Dielektrische Relaxation Polymerer bei Temperaturen bis 1 °K

Zusammenfassung Es werden Messungen des dielektrischen Verlustes tan im Temperaturbereich von 1 bis 80 °K und bei verschiedenen Frequenzen zwischen 10 Hz und 10 kHz an einer Reihe von Polymeren mitgeteilt.Der dielektrische Verlust sinkt im allgemeinen mit Annäherung an den absoluten Nullpunkt monoton ab. Es scheint dies anzudeuten, daß immer ein dielektrischer Untergrund, beruhend auf allgemeinen thermischen Fluktuationen, existiert, der im übrigen für Polymere mit polaren Gruppen höher liegt als für unpolar gebaute. Zu tiefsten Temperaturen hin überlagert sich diesem allgemeinen Trend oft noch ein Maximum, wenngleich bei Temperaturen bis 1 °K herab zuweilen nur erst in einer Konstanz der Verlustwinkel-Werte angedeutet. Es sieht also so aus, als ob auch noch bei tiefsten Temperaturen singuläre Relaxationsmechanismen eine Rolle spielen können. In einer Reihe von Fällen findet man weitere Relaxationsprozesse zwischen 15 und 40 °K.Soweit sich Aktivierungsgrößen aus der Auftragung der Maximallage in der Temperatur mit der Frequenz nach Abtrennung des allgemeinen Untergrundes abschätzen lassen, werden diese mit sinkender Temperaturlage immer kleiner.Die dielektrischen Verluste sind in allen Fällenextrem abhängig von der Vorgeschichte der Proben und zwar insofern, daß offensichtlich Verspannungen im Material infolge von Deformationsprozessen und anderen Behandlungen zu einer erheblichen Erhöhung der Verluste führen, sowohl des Untergrundes als der singulären Mechanismen.

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Summary Investigations of dielectric loss in the temperature range 1–80 °K and with frequencies between 10 c/sec and 10 kc/sec for diverse polymers a presented. For all polymers the dielectric loss decreases in principle monotonely with the approximation of the absolute Zero-point.Thus we suppose the existence of a common dielectric background loss depending from the thermal fluctuations in the material. Moreover this background losses are higher for substances with polar groups.At the lowest temperatures in most cases there seems to appear a loss peak. For temperatures down to 1 °K often this can be only suggested from the constancy of losses. But it seems to be a quite normal fact, that for extremely deep temperatures something as a singular relaxation mechanism may exist.Further discrete mechanisms exist for the range between 15 and 40 °K. Activation energy evaluated formally from the experimental dates in the normal manner after separation of the peaks from the background becomes smaller and smaller with decreasing temperatures.In all investigated cases the dielectric losses are very sensible to prehistory of the samples. It seems, that expecially stress, by deformation and other treatments, gives rise for an increase of loss for the background as for discrete mechanisms.

     

Pyrimidines

The reaction of cyclohexanone with arylidenebisureas (e.g. benzal-bisurea) in an acid medium has given 4, 4-diaryl-2, 2-dioxo-5, 5-trimethylene-6, 6-spirobishexahydropyrimidines (II). The acid hydrolysis of IIa (aryl-C₆H₅) in the presence of 2, 4-dinitrophenylhydrazine leads to the 2, 4-dinitrophenylhydrazone of 2-hydroxy-8-oxo-4-phenyl-5, 6, 7, 8-tetrahydroquinazoline (IV). Compound IV was also obtained by the ozonization of 2-acetoxy-8-benzal-4-phenyl-5, 6, 7, 8-tetrahydroquinazoline (IX) and subsequent decomposition of the ozonide with a solution of 2, 4-dinitrophenylhydrazine. The structure of the compounds obtained was confirmed by means of their IR, UV, and PMR spectra. Corresponding 6, 6-spirobishexahydropyrimidines have also been obtained from 2-methylcyclohexanone, acetone, and methyl ethyl ketone and benzalbisurea.For part XIV, see [1].     

Structure of polymers obtained from sulfur monochloride and olefins containing sulfonium salt structures

Reactions of sulfur monochloride with diolefins lead to polymeric products which can be reduced to diepisulfides in low yield. In reactions with cyclic triolefins, polymers containing tricyclic sulfonium structures are obtained as a results of transannular additions and subsequent transannular displacements. Due to the insolubility and reactivity of these ionic structures, only incomplete structural assignements could be made, but the reactions are studied on similar cyclic structures which provide model systems.     

The vinylation of benzotriazole

The reaction of benzotriazole with acetylene under pressure in the presence of potassium hydroxide and cuprous chloride has been examined. 1-Vinylbenzotriazole was obtained in 75% yield.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1289–1290, September, 1970.     

Structure of convosine

From the roots of the plantConvolvulus subhirsutum Regel et Schmalh. have been isolated seven known alkaloids and one new one, for which, on the basis of spectral characteristics, a comparative study with known alkaloids of the tropane series, and synthesis, the structure of (+)-N-isopropyl-3-veratroyloxynortropane has been established.Institute of the Chemistry of Plant Substances of the Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 618–620, September–October, 1986.     

Über Spurenelementbestimmungen in Leberproben Mittels Protoneninduzierter Röntgenfluoreszenz (Pixe)

Multi-element-analysis by PIXE in respect to medical applications is discussed. Examples of trace-element determinations in liver tissues are given, demonstrating the applicability and usefulness of this rather new analytical technique.      

Oxydation photochimique d'amines tertiaires et d'alcaloideS—IX: Oxydation photochimique d'alcaloides quinolizidiniques et indolizidiniques tetracycliques: sparteine et α-isosparteine,lupanine et α-isolupanine,camoensidine et tetrahydroleontidine

The influence of ring size and ring conformation on the site of photosensitized oxidation of tertiary amines was illustrated by the photooxidation of tetracyclic indolizidine and quinolizidine alkaloids. An amino radical intermediate has been supposed during photooxidation of lupanine sensitized by eosin under nitrogen atmosphere.     

Investigation of the interaction between zinc oxide and phosgene

It has been shown that in the interaction of zinc oxide and phosgene, the most active are the samples having oxygen vacancies. A mechanism for this process is suggested.

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ESR spectra of AsF2−6 and SbF2−6

ESR spectra observed in γ-irradiated CsAsF₆ and CsSbF₆ matrices have been assigned to the free radicals AsF^2?₆ and SbF^2?₆ respectively. The large, isotropic central-atom hyperfine interactions and isotropic g-values of these species suggest that they possess ²A_tg ground-states in O_h symmetry. The contribution to the semi-occupied orbital of the central-atom valence s atomic orbital is ≈ 0.6, greater than in the halogen hexafluorides (≈0.4) and the chalcogen hexafluoride anions (≈ 0.5). Variation of the central-atom hyperfine interaction with temperature is interpreted in terms of a second-order Jahn-Teller effect involving a low-lying ²T_1u excited state.     

Electron-impact fragmentation of penta-fluorophenyldimethylsilyl ethers of some sterols of biological importance

The mass spectral properties under medium and high resolution of a new protecting group for sterols is described and its ability to direct fragmentation is compared with established derivatives. The mass spectra obtained are characterised by strong molecular ions which fragment to produce a more even ion distribution than the familiar TMS ethers. This results in enhanced abundance of hydrocarbon fragments, with molecular structural details given greater prominence than is found with other derivatives.