Polymer, Vol.44, No.11, 3395-3405, 2003
Effect of molecular structure and topology on network formation in peroxide crosslinked polyethylene
The present study compared the crosslinking performance of single site linear low density polyethylenes (LLDPE) with high pressure, free radical polymerised, low density polyethylenes (LDPE). The difference in crosslinking performance is not fully explained by different structural parameters such as molar mass distribution (MMD), M-n, MFR2 value and vinyl groups but is related more to the phenomenon of a long chain branched LDPE macromolecule being smaller in size in the molten state than a macromolecule of a linear LLDPE sample of the same molar mass. The result of the difference in size is that the LDPE will contain a larger number of intramolecular crosslinking points than the LLDPE, which, on the other hand, will contain a larger fraction of intermolecular crosslinking points. The crosslinking points mentioned are of either a physical or chemical nature. From the perspective of the network build-up, the intermolecular crosslinking points are the most efficient. To compensate for the larger fraction of intramolecular crosslinking points in LDPE, more peroxide can be added or vinyl groups can be introduced. (C) 2003 Elsevier Science Ltd. All rights reserved.