Arylene Ether Nitrile Research Articles

Synthesis and performance of cross-linked poly(aryl ether nitrile) anion exchange membranes with dense cations and flexible side-chain structures for water electrolysis

Anion exchange membranes (AEMs) are the core components in anion exchange membrane water electrolysis (AEMWE), which play crucial role and affect the performance of AEMWE. In this work, a series of cross-linked poly(aryl ether nitrile) anion exchange membranes (CPAEN-dDQA-x) with dense cations and flexible side-chain structures are synthesized. By introducing multiple modification elements into the polymer structure simultaneously, the ion conductivity, dimensional stability, and alkali resistance stability of the prepared AEMs are effectively improved and balanced. The representative CPAEN-dDQA-0.25 showed water absorption of only 27.6 %, swelling rate of 11.2 %, and conductivity of 115.37 mS/cm at 80°C. The IEC and conductivity retention value of CPAEN-dDQA-0.25 after in 2 M NaOH solution at 80°C for 480 h were up to 86.2 % and 82 %, respectively. Meanwhile, the current density of the water electrolysis cell based on CPAEN-dDQA-0.25 is up to 477.0 mA/cm2 in 1 M KOH and 2.2 V, and its voltage don’t has significant change after 480 h of operation at a constant current density of 500 mA/cm2.

Self-Healing, Recyclable, and Solvent Resistant Poly(aryl ether nitrile) Triple Shape Memory Thermosets Cross-Linked with Dynamic Boroxines

Self-Healing, Recyclable, and Solvent Resistant Poly(aryl ether nitrile) Triple Shape Memory Thermosets Cross-Linked with Dynamic Boroxines

Construction of Cross-Linked Poly(aryl Ether Nitrile) Anion Exchange Membranes Containing Bilateral Linked Branches for Water Electrolyzer

Construction of Cross-Linked Poly(aryl Ether Nitrile) Anion Exchange Membranes Containing Bilateral Linked Branches for Water Electrolyzer

Strong and tough semi-crystalline poly(aryl ether nitrile) with low coefficient of thermal expansion

The crystallization of poly (aryl ether nitrile) (PEN) has an essential impact on improving heat resistance, mechanical properties, chemical resistance, and dielectric properties. However, during the synthesis process, high crystallinity PEN is prone to precipitate out, which makes it difficult to carry out the synthesis reaction, which poses a significant challenge to synthesizing high crystallinity and high molecular weight PEN. In this work, hydroquinone (HQ) as the main phenolic monomer and 4,4′-biphenol (BP) as the second phenolic monomer were used to solve the technical difficulties in synthesis by copolymerization. The crystalline PEN with high molecular weight and significant crystallinity was obtained by regulating the molar ratio of BP to HQ. The effects of isothermal heat treatment on its crystalline, mechanical, and thermal properties were investigated. The influence laws of molecular chain structure and heat treatment process on the properties of PEN films were revealed. Among them, when the isothermal treatment temperature was 270 °C and the HQ: BP was 85:15, the mechanical strength reached 130 MPa, and the elongation at break could be up to an astonishing 50 %. Besides, the CTE value from 50 °C–150 °C is 40.84 ppm/°C, which is lower than most thermoplastics. Therefore, PEN with the HQ to BP molar ratio of 85:15 is suitable for large-scale production, providing new crystalline plastic specifications for high-performance special engineering plastics. A crystal bridge-tie chain model is summarized by the properties of HQ/BP-PEN films under different crystallization conditions, which provides an idea for preparing stiff and tough films.

Aromatic phase change microspheres constructed nanocomposite films for fluorine-free self-cleaning, absorption-dominated EMI shielding, and high-temperature thermal camouflage

The combination of high shielding effectiveness and excellent thermal insulation is highly attractive for electromagnetic interference (EMI) shielding materials, yet remains challenging in the absence of thermal stability and self-cleaning effect. Here, poly(arylene ether nitrile) (PEN), an aromatic super engineering polymer, is synthesized and one-step self-assembled into phase-changeable microspheres in an oil-in-water microemulsion system, synchronously settling thermal lability and leakproof of conventional phase change materials. Pre-functionalized multi-wall carbon nanotubes are subsequently immobilized on PEN-based phase change microspheres for EMI shielding and thermal camouflage compartments. The resultant compartments are integrated into macroscopical nanocomposite films with segregated structures via hot-compressing densification. Due to the 3D interconnected cavities, the shielding effectiveness of the PEN-based nanocomposite film is strikingly up to 43 dB with an excellent absorption coefficient of 0.99. Meanwhile, the nanocomposite film exhibits outstanding thermal camouflage throughout a wide temperature range of 80–200 °C at a low thickness of ∼1.5 mm. Interestingly, superb fluorine-free self-cleaning is endowed with its inherent hydrophobic surface (contact angle up to 148.6°) overlaid with micropapillaes. Our work sheds light on such application integration of fluorine-free self-cleaning, absorption-dominated EMI shielding, and high-temperature thermal camouflage.

Enhancing energy storage density of poly(arylene ether nitrile) via incorporating modified barium titanate nanorods and hot-stretching

Enhancing energy storage density of poly(arylene ether nitrile) via incorporating modified barium titanate nanorods and hot-stretching

Interlaminar reinforced carbon fiber/epoxy composites by electrospun ultrafine hybrid fibers

The demand for high-strength composites in the aerospace industry is increasing; however, their low-impact resistance poses a danger to aircraft. Consequently, significant attention has been devoted to researching the interlaminar toughening of carbon fiber-epoxy composite laminates, focusing on electrospun fibers due to their high porosity and specific surface area. Our previous work explored the potential of poly(aryl ether nitrile) as an interlaminar toughening option. Nonetheless, these materials exhibited a decline in flexural properties. To address this concern, we developed poly(arylene ether nitrile)-poly(ε-caprolactone) ultrafine hybrid fiber membranes via electrospinning to enhance the interlaminar performance of composite laminates. The interlaminar fracture toughness demonstrated a remarkable improvement of 132.5 %. Additionally, the flexural strength in-creased by at least 12.3 %, while the flexural modulus experienced a minimum in-crease of 17.9 %. The interlaminar shear strength improved by approximately 27%–28 %, and the impact strength increased by 99.2 %. This study demonstrates the significant potential of electrospun hybrid fiber membranes in improving the interlaminar properties of carbon fiber-epoxy composite laminates, con-tributing to developing safer and more durable materials for the aerospace industry.

An investigation on the mechanical and corrosion protection properties of poly(arylene ether nitrile) reinforced epoxy coating

To follow the current industrial demand, epoxy coatings which feature extraordinary comprehensive properties have been considered as a versatile and promising thermosetting resin for application in various middle and high-end sectors of multitudinous industries. Regrettably, epoxy coatings possess the inherent shortcoming of poor durability to external force and deformation, severely restricting further introjection in various fields. Herein, this study employs poly(arylene ether nitrile) with bisphenol A structure (PENBA) as superior intensifying agent to ameliorate the toughness and corrosion resistance of brittle epoxy coatings. As a linear thermoplastic polymer with satisfying mechanical performances, PENBA serves as epoxy's energy-dissipating medium and forms a semi-interpenetrating polymer network (SIPN) with epoxy matrix, efficiently impeding epoxy's fracture and crack propagation. As a result, the tensile strength, elongation at break, impact strength, and flexural strength of PENBA-modified epoxy possess considerable increments of 214 %, 360 %, 148 %, and 295 % in sequence by contrast with the pristine epoxy. Meanwhile, according to the potentiodynamic polarization analysis, the PENBA with outstanding chemical resistance also significantly promoted the epoxy's corrosion resistance, endowing the epoxy coating with the most positive Ecorr and icorr of −0.453 V and 9.439 × 10−10 A/cm2 when PENBA reached 15 % (mass percent) at the end of entire soaking process.

Enhanced thermal conductivity of BN/PEK‐CN composites by bionic polydopamine modified BN

AbstractThe rapid advancement of energy, electronic, and microelectronic technology has resulted in a surge of interest in the study of functional composites. One of the current hotspots in this field is the exploitation of polymer composites with excellent thermal conductivity and great thermal stability. Based upon the composition of the adhesion proteins of shellfish, dopamine chemistry was applied to the non‐chemical surface modification of chemically inert fillers by generating polydopamine (PDA) films on their surfaces. In this paper, we utilized poly(aryl ether nitrile ketone) (PEK‐CN) resin as matrix and DA modified boron nitride (BN) as filler to prepare BN@PDA/PEK‐CN composites by hot‐pressing method. The thermal conductivity and thermal stability of the composites for a given BN loading can be enhanced by surface functionalization of BN. The composites based on 30%BN@PDA/PEK‐CN exhibited a through‐plane thermal conductivity (λ⊥) of 0.941 Wm−1 K−1, upward 275% from a pure resin matrix and higher than that of the untreated 30 wt% BN/PEK‐CN composites (0.713 Wm−1 K−1). The Heat resistance index (THRI) of 30% BN@PDA/PEK‐CN was subsequently raised to 329.8°C. Overall, our developed BN@PDA/PEK‐CN composites exhibit favorable thermal conductivity along with remarkable thermal stability, making them highly promising for utilization in electronic packaging applications.Highlights BN@PDA/PEK‐CN were prepared via a DA self‐polymerization bionic mussel strategy. Thermal conductivity (λ⊥) increased to 0.941 Wm−1 K−1 for 30% BN@PDA/PEK‐CN. The THRI increased to 329.8°C, with an increase of 61.1°C.

Synthesis, characterization, and thermal pyrolysis mechanism of high temperature resistant phenolphthalein-based poly (arylene ether nitrile)

Phenolphthalein (PP) is usually used as a functional monomer to design novel high performance polymers with adjustable thermal, mechanical, and fluorescent properties. In this study, a soluble, amorphous, high temperature resistant PP-based poly (arylene ether nitrile) (PAEN) was synthesized and its corresponding thermal decomposition mechanism was reported via TGA/DTG, TGA/FTIR and TGA/MS analysis. PP-based PAEN showed a Tg of 250 °C a Tdmax of 503 °C and a char residue of 59.2 % at 800 °C, respectively. According to Kissinger and Flynn–Wall–Ozawa model, the activation energy of thermal pyrolysis was calculated as 225 ± 4 and 284 ± 17 kJ/mol respectively, higher than those of other poly arylene ethers. PP-based PAEN showed a three-stage thermal pyrolysis mechanism. Its initial degradation happened before 400 °C and liberated the inherent moisture. The latter backbone decomposition between 400 and 600 °C involved multiple routes mainly from the CO and CC cleavages of lactone ring, resulting in a Ph2CHPhOPh intermediate by releasing HCHO, HCOOH, CO2, H2O, CH4, C6H6, and C6H5OH. The third carbonization stage over 600 °C included the transformation from biphenyl linkages to aromatic graphite by dehydrogenation. This study not only gives a comprehensive understanding of the thermal pyrolysis behavior of PP-based PAEN, but also provides valuable references for the thermal behaviors of other PP-containing polymers.

Synthesis and performance of poly(aryl ether nitrile) anion exchange membranes containing highly dense quaternary ammonium cationic side chains for water electrolysis

Anion exchange membranes (AEMs) are the core components of water electrolysis and suffer from the critical obstacles such as low ionic conductivity and poor alkali resistance stability in practical applications. In this work, a series of AEMs based on poly(arylene ether nitrile)s with high-density quaternary ammonium cationic side chains (PAEN-DQA-x) are synthesized to optimize the conductivity and alkali resistance stability. Their surface morphology and microstructure are characterized by scanning electron microscopy and atomic force microscopy, respectively. The obtained AEMs exhibit good conductivity and the values are in the range of 76.13–119.72 mS/cm at 80 °C. The conductivity retention for the representative PAEN-DQA-0.35 membrane is up to 73% after immersion in 2 M NaOH at 80 °C for 480 h. The current density of the water electrolyzer by PAEN-DQA-0.35 reaches 521.3 mA/cm2 at 2.0 V, and it also remains good stable at a current density of 500 mA/cm2 in a 0.1 M KOH environment.

Biomimetic metal-phenolic network with cyclolactam hydrogel coating on PPENK implant facilitate bone repair

Bone defects are often accompanied by infection, which causes great physical pain to patients. Metal-phenolic networks (MPNs) are a newly organic–inorganic hybrid networks system, which has become a multifunctional surface modifier based on the universal adhesion properties of phenolic molecules. Hence, we fabricate a MPN hydrogel coating based on cyclolactam network by spin-coating a mixture of gelatin, iron ions, and polyphenol monomer containing phthalazinone structure (THPZB) on the surface of poly(aryl ether nitrile ketone) (PPENK) (G/THPZB/Fe/PPENK). The method can easily obtain a high strength and versatile surface hydrogel coating based on the combination of the entangled structure on phthalazinone and the characteristic functions of MPNs. The residual polyphenol on the surface not only confer good adhesion ability, but also can cooperate with lactam ring to confer outstanding antibacterial ability to the PPENK implant. Importantly, the antibacterial mechanism of this modified PPENK implant might be consistent with that of penicillin. Besides, it has excellent ability to promote angiogenesis and healing in vitro. Notably, significant effects on biomineralization and osteogenesis in vitro and in vivo are observed. We hypothesis that cyclolactam-based MPN multifunctional hydrogel coating can provide great application prospects for PPENK bone implant materials in the field of bone defect repair.

Covalently cross-linked CaCu3Ti4O12 and poly(arylene ether nitrile) hybrids with enhanced high temperature energy storage properties

Ensuring polymer dielectrics with stable high energy storage density at high temperatures via improving interfacial compatibility remains a challenge. Based on this principle, calcium copper titanate and poly(arylene ether nitrile) (CCTO-PEN) hybrids dielectrics are developed to exhibit improved high temperature energy storage properties through the interfacial cross-linked high-temperature resistant cyano. Herein, CCTO-PEN hybrid dielectrics are fabricated through the thermal induced self-crosslinking reaction of phthalonitrile between the phthalonitrile modified CCTO (CCTO-CN) and phthalonitrile end-capped PEN (PEN-CN). SEM, XPS, FTIR, mechanical, dielectric, and breakdown tests of the CCTO-PEN hybrids reveal that the phthalonitrile modified CCTO-CN possessed superior interfacial compatibility in PEN dielectrics, together with enhanced dielectric, breakdown, mechanical, and energy storage properties compared to CCTO directly doped PEN dielectrics. Benefitting from the improved interfacial compatibility and the appropriate distribution of CCTO-CN within PEN-CN matrix, the CCTO-PEN hybrids demonstrate stable dielectric properties from room temperature to 200 °C, and the energy storage density of CCTO-PEN hybrid reaches up to 0.785 J/cm3, suggesting that the CCTO-PEN hybrids can be utilized as high temperature dielectric materials.

Enhancing high-temperature energy storage performance of poly(arylene ether nitrile) hybrids synergistically via phthalonitrile modified boron nitride and carbon nanotube

Enhancing high-temperature energy storage performance of poly(arylene ether nitrile) hybrids synergistically via phthalonitrile modified boron nitride and carbon nanotube

Effect of thermal processing conditions on the structure and properties of porous PENK/PVDF composite films and its application as lithium-ions separators

By developing high-performance lithium-ion battery technology, the demands on the design of separator modification have increased. However, battery performance and safety are limited by conventional polyolefin separators' poor thermal resistance and electrolyte wettability. Biphenyl-type poly (arylene ether nitrile ketone) (BP-PENK) is synthesized. PENK polymers are a class of poly (aryl ether) with excellent properties of both Poly (aryl ether nitrile) (PEN) and Poly (ether ketone) (PEEK). The BP-PENK/PVDF composite film is further processed by non-solvent induced phase separation (NIPS), and the impact of annealing temperatures on the thermal resistance and crystalline phase structure of composite separators has been studied. The composite separator owns enhanced ionic conductivity, excellent electrolyte wettability, and superior thermal durability. The cell equipped with the composite separator has a discharge-specific capacity of 146.5 mAh·g−1 and a capacity retention rate of 86.64 %. In this way, A novel approach to producing lithium-ion battery separators that possess outstanding electrochemical properties and high thermal durability is provided.

Poly(arylene ether nitrile) composites modulated via core@double-shell structured barium titanate for high-temperature dielectric applications

Organic film capacitors for modern electronic devices and electrical systems are greatly reliant on polymer-based composites with superior breakdown strength, preeminent dielectric properties, and remarkable permittivity-temperature stability. Herein, the barium titanate@polydopamine@carboxyl-functionalized poly(arylene ether nitrile) (BTOH@PDA@CPEN) with core@double-shell structure was successfully achieved through in-situ polymerization assisted with strong electrostatic interaction. The results of structural characterization demonstrated that the PDA and CPEN shells were completely wrapped on the surface of BTOH core to form core@double-shell structure. Furthermore, the dielectric composite films were prepared by using BTOH@PDA@CPEN as the filler and poly(arylene ether nitrile) (PEN) as the matrix. The synergistic effects of improved interfacial compatibility, multi-interfacial polarization induced by PDA, and insulating barrier of CPEN enhance dielectric constant and synchronously suppress dielectric loss of PEN-based composite films. The as-gained composite film with 20 wt% BTOH@PDA@CPEN loading reveals an preeminent dielectric properties with a constant of 12.258 @ 1 kHz and a loss of 0.023 @ 1 kHz, while the PEN matrix is just 3.750 @ 1 kHz and 0.015 @ 1 kHz, respectively. The dielectric constant-temperature coefficients of composite films are lower than 2 × 10−3 oC−1 at 30–170 °C, indicating excellent permittivity-temperature stability. The maximal values of breakdown strength and energy density of the composite films achieve to 253.8 kV mm−1 and 1.537 J cm−3, respectively, higher than that of PEN, presenting enhanced energy storage capacity. Furthermore, the composite films also manifest surpassing flexibility and outstanding thermal stability. This work demonstrates the potential value of using core@double-shell structure fillers for the construction of polymer dielectrics to accommodate extreme harsh environment.

Preparation and properties of high-temperature resistant bisphthalonitrile resins containing trifluoromethyl groups reinforced by poly (aryl ether nitrile) capped by phthalonitrile and their composites

A new series of high-temperature resistant bisphthalonitrile resins containing trifluoromethyl groups were prepared based on 4,4’-(hexafluoroisopropylidene) bisphthalonitrile (BFPh), which was toughened by hexafluoroisopropylidene-containing poly (aryl ether nitrile) oligomer capped by phthalonitrile (FPEN-Ph) in the different content. In addition, glass fiber reinforced composites were prepared by hot pressing process. The structure of the oligomer was characterized by FTIR and 1HNMR. The curing behavior of the blends was studied by DSC. Thermal stability and mechanical properties were also studied. The results showed that the introduction of appropriate content of FPEN-Ph could improve the reactivity of the curing reaction. TGA and DMA results showed that the cured polymers and composites had excellent thermal properties. The residual mass of FPEN-Ph content of 10% at 800°C was 72.4%, and the 5% thermal degradation temperature (T5%) under inert atmosphere was 530°C. The flexural strength of glass fiber reinforced composites was about 592.7 MPa, and the shear strength was about 61.6 MPa, showing excellent mechanical properties. The high-tech thermosetting resin was toughened and enhanced at the same time without reducing heat resistance.

Rational Design of Two-Step Functionalized Barium Titanate for Improving Dielectric Properties of poly(Arylene Ether Nitrile) Composites

Rational Design of Two-Step Functionalized Barium Titanate for Improving Dielectric Properties of poly(Arylene Ether Nitrile) Composites

Enhanced dielectric properties induced by the rational design of interfacial buffer layer in MoS2/poly(arylene ether nitrile) composites

Enhanced dielectric properties induced by the rational design of interfacial buffer layer in MoS2/poly(arylene ether nitrile) composites

Poly(arylene ether nitrile) composite foams with magnetically and electrically separated structures for frequency-selective electromagnetic interference shielding

With the rapid development of communication technology and modern intelligent electronic systems, the demand for frequency-selective electromagnetic interference (EMI) shielding materials has grown. In this work, poly(arylene ether nitrile) (PEN) composite foams with separated magnetic and conductive layers were prepared via delayed non-solvent induced phase separation, where the distribution of magnetic and conductive layers was designed to construct double-layer asymmetric structures and sandwich structures. Benefiting from destructive interference between electromagnetic waves (EMWs) in the magnetically and electrically separated porous structures, the double-layer asymmetric composites (M−C) exhibited outstanding absorption-dominated EMI shielding performance with favorable frequency selectivity, which did not occur in conventional double-layer composites. Specifically, M−C achieved a maximum shielding efficiency (SE) of 49.3 dB and a maximum average absorption ratio (Ar) of 93.9 %. Meanwhile, increasing the thickness of the magnetic layer of M−C can lower the characteristic frequency (fc) of the shielding peak and enhance average SE and average Ar. Moreover, M−C could show higher fc, average Ar, and average adsorption coefficient in the X-band when the incident EMWs first met with the magnetic layer, which was unavailable in frequency-selective PEN-based sandwich-structured composites. This effort offers a novel, flexible design to fabricate absorption-dominated EMI shielding materials with frequency selectivity.