In view of the fact that alkyl α-cyanoacrylates are usually prepared by thermal degradation of the corresponding polymers, the degradation of polycyanoacrylates under nitrogen at 230-160°C was investigated by means of a heat balance. The degradation velocity of the polymer decreased in the following order: when anionic polymerization products were used, methyl-> ethyl-> isopropyl-> n-butyl-> cyclohexyl-> 2-ethylhexyl-> isobutyl-; when products obtained from alkyl cyan-oacetes through coudensation with formaldehyde were used, ethyl-> methyl-> cyclohexyl-. The degradation velocities were found to be of the first order of the polymer for the cyclohexyl derivative and of the 1/2 order for the rest of the polymers. The effects of the polymerization degree on the degradation were clarified and the activation energies calculated.
Para- and o-hydroxybenzoic acids were obtained by heating potassium phenolate-carbon dioxide complex under the pressure of carbon dioxide at a temperature below 170°C by Kolbe-Schmidt reaction. The effects of the reaction temperature, reaction time, and initial pressure of carbon dioxide on the ratio of the p-isomer to the o-isomer formed have been clarified.
It was found that alkali phenoxides, insoluble in usual organic solvents, could be dissolved easily in aprotic-polar solvents such as N, N-dimethylf ormamide, dimethyl sulf oxide, and hexamethylphosphoramide at room temperature. Carbox-ylation of the phenoxides with carbon dioxide was thus investigated in those solvents. Alkali phenoxides were very readily carboxylated with carbon dioxide under pressure or even under atmospheric pressure to form p-hydroxybenzoic acid and salicylic acid.
Disperse dyes, 6-phenoxy-1, 4-disubstituted anthraquinones and 6, 7-diphenoxy-1, 4-disubstituted anthraquinones were prepared and their dyeing properties on acetate and Tetoron examined. The colors of dyed cloth varied from violet to blue. Their dyeabilities on Tetoron were good; particularly, 6-phenoxy-1, 4-disubstituted anthraquinones sho-wed excellent affinities to Tetoron in high temperature dyeing treatment. Their dyeabilities on acetate, however, were not satisfactory. The λmax of 6, 7-diphenoxy-1, 4-disubstituted anthraquinones in ethyl alcohol shifts toward longer wavelength than that of the corresponding 1, 4-disubstituted anthraquinones. Their light-fastness on acetate was good, and their abrasion-as well as wash-fastness was excellent. They, particularly 6, 7-diphenoxy-1, 4-disu-bstituted anthraquinones, showed good sublimation-fastness.
1-Cyclohexylamino-, 1-bromo-4-cyclohexylamino-, 1-amino-4-cyclohexylamino-and 1, 4-his (cyclohexylamino)-anthraquinones were synthesized from 1-chloroanthraquinone. Their visible absorption spectra in solution were measured and their dyeing properties on synthetic fibers evaluated. When compared with the corresponding amino-, methylamino-, isopropylamino-, and anilin oanalogs, etc., cyclohexylaminoanthraquinones showed the absorption peaks at longer wavelength. It thus seems that cyclohexylamino group is most effective in shifting the absorption maximum. In general, those visible absorption peaks appeared at longer wavelengths in nonpolar solvent such as benzene than in polar solvent such as ethanol. Their dyeing properties on synthetic fibers were of 2-3 grade, except that of 1, 4-his (cyclohexylamino) anthraquinone which is of 1 grade.