Chain Length Distributions of Polyolefins Made in Stopped‐Flow Reactors for Non‐Instantaneous Site Activation

Abstract We developed an analytical solution to describe how the chain length distribution (CLD) of polymers made with coordination polymerization catalysts vary as a function of time for very short polymerizations considering non‐instantaneous site activation. This solution is an extension of our previous analytical expression for instantaneous site activation. We validated the analytical solution with dynamic Monte Carlo simulation and obtained excellent agreement. Simulation results indicate that, unless the catalyst activation rate is much lower than the propagation rate, it will have only a minor effect on the initial shape of the CLD of polymers made in stopped‐flow reactors (SFR). We also show how incorrect polymerization kinetic parameters may be estimated when assuming instantaneous site activation when this hypothesis is not applicable to the polymerization data under investigation. magnified image