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T. L. Lebedeva I. I. Vointseva L. M. Gil’man P. V. Petrovskii T. A. Larina 《Russian Chemical Bulletin》1997,46(4):732-738
It was established by Fourier-transform IR and1H NMR spectroscopy that a portion of the units of poly(1,1,2- and 1,2,3-trichlorobuta-1,3-diene) chains rearrange with migration
of the allylic chlorine (1–4%) and allylic hydrogen (3–10%) under the influence of chloroform. Rearrangement with the migration
of hydrogen under the influence of CDCl3, CCl4, and THF was also observed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 763–768, April, 1997. 相似文献
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The temperature dependences of the heat capacity (C
p°) of carbynoid structures prepared by alkaline dehydrochlorination of poly(vinylidene chloride) and 1,1,2- and 1,2,3-polytrichlorobutadienes were studied by adiabatic vacuum calorimetry between 5 and 340 K with an accuracy of 0.2%. The low-temperature relaxation transitions and abnormal patterns of the C
p° vs.
T dependences were identified and characterized. The experimental results were used to calculate the thermodynamic functions C
p°(T), H°(T) – H°(0), S°(T) – S°(0), and G°(T) – H°(0) for 0—340 K. These data were compared with the corresponding data for carbyne produced by oxidative dehydropolycondensation of acetylene, which is a mixture of amorphous - and -forms with a minor impurity of crystals of both forms. 相似文献
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B. V. Lebedev T. A. Bykova K. V. Kir'yanov I. I. Vointseva L. M. Gil'man 《Russian Chemical Bulletin》1996,45(10):2345-2349
Thermodynamic parameters of the interpolymer reaction between poly-1,1,2-trichlorobuta1,3-diene and poly(ethylene imine) giving a polymer-polymer compound (incorporating the starting components in a molar ratio of 1 : 2) have been determined by calorimetry. The enthalpy (H°m), entropy (S°m), and Gibbs function (G°m) for this reaction are negative over the whole temperature range studied. The enthalpy of the reaction in chloroform at 298.15 K is about two times smaller, due to the difference in the enthalpies of dissolution of the starting polymers and the enthalpy of swelling of the interpolymer in the same solvent. The glass transition temperature of the interpolymer lies between those of the starting polymers and coincides with the value calculated from the Fox equation. The heat capacity of the interpolymer is smaller than additive values calculated fromC
p
°
of the starting polymers. From the experimentally determinedC
p
°
for the polymers, the thermodynamic functionsC
p
°
(T),H°(T) – H°(O), andS°(T) were calculated for the 0–330 K temperature range, and their configurational entropiesS
c
°
were estimated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2474–2478, October, 1996. 相似文献
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