Preparation of phosphinated bisphenol from acid‐fragmentation of 1,1,1‐tris(4‐hydroxyphenyl)ethane and its application in high‐performance cyanate esters

We reveal a route for the preparation of phosphinated bisphenol, 1,1‐bis(4‐hydroxyphenyl)‐1‐(6‐oxido‐6H‐dibenz <c,e> <1,2> oxaphosphorin‐6‐yl)ethane (2) , via a one‐pot reaction of 1,1,1‐tris(4‐hydroxyphenyl)ethane and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) in the catalysis of p‐toluenesulfonic acid. A two‐step reaction mechanism, acid‐fragmentation of 1,1,1‐tris(4‐hydroxyphenyl)ethane followed by nucleophilic addition of DOPO, is proposed for the synthesis. Based on (2) , a dicyanate ester derivative, 1,1‐bis(4‐cyanatophenyl)‐1‐(6‐oxido‐6H‐dibenz <c,e> <1,2> oxaphosphorin‐6‐yl)ethane (3) was prepared and co‐cured with a commercially available dicyanate ester, the dicyanate ester of bisphenol A (BACY). Experimental data show that incorporating (3) into BACY enhances the flame retardancy and dielectric properties with little penalty to the thermal properties. A thermoset with T_g 274 °C, coefficient of thermal expansion (CTE) 49 ppm/°C, D_k 3.04 (1 GHz), T_d (5%,) N₂: 435 °C, air: 424 °C, and UL‐94 V‐0 rating can be achieved via this approach. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Characterizing fracture energy of proton exchange membranes using a knife slit test

Pinhole formation in proton exchange membranes (PEM) may be caused by a process of flaw formation and crack propagation within membranes exposed to cyclic hygrothermal loading. Fracture mechanics can be used to characterize the propagation process, which is thought to occur in a slow, time‐dependent manner under cyclic loading conditions, and believed to be associated with limited plasticity. The intrinsic fracture energy has been used to characterize the fracture resistance of polymeric material with limited viscoelastic and plastic dissipation, and has been found to be associated with long‐term durability of polymeric materials. Insight into this limiting value of fracture energy may be useful in characterizing the durability of proton exchange membranes, including the formation of pinhole defects. In an effort to collect fracture data with limited plasticity, a knife slit test was adapted to measure fracture energies of PEMs, resulting in fracture energies that were two orders of magnitude smaller than those obtained with other fracture test methods. The presence of a sharp knife blade reduces crack tip plasticity, providing fracture energies that may be more representative of the intrinsic fracture energies of the thin membranes. Three commercial PEMs were tested to evaluate their fracture energies (G_c) at temperatures ranging from 40 to 90 °C and humidity levels varying from dry to 90% relative humidity (RH). Experiments were also conducted with membrane specimens immersed in water at various temperatures. The time temperature moisture superposition principle was applied to generate fracture energy master curves plotted as a function of reduced cutting rate based on the humidity and temperature conditions of the tests. The shift with respect to temperature and humidity suggests that the slitting process is viscoelastic in nature. Also such shifts were found to be consistent with those obtained from constitutive tests such as stress relaxation. The fracture energy is more sensitive to temperature than on humidity. The master curves converge at the lowest reduced cutting rates, suggesting similar intrinsic fracture energies; but diverge at higher reduced cutting rates to significantly different fracture energies. Although the relationship between G_c and ultimate mechanical durability has not been established, the test method may hold promise for investigating and comparing membrane resistance to failure in fuel cell environments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 333–343, 2010     

Robust Kriging models in computer experiments

In the Gaussian Kriging model, errors are assumed to follow a Gaussian process. This is reasonable in many cases, but such an assumption is not appropriate for the situations when outliers are present. Large prediction errors may occur in those cases and more robust estimation is critical. In this article, we propose a robust estimation of Kriging parameters by utilizing other loss functions rather than classical L₂. In the Gaussian Kriging model, regression parameters are estimated by generalized least squares, which are also referred to as L₂ criterion. To make these estimators more robust to outliers, the L₁ and the ?-insensitive loss functions are introduced in place of L₂ in this article. Mathematical programming formulations are developed upon the idea of support vector machine. A machining experiment data are analysed to verify usefulness of the proposed method.     

On the convergence of the product of independent random operators

In this paper, we study infinite products of independent random operators. Conditions for the existence a.s. and the convergence in mean of order p of such infinite products are established.     

Bounds of <Emphasis Type="Italic">p</Emphasis>-adic weighted Hardy-Cesàro operators and their commutators on <Emphasis Type="Italic">p</Emphasis>-adic weighted spaces of Morrey types

In this paper we aim to investigate the boundedness of the p-adic weighted Hardy-Cesàro operators and their commutators on weighted functional spaces of Morrey type. In each case, we obtain the corresponding operator norms.     

A convenient and sensitive method for haloacetic acid analysis in tap water by on‐line field‐amplified sample‐stacking CE–ESI‐MS

In this study, we propose a simple strategy based on flow injection and field‐amplified sample‐stacking CE–ESI‐MS/MS to analyze haloacetic acids (HAAs) in tap water. Tap water was passed through a desalination cartridge before field‐amplified sample‐stacking CE–ESI‐MS/MS analysis to reduce sample salinity. With this treatment, the signals of the HAAs increased 300‐ to 1400‐fold. The LODs for tap water analysis were in the range of 10 to 100 ng/L, except for the LOD of monochloroacetic acid (1 μg/L in selected‐ion monitoring mode detection). The proposed method is fast, convenient, and sensitive enough to perform on‐line analysis of five HAAs in the tap water of Taipei City. Four HAAs, including trichloroacetic acid, dichloroacetic acid, dibromoacetic acid, and monobromoacetic acid, were detected at concentrations of approximately 1.74, 1.15, 0.16, and 0.15 ppb, respectively.     

Solvent-Polymer Interaction. II. Measurements of Liquid Solvent Molecules Associating with Polymer Sites and of Their Transport Behavior in Polymer Membrane by Thermogravimetry,GLC, and Mass Spectrometry

The measurement of sorption and diffusion behavior of liquid ethanol and water solvent mixtures in polyurethane membrane were made simultaneously by thermogravimetry. The individual amounts of sorbed water and ethanol in the polymer membrane were estimated by thermogravimetry and differentiated by mass spectrometry. In addition, from a single dynamic thermogravimetric experiment the activation energy for solvent molecules desorbing from the polymer membrane was also determined. The thermodynamic activity of ethanol vapor in equilibrium with the ethanol-water-polyurethane system was determined by gas-liquid chromatography. The clustering functions, the mean numbers of solvent molecules in the clusters, and those associating with polymer sites were evaluated by applying simplified mathematical derivatives using the experimentally determined values of activity and volume fraction of solvent molecules. It was found that at lower ethanol concentration the tendency for ethanol molecules to cluster together is high. At higher ethanol activity, ethanol-polymer site interactions predominantly occurred.

Similar results were observed for ethanol-water molecules. However, water molecules in this particular system did not exhibit a self-associating tendency nor interact with the polymer sites. It was concluded that the Zimm-Lundberg clustering theory can be adequately applied to the interpretation of sorption and diffusion behavior of liquid ethanol-water mixtures in the polymer membrane.