Rubber networks containing unattached macromolecules. I. Linear viscoelastic properties of the system butyl rubber–polyisobutylene

Mixtures of butyl rubber with polyisobutylene (molecular weights 0.055 and 2.3 × 10⁶) up to 50% by weight were crosslinked by sulfur, leaving the polyisobutylene molecules free to reptate in the butyl rubber network. Linear viscoelastic properties were measured in shear creep for periods up to 5 × 10⁵ sec at 25°C and oscillating shear deformations from 0.1 to 3 Hz, at temperatures from 2 to 63°C. Comparison with the properties of a butyl rubber crosslinked without polyisobutylene showed contributions to creep and mechanical loss attributable to the reptating species. Comparison with the properties of polyisobutylene (higher molecular weight) showed that the relaxation times associated with the reptating species in the upper part of the terminal zone are the same for different polyisobutylene contents (25% and 50%) and for 100% polyisobutylene in which no permanent network is present; their contributions to modulus appear to be proportional to the volume fraction of polyisobutylene to a power of about 2/3. The time required in stress relaxation for the portion of the modulus attributable to the reptating species to decay to half its plateau value is, based on the two molecular weights employed, proportional to the polyisobutylene molecular weight to the third power. The magnitude of the associated mechanical loss and its location on the frequency scale can thus be controlled independently.