Fluoroaliphatic esters of fluorosulfonic acid. 4. Reactions of α-fluorosulfatoperfluoro ketones with nucleophilic reagents

-Fluorosulfatoperfluoroethyl isopropyl ketone I and fluorosulfatopentafluoroacetone II react with alkali metal chlorides and bromides to form the corresponding -haloperfluoro ketones as a result of direct nucleophilic substitution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2066–2069, September, 1990.     

Effect of pressure on free-radical copolymerization kinetics. I. A concept of additivity of partial molar volumes of activation

A short review of the effect of pressure on copolymerization kinetics shows the necessity of simple models for a better understanding of activation volumes. Therefore, a simple concept, possibly generally valid for free-radical polymerization, is proposed, based on the assumption that molar volumes of activation can be expressed as an addition of a characteristic radical and a monomer contribution, regardless of the combination involved. The scheme may facilitate the visualization of the transition state and contribute to the understanding of reaction mechanisms of radical polymerizations. Ethylene–vinyl acetate copolymerization at 62°C with tert-butyl alcohol as solvent agrees with the proposed scheme, appearing from the pressure independence of the product of reactivity ratios at the different levels (35,600, and 1200 kg/cm²). Implicitly it can be shown that an ethylene monomer contributes about 2 cm³/mole more to the activation volumes of the propagation reactions than does the vinyl acetate monomer, whereas for the radicals the difference of the respective contributions to the activation volumes is opposite in sign.     

Substitutive sulfotrioxidation of unsaturated and araliphatic organofluorine compounds

Conclusions Reaction of SO₂ or SO₃/[B₂O₃] with terminal fluoroolefins or fluoroalkylbenzenes gives the corresponding fluoroalken-2-yl fluorosulfates and fluorobenzyl fluorosulfates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2791–2795, December, 1982.     

Effect of molar mass ratio of monomers on the mass distribution of chain lengths and compositions in copolymers: Extension of the stockmayer theory

In statistical copolymers, there exists a distribution according to molar mass as well as according to chemical composition. Stockmayer derived distribution functions, describing the relative weight of a particular molar mass and composition interval, assuming equal molar masses of the monomer units. In this article we present an extension of the distribution functions, suited for those cases where the aforementioned assumption is not valid. The final mathematical results is a product of the original Stockmayer distribution function and a correction function, due to the unequality of molar masses. It appears the correction function is dependent on the average composition, the composition deviation, and the ratio of molar masses of the monomers. Furthermore, a three-dimensional representation of distributions has been developed to get insight in the shape of the distributions.     

Isomerization of perfluorinated cyclic amines under the action of antimony pentafluoride

Conclusions When perfluorinated tertiary cyclic amines containing a substituent at the nitrogen atom are heated with antimony pentafluoride, they isomerize to the corresponding azomethines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 646–649, March, 1989.     

A novel synthesis of vinyl esters from vinylversatate-10

Vinylversatate-10 (VV10)¹ has successfully been used to synthesise a large number of lower vinyl esters by transvinylation in presence of mercuric acetate and sulfuric acid. The synthesis of vinylhalo esters proceeds with more difficulty. It has been observed that neither Hg(OAc)₂ nor H₂SO₄ alone is capable of initiating the transvinylation. Furthermore, it has been found that a molar ratio 2:1 of VV10 to carboxylic acid is sufficient to drive the reaction to the right by continuous distillation of the vinyl ester formed, and as a result a high yield of vinyl ester is obtained. A mechanism for this reaction and for the formation of side products has been proposed.     

Simultaneous measurement of gamma-rays and neutron fluences</p> using a HPGE detector</o:p></p> </p>

Summary A simultaneous determination of gamma and neutron fluences in a mixed neutron + gamma field can be achieved by gamma-ray spectrometry, optimizing the moderator-converter-detector assembly and measuring both the direct gamma-lines and the neutron induced prompt gammas. For the prompt gamma-lines a combination of high efficiency and low background is the goal, and it can be best achieved if the gamma-energy is in the range above about 1 MeV up to 2.5 MeV. The optimal moderator-converter thickness can be determined experimentally. Most converter elements produce gamma-rays in the low energy range. If chlorine is used as a converter, the 1164.7 keV peak and the 1950-1960 keV peaks seems to be a good choice. A very practical material containing chlorine is PVC. It is an efficient moderator, it is solid, common, and can be handled easily.</p> </p>     

Nucleophilic isomerization of perfluoropentenes

Conclusions The isomerization of perfluoro-1-pentene by CsF in polar aprotic solvents leads to a mixture of trans- and cis-perfluoro-2-pentene in an isomer ratio of 61.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2646–2647, November, 1981.