| Abstract: | The statistical product distribution for a linear polydisperse polymer of finite molecular weight was included into the statistical analysis for a system undergoing random chain scission showing the effect of volatilization of species other than monomer. Two sets of equations were derived. One set is for the nonvolatile fraction; the other is for the volatile fraction. Within each set there are three equations, one for the number of polymer molecules, the second for the molar (or number) fraction, and the third for the weight fraction of polymer molecules containing a specific number of repeat units. As degradation proceeds the polydispersity index should converge to a value of 1 rather than 2, which has been reported previously. The expected effects of polydispersity, number‐average degree of polymerization, and volatility were treated individually, and we determined that the molecular weight of a polymer has no theoretical influence on the product distribution. As for the effect of volatility, we determined that only the volatile product distribution would change. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3690–3696, 2000 |
