Random homogeneous sodium sulfonate polysulfone ionomers: Preparation,characterization, and blend studies

The sodium salts of randomly sulfonated polysulfone (Na-SPSF), derived from 1,1′-sulfonylbis-[4-chlorobenzene] with 4,4′-(1-methylethylidene)-bis-[phenol], were prepared over the composition range of 3–30 mol% sodium sulfonate, using improved procedures in which the sulfonating complex was introduced into an intensely agitated polymer solution. In contrast to earlier work, T_g was found to increase nonlinearly with sodium sulfonate content. A SAXS study provided no evidence of ionic clustering in these polymers. Binary blends of Na-SPSFs differing only in composition were prepared by casting films from solution, and their phase behavior was studied by dynamic mechanical analysis after annealing at 250°C. It was found that the blends were miscible up to a composition difference of about 9–10 mol% sodium sulfonate. Using this fact it was possible to calculate a value for χ_ABn of 200–250, where χ_AB represents the segmental interaction parameter between unmodified and modified repeat units, and n is the degree of polymerization. Uncertainty in the degree of ionic association places a degree of uncertainty on the effective value of n and therefore on χ_AB. The product, however, is independent of any assumptions regarding molecular associations.     

Kinetics of the reactions of the hydroxyl radical with dimethyl ether and diethyl ether

Absolute rate coefficients for the reactions of the hydroxyl radical with dimethyl ether (k₁) and diethyl ether (k₂) were measured over the temperature range 295–442 K. The rate coefficient data, in the units cm³ molecule^?1 s^?1, were fitted to the Arrhenius equations k₁ (T) = (1.04 ± 0.10) × 10^?11 exp[?(739 ± 67 cal mol^?1)/RT] and k₂(T) = (9.13 ± 0.35) × 10^?12 exp[+(228 ± 27 kcal mol^?1)/RT], respectively, in which the stated error limits are 2σ values. Our results are compared with those of previous studies of hydrogen-atom abstraction from saturated hydrocarbons by OH. Correlations between measured reaction-rate coefficients and C? H bond-dissociation energies are discussed.     

Dressed energy of the XXZ chain in the complex plane

We highlight what seems to be a remaining subtlety in the argument for the cancellation of the total anomaly associated with the M5-brane in M-theory. Then, we prove that this subtlety is resolved under the hypothesis that the C-field flux is charge-quantized in the generalized cohomology theory called J-twisted cohomotopy.

     

Novel methods to functionalize thiazolo[4,5-c]pyridines

Novel substituted thiazole[4,5-c]pyridines have been synthesized in good yields from unsubstituted thiazole[4,5-c]pyridine using direct C-H coupling reactions and N-oxide rearrangement chemistry.