Polychlorinated polyamides. II. Synthesis and characterization of polyamides derived from 2, 5-dichloroterephthaloyl dichloride and perchloroterephthaloyl dichloride

New thermally stable polyamides were prepared by interfacial polymerization of the title compounds and various aliphatic and aromatic diamines. The polymers were characterized by infrared spectrometry, elemental analysis, and differential scanning calorimetry. The molecular weights of the polymers were estimated by viscosity measurements. The influence of the halogen content on the thermal properties and degree of polymerization of the polymers was studied. One of the polyamides was fractionated to determine the degree of polydispersity.     

The application of multivariate techniques to data from spanish glass-making objects from the Roman Era

Three multivariate techniques (principal components analysis, correspondence factor analysis and spectral map analsis) are applied to x-ray fluorescence data from glass-making objects from the 5th century AD found in Tarragona (Tarraco in the Roman Empire). The information obtained by displaying th eobjects and variables in each reduced factor space is compared. The presence of redundant information is shown. The visualization of groups of objects and of the relationship between objects and variables allows the formulation of hypotheses concerning the origin of the samples and the presence of local glassworks.     

Flow injection reagent introduction by supported liquid and nafion membranes: determination of phosphate

The use of membrane tubing for the introduction of reagents for the determination of phosphate in waters by flow injection analysis was studied. The use of membranes eliminates the need for confluence points in the design of flow injection manifolds. This increases the sensitivity of the manifold by providing a sufficient reagent excess for the reaction without diluting the sample. Methods for the introduction of acid, molybdate and hydrazine were devised for the determination of phosphate by the Molybdenum Blue method. Several membranes were examined and Nafion and Accurel (microporous polypropylene) were found to be most useful. Molybdate introduction was achieved using a supported liquid membrane (SLM). Calibration was linear and a detection limit of 12 ppb phosphate (4 ppb phosphorus) was obtained.     

Synthese von 8-Alkylamino-8-aryl-1,2,3,4,5,6-hexathiocan-7-thionen

Zusammenfassung Durch gemeinsame Einwirkung von primären aliphat. Aminen und Schwefel auf Methylarylketone in Methanol bei Raumtemp. erhält man in meist guten Ausbeuten 8-Alkylamino-8-aryl-1,2,3,4,5,6-hexathiocan-7-thione (1a-h). Die Umsetzung von 1,4-Diacetylbenzol mit n-Propyl-bzw. n-Butylamin und Schwefel liefert Phenylen-1,4-di-hexathiocanderivate (3 a, b).Bei der Reaktion von Acetophenon mit 3-N,N-Diäthylaminopropylamin und Schwefel entstehen neben dem 8-(3-N,N-Diäthylaminopropylamino)-8-phenyl-1,2,3,4,5,6-hexathiocan-7-thion (1e) 51% einer Verbindung der Summenformel C₁₅H₂₂N₂S₂ (2), der die Struktur der (3-N,N-Diäthylaminopropylimino)-phenyldithioglyoxylsäure zugeordnet wird.1 e läßt sich durch Behandlung mit wäßr. Natriumsulfit-Lösung zu2 abbauen,2 durch Reaktion mit Schwefel wieder in1 e überführen.

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Synthesis of 8-alkylamino-8-aryl-1,2,3,4,5,6-hexathiocan-7-thiones (Joint action of elemental sulfur and gaseous ammonia upon ketones, LXXVIII: Action of sulfur and amines on acetophenone, IX)

8-Alkylamino-8-aryl-1,2,3,4,5,6-hexathiocan-7-thiones (1a toh) are obtained mostly in good yields by the concomitant action of primary aliphatic amines and sulfur upon methyl aryl ketones in methanol at room temperature. Reaction of 1,4-diacetyl benzene and sulfur with n-propylamine or n-butylamine respectively leads to phenylene-1,4-dihexathiocane derivatives (3 a, b).Besides 8-(3-N,N-diethylaminopropylamino)-8-phenyl-1,2,3,4,5,6-hexathiocan-7-thione (1 e), which is obtained by reaction of acetophenone with 3-N,N-diethylaminopropylamine and sulfur, a product with the formula C₁₅H₂₂N₂S₂ (2) is isolated in 51% yield, to which the structure (3-N,N-diethylaminopropylimino)phenyl dithioglyoxylic acid is assigned. By treatment of1 e with aqueous sodium sulfite solution2 is obtained, which can be transformed back into1 e by reaction with sulfur.

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77. Mitt.:F. Asinger, A. Saus, H. Offermanns undP. Scherberich, Ann. Chem.753, 151 (1971).

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8. Mitt.:F. Asinger, A. Saus, H. Offermanns undF. Abo Dagga, Ann. Chem.723, 119 (1969).

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Teil der DiplomarbeitJ. Hartig, Techn. Hochschule Aachen, 1969.     

Studies on the photooxidation mechanism of polymers. IV. Effect of ultraviolet light (2537 Å) on solid PVC particles suspended in different liquids

The photolysis of virgin PVC powder suspended in water, methanol, n-hexane, aqueous NH₄OH (30 wt-%), and 0.1 wt-% iodine in methanol and also as dry powder was studied. The mechanism of photolysis of PVC powder has been investigated by using ESR spectroscopy, conductivity titration, gel-permeation chromatography (GPC), and absorption spectroscopy. Photolysis of PVC has been found to occur by a free-radical mechanism. ESR spectroscopy permits a partial identification of several different types of free radicals in PVC such as alkyl, polyenyl, and peroxy radicals. An interpretation is proposed of the mechanism of formation of conjugated polyene structures, and also a new explanation of the crosslinking mechanism, in which transfer of unpaired electrons to double bonds occurs, is suggested. It has also been found that conjugated double bonds can photosensitize free-radical formation as a result of increased ultraviolet absorption due to polyene structures.     

Interaction of polyvinylpyrrolidone and iodine

A nonsolvent preparation of the polyvinylpyrrolidone (PVP) complex provides new insight into the nature of the polymer-iodine interaction. The preparation is obtained by simply mixing PVP with crystalline iodine and is of interest because it provides a system in which no interfering ions are present and only one type of iodine is initially present. The iodine is shown to undergo hydrolysis with moisture in the polymer to give iodide and hypoiodite. The ionic forms of iodine appear to associate with the molecular iodine, resulting in the final stable PVP-iodine complex.     

Buchbesprechungen

Ohne Zusammenfassung     

Neue Derivate der 2-Phenyl-benzo[b]thiophen-3-carbonsäure

Zusammenfassung 2-Phenyl-5-methoxy-benzo[b]thiophen-3-carbonsäure und 2-Phenyl-5,6-dimethoxy-benzo[b]thiophen-3-carbonsäure wurden durch Ringschlußreaktionen hergestellt und in eine Reihe von Säureamiden und basisch substituierten Estern übergeführt.

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New derivatives of 2-Phenyl-benzo[b]thiophene-3-carboxylic acid

2-Phenyl-5-methoxy-benzo[b]thiophene-3-carboxylic acid and 2-phenyl-5,6-dimethoxy-benzo[b]thiophene-3-carboxylic acid, prepared by ring closure reactions, were used for the synthesis of amides and of basically substituted esters.

     

Zur Ermittlung und rechnerischen Überprüfung thermodynamischer Daten aus experimentell gefundenen Werten, 12. Mitt.: Ein Programm zum Ausgleich von Dampfdruckdaten

Zusammenfassung Es wird ein Rechenprogramm zur Ermittlung der Konstanten der Dampfdruckgleichung nachvan Laar beschrieben. Als Ausgleichsbedingung kann sowohl die kleinste Summe der Quadrate der absoluten, wie auch der relativen Fehler benützt werden. Das Programm wurde in FORTRAN IV für die UNIVAC-490 des Rechenzentrums Graz erstellt

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Determination and verification by calculation of thermodynamic data from experimentally obtained values, XII: A computer program for the calculation of vapor pressure parameters

A computer program for the calculation of the parameters of thevan Laar vapor-pressure equation is presented. A least square approach of the absolute or of the relative deviations can be used.

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1.–6. Mitt.:F. Gölles. Mh. Chem.92, 981 (1961);93, 191, 201 (1962);94, 1108 (1963);96, 1656 (1964);95, 1366 (1965); 7.–9. Mitt.:F. Gölles undA. Höpfner, Mh. Chem.97, 368, 911 (1966);99, 230 (1968); 10. und 11. Mitt.;F. Gölles undO. Wolfbauer, Mh. Chem.99, 1814 (1968);100, 688 (1969).     

Komplexboride mit ReB2-Struktur

Ohne Zusammenfassung

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Complex borides with anReB ₂ structure

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Mit 1 Abbildung