Properties of amorphous and crystallizable hydrocarbon polymers. IV. Melt rheology of linear and star‐branched hydrogenated polybutadiene

Abstract

AbstractSome results on the melt rheology of hydrogenated polybutadiene (HPB) with narrow‐molecular‐weight distribution are reported and compared with the corresponding properties of the precursor polybutadienes (PBD) and fractions of linear polyethylene (PE). In linear samples the dynamic moduli obeyed frequency‐temperature superposition. The relationship between melt viscosity and intrinsic viscosity at 190°C for HPB was indistinguishable from that for PE, but their flow activation energies were slightly different (Ea = 7.2 kcal for HPB and 6.4 kcal for PE). Like PE, but unlike the PBD precursors, the dynamic storage modulus at low frequencies was anomalous. Otherwise, the dynamic moduli of HPB and its PBD precursor were essentially superposable. Plateau moduli from different samples were somewhat variable around an average of G = 2.31 × 107 dyn/cm2. The dynamic moduli for the HPB stars, unlike their PBD precursors, did not obey temperature‐frequency superposition. At high frequencies the temperature coefficient approached that for linear HPB, but it increased with decreasing frequency, reaching limiting values which depended on the arm length. The flow activation energy ranged from 9 kcal to more than 15 kcal as arm length increased.