Simulation of the effects of chain architecture on the sorption of ethylene in polyethylene.
An osmotic ensemble hyperparallel tempering technique has been developed to study the solubility of ethylene in amorphous linear low-density polyethylene of different chain architectures. The NERD united-atom force field (Nath, Escobedo, and de Pablo revised united-atom force field) is used in all simulations. We have investigated the effect of polyethylene chain length and branching on ethylene solubility. In this study, we have considered short-chain branching of amorphous linear low-density ethylene-1-hexene copolymers under typical polymerization reactor conditions. It is observed that, in the polymer, ethylene prefers to reside in the vicinity of polymer chain ends. This clustering causes a decrease in ethylene solubility with polymer chain length. When short-chain branches are introduced to a linear polymer chain, however, the chain-end clustering effect is counteracted by a higher density, thereby leading to an ethylene solubility almost identical to that in the linear polymer.
Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA.
Brian J
BJ
Banaszak
Roland
R
Faller
Juan J
JJ
De Pablo
D000327:Adsorption; D003198:Computer Simulation; D005030:Ethylenes / Q000737:chemistry*; D046911:Macromolecular Substances / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D020959:Polyethylene / Q000737:chemistry*
D005030:Ethylenes; D046911:Macromolecular Substances; D020959:Polyethylene; C036216:ethylene