Syntheses and degradations of fluorinated heterocyclics III. Perfluoroalkyl and perfluoroalkylether-1,3,4-oxadiazoles

2,5-Bis(perfluoro-n-heptyl)-, 2-perfluoroalkylether-5-perfluoro-n-heptyl-, and 2,5-bisperfluoroalkylether-1,3,4-oxadiazoles were synthesized and characterized. 2,5-Bis(perfluoro-n-heptyl)-1,3,4-oxadiazole was thermally and hydrolytically stable at 325°C; however, in the presence of air, degradation took place at 235°C. The perfluoroalkylether analogue exhibited thermal and hydrolytic stability at 325°C; it was found to be unaffected by Jet-A fuel and air at 235°C. At 325°C in air some degradation occured as evidenced by volatiles production, oxygen consumption, and 96% starting material recovery.     

Reactions of sodium sulphide—I : With compounds containing hydroxyl groups

Aqueous solutions of sodium sulphide (ca 10%) reagent were reacted at 250° with compounds containing OH groups. This work was part of a programme designed to test the usefulness of the Na₂S solution degradation technique for determining the primary structure of humic acids. The compounds reacted here and the principal products detected (shown in brackets) were: cinnamyl alcohol (benzyl alcohol, benzoic acid, 3-phenylpropan-1-ol, 3-phenylpropionic acid), benzyl alcohol (little reaction), 3-phenylpropan-1-ol (little reaction), 1,2-dihydroxy-1-phenylethane (phenylacetic acid, acetophenone, 1-phenylethanol), catechol and hydroquinone (recovered starting compounds+ polymer products). Sodium hydroxide gave the same products with cinnamyl alcohol, but in different proportions. Possible mechanisms for these reactions are discussed.     

X-ray diffraction and morphology of crystalline,hard, elastic materials

Summary X-ray diffraction and electron microscopic results on several crystalline polymers which demonstrate elastic properties (polypropylene, Celcon^®, poly-4-methyl-pentene) are reported. Photographic small angle X-ray diffraction techniques provided considerable qualitative information, concerning the morphological features of these elastic materials both as extruded, annealed and during extension. Lamellar thickness, thickness distribution and perfection of lamellae could be estimated. Lateral order features and orientation of the lamellar structures were obtainable from the sharpness and length of the equatorial wide angle diffraction arcs. Electron microscopic results essentially confirm the morphological features postulated on the basis of the X-ray results. These morphological features are discussed in terms of a general structural model which appears consistent with the mechanical properties of these materials.

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Zusammenfassung Röntgenbeugung und elektronenmikroskopische Daten von einigen kristallinen Polymerprodukten mit elastischen Eigenschaften (Polypropylen, Celcon, Poly-4-methylpenten) werden berichtet. Die photographische Röntgen-Kleinwinkelmethode liefert wichtige qualitative Messungen der morphologischen Struktur dieser elastischen Materialien in den Zuständen sowohl wie hergestellt als auch nach Tempern und während des Dehnungsprozesses. Die Dicke der Lamellen, ihre Dikkenverteilung und die Güte der Lamellen konnten abgeschätzt werden. Die laterale Ordnung und die Orientierung der Lamellen kann aus Weitwinkelbeugungsdaten abgeleitet werden. Die Elektronenmikroskopie bestätigt die Morphologie, die aus Röntgendaten folgt. Ein allgemeines Strukturmodel dieser Morphologie, das im Einklang mit den mechanischen Eigenschaften dieser Produkte steht, wird diskutiert.

     

Modern Analysis

The important advances being made in modern analytical methods are indicative of the fundamental changes that are occuring in the theory and practice of “analytical chemistry”. “Information optimization” demands a new approach in teaching and research, and calls for the intergration of chemistry with other scientific and technical disciplines.     

Darstellung verschiedener 2,6-disubstituierter 4-Sulfanilamidopyrimidine 7. Mitt. über neue N1-substituierte Sulfanilamide

Zusammenfassung Im 2,6-Dichlor-4-aminopyrimidin wurden die beiden Chloratome wahlweise gemeinsam oder zweistufig gegen Alkoxyoder Alkylmercaptoreste ausgetauscht. Partiell reagiert bevorzugt das 2-ständige Halogenatom, während das 6-ständige derberer Bedingungen zum Umsatz bedarf. Die so erhaltenen gleichartig oder verschieden in 2,6-Stellung durch Alkoxy- bzw. Alkylmercaptoreste substituierten 4-Aminopyrimidine wurden mit N-Carbäthoxysulfanilsäurechlorid acyliert und durch alkal. Verseifung die entsprechenden 2,6-disubstituierten 4-Sulfanilamidopyrimidine gewonnen.     

Investigation of HfO(+) interference in the determination of platinum in a catalytic converter (cordierite) by inductively coupled plasma mass spectrometry

The determination of Pt in cordierite is subject to strong interference by spectral overlap from HfO(+) ions with all Pt isotopes. Two mathematical correction methods based on the HfO(+)Hf(+) ratio and a method for the chemical separation of Hf based on adsorption chromatography and isotope dilution were investigated to correct for this interference. Flow infection was used to prevent clogging of the cone orifice. To enhance the sensitivity and thus lower the detection limit, thermospray nebulization was used for sample introduction and the method was compared with pneumatic nebulization. In addition, the memory effects were evaulated for both systems. Analysis of artificial solutions (1 ng Pt ml(-1)) yielded results within 3% of the true value. Th Pt content (ca. 50 ng g(-1)) of a cordierite sample, previously exposed to exhaust gases, could be determined with precisions of about 10-25% and the results agreed with earlier determinations by other workers.     

Analysis and classification of individual outdoor aerosol particles with SIMS time-of-flight mass spectrometry

Individual aerosol particles sampled in the north of the city Karlsruhe were analysed with a TOF-SIMS instrument. The results confirmed the integral analysis of many particles [1]. In order to employ a signal pattern analysis of the negative secondary ions for the classification of organic compounds an earlier classification scheme for 5 keV Ar⁺ bombardment was found to be generally also applicable for the TOF-SIMS conditions. Two main classes of particles were distinguished, which consist of submicron mainly organic particles of vehicle traffic provenance on one side and coarse particles of geogenic sources on the other side. Additionally, the geogenic class could be devided into a fraction consisting of lime soil and a fraction with alumo-silicate soil. A quantification of the class population was performed by counting the particles of different type.     

Styrene emulsion polymerization: Particle-size distributions

Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments.     

Caracterisation physico-chimique de couches minces de polymere obtenues par decharge electrique dans des vapeurs de styrene

Thin polymer layers, obtained by polymerization of styrene vapour in an electrical discharge, are insoluble in solvents for usual polystyrene. However, characterization of the gas discharge polymer, by i.r. spectroscopy, by visible and near u.v. spectroscopy and by chemical microanalyses, show that this material is very near to ordinary polystyrene; this conclusion is further indicated by similarity of the glass transition temperatures of the polymers. However, there are some spectral differences, and an evident reactivity to oxygen and to atmospheric moisture.