Further studies on the thermal decomposition of AIBN—implications concerning the mechanism of termination in methacrylonitrile polymerization
✍ Scribed by Julia Krstina; Graeme Moad; R. Ian Willing; Stefan K. Danek; David P. Kelly; Stephen L. Jones; David H. Solomon
- Publisher
- Elsevier Science
- Year
- 1993
- Tongue
- English
- Weight
- 767 KB
- Volume
- 29
- Category
- Article
- ISSN
- 0014-3057
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✦ Synopsis
The products formed during thermal decomposition of AIBN-~J3C at 60 ° in benzene and dimethyl sulphoxide have been identified and quantified by ~3C-NMR. Analysis of the oligomeric products demonstrates that there is selectivity in the reaction of oligo(methacrylonitrile) radicals ( ) with cyanoisopropyl radicals (1). There is a marked preference for C-N coupling over C~ coupling and the major product observed results from combination of the nitrogen of 5 with the carbon of I. The reaction kinetics of AIBN decomposition and product formation have been analysed to yield absolute rate constants (60% benzene) for ketenimine decomposition and for the addition of 1 to methacrylonitrile. The implications of our findings are discussed with respect to the kinetics and mechanism of methacrylonitrile and other polymerizations.