Biphenyl Diamine Research Articles

Mitigation of Dendrite Growth in Zinc-iodide Flow Battery with Tröger’s Base Anion Exchange Membrane

Tröger’s base anion exchange membrane (TB-AEM) was readily prepared by condensation polymerization of biphenyl diamine and dimethoxymethane in the presence of trifluoroacetic acid followed by quaternization with methyl iodide. The film cast from N-Methyl-2-Pyrrolidone (NMP) solvent displayed good mechanical strength, a tensile modulus of 1.18 GPa with elongation at break of 17%, and a glass transition temperature (Tg) at 248 °C. It exhibited OH− ion conductivity of 108 mS cm−1 by impedance measurement at 80 °C in 1M KOH. The membrane exhibited good affinity toward I2, resulting in the formation of I2Br− ions in the membrane matrix. Over 300 charge/discharge cycles at a 50 mA cm−2 current density, the battery exhibited 95.5% Coulombic efficiency (CE), 76.4% voltage efficiency (VE), and 74.0% energy efficiency (EE) and delivered a capacity of 24.8 Ah L−1. Over a span of 60 h, the open-circuit voltage (OCV) of the cell remained constant at 1.2 V. Collectively, our findings suggest that the anion exchange membrane's charge and porosity tuning are key factors in the design of new generation separators for zinc-iodide flow batteries.

Photocatalytic benzylamine coupling dominated by modulation of linkers in donor-acceptor covalent organic frameworks

The strong excitonic effect is widely prevalent in covalent organic frameworks (COFs)-based catalysts, while the high exciton binding energies (Eb) of COFs seriously limit their photocatalytic performance. Herein, theoretical calculations are conducted to evaluate the Eb values of potential COFs derived from benzo[1,2-b:3,4-b'-b'']trithiophene-2,5,8-tricarbaldehyde (BTT) and 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde (Bp) as aldehyde monomers. Diverse aromatic amine linkers including dipyridine diamine (BPy), biphenyl diamine (BPh), and p-phenylenediamine (MPh) with different molecular lengths and N-sites are used as linker models to regulate the excitonic effect. The obtained BTT-BPy-COF with a long BPy linker and the lowest calculated Eb value possesses the best photocatalytic performance for benzylamine coupling, with conversion and selectivity up to 99% accompanied by a high oxidation rate, outperforming most of the reported works. Further mechanistic investigation reveals that the bipyridine-N sites in BTT-BPy-COF exhibit strong electron transfer as well as enhanced O2 adsorption and activation that is beneficial to photocatalytic benzylamine coupling.

Tailoring β-ketoenamine covalent organic framework with azo for blue light-driven selective oxidation of amines with oxygen

Covalent organic frameworks (COFs) present bright prospects in visible light photocatalysis with abundant active sites and exceptional stability. Tailoring an established COF with photoactive group is a prudent strategy to extend visible light absorption toward broad photocatalysis. Here, a β-ketoenamine COF, TpBD-COF, constructed with 1,3,5-triformylphloroglucinol (Tp) and 4,4′-biphenyldiamine (BD), is tailored with azo to validate this strategy. The insertion of azo into BD affords 4,4′-azodianiline (Azo); TpAzo-COF is successfully constructed with Tp and Azo. Intriguingly, the insertion of azo enhances π-conjugation, thereby facilitating visible light absorption and intramolecular electron transfer. Moreover, TpAzo-COF, with an appropriate electronic structure and impressive specific surface area of 1855 m2 g−1, offers substantial active sites conducive to the reduction of oxygen (O2) to superoxide. Compared with TpBD-COF, TpAzo-COF exhibits superior performance for blue light-driven oxidation of amines with O2. Superoxide controls the selective formation of product imines. This work foreshadows the remarkable capacity of tailoring COFs with photoactive group toward broad visible light photocatalysis.

Synthesis of novel biphenyl‐fused alicyclic tetracarboxylic dianhydride and its performance in thermostable and transparent colorless polyimides

AbstractBiphenyl fused alicyclic tetracarboxylic dianhydride, 6,6′,7,7′‐tetracarboxylic dianhydride‐5,5′,6,6′,7,7′,8,8′‐octahydro‐2,2′‐binaphthalene (OHBNDA) was successfully synthesized from biphenyltetracarboxylic dianhydride (BPDA) through hydrolysis, reduction, bromination, and Diels–Alder reaction. Three OHBNDA‐based polyimides (PIs) were synthesized by one‐step polycondensation at high temperature with 9,9‐bis(4‐aminophenyl)fluorene (BAFL), 2,2′‐bis(trifluoromethyl)‐4,4′‐diaminobiphenyl (TFMB), and 4,4′‐diamino‐2,2′‐dimethyl‐1,1′‐biphenyl (m‐TolDA) diamines, respectively. These PIs have moderate molecular weights and good solubility in polar organic solvents, such as N,N‐dimethylformamide, dimethylacetamide (DMAc), and dimethyl sulfoxide (DMSO). OHBNDA‐TFMB, OHBNDA‐m‐TolDA, and OHBNDA‐BAFL display glass transition temperatures (Tgs) of 309, 329, and 377°C from differential scanning calorimetry (DSC) curves, and the decomposition temperatures at 5% weight loss (Td5) of as high as 522, 507, and 548°C under nitrogen, respectively. Meanwhile, these PI films also show good optical transparency with the cut‐off wavelength <315 nm and the transmittance >75% at 400 nm. These results confirm that aryl‐fused alicyclic tetracarboxylic dianhydrides can afford transparent/colorless PIs with high thermal stability, especially the higher decomposition temperatures than the wholly alicyclic dianhydrides.

Design of porous organic polymer photocatalysts based on heptazine for efficient photocatalytic aerobic oxidation

• Four heptazine-based porous organic polymers with different diamines were prepared. • The structure–activity relationships of the POPs have been systematically studied. • The diamine linker has important roles on its physicochemical property and activity. • POP-4 has the best performance for the photocatalytic oxidation of benzylamine. • Its conversion and selectivity of benzylamine oxidation are both>99 %. Heptazine-based porous organic polymers (POPs), as new potential photocatalytic materials, have spurred extensive research interest, but there are few reports on the systematic study of the relationship between their structure and properties. Herein, we have prepared four heptazine-based POPs by using cyameluric chloride (C 6 N 7 Cl 3 ) as precursor, piperazine (POP-1), p-phenylenediamine (POP-2), biphenyl diamine (POP-3) and 4,4′'-diamino-p-terphenyl (POP-4) as basic blocks, respectively, and studied the effects of the composition and structure of POPs on their spectrum, specific surface area, interface contact in acetonitrile, electronic structure, carrier separation and photocatalytic aerobic oxidation of amine through experiments and density functional theory (DFT) calculations systematically. The results show that with the increase of the benzene rings and electron density of diamine linker, the electron-donating ability of these heptazine-based POPs significantly enhances, which reduces the band gap of the materials, improves their electronic donor–acceptor (D-A) interaction with heptazine, promotes the transfer and separation of photogenerated carriers, and thus endowing them significantly higher photocatalytic performance. Notably, POP-4 shows the best photocatalytic aerobic oxidation activity of benzylamine, which is significantly higher than that of g-C 3 N 4 . The conversion and selectivity of benzylamine to corresponding imine are both>99 % within 4 h under 10 W 420 nm LED light irradiation. This work paves the way for the rational design of efficient heptazine-based POP photocatalysts and promotes the development of heptazine-based functional materials.

A conveniently synthesized redox-active fluorescent covalent organic framework for selective detection and adsorption of uranium

Uranium is a key element in the nuclear industry and also a global environmental contaminant with combined highly toxic and radioactive. Currently, the materials based on post-modification of amidoxime have been developed for uranium detection and adsorption. However, the affinity of amidoxime group for vanadium is stronger than that of uranium, which is the main challenge hindering the practical application of amidoxime-based adsorbents. Herein, we synthesized a fluorescent covalent organic framework (TFPPy-BDOH) through integrating biphenyl diamine and pyrene unit into the π-conjugated framework. TFPPy-BDOH has an excellent selectivity to uranium due to the synergistic effect of nitrogen atom in the imine bond and hydroxyl groups in conjugated framework. It can achieve ultra-fast fluorescence response time (2 s) and ultra-low detection limit (8.8 nM), which may be attributed to its intrinsic regular porous channel structures and excellent hydrophilicity. More excitingly, TFPPy-BDOH can chemically reduce soluble U (VI) to insoluble U (IV), and release the binding site to adsorb additional U (VI), achieving high adsorption capacity of 982.6 ± 49.1 mg g−1. Therefore, TFPPy-BDOH can overcome the challenges faced by current amidoxime-based adsorbents, making it as a potential adsorbent in practical applications.

Synthesis, characterization and properties of novel polyamides derived from 4 4ʹ bis(4-carboxy methylene) biphenyl and various diamines

ABSTRACT Novel aromatic aliphatic diacid monomer, 4 4ʹ bis(4-carboxy methylene) biphenyl was synthesized via friedel craft acylation with acetic anhydride followed by willgerodot reaction and used in the preparation of polyamides by direct polycondensation using the Yamazaki phosphorylation reaction with commercial aromatic diamines. These polyamides were obtained in good yield with moderate-to-high-molecular-weight build up as evidenced by inherent viscosities in the range of 0.52–0.96 dlg−1. The XRD studies showed that all the polyamides were amorphous in nature and these polymers dissolved in polar aprotic solvents such as N-methyl-2-pyrrolidone(NMP),N,N-dimethylsulfoxide(DMSO), N,N-dimethyl formamide (DMF) and N,N-dimethyl acetamide. The resulting polyamides were characterized by inherent viscocity measurements, FT-IR, 1H NMR and 13C NMR spectroscopy, solubility, thermogravimetry, X-ray diffraction studies. These polyamides had glass transition temperatures between 210°C and 261°C, and their temperatures at a 10% weight loss were 620 to 710°C and 497 to 597°C in nitrogen and air atmospheres, respectively, which indicates thermally stable polymers.

Decolorization of Congo red mediated by marine Alcaligenes species isolated from Indian West coast sediments

Alcaligenes species capable of degrading highly recalcitrant, carcinogenic, water-soluble dye—Congo red—were isolated from Indian West coastal sediments. Individual strains showed decolorization rates ranging from 76.49 to 98.76% within 24–48 h. Decolorization was most efficient at anoxic conditions catalyzed by intracellular azoreductase enzyme with an activity of 0.032 µmol min−1 mg−1 of protein. Degradation was confirmed by HPLC and FTIR analysis. LC/MS analysis of degraded metabolites established the cleavage of the azo bond-producing biphenyl diamine and 1,2′-diaminonapthalene-4-sulfonic acid. These results signify the effectiveness and ease to engineer processes such as feed batch/immobilized cell systems using these strains as biocatalysts to address the problem of global coastal water pollution caused by increased disposal of azo dye-containing industrial effluents.

Synthesis, fluorescence, electrochromic properties of aromatic polyamide with triarylamine unit serving as functional group

Two series of novel aromatic polyamides (PAs) were synthesized via polymer condensation reaction based on N,N'-bis(4-aminophenyl)-N,N'-di-1-naphthalenyl-[1,1′-biphenhyl]-4,4′-diamine, N,N'-bis(4-aminophenyl)-N,N'-diphenyl-4,4′-biphenyl diamine and different binary acids compounds. The structures of the monomers and polymers were characterized by Fourier transform infrared spectroscopy (FT-IR), hydrogen nuclear magnetic resonance (1H NMR). The electrochromic properties of the PAs were investigated by using the ultra-visible-near infrared (UV–Vis–NIR) spectrophotometer and electrochemical workstation. The color of the polymer films changed from light yellowish to brown, then atroceruleous or brilliant blue with an increasing potential. Then we discussed the relationship of morphology on coloration efficiency. The electrochemical impedance spectroscopy (EIS) also has been used to characterize the internal resistances of PAs film electrodes.

Current shot noise characteristics in biphenyl diamine and biphenyl dithiol devices

Current shot noise characteristics, away from their average current, in biphenyl diamine and biphenyl dithiol devices are investigated. The relations among the shot noise and the applied bias, the coupling factors, as well as the alligator clips are revealed. The regular change of the shot noise in biphenyl diamine device and irregular change of the shot noise in biphenyl dithiol device are shown as the coupling strength change from full coupling to weak coupling. It is found that the shot noise suppression in biphenyl diamine device is enhanced at the higher bias. The large differences of the shot noise suppression in the biphenyl dithiol device are revealed.

Synthesis and memory characteristics of polyimides containing noncoplanar aryl pendant groups

A series of soluble aromatic polyimides were prepared from 2,2′-diphenyl-4,4′-biphenyl diamine (DPBD), 2,2′-bis(biphenyl)-4,4′-biphenyl diamine (BBPBD), 2,2′-bis[4-(naphthalen-1-yl)phenyl]-4,4′-biphenyl diamine (BNPBD) and 2,2′-bis(3,5-dimethoxyphenyl)-4,4′-biphenyl diamine (BMPBD) by polycondensation with 2,2′-bis[4′-(3′′,4′′,5′′-trifluorophenyl)phenyl]-4,4′,5,5′-biphenyl tetracarboxylic dianhydride via a two-step procedure. The resulting polymers were fully characterized and they exhibited excellent organosolubility, high thermal and dimensional stability. Resistive switching devices with the configuration of Al/polymer/ITO were constructed from these polyimides by using conventional solution coating process. Devices with the active layer based on DPBD, BBPBD and BNPBD exhibited nonvolatile and rewritable flash type memory characteristics with the turn-on voltage at −2.0 to −3.0 V and the turn-off voltage at 2.0–3.0 V. Whereas, device based on BMPBD demonstrated a bipolar write-once read-many times (WORM) memory capability with the writing voltage around ±3.0 V. The ON/OFF current ratio of these devices was of about 106 and the retention times can be as long as 104 s.

Resistive switching characteristics of polyimides derived from 2,2′‐aryl substituents tetracarboxylic dianhydrides

Abstract2,2′‐Position aryl‐substituted tetracarboxylic dianhydrides including 2,2′‐bis(biphenyl)‐4,4′,5,5′‐biphenyl tetracarboxylic dianhydride and 2,2′‐bis[4‐(naphthalen‐1‐yl)phenyl)]‐4,4′,5,5′‐biphenyl tetracarboxylic dianhydride were synthesized. A new series of aromatic polyimides (PIs) were synthesized via a two‐step procedure from 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride and the newly synthesized tetracarboxylic dianhydrides monomers reacting with 2,2′‐bis[4′‐(3″,4″,5″‐trifluorophenyl)phenyl]‐4,4′‐biphenyl diamine. The resulting polymers exhibited excellent organosolubility and thermal properties associated with Tg at 264 °C and high initial thermal decomposition temperatures (T5%) exceeding 500 °C in argon. Moreover, the fabricated sandwich structured memory devices of Al/PI‐a/ITO was determined to present a flash‐type memory behaviour, while Al/PI‐b/ITO and Al/PI‐c/ITO exhibited write‐once read‐many‐times memory capability with different threshold voltages. In addition, Al/polymer/ITO devices showed high stability under a constant stress or continuous read pulse voltage of − 1.0 V. Copyright © 2011 Society of Chemical Industry

Low dielectric constant polyimide nanomats by electrospinning

The proper combination of material (i.e. fluorinated polyimides) and processing technique (electrospinning) could lead to the formation of polyimides with low dielectric constant, high thermo‐oxidative stability and glass transition temperature, and high hydrophobicity. The polyimides in this work were based on 4, 4‐bis [3′‐trifluoromethyl‐4′ (4′‐amino benzoxy) benzyl] biphenyl (Q) and various fluorinated and non‐fluorinated dianhydrides namely benzene‐1,2,4,5‐tetracarboxylic dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride, benzophenone‐3,3′,4,4′‐tetracarboxylic dianhydride, and 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA). Processing of the polyimides was carried out in poly(amic acid) stage by two different methods—electrospinning and solution casting for comparison purposes. The processing of polyimides by electrospinning led to enhancement in mechanical properties (dianhydride‐structure dependent) and hydrophobicity without sacrificing thermo‐oxidative stability and glass transition temperatures significantly. Also, low dielectric constants (as low as 1.43) could be attained by suitable combination of dianhydride (6FDA) with 4, 4‐bis [3′‐trifluoromethyl‐4′ (4′‐amino benzoxy) benzyl] biphenyl diamine. Copyright © 2011 John Wiley & Sons, Ltd.

Synthesis and memory characteristics of highly organo-soluble polyimides bearing a noncoplanar twisted biphenyl unit containing aromatic side-chain groups

Two novel 3′,4′,5′-trifluorobiphenyl-based aromatic polyimide monomers, 2,2′-bis[4′-(3′′,4′′,5′′-trifluorophenyl)phenyl]-4,4′-biphenyl diamine (BTFBPD) and 2,2′-bis[4′-(3′′,4′′,5′′-trifluorophenyl)phenyl]-4,4′,5,5′-biphenyltetracarboxylic dianhydride (BTFBPDA) were synthesized. Two fluorinated polyimides (PIs), PI(BTFBPD-DPBPDA) and PI(BTFBPD-BTFBPDA) were prepared via a two-step procedure using BTFBPD reacting with 2,2′-diphenyl-4,4′,5,5′-biphenyltetracarboxylic dianhydride (DPBPDA) and BTFBPDA, respectively. BTFBPD was characterized with single crystal X-ray diffraction analysis and the geometric parameters showed the noncoplanar twisted character. PIs exhibited highly organo-solubility and thermal stability. The PI films sandwiched between an indium-tin oxide(ITO) bottom electrode and Al top electrode exhibited two accessible conductivity states and can be switched from the low-conductivity to the high-conductivity. The memory devices with the configuration of Al/PI(BTFBPD-DPBPDA)/ITO exhibited a flash type memory capability, whereas the Al/PI(BTFBPD-BTFBPDA)/ITO presented a write once read many times (WORM) memory capability. The fabricated devices showed low turn-on threshold voltages of −1.3 V (PI(BTFBPD-DPBPDA)) and −1.7 V (PI(BTFBPD-BTFBPDA)) and both ON/OFF current ratios on the order of 103 to 104.

Axial [6,6′-(2,4-pentadioxy)]-1,1′-biphenyl-2,2′-diamine (PD-BIPHAM): practical synthesis and applications in asymmetric hydrogenation

A rapid, reliable, and atom-economical procedure for the novel axially biphenyl diamine, ( R, R, S ax)-PD-BIPHAM 1, has been developed successfully by using highly efficient central-to-axial transformation strategy. The attractive feature of this methodology is that no tedious resolution was needed. The effectiveness of this new chiral skeleton was initially demonstrated by highly enantioselective hydrogenation of α-dehydroamino acid esters.

Diglycidylphenylphosphate based fire retardant liquid crystalline thermosets

Organophosphorus liquid crystalline thermosets (LCTs) were developed using diglycidylphenylphosphate (DGPP) and various aromatic diamines. DGPP was prepared by the esterification of phenylphosphorodichloridate with glycidol. 2,5-Bis( p-aminophenyl)-1,3,4-oxadiazole (BPOD) was synthesized and three different commercial diamines, 4,4′-diaminodiphenyl sulphone (DDS), 4,4′-diaminodiphenyl methane (DDM) and biphenyl diamine (BPD) were used as curing agents. The mesomorphic behaviour of DGPP/diamine mixtures and their curing kinetics were monitored by differential scanning calorimetry and hot stage optical polarized microscopy. The thermogravimetric analysis data showed that the LCTs are stable in the range 261–292 °C and afford 36–48% char yield. The limiting oxygen index values are between 35 and 47 proving fire retardance. The mechanical properties of the cured LCTs were characterized by dynamic mechanical analysis.

Application of a New Biphenyl Diamine Ligand in Enantioselective Hydrogenation

Application of a New Biphenyl Diamine Ligand in Enantioselective Hydrogenation

Synthesis and Characteristics of Hole-transporting Materials Based on Biphenyl Diamine Derivatives with Carbazole Groups

Two hole-transporting materials containing carbazole moieties with TPD- and NPB-like structures, 4,4′-bis [N-(4-carbazolylphenyl)-N-phenylamino] biphenyl (CPB) and 4,4′-bis [N-(4-carbazolylphenyl)-N-(1-naphthyl) amino]biphenyl(CNB), were synthesized via a modified Ullmann reaction. The resulting compounds were thermally stable with high glass transition temperatures ranging from 145 to 147 °C and possessed a good electrochemical reversibility and hole-transporting properties. Typical double-layer device evaluation with the structure ITO/CPB(40 run)/Alq3(60 nm)/LiF/Al demonstrated that they were promising hole-transporting materials with a current efficiency of 5. 25 cd/A and a power efficiency of 2. 00 lm/W.

Side chain length dependence on supra-molecular structures in a series of aromatic polyimides having terminal 4-cyanobiphenyl liquid crystalline side chains

A series of newly designed polyimides, composed of aromatic polyimide backbones and methylene side chains with terminal 4-cyanobiphenyl groups, were synthesized based on the polycondensation of 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA) with 2,2′-bis{ω-[4-(4-cyanophenyl)phenyoxy- n-alkoxycarbonyl]}-4,4′-biphenyl diamine ( nCBBP, where n is the number of methylene units in the side chains). We report our structural and morphological studies on this series of BPDA– nCBBP, which possesses n=7, 9, and 11 methylene units in the side chains. For these three polyimides, a nematic (N) phase was first formed at high-temperatures during cooling from the isotropic melt. The transition temperatures and enthalpies were cooling-rate independent as observed in differential scanning calorimetry. This N phase was further confirmed by the results of wide angle X-ray diffraction (WAXD) and polarized light microscopic experiments. At lower temperatures, ordered structures were formed. It was surprising that in the cases of BPDA– nCBBP ( n=7 and 9), triclinic lattices were observed; while in the case of BPDA-11CBBP, a hexagonal lattice was evident, as determined by 2D WAXD experiments. This indicated that by increasing the number of methylene units in the LC side chains, the individual chains (base unit) used in constructing these supra-molecular structures changed their packing symmetry. Namely, when the number of methylene units in the side chains was relatively low (i.e. the length is short), the individual chains were packed into a ribbon-like structure. However, when the side chain length is long enough, the individual chains exhibit cylindrical symmetry. Regardless of the lattice formed by the supra-molecular structures, they are all on the nanometer length scale.

Synthesis and Properties of Novel Fluorinated Poly(amide-imide)s from the 4,4′-Bis(4-trimellitimido-2-trifluoromethylphenoxy)biphenyl and Aromatic Diamines

A novel fluorinated diimide dicarboxylic acid, 4,4′-bis(4-trimellitimido-2-trifluoromethylphenoxy)biphenyl (III), was synthesized from the condensation of 4,4′-bis(4-amino-2-trifluoromethylphenoxy)biphenyl (I) and trimellititc anhydride. A series of soluble poly(amide-imide)s (PAI) Va–h having inherent viscosities of 0.56–0.97 dL/g were prepared from reacting III with an equivalent amount of diamines by direct polycondensation using triphenyl phosphite and pyridine as condensing agents. The polymer V series afforded tough, transparent, and flexible films. They had tensile strengths ranging from 88 to 112 MPa, elongations at break from 8 to 31%, and initial moduli from 1.9 to 2.7 GPa. The glass-transition temperature (Tg) of the polymers was recorded at 235–300 ○C. They had 10% weight loss at a temperature above 502 ○C and left more than 54% residue even at 800 ○C in nitrogen. In comparison with the nonfluorinated PAI VI series, the fluorinated V exhibited better solubility.