Crosslink Density in Polybutadiene
Abstract 1. A method has been developed for the measurement of crosslink density of diene polymers. This method, which involves the use of radioactive chain transfer agents, is applicable to ungelled polymer prepared under a wide variety of conditions so that any polymerization variable can be studied independently. 2. The crosslink density in polybutadiene decreases with decreasing polymerization temperature. At low molecular weight of polymers, the amount of crosslinking varies linearly with the polymerization temperature. 3. The crosslink density of polybutadiene increases with increasing number-average polymer molecular weight. The rate of increase is less for polymer prepared at −18° C than for that polymerized at 5° to 50° C. This means that, in a polymerization, as the average molecular weight increases with conversion the crosslink density increases. However, when the molecular weight is kept constant, by changes in the modifier loading, the crosslink density of polybutadiene appears to be independent of the degree of conversion attained within the range of 0.12–0.48. 4. The crosslink density of a high molecular weight fraction of polybutadiene was not significantly different from that of the whole polymer (from which about 3% of low molecular weight material had been removed). 5. The kind of initiator system does not affect the crosslink density of polybutadiene, providing the initiator loading is not too high. However, if large amounts of initiator are used in the polymerization, 10% or more of the polymer molecules may not contain mercaptan modifier. 6. Tertiary alkyl mercaptans are necessary for the crosslinking studies because they do not appear to give side reactions. Primary dodecylmercaptan and diisopropyl xanthogen disulfide are unsatisfactory for determinations because they appear to add to the double bonds of the polymer molecule in addition to the usual chain transfer reactions. 7. Incomplete emulsification of monomers in some 5° C recipes apparently increased the crosslink density of polybutadiene by retarding the diffusion of monomer into the monomer-polymer particles.