application, and the energy density is closely related to the operating potential window of the supercapacitor. The polymer electrolyte is the main contributor to the safe operation and good ion conductivity of the supercapacitor. In this study, a crosslinked quaternized poly(arylene ether sulfone) (PAES) membrane was prepared via crosslinking during membrane formation with a thermal-only treatment and applied in an electric double-layer capacitor (EDLC). The pre-prepared PAES membrane formed a polymer electrolyte with 1 mol/L Li₂SO₄ and was then fabricated into an EDLC single cell. The properties of both the membrane and ELDC were investigated. The preferred cPAES-N-0.2 polymer electrolyte showed an ionic conductivity of 1.18 mS/cm. The optimized EDLC exhibited a single-electrode gravimetric capacitance of 104.92 F/g at a current density of 1.0 A/g and a high operating potential window (1.5 V); it, thereby, achieved a high energy density of 8.20 W h/kg. The EDLC also exhibited excellent cycling properties over 3000 charge–discharge cycles. The crosslinked structures promoted the tensile strength and thermal stability of the PAES membranes; this was accompanied by a slight decrease in the ionic conductivity. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47759.     

High molecular weight poly(butylene terephthalate-co-butylene 2,5-furan dicarboxylate) copolyesters: From synthesis to thermomechanical and barrier properties

Poly(butylene terephthalate-co-butylene 2,5-furandicarboxylate) copolyesters (PBTFs) were synthesized from 1,4-butanediol, dimethyl terephthalate (DMT), and 2,5-furandicarboxylic acid (FDCA) by a two-step polymerization method. Their chemical structures were confirmed by Fourier-transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and carbon nuclear magnetic resonance before thermal properties were explored with differential scanning calorimeter and thermogravimetric analyzer. Results showed that PBTFs changed from semi-crystalline to completely amorphous when the content of FDCA unit was increased to 45 mol% at first, and then became crystallographic again with the further increment of FDCA unit to 75 mol%. For their mechanical properties, the tensile modulus and strength showed the similar trend, decreasing firstly and then increasing later. Their barrier to carbon dioxide and oxygen became better with the increasing of furan content due to the rigidity and higher polarity of furan ring. The performance of PBTFs copolyesters was investigated clearly, and the relative content of FDCA and DMT can be adjusted to satisfy different performance requirements.     

1,5-己二烯交联烯烃聚合物的合成及其抗剪切稳定性

以金属配合物为催化剂、1,5-己二烯为交联剂,采用本体聚合法合成了交联超高相对分子质量烯烃类聚合物(简称交联聚合物)。用傅里叶变换红外光谱、核磁共振、凝胶渗透色潜表征交联聚合物的结构和相对分子质量。用旋转黏度计和超声波仪研究了1,5-己二烯用量对交联聚合物溶液表观黏度的影响及交联聚合物的相对分子质量对交联聚合物溶液抗剪切稳定性的影响。实验结果表明,在最佳聚合条件(单体80mL、助催化剂0．4mL、CS-1催化剂0．090g、1,5-己二烯0．40mL、0℃、24 b)下所合成的交联聚合物的重均相对分子质量为7．7×106,数均相对分子质量3．6×106。加入少量1,5-己二烯能提高交联聚合物的抗剪切能力,同时也能提高交联聚合物的相对分子质量。交联聚合物的相对分子质量越大,抗剪切稳定性越好。1,5-己二烯用量约为0．1 mL时(单体40 mL),交联聚合物溶液的表观黏度达到最大值(16．8 mPa·s)。     

On the origin of strain hardening in glassy polymers

The influence of network density on the strain hardening behaviour of amorphous polymers is studied. The network density of polystyrene is altered by blending with poly(2,6-dimethyl-1,4-phenylene-oxide) and by cross-linking during polymerisation. The network density is derived from the rubber-plateau modulus determined by dynamic mechanical thermal analysis. Subsequently uniaxial compression tests are performed to obtain the intrinsic deformation behaviour and, in particular, the strain hardening modulus. At room temperature, the strain hardening modulus proves to be proportional to the network density, irrespective of the nature of the network, i.e. physical entanglements or chemical cross-links. With increasing temperature, the strain hardening modulus is observed to decrease. This decrease appears to be related to the influence of thermal mobility of the chains, determined by the distance to the glass-transition temperature (T−T_g).     

Oligo(ethylene oxide) side‐chain steric screening effects on conductimetric properties of grafted poly(4‐vinylpyridinium) salts in aqueous solutions

A set of poly[N‐oligo(ethylene oxide)yl 4‐vinylpyridinium tosylate] (P4VOEOOTs) has been prepared by spontaneous polymerization of 4‐vinylpyridine. This method gives a grafted polyelectrolyte having a positive charge on every backbone pyridinic moiety. The P4VP15Ts, P4VP164Ts, P4VP350Ts and P4VP750Ts aqueous solution conductivities were determined in the concentration range from 6 × 10^?4 to 10^?2 M at 25 °C. The variation of the conductivity versus concentration of the investigated system exhibits typical polyelectrolyte behaviour. The polyelectrolyte mobility was found to be dependent on the oligo(ethylene oxide) (OEO) side‐chain length. Manning's rod‐like model fails to describe these results. A simple steric effect is proposed to explain the influence of the OEO length. Copyright © 2003 Society of Chemical Industry     

On the linear correlation between microhardness and mechanical properties in polar polymers and blends

The tensile elastic modulus (E), yield stress (σ_Y) and microhardness (MH) of neat and binary and ternary blends of glassy semicrystalline ethylene–vinyl alcohol copolymer (EVOH), a glassy amorphous polyamide and a semicrystalline nylon‐containing ionomer covering a broad range of properties were examined. The tests were carried out on dry and water‐equilibrated samples to produce stiffer and softer materials, respectively. From the results, more accurate linear correlations were found to describe adequately the microhardness, modulus and yield stress of these strongly self‐associated polymers through hydrogen bonding. Copyright © 2003 Society of Chemical Industry     

Rheological cure characterization of phosphazene–triazine polymers

Cyclomatrix phosphazene–triazine network polymers were synthesized by co‐curing a blend of tris(2‐allylphenoxy), triphenoxy cyclotriphosphazene (TAP), and tris(2‐allylphenoxy) s‐triazine (TAT) with bis(4‐maleimido phenyl) methane (BMM). The co‐curing of the three‐component resin was investigated by dynamic mechanical analysis using rheometry. The cure kinetics of the Diels–Alder step was studied by examining the evolution of the rheological parameters, such as storage modulus (G′), loss modulus (G″), and complex viscosity (η*), for resins of varying compositions at different temperatures. The curing conformed to an overall second‐order phenomenological equation, taking into account a self‐acceleration effect. The kinetic parameters were evaluated by multiple‐regression analysis. The absence of a definite trend in the cure process with blend composition ratio was attributed to the occurrence of a multitude of competitive reactions whose relative rates depend on the reactant ratio and the concentration of the products formed from the initial phase of reaction. The cure was accelerated by temperature for a given composition, whereas the self‐acceleration became less prominent at higher temperature. Gelation was accelerated by temperature. The gel conversion decreased with increase in maleimide concentration and, for a given composition, it was independent of the cure temperature. The activation energy for the initial reaction and the crosslinking process were estimated for a composition with a maleimide‐to‐allyl ratio of 2 : 1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 908–914, 2003     

Synthesis and characterization of conducting copolymers from aniline and o‐anisidine in HCl solutions

Conducting poly(aniline‐co‐o‐anisidine) (PAS) films with different ratios of aniline units in the polymer chain were prepared by oxidative polymerization of different molar ratios of aniline and o‐anisidine in 1 M HCl using cyclic voltammetry. Due to the much higher reactivity of o‐anisidine, the structure and properties of PASs were found to be dominated by the o‐anisidine units. The polymerization of poly‐o‐anisidine and PASs followed zero‐order kinetics with respect to formation of the polymer (film thickness) and the autocatalytic polymerization of aniline was completely inhibited. In contrast to polyaniline, a decrease in the polymerization temperature was found to increase the amount of copolymer formed and its redox charge. The presence of aniline units in PASs led to a pronounced increase in the molecular weight and conductivity, and a decrease in the solubility in organic solvents. Repetitive charging/discharging cycles showed that PASs resist degradation more than polyaniline. Copyright © 2003 Society of Chemical Industry     

Inhibition of radical polymerization in solvent‐based systems (security of solvent‐based radical polymerization of PSA‐acrylic in a plant reactor)

This article shows the influence of some chain‐transfer agents as inhibitors for acrylic solvent‐based polymerization. These chain‐transfer agents can offer significant advantages, as outlined below. The following chain‐transfer agents were studied to stop or slow down the polymerization process in the case of a runaway: n‐dodecyl mercaptan, trimethylolpropane‐trimercaptoacetate, phenothiazine, diphenylphenylen diamine, cuprum oxide, isopropanol, toluene, and carbon tetrachloride. Synthesized pressure‐sensitive adhesive based on acrylic polymers and containing 2‐ethylhexyl acrylate, methyl acrylate, and acrylic acid were used for the production of self‐adhesives with high cohesion. The polymerization was accomplished in ethyl acetate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1354–1357, 2003