Formation of peroxide compounds on the oxidation of lignin by oxygen in an organic solvent

The results are given of a determination of the steady-state concentrations of peroxide compounds on the oxidation of lignin by oxygen in dioxane. An iodometric method of determining peroxides was used, with spectrophotometric control of the amount of iodine formed. It was established that the achievable steady-state concentration of peroxide compounds on the oxidation of lignin is 0.28–0.44 wt. % of O_act (oxygen pressure 1 atm, temperature 50–80°C). With a rise in the temperature, the steady-state concentration of peroxide compounds decreased. The addition of water (30 vol. %) to the organic solvent led to an increase in the rate of accumulation of peroxide compounds. It has been shown that the presence of alkaline and acidic catalysts exerts no appreciable influence on the achievable steady-state concentration and the rate of accumulation of peroxide compounds during the oxidation of lignin.Bratsk Industrial Institute. All-Union Scientific Production Combine of the Pulp and Paper Industry, Leningrad. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 413–417, May–August, 1992.     

A polymer thin-film technique to study the micromorphology of core/shell latexes

A series of poly(styrene)/poly(styrene-co-acrylonitrile) core-shell latexes were synthesized by seeded emulsion polymerization. The dried latex was dissolved in toluene and then cast on the surface of water to form a very thin film (60–90 nm). Phase separation in the thin film was studied by transmission electron microscopy (TEM). Electron micrographs of these thin films yielded fine structure and interesting morphology that was unattainable by ultramicrotoming of the corresponding compression-molded specimens. Glass transition temperatures and percent grafted polystyrene were correlated with the TEM results. As grafting increases, mixing of the two phases improves, with the resulting T_g value being between the two T_g's of poly(styrene) and poly(styrene-co-acrylonitrile).     

Reaction gas chromatography/mass spectrometry. 2—the use of catalytic on-line dehydrogenation for the investigation of alcohols by gas chromatography/mass spectrometry

A method for structure determination of aliphatic alcohols within mixtures is described. It involves the use of a vapour phase dehydrogenation micro-reactor (Cu, 300°C) located between the chromatographic column and the mass spectrometer or between the injection port and the column. Since primary and secondary alcohols are converted into corresponding carbonyl compounds, they can be readily differentiated from tertiary alcohols and dialkyl ethers. An examination of the mass spectra of alcohols and carbonyl compounds permits the determination of molecular mass, the location of hydroxyl group and the determination of branching at the β-carbon atom.     

Fluoroaliphatic esters of fluorosulfonic acid. 4. Reactions of α-fluorosulfatoperfluoro ketones with nucleophilic reagents

-Fluorosulfatoperfluoroethyl isopropyl ketone I and fluorosulfatopentafluoroacetone II react with alkali metal chlorides and bromides to form the corresponding -haloperfluoro ketones as a result of direct nucleophilic substitution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2066–2069, September, 1990.     

(1-Adamantanethio)pyridines and tetrahydropyridines from the reaction of 1-adamantanethiol with pyridine I-oxide in acetic anhydride

The reaction of pyridine 1-oxide with 1-adamantanethiol in acetic anhydride produced a mixture of 2- and 3-(1-adamantanethio)pyridines, 1-aeetyl-2-(1-adamantanethio)-3-hydroxy-4-acetoxy-1,2,3,4-telrahydropyridine and the corresponding 3-acetoxyderivative. Pure substances were separated by means of column chromatography on alumina. The tetrahydropyridines were identified by means of their proton magnetic and mass spectra. 4-(1-Adamantanethio)pyridine was synthesized from 4-chloropyridinc and 1-adamantanethiol. The three isomeric (1-adamantanethio)-pyridines were, each, cleaved by concentrated hydrochloric acid to give 1-chloroadamantane and the corresponding pyridinethiol.