A CALORIMETRIC INVESTIGATION ON HIGH-MOLECULAR-WEIGHT POLYETHYLENE REACTOR POWDERS

Reactor powders of high- and ultrahigh-molecular weight polyethylene have been investigated. Two different Ziegler-Natta synthesis processes were used: polymerization in a slurry and in the gas phase. Synthesis temperature range was 30-85-degrees-C. Monoclinic crystals were identified in samples synthesized at 30-degrees-C. Investigations of thermal parameters were carried out by differential scanning calorimetry. A range of heating rates (0.4-10.0-degrees-C/min) was used to obtain information on sample reorganization on heating. The corresponding melt-crystallized samples were scanned and their thermal parameters were compared with those obtained from the original nascent powders. Percent crystallinity and average lamellar thickness, computed by the Thompson-Gibbs equation, were found to be controlled by conditions of synthesis. For reactor powders, the fraction of crystallinity is found to be insensitive to synthesis temperature. Crystallinity is controlled mainly by the synthesis process type: slurry or gas phase. Lamellar thickness was found to decrease as synthesis temperature was increased. This trend is the opposite of what is obtained on melt crystallization and can be interpreted on the basis of Lauritzen and Hoffman's theory of crystal growth. Nascent reactor powders give experimental support for the dependence of lamellar thickness on crystallization temperature that follows the pattern described in the theory at high undercooling. The influence of molecular weight on crystallinity and lamellar thickness of both nascent powders and melt-crystallized samples was also studied. Catalyst and synthesis conditions were found to control crystallinity and crystallite dimensions of the reactor powders. Thus, polyethylenes suitable for a specific purpose can be obtained directly on synthesis.