The use of polymeric materials requires the continuous expansion of the range of peroxide initiators. Silicon-containing peroxides have high thermal stability and are used as high-temperature initiators of polymerization. Nitrogen-containing peroxides are used as low-temperature polymerization initiators. The question of thermal stability is often decisive for the practical application of these compounds. Therefore, the thermolysis of Carbon, Silicon, and Nitrogen-containing organic peroxides was investigated by differential thermal and thermogravimetric analysis.
Peroxide samples were identified by cryoscopy, elemental and spectroscopic analysis using a spectrophotometers UR-20, Specord UV-Vis, Tesla BS-567 A.
The purity of the compounds was measured by the high pressure solution chromatography method. The content of the major component consisted not less than 99.2 weight per cent for all the studied compounds.
Thermolysis of peroxides was studied on the Derivatograph-1500D of the Paulik-Paulik-Erday system in a dynamic mode for identical conditions in the air and atmosphere of the inert gas of nitrogen for all compounds. The main focus was on the temperature of the beginning of the decomposition of the studied peroxides.
It was established that in the atmosphere of nitrogen, the destruction of peroxide begins at higher temperatures than in the air, and proceeds more slowly. Obviously, the oxygen of the air is involved in the process of thermal destruction, which leads to a decrease in the temperature of the beginning of the decomposition and increase the speed of the process. The destruction of peroxides in the nitrogen atmosphere is accompanied by less exo (endo) effects than in the air, which indicates the influence of the nature of the environment.
An inverse proportional relationship between the temperature of the beginning of the thermolysis and the relative content of peroxide oxygen for peroxides with one peroxide group in the molecule was revealed. The equation of this dependence (with a correlation coefficient R = 0,9403) has the form:
The equation can be used to assess the possibility of using and storing derivatives of peroxide compounds.
1. Emanuel N. M. // Uspehi himii organicheskih perekisnyih soedineniy i autookisleniya. - M.: Himiya, 1969. 495 s.
2. Paulic F. A Complex Method in Thermal Analisis / F. Paulic, G. Paulic, Z.Erdey // J. Analit. Chem. - 1958. - Vol. 160. №1. - P. 242.
3. Lipskis A.L., Kviklis A.V., Lipskine A.M., Machyulis A.N. // Vyis. molek. soed. 1976. T. 18. № 2. S. 426.
4. Severini F., Gallo G.// J. Therm. Anal. 1985. Vol. 30. № 4. - P. 841.
5. Dibrivnyiy V. N., Butyilina N. A., Kochubey V. V.,Gerasimchuk S. I., Van-Chin-Syan Yu. Ya.Fiziko-himicheskie svoystva nekotoryih azotsoderzhaschih peroksidov // ZhFH. - 2004. - T. 78. - № 8. - S. 1384.
6. Dibrivnyiy V. N., Melnik G. V., Van-Chin-Syan Yu. Ya., Yuvchenko A. P. Termodinamicheskie svoystva chetyireh trifenilsilanovyih atsetilenovyih peroksidov // ZhFH. - 2006. - T. 80. - № 3. - S. 408.
7. Buncel. E., Davies A. // J. Chem. Soc. - 1958. - № 4. - Р. 1550.
8. Antonovskiy V. L., Hursan S. L. // Fizicheskaya himiya organicheskih peroksidov. - M: IKTs "Akademkniga", 2003. - 391 s.
9. Yuvchenko A. P., Dikusar E. A., Zhukovskaya N. A., Moyseychuk K. L. Sintez atsetilenovyih kremniysoderzhaschih peroksidov cherez peroksiatsetilenidyi litiya // ZhOH. - 1993. - T.63. - Vyip. 1. - S. 143.