Synthesis and Properties of Semicrystalline Poly(ether nitrile ketone) Copolymers.

As a high-performance engineering plastic, polyarylene ether nitrile (PEN) is widely used in many fields. The presence of cyano groups of PEN ensures its good adhesion to other substrates, but the inherent low crystallinity of PEN limits its application. In this work, the poly(aryl ether ketone) segment was introduced into PEN via copolymerization using both 2,6-Dichlorobenzonitrile and 4,4'-Difluorobenzophenone as the starting reagents to prepare poly (ether nitrile ketone) (BP-PENK). The effect of composition and thermal treatment on the crystallization behavior and properties of poly (ether nitrile ketone) were systematically studied. It was found that when the content of DFBP is 30%, the copolymer BP-PENK30 had the best mechanical properties, with a tensile strength of 109.9 MPa and an elongation at a break value of 45.2%. After thermal treatment at 280 °C for 3 h, BP-PENK30 had the highest crystallinity with a melting point of 306.71 °C, a melting enthalpy of 5.02 J/g, and crystallinity of 11.83%. Moreover, with the increase in crystallinity, the dielectric constant and energy density increased after thermal treatment. Therefore, the introduction of poly(aryl ether ketone) chain segments and thermal treatment can effectively improve the crystallization and the comprehensive properties of PEN.

Effect of Plasticizer and Shearing Field on the Properties of Poly(arylene ether nitrile) Composites.

A novel composite film of hydroquinone/resorcinol-based poly(arylene ether nitrile) (HQ/RS-PEN) improved by bisphenol A based poly(arylene ether nitrile) (BPA-PEN) was prepared, in which BPA-PEN acts as a plasticizer, leading to improved fluidity of the material, thereby favoring the crystallinity of HQ/RS-PEN. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and mechanical and rheological tests have shown that the composites exhibited outstanding thermal and mechanical properties as well as improved fluidity and processing applicability compared with HQ/RS-PEN. At the same time, the crystallization of the poly(arylene ether nitrile) blends with 5 wt % BPA-PEN could be promoted under both static and shear flow fields. Polarizing microscope (POM) and scanning electron microscopy (SEM) showed that the crystalline morphology of HQ/RS-PEN was converted from spherulites to fibrous crystals under shearing. DSC, X-ray diffraction (XRD), and dynamic storage modulus results proved that the crystallization rate and crystallinity of HQ/RS-PEN increased significantly under the shear field. The crystallinity enhanced to a maximum of 20.1% and the melting enthalpy increased to 33.4 J/g at 310 °C under the frequency of 0.01-100 Hz for 20 min.

An Immunosensor Based on Au-Ag Bimetallic NPs Patterned on a Thermal Resistant Flexible Polymer Substrate for In-Vitro Protein Detection.

Nanosensors based on flexible polymers have emerged as powerful tools for next generation smart devices in the recent years. Here, we report a facile protocol to fabricate an immunosensor supported by a thermally resistant flexible polymer substrate (polyarylene ether nitrile, PEN). The immunosensor is a localized surface plasmon resonance (LSPR) optical sensor for in-vitro protein detection based on anti-body coated gold-silver bimetallic nanoparticles (Au-Ag NPs) immobilized on a PEN substrate. Plasmonic spectroscopy and morphological characterization show that the Au-Ag NPs essentially exhibit a more uniform size distribution and higher quality factors than those from single-component Au NPs. Furthermore, it should be noted that the robust PEN substrate in this nanosensor acts a flexible substrate to support Au-Ag NPs and immobilize the nanoparticles via quick thermal annealing at 290 °C. Thanks to these merits, a prostate-specific antigen (PSA) concentration as low as 1 ng/mL can be specifically discriminated via the prepared PEN/Au-Au NPs, which confirms that the protocol reported in this work can be readily adapted for the construction of various flexible immunosensors for different applications.

Self-Toughening and Self-Enhancement Poly(arylene ether nitrile) with Low Dielectric Constant by Solid Crosslinking Reaction.

A novel poly(arylene ether nitrile) terminated with hydroxyl groups (PEN-OH) was synthesized successfully. The effects of heat-treatment temperature on the thermal properties, mechanical properties, and dielectric properties of the PEN-OH films were studied in detail. Due to the cross-linking reaction occurring, at high temperature, among the nitrile groups on the side of the PEN-OH main chain to form a structurally stable triazine ring, the structure of materials changes from a linear structure to a bulk structure. Thus, the thermal properties and mechanical properties were improved. In addition, the occurrence of cross-linking reactions can reduce the polar groups in the material, leading to the decrease of dielectric constant. As the heat-treatment temperature increased, the glass-transition temperature increased from 180.6 °C to 203.6 °C, and the dielectric constant decreased from 3.4 to 2.8 at 1 MHz. Proper temperature heat-treatment could improve the tensile strength, as well as the elongation, at the break of the PEN-OH films. Moreover, because of the excellent adhesive property of PEN-OH to copper foil, a double-layer flexible copper clad laminate (FCCL) without any adhesives based on PEN-OH was prepared by a simple hot-press method, which possessed high peel strength with 1.01 N/mm. Therefore, the PEN-OH has potential applications in the electronic field.

Achieving Secondary Dispersion of Modified Nanoparticles by Hot-Stretching to Enhance Dielectric and Mechanical Properties of Polyarylene Ether Nitrile Composites.

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.

Polyethylenimine Assisted Bio-Inspired Surface Functionalization of Hexagonal Boron Nitride for Enhancing the Crystallization and the Properties of Poly(Arylene Ether Nitrile).

Semi-crystalline poly(arylene ether nitrile) (PEN) has exhibited remarkable potential in various fields. However, the inherent drawbacks of PEN such as slow crystalline rate and low crystallinity limit its further development. To alleviate this problem, the choice of nanofiller as nucleation agent and the interfacial compatibility between nanofiller and PEN matrix are two momentous factors that need to be considered. Accordingly, in this work, functionalized hexagonal boron nitride (h-BN@(PDA+PEI)) was successfully synthesized via polyethylenimine (PEI) assisted bio-inspired surface functionalization, and then homogeneously dispersed in the PEN resin using solution casting method to obtain functional polymer nanocomposite films with strengthening the crystallization behavior, mechanical and dielectric properties. Various testing methods including differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X-ray diffraction (XRD), and polarizing microscope (POM) were applied to intricately analyze the effect of h-BN@(PDA+PEI) on the crystallization behavior of PEN composites. The testing results certificated that the h-BN@(PDA+PEI) can effectively improve the crystallinity (from 6.56% to 14.90%), and the spherulite size of PEN was reduced while the nucleation density of nanocomposites was raised. Furthermore, the non-isothermal crystallization kinetics demonstrated that 2 wt% h-BN@(PDA+PEI) could significantly reduce the cold crystallization temperature (Tp) and the crystallization activation energy (Ea) (from 359.7 KJ/mol to 292.8 KJ/mol), while it improved the crystallization rate (Kc) of PEN. In addition, the mechanical and dielectric properties of nanocomposite films were also reinforced to further broaden the application of semi-crystalline PEN. Therefore, the h-BN@(PDA+PEI) can function as an effectual nucleating agent and enhance the performance of PEN.

Post Self-Crosslinking of Phthalonitrile-Terminated Polyarylene Ether Nitrile Crystals.

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.

Interface Modulation of Core-Shell Structured BaTiO3@polyaniline for Novel Dielectric Materials from Its Nanocomposite with Polyarylene Ether Nitrile.

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.

Crosslinked polyarylene ether nitrile film as flexible dielectric materials with ultrahigh thermal stability.

Dielectric film with ultrahigh thermal stability based on crosslinked polyarylene ether nitrile is prepared and characterized. The film is obtained by solution-casting of polyarylene ether nitrile terminated phthalonitrile (PEN-Ph) combined with post self-crosslinking at high temperature. The film shows a 5% decomposition temperature over 520 °C and a glass transition temperature (Tg) around 386 °C. Stable dielectric constant and low dielectric loss are observed for this film in the frequency range of 100-200 kHz and in the temperature range of 25-300 °C. The temperature coefficient of dielectric constant is less than 0.001 °C-1 even at 400 °C. By cycling heating and cooling up to ten times or heating at 300 °C for 12 h, the film shows good reversibility and robustness of the dielectric properties. This crosslinked PEN film will be a potential candidate as high performance film capacitor electronic devices materials used at high temperature.