NMR and DSC investigations of the miscibility of blends of cis-1,4-polyisoprene with polybutadienes of different microstructures

Differential scanning calorimetry and torsional braid analysis investigations of the phase diagram of cis-1,4-polyisoprene/polybutadiene blends as a function of the polybutadiene microstructure were reported by several authors. Polybutadienes containing a high vinyl content were shown to be miscible with cis-1,4-polyisoprene on the DSC spatial scale, whereas polybutadienes containing a low vinyl content were immiscible. In this article, we used variable-temperature determinations of ¹H NMR free induction decays and low-temperature, high-resolution solid-state ¹³C NMR measurements of proton spin-lattice relaxation times in the rotating frame to probe the phase behavior of the cis-1,4-polyisoprene/polybutadiene blends at the smaller spatial scale of the NMR technique. Blends of cis-1,4-polyisoprene with a polybutadiene having a large number of vinyl 1,2 linkages appeared to be miscible on the molecular scale, in spite of small regions in which the polybutadiene component is not uniformily dispersed in the other polymer. On the contrary, blends in which the polybutadiene has a low content of vinyl 1,2 sequences were phase separated over the whole temperature range considered and no intermixed regions could be detected. The limiting case was observed with the polybutadiene containing 33 wt % vinyl 1,2 units, for which miscibility on a molecular scale is highly dependent on the blend composition. © 1995 John Wiley & Sons, Inc.