AbstractThe crosslink density in polybutadiene has been determined by measurement of the polymer molecular weight by osmometry and the primary chain molecular weight by modifier analysis involving radioactive materials. Since the number of polymer molecules is equal to the number of primary chains less the number of crosslinkages, the experimental measurements may be used to calculated the crosslink density. This method can be used to determine crosslink density at a combination of conversions, modifier loadings, and polymerization temperatures which could not be done by other methods. Branching and cyclic structure forming crosslinks are not measured by this method, the principal assumption of which is that one and only one modifier fragment is attached to each primary chain. Initiation and termination processes tend to reduce the validity of this assumption, but these have been minimized by reduction of the amounts of initiator and found insignificant by comparison of different systems. Modifiers which react with polymer in nonterminal positions also reduce the validity so that primary dodecyl mercaptan was not satisfactory as a modifier in this work, while tertiary alkyl mercaptans were. Also, diisopropyl xanthogen disulfide was not satisfactory because of secondary reactions. The crosslink density of polybutadiene prepared in emulsion decreases with decreasing polymerization temperature. At a given molecular weight, the crosslink density does not appear to be a function of conversion within the range studied. At a given polymerization temperature, increasing polymer number average molecular weight was accompanied by increasing crosslink density although the rate of such increase was smaller at subfreezing polymerization temperatures. These results agree with kinetic theory of crosslinking in emulsion polymerization, but actual values are higher than those obtained in comparable systems by the gel point method.