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Phosphazenes 2014

Phosphazene chemistry continues to expand in its breadth and application. This article discusses new research published in 2013 covering mono- and dimeric structures, cyclotriphosphazenes, linear polymers, and the use of phosphazenic structures as ligands on metal centres. Papers report new reactions and structures as well as materials designed for specific applications, such as biomedical, energy storage, flame retardant, and optical, among others. The critical similarity is the phosphazene P-N structure that gives this area of study wide variation. Mirroring the diversity in chemistry are the tools used to probe structure and behaviour. These techniques include Nuclear Magnetic Resonance (NMR) spectrometry, various optical methods, electrochemistry, membrane transport experiments, etc. Furthermore, computational methods, such as Density Functional Theory (DFT), have been used to provide additional insight. This article is organized by structure, beginning with monomeric, dimeric, and non-cyclic phosphazenes first, followed by the cyclic and linear morphologies, with reported potential applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phosphazene diamines

The synthesis of a specific phosphazene diamine was optimized, other phosphorus-containing diamines were prepared, and their effect upon certain characteristics of epoxy resins, prepared via reaction with MY 720, in particular, char yield at elevated temperatures was evaluated. The synthesis of the phosphazene diamine resulting from the interaction of methylenedianline with 4,4'-bis(diphenylphosphino)biphenyl was simplified into a one step process giving 77 percent yield of the pure product. Using this procedure, a related diamine containing bis(diphenylphosphino)methane was obtained in a 70 percent yield. Preparation of another class of phosphorus containing amines based upon p-aminophenyldiphenyl-phosphine was unsuccessful; the inability to produce p-aminophenylithlum was responsible for this failure. Seven epoxy resins employing Araldite MY 720, diaminodiphenylsulfone, and two of the phosphorus containing diamines were prepared, characterized, and their char yield capacity at elevated temperatures assessed. Based on these investigations, the resins containing phosphorus appear to exhibit significantly better char formation characteristics than materials hardened using conventional amines, without impairing the other properties measured.

Paciorek, K. L.↗

Carboranylmethylene-substituted phosphazenes and polymers thereof

Carboranylmethylene-substituted cyclophosphazenes are described which can be thermally polymerized into carboranylmethylene-substituted phosphazene polymers. The polymers are useful as thermally stable coatings. Also, due to the characteristics of these polymers in acting as a ligand for transition metals, metalocarboranylmethylene phosphazene polymers are described which can act as immobilized catalyst systems, and are electrically conductive and superconductive.

Allcock, H. R.↗

Molecular dynamics study of carbon dioxide and nitrogen selectivity through poly[bis((methoxyethoxy)ethoxy)phosphazene] (MEEP) membrane

Here, a molecular dynamics simulation model was developed to comprehensively understand carbon dioxide over nitrogen (CO 2 /N 2 ) selectivity through polyphosphazene-based membrane comprising of poly[bis((methoxyethoxy)ethoxy)phosphazene] (MEEP) selective layer at the molecular level. The effects of temperature, pressure, and initial feed gas composition on the CO 2 transport on a polymer membrane were studied. The computed free energy and density profile of the permeating gas mixture exhibited that CO 2 molecules express higher interactions with the membrane than N 2 molecules, resulting in higher CO 2 /N 2 selectivity. Statistical analysis of gas molecules (CO 2 , water (H 2 O), and N 2 ) transportation suggested that hydro- and CO 2 -philic functional groups in the membrane significantly impact CO 2 permeability and CO 2 /N 2 selectivity. This study suggested that Lewis acid–base and hydrogen bonding combinations contribute to CO 2 permeation and CO 2 /N 2 selectivity. An equal CO 2 /N 2 selectivity was observed with and without water vapor in the feed gas suggesting that water does not hinder CO 2 transport through the membrane.

36 MATERIALS SCIENCE↗

An e.s.c.a. study of atomic oxygen interactions with phosphazene-coated polyimide films

Metallic as well as most nonmetallic materials experience oxidation and mass loss via surface erosion in low earth orbit as shown in previous Space Shuttle flights. This study is an evaluation of select polyphosphazene polymers and their resistance to atomic oxygen attack. Electron spectroscopy for chemical analysis examinations of the surfaces of polyphosphazene coatings were monitored for microstructural changes induced during exposures to atomic oxygen. Sample exposures in oxygen plasmas and O(3P) beam were compared as to their effect on surface compositional changes in the polyphosphazene coating. High resolution line scans revealed rearrangements in the polymer backbone and scissioning reactions involving fluorocarbon units of long chain fluoroalkoxy pendant groups. Atom percents and peak areas of all species provided a detailed profile of the microstructural changes induced in phosphazene polymers as a result of exposures to atomic oxygen.

Fewell, Larry L.↗

Synthesis and thermal stability of carborane containing phosphazenes

Carborane substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl penta chlorocyclotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy. The degradation products were ascertained by gas chromatography-mass spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring chain equilibrium processes of decomposition.

Fewell, L. L.↗

Synthesis and thermal stability of carborane-containing phosphazenes

Carborane-substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl pentachlorocylotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy. The degradation products were ascertained by gas chromatography-mass spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring-chain equilibrium processes of decomposition. Previously announced in STAR as A83-21034

Fewell, L. L.↗

Phosphazene Polymers Containing Carborane

Addition of carborane increases thermal stability. Carborane-substituted polyphosphazenes prepared by thermal polymerization of phenylcarbonyl-pentachlorocyclotriphosphazene followed by reaction with sodium trifluoroethoxide to replace remaining chlorine atoms with trifluoroethoxy groups. Improved polymers offer high char yields and resistance to hydrolysis.

Fewell, L. L.↗

Biocompatible Nanocoatings of Fluorinated Polyphosphazenes through Aqueous Assembly

Nonionic fluorinated polyphosphazenes, such as poly[bis(trifluoroethoxy)phosphazene] (PTFEP), display superb biocompatibility, yet their deposition to surfaces has been limited to solution casting from organic solvents or thermal molding. Here in this paper, hydrophobic coatings of fluorinated polyphosphazenes are demonstrated through controlled deposition of ionic fluorinated polyphosphazenes (iFPs) from aqueous solutions using the layer-by-layer (LbL) technique. Specifically, the assemblies included poly[(carboxylatophenoxy)(trifluoroethoxy)phosphazenes] with varied content of fluorine atoms as iFPs (or poly[bis(carboxyphenoxy)phosphazene] (PCPP) as a control nonfluorinated polyphosphazene) and a variety of polycations. Hydrophobic interactions largely contributed to the formation of LbL films of iFPs with polycations, leading to linear growth and extremely low water uptake. Hydrophobicity-enhanced ionic pairing within iFP/BPEI assemblies gave rise to large-amplitude oscillations in surface wettability as a function of capping layer, which were the largest for the most fluorinated iFP, while control PCPP/polycation systems remained hydrophilic regardless of the film top layer. Neutron reflectometry (NR) studies indicated superior layering and persistence of such layering in salt solution for iFP/BPEI films as compared to control PCPP/polycation systems. Hydrophobicity of iFP-capped LbL coatings could be further enhanced by using a highly porous polyester surgical felt rather than planar substrates for film deposition. Importantly, iFP/polycation coatings displayed biocompatibility which was similar to or superior to that of solution-cast coatings of a clinically validated material (PTFEP), as demonstrated by the hemolysis of the whole blood and protein adsorption studies.

36 MATERIALS SCIENCE↗

Synthesis of Poly(dichlorophosphazene) by the Melt Phase Polymerization of P-Trichloro-N-(dichlorophosphoryl)monophosphazene

A major barrier to commercialization of any of the many exciting applications of the poly(phosphazenes) has been the cost and ease of preparation of the most widely utilized starting polymer, poly(dichlorophosphazene) (Cl2PN)n (1). One attractive route is the thermal polycondensation reaction of P-trichloro-N-(dichlorophosphoryl)monophosphazene, Cl3P=N–P(O)Cl2 (2). We are reporting a modified bulk polymerization of 2 which represents a convenient route to laboratory scale amounts of (NPCl2)n with moderate molecular weights and polydispersity. GPC characterization data were obtained on the corresponding phenoxy derivatives, [(PhO)2PN]n. We also have developed a one pot synthesis of 1 from ammonium sulfate and phosphorus pentachloride which are the starting materials for the synthesis of 2 and examined the major variables, time and temperature, for this process. The resulting poly(phosphazene) exhibits more branching than the product of bulk polymerization of 1.

99 GENERAL AND MISCELLANEOUS↗

High resolution mobility spectrometry in a co-axial platform

Ion mobility spectrometry is an analytical technique that separate ions in the gas phase based on their interaction with a neutral buffer gas. Ion mobility spectrometry performs separations quickly (typically less than a second) and the ion mobilities are very reproducible across different laboratories. This project aimed at evaluating the performance of a new ion mobility device. The new device relies on conducting ion mobility separation in a curved geometry. The project explored the operation landscape of the device using ion trajectory simulations then fabricated and experimentally demonstrated the device's performance. Ion trajectory simulations on a set of tetraalkylammonium and phosphazene ions indicate that ions traveling a curved path length undergo mobility separation that is similar to a straight path. The ion mobility resolution of the curved device was found to be similar to that of a straight path of a similar length. The experimental validation of the new device confirmed the device's ability to separate ions according to their mobilities. Sets of mixtures (tetraalkylammonium ions, phosphazene ions, and peptide ions) were evaluated for separation and transmission.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of thermally stable phosphonitrile elastomers for advanced aerospace structures

Both high and low molecular weight, curable poly(fluoroalkoxy phosphazene) terpolymers were prepared. These terpolymers resulted from reaction of (Cl2PNn) polymer with alkoxides derived from CF3CH2OH and C3F7CH2OH, and an alkoxide derived from CH3CH(OH)C2H4OH. The terpolymers were crosslinked with polyisocyanates at room temperature. High molecular weight materials were converted into isocyanate prepolymers which as films underwent moisture cures at room temperature. Prepolymer solutions were stable for several days, and showed good adhesion. Also the effects of polymerization of (Cl2PN)3 were studied. Purified octachlorophosphazene, thiocyanate salts, or hydrogen chloride were employed in attempts to decrease molecular weight. Hydrogen chloride was found to be a good agent for preparation of low molecular weight poly(dichloro phosphazene).

Reynard, K. A.↗

Survey of inorganic polymers

A literature search was carried out in order to identify inorganic, metallo-organic, and hybrid inorganic-organic polymers that could serve as potential matrix resins for advanced composites. The five most promising candidates were critically reviewed and recommendations were made for the achievement of their potential in terms of performance and cost. These generic polymer classes comprise: (1) Poly(arylsil sesquioxanes); (2) Poly(silyl arylene siloxanes); (3) Poly(silarylenes); (4) Poly(silicon-linked ferrocenes); and (5) Poly(organo phosphazenes). No single candidate currently possesses the necessary combination of physicomechanical properties, thermal stability, processability, and favorable economics. The first three classes exhibit the best thermal performance. On the other hand, poly (organo phosphazenes), the most extensively studied polymer class, exhibit the best combination of structure-property control, processability, and favorable economics.

Gerber, A. H.↗

Electrolytes including fluorinated solvents for use in electrochemical cells

Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include ion-supplying salts and fluorinated solvents capable of maintaining single phase solutions with the salts at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and increase safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Fluorinated salts, such as fluoroalkyl-substituted LiPF.sub.6, fluoroalkyl-substituted LiBF.sub.4 salts, linear and cyclic imide salts as well as methide salts including fluorinated alkyl groups, may be used due to their solubility in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene or, more specifically, a cyclic phosphazene and/or one or more ionic liquids.

30 DIRECT ENERGY CONVERSION↗

Draw solutions and methods of treating an aqueous liquid

A method of treating an aqueous liquid. The method comprises providing an aqueous feed liquid comprising water and at least one solute to a first side of a membrane. A draw solution comprising water and a draw solute comprising at least one of a phosphazene compound and a triazine compound is provided to a second side of the membrane. At least a portion of the water of the aqueous feed liquid is osmosed across the membrane and into the draw solution to form a diluted draw solution comprising water and the draw solute. The water of the diluted draw solution is separated from the draw solute of the diluted draw solution to form a purified water product. Draw solutes comprising phosphazene compounds and draw solutes comprising triazine compounds are also disclosed, as are methods of forming the draw solutes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Use of phosphoranimines to reduce organic carbonate content in Li-ion battery electrolytes

In this study, the use of phosphoranimines (PAs), a class of linear, monomeric phosphazenes, as electrolytes for Li-ion battery applications has been investigated as a route to improve safety and stability for Li-ion batteries. Of the potential PAs for use in battery applications, this work focuses on the initial synthetic preparation and analysis of N-trimethylsilyl-P,P-bis((2-methoxyethoxy)ethoxy)-P-ethylphosphoranimine (PA-5). PA-5 has high LiPF6 solubility in excess of 2 M, high thermal stability with a melting point below -80°C and high thermal stability as a neat compound to at least 250°C. As part of electrolyte blends, the inclusion of PA-5 shifts the onset of thermal degradation by close to 40°C at 35% loading and by 20°C at a 10% loading, improves the low temperature performance of the electrolyte, and when used as a primary solvent leads to increases in the flash point (by 20°C) when compared to more traditional EC:EMC blends. Cycling capabilities of full-coin cells with graphite negative electrodes and Li 1+w [Ni 0.5 Mn 0.3 Co 0.2 ] 1-w O 2 positive electrodes using PA-5:EC:EMC electrolyte blends are comparable with the performance seen for traditional EC:EMC blends. Analysis of the impact of the use of additives such as vinylene carbonate in PA-5:EC:EMC blended electrolyte results in enhanced capacity retention and improved coulombic efficiency.

25 ENERGY STORAGE↗

Techno-economic analysis of carbon dioxide capture from low concentration sources using membranes

Rising carbon dioxide (CO 2 ) levels in the atmosphere lead to global warming, causing climate change. As such, carbon capture has become necessary to slow the increase and reduce CO 2 levels in the atmosphere. Point source emissions have a wide range of CO 2 concentrations, but emissions below 3% CO 2 have mostly been ignored because Carbon capture from these sources has been viewed as costly and economically unsustainable. Membrane technologies are considered the most viable solution by virtue of more energy-efficient operation. Our group at Idaho National Laboratory (INL) has developed poly[bis((2-methoxyethoxy)ethoxy)phosphazene] (MEEP)-based carbon dioxide selective membranes with CO 2 /N 2 selectivity greater than 40 and CO 2 permeability greater than 450 Barrer. To understand the economics of carbon capture, a spreadsheet-based techno-economic analysis (TEA) model was developed to consider multiple parameters, including selectivity and permeability of the membranes, performance conditions such as the number of stages, module material, electricity price, membrane price, and capital financing. The cost of carbon capture in US $\$$/metric ton was calculated at various purities and compared with other membrane processes, cryogenic capture, solvent-based capture, and pressure swing adsorption-based capture. It was determined that a MEEP-based three-stage process had a capture cost of US $\$$ 50.1/metric ton for 99.8% purity CO 2 from a 1% CO 2 feed source in nitrogen (N 2 ). In conclusion, the capture cost using the best performing Pebax-based membrane was 464% higher, cryogenic capture was 60%–140% higher, pressure swing adsorption was 55%–165% higher, and chemical absorption was -10%–110% higher than MEEP-based membrane capture, respectively.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗