Average propagation rate coefficients in the free-radical copolymerization of styrene and α-methylstyrene measured by pulsed-laser polymerization

Dax Kukulj, Thomas P. Davis

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Abstract

The average propagation rate coefficient, 〈kp〉, has been measured in the free-radical copolymerization of styrene (STY) and α-methylstyrene (AMS) using pulsed-laser polymerization. The value of 〈kp〉 was found to decrease by 2 orders of magnitude as the mole fraction of STY, fSTY, is decreased from 1.00 to 0.12. The effect of temperature on 〈kp〉 was measured over the range 17.9-47.4 °C, and the Arrhenius parameters were determined. The reduction in 〈kp〉 with decreasing fSTY is primarily attributed to entropic factors associated with the α-methyl group in AMS, as revealed by a reduction in the Arrhenius preexponential factor, A. Homopolymerizations of AMS did not yield molecular weight distributions suitable for successful evaluation of kp which is attributed to transfer to monomer dominating the chain stopping events. Mathematical expressions relating 〈kp〉 to monomer composition, allowing for different depropagation kinetics, are derived. It was found that depropagation events did not play a significant role in this work and that the terminal model for 〈kp〉 provided an adequate description of the observed propagation kinetics. Since kp for pure AMS could not be measured directly, values were estimated by extrapolation of the copolymerization 〈kp〉 data and the resulting Arrhenius parameters are Ea = 36.7 kJ·mol-1 and A = 106.17 dm·mol-1·s-1.

Original languageEnglish
Pages (from-to)5668-5680
Number of pages13
JournalMacromolecules
Volume31
Issue number17
DOIs
Publication statusPublished - 25 Aug 1998
Externally publishedYes

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