Evaluation of the residual stability of polyurethane automotive coatings by DSC

Degradation of poly(ester-urethanes), poly(ether-urethanes) and poly(acrylic-urethanes), as a base for automotive paintings in interior applications, has been studied by DSC. The samples were clearcoat and black-pigmented paints, unstabilized and stabilized with HALS Tinuvin 292, UV absorber Tinuvin 1130 and antioxidant Hostanox O3, exposed to weathering in Xenotest and in Arizona desert. From the dependences of oxidation onset temperature on the heating rate, the kinetic parameters enabling to calculate the oxidation induction time for a chosen temperature have been obtained. From the values of oxidation induction time, the protection factors of the additives and the residual stability of the polymer after an ageing stress has been evaluated. It has been shown that the equivalence between the two methods of weathering depends on the polymer composition. A new criterion for the evaluation of synergism/antagonism of additives in the stabilizing mixture has been proposed.     

Low-dimensional Compounds Containing Cyano Groups. XIII. Structural–spectral Correlation of Copper Dicyanoargentates

The new mixed-valence mixed-metal complex Cu(py)₆Cu₂Ag₂(CN)₆ (py = pyridine) possesses a three dimensional polymeric crystal structure. The Cu(I) atom is tetrahedrally coordinated by two nitrogen atoms of pyridine molecules, by one nitrogen atom of the dicyanoargentate anion and by one carbon atom of the cyano group. Both the dicyanoargentate anion and the cyano group bridge the Cu(I) atom with neighboring Cu(II) atoms. These are hexacoordinated in the form of an elongated tetragonal bipyramid. The equatorial plane is formed by two nitrogen atoms from two pyridine molecules and two nitrogen atoms from bridging cyano groups. Axial positions are occupied by nitrogen atoms of the bridging [Ag(CN₂]⁻ anions. Correlation between structures of the title compound and seven other dicyanoargentates with their i.r. spectra has been studied. The coordination mode of [Ag(CN₂]⁻ anions in compounds Cu_8-xAg_x(tn)₃(CN)₁₀ x = 0.25, Cu(3-Mepy)₂Ag₂(CN)₄, Cu(py)₂Ag₂(CN)₄ and Cu(py)₄Ag₂(CN)₄ (tn is 1,3-diaminopropane, 3-Mepy is 3-methylpyridine) is predicted based on this correlation.     

Neighbouring group participation in formation of condensed azines. Formation of pyrazolo(3,4-b)pyrazines,isoxazolo(4,5-b)pyrazines and isothiazolo(5,4-b)pyridine

Pyrazine- and pyridinecarboxamidoximes with an amino, potentially tautomeric hydroxy or mercapto group inortho position could be transformed in the appropriate condensed azines. In this manner, representatives of pyrazolo(3,4-b)pyrazine, isoxazolo(4,5-b)pyrazine and isothiazolo(5,4-b)pyridine ring system were synthesized and some transformations investigated.Presented in part at the 8th International Congress of Heterocyclic Chemistry, Graz, 1981.     

Strukturanalyse organischer Sulfide mit Hilfe der Gras-Chromatographie

Zusammenfassung Eine Methode der Identifizierung von Alkyl- und Arylgruppen organischer Sulfide wurde ausgearbeitet, die die Spaltung dieser Stoffe mit Raney-Nickel zur gaschromatographischen Bestimmung der dabei entstandenen Kohlenwasserstoffe ausnützt.

---

Summary A method was developed for identifying alkyl- and aryl groups of organic sulfides. The method employs the cleavage of these materials with Raney nickel for the gas chromatographic determination of the resulting hydrocarbons.

---

Résumé On a mis au point une méthode d'identification des groupes alkylés et arylés des sulfures organiques exploitant la dissociation de ceux-ci par le nickel Raney pour le dosage par chromatographic en phase gazeuse des carbures d'hydrogène qui se forment.

---

---

Die Autoren danken den Kollegen Dr.M. Veea, Ing.J. Petránek und Ing.J. Gaspari für die Überlassung von Proben organischer Sulfide.     

Influence of the composition of perovskites based on SrMnO<Subscript>3</Subscript> on their catalytic properties in the oxidative coupling of methane

The oxidative coupling of methane (OCM) in a periodic regime over the SrMnO₃ and its derivatives has been investigated. It has been established that partial replacement of the strontium ion by alkali metal ions leads to an increase in both catalytic activity and in selectivity with respect to higher hydrocarbons. Comparison of the results obtained in the present work with those obtained earlier for catalysts based on SrCoO₃ led to the conclusion that the Co-containing catalysts were preferable to the Mn-containing catalysts for carrying out oxidative coupling of methane in a periodic regime.__________Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol. 41, No. 1, pp. 30–34, January–February, 2005.     

The study of degradable polystyrene: Photolysis in solution and photo-oxidation in films

Radical copolymerization of styrene with benzalacetophenone or benzalacetone in bulk or in suspension yielded copolymers with as much as 10 wt% of carbonyl monomer. They were characterized by GPC, viscometry and spectroscopy. Photolysis of copolymers was investigated in benzene at 313 nm. Quantum yields for main chain scissions were about 0.005 and the life-time of the triplet state was 5 nsec. Photo-oxidation in films was followed by monitoring the decrease in molecular weight and by i.r. and emission spectra. Quantum yield for main chain scission in films was about 0.0002. During photooxidation in film, the molecular weight distribution widened. A new i.r.-band appeared at 3580 cm^?1 and the carbonyl band was spread between 1700 and 1800 cm^?1. In the emission spectra, the vibrational resolved emission (typical of the carbonyl chromophore) disappeared.     

Combination of flow injection analysis and voltammetry

The flow injection analyzer for students, teaching and research (FIAstar) is used in conjunction with a new micropool mercury flow-through electrode, to explore the possibilities offered by using d.c. polarography, rapid scan and amperometric titrations on a dispersed sample zone in motion. The work outlines the principles of the use of a scanning detector for investigation of the concentration gradients and chemical reactions taking place during the dispersion of sample solution within a carrier stream. The data, which are collected in real time, are displayed in three-dimensional diagrams.     

Bedeutung der GC-Detektoreigenschaften

Ohne Zusammenfassung

---

---

     

Polarographische Bestimmung des Pyridoxols in pharmazeutischen Präparaten

Zusammenfassung Es wird eine neue polarographische Methode zur direkten Bestimmung des Pyridoxols in Injektionspräparaten und Tabletten beschrieben. Die ausgearbeitete Methode beruht auf der polarographischen Reduktion des Pyridoxolmoleküls im Milieu von Ammoniak-Ammoniumchlorid-Puffern und weiter auf der Bildung einer katalytischen Stufe des Pyridoxols in Veronalpuffern. Die polarographische Methode ist rascher und in manchen Fällen genauer und empfindlicher als die bisher in Gebrauch stehenden Methoden. Die Anwesenheit der in den Präparaten laufend vorkommenden Begleitstoffe des Pyridoxols stört nicht die polarographische Bestimmung. Die Methode kann auch zur Bestimmung des 3-Hydroxy-4-methoxymethyl-5-oxymethyl-2-methylpyridins benutzt werden, das ein Zwischenprodukt bei der Pyridoxolerzeugung ist.

---

Summary A new polarographic method is described for the direct determination of pyridoxol in injection preparations and tablets. This method is based on the polarographic reduction of the pyridoxol in ammonia-ammonium chloride buffer medium and also on the formation of a catalytic stage of the pyridoxol in veronal buffers. The polarographic method is faster and in many cases more accurate and more sensitive than the methods now in use. The presence of the materials which always accompany the pyridoxol in the preparations does not interfere with the polarographic determination. The method can likewise be used for determining 3-hydroxy-4-methoxymethyl-5-oxymethyl-2-methylpyridine, which is an intermediate product in the manufacture of pyridoxol.

---

Résumé On décrit une nouvelle méthode polarographique pour le dosage direct du pyridoxol dans les préparations pour injections et dans les comprimés. La méthode élaborée repose sur la réduction polarographique de la molécule de pyridoxol dans le milieu tampon ammoniaque-chlorure d'ammonium, et, en outre, sur la formation d'une phase catalytique du pyridoxol dans les tampons au véronal. La méthode polarographique est plus rapide et dans de nombreux cas plus exacte et plus sensible que les méthodes utilisées jusqu'ici. La présence d'impuretés existant couramment dans les préparations à côté du pyridoxol ne gêne pas le dosage polarographique. On peut aussi utiliser la méthode pour le dosage de l'hydroxy-3 méthoxyméthyl-4 oxyméthyl-5 méthyl-2 pyridine, substance intermédiaire dans la préparation du pyridoxol.

---

---

Herrn Dr.P. Zuman danken wit für Ratsehläge bei der Abfassung dieser Arbeit.