Phosphorus Containing Research Articles

Preparation of Narrow Pore Diameter Phosphorus Containing Cotton Stalk Carbon and Its Adsorption Mechanism for Tetracycline

Using cotton stalk as biomass raw material and phosphoric acid as a modifier, narrow pore distribution phosphorus-containing cotton stalk biochar (CSP) with a high surface area (1916 m2·g-1) and pore volume (1.3982 mL·g-1) was prepared through one-step carbonization, and the adsorption characteristics and mechanisms for tetracycline (TC) were investigated. The results showed that the TC adsorption capacity of CSP was up to 669 mg·g-1, which was 43.6 times that of unmodified cotton stalk carbon. FTIR, XPS, and isothermal adsorption studies showed that the high adsorption capacity of CSP for TC resulted from the joint action of complexation, hydrogen bonding, pore filling, and π-π dispersion forces, and the highly active phosphate ester group (P-O-C) endowed by phosphoric acid modification greatly enhanced the chemical interaction with TC molecules, which was the key factor for the significant increase in adsorption capacity. Isotherm and thermodynamic study further confirmed that chemical adsorption played a major role in the adsorption process, the adsorption process was spontaneous and endothermic, and the material had good regeneration performance. This study provides theoretical guidance for the preparation of modified biomass carbon with high adsorption performance to remove tetracycline antibiotic pollution.

Phosphorus Containing Rubber Seed oil as a Flame Retardant Plasticizer for Polyvinyl Chloride

The application of phthalate plasticizers has been restricted around the world due to their poor migration and potential harm to the human body. Hence, producing functional bio-based plasticizers via exploiting clean and reusable resources meets the satisfaction of current demands. In this study, flame-retardant rubber seed oil-based plasticize (FRP) was prepared via epoxidation reaction and ring opening addition reactions, which was used as a flame-resistant plasticizer for polyvinyl chloride to replace petroleum-based phthalate plasticizer. When DOP was replaced with FRP, the torque of PVC blends increased from 11.4 to 18.4 N⋅m, the LOI value increased from 24.3% for PVC-FRP-0% to 33.1% for PVC-FRP-20. The THR value diminished from 39 MJ/m2 (pertaining to PVC-FRC-0) to 22 MJ/m2 Tg increased from 23°C to 47°C, the weight loss of plasticized PVC blends significantly reduced from 22.6% to 2.8% in leaching tests. The study provided a new way to prepare flame retardant plasticizer using rubber seed oil as raw material.

Phosphorus Containing Coatings: Technologies and Applications

AbstractPhosphorus Containing Coatings (PCCs) are an interesting class of materials that attracted considerable attention for use in different domains. A variety of PCCs characterized by outstanding electrical, biological, and chemical properties have been manufactured using various physical and chemical deposition processes. Thanks to developments in thin film and surface deposition technologies, it has become possible to manipulate the formation of PCCs according to the desired application, which has therefore been a mean of promoting this type of material towards new products and processes. This review explores the potential of the PCCs and deposition methods which can be used for their fabrication. Highlights on the connections between processing methods and the resulting film characteristics will be provided. The resulting coatings’ properties are discussed in the context of the characteristics necessary for achieving high‐performance PCCs in different sectors. Important prospects for PCCs research and their practical use in different fields will also be provided, and light will be shed on the future research directions for further progress of promising PCCs for the next film technology generations.

Synthesis and Characterization of New Phosphorus Containing Sulfonated Polytriazoles for Proton Exchange Membrane Application

ABSTRACTSulfonated polytriazoles have drawn a great attention as high performance polymers and their good film forming ability. In the present study, a phosphorus containing new diazide monomer namely, bis‐[4‐(4′‐aminophenoxy)phenyl]phenylphosphine was synthesized and accordingly, a series of phosphorus containing sulfonated polytriazoles (PTPBSH‐XX) was synthesized by reacting equimolar amount of this diazide monomer (PAZ) in combination with another sulfonated diazide monomer (DSAZ) and a terminal bis‐alkyne (BPALK) by the Cu (I) catalyzed azide–alkyne click polymerization. The polymers were characterized by nuclear magnetic resonance (1H, 13C, 31P NMR) and Fourier transform infrared spectroscopic techniques. The sulfonic acid content of the copolymers also determined from the different integral values obtained from the 1H NMR signals. The small‐angle X‐ray scattering results unfolded the well‐separated dispersion of the hydrophilic and hydrophobic domains of the polymers. As a whole, the copolymer membranes displayed sufficient thermal, mechanical, and oxidative stabilities high with high proton conductivity and low water uptake that are essential for proton exchange membrane applications. The copolymers exhibited oxidative stability in the range of 15–24 h and had proton conductivity values were found as high as 38–110 mS cm−1 at 80 °C in completely hydrated condition. Among the all copolytriazoles, PTPBSH‐90 (BPALK:DSAZ:PAZ = 100:90:10) having IECW = 2.44 mequiv g−1, showed proton conductivity as high as 119 mS cm−1 at 90 °C with an activation energy of 10.40 kJ mol−1 for the proton conduction. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 263–279

Modified Epoxy Resin Synthesis from Phosphorus-Containing Polyol and Physical Changes Studies in the Synthesized Products.

Epoxy resins are commonly used to manufacture the molding compounds, reinforced plastics, coatings, or adhesives required in various industries. However, the demand for new epoxy resins has increased to satisfy diverse industrial requirements such as enhanced mechanical properties, thermal stability, or electrical properties. Therefore, in this study, we synthesized new epoxy resin (PPME) by modifying phosphorous-containing polyol. The prepared resin was analyzed and added to epoxy compositions in various quantities. The compositions were cured at high temperatures to obtain plastics to further test the mechanical and thermal properties of the epoxy resin. The measured tensile and flexural strength of epoxy compositions were similar to the composition without synthesized epoxy resin. However, the heat release rates of the compositions exhibited tendencies of a decrease proportional to the amount of PPME.

Boron and Phosphorus Containing Heterosiliconoids: Stable p- and n-Doped Unsaturated Silicon Clusters.

Unsaturated silicon clusters (siliconoids) are short-lived intermediates during the transition from molecules to the elemental bulk; stable representatives reiterate surface features of silicon materials. The incorporation of suitable heteroatoms into the cluster scaffold of stable siliconoids extends this analogy to the technological process of silicon doping. Here, we report boron- and phosphorus-containing heterosiliconoids with BSi5 and PSi5 core based on the global minimum Si6R6 platform (dubbed benzpolarene for its relationship to benzene). The reductive cleavage of an SiR2 moiety (R = 2,4,6-iPr3C6H2) from Si6R6 selectively yields a dianionic Si5R42- cluster as its lithium salt. Treatment with Me3SiCl affords the corresponding trimethylsilyl-substituted (Me3Si)2Si5R4. Reaction of Si5R42- with iPr2NECl2 (E = B, P) yields the unprecedented p- and n-doped heterosiliconoids iPr2NESi5R4. Their peculiar electronic features are compared to those of the hexasilabenzpolarene starting material on grounds of NMR spectroscopy, X-ray diffraction, and DFT calculations.

Microwave‐Assisted Domino Heck Cyclization and Phosphorylation: Synthesis of Phosphorus Containing Heterocycles

A domino [Pd]‐catalyzed intramolecular Heck cyclization followed by intermolecular phosphorylation, for the construction of phosphorus containing heterocyclic compounds, is presented. Notably, the process is accelerated by microwave heating conditions and enabled the construction of C–C and C–P bonds in short reaction times.

Phosphorus Containing Polyacrylamides as Flame Retardants for Epoxy-Based Composites in Aviation.

Novel polymeric flame retardants based on two acrylamides and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) or 5,5-dimethyl-[1,3,2]dioxaphosphinane-2-oxide (DDPO) are described for several applications in HexFlow® RTM6, a high-performance epoxy resin. Neat resin samples and carbon fiber-reinforced composites were tested for their glass transition temperatures (dynamic mechanical analysis), thermal stability (thermogravimetric analyses), flammability (UL94) and flame-retardant performance (Cone Calorimetry). Additionally, the fiber degradation occurring during combustion of carbon fiber-reinforced epoxy resins was observed by scanning electron microscopy to show the fiber protecting effect of these flame retardants. Whereas DOPO-containing polyacrylamides acting mainly in the gas phase showed the best flame retardant efficiency, DDPO-containing polyacrylamides acting mainly in the condensed phase showed the best fiber protection. A mixed polyacrylamide was synthesized to combine these effects. This thermoplastic is soluble in the resin and, therefore, suitable for injection molding processes. Interlaminar shear strength measurements showed no negative effect of the flame retardant. The versatility of these flame retardants is shown by investigations dealing with boehmite as synergist in neat resin samples.

Mercury Ions Mediated Phosphorus Containing Carbon Dots as Fluorescent Probe for Biothiols Screening

In this study, we report the mercury ions (Hg[Formula: see text]) mediated phosphorus-containing carbon dots (PCDs) as a selective “off–on” fluorescence probe for glutathione (GSH), cysteine (Cys) and homocysteine (Hcys). PCDs obtained by hydrothermal reaction are sensitive to Hg[Formula: see text] ions and its fluorescence can be significantly quenched owing to the electron transfer from the lowest unoccupied molecular orbital (LUMO) of PCDs to Hg[Formula: see text]. Interestingly, the weak fluorescence of Hg[Formula: see text]-mediated PCDs could be gradually recovered with the addition of GSH, Cys and Hcys. This can be attributed to the formation of Hg[Formula: see text]–S complex due to the super affinity of Hg[Formula: see text]–sulfydryl bond. The formation of Hg[Formula: see text]–S complex extremely reduces the oxidation ability of Hg[Formula: see text] that inhibits the electron transfer from LUMO of PCDs to Hg[Formula: see text] and re-opens the native electron transition from LUMO to the highest occupied molecular orbital (HOMO) of PCDs. Thus, the green fluorescence of PCDs is switched on. Furthermore, the present Hg[Formula: see text]-mediated PCDs assay exhibits a high selectivity for GSH, Cys and Hcy and has been successfully used to detect the total biothiols content in human urine samples.

Optimization of the oil drain interval of non-phosphorus and non-ash engine oil

Purpose Zinc dialkyldithiophosphate (ZDDP) is the most common anti-wear and anti-oxidant additive. ZDDP is the primary origin of zinc, sulfur and phosphorus, which are well-known poisonous elements for commercial after-treatment systems. The aim of this study is to investigate the optimum oil drain interval of non-phosphorus and non-ash (NPNA) engine oil that was developed as a prospective alternative to commercial phosphorus-containing (PC) engine lubricants. Design/methodology/approach The results of a fleet test wear debris analysis were used to optimize the oil drain intervals from the perspective of cost. Findings Drain intervals of 32,000 and 28,000 km were computed as the optimum values for NPNA and PC engine oils, respectively. Extending the oil drain intervals up to the obtained mileage may go to a total saving of €43,045,084.2 for PC engine oil and €49,253,998.6 for NPNA engine oil with respect to the total sales figures of test vehicles in Turkey. Originality/value Maximizing the lubricant life has environmental benefits and is the easiest way to reduce the maintenance cost of a vehicle. The protection of after-treatment systems against lubricant-induced poisoning is a great challenge. The most important result of this investigation is the lower operation costs of catalyst-friendly lubricants in spite of their low anti-wear additive performance.

Phosphorus Containing Water Dispersible Nanoparticles in Arable Soil.

Due to the limited solubility of phosphorus (P) in soil, understanding its binding in fine colloids is vital to better forecast P dynamics and losses in agricultural systems. We hypothesized that water-dispersible P is present as nanoparticles and that iron (Fe) plays a crucial role for P binding to these nanoparticles. To test this, we isolated water-dispersible fine colloids (WDFC) from an arable topsoil (Haplic Luvisol, Germany) and assessed colloidal P forms after asymmetric flow field-flow fractionation coupled with ultraviolet and an inductively coupled plasma mass spectrometer, with and without removal of amorphous and crystalline Fe oxides using oxalate and dithionite, respectively. We found that fine colloidal P was present in two dominant sizes: (i) in associations of organic matter and amorphous Fe (Al) oxides in nanoparticles <20 nm, and (ii) in aggregates of fine clay, organic matter and Fe oxides (more crystalline Fe oxides) with a mean diameter of 170 to 225 nm. Solution P-nuclear magnetic resonance spectra indicated that the organically bound P predominantly comprised orthophosphate-monoesters. Approximately 65% of P in the WDFC was liberated after the removal of Fe oxides (especially amorphous Fe oxides). The remaining P was bound to larger-sized WDFC particles and Fe bearing phyllosilicate minerals. Intriguingly, the removal of Fe by dithionite resulted in a disaggregation of the nanoparticles, evident in higher portions of organically bound P in the <20 nm nanoparticle fraction, and a widening of size distribution pattern in larger-sized WDFC fraction. We conclude that the crystalline Fe oxides contributed to soil P sequestration by (i) acting as cementing agents contributing to soil fine colloid aggregation, and (ii) binding not only inorganic but also organic P in larger soil WDFC particles.

Surface and wear mechanisms analysis of phosphorous-free and conventional engine lubricants on cylinder liner and piston rings surfaces

Purpose – This paper aims to investigate the wear mechanisms, formations and effectiveness of tribofilms of new developed, antiwear additive which is called mercapthocarboxylate. The mercapthocarboxylate is a sulphur-based and non-phosphorus additive. Design/methodology/approach – The effectiveness of the additive was examined through a set of laboratory endurance tests that applied with single cylinder spark ignition engine. Two types of lubricants were used to compare the engine tests which were thiophosphate (ZDDP) containing engine lubricant (phosphorus containing) and mercapthocarboxylate containing non-phosphorus and non-ash crankcase oil. Lubricants were tested under identical operating conditions for 100 hrs. The surfaces of cylinder liner and piston rings were inspected through optical microscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy techniques. Findings – Catalysis-friendly and sulphur-based mercapthocarboxylate additive can be an alternative antiwear additive package for lubrication oil due to better wear performance when compared to ZDDP. Originality/value – Sulphur-based mercapthocarboxylate is a new developed antiwear additive and was applied to lubrication oil in this study. This lubrication oil was tested in the real engine environment by using 100-hr engine bench tests.

Detection of Two Phosphorus Containing Anacardic Compounds by Paper Chromatography

A method based on paper chromatography for detection and determination of tris-tetrahydroanacardoxy phosphite and tris-(2 terat-hydroanacardoxyethyl)-phosphite. The Rf values for these compounds in four solvent systems are recorded.

The Generation of a Reduced Mechanism for Flame Inhibition by Phosphorus Containing Compounds Based on Path Flux Analysis Method

In order to analyze the complex chemical kinetic mechanism systematically and find out the redundant species and reactions, a numerical platform for mechanism analysis and simplification is established basing on Path Flux Analysis (PFA). It is used to reduce a detailed mechanism for flame inhibited by phosphorus containing compounds, a reduced mechanism with 65 species and 335 reactions is obtained. The detailed and reduced mechanism are both used to calculate the freely-propagating premix C3H8/air flame with different dimethyl methylphosphonate doped over a wide range of equivalence ratios. The concentration distributions of free radicals and major species are compared, and the results under two different mechanisms agree well. The laminar flame speed obtained by the two mechanisms also matches well, with the maximum relative error introduces as a small value of 1.7%. On the basis of the reduced mechanism validation, the correlativity analysis is conducted between flame speed and free radical concentrations, which can provide information for target species selection in the further mechanism reduction. By analyzing the species and reactions fluxes, the species and reaction paths which contribute the flame inhibition significantly are determined.

Equilibrium Acidities and Homolytic Bond Dissociation Enthalpies of the Acidic C−H Bonds in Phosphonates and Related Phosphorus Containing Compounds

The homolytic bond dissociation enthalpies (BDEs) of the acidic C-H bonds in a series of phosphonates and related phosphorus-containing compounds have been determined by a combination (eq 3) of their equilibrium acidities (pK(HA)'s) and the oxidation potentials [E(ox)(A(-))'s] of their conjugate anions, which were measured in DMSO solution. The equilibrium acidity increases by 15.5, 14.9, and 10.9 pK units for the introduction of an alpha-P(O)(OEt)(2) group into toluene, acetonitrile, and ethyl acetate, respectively. Comparison with the published equilibrium acidity increases by 25.6, 24.4, and 21.0 pK units for the introduction of an alpha-(+)PPh(3) group into the same series of substrates indicates that the phosphoryl carbanions (Horner-Wadsworth-Emmons reagents) are about 10 pK units more reactive than the corresponding triphenylphosphonium ylides (Wittig reagents). However, both alpha-P(O)(OEt)(2) and alpha-(+)PPh(3) groups have negligible effects on the adjacent C-H BDEs, indicating that there is no resonance delocalization into the 3d vacant orbitals of phosphorus and that their acidifying effects are exclusively associated with the field/inductive (electrostatic) and polarizability effects. The acidifying effect of an alpha-CO(2)Et group is shown to be ca. 3.5 pK units stronger than that of an alpha-P(O)(OEt)(2) group in the same substrates, suggesting that the larger acidifying effect of the alpha-CO(2)Et group is predominantly associated with the resonance delocalization rather than with the field/inductive (electrostatic) and polarizability effects.

Synthesis and Characterization of Methylmethacrylate-alt-N-vinyl-2-pyrrolidone Initiated by Phosphorus Containing 1,2 Dipolar Compound

Copolymerization of methylmethacrylate (MMA) with 1-vinyl-2-pyrrolidone (N-VP), initiated by p-nitrobenzyl triphenyl phosphonium ylide in dioxane at 60°C for 60 min under inert atmosphere of nitrogen yields alternating copolymer as evidenced by the values of r 1 = 0.01 and r 2 = 0.02. The kinetic expression was Rp ∝ [I]0.75[MMA]1.2[VP]1.2. The overall activation energy is 45.4 kJ/mol. The FTIR bands of OCH3 of MMA at 1725 cm−1 and –C=O of N-VP at 1679 cm−1, confirms the incorporation of both the monomers in the copolymer. The glass transition temperature of the copolymer is 133°C. The GPC data shows the polydispersity index at about 1.5. The ESR spectroscopy confirm phenyl radical responsible for initiation.

New Anions of Pentacoordinate Phosphorus Containing Fluorine and Trifluoromethyl Groups

AbstractThe unique pseudo‐trigonal‐bipyramidal CF3PF3O– and (CF3)2PF2O– anions were obtained and characterised for the first time. They were formed by the reactions of (PhO)3P(O), Me3SiCF3 and the fluoride ion sources [Me4N]F and CsF, respectively, in glyme. These anions represent the stable transition states postulated for nucleophilic substitution at a tetrahedral phosphorus atom. The salt Cs[(CF3)2PF2O] (7) is stable at room temperature for a month, while [Me4N][CF3PF3O] (1) dismutates into [Me4N][CF3PF(O)O] (2) and [Me4N][CF3PF5] (3) above 0 °C. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2007)

ChemInform Abstract: Phosphorus Containing Radicals. Part 9. A Novel Synthesis of Diethyl 3‐Iodoalkyl‐ and 3‐Iodoalkenylphosphonates via the Iodine Atom Transfer Addition Reaction.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Ring-Closing Olefin Metathesis for the Synthesis of Phosphorus Containing Heterocycles

A series of cyclic phosphorus containing heterocycles 9a– k was prepared in a one-step procedure by ring closing metathesis of dienes 7a– k.

Boundary Lubrication of Steel Surfaces with Borate, Phosphorus, and Sulfur Containing Lubricants at Relatively Low and Elevated Temperatures

Prolonging the life of engineering components through lubricant formulation to achieve better wear resistance and higher oxidation stability is of paramount importance to many mechanical systems, such as automotive gears and bearings. This can be accomplished with formulated lubricants that limit the generation of wear debris causing severe abrasion and protect the contacting surfaces through the formation of wear-resistant tribofilms. In this study, a ball-on-disk tribometer was used to characterize the friction and wear properties of steel surfaces slid in the boundary lubrication regime. An experimental scheme was developed to allow the statistical screening of various lubricant formulations. Sliding experiments were performed in baths of different lubricants at relatively low and elevated temperatures, approximately 32 and 100°C, respectively, under conditions of constant load and sliding speed. Surface profilometry, optical microscopy, and scanning electron microscopy were used to characterize the dominant friction and wear mechanisms. The tribological properties were found to strongly depend on the temperature and the additives (e.g., borate, phosphorus, and sulfur) present in the blended lubricants. The superior high-temperature wear performance of the lubricant with the higher borate content is indicative of the formation of a durable tribofilm that reduces metal-to-metal adhesion, material transfer, and surface plowing by wear debris. Presented as a Society of Tribologists and Lubrication Engineers Paper at the ASME/STLE Tribology Conference in Seattle, Washington, October 1–4, 2000