Effect of long chain branching on rheological properties of metallocene polyethylene

Abstract

Polyethylenes (PE) with long chain branching (LCB) densities up to 0.44 carbons/10 000 carbons and narrow molecular weight distributions were synthesized using a continuous stirred-tank reactor (CSTR) with the Dow Chemical's constrained geometry catalyst system, CGC-Ti/TPFPB/MMAO, in Isopar E solution at 500 psig and 140–190°C. Rheological properties of these metallocene polyethylenes (mPE) were evaluated and correlated to the LCB density. Measurements included steady-state viscosity, dynamic viscoelasticity, melt flow index and extrudate swell. Compared to their linear counterparts with the same molecular weights, LCB PEs gave higher viscosities at low shear rates and lower viscosities at high shear rates. These shear-thinning properties measured by a melt flow index ratio I 10/ I 2 strongly depended on the LCB density. PE with an average of fewer than one branch per six polymer molecules exhibited a I 10/ I 2 value of 25.7 compared to linear PEs I 10/ I 2=6~8 having similar molecular weights. An increase in the LCB density also significantly reduced the ratio of loss modulus over storage modulus, and yielded longer relaxation lifetime and higher level of extrudate swell. In contrast to the rheological properties, tensile strength, melting temperature, and other physical and mechanical properties were not noticeably affected by LCB.