Synthesis, characterization and kinetics of thermal decomposition of dimeric peroxycarbamates |
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Authors: | Çi?dem Kad? |
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Institution: | Department of Chemistry, Yildiz Technical University, Esenler-Istanbul 34210, Turkey |
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Abstract: | Several dimeric peroxycarbamates (PCs) have been synthesized by using cycloaliphatic and aromatic diisocyanates with mono- and di-hydroperoxides. The reactions were carried out under suitable conditions either in the presence of T-12 (dibutyltin dilaurate) as catalyst or in the absence of this catalyst. The products were characterized by IR-spectra and molecular weight measurements from isocyanate and peroxygen analyses. Thermal decomposition kinetics of these PCs were studied in THF solution at 80, 90 and 100 °C; the reactions were found to be first-order and decomposition rate constants (kd) were found. Activation energies and frequency factors for the decomposition were calculated. Activation energies were found to be in the range 67-121 kJ mol−1 and frequency factors were of the order of 1011-1015 s−1 depending on the structure of the PC. The results for the PCs agree well with literature values. |
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Keywords: | Peroxycarbamates Diisocyanates Mono- and di-hydroperoxides Characterization Thermal decomposition |
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