Shear degradation of polyisobutene

Abstract

A polyisobutene of M̄w 1.98 × 106, M̄w/M̄n 1.8, was extruded in an Instron capillary rheometer. Shear degradation occurred at high shear stresses, approaching melt fracture, and was more prominent at lower extrusion temperatures for tests at 60–140°C. The capillary was 2.0 in. long with a length/diameter ratio of 66.7 and a 90° entrance angle. Repetitive extrusions at constant shear rate caused a decrease in a molecular weight and a simultaneous narrowing of the molecular weight distribution. Extrudate expansion was measured after each successive capillary pass for tests at 80°C. Extrudate swelling correlated well with (M̄z+1) M̄z/M̄w, except for the two first passes, where melt fracture was pronounced. The correlation with equilibrium extrudate expansion was almost as good for (M̄z/M̄w)3.7 (Mill's correlation) and for M̄z+1 alone. The efficiency of bond rupture is low, with the energy required to rupture 1 mole of bonds being about 200,000 kcal at 80°C.