Influence of Functionalization on the Crystallinity and Basic Thermodynamic Properties of Polyethylene

Polymerfunctionalization, the grafting of functional groups ontopolymer chains with strong intermolecular interactions, is a promisingapproach currently being explored to improve the recyclability andfield use properties of commercially important polymeric materials.The mechanical properties of polyethylene (PE) are closely tied tothe degree of crystallinity, which is expected to be influenced bypolymer functionalization. We perform atomistic molecular dynamics(MD) simulations to study the effect of the functional groups on thechange of the degree of crystallinity, as well as thermodynamicaland local mechanical properties of a linear PE melt. In particular,we consider ester and amide groups as model polar functional groups.In both of these functionalized PE materials, we observe the densificationand suppression of crystallization for functionalized PEs in the melt.Our simulation findings inform on the potential use of functionalizationof PE as an approach to improve the recyclability of petroleum-basedpolymer materials.