Mesoscale modeling of random chain scission in polyethylene melts

Abstract

Abstract Polyolefins account for more than half of global primary polymer production, however only a small fraction of these polymers are currently being recycled. Fragmentation of polymer chains into shorter chains with a targeted molecular weight distribution with the goal of reusing these fragments in subsequent chemical synthesis can potentially introduce an alternative approach to polyolefins recycling. Herein we develop a mesoscale framework to model degradation of polyethylene melts at a range of high temperatures. We use the dissipative particle dynamics approach with modified segmental repulsive potential to model the process of random scission in melts of linear polymer chains. We characterize the fragmentation process by tracking the time evolution of the distribution of degrees of polymerization of chain fragments. Specifically, we track the weight average and the number average degrees of polymerization and dispersity of polymer fragments as a function of the fraction of bonds broken. Furthermore, we track the number fraction distribution and the weight fraction distribution of polymer fragments with various degrees of polymerization as functions of the fraction of bonds broken for a range of high temperatures. Our results allow one to quantify to what extent the distribution of polymer chain fragments during random scission can be captured by the respective analytical distributions for the range of conversions considered. Understanding the thermal degradation of polyolefins on the mesoscale can result in the development of alternative strategies for recycling a range of thermoplastics.