Determination of dispersive and nondispersive components of the surface free energy of glass fibers

The dispersive component _s ^d of the surface free energy of glass fibers and its interaction energy with alkanes, benzene, 1-nitropropane, ethyleneglycol, glycerol, formamide, and water were quantitatively determined by the tensiometric method within two liquids. The values of nondispersive interaction energy I _SL ^p were found to be a linear function of the square root of the nondispersive component of the surface free energy of liquids. This suggests that the nondispersive interaction energy may be represented by the geometric mean of the nondispersive component of the surface free energy of a solid and a liquid. The slope gave the nondispersive component _s ^p of the surface free energy. The _s ^p values are 33 and 14 mJ/m² for the untreated and aminosilane-treated fibers, respectively, suggesting that organophilic character has developed on the surface after aminosilane treatment. The _s ^p value was almost similar after the treatment, probably because of the polar characteristics of amino groups.     

Paterno-Buchi photocyclization of 2-siloxyfurans and carbonyl compounds. Notable substituent and carbonyl (Aldehyde vs ketone and singlet- vs triplet-excited state) effects on the regioselectivity (Double-bond selection) in the formation of bicyclic exo-oxetanes

Paterno-Buchi coupling, photochemical [2 + 2] cycloaddition, of carbonyl compounds 2a-f with 2-siloxyfurans 1a-d has been investigated in detail. The stereoselective formations of exo-oxetanes 3 and 4 were observed in high yields. The regioselectivity (double-bond selection, 3 vs 4) was found to be largely dependent upon the carbonyls, the substituents at the furan ring, and the excited state of the carbonyls (singlet vs triplet). The photoreaction of aldehydes 2a-c gave bicyclic exo-oxetanes 3 and 4 at regio-random, independent upon their excited states and the substituents at furan ring. However, the photoreaction of the triplet state of ketones 2d-f was found to give regioselectively exo-oxetanes 4, except for the 4-methyl-2-siloxyfurane 1d case. The singlet-excited state of acetone 2f gave both oxetanes 3 and 4 at regio-random. For the singlet-state photochemistry, the approach direction of the electrophilic oxygen of the excited carbonyls to the furan ring is proposed to be an important factor for the exo-stereoselection. The Griesbeck model can rationalize the regio- and exo-selective formation of oxetanes in the triplet-state photoreaction.     

Liquid-liquid extraction of copper (I) and copper (II) as ion-paired complexes with acyclic 2-thienyl-containing polythioether and triphenylmethane dye anion

Three acyclic polythioethers containing 2-thienyl units at both ends were synthesized and the effect of substituent on the extraction of copper(II) was studied. The methyl groups in the terminal thiophene ring have imparted an appreciable degree of increase in the percent extraction of copper(II), while the introduction of chlorine atoms into the 2-thienyl unit resulted in the reverse effect. Among the counter dye anions examined, tetrabromophenolphthalein ethylester was the best one for copper(II) extraction. The composition of extracted species was evaluated to be 122 (Cu(II)/polythioether/dye anion). Quantitative extraction of copper(I) was attained as complexes with various triphenylmethane dyes, i.e., bromocresol green, bromothymol blue, bromo-phenol blue and pyrogallol red. Copper(I) in organic phase was completely back-extracted with 2 mole/l sulfuric acid containing 10% hydrogen peroxide.