Triallyl Phosphate Research Articles

Unraveling the conformational landscape of triallyl phosphate: matrix isolation infrared spectroscopy and density functional theory computations.

The conformations of triallyl phosphate (TAP) were studied using matrix isolation infrared spectroscopy and density functional theory (DFT) calculations. TAP was trapped in N2, Ar, and Xe matrixes at 12 K using an effusive source and the resultant infrared spectra recorded. The computational analysis on conformers of TAP is a challenging problem due to the presence of the large number of conformations. To simplify this problem, conformational analysis was performed on prototypical molecules such as dimethyl allyl phosphate (DMAP) and diallyl methyl phosphate (DAMP), to systematically arrive at the conformations of TAP. The above methodology discerned 131 conformations for TAP, which were found to contribute to the room temperature population. The computations were performed using B3LYP/6-311++G(d,p) level of theory. Vibrational wavenumber calculations were performed for the various conformers to assign the experimental infrared features of TAP, trapped in solid N2, Ar, and Xe matrixes.

Development of Pyridine-Boron Trifluoride Electrolyte Additives for Lithium-Ion Batteries

A series of novel electrolyte additives based on Lewis acid/base adducts has been designed and successfully synthesized. The synthesis is very simple: a pyridine derivative is mixed with boron trifluoride dissolved in diethyl ether to yield a solid crystalline product. The effect of Pyridine-Boron Trifluoride (PBF) and its derivatives have been thoroughly evaluated in Li[Ni1/3Mn1/3Co1/3]O2/graphite and Li[Ni0.42Mn0.42Co0.16]O2/graphite pouch cells. Evaluation experiments, including high voltage storage, gas production, electrochemical impedance spectroscopy measurements, ultra high precision cycling and long-term cycling were carried out on cells containing the novel additives. The results were compared to baseline experiments on cells with well-known additives such as vinylene carbonate (VC), prop-1-ene sultone (PES), methylene methane disulfonate (MMDS), tris(-trimethyl-silyl)-phosphite (TTSPi) and triallyl phosphate (TAP). The PBF additives are competitive with all known additives in NMC/graphite cells, which, combined with their low cost and facile synthesis, suggest this series of novel additives will be useful in high-voltage/high-temperature lithium ion battery applications. The PBF additives yield cells which show excellent capacity retention and maintain low impedance during high voltage cycling, in contrast to cells containing VC.

Studies of the Effect of High Voltage on the Impedance and Cycling Performance of Li[Ni0.4Mn0.4Co0.2]O2/Graphite Lithium-Ion Pouch Cells

Li[Ni0.4Mn0.4Co0.2]O2 (NMC442)/graphite pouch cells containing various electrolyte additives, either singly or in combination, were studied using cycling experiments up to 4.4 and 4.5 V coupled with simultaneous electrochemical impedance spectroscopy (EIS) measurements. The impedance of most cells increased dramatically at 4.4 and 4.5 V, but was nearly reversible over one cycle. However, during continued cycling, the impedance of all cells slowly increased at all potentials. Electrolyte additives were found to dramatically affect this behavior. The impacts of adding prop-1-ene-1,3-sultone (PES), vinylene carbonate (VC), triallyl phosphate (TAP), methylene methane disulfonate (MMDS), ethylene sulfate (DTD) and/or tris(-trimethyl-silyl)-phosphite (TTSPi) to 1M LiPF6 ethylene carbonate:ethyl methyl carbonate (EC:EMC) electrolyte were studied. PES-containing cells had dramatically lower impedance and better capacity retention than VC and TAP-containing cells during both 4.4 and 4.5 V experiments. When MMDS, DTD and/or TTSPi were added in combination with PES, the performance was improved further. Finally, continuous charge-discharge cycling was compared to cycling with a 24-hour hold applied at the top of charge at 4.4 V. The high voltage hold led to severe impedance growth which could be partially overcome through the use of optimal additive combinations.

Thermal analyses of organic powders made from precipitation polymerization of triallyl monomers

Organic solids have been prepared from radical-initiated activation of solutions composed of tetradecane and triallyl trimesate (TAM) monomer or triallyl phosphate (TAP) monomer using a recently developed variation of precipitation polymerization methods. The powders, which comprise fused aggregates, are shown to be rich in monomer (83–88 wt% TAM or 86–92 wt% TAP), and are believed to be formed by a combination of hydrocarbon addition and allyl group oligomerization. TAM-g-tetradecane primary particles are on the order of 500 nm in diameter, while TAP-g-tetradecane particles are on the order of 100–200 nm diameter. These products are thermochemically assessed using a combination of differential scanning calorimetry, thermogravimetry and pyrolysis combustion flow calorimetry. The phosphorus-containing TAP-g-tetradecane shows exothermic activity around 230 °C, likely due to thermal decomposition of the trialkyl phosphate moiety, and may find use in advanced materials applications.

Chemical modification of PP architecture: Strategies for introducing long-chain branching

Two strategies for introducing long chain branching (LCB) to a polypropylene homopolymer (PP) are evaluated in terms of the product's molecular weight and branching distributions, and in terms of melt-state shear and extensional rheological properties. Single step processes involving radical-mediated addition of PP to triallyl phosphate are shown to generate bimodal products with highly differentiated chain populations, while a two step sequence involving PP addition to vinyltriethoxysilane followed by moisture-curing is shown to generate more uniform architectures. As a result, the sequential approach can improve low-frequency shear viscosity and extensional strain hardening characteristics while staying below the polyolefin's gel point. The composition and molecular weight distribution transformations that underlie sequential LCB techniques are discussed.

Selectivity of allylic coagent‐mediated polypropylene maleation

AbstractThe peroxide‐initiated cografting of maleic anhydride (MAn) and allylic coagents to polypropylene (PP) is described. Both triallyl trimesate (TAM) and triallyl phosphate (TAP) are shown to be compatible with MAn, as the presence of either coagent has no apparent effect on the yield or distribution of anhydride grafts within functionalized PP. Therefore, the influence of chain scission on the melt‐state rheological properties of maleated PP can be mitigated using coagent‐assisted crosslinking. The success of this cografting strategy for controlling melt viscosity is shown to depend on the extent that a bimodal, branched architecture can provide the rheological properties demanded by a given application. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers

Structure–rheology relationships of long-chain branched polypropylene: Comparative analysis of acrylic and allylic coagent chemistry

The relationship between product structure and melt-state rheological properties is established for series of branched PP derivatives prepared by the radical-mediated grafting of tri-functional coagents. Peroxide-initiated, solvent-free additions of linear PP to triallyl trimesate (TAM), trimethylolpropane triacrylate (TMPTA) and triallyl phosphate (TAP) at high temperature are shown to produce bimodal molecular weight and branching distributions. Low-frequency dynamic shear viscosities as well as extensional viscosities are shown to be highly responsive to a hyper-branched chain population, whose abundance and molecular weight correlate with the kinetic chain length of the grafting process, and the propensity of a coagent to oligomerize.

Effect of phosphorus flame retardants on thermo-oxidative decomposition of cotton

The effect of six organophosphorus compounds, including Pyrovatex CP (PCP), diammonium phosphate (DAP), phosphoric acid (PA), tributyl phosphate (TBP), triallyl phosphate (TAP) and triallyl phosphoric triamide (TPT) on the flame retardancy of cotton cellulose was studied. PCP, PA, and DAP are more efficient compared with the other three compounds in improving the limiting oxygen index (LOI) of cotton. The effectiveness of these compounds was investigated using scanning electron microscope (SEM) images of char formed after LOI tests, char content, activation energy of decomposition and heat of combustion data. SEM images showed that DAP, PCP and PA chars maintain the surface morphology during the burning process, which might be due to the formation of a protective layer or crosslinking effect. PA, PCP, and DAP treated fabrics have a higher activation energy of decomposition, higher char content and lower heat of combustion.

Effect of phosphorus and nitrogen on flame retardant cellulose: A study of phosphorus compounds

Three organophosphorus compounds, N-hydroxymethyl-3-dimethylphosphonopropionamide (HDPP), triallyl phosphate (TAP) and triallyl phosphoramide were employed in a study on flame retardant (FR) mechanisms. N-hydroxymethyl-3-dimethylphosphonopropionamide was more efficient in providing flame retardancy to cellulosic fabrics at the same phosphorus content on cotton fabrics. The flame retardance of the flame retardant treated cotton fabrics were characterized by using limiting oxygen index (LOI). Structural changes of the treated cotton fabrics and the compounds were carried out by using thermal analysis methods such as differential scanning calorimeter (DSC) and thermal gravimetric analysis and Fourier transform infrared (FTIR) spectroscopy. A new mechanism was proposed based on the efficient flame retardant performance of N-hydroxymethyl-3-dimethylphosphonopropionamide.

EPR investigations of gamma-irradiated triallyl compounds

The structure and the reactions of allyl radicals produced by γ-irradiation at 77 K of triallyl phosphate, triallyl borate, triallyl cyanurate and triallyl isocyanurate are reported. By variation of temperature and microwave power it was shown that the EPR spectra consist of a quartet and a quintet feature which are both assigned to allylic radicals. One radical (the quintet) is identified as the allyl radical C 3H 5. It is suggested to be formed by release from the radical anion or cation of the parent compounds. The other radical (the quarter) is formed by loss of an hydrogen atom from the precursors.

Phosphate, Phosphonate, and Phosphinate Complexes of Some Metal(II) Tetrafluoroborates

AbstractA number of anhydrous cobalt(II), nickel(II), and copper(II) tetrafluoroborate complexes of the ligands trimethyl phosphate, triethyl phosphate, triallyl phosphate, dimethyl methylphosphonate, diisopropyl methylphosphonate, dibutyl butylphosphonate and O,P‐dimethyl‐P‐phenylphosphinate have been prepared using a two step preparative procedure via the methanol complexes. For this type of ligand, this method gives better results than the usual one step procedure. The complexes are characterized with the aid of physical measurements such as ligand‐field spectroscopy.

Thermal decomposition studies of cotton radiolytically grafted with phosphorus- and bromine-containing flame retardants

Thermal analysis of cotton samples grafted with triallylphosphate (TAP) and 2,2,2-tribromoethyl acrylate (TBEA) was carried out. Grafting of poly-TAP causes a significant decrease in the decomposition temperature of cotton. The cotton decomposition is acid catalyzed by H3PO4 formed during the decomposition of the grafted poly-TAP. The HBr evolved during decomposition was monitored continuously during thermal analysis of cotton grafted with poly-TBEA. No significant flame-retarding effect by HBr was found. Since grafted poly-TBEA causes a decrease in the decomposition temperature of cotton, it is suggested that the flame retardant mechanism for poly-TBEA in cotton occurs mainly in the solid phase before most of the HBr is released.

Metal Complexes of Poly(Triallyl Phosphate)

AbstractPolymerization of triallyl phosphate results in an insoluble polymer that is capable of coordination to metal ions. The solid products obtained when the polymer was reacted with metal salts in water, ethanol and acetone were studied with the aid of spectroscopic techniques. The stoichiometry of the products depends on the concentration of the metal salt and the nature of the solvent used in the preparation. The final products can be described as species M(p ‐ TAP)m (anion)n, M = Mg, Mn, Co, Ni, Cu, Zn, Cd(II), Fe(III); p ‐ TAP = one unit of the polymer; anion = ClO4−, BF4−, NO3− Cl−, I−, NCS−; n = 2,3; m = 2‐4. The composition and structure(the first coordination sphere) of the final products are similar to those found for monomeric phosphoryl ligands.

ChemInform Abstract: ALLYLATION OF NUCLEIC ACID BASES WITH TRIALLYL PHOSPHATE

AbstractUracil bzw. Thymin (I) reagieren mit Triallylphosphat (II) zu den 1‐Allylderivaten (III).

Allylation of Nucleic Acid-Bases with Triallyl Phosphate

Abstract Triallyl phosphate alkylated uracil (N-1), thymine (N-1), cytosine (N-1), adenine (N-3 and N-9), and guanine (presumably N-1 or N-7) in a water solution at 60 °C (pH values were 10–10.5 for uracil, thymine, cytosine, and adenine, and 12 for guanine), giving the corresponding allyl derivatives in considerable yields.

Ion-selective polymeric-membrane electrodes with immobilised ion-exchange sites. Part I. Development of a calcium electrode

A new type of ion-selective electrode is described in which ion-exchange sites are immobilised in a polymeric membrane by covalent bonding. Membranes were prepared by cross-linking a styrene-butadiene-styrene triblock copolymer with triallyl phosphate. After subsequent hydrolysis these membranes were evaluated as Ca2+ sensors. The electrodes formed exhibited an extended Nernstian response to Ca2+(10–1– 10–6M) and good selectivity over other alkaline earth and alkali metals. Such electrodes offer very fast response times, extended lifetimes and a wide pH working range. The possibilities of this new class of ion-selective electrode are also discussed.

Electron-Beam-Initiated Grafting of Flame Retardants to Fabrics Containing Cellulose. I. Reaction Rate Studies

Abstract Triallyl phosphate (I), bis(β-chloroethyl) vinyl phosphonate (II), and a multi-functional condensate of n were grafted to cotton and rayon fabrics and the grafted products screened for potential flame retardancy. Grafting was initiated by a 48 × 6 in. electron beam, in air, from a 550 kV, 20 mA accelerator powered by an insulated core transformer, with a dose rate of approximately 1 Mrad/sec. The monomers were either copolymerized in untreated fabric with N-methylol acrylamide as a coreactant or were copolymerized with pendant double bonds in fabric that had been acrylamidomethylated in a prior step.

Biosynthesis of mercapturic acids from allyl alcohol, allyl esters and acrolein.

1. 3-Hydroxypropylmercapturic acid, i.e. N-acetyl-S-(3-hydroxypropyl)-l-cysteine, was isolated, as its dicyclohexylammonium salt, from the urine of rats after the subcutaneous injection of each of the following compounds: allyl alcohol, allyl formate, allyl propionate, allyl nitrate, acrolein and S-(3-hydroxypropyl)-l-cysteine. 2. Allylmercapturic acid, i.e. N-acetyl-S-allyl-l-cysteine, was isolated from the urine of rats after the subcutaneous injection of each of the following compounds: triallyl phosphate, sodium allyl sulphate and allyl nitrate. The sulphoxide of allylmercapturic acid was detected in the urine excreted by these rats. 3. 3-Hydroxypropylmercapturic acid was identified by g.l.c. as a metabolite of allyl acetate, allyl stearate, allyl benzoate, diallyl phthalate, allyl nitrite, triallyl phosphate and sodium allyl sulphate. 4. S-(3-Hydroxypropyl)-l-cysteine was detected in the bile of a rat dosed with allyl acetate.

A Laboratory Study of Flame-Retardant Textiles Produced by an Ionizing Radiation Cure

Methods for polymerizing triallyl phosphate on a cotton fabric were examined under conditions feasible for application in a commercial radiation textile finishing process. Although triallyl phosphate does not polymerize with irradiation at low dose levels at room temperature in air under the specific conditions described, it was found that copolymerization of triallyl phosphate with acrylic acid derivatives can be used to produce flame-resistant cotton fabric. A cotton fabric treated with triallyl phosphate and N-methylol acrylamide and exposed to 2 megarads of radiation from high-energy electrons, in air at room temperature produced a flame-resistant fabric durable to 15 accelerated cotton mobile launderings.

Heat Transferred by Decomposition Products from Cotton Fabrics Exposed to Intense Thermal Radiation

Heat is transferred to skin protected against intense thermal radiation by several mechanisms. Textile fabrics provide considerable protection but some of them tend to decompose, producing tars which condense on the skin. The amount of energy trans ferred by tars from cotton fabrics was estimated by determining the amount of tar deposited and the amount of energy required to re-evaporate the tar. Two fabrics were used; one untreated, the other fire resistant treated (FR) with brominated triallyl phosphate. The energy amounts to about 500 cal for each gram of tar evaporated and is about the same for the two fabrics. Over the range of interest, the amount of tar deposited increased with increase in exposure. For fabric in contact with a skin simu lant, the energy transferred by this mechanism varied up to 1 cal cm-2 of fabric; for the spaced arrangement, up to 1.5 to 2 cal cm-2. For low and intermediate exposures, the energies transferred by the tar were about the same for the two fabrics; at the highest exposures, the values were considerably greater for the FR treated fabric. At exposures which produce disabling burns, the heat transferred by the tars is negligible for fabric in contact with the skin but for fabrics spaced from the skin, the tars may account for a fourth or more of the total energy transferred. Without this energy, the burn would be greatly reduced.