Computer modeling of the crystallization process of single-chain ethylene/1-hexene copolymers from dilute solutions

Langevin molecular dynamics (LMD) simulations have been performed to understand the role of the short chain branches (SCB) on the formation of ordered domains by cooling dilute solutions of ethylene/α-olefins copolymer models. Three different long single-chain models (C2000) with 0, 5, and 10 branches each 1000 carbons were selected. These models were equilibrated at high reduced temperature (T* = 13.3) and cooling in steps of 0.45 until the final temperature (T* = 6.2) by running a total of 35 × 106 LMD steps. During the cooling process, global order parameter, torsion distribution, position of the branches, and local-bond order parameter were calculated and monitored. The peaks of crystallization for each model were calculated by differentiating the global order parameter with temperature. The Tc (crystallization temperature) decreases as the number of branches increases as has been experimentally reported. The formation of order in the copolymers is affected by the amount of the SCB in the backbone of the polymer chain. Initially, the SCB move to the folding surface. Once the SCB are located near the folding surface the order starts to grow. In all cases here shown, the C4 branches are excluded from the ordered domains. To take into account, the influence of the branch distribution, a different branch distribution model has been considered for the two-branched systems. The crystallization fraction (α) and the density of the amorphous and ordered fractions was defined using the local-bond order parameter. Both magnitudes decrease as the number of branches increases. These facts fairly agree with experimental literature data. © 2011 Wiley Periodicals, Inc.Thanks are due to the MICINN (MAT2009-12364 project) for financial support. J. Ramos thanks the CSIC for an I3P tenure trackPeer Reviewe