Methyl Phosphine Oxide Research Articles

THIRD PHASE FORMATION IN THE EXTRACTION OF Nd(III) BY OCTYL(PHENYL)-N,N-DHSOBUTYL CARBAMOYL METHYL PHOSPHINE OXIDE (OΦCMPO)

ABSTRACT Third phase formation in the extraction of Nd(III) by 0.2 M Octyl(Phenyl)-N,N-Diisobutyl Carbamoyl methyl phosphine oxide (OΦCMPO) in n-dodecane has been studied with tri-n-butyl phosphate (TBP) and tri-n-amyl phosphate (TAP) as modifiers to provide a comparison between these two modifier systems. The effect of concentration of TAP as modifier for the extraction of Nd(III) by 0.2 M OΦCMPO has been studied. The extraction of Nd(III) by TAP/n-dodecane in the absence of OΦCMPO has also been studied and the results are reported here.

Epoxy resins cured with aminophenylmethylphosphine oxide—II. Mechanism of thermal decomposition

The thermal decomposition behaviour of the mixed epoxy resin, tetraglycidyl 4,4′-diaminodiphenylmethane (TGDDM) and diglycidylether of bisphenol A (DGEBA), in a 1:1 ratio, cured with 3,3′,5,5′-tetraethyl-4,4′-diaminodiphenylmethane (M-DEA) or bis( m-aminophenyl)methylphosphine oxide (BAMPO) or with mixtures of the hardeners was studied. On heating, the resins rapidly decompose above 290 °C in an exothermic process involving dehydration, bond scission and chain fragment volatilisation. However, as the temperature increases, unsaturations created in the bond scission process polymerise to give a residue which, above 400 °C, undergoes aromatisation to form a thermostable ‘char’. In the presence of the phosphorous-containing hardener (BAMPO), the volatilisation is reduced and aromatisation is accelerated which leads to a larger amount of stable ‘char’. This is suggested to be a reason for the fire-retardant action of BAMPO which, however, at high BAMPO content is overwhelmed by flame quenching by volatilising phosphorus-containing moieties from BAMPO decomposition.

Solubility of Organophosphorus Metal Extractants in Supercritical Carbon Dioxide

The solubility (S) of several liquid organophosphorus compounds, tributyl phosphate (TBP), diisodecylphosphoric acid (DIDPA), di-(2-ethylhexyl)phosphoric acid (DEHPA), dihexyl-(N,N-diethylcarbamoyl)methylphosphonate (CMP), and octyl(phenyl)(N,N-diisobutylcarbamoyl)methylphosphine oxide (CMPO), in supercritical CO2 was determined over temperature and pressure ranges of 30−90 °C and 7.5−25 MPa. The solubility of the compound increases with increasing density (ρ) of CO2 fluid, showing a linear relationship: ln S = p ln ρ + q (p and q are constants). The slope p measured at 60 °C is 21.8, 11.4, 13.1, 10.8, or 7.5, and the constant q, given solubility at ρ = 1 g/mL, is 26.3, 0.4, 2.7, 5.1, or −0.1 respectively for TBP, DIDPA, DEHPA, CMP, or CMPO. A homogeneous mixture of TBP or CMP with CO2 is readily obtained even at relatively low pressure, where the density of CO2 is relatively low. It is found that all the compounds examined are soluble enough in CO2 to prepare an organophosphorus compound−CO2 mixture whi...

Synthesis and characterization of arylene ether imide reactive oligomers and polymers containing diaryl alkyl phosphine oxide groups

The diamine monomer bis(m-aminophenyl) methyl phosphine oxide (DAMPO) was synthesized via nitration and reduction of diphenyl methyl phosphine oxide. Rigorous purification of this monomer enabled its utilization in the synthesis of high molecular weight poly(ether imide)s. Both thermoplastic materials and thermosetting systems, endcapped with either phthalic or phenylethynylphthalic anhydride, respectively, have been produced. Major emphasis has been placed on polyimides derived from 2,2′-bis(4-(3,4-dicarboxyphenoxy) phenyl) propane dian- hydride, also known as bisphenol-A dianhydride, or BPADA. High molecular weight homo- and copolyimides based on BPADA/DAMPO had glass transition temperature values in the range of 215–223°C, and were totally amorphous. They displayed higher modulus and tensile strength values than the polyetherimide control based on meta-phenylene diamine and also generated high TGA char yields in air. Phenylethynyl crosslinkable materials were effectively cured at 380°C to produce networks that are ductile, very solvent resistant and also generate high char yields, which suggest their possible utilization in fire resistant matrix systems. © 1998 John Wiley & Sons, Ltd.

Synthesis and characterization of flame resistant poly(arylene ether)s

AbstractHydrolytically stable phosphorus‐containing monomers, such as 4,4′‐bis(fluorophenyl)methylphosphine oxide (BFPMPO), 4,4′‐bis(hydroxyphenyl)methylphosphine oxide (BOHPMPO), and 4,4‐bis(hydroxyphenyl)phenylphosphine oxide (BOHPPO), were synthesized and used in nucleophilic aromatic substitution poly‐condensation to prepare poly(arylene ether phosphine oxide) engineering thermoplastics. The synthesis and characterization of these novel polymers are described. It was determined that by incorporating the phosphine oxide moiety into the polymer backbone, certain properties of the resulting poly(arylene ether) were substantially improved, such as an increase in Tg, thermal stability in air, modulus, and char yield compared with control poly(arylene ether sulfone)s. The high char yields obtained for these polymers in air along with observed intumescence indicates that these materials have improved fire resistance. Preliminary cone calorimetry measurements support this conclusion.

Mechanistic study of thermal behaviour and combustion performance of carbon fibre-epoxy resin composites fire retarded with a phosphorus-based curing system

The fire retardant action in epoxy resins based on tetraglycidyl 4,4'-diaminodiphenylmethane (TGDDM) either alone or combined with the diglycidylether of bisphenol A (DGEBA), cured with bis( m-aminophenyl)methylphosphine oxide (BAMPO) was studied. Comparison of oxygen index (OI) and nitrous oxide index suggests a condensed phase fire retardant mechanism. The yield of the intumescent char continuously increases providing polymer shielding upon increasing the concentration of the fire retardants. In the composite the carbon fibres play the role of inert fillers in combustion in the oxygen index test with, however, fibre orientation having an important effect. The carbon fibres suppress the intumescence behaviour of the char. The chemical mechanism of thermal degradation and charring of the resins is studied using thermogravimetry, thermal volatilisation analysis, char characterisation by FTIR, solid state NMR, X-ray, EPR and elemental analysis.

Validation with in vitro test systems of the quantitative structure activity relationships (QSARA) used for the prediction of toxicology of new fire retardants

Selection of the chemicals for development as new fire retardants required an assessment of their potential toxicity. Conventional in vivo toxicological studies were proscribed under the terms of this project. Consequently, toxicological predictions were based on SARs and QSARs and selected in vitro biological tests. The TOPKAT programme was used to provide estimates of: rat acute oral toxicity (LD 50), rat maximum tolerated dose (MTD), mouse inhalational toxicity (24 h LC 50), eye and skin irritation, mutagenesis, carcinogenesis, teratogenesis, aerobic biodegradation, fish 96 h LC 50, and Daphnia magna 48 h LC 50. The toxicological activity of all the chemicals was also evaluated using Microtox ™, Mutatox ™. Some evidence of mutagenic and carcinogenic potential was detected. Good correlation was shown between the prediction of some of the experimental parameters of toxicity. TOPKAT predicted bis(aminophenyl)methyl phosphine oxide to be very toxic. Expert judgement contradicted this finding. Experimentally it did not inhibit acetylcholinesterase which supported the hypothesis that the P=O moiety was hindered and hence inactive as an anticholinesterase.

Effect of structure on the thermal behaviour of ethynyl‐terminated imide resins

AbstractA series of ethynyl‐terminated aromatic imide monomers containing phosphine oxide in the backbone were synthesized by the reaction of tris(3‐aminophenyl) phosphine oxide (TAP) or bis(3‐aminophenyl)methyl phosphine oxide (BAP) with pyromellitic dianhydride (PMDA) or 3, 3′,4, 4′‐benzophenone tetracarboxylic acid dianhydride (BTDA) or 4, 4′‐perfluoroisopropylidenebis(phthalic anhydride), and 3‐ethynyl aniline. Structural characterization was done by infrared, nuclear magnetic resonance spectroscopy and elemental analysis. Thermal characterization was done by differential scanning calorimetry and thermogravimetric analysis. The decomposition temperatures of cured resins were above 500°C in nitrogen atmosphere. Char yield at 800°C ranged from 52–63.5%.

Syntheses, structure, reactivity, and thermal properties of new cyclic phosphine oxide epoxy resins cured by diamines

A new type of epoxy resin which contained cyclic phosphine oxide group in the main chain was synthesized. The structure of the new type of epoxy resin was confirmed by elemental analyses (EA), infrared spectroscopy (IR), and 1H-NMR and 13C-NMR spectroscopies. In addition, compositions of the new synthesized cyclic phosphine oxide epoxy resin (EPCAO) with three curing agents, e.g., bis(3-aminophenyl)methylphosphine oxide (BAMP), 4,4′-diamino-diphenylmethane (DDM), and 4,4′-diaminodiphenylsulfone (DDS), were used for making a comparison of its curing reactivity, heat, and flame retardancy with that of Epon828 and DEN438. The reactivities were measured by differential scanning calorimetry (DSC). Through the evaluation of thermal gravimetric analysis (TGA), those polymers which were obtained through the curing reactions between the new epoxy resin and three curing agents (BAMP, DDM, DDS) also demonstrated excellent thermal properties as well as a high char yield. © 1996 John Wiley & Sons, Inc.

Synthesis of Stable Spirooxyphosphoranes - Potential Promoters of Catalytic Antibodies

Abstract Bis-[ortho-carboxyaryl]- and bis[ortho-amidoaryl]methylphosphine oxides, in acidic medium, spontaneously cyclodehydrate to give trigonal bipyramidal (TBP) spirodioxy- and azoxyphosphoranes, respectively. Regioselectivity with a few nucleophiles and electrophiles, unexpectedly, accompany some of their reactions. Their structural similarity to pentacoordinate intermediates, obtained on the hydrolysis of organophosphorus (OP) poisons, and their stability at the physiological pH, renders them, as transition state analogs (TSA), useful promoters of catalytic antibodies.

3,3-Dimethyl-1-(2-pyridylthio)butyl]methyl(2,4,6-trimethylphenyl)phosphine Oxide

In the molecule of [3,3-dimethyl-1-(2-pyridylthio)-butyl]methyl(2,4,6-trimethylphenyl)phosphine oxide, C 21 H 30 NOPS, the P=O bond is nearly coplanar with the mesityl ring and nearly parallel to the pyridyl ring. In the chain connecting the mesityl and pyridyl rings two extended fragments are found, twisted at the C11-S bond; likewise, two extended fragments exist in the chain connecting the methyl atom C10 and the terminal atom C15 of the butyl moiety, twisted at the C11-C12 bond. The structure is stabilized by C11-H111...N intramolecular and C20(py)-H201...O intermolecular hydrogen bonds.

Synthesis, structure, and thermal properties of epoxy‐imide resin cured by phosphorylated diamine

AbstractNew phosphorylated epoxy‐imide polymer was obtained using diimide‐diepoxide (DIDE) cured with bis(3‐aminophenyl)methylphosphine oxide (BAMP). In addition, composition of the synthesized diimide‐diepoxide (DIDE) with common curing agents, e.g., 4,4′‐diaminodiphenylether (DDE) and 4,4′‐diaminodiphenylsulfone (DDS), were used for making a comparison of its curing reactivity, heat and flame retardation with that of bis(3‐aminophenyl)methylphosphine oxide. The reactivity of those curing agents toward epoxy‐imide, as measured by differential scanning calorimetry (DSC), was of the order DDE > BAMP > DDS. Through the evaluation of thermal gravimetric analysis (TGA), the new phosphorylated epoxy‐imide polymer demonstrated excellent thermal properties as well as a high char yield. © 1995 John Wiley & Sons, Inc.

Measurements of Al(NO 3) 3 activities in aqueous nitrate solutions

Aluminum nitrate activity coefficients obtained by vapor pressure osmometry are compared with activity coefficients derived from nitric acid extraction measurements and Bromley's correlation. This solvent extraction approach was possible because of the poor extraction of Al 3+ (distribution ratio ≤ 10 3) by the chosen solvents. The solvents compositions were 0.25M CMPO (octyl(phenyl)-N, N-diisobutylcarbamoyl methylphosphine oxide) in tetrachloroethylene (TCE) and 0.25M CMPO with 0.75M tributyl phosphate (TBP) in TCE. In both approaches, nitric acid was used to supress the hydrolysis of Al 3+. At high ionic strengths, the two techniques yielded very similar activity coefficients for Al(NO 3) 3. However, at intermediate and very low ionic strengths, the two procedures produced considerably different activity coefficients.

Partitioning of Nitric Acid Intermediate-Level Waste Solutions by Sorption

The technical feasibility of partitioning concentrated nitric acid intermediate-level waste (ILWC) solutions from the Purex process into a small volume of high-level waste and a large volume of low-level waste using sorption methods is demonstrated for 1-ℓ batches. Cesium-134 and 137Cs are selectively separated with a decontamination factor (DF) greater than 1 × 105 in a newly developed “suspended-bed” column filled with the microporous inorganic exchanger ammonium molybdophosphate. The 125Sb and the actinides and lanthanides with a 3+ valence state are retained with DFs between 40 and 1000 on metal oxides of antimony and manganese and on an extraction column containing n-octyl(phenyl) N,N-diisobutyl carbamoyl methyl phosphine oxide, respectively. Ruthenium-106 and 60Co are removed in a column loaded with dimethyl glyoxime and have DFs greater than 20.The amount of secondary wastes arising from absorber materials is calculated to be 300 kg for a 350 t/yr reprocessing plant with an ILWC volume of ∼0.5 m3/t of heavy metal.

THE SEPARATION OF NEPTUNIUM AND PLUTONIUM FROM NITRIC ACID USING n-OCTYL(PHENYL)-N, N DIISOBUTYLCARBAMOYLMETHYLPHOSPHINE OXIDE EXTRACTION AND SELECTIVE STRIPPING†

ABSTRACT The extraction of neptunium and plutonium in several oxidation states was studied as a function of nitric acid concentration for 0.1M n-octyl(phenyl)-N, N-diisobutylcarbamoyl -methylphosphine oxide in 1.4M tributylphosphate with dodecane diluent. Np(V) is only weakly extractable over the range of acid concentrations studied while Np(IV) and Np(VI) are highly extractable. Pu(IV) and Pu(VI) are also highly extractable while Pu(III) was extracted but with lower efficiency. An Fe(II) reductant was used to reduce neptunium to Np(IV) and plutonium to Pu(III) for the initial extraction. Pu(III) was then stripped with dilute HNO3 in the presence of a holding reductant leaving the Np(IV) in the organic phase. Neptunium may then be recovered to an aqueous phase with one of a number of complexing agents.

Nylon 6,6 copolyamides of bis(2‐carboxyethyl) methylphosphine oxide

AbstractCopolyamides of nylon 6,6 with bis(2‐carboxyethyl)methylphosphine oxide (CEMPO) were prepared by melt polycondensation of nylon 6,6 salt with CEMPO and hexamethylene diamine. The effect of CEMPO upon melting point, moisture regain, boiling water shrinkage, water wicking, tensile properties, thermal stability, static dissipation, and flammability of nylon 6,6 fibers and fabrics was determined. The fiber properties were greatly affected by the high water absorption and solubility characteristics of the phosphine oxide linkage. However, crystallinity and orientation were not greatly disturbed by up to 30–40M% CEMPO substitution in nylon 6,6. The copolyamides were of improved flame resistance compared to nylon 6,6 and were also found to give improved flame resistance in blends of the copolymer with various commercial plastics. In addition, CEMPO and the corresponding diamine, bis(3‐aminopropyl)methylphosphine oxide were used to prepare a series of cycloaliphatic and aromatic ring‐containing polyamides, but problems were encountered with moisture sensitivity and low melting points with some of these polymers.

PARTITIONING STUDIES TO SEPARATE ACTINIDES FROM ICPP HLWa

ABSTRACT Studies at the Idaho National Engineering Laboratory (INEL) are in progress to evaluate the latest generation of bidentate organophosphorus actinide extractants. The Idaho Chemical Processing Plant (ICPP) dissolves defense nuclear fuel in a mixture of hydrofluoric and nitric acids to recover unspent uranium. Therefore, the waste stream is both acidic and has a high concentration of Zr and Al complexed fluoride. The focus is on octyl(phenyl)-N,N-diisobutylcarbamoyl -methylphosphine oxide (CMPO) as it may exhibit large actinide separation factors compared to bulk waste constituents such as Zr and Al. This paper describes the traced batch extractions that have been completed using CMPO and synthetic high-level waste.

ORGANISCHE PHOSPHORVERBINDUNGEN 81 HERSTELLUNG VON HETEROCYCLISCH SUBSTTTUIERTEN PHOSPHINOXIDEN UND DEREN VERWENDUNG IN DER WITTIG-HORNER REAKTION

Abstract The reaction of dimethyl-chloromethylphosphinoxide with the alkali salts of imidazole, pyrazole, triazole, benztriazole, 2-methyIimidazole, benzimidazole, tetrazole, and indazole yields the corresponding dimethyl-heterocyclic substituted methylphosphine oxides 1a-1i (Table I). These phosphine oxides easily undergo a Wittig-Horner reaction when treated with aldehydes and ketones and give a cis/trans = 1:1 mixture of the corresponding olefines 2a, 2a′, 2b, 2d and 2f. Several of these can be separated by flash chromatography into the pure cis and trans isomers. It was observed that only the cis compounds exhibit fungicidal activity against Erysiphe graminis.

Curing of Epoxy Resin with Phosphorylated Diamine

Abstract The diglycidyl ether of Bisphenol-A (DGEBA), suitable for the manufacture of epoxy-glass fiber laminates, has been cured with bis(m-aminophenyl)methylphosphine oxide (BAPO), and the results have been compared with a commercially available 4,4′-diaminodiphenyl sulfone (DDS). DSC studies indicated that an increase in the concentration of diamine resulted in an increase in the extent of the curing reaction even above the optimum level of diamine. Cured resins were stable up to 300°C and started losing weight above this temperature. Glass fabric-reinforced laminates based on DGEBA:BAPO exhibited a higher limiting oxygen index (LOI), as well as higher shear and flexural strength than those based on the DGEBA:DDS system. Thermal aging at 185°C for 100 h did not affect the mechanical properties of laminates. However, a significant decrease was observed in interlaminar shear strength by boiling in water for 100 and 200 h.

Addition polyimides. IV. Effect of structure on thermal characteristics

AbstractChain extension reaction of bis(m‐maleimido phenyl) methyl phosphine oxide (BP) with 4,4′‐diaminodiphenylmethane (BP–M), 4,4′‐diaminodiphenyl ether (BP–E), 3,3′‐ and 4,4′‐diaminodiphenyl sulfone (BP–DDSm and (BP‐DDSm respectively), tris (m‐aminophenyl) phosphine oxide (BP–TAP), and 9,9‐bis(p‐aminophenyl) fluorene (BP–BAF) was carried out by refluxing 1:0.3 molar solution of BP:diamine. The melting temperature and exothermic peak associated with curing of BP decreased by such chain extension. The thermogravimetric analysis indicated more than 60% residual weight at 800°C in nitrogen atmosphere in BP–DDSm, BP–DDSp, and BP–TAP resins. These resins can be processed at low temperature and can be used for fabrication of composites with improved properties.