Towards the propagation rate coefficient for the free‐radical polymerization of 1,3‐butadiene
- 12 March 1996
- journal article
- Published by Wiley in Macromolecular Chemistry and Physics
- Vol. 197 (3) , 1055-1069
- https://doi.org/10.1002/macp.1996.021970324
Abstract
The propagation rate coefficient kp for the free‐radical polymerization of 1,3‐butadiene was determined as a function of temperature in the range of 30–60°C in bulk and as a function of the concentration of 1,3‐butadiene in chlorobenzene at 50°C using a combination of a UV flash‐lamp induced polymerization and a measurement of the molecular weight distribution of the produced polymer by size exclusion chromamgraphy. Differences of up to around 45% resulted even for the same concentrations and temperatures when these measurements were compared with recent determinations of kp of 1,3‐butadiene in chlorobenzene in which just such an experimental setup was used. This finding was essentially attributed to large differences in the radical termination rates which prevailed in the reaction volumes under the current conditions of the pulse‐induced polymerization experiments. Moreover, in the vicinity of bulk concentrations of 1,3‐butadiene in chlorobenzene, kp apparently decreases with concentration.Keywords
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