Polyimide-silver nanocomposite containing phosphine oxide moieties in the main chain:Synthesis and properties

New flame-retardant polyimide-silver nanocomposite containing phosphine oxide moiety in the main chain was synthesized by a convenient ultraviolet irradiation technique.A precursor such as AgNO_3 was used as the source of the silver particles.Polyimide 6 as a source of polymer was synthesized by polycondensation reaction of bis（3-aminophenyl） phenyl phosphine oxide 4 with pyromellitic anhydride 5 in the presence of iso-quinoline as base and in m-cresol solution.The resulting composite film was characterized by FTIR spectroscopy,X-ray diffraction（XRD）,transmission electron microscopy（TEM）,thermogravimetry（TGA） and differential scanning calorimetry（DSC）.The average size of the nanometer Ag particles is about 10 nm.The temperature of 5 and 10%weight loss and also the char yield at 600℃of polyimide-silver nanocomposite 6a were higher than the pure PI 6.

A New Ternary Fluorescent Europium Complex with Bis(Diphenyl Phosphine Oxide) Methane and Thenoyltrifluoroacetone

A fluorescent ternary europium complex containing bis (diphenyl phosphine oxide) methane which functioned as both a neutral and anion ligand, and thenoyltrifluoroacetonato anion was synthesized and characterized by elemental analysis, DTA TG analysis, UV Vis, FT IR and MS spectroscopy. The chemical formula is proved to be Eu(TTA)(MPPO)(HMPPO)·(NO 3)·2H 2O. Its luminescence quantum efficiency(in acetonitrile, 26 3%) is approximately the same as that of the commonly used red emission luminescent compound, Eu(TTA) 3(TPPO) 2 (TPPO is triphenyl phosphine oxide). The new complex has comparatively long fluorescence lifetime.

Chiral Phosphine Ligands Derived from Sugars8. Crystal and Molecular Structure of Diphenyl (methyl 4', 6'-O-benzylidene-2'-deoxy-α-D-altropyranoside-2-)phosphine Oxide

The crystal structure of the title compound, C26H27O6P, has been determined by single--crystal X-ray diffraction. The crystal is monoclinic with space groupP21, a=16. 193(l), b=5. 804(1), c=12. 512(2) A, β=93. 187(5)°, V=1174. 13A3, Dc=1. 319 g/cm3, F(000) =492, μ= 13. 52 cm-1, Z= 2, and final R= 0. 042and Rw= 0. 040 for 2349 reflections (I≥3σ(I)). Structure analysis revealed that thepyranose and 4, 6-O-benzylidene ring of the title compound adopts a distorted chair conformation.

SYNTHESIS AND CHARACTERIZATION OF POLY(PHTHALAZINONE ETHER PHOSPHINE OXIDE)S BY N-C COUPLING REACTION

Based on several unsymmetrical, twist, noncoplanar phthalazinone-containing monomers 2a-2e and an active bis（4-fluorophenyl）phenyl phosphine oxide （BFPPO） monomer, a series of novel poly（phthalazinone ether phosphine oxide）s （PPEPO） was synthesized by anhydrous K2CO3 mediated N-C coupling reaction in DMAc. The polymers exhibited good thermal properties with Tgs ranging from 267℃ to 306℃ and 5% weight loss temperatures in nitrogen higher than 430℃, together with high char yield upon prolonged heating at 800℃ （35%-56%）. Moreover, the polymers were readily soluble in common organic solvents, such as N-methyl-2-pyrrolidone, chloroform and m-cresol. These polymers had inherent viscosities in the range of 0.45-0.72 dL/g and could be cast into flexible and colorless films by spin coating or casting approach.

Synthesis of Bio-based Epoxy Containing Phosphine Oxide as a Reactive Additive Toward Highly Toughened and Fire-retarded Epoxy Resins

The integration of high mechanical toughness,impact strength as well as excellent flame-retardant properties toward epoxy resins(EPs)have always been a dilemma.The inadequate overall performance of EPs severely restricts their sustainable utilization in engineering aspects over long-term.Herein,a new bio-based agent(diglycidyl ether of magnolol phosphine oxide,referred as DGEMP)derived from magnolol(classified as lignan),extracted from natural plants Magnolia officinalis,was successfully synthesized and further employed as a flameretardant reactive additive to diglycidyl ether of bisphenol A(DGEBA).As demonstration,the composite resin,DGEBA/15DGEMP(15 wt%DGEMP),achieved an Underwriters Laboratories-94 V-0 rating with a high limiting oxygen index(LOI)value(41.5%).In cone calorimeter tests,it showed that heat release and smoke production were effectively inhibited during combustion,wherein the peak heat release rate(PHRR)value of DGEBA/15DGEMP was reduced by 50%compared to neat DGEBA.Additionally,it exhibited a superior tensile strength(82.8 MPa),toughness(5.11MJ/m^(3))and impact strength(36.5 k J/m^(2)),much higher than that of neat DGEBA(49.7 MPa,2.05 MJ/m^(3)and 20.9 k J/m^(2)).Thus,it is highly anticipated that DGEMP imparts significantly improved mechanical and fire-retarded properties to conventional EPs,which holds a great potential to address the pressing challenges in EP thermosets industry.

Nickel-catalyzed kinetic resolution to achieve P-chiral phosphine oxides and sec-phosphine oxides

P-Chiral phosphines and sec-phosphine oxides(SPO) are found in a diverse range of compounds that play crucial roles in various fields, including asymmetric catalysis, materials, agrochemistry, and pharmaceutical chemistry. Herein, we describe an enantioselective Ni-catalyzed kinetic resolution of racemic sec-phosphine oxides to obtain the corresponding optically pure Pchiral phosphine oxides and sec-phosphine oxides, respectively. These products are versatile chiral phosphine building blocks that can be used to construct an extensive range of P-chiral phosphines.

Organophosphorus catalytic reaction based on reduction of phosphine oxide

The special electronic configuration of phosphorus atoms endows organophosphorus reagents with unique chemical properties,which enable them to be used to catalyze various organic reactions,such as the Wittig reaction,Staudinger reaction,Appel reaction and Mitsunobu reaction.However,the catalytic process will be accompanied by the generation of large amounts of phosphine oxide waste,resulting in the reduction of atom utilization of the reaction,and it is difficult to separate the product.Therefore,it is essential to explore a greener and more sustainable organic synthesis route based on the catalytic cycle of phosphine oxide as a model.This paper summarizes the catalytic cycle and recycling of phosphorus with or without reducing agents and reviews the related developments in recent decades:from the addition of stoichiometric strong reducing agents,to the design of ring phosphines with specific structures,to the development of new energy inputs(electrochemistry),to the addition of a series of compounds to activate the P(V)––O double bond,driving the catalytic cycle of phosphine oxide through chemical transformation.This review also points out the development potential of this field in the future,which will promote its development and progress in a greener direction.

Molecular engineering of an electron-transport triarylphosphine oxide-triazine conjugate toward high-performance phosphorescent organic light-emitting diodes with remarkable stability

Organic electron-transport materials are an essential component to boost performances and stability of organic light-emitting diodes. We present a robust organic electron-transport compound 3-(6-(3-(4,6-bis(4-biphenylyl)-1,3,5-triazin-2-yl)phenyl)pyridin-2-yl)phenyldiphenylphosphine oxide by facilely coupling the triphenylphosphine oxide moiety to the 2-phenyl-4,6-bis(4-biphenylyl)-1,3,5-triazine unit via a 2,6-pyridinylene linker. It is well soluble in weakly polar solvents and possesses a high Tg of 123 ℃ with an exceptional Td≈470 ℃ at 1% weight loss and deep HOMO/LUMO levels of ca.-6.45/-3.06 eV. The phosphorescent spectrum measured in solid state at 77 K reveals a notable triplet energy of 2.88 eV. n-Doping with 8-hydroxyquinolatolithium(Liq) produces the electron mobility value of 4.66×10-5–3.21×10-4 cm2 V-1 s-1@(2–5)×105 V cm-1.Moreover, the contrasting solubility of the bromo reaction intermediate and the new compound in alcoholic solvents facilitates separation. The characterizations of bottom-and top-emission green phosphorescent OLEDs involving this single Liq-doped electron-transport layer reveal long stability. In particular, the latter provides outstanding performances with 77.4 cd A–1(corresponding to an EQE of 18.7%) and 86.8 lm W–1@ca. 1000 cd m-2, based on the green emitter bis(2-phenylpyridine)(2-(4-methyl-3-phenylphenyl)pyridine)iridium(Ⅲ). Moreover, driven by a constant current for ca. 640 h, the initial luminance of 1000 cd m–2 appears almost no decay.

Influence of bidentate structure of an aryl phosphine oxide ligand on photophysical properties of its Eu~Ⅲ complex

The bidentate phosphine oxide ligand 1,8-bis(diphenylphosphino) naphthalene oxide (NAPO) and its EuⅢ complex 1 Eu(TTA)3(NAPO) (TTA=2-thenoyltrifluoroacetonate) were chosen to study the effect of bidentate phosphine oxide ligand on the photophysical properties of the corresponding complex. The intramolecular energy transfer processes of 1 were studied. The investigation showed that with bidentate structure NAPO could suppress solvent-induced quenching by enforcing the ligand-ligand interaction and the rigidi...

Triphenyl Phosphine Oxide and Carbazole-based Polymer Host Materials for Green Phosphorescent Organic Light-emitting Diodes

Four novel polymers, poly（3,6-9-decyl-carbazole-alt-1,3-benzene） （PB13CZ）, poly（3,6-9-decyl-carbazole-alt- bis（4-phenyl） （phenyl） phosphine oxide） （PTPPO38CZ）, poly（3,6-9-decyl-carbazole-alt-2,4-phenyl（diphenyl） phosphine oxide） （PTPPO13CZ） and poly（3,6-9-decyl-carbazole-alt-bis（3-phenyl） （phenyl） phosphine oxide） （PTTPO27CZ） were synthesized, and their thermal, photophysical properties and device applications were further investigated to correlate the chemical structures with the photoelectric performance of bipolar host materials for phosphorescent organic light emitting diodes. All of them show high thermal stability as revealed by their high glass transition temperatures and thermal decomposition temperatures at 5% weight loss. These polymers have wide band gaps and relatively high triplet energy levels. As a result, the spin coating method was used to prepare the green phosphorescent organic light emitting diodes with polymers PTPPO38CZ, PTPPO13CZ and PTTPO27CZ as the typical host materials. The green device of polymer PTPPO38CZ as host material shows electroluminescent performance with maximum current efficiency of 2.16 cd.A-1, maximum external quantum efficiency of 0.7%, maximum brightness of 1475 cd.m-2 and reduced efficiency roll-off of 7.14% at 600 cd.m-2, which are much better than those of the same devices hosted by polymers PTTPO27CZ and PTPPO13CZ.

Cu/Picolinamides-Catalyzed Coupling of (Hetero) aryl Halides with Secondary Phosphine Oxides and Phosphite

Some 4-hydroxy-picolinic acid derived amides were revealed as more efficient ligands for Cu-catalyzed coupling of(hetero)aryl halides with secondary phosphine oxides and phosphites.Only 3—5 mol%CuI and ligands were required to ensure coupling with a number of(hetero)aryl bromides and iodides to complete at 120 ℃ in 10—20 h.

Metal-free reduction of tertiary phosphine oxides with Hantzsch ester

The （COCl）2/Hantzsch ester is found to be an effective system for the metal-free reduction of tertiary phosphine oxides. The reaction proceeds under mild conditions, and is applicable to triarylphosphine oxides and alkyldiarylphosphine oxides to produce the corresponding tertiary phosphines in good to excellent yields. This new finding provides a practical, convenient and metal-free method for the reduction of tertiary phosphine oxides to tertiary phosphines, and shows potential application in organic synthesis.

Inclusion property and Diels-Alder reaction of bis (diphenylphosphine oxide) butadiyne

The host molecule, bis (diphenylphosphine oxide) butadiyne (2), includes a variety of guests to form five complexes (2a—2e). In addition, the Diels-Alder reaction between 2 and anthracene gives 9, 9′, 10, 10′-tetrahedron-9, 9′, 10, 10′-bi-ethenoantracene-11, 11′-bis (diphenylphosphine oxide) (3) which is a potential di-π-methane reactant and can undergo photorearrangement.

Chiral Phosphine Ligands Derived fro m Sugars .14 . Crystal Structure of Diphenyl( m ethyl4’,6’-O-benzylidene-3’-deoxy-α- D-altropyranoside-3-)phosphine Oxide

The crystal structure of the title compound, C 26 H 27 O 6P, has been determined by single crystal X ray diffraction analysis. The crystal is orthorhombic with space group P2 12 12 1, a=6.154(4), b=17.199(8), c=22.180(3) , V=2347.6 3, D c=1.32 g/cm 3, F(000)=984, μ=1.5 cm -1 , Z =4, and final R =0.075 and R w =0.080 for 1417 reflections (I≥3σ(I)) . The X ray diffraction analysis revealed that the structure of the title compound s similar to that of its parent phosphine and the pyranose and 4, 6 O benzylidene rings remain distorted chair conformations.

Mathematical model and reaction mechanism of molybdenum and tungsten extraction with TRPO from peroxide solution

To understand the behavior of molybdenum and tungsten extracted by tri-alkyl phosphine oxide(TRPO)from peroxide solution,the extraction mechanism was studied by slope method and Raman and FTIR spectroscopy.The empirical formulas of molybdenum and tungsten extraction distribution ratio(D_(Mo)and D_(W))as functions of equilibrium pH,TRPO concentration and temperature were obtained by establishing mathematical models.Furthermore,the reliability of the empirical formula was verified in the H^(+)-W-Mo-H_(2)O_(2) solution.The results indicate that the calculated values of D_(Mo)or D_(W)were consistent with the experimental values.The apparent extraction equilibrium constants of molybdenum and tungsten wereK_(Mo)^(app)=8.51×10^(3)(0.74≤pH_(e)≤1.7),K_(Mo)^(app)=99.89×10^(3)(1.7<pH_(e)≤4.62)andK_(W)^(app)=2.65×10^(3)(0.92<pH_(e)<2.16)at 20°C,respectively.The main extraction complex of molybdenum or tungsten was[H_(2)(Mo or W)_(2)O_(3)(O_(2))_(4)(H_(2)O)_(2)]·2TRPO.These empirical formulas can be used to analyze and estimate the extraction and separation of Mo and W from low molybdenum and tungsten concentration solutions.

STRUCTURE AND PROPERTIES OF PHOSPHROUS-CONTAINING POLY(ARYLETHER KETONE)WITH BISPHENOL-A MOIETY

A phosphrous-containing poly（aryl ether ketone） was synthesized derived from bisphenol-A and bis[4-（4- fluorobenzoyl）phenyl] phenyl phosphine oxide （FPPPO） by nucleophilic substitution reaction. The structure of the polymer was characterized by FT-IR, ^1H-NMR and ^31p-NMR. The thermal property of the PAEK was measured by DSC and TGA. The glass transition temperature （Tg） of the polymer was 205℃, and the 5% weight loss temperature under nitrogen was 475℃. Good solubility of the polymer in organic solvents, such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide and chloroalkanes was observed, flexible film was obtained from the polymer＇s CH2Cl2 solution. The limiting oxygen index （LOI） of the PAEK was 40, which indicated that organic phosphorus moiety can offer good flame retardant property to the polymer.

Extraction and Separation Factor for Lanthanum(III) and Cerium(III) Complexes from Aqueous Medium Using Ionic Liquid and Kerosene

In this work, an experimental study was carried out to find the best-operating conditions for the study of the extraction percentage (%E) and the separation factor (SF) of La(III) and Ce(III) complexes. To carry out this study, a variation of β-diketone concentrations was used, keeping the concentration of tri-octyl phosphine oxide (TOPO) continuous at 0.05 M. The ratio of organic phase to the aqueous phase (O/A) was also studied. The %E and SF were analyzed and compared in the 1,1,1-trifluoro-2, 4-pentanedione (TFA) with TOPO, and 1,1,1,5,5,5-Hexafluoro-2,4-pentanedione (HFAc) with TOPO in Ionic Liquid (IL) and Kerosene. The one-stage extraction efficiency in IL of La(III) and Ce(III) complexes was 42.13% and 77.48% for the TFA-TOPO system and La(III) and Ce(III) complexes were 94.33% and 97.67% for the HFAc-TOPO system. While the SF between Ce(III) and La(III) complexes was 4.91 for TFA-TOPO and 2.64 for HFAc-TOPO. On the other hand, the one-stage extraction efficiency in Kerosene of La(III) and Ce(III) complexes was 27.57% and 63.70% in the TFA-TOPO system. The one-stage extraction efficiency of La(III) and Ce(III) complexes were 99.87% and 99.73% for the HFAc-TOPO system in Kerosene while the SF between Ce(III) and La(III) complexes was 4.62 for TFA-TOPO and 0.49 for HFAc-TOPO. The main conclusion was that using two extractants (β-diketone and TOPO) produced a synergistic effect improving the extraction capacity and SF of La(III) and Ce(III) complexes for both systems in IL and Kerosene.

The Influence of Aziridine on the Aging of Composite Solid Rocket Propellant

Aging of a solid composite propellant containing HTPB/AP/AL was performed in order to validate the conformance of the accelerated aging data to the Arrhenius law. The main objective of the work was to examine the influence of the aziridine bonding agents family on the propellant aging. Aging of the prepared propellant samples was conducted as follows: 1. Four samples, one free of bonding agents, and three containing aziridine based bonding agents MAPO,HX-752, MAT4 were aged at 65°C. 2. Another four samples based on HX-752, MAT4 with different curing agents were aged at 65°C. The measured mechanical properties of the free bonding agent propellant samples were very far from the specifications and this illustrates the importance of the bonding agents in both the preparation and the aging phases.The prepared bonding agent 'MAT4' gave remarkable improvements of the mechanical properties comparing with HX-752 and MAPO. The aziridine bonding agents family inhibited the rate of decomposition of the propellant during the aging periods and supported the propellant matrix against decomposition at the elevate temperatures. Using of HMDI as curing agent gave slight better mechanical properties to the IPDI.

Development of sterically hindered SPOs and enantioselective Ni-Al bimetallic catalyzed C-H cyclization of 4-oxoquinazolines with tethered alkenes

The Ni-Al bimetallic catalysis of intramolecular enantioselective and regioselective C-H cyclization of4-oxoquinazolines with tethered alkenes has been successfully developed.Some new secondary phosphine oxides(SPOs)with large steric hindrance(SPO6-11)were designed and successfully synthesized from readily available chiral amines or amino acids.The developed chiral SPOs as ligands or preligands demonstrate much higher efficiency in the asymmetric catalytic reactions than the reported traditional ones.A new class of chiral tricyclic pyrroloquinazolinones were obtained in up to 95%yield and 99%ee.

Overriding the inherent alkalinity to dual phosphinito bimetallic catalyst for C(sp^(2))-C(sp^(3))formation:A combined computational and experimental study

Unraveling the catalytic reaction mechanism is a long-term challenge for developing efficient catalysts.The blooming bimetallic catalyst have enabled to activate inert bonds and realize complex C-C formation.Herein,we theoretically discover a dual-phosphinito bridged hetero-bimetallic species that verified by NMR experiments.Our results indicate only dual-phosphinito Ni-Al model can be an active catalyst in asymmetric cycloadditions via C-C activation and C-H activation,which can well rationalize the experimental observations for both reactivity and stereo-selectivity.An unprecedented tandem redox dehydrogenation mechanism was revealed to control the formation of this active species overriding the inherent basicity.Synergistic Lewis acid and eg orbital interactions,including dz2 orbital reoccupation and d_(x^(2)−y^(2))orbital recombination,were disclosed to understand both thermodynamic and kinetic advance of dual-bridged model,displaying feasible redox properties.