Selective initiation of nonconjugated dienes containing electron donor–electron acceptor systems. II. Polymerization studies of vinyl ether–β-nitrostyrenes

The monomer series, o-, m-, and p-(2-vinyloxyethoxy)-β-nitrostyrenes, was studied. All three monomers were selectively polymerized through the electron-donating vinyloxy group via cationic initiation. The linear polymers from the meta and para isomers containing the electron-accepting nitrovinyl group were readily crosslinked via anionic initiation. The polymer derived from the ortho isomer was not crosslinked by this mechanism, an observation in accord with results previously reported from these laboratories in which it was shown that all o-substituted-β-nitrostyrenes having ortho substituents larger than fluorine exhibited a sterically inhibited propagation step. The meta and para isomers of this series were selectively polymerized through the electron-accepting nitrovinyl group via anionic initiation. Because of the fact that the resulting polymers were soluble only in highly polar solvents, subsequent crosslinking of these polymers via cationic initiation could not be accomplished. However, these polymers showed strong tendencies to undergo crosslinking upon long exposure to air. Because of the sterically induced ortho effect referred to above, no significant polymerization occurred in the case of the ortho isomer of this series via anionic initiation. However, it was shown in this case that initiation via the anion was rapid, and that the slow step was propagation.     

Propriétés des copolymères biséquencés polyoxyéthylène-polystyrène

Résumé On a préparé des monocristaux de copolymères biséquencés polyoxyéthylène-polystyrène (POE-PS) à partir de leurs solutions diluées, qui peuvent contenir jusqu'à 55% de PS. Les principales formes de ces cristaux et leurs variantes morphologiques, observées sous microscope optique, sont décrites et rattachées à la maille cristallographique du POE. On présente aussi quelques exemples de monocristaux obtenus par ensemencement, dans lesquels les différentes formes se succèdent par filiation; on discute les transitions des formes et leur dépendance vis à vis des conditions de cristallisation.La cristallisation de ces copolymères provoque généralement un fractionnement en composition, car la proportion de PS dans les cristaux est limitée. On propose deux modèles de structure différents, dans lesquels une ou deux couches cristallines de POE en configuration repliée sont recouvertes par le PS amorphe. Le processus de fractionnement est interprété à partir de ces deux structures en admettant une extension critique pour les séquences de PS, dont l'une des extrémités est ancrée sur la surface des repliements du POE.

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Summary Single crystals of copolymers, composed of one Poly(ethylene-oxide), (POE), and one Polystyrene (PS) block, (which may contain 55% of PS, by weight), have been prepared from dilute solutions. The principal crystal habits and their morphological variations, as observed with an optical microscope, are described and related to the unit cell of POE. Single crystals grown from various types of seeds, in which different external habits succeed one another, are also shown. Transitions of crystal habits and their dependence on crystallisation conditions are discussed in some detail.Generally, crystallisation of these copolymers produces some fractionation with respect to composition, for only a limited fraction of the initial PS can enter into the crystal. Two different crystal structures are proposed in which a single, or a double crystalline layer of folded POE is covered by amorphous PS. The fractionation process is interpreted on the basis of these two structural models, assuming a critical extension of the PS blocks anchored at one end to the fold surface of PEO.

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Zusammenfassung Einkristalle von Copolymeren aus einem Polyäthylenoxyd (PEO) und Polystyrol (PS)-Block, die gewichtsmäßig 55% PS enthalten können, wurden aus verdünnten Lösungen präpariert. Der grundsätzliche Charakter der Kristalle und ihre morphologischen Variationen, wie es in einem optischen Mikroskop beobachtet wird, ist beschrieben und mit der Elementarzelle PEO in Beziehung gebracht. Einkristalle, entstanden aus verschiedenen Typen von Kristallkeimen, in welchen verschiedene äußere Formen auftreten, die aufeinanderfolgen, werden gezeigt. Die übrigen Kristallformen und ihre Abhängigkeit von den Kristallisationsbedingungen werden im einzelnen diskutiert.Im allgemeinen verursacht die Kristallisation dieser Copolymeren gewisse Fraktionierung hinsichtlich der Zusammensetzung, da nur eine begrenzte Menge des ursprünglichen Polystyrols in den Kristall eintreten kann. Zwei verschiedene Kristall-Strukturen werden vorgeschlagen, in denen bzw. eine oder zwei Schichten von gefaltetem PEO mit amorphem Polystyrol bedeckt ist. Der Fraktionierungsprozeß wird auf Grund dieser zwei Struktur-Modelle interpretiert, die eine kritische Größe der PS-Blöcke, verankert an einem Ende der gefalteten Oberfläche von PEO, annehmen.

     

Photoelectron spectra and electronic structure of derivatives of imidazoline

We have obtained for the first time the photoelectron spectra (PES) of 20 diamagnetic and paramagnetic derivatives of imidazole. On the basis of calculations in the MNDO approximation, analysis of the vibrational structure, and comparisons in a series we have interpreted the bands in the range 7–11 eV. In the nitroxyl radicals of 3-imidazoline the highest occupied molecular orbital is the _NO ^* orbital, having also a contribution on the C⁴ atom. On introducing N-oxide groups there is a considerable rearrangement of the electronic structure of the radicals. In the PES of the nitroxyl radicals of 3-imidazoline-3-oxide there is multiplet splitting of the ionization band of the n_o·MO, amounting to 0.3–0.4 eV. Replacement of the methyl groups on the C² atom by methoxyl groups leads to an increase in the interactions of the unshared pairs of the O atoms of the nitronium and nitroxyl groups, while the same replacement on the C⁵ atoms leads to a considerable decrease in this interaction. When the substituent on the N¹ atom in derivatives of 3-imidazoline-3-oxide is varied the energy of ionization of the _C-NO MO decreases in the series: CH₃ < H OH < O < NO.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1769–1777, August, 1990.     

Synthesis and catalytic activity of uranium(IV) tetraphenylporphinate chloride

Conclusions The synthesis of a new complex, uranium(IV) tetraphenylporphinate chloride, was reported. This complex is an active catalyst for the oxidation of cholesterol.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2131–2132, September, 1986.     

Addition of amines to ethyl α-fluoroacrylate and phenyl α-fluorovinyl ketone

Conclusions The reaction of diethylamine, piperidine, ethylenimine, and cyclohexylamine with ethyl-fluoroacrylate, and also of ethylenimine with phenyl-fluorovinyl ketone, leads to the addition of the amines to the-fluorovinyl group with the formation of-fluoro--aminopropionic acid derivatives.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicneskaya, No. 10, pp. 2362–2363, October, 1975.     

Kinetics of the reaction between phenylacetylene and the complex of decaborane with diethyl sulfide

Conclusions The manometric method was used to study the kinetics of the reaction of phenylacetylene with the complex of decaborane and diethyl sulfide, with the formation of 1-phenyl-o-carborane. The reaction is described by a second order equation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, p. 1818, August, 1971.