Quantitative characterization of polybutadiene networks

Abstract

Using a relationship found to be applicable for natural rubber networks in establishing contributions of chemical crosslinking, entanglements, and networks defects to physical crosslinking, a physical versus chemical crosslinking “calibration” is developed for polybutadiene prepared by organolithium initiation. This calibration is then used to determine chemical crosslink yields for sulfur‐sulfenamide, thiuram, and peroxide vulcanization. Crosslink yields for polybutadiene in the sulfur‐sulfenamide and thiuram curing systems are shown to be similar to those of natural rubber. In peroxide vulcanization the crosslink yield is in excess of unity for polybutadiene. Evidence is presented which indicates that this is due to a polymerization type reaction involving vinyl groups resulting from 1,2‐addition during polymerization.