Search results for "Radical"
showing 10 items of 1401 documents
Emulsionspolymerisation von styrol mit intermittierendem kettenstart. I. Molekulargewichtsverteilungen
1965
Die Molekulargewichtsverteilungen von Polymerisaten, die nach der von BIANCHI, PRICE und ZIMM beschriebenen Methode hergestellt wurden, sind sehr breit und weisen bei niedriger Radikalbildungsgeschwindigkeit mehrere Maxima auf. Eine Analyse dieser Verteilungen ergibt, das 3 Effekte die Verbreiterung bewirken: (1) Die in den Latexteilchen wachsenden Polymerradikale haben eine Chance, den nachsten Radikalstos zu uberleben, wodurch Makromolekule doppelter, dreifacher usw. Lange entstehen. (2) Auch bei 0°C spielen Ubertragungsreaktionen am Monomeren und Polymeren eine nicht zu vernachlassigende Rolle. (3) Auserhalb der regularen Latexteilchen findet eine langsame Polymerisation in „Mikroteilche…
Understanding the Bond Formation in Hetero Diels-Alder Reactions. An ELF Analysis of the Reaction of Nitroethylene with Dimethylvinylamine
2012
[EN] The bonding evolution in hetero-Diels-Alder (HDA) reactions has been studied by an ELF analysis of the electron reorganization along the HDA reaction between nitroethylene 6 and dimethylvinylamine (DMVA) 9 at the B3LYP/6-31G* level. This cycloaddition takes place along a two-stages one-step mechanism. In the first stage of the reaction, the C1-C6 bond is formed by coupling of two pseudoradical centers positioned at the most electrophilic carbon of nitroethylene 6 and the most nucleophilic center of DMVA 9. In the second stage, the formation of the second O4-C7 bond takes place between a pseudoradical center positioned at the C7 carbon of DMVA and some electron-density provided by the l…
The effect of chlorine substituent(s) on the primary loss of a methyl radical from chlorinated veratroles (1,2-dimethoxybenzenes)
1989
Der nachweis der primärreaktion bei der autoxydation des tetralins
1964
Die Autoxydation des Tetralins wurde bei kleinen Umsatzen durch polarographische oder kolorimetrische Bestimmung des Peroxidgehaltes verfolgt und eine Anfangsgeschwindigkeit gefunden, die groser ist, als sie nach dem Peroxidgehalt des Tetralins sein sollte. Diese zusatzliche Reaktionsgeschwindigkeit ist die der Primarreaktion der Autoxydation. Dabei bilden sich aus Tetralin und molekularem Sauerstoff Radikale. Diese Primarreaktion ist nur dann beobachtbar, wenn der Peroxidgehalt des Tetralins etwa 10−5 Mol/l betragt oder kleiner ist. The autoxidation of tetraline was measured to a low degree of conversion by polarographic or colorimetric determination of tetraline hydroperoxide. The extrapo…
Theoretical characterization of the absorption spectra of phenanthrene and its radical cation
2003
The vertical absorption spectra of phenanthrene and its radical cation have been studied theoretically by means of a multiconfigurational second-order perturbation approach. Singlet-singlet transition energies and oscillator strengths, and singlet-triplet excitation energies have been studied in the absorption spectrum of phenanthrene up to 6 eV. The absorption spectrum of the pehnanthrene radical cation has been computed up to 3.4 eV. The results obtained confirm previous assignments and also lead to new interpretations of the main features of the spectra of these systems.
1984
A dimeric biradical •M plays a central role in the initiation of the spontancous polymerization of methyl methacrylate (M1). Besides the initiation step by chain transfer reaction, a change of the multiplicity of ˙M seems to be of importance. Evidence is given by heavy atoms in the solvent or in an inert gas atmosphere, leading to an acceleration of the overall polymerization rate. The observed effect is related to the atomic number of the respective heavy atom. Measurements of the temperature dependence of the effect for carbon tetrachloride show that — as expected — no activation energy is needed for this reaction step. The results are summarized in a reaction scheme for the initiation me…
Gemischte Diester von 2,2′-Methylendiphenolen mit Methacryl- und Crotonsäure und ihre Polymeren. 13C NMR-Untersuchungen zur Strukturaufklärung
1984
The structure of mixed diesters of three 2,2′-methylenediphenols with crotonic acid and methacrylic acid was studied by 13C NMR-spectroscopy. The position of the two acyl groups, expected from the synthetic pathway, was unambiguously confirmed by comparison with the corresponding mono- and diesters containing the same acyl group. In the same way, it was shown that the crotonoyl residue is not involved in the radical polymerisation of these esters.
ChemInform Abstract: Aryl Radicals by Copper(II) Oxidation of Hydrazines: A New Method for the Oxidative and Reductive Arylation of Alkenes.
1990
Abstract A new source of aryl radicals interesting from the preparative point of view has been found in the reaction of arylhydrazines and copper(II) sulfate. The process allows selectively both the reductive and oxidative arylation of alkenes.
Thermische Autoxydation und thermische Polymerisation des Styrols. Der Mechanismus der Startreaktion
1964
Die thermische Autoxydation des Styrols wurde bei verschiedenen Sauerstoffpartial drucken und in verschieden konzentrierten Losungen in Chlorbenzol mit Hilfe einer WARBURG-Apparatur gemessen. Aus den kinetischen Beziehungen folgt, das sich zuerst aus swei Styrolmolekulen ein Zwischenprodukt bildet, das von molekularem Sauerstoff unter Radikalbildung dehydriert wird. The thermal autoxidation of styrene was carried out in a WARBURG apparatus in different concentrations in chlorobenzene and under different partial pressures of oxygen. In consequence of the kinetic relations an intermediate is formed by two styrene molecules and this intermediate is dehydrated by molecular oxygen under the form…
Fate of several hydroxyalkyl isoprene radicals: Formation of hydroxycarbonyl compounds
2005
Abstract The fate of two hydroxyalkyl radicals derived from the oxidation of isoprene with OH radical, resulting in the formation of two hydroxycarbonyls, was investigated by means of theoretical quantum chemistry methods. All the stationary points were optimised at the UMP2/6-31G(d) level, and high-level ab initio calculations were performed at the QCISD(T)/6-31G(d) level of computation upon MP2 optimised structures in order to refine the energy of the molecules characterised. Our results show that the reaction of hydroxyalkyl radicals with O 2 is a very favoured pathway that explains the formation of the two hydroxycarbonyls optimised.