Browse > Article

Effect of Substituent of Chain Transfer agent in the Free Radical Polymerization  

Chung, I. (Department of Applied Chemical Engineering, Mokwon University)
Publication Information
Elastomers and Composites / v.40, no.1, 2005 , pp. 53-58 More about this Journal
Abstract
Carbon tetrachloride is very reactive chain transfer agent due to the resonance stability of the trichlorocarbon radicals after breaking of C-Cl bond. Effect of benzylic radical comparing to trichlorocarbon radicals in the chain tranrfer reactions was investigated. From the structural point of view, cumyl chloride is a good candidate because it has the C-Cl bond with benzylic radicals after displacement of C-Ci bond. The reactivity of free radical polymerization of styrene in the presence of cumyl chloride was compared with that of carbon tetrachloride by calculating chain transfer constants. Results show that the cumyl chloride acts as a stronger chain transfer agent than carbon tetrachloride. The calculated chain transfer constant of cumyl chloride shows higher value (0.0463) than that of carbon tetrachloride (0.0011) in the styrene polymerization. High reactivity of cumyl chloride comparing to that of carbon tetrachloride is probably due to the higher resonance stability or benzylic radical than that or trichlorocarbon radicals after breaking of C-Cl bond. Monte Carlo simulation method is applied for characterizing the validity of kinetic constants according to the ratio of chain transfer agent to monomer.
Keywords
free radical polymerization; cumyl chloride; chain transfer constants; Monte Carlo simulation method;
Citations & Related Records
연도 인용수 순위
  • Reference
1 P.J. Flory, 'Principle of Polymer Chemistry', London Cornell University Press, 1953
2 J. Brandrup, E.H. Immergut, and E.A. Grulke, 'Polymer Handbook', 4th Ed., John Wiley & Sons, New York, 1999
3 L.N. Patnaik, M.K. Rout, S.P. Rout, and A. Rout, 'Rate Parameters for Transfer Reactions of Some Polymer', Eur. Polym. J., 15, 509 (1979)
4 J. He, H, Zang, and Y. Yang, 'Monte Carlo Simulation of Chain Length Distribution in Radical Polymerization with Transfer Reaction', Macromol. Theory Simul., 4, 811 (1995)   DOI
5 I. Chung, 'Monte Carlo Simulation of Free Radical Telomerization', Polymer, 41, 5643 (2000)
6 D. A. McQuarrie, 'Stochastic Approach to Chemical Kinetics', J. Appl. Probab., 4, 413 (1967)
7 C. Walling, 'Free Radicals in Solution', Wiley Interscience, New York, 1957