Preparation and ionic conductivity of solid polymer electrolyte based on polyacrylonitrile‐polyethylene oxide

The transparent and flexible solid polymer electrolytes (SPEs) were fabricated from polyacrylonitrile‐polyethylene oxide (PAN‐PEO) copolymer which was synthesized by methacrylate‐headed PEO macromonomer and acrylonitrile. The formation of copolymer is confirmed by Fourier‐transform infrared spectroscopy (FTIR) measurements. The ionic conductivity was measured by alternating current (AC) impedance spectroscopy. Ionic conductivity of PAN‐PEO‐LiClO₄ complexes was investigated with various salt concentration, temperatures and molecular weight of PEO (Mn). And the maximum ionic conductivity at room temperature was measured to be 3.54 × 10^?4 S/cm with an [Li⁺]/[EO] mole ratio of about 0.1. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 461–464, 2006     

Solid polymer electrolyte based on waterborne polyurethane for all‐solid‐state lithium ion batteries

A series of solid polymer electrolytes (SPEs) based on comb‐like nonionic waterborne polyurethane (NWPU) and LiClO₄ are fabricated via a solvent free process. The NWPU‐based SPEs have sufficient mechanical strength which is beneficial to their dimensional stability. Differential scanning calorimetry analysis indicates that the phase separation occurs by the addition of the lithium salt. Scanning electron microscopy and X‐ray diffraction analyses illustrate the good compatibility between LiClO₄ and NWPU. Fourier transform infrared study reveals the complicated interactions among lithium ions with the amide, carbonyl and ether groups in such SPEs. AC impedance spectroscopy shows the conductivity of the SPEs exhibiting a linear Arrhenius relationship with temperature. The ionic conductivity of the SPE with the mass content of 15% LiClO₄ (SPE15) can reach 5.44 × 10^?6 S cm^?1 at 40 °C and 2.35 ×10^?3 S cm^?1 at 140 °C. The SPE15 possesses a wide electrochemical stability window of 0–5 V (vs. Li+/Li) and thermal stability at 140 °C. The excellent properties of this new NWPU‐based SPE are a promising solid electrolyte candidate for all‐solid‐state lithium ion batteries. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45554.     

Fabrication and characterization of PEO/PPC polymer electrolyte for lithium‐ion battery

A new poly(propylene carbonate)/poly(ethylene oxide) (PEO/PPC) polymer electrolytes (PEs) have been developed by solution‐casting technique using biodegradable PPC and PEO. The morphology, structure, and thermal properties of the PEO/PPC polymer electrolytes were investigated by scanning electron microscopy, X‐ray diffraction, and differential scanning calorimetry methods. The ionic conductivity and the electrochemical stability window of the PEO/PPC polymer electrolytes were also measured. The results showed that the T_g and the crystallinity of PEO decrease, and consequently, the ionic conductivity increases because of the addition of amorphous PPC. The PEO/50%PPC/10%LiClO₄ polymer electrolyte possesses good properties such as 6.83 × 10^?5 S cm^?1 of ionic conductivity at room temperature and 4.5 V of the electrochemical stability window. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterization of (PEO)LiClO4‐Li1.3Al0.3Ti1.7(PO4)3 composite polymer electrolytes with different molecular weights of PEO

A group of polyethylene oxide (PEO)LiClO₄‐Li_1.3Al_0.3Ti_1.7(PO₄)₃ composite polymer electrolyte (CPE) films was prepared by the solution‐cast method. In each film, EO/Li = 8 and the Li_1.3Al_0.3Ti_1.7(PO₄)₃ content of 15 wt % were fixed, but the number averaged molecular weight of PEO (M_n) was altered from 5 to 7 × 10⁴ to 10⁶, 2.2–2.7 × 10⁶, 3–4 × 10⁶, 4–5 × 10⁶, and 5.5–6 × 10⁶, respectively. Several techniques including X‐ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and electrical impedance spectroscopy (EIS) were used to characterize the CPE films. LiClO₄ was found to have a strong tendency to complex with PEO, but Li_1.3Al_0.3Ti_1.7(PO₄)₃ was rather dispersed in PEO matrix. DSC analysis revealed that the amorphous phase was dominant in the CPE films although the PEOs before‐use was considerably crystalline. SEM study showed smooth and homogeneous morphologies of the films with low molecular weight PEO and a dual phase characteristic for those with high molecular weight PEO. EIS results indicated that the CPE films are all ionic conductor and the conducting behavior obeys Vogel‐Tamman‐Fulcher (VTF) equation. The parameters in VTF equation were obtained and discussed by taking into considerations PEO molecular weights and crystallinities of the CPE films. Of all the films, the one with PEO with the smallest M_n = 5–7 × 10⁴ had the maximum conductivity, i.e., 1.590 × 10^?5 S cm^?1 at room temperature and 1.886 × 10^?3 S cm^?1 at 373 K. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4269–4275, 2006     

Preparation and evaluation of two kinds of solid polymer electrolytes made from crosslinked poly(ether urethane) elastomers consisting of a comb‐like and a hyperbranched polyether

Two novel polyethers, one comb‐like and another hyperbranched, were synthesized by the cationic ring‐opening polymerization of 3‐(methoxy(triethylenoxy))methyl‐ and 3‐(hydroxy‐(triethylenoxy))methyl‐3′‐methyloxetane, respectively. The former reacted with a multifunctional isocyanate and the latter with a difunctional isocyanate to give rise to the corresponding crosslinked poly(ether urethane) elastomers, PCEU and PHEU. Accordingly, two kinds of solid polymer electrolytes (SPEs) were prepared from these two elastomers in situ in the presence of lithium salt trifluoromethanesulfonimide. It was found that the PCEU‐based SPEs shows a higher ionic conductivity than that PHEU‐based ones due to its more mobile pendent chains and appropriate crosslinking density in the polymeric network. The maximum ionic conductivities of 1.4 × 10^?5 S/cm at 30°C and 3.5 × 10^?4 S/cm at 80°C were attained at the molar ratio of O/Li = 7.5. The DSC measurements clearly demonstrated that PCEU indeed possesses the more flexible chain motion ability than PHEU. The electrochemical stability window of PCEU, which is 1.7–4.0 V was measured by cyclic voltammogram. Additionally, the significantly high decomposition temperature as evidenced by TGA analyses endowed these SPEs a good safe performance. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Microbial origin xanthan gum‐based solid polymer electrolytes

Natural polymers are widely used as matrices for solid polymer electrolytes (SPEs) in electrochemical devices due to their richness in nature, low cost, and biodegradation properties. Xanthan gum (XG) is a natural polymer obtained from microbial origin and when dissolved form transparent solution with high viscosity and stability even in different temperature conditions. This article describes the synthesis of XG‐based SPEs with proton conduction. These new materials were obtained by crosslinking XG with glutaraldehyde, plasticized with ethylene glycol, and doped with acetic acid as ions source. The ionic conducting membranes, casted from this polymer solution, showed a high ionic conductivity of 7.93 × 10^?5 S cm^?1 at room temperature, a microscopically homogeneous surface, thermal stability, and predominantly amorphous structure. These results prove that XG‐based SPEs are very promising new materials that could be applied in modern electrochemical devices. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46229.     

Synthesis of high molecular weight polyoxyethylene with a quaternary catalyst and study of its conductive blends with poly(2‐vinyl pyridine)

High molecular weight polyoxyethylene (PEO) was synthesized by using a quaternary catalyst composed of triisobutyl aluminum, phosphoric acid, water, and N,N‐dimethylaniline (DMA). Optimum synthesis conditions and some properties of the product were studied. This catalyst showed high activity and the molecular weight of the polyoxyethylene obtained can approach one million. The activity of polymerization mainly depends upon the composition of catalyst. The optimum composition is as follows: i‐Bu₃Al:H₃PO₄:H₂O:DMA = 1 : 0.17 : 0.17 : 0.10–0.15 (molar ratio).The active centers of the catalyst was thus proposed. The high molecular weight PEO synthesized by this catalyst was blended with poly(2‐vinyl pyridine) (PVP) and then doped with LiClO₄ and TCNQ to obtain a conductive elastomeric material. Ionic, electronic, and mixed (ionic–electronic) conductivities of blends were investigated. At a Li/EO molar ratio of 0.1 and a TCNQ/VP molar ratio of 0.5, the mixed conductivity of the blend of PEO/PVP/LiCIO₄/TCNQ is higher than the sum of ionic conductivity of PEO/PVP/LiCIO₄ and electronic conductivity of PEO/PVP/TCNQ, when the weight ratio of PEO to PVP is 6/4 or 5/5. It can reach 4 × 10^?6 S/cm at room temperature. Differential scanning calorimetry, thermal gravimetric analysis, and the appearance of the blend showed that both TCNQ and LiClO₄ can complex with PEO and PVP, thus enhancing the compatibility between PEO and PVP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis,physical properties,and crystallization of optically active poly(L‐phenyllactic acid) and poly(L‐phenyllactic acid‐co‐L‐lactic acid)

Optically active poly(L ‐phenyllactic acid) (Ph‐PLLA), poly(L ‐lactic acid) (PLLA), and poly(L ‐phenyllactic acid‐co‐L ‐lactic acid) with weight‐average molecular weight exceeding 6 × 10³ g mol^?1 were successfully synthesized by acid catalyzed direct polycondensation of L ‐phenyllactic acid and/or L ‐lactic acid in the presence of 2.5–10 wt % of p‐toluenesulfonic acid. Their physical properties and crystallization behavior were investigated by differential scanning calorimetry, thermogravimetry, and polarimetry. The absolute value of specific optical rotation ([α]) for Ph‐PLLA (?38 deg dm^?1 g^?1 cm³) was much lower than that of [α] for PLLA (?150 deg dm^?1 g^?1 cm³), suggesting that the helical nature was reduced by incorporation of bulky phenyl group. PLLA was crystallizable during solvent evaporation, heating from room temperature, and cooling from the melt. Incorporation of a very low content of bulky phenyllactyl units even at 4 mol % suppressed the crystallization of L ‐lactyl unit sequences during heating and cooling, though the copolymers were crystallizable for L ‐phenylactyl units up to 6 mol % during solvent evaporation. The activation energy of thermal degradation (ΔE_td) for Ph‐PLLA (200 kJ mol^?1) was higher than that for PLLA (158 kJ mol^?1). The ΔE_td for the copolymers increased with an increase in L ‐phenyllactyl unit content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Combined experimental and ab initio based determination of the thermal expansion of La0.5Sr0.5Co0.25Fe0.75O3

The thermal expansion of La_0.5Sr_0.5Co_0.25Fe_0.75O₃ (LSCF55) is investigated both by first principles phonon calculations combined with the quasi‐harmonic approximation (QHA) and by experimental approaches. Within the framework of the QHA, the volumetric thermal expansion coefficient of rhombohedral LSCF55 is calculated as α_V,GGA = 50.34 × 10^?6 K^?1. For comparison, the lattice expansion and the volume expansion of LSCF55 grain are measured by in situ high‐temperature X‐ray diffractometer (HT‐XRD). An anisotropic thermal expansion of rhombohedral LSCF55 with α_a,hex = 10.89 × 10^?6 K^?1 and α_c,hex = 21.18 × 10^?6 K^?1 is obtained. The volumetric thermal expansion coefficient is measured as α_V,HT‐XRD = 43.17 × 10^?6 K^?1. In addition, the effectively isotropic expansion coefficients of a polycrystalline LSCF55 bar specimen are measured using a vertical high‐performance thermo‐mechanical analyzer and yield α_{l,bar specimen} = 17.37 × 10^?6 K^?1 and α_{V,bar specimen} = 52.11 × 10^?6 K^?1.     

Near‐Zero Thermal Expansion in In(HfMg)0.5Mo3O12

In(HfMg)_0.5Mo₃O₁₂, which can be considered as a 1:1 mole ratio solid solution of the low‐positive thermal expansion material HfMgMo₃O₁₂ and the low‐negative thermal expansion (NTE) material In₂Mo₃O₁₂ was prepared. From DSC and XRPD results, we show that In(HfMg)_0.5Mo₃O₁₂ exists in a monoclinic (P2₁/a) structure at low temperature and undergoes a phase transition at ~425 K to an orthorhombic phase (Pnma), with an associated enthalpy change of 0.89 kJ mol^?1. Thermal expansion is large and positive in the low‐temperature monoclinic phase (average α_? = 16 × 10^?6 K^?1 and 20 × 10^?6 K^?1, from dilatometry and XRPD, respectively). Remarkably, this material has a near‐zero thermal expansion (ZTE) coefficient over the temperature range ~500 to ~900 K in the high‐temperature orthorhombic phase, both intrinsically and for the bulk sample. The average linear intrinsic (XRPD) value is α_? = ?0.4 × 10^?6 K^?1, and the average bulk (dilatometric) value is α_? = 0.4 × 10^?6 K^?1 with an uncertainty of ± 0.2 × 10^?6 K^?1. The slight difference between intrinsic and bulk thermal expansion is attributed to microstructural effects. XRPD results show that the thermal expansion is more isotropic than for the parent compounds HfMgMo₃O₁₂ and In₂Mo₃O₁₂.     

Ceric ion‐induced graft copolymerization of acrylamide on cationic guar gum at low temperature

The solution polymerization of acrylamide (AM) on cationic guar gum (CGG) under nitrogen atmosphere using ceric ammonium sulfate (CAS) as the initiator has been realized. The effects of monomer concentration and reaction temperature on grafting conversion, grafting ratio, and grafting efficiency (GE) have been studied. The optimal conditions such as 1.3 mol of AM monomer and 2.2 × 10^?4 mol of CAS have been adopted to produce grafted copolymer (CGG1‐g‐PAM) of high GE of more than 95% at 10°C. The rates of polymerization (R_p) and rates of graft copolymerization (R_g) are enhanced with increase in temperature (<35°C).The R_p is enhanced from 0.43 × 10^?4 mol L^?1 s^?1 for GG‐g‐PAM to 2.53 × 10^?4 mol L^?1 s^?1 for CGG1‐g‐PAM (CGG1, degree of substitute (DS) = 0.007), and R_g from 0.42 × 10^?4 to 2.00 × 10^?4 mol L^?1 s^?1 at 10°C. The apparent activation energy is decreased from 32.27 kJ mol^?1 for GG‐g‐PAM to 8.09 kJ mol^?1 for CGG1‐g‐PAM, which indicates CGG has higher reactivity than unmodified GG ranging from 10 to 50°C. Increase of DS of CGG will lead to slow improvement of the polymerization rates and a hypothetical mechanism is put forward. The grafted copolymer has been characterized by infrared spectroscopy, thermal analysis, and scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3715–3722, 2007     

On the thermodynamics of solid solutions of polymer and salt

Solid solutions of poly(ethylene oxide) of different molecular masses (M_η from 6 × 10⁵ to 4 × 10⁶ g mol^?1) and lithium perchlorate (LiClO₄) were prepared by solution casting method. Salt concentrations of solutions vary between around 2 and 13 wt%. Thermodynamic properties of these solutions are reported in the range of low salt content. The solutions represent two‐phase systems mostly not in equilibrium at room temperature. They consist of neat crystalline PEO and an amorphous mixture of salt and polymer. Crystallinity of PEO in salt solutions stays constant with increasing salt content and is independent of molecular mass. Crystallinities serve determining share and composition of the amorphous phase. Glass transition temperature increases linearly with salt content in the amorphous phase. Depression of equilibrium melting points by addition of salt provides activity coefficients in solutions and allows for estimation of degrees of dissociation. Rate of crystallization of poly(ethylene oxide) depends exponentially on inverse undercooling. In that way, it is also coined by equilibrium melting point depression. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Hyperbranched Poly(Glycidol)-Grafted Silica Nanoparticles for Enhancing Li-Ion Conductivity of Poly(Ethylene Oxide)

Silica nanoparticles bearing hyperbranched polyglycidol (hbP) grafts are synthesized and blended with poly(ethylene oxide) (PEO) for the fabrication of composite solid polymer electrolytes (SPEs) for enhancing Li-ion conductivity. Different batches of hbPs are prepared, namely, the 5th, 6th, and 7th with increasing molecular weights using cationic ring-opening polymerization and grafted the hbPs onto the silica nanoparticles using quaternization reaction. The effect of end functionalization of hbP-grafted silica nanoparticles with a nitrile functional group (CN–hbP–SiO₂) on the ionic conductivity of the blends with PEO is further studied. High dipole moments indicate polar nature of nitriles and show high dielectric constants. Among all the hbPs, the 6th-batch CN–hbP–SiO₂ nanoparticles exhibit better ionic conductivity on blending with PEO showing ionic conductivity of 2.3 × 10⁻³ S cm⁻¹ at 80 °C. The blends show electrochemical stability up to 4.5 V versus lithium metal.     

An activated neodymium‐based catalyst for styrene polymerization

Coordination polymerization of styrene with a ternary catalyst system composed of catalyst neodymium tricarboxylate (Nd), co‐catalyst Al(i‐Bu)₃ (Al) and chlorinating agent trichloroethane (Cl) was carried out in cyclohexane. The effects of the catalyst system preparation procedure and of the reaction conditions on catalytic activity, molecular weight and molecular weight distribution of the resultant polymers were investigated. The catalytic activity depended mainly on the molar ratios of Al/Nd and of Cl/Nd and on the ageing temperature and polymerization temperature. High polymerization conversion and high catalytic activity could be obtained at high Al/Nd ratios and/or at high ageing temperature. The catalyst system exhibited high activity of 8.32 × 10⁴ g polystyrene (mol Nd h)^?1 at 50 °C. The molecular weight of the polymers obtained reached high weight‐average (M_w) values (M_w = 4.35 × 10⁵ g mol^?1) when Al/Nd = 8, but relatively low values (6000–11 000 g mol^?1) at high Al/Nd ratios. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of polyaniline/NiO nanocomposite

Spherical nickel oxide (NiO) nanoparticles were prepared by using nickel chloride as precursor in the ethylene glycol as solvent and urea as precipitant. The X‐ray diffraction study showed that NiO has single‐phase cubic structure with average crystallite size of 35 nm. The prepared NiO nanoparticles were incorporated into polyaniline (PANI) matrix during in situ chemical oxidative polymerization of aniline with different molar ratios of aniline: NiO (12 : 1, 6 : 1, and 3 : 1) at 5°C using (NH₄)₂S₂O₈ as oxidant in aqueous solution of sodium dodecylbenzene sulfonic acid, as surfactant and dopant under N₂ atmosphere. The synthesized composites have been characterized by means of X‐ray diffraction (XRD), thermogravimetric analysis, Fourier transform infrared (FTIR), scanning electron microscopy, TEM, and vibrating sample magnetometer for its structural, thermal, morphological, and magnetic investigation. The XRD and FTIR studies show that the NiO particles are in the composite. The room temperature conductivities of the synthesized PANI, PANI/NiO (12 : 1), (6 : 1), and (3 : 1) composites were found to be 3.26 × 10^?4, 1.88 × 10^?4, 1.5 × 10^?4, and 4.61 × 10^?4 S/cm, respectively. The coercivity (H_c) and remnant magnetization (M_r) of NiO, PANI/NiO NCs (12 : 1), (6 : 1), and (3 : 1) at 5 K was found to be 8.22 × 10^?2, 6.31 × 10^?2, 6.42 × 10^?2, 6.27 × 10^?2 T, and 6.64 × 10^?3, 1.83 × 10^?4, 3.07 × 10^?4, and 3.98 × 10^?4 emu/g, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of novel poly(arylene ether)s based on 9,10‐bis‐(4‐fluoro‐3‐trifluoromethylphenyl) anthracene and 2,7‐bis‐(4‐fluoro‐3‐trifluoromethylphenyl) fluorene

Two new bisfluoro monomers 9,10‐bis‐(4‐fluoro‐3‐trifluoromethylphenyl) anthracene and 2,7‐bis‐(4‐fluoro‐3‐trifluoromethylphenyl) fluorene have been synthesized by the cross‐coupling reaction of 2‐fluoro‐3‐trifluoromethyl phenyl boronic acid with 9,10‐dibromo anthracene and 2,7‐dibromo fluorine, respectively. These two bisfluoro compounds were used to prepare several poly(arylene ether)s by aromatic nucleophilic displacement of fluorine with various bisphenols; such as bisphenol‐A, bisphenol‐6F, bishydroxy biphenyl, and 9,9‐bis‐(4‐hydroxyphenyl)‐fluorene. The products obtained by displacement of the fluorine atoms exhibits weight‐average molar masses up to 1.5 ×10⁵ g mol^?1 and number average molecular weight up to 6.8 × 10⁴ g mol^?1 in GPC. These poly(arylene ether)s show very high thermal stability even up to 490°C for 5% weight loss occurring at this temperature in TGA in synthetic air and showed glass transition temperature observed up to 310°C. All the polymers are soluble in a wide range of organic solvents, e.g., CHCl₃, THF, NMP, and DMF. Films cast from DMF solution are brittle in nature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Ionic conductivity of unsaturated polyester resin networks containing LiCIO4

Poly(ethylene oxide) (PEO) 400-maleate-isophthalate resins have been prepared and LiCIO₄ dissolved in the resins before crosslinking with 30% of styrene, vinylpyrrolidone or vinylpyridine. The DC conductivities of the resins were measured and found to increase in the order vinylpyridine 〈vinylpyrrolidone〉 styrene for the same [EO]/[Li⁺] ratio ( = 50). For the styrene system σ = 3 × 10^?6Scm^?1 at ambient temperatures and for the vinylpyridine system σ = 1 × 10^?7 Scm^?1. The T_gs of the system were also measured using dynamic mechanical thermal analysis and were found to be very close (257-260 K). The above sequence was therefore attributed to stronger site-binding of lithium ions at the more polar comonomers. An interpenetrating network (IPN) consisting of the styrene-polyester and incorporating 40% PEO 400 was also prepared with[EO]/[Li⁺]ratios of 20 and 50. These gave ambient temperature conductivities of 1 × 10^?5 and 3 × 10^?5 Scm^?1, respectively.     

Improvement of the magnesium battery electrolyte properties through gamma irradiation of nano polymer electrolytes doped with magnesium oxide nanoparticles

Nanocomposite polymer electrolytes (NCPE) were prepared using nano polyethylene oxide PEO doped with Magnesium (Mg) salts. Gamma irradiation was utilized to improve the PEO‐Mg salts particle sizes. Consequently, Magnesium Oxide (MgO) nanoparticles were prepared by green synthesis and incorporated into PEO‐Mg salts to improve their properties toward magnesium battery electrolyte applications. The prepared samples were examined before and after exposures to the radiation doses. Dynamic light scattering (DLS) indicated the particles size of the synthesized nano polymer‐Mg salts and MgO nanoparticles. Fourier transform infra‐red (FTIR) spectroscopic measurements, transmission electron microscopy (TEM), electrical conductivity, electrochemical properties, and thermal stability of the samples were determined. FTIR indicated the interaction between PEO with Mg salts and MgO nanoparticles which confirmed the structure. The TEM results showed a spherical nanoparticles of MgO and a good dispersion of MgO in PEO matrix. It was found that the irradiation dose 70 kGy gave the best results for the nano polymer‐Mg salts (13 nm). The electrical conductivity (σ) evaluated for NCPE, was more than three orders of magnitude of pure PEO. The liquid NCPE of 20 mL MgO NPs at 100 kGy exhibited a maximum conductivity of 3.63 × 10^–3 Scm^?1 at room temperature. The increase in temperature caused a slight effect on conductivity, 4.85 × 10^–3 Scm^?1 at temperature 250°C, at the same concentration. While un‐irradiated sample of 30 mL MgO NPs (σ) reached to 3.8 × 10^?3 Scm^?1 then became 5.03 × 10^?3 Scm^?1 by increasing temperature. From the cyclic voltammetry results, the polymer electrolytes containing MgO filler, 20 and 30 mL, for irradiated and un‐irradiated samples, respectively exhibited wider electrochemical stability window than the others due to the appearance of Mg deposition/desolution peak in CV curve showed that magnesium effectively migrating through electrolytes. Thermogravimetric analysis (TGA) was enhanced by adding Mg salts electrolyte and also MgO nanoparticles to PEO. J. VINYL ADDIT. TECHNOL., 25:243–254, 2019. © 2018 Society of Plastics Engineers     

The investigation of novel non‐metallocene catalysts with phenoxy‐imine ligands for ethylene (co‐)polymerization

Phthaldialdehyde and phthaldiketone were treated with substituted phenols of 2‐amino‐4‐methylphenol, 2‐amino‐5‐methylphenol and 2‐amino‐4‐t‐butylphenol, respectively, and then treated with transition metal halides of TiCl₄, ZrCl₄ and YCl₃. A series of novel non‐metallocene catalysts (1–12) with phenoxy‐imine ligands was obtained. The structures and properties of the catalysts were characterized by ¹H NMR and elemental analysis. The catalysts (1–12) were used to promote ethylene (co‐)polymerization after activation by methylaluminoxane. The effects of the structures and center atoms (Ti, Zr and Y) of these catalysts, polymerization temperature, Al/M (M = Ti, Zr and Y) molar ratio, concentration of the catalysts and solvents on the polymerization performance were investigated. The results showed that the catalysts were favorable for ethylene homopolymerization and copolymerization of ethylene with 1‐hexene. Catalyst 10 is most favorable for catalyzing ethylene homopolymerization and copolymerization of ethylene with 1‐hexene, with catalytic activity up to 2.93 × 10⁶ gPE (mol Y)^?1 h^?1 for polyethylene (PE) and 2.96 × 10⁶ gPE (mol Y)^?1 h^?1 for copolymerization of ethylene with 1‐hexene under the following conditions: polymerization temperature 50 °C, Al/Y molar ratio 300, concentration of catalyst 1.0 × 10^?4 L^?1 and toluene as solvent. The structures and properties of the polymers obtained were characterized by Fourier transform infrared spectroscopy, ¹³C NMR, wide‐angle X‐ray diffraction, gel permeation chromatography and DSC. The results indicated that the obtained PE catalyzed by 4 had the highest melting point of 134.8 °C and the highest weight‐average molecular weight of 7.48 × 10⁵ g mol^?1. The copolymer catalyzed by 4 had the highest incorporation of 1‐hexene, up to 5.26 mol%, into the copolymer chain. © 2012 Society of Chemical Industry     

Vinyl‐type homo‐ and copolymerization of norbornene catalyzed by bis(phenoxyimine) titanium complex

A ternary catalytic system consisting of a bis(phenoxyimine) titanium complex, triisobutylaluminium and an organoboron compound exhibited high activity in the vinyl‐type homopolymerization of norbornene. The obtained polynorbornene showed a modest molecular weight (M _n ≈ 5 × 10⁴ g mol^?1) and broad molecular weight distribution (polydispersity index ≈ 3.5). A copolymer of norbornene with 1,3‐butadiene was prepared using a binary catalytic system consisting of bis(phenoxyimine) titanium complex and triisobutylaluminium. The norbornene units in the copolymer adopted a vinyl‐type addition structure confirmed using distortionless enhancement by polarization transfer 135 ¹³C NMR microstructure analyses. Polymerization kinetics studies showed that neither monomer feed ratio nor conversion had an effect on the composition of the copolymer backbone which was composed of 55% norbornene units and 45% 1,3‐butadiene units. The essentially constant polymer composition implied an alternating nature of chain propagation. The copolymer exhibited good thermal stability and moderate glass transition temperature (50.9–68.2 °C) with a relatively high molecular weight (M _w = 0.18 × 10–1.31 × 10⁵ g mol^?1), and excellent transparency (maximal transmittance >80%). © 2017 Society of Chemical Industry