The Vapor-Liquid Polycondensation of Cyclohexylphosphoric Dichloride with Hydroquinone

The vapor-liquid polycondensation of cyclohexylphosphoric dichloride with hydroquinone was investigated. The influence of the temperature, reaction time, base concentration, and molar ratio of reagents on the yield, inherent viscosity, and molecular weight of the obtained polymer was studied. Second order, central, composite, rotatable experimental design was used in order to carry out this work and to mark limits of the experimental field for optimal yields and high inherent viscosities.     

Structure of the Polymer Obtained from Bisphenol-A and Cl 2 P(O)CH 3

Using the step-by-step build-up approach, the possible conformations of compound PhOP(O)(Me)OPh(Me) 2 Ph were constructed and geometrically optimized. Among the obtained structures 32 conformations belonging to low, comparable energy levels were used to construct the most stable dimers and tetramers of the title polymer. The results allowed us to estimate the geometrical structure of the polymer.     

Synthesis of Mixed Alkylphosphites and Alkylphosphates

Some mixed phosphites having two different alkyl chain were obtained as forerunners for mixed phosphates Mixed dialkyl phosphates were obtained in good yields (40-80%) by phase transfer catalysis in liquid-liquid sistem, starting from different dialkyl phosphites and aliphatic alcohols. The reaction conditions were optimized in order to obtain good yields in phosphites and phosphates respectively. Compounds were analyzed by IR, P 31 -NMR.     

Polymeric Membranes Containing Phosphorus in the Chain for Solid Polymer Electrolytes

Abstract

Two new series of solid polymer electrolytes (SPEs) based on phosphorus containing (co)polyesters (PPE) and Lithium triflate were obtained. PPEs are composed of phosphonate moeties (cyclohexyldichlorophosphonate (CHDP)) as linking agent and two diols: PEG (6000) and poly(tetramethylene glycol) (PTMG) in PPE I, and PEG (6000) and 4,4′-cyclohexylidenebisphenol (bisphenol Z, BZ) in PPE II. Polycondensation was carried out in solution in the presence of triethylamine (TEA) as scavenger of HCl side product (PPE I–IIa) and in the absence of any acid acceptor (PPE I–IIb). The Limiting Oxygen Index (LOI) and thermal analysis were performed both on polymers and membranes. The ionic conductivity of SPE membranes based on PPE-salt complexes, with various salt concentrations, was investigated at different temperature and ionic transference numbers were determined. Optimum composition was obtained for the polymer which contains in structure only alkyl units and 15% Lithium triflate.     

ac-Driven double quantum dots as spin pumps and spin filters

We propose and analyze a new scheme of realizing both spin filtering and spin pumping by using ac-driven double quantum dots in the Coulomb blockade regime. By calculating the current through the system in the sequential tunneling regime, we demonstrate that the spin polarization of the current can be controlled by tuning the parameters (amplitude and frequency) of the ac field. We also discuss spin relaxation and decoherence effects in the pumped current.     

Cavity induced shift and narrowing of the positronium Lyman-α transition

We report experiments in which the line shape of the Lyman-alpha (1S-2P) transition was measured for positronium (Ps) atoms both inside and outside a porous silica target. The energy interval ΔE for confined atoms was observed to be larger than that of free Ps by 1.26±0.06 meV. A configuration interaction calculation yields results that are consistent with our ～5 nm sample, and suggests that ΔE decreases dramatically for larger cavity diameters. The linewidth of the transition, (0.066±0.004) nm (FWHM), is about half of what one would expect for free Ps at room temperature due to the Dicke line narrowing effect of confinement. Such measurements can be used to determine void sizes in porous films and Ps dynamics therein, and elimination of the Doppler spread of atoms in a porous film could be useful for the efficient excitation of a Ps gas.     

Bloch wave homogenization of a non-homogeneous Neumann problem

In this paper, we use the Bloch wave method to study the asymptotic behavior of the solution of the Laplace equation in a periodically perforated domain, under a non-homogeneous Neumann condition on the boundary of the holes, as the size of the holes goes to zero more rapidly than the domain period. This method allows to prove that, when the hole size exceeds a given threshold, the non-homogeneous boundary condition generates an additional term in the homogenized problem, commonly referred to as “the strange term” in the literature.     

Thermogravimetric characterization of styrene–divinylbenzene copolymers containing alpha-isopropylaminophosphonic acid groups

A commercial styrene–divinylbenzene copolymer was functionalized by multistep reactions with alpha-isopropylaminophosphonic acid groups. Three different functionalized copolymers were obtained in which the phosphonic groups are in meta (1E), para (2E), and ortho (3E) positions. The thermal behavior was studied using the TG/IR hyphenated technique and kinetic analysis of thermo-oxidation under nonisothermal conditions. The evolved gas analysis confirms the partial thermo-oxidative degradation of polymeric materials, with significant preservation of the aromatic ring. The kinetic analysis was performed by three methods: Friedman, Flynn–Wall–Ozawa, and nonparametric kinetic.     

Isolation of pure disubstituted E olefins through Mo-catalyzed Z-selective ethenolysis of stereoisomeric mixtures

Monoaryloxide-pyrrolide (MAP) complexes of molybdenum were employed for the selective ethenolysis of 1,2-disubstituted Z olefins in the presence of the corresponding E olefins. Reactions were performed in the presence of 0.02-3.0 mol % catalyst at 22 °C under 20 atm ethylene. We have demonstrated that the Z isomer of an easily accessible E:Z mixture can be destroyed through ethenolysis and the E alkene thereby isolated readily in high yield and exceptional stereoisomeric purity.     

A time discretization scheme of a characteristics method for a fluid–rigid system with discontinuous density

We propose a new characteristics method for the time discretization of a fluid–rigid system in the case when the densities of the fluid and the solid are different. This method is based on a global weak formulation involving only terms defined on the whole fluid–rigid domain. The main idea is to construct a characteristic function which preserves the rigidity of the solid at the discrete time levels. A convergence result for this semi-discrete scheme is then given.