Summary: A new analysis tool is presented that uses the governing kinetic scheme to predict properties of low‐density polyethylene (LDPE) such as the detailed shape of the molecular weight distribution (MWD). A model that captures mixing details of autoclave reactor operation is used to provide a new criterion for the onset of MWD shouldering. Kinetic effects are shown to govern the existence of MWD shoulders in LDPE reactors, even when operation is far from perfectly‐mixed. MWD shoulders occur when the mean reaction environment has a relatively high radical concentration and has a high polymer content, and is at a low temperature. Such conditions maximize long chain formation by polymer transfer and combination‐termination, while limiting chain scission. For imperfectly‐mixed reactors, the blending of polymer‐distributions produced in different spatial locations has a small effect on the composite MWD. However, for adiabatic LDPE autoclaves, imperfect mixing broadens the stable range of mean reactor conditions, and thereby increases the possibility for MWD shouldering.
Polymer MWD produced in an LDPE autoclave reactor by various kinetic mechanisms.
