The core-shell structured polyaniline-functionalized-BaTiO₃ (BT@PANI) nanoparticles with controllable shell layer thicknesses are developed via in-situ aniline polymerization technology and characterized in detail. The results prove that the PANI shell layer with the adjustable and controllable thicknesses of 3–10 nm are completely stabilized on the surface of the BaTiO₃ core. In addition, the BT@PANI nanoparticles are regarded as the hybrid nanofillers to prepare PEN/BT@PANI nanocomposite films with a PEN matrix. The research results indicate that the surface functionalized nanoparticles facilitate the compatibility and dispersibility of them in the PEN matrix, which improves the properties of the PEN/BT@PANI nanocomposites. Specifically, the PEN/BT@PANI nanocomposites exhibit thermal stability, excellent permittivity-frequency, and dielectric properties-temperature stability. Most importantly, the energy density of nanocomposites is maintained at over 70% at 180 °C compared with that at 25 °C. All these results reveal that a new way to prepare the high-performance PEN-based nanocomposites is established to fabricate an energy storage component in a high temperature environment.

Barium titanate (BT) and polyarylene ether nitrile (PEN) nanocomposites with enhanced dielectric properties were obtained by using carboxylatedzinc phthalocyanine (ZnPc-COOH) buffer as the plasticizer. Carboxylated zinc phthalocyanine, prepared through hydrolyzing ZnPc in NaOH solution, reacted with the hydroxyl groups on the peripheral of hydrogen peroxide treated BT (BT-OH) yielding core-shell structured BT@ZnPc. Thermogravimetric analysis (TGA), transmission electron microscopy (TEM), TEM energy dispersive spectrometer mapping, scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) demonstrated successful preparation of BT@ZnPc. The fabricated BT@ZnPc was incorporated into the PEN matrix through the solution casting method. Rheological measurements demonstrated that the ZnPc-COOH buffer can improve the compatibility between BT and PEN effectively. With the existence of the ZnPc-COOH buffer, the prepared BT@ZnPc/PEN nanocomposites exhibit a high dielectric constant of 5.94 and low dielectric loss (0.016 at 1000 Hz). BT@ZnPc/PEN dielectric composite films can be easily prepared, presenting great application prospects in the field of organic film capacitors.

In this paper, barium titanate@zinc phthalocyanine (BT@ZnPc) and graphene oxide (GO) hybrids (BT@ZnPc-GO) connected by calcium ions are prepared by electrostatic adsorption, and then introduced into polyarylene ether nitrile (PEN) to obtain composites with enhanced dielectric and crystallization properties. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) results confirm the successful fabrication of the BT@ZnPc-GO. BT@ZnPc-GO and PEN composites (BT@ZnPc-GO/PENs) are obtained through the solution-casting method. BT@ZnPc-GO demonstrates well compatibility with PEN due to its unique structure and the organic layer of ZnPc at the periphery of BT. On the other hand, BT and GO contribute a high dielectric constant of the composites obtained. In addition, the BT@ZnPc-GO can be used as a nucleating agent to promote the crystallization of the nanocomposites. As a result, The BT@ZnPc-GO/PEN exhibits a dielectric constant of 6.4 at 1 kHz and crystallinity of 21.03% after being isothermally treated at 280 °C for 2 h at the GO content of 0.75 wt %. All these results indicate that the hybrid nanofiller BT@ZnPc-GO can be an effective additive for preparing high-performance PEN-based nanocomposites.

Enhanced dielectric and mechanical properties of polyarylene ether nitrile (PEN) are obtained through secondary dispersion of polyaniline functionalized barium titanate (PANI-f-BT) by hot-stretching. PANI-f-BT nanoparticles with different PANI content are successfully prepared via in-situ aniline polymerization technology. The transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopic instrument (XPS) and Thermogravimetric analysis (TGA) results confirm that the PANI layers uniformly enclose on the surface of BaTiO₃ nanoparticles. These nanoparticles are used as functional fillers to compound with PEN (PEN/PANI-f-BT) for studying its effect on the mechanical and dielectric performance of the obtained composites. In addition, the nanocomposites are uniaxial hot-stretched by 50% and 100% at 280 °C to obtain the oriented nanocomposite films. The results exhibit that the PANI-f-BT nanoparticles present good compatibility and dispersion in the PEN matrix, and the hot-stretching endows the second dispersion of PANI-f-BT in PEN resulting in enhanced mechanical properties, crystallinity and permittivity-temperature stability of the nanocomposites. The excellent performances of the nanocomposites indicate that a new approach for preparing high-temperature-resistant dielectric films is provided.

A novel phthalonitrile-terminated polyaryl ether nitrile (PEN-Ph) was synthesized and characterized. The crystallization behavior coexisting with the crosslinking behavior in the PEN-Ph system was confirmed by rheological measurements. DSC was applied to study the crystallization kinetics and crosslinking reaction kinetics. Through the Avrami equation modified by Jeziorny, the nonisothermal crystallization kinetics were analyzed, and the Avrami exponent of about 2.2 was obtained. The analysis results of more intuitive polaring optical microscopy (POM) and SEM indicated that the shape of the crystals is similar to spherical. Moreover, the activation energy of the crystallization behavior and crosslinking behavior were obtained by the Kissinger method, and the values were about 152.7 kJ·mol⁻¹ and 174.8 kJ·mol⁻¹, respectively. This suggests that the activation energy of the crystallization behavior is lower than that of the crosslinking behavior, indicating that the crystallization behavior is more likely to occur than the crosslinking behavior and the crystals of PEN-Ph can be self-crosslinked to form single-polymer composites.

A series of polymers containing nunchaku-like unit with an azo chromophore and a mesogen group was successfully prepared and photoinduced anisotropy of the obtained polymers was minutely investigated. Firstly, monomers containing nunchaku-like unit with an azo chromophore and a mesogen group linked by flexible group were synthesized. The structure of the monomers was confirmed via NMR COSY spectra. Subsequently, the obtained monomers were polymerized into corresponding polymers through RAFT polymerization. The prepared polymer samples were characterized through NMR, FTIR, gel permeation chromatography (GPC), and UV-vis testing while the thermal properties of the samples were investigated through differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) measurements. The photoinduced isomerization of the polymers, which was researched in situ via measuring UV-vis spectra of the polymer solutions and spin-coated films under irradiation with 450 nm light or putting in darkness, demonstrated the rapid trans-cis-trans isomerization of the polymers. When irradiated with a linearly polarized light, significant photoinduced birefringence and dichroism were observed, suggesting photoinduced isomerization of azobenzene can drive orientation of mesogen in the system. This study blazes a way to design the optical materials with light-controllable birefringence and dichroism.