聚氯乙烯接枝丙烯酸稀土的研究

将无机稀土有机化后与聚氯乙烯(PVC)进行接枝共聚。探讨了氧化稀土与丙烯酸反应、PVC接枝丙烯酸稀土的原理和方法，并通过红外光谱、扫描电镜对接枝共聚物进行定性表征，用微量热天平对接枝共聚物的热性能进行测定。实验结果表明，经丙烯酸稀土接枝共聚后的PVC，其耐热分解性能和韧性有了明显的提高。     

Diffusion in organic solvents: Interdiffusion coefficient of 1,1,2,2-tetrabromoethane

Interdiffusion coefficient have been measured for 1,1,2,2-tetrabromoethane in 21 organic solvents in order to ascertain the influence of shape, size, viscosity, nature and degree of branching, of the solvent molecules on transport properties. None of the existing correlations for diffusion in binary liquid systems appear to fit all the experimental data. Steric effects due to the solvent molecules are shown to be very important in the interpretation of the diffusion process.     

Enzymatic synthesis of neopentylpolyol esters in organic media

Utilization of lipases for synthesis of esters of hydrophilic polyols has been investigated. The choice of a suitable solvent is crucial in this type of reaction. An interesting case is fatty acid esters from neopentylpolyols, such as trimethylolpropane, which are of great interest as high temperature lubricants. Enzymatic synthesis of trimethylolpropane tricaprylate was studied as an alternative to chemical manufacturing. Triester production occurred only if the water produced by esterification was continuously removed from the medium. In these condition, kinetics of appearance and transformation of mono-, di- and triesters were determined in order to define optimal conditions.     

Investigation of gas chromatographic interaction mechanism on permethylated cyclodextrins by molecular modelling

Summary The capillary gas chromatographic retention behavior of -pinene and tricyclene has been investigated on stationary phases of different polarities. On all but one of the columns employed, tricyclene eluted before -pinene; only permethylated -cyclodextrins dissolved in moderately polar polisiloxanes gave a reversed elution order. The intermolecular interactions which caused the unexpected retention behavior were investigated in detail, applying methods of computer simulation. To achieve this, we have developed a calculation algorithm on the basis of molecular mechanical optimizations and programmed it in a macro. This makes it possible to systematically investigate a given configuration space in which all the possible interactions can take place. It was shown that permethylated -cyclodextrin as host molecule for both guest molecules offers an optimum cavity size. As a result the number of energetically favorable contacts between host and guest molecules as well as the strength of the interactions in this stationary phase were larger. As a consequence the elution order, normally only influenced by the vapor pressure of the compounds at a given temperature, was changed. Nonspecific interactions played an especially important role for these kinds of substances.     

Fermi and Coulomb correlations in the 21 S state of the helium isoelectronic sequence

The Fermi and Coulomb holes of the 2¹ S state of the helium isoelectronic sequence are investigated. Several interesting differences between the results obtained and those which might be expected on the basis of the corresponding 2³ S state are pointed out and discussed.     

Electron diffraction study of the molecular structure of gaseous 1,1-dibromo-3,3,5,5-tetramethyl-1-stanna-3,5-disila-4-oxacyclohexane,Br2Sn(CH2SiMe2)2O

The molecular structure of gaseous Br₂Sn(CH₂SiMe₂)₂O was studied by electron diffraction. The six-membered ring has a chair conformation whereas the entire molecule possessesC _s symmetry. The existence of a boat conformer cannot be completely excluded. The results of theoretical calculations for a twisted-boat conformation are at variance with the experimental data. Steric strain caused by mutual repulsion of the two axial methyl groups is reduced to the tilt of the Me₂Si fragments in opposite directions. This results in an increase (up to 26°C) in the angle formed by the bisector of the C_M-Si-C_M angle with the C_cSiO plane. The main geometrical parameters are as follows:r _g (Å): Si-O 1.708(20); Si-C_M 1.862(20); Si-C_c 1.882(9); Sn-C 2.108(26); Sn-Br 2.456(3); C-H 1.099(30); (degr.): C-Sn-C 105(2); Br-Sn-Br 107.9(1.2); Si-O-Si 129.6(3); C_M-Si-C_M 112; Si-C-H 113 (fixed value in accordance with experiment); C_c-Si-O 107(2); Sn-C-Si 109(2); torsion angles: (Si-C) 52(2); (Si-O) 62(1); (C_c-Sn) 54(1). The average amplitudes were fixed at the values calculated from the force field. Structural parameters of molecules with similar structures were analyzed and compared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 384–387, February, 1993.     

Synthesis and structure of novel derivatives of thieno[2,3-b]thiocine. An unusual product of intramolecular cycloaddition of 2-homomethallylthio-5-methyl-3-thiophenecarbonitrile oxide

9-Methyl-3,3a,4,5-tetrahydro-6H-thieno[2,3-b]thiocino[4,5-c]isoxazole and 9-hydroxyimino-2-methyl-7-methylene-6, 7,8,9-tetrahydro-5H-thieno[2,3-b]thiocine have been prepared for the first time by the oxidation of 2--alkenylthio-3-thiophenecarbaldoximes with NaOCl. X-ray structural investigations of thieno[2,3-b]thiocine and 2-homomethallylthio-5-methyl-3-thiophenecarbaldoxime have been carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1262–1266, July, 1993.