Influence of hot-melt extrusion and compression molding on polymer structure organization, investigated by differential scanning calorimetry

A blend of a pullulan polymer and 1,2,6-hexanetriol as a plasticizer were u sed to study the effect of melt processing techniques on the physical prope rties of the resulting materials. The main advantage of pullulan is its lin ear polysaccharide chain model structure. Hot-melt extrusion and compressio n molding were performed under the same temperature and pressure conditions . The materials obtained were analysed by differential scanning calorimetry . For the first time, the comparative effect of the two processing techniqu es, i.e., extrusion and compression molding, on the polymer arrangement is reported. Endothermic events resulted from the melt extrusion process were shown to be related to different structures of oriented populations of macr omolecules and to microphase separation. Orientation was enhanced by coolin g the extrudate at the die exit, with a corresponding increased enthalpy fr om 34.7 to 51.4 J/g. In contrast, when using compression molding, the endot herm was less marked (11.9 J/g), suggesting less orientation, but the shape of the thermogram was quite similar to that of the extrudate. In both case s, we observed a loss of orientation when the molded materials were milled. A semiquantitative kinetic study of the disorientation process of the extr udate upon isothermic tempering suggests that a disorientation phenomenon o ccurs at the same time as a swelling process due to the presence of microph ase separation. The extrudate was shown to be stable at 25 degreesC. (C) 20 01 John Wiley & Sons, Inc.