Preparation and characterization of branched and linear sulfonated poly(ether ketone sulfone) proton exchange membranes for fuel cell applications

Branched sulfonated poly(ether ketone sulfone)s (Br‐SPEKS) were prepared with bisphenol A, bis(4‐fluorophenyl)sulfone, 3,3′‐disodiumsulfonyl‐4,4′‐difluorobenzophenone, and THPE (1,1,1‐tris‐p‐hydroxyphenylethane), respectively, at 180 °C using potassium carbonate in NMP (N‐methylpyrrolidinone). THPE, as a branching agent, was used with 0.4 mol % of bisphenol A to synthesize branched copolymers. Copolymers containing 10–50 mol % disulfonated units were cast from dimethylsulfoxide solutions to form films. Linear sulfonated poly(ether ketone sulfone)s (SPEKS) were also synthesized without THPE. The films were converted from the salt to acid forms with dilute hydrochloric acid. A series of copolymers were studied by Fourier transform infrared, ¹H‐NMR spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. The ion‐exchange capacity (IEC), a measure of proton conductivity, was evaluated. The synthesized Br‐SPEKS and SPEKS membranes exhibit conductivities (25 °C) from 1.04 × 10^?3 to 4.32 × 10^?3 S/cm, water swell from 20.18 to 62.35%, IEC from 0.24 to 0.83 mequiv/g, and methanol diffusion coefficients from 3.2 × 10^?7 to 4.7 × 10^?7 cm²/S at 25 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1792–1799, 2008     

Novel long chain unsaturated diisocyanate from fatty acid: Synthesis,characterization, and application in bio‐based polyurethane

A novel long chain linear unsaturated terminal diisocyanate, 1,16‐diisocyanatohexadec‐8‐ene (HDEDI) was synthesized from oleic acid via Curtius rearrangement. Its chemical structure was identified by FTIR, ¹H NMR, ¹³C NMR, and HRMS. This diisocyanate was used as a starting material for the preparation of entirely bio‐based polyurethanes (PUs) by reacting it with canola diol and canola polyol, respectively. The physical properties and crystalline structure of the PUs prepared from this diisocyanate were compared to their counterparts prepared from similar fatty acid‐derived diisocyanate, 1,7‐heptamethylene diisocyanate (HPMDI). The HDEDI based PUs demonstrated various different properties compared to those of HPMDI based PUs. For example, HDEDI based PUs exhibited a triclinic crystal form; whereas HPMDI based PUs exhibited a hexagonal crystal lattice. In addition, canola polyol‐HDEDI PU demonstrated a higher tensile strength at break than that of canola polyol‐HPMDI, attributed to the higher degree of hydrogen bonding associated with the former sample. Nevertheless, lower Young's modulus and higher elongation in canola polyol‐HDEDI PU were obtained because of the flexibility of the long chain introduced by the HDEDI diisocyanate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3302–3310, 2010     

Intermolecular Heterocoupling Reaction between N‐Sulfonylimines and Aliphatic Ketones Promoted by Samarium (II) Iodide

N‐sulfonylimines (1) were induced by samarium(II) iodide to produce radical anion intermediates (2) in situ, which were trapped by aliphatic ketones (4) to afford heterocoupling products β‐sulfonamido alcohols (5) in moderate to good yields under mild and neutral conditions.     

KF‐Melamine Formaldehyde Resin (KF‐MFR) as a Versatile and Efficient Heterogeneous Reagent for Aldol Condensation of Aldehydes and Ketones under Microwave Irradiation

KF‐Melamine formaldehyde resin (KF‐MFR) was demonstrated to be a highly efficient heterogenious catalyst for cross‐aldol condensation under microwave irradiation. In this synthesis, various aldehydes and ketones were condensed together in the presence of supported KF on melamine‐formaldehyde resin to afford different chalcone derivatives in good to excellent yields. KF‐MFR proved to have unique termal and chemical resistance and can be reused for many consecutive runs without remarkable loss in catalytic activity.     

Diastereoselective reductive amination of pyrazolidinyl alkyl ketones

Reductive amination of pyrazolidinyl alkyl ketones with sodium triacetoxyborohydride or sodium tripivaloyloxyborohydride takes place diastereoselectively with the formation of aminoalkylpyrazolidines of trans structure. The volume of the substituent in the borohydrides does not affect the ratio of stereoisomers. Dedicated to the memory of A. A. Potekhin, renowned teacher, scientist, and editor of journal “Chemistry of Heterocyclic Compounds” __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 691–698, May, 2008.     

Two-Sided Optimal Bounds for Green Functions of Half-Spaces for Relativistic <Emphasis Type="Italic">α</Emphasis>-Stable Process

The purpose of this paper is to find optimal estimates for the Green function of a half-space of the relativistic α -stable process with parameter m on ℝ ^d space. This process has an infinitesimal generator of the form mI–(m ^2/α I–Δ) ^α/2, where 0<α<2, m>0, and reduces to the isotropic α-stable process for m=0. Its potential theory for open bounded sets has been well developed throughout the recent years however almost nothing was known about the behaviour of the process on unbounded sets. The present paper is intended to fill this gap and we provide two-sided sharp estimates for the Green function for a half-space. As a byproduct we obtain some improvements of the estimates known for bounded sets. Our approach combines the recent results obtained in Byczkowski et al. (Bessel Potentials, Hitting Distributions and Green Functions (2006) (preprint). ), where an explicit integral formula for the m-resolvent of a half-space was found, with estimates of the transition densities for the killed process on exiting a half-space. The main result states that the Green function is comparable with the Green function for the Brownian motion if the points are away from the boundary of a half-space and their distance is greater than one. On the other hand for the remaining points the Green function is somehow related the Green function for the isotropic α-stable process. For example, for d≥3, it is comparable with the Green function for the isotropic α-stable process, provided that the points are close enough. Research supported by KBN Grants.     

A comparative study on aldol‐type condensation reactions of cyclic,acyclic and substituted cyclic ketones by the W(CO)6/CCl4/UV system

Aldol‐type condensation reactions of a number of cyclic, acyclic and substituted cyclic ketones were investigated using the W(CO)₆/CCl₄/UV system. The progress of the reactions was followed by IR and GC‐MS techniques. The cyclic ketone derivatives with β‐ and γ‐substituent gave the expected condensation products. However, the α‐substituted cyclic, acyclic and unsubstituted cyclic ketones with rings larger than six did not. Formation of [W]–ketone complexes with all of the ketones used was observed by FTIR. With respect to our studies, a mechanism involving an intermediate seven‐coordinate tungsten complex has been proposed. Copyright © 2005 John Wiley & Sons, Ltd.     

An improved theory of microwave open resonators

The analytic theory of microwave open resonators is improved here by means of solving the complex Airy equation, that the Q-value as well as the argument of field profile may be given accurately. The resonance conditions for open cavities with high and moderate Q-values are derived analytically. Theoreticl Q-values are well agreed with the measured ones from experiments.