Hydrophilic polymer membranes containing carboxylic groups—I. Acrylic acid—methyl methacrylate—glycidyl methacrylate copolymers

Copolymers of acrylic acid, methyl methacrylate and glycidyl methacrylate have been synthesized and converted into cross-linked hydrophilic membranes by successive treatments with heat, alkali solution and acidic solution. The copolymerization was carried out in solution using tetrahydrofuran and p-dioxane as solvents. The polymer was obtained as a clear viscous solution at yields of approximately 95%. The polymerization was stopped before gelation took place. This gelation resulted from the reaction of epoxy and carboxylic groups of the polymeric chain. The polymerization time ranged from 3.5 to 7 hr depending on the content of the glycidyl methacrylate in the feed. The monomer mixture consisted of 25–45 mol% of acrylic acid, 40–70 mol% of methyl methacrylate and 2.5–15 mol% of glycīdyl methacrylate. With increasing content of acrylic acid, the membranes became soft and elastic; with decreasing content, they became brittle and hydrophobic. The swelling of the cured polymeric film increased with increase in the acrylic acid content of the monomer mixture and decreased with increasing glycidyl methacrylate content. Dialysis runs were conducted with sodium chloride, urea and a series of ethylene glycols with molecular weights up to 600. The permeability coefficients through the membranes for the ethylene glycols were similar to those through a commercial cellulose membrane (Cuprophane). The permeability proportional to $\text{(permeant molecular wt)}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}$. The membranes showed very low permeabilities to sodium chloride compared with those of commercial nonionic membranes. This appears to be due to the ionic exclusion mechanisms expected for ion exchange membranes.     

Metallchelate mit Acetophenon-Benzoylhydrazon und Acetophenon-Salicoylhydrazon

The stoichiometry and structure of acetophenone benzoylhydrazone and acetophenone salicoylhydrazone chelates with some divalent metal ions are studied by conductometric titration and visible and infra-red absorption spectrophotometry. The results are supported by analysis of the solid complexes. The infra-red study revealed that coordination occurs through C=O and C=N groups. The shift in the C=O and C=N bands is utilised for the determination of bond lengths.     

Zur Kenntnis der thermischen Zersetzung von Ammoniumhexafluoroscandat,-titanat,-vanadat und-chromat

Thermal analysis supported by kinetic calculations was applied exhaustively to these compounds. Under dynamic conditions, tetrafluorometallates(III), which as intermediates, could not be isolated, for the first three compounds. In each case, the final step was the pure metal(III) fluoride. Ammonium hexafluorochromate(III) decomposed directly to the pure chromium(III) fluoride. The decomposition rate of all compounds slowed down towards the end, probably for kinetic reasons. Polymorphic transitions of ammonium hexafluorotitanate(III) were observed at 35 and 100°C. Ammoniumhexafluoroscandate(III) underwent polymorphic transition at 47°C. The decomposition patterns for all these compounds were similar. Conditions for the preparation of pure ammonium tetrafluorometallates(III) of Sc, Ti and V are described.     

Untersuchungen zur 3-Phononenabsorption in partiell kristallinen Polymeren

Zusammenfassung In dieser Arbeit wird die Dreiphononenabsorption in Polymeren, die den Hauptanteil an den dielektrischen Verlusten im Millimeterwellengebiet stellt, theoretisch und experimentell untersucht. Aus der Störungsrechnung bis zur 2. Ordnung wird die Temperaturabhängigkeit der Absorption abgeschätzt. Damit ist eine befriedigende Deutung des gesamten Temperaturverlaufs der dielektrischen Verlust-Kurven möglich. Im Hochtemperaturbereich läßt sich die Mehrphononenabsorption eindeutig gegenüber restlichen Relaxationsprozessen abgrenzen. Im Tieftemperaturgebiet konnte erstmals auch für das Millimeterwellengebiet ein temperaturunabhängiger Bestandteil fehlordnungsinduzierter Einphononenabsorption nachgewiesen werden. Im Übergangsbereich durchlaufen die Absorptionskurven einen Wendepunkt bei einer charakteristischen TemperaturT ₀, die dem Schwerpunkt der am Absorptionsprozeß beteiligten Phononenfrequenzen entspricht. Daraus konnten in Übereinstimmung mit dem Experiment die Frequenzen der niedrigsten optisch aktiven Phononen für die verschiedenen Polymeren abgeschätzt werden.

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Summary The 3-phonon absorption in polymers, which gives the main contribution to their dielectric loss in the microwave region, is theoretically and experimentally investigated. Perturbation theory up to the second order is used for the evaluation of its temperature dependence. The theoretical results allow an interpretation of the total absorption-temperature-curves: In the high temperature region 3-phonon absorption can be distinguished from residual relaxation losses (above the glass temperature). In the low temperature region the existence of a low frequency tail of temperature independent disorderinduced one-phonon absorption became evident. At intermediate temperatures (50–150°K) the curves show an inflexion point or plateau at a characteristic temperatureT ₀, which according toT ₀= ⁰, corresponds to the frequencies of those phonons, that mainly contribute to the multiphonon absorption. The plateau gives, in good agreement with the experiment, the frequencies of the lowest optically active phonons in the various polymers.

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Mit 6 Abbildungen in 8 Einzeldarstellungen

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Vorgetragen auf der Arbeitssitzung des Fachausschusses Physik der Hochpolymeren in der Frühjahrstagung 1970 des Regionalverbandes Hessen-Mittelrhein-Saar der Deutschen Physikalischen Gesellschaft in Darmstadt, 10.–13. März 1970.     

Structure des savons alcalins

Summary This is a systematic X-ray diffraction study of the structure of the mesomorphic phases occurring with potassium soaps ranging from C₈ to C₂₂.Four types of structure have been identified. The first is lamellar with both polar groups and paraffin chains in the crystalline state. The second is also lamellar, but with both polar groups and paraffin chains in the liquid state. The third corresponds to the localization of indefinitely long ribbons on a two-dimensional oblique lattice; polar groups are crystalline and paraffin chains desorganized. The fourth corresponds to the localization of discs on a three-dimensionnalB-faces centered orthorhombic lattice; polar groups are crystalline and paraffin chains disorganized.The structural parameters and the polymorphism of the polar groups have been discussed.

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Zusammenfassung Wir beschreiben hier eine systematische Röntgenstrahlendiffraktionsforschung der Struktur der mesomorphen Phasen von Kalium Seifen von C₈ bis C₂₂.Vier Strukturtypen wurden gefunden. Die erste Struktur ist lamellar; beides, die polaren Gruppen und die Paraffinketten sind kristallisiert. Die zweite Struktur ist auch lamellar; aber in diesem Falle sind beides, die polaren Gruppen und Paraffinketten geschmolzen. Die dritte Struktur entspricht einer Lokalisation von Seifenbändern in einem zweidimensionalen monoklinen Gitter; die polaren Gruppen sind kristallisiert und die Paraffinketten geschmolzen. Die vierte Struktur entspricht einer Lokalisation von Seifenscheiben in einemB-flächenzentrierten orthorhombischen Raumgitter; die Polargruppen sind kristallisiert und die Paraffinketten geschmolzen.Wir haben aus den experimentellen Resultaten einige Schlußfolgerungen gezogen.

     

Determination of zinc in high purity bismuth by thermal neutron activation

A neutron activation analysis for the determination of zinc in bismuth was developed. After irradiating the samples for 44 days at 4·10¹¹n/cm²/sec, zinc was separated quantitatively by hexone extraction and precipitation as quinaldate. The sensitivity of the method was estimated as 0.05 p.p.m. No zinc could be detected in the high purity bismuth samples. An addition method of analysis showed that the precision was 1.2%.     

2,6-di-tert-butyl-4-perimidylphenols and their oxidation

1,8-Naphthylenediamine was reacted with 2,6-di-tert-butyl-4-formyl-phenol to produce 2,6-di-tert-butyl-4-(1,3-dihydro-perimidyl) phenol (I). The latter was coverted into 2,6-di-tert-butyl-4-(1H-perimidyl)phenol (II) by oxidizing I with sodium pyrosulfate. When phenol II was oxidized by lead dioxide in toluene and THF, the EPR spectra revealed a 12-component multiplet with perimidyl splitting constants a¹ _N=a³ _N=a_H ^NH=0.2 mT; a_H ^6.7=0.6 mT.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 1, pp. 64–67, January, 1992.     

Synthesis of 1,2,3,4,8,9,10,11-octahydro-[1,4] diazepino[6,5,4-jk ]earbazole and related compounds

1,2,3,4,8,9,10,11-Octahydro[1,4]diazepino[6,5,4-jk]earbazole (VIa) was synthesized from 2,3,4,5-tetrahydro-1H-benzodiazepine (la) via the route shown in Scheme 1. Other compounds which were prepared similarly are 3-acetyl-6-chloro-1,2,3,4,8,9,10,11-octahydro[1,4]diazepino-[6,5,4-jk]carbazole(Vb) and 3-methyl-1,2,3,4,8,9,10,11-octahydro[1,4]diazepino[6,5,4-jk]carb-azole (VIII). Chemical transformations which were carried out with VI and 3-acetyl-1,2,3,4,8,9, 10,11-octahydro[1,4]diazepino[6,5,4-jk]carbazole (Va) are also described.