Abstract
By use of radioactive sulfur it has been shown that sulfur-modified Neoprene, i.e., Neoprene Type GN, is essentially a copolymer of chloroprene and sulfur in the approximate ratio of 100 chloroprene units per sulfur atom. The sulfur units, possibly disulfides, are cleaved by an alkaline emulsion of tetraethylthiuram disulfide, so that a gel polymer containing combined sulfur can thus be converted to a soluble, plastic product. The mechanism of this cleavage reaction has not been completely elucidated as yet. Potassium persulfate, used as initiator for the polymerization of Neoprene, appears to be combined with the polymer in Neoprene Type GN in amounts equivalent to 8–17 polymer molecules formed for each sulfur-cpntaining initiator fragment. However, when dodecanethiol is used as modifier, a large proportion of the polymer molecules contain essentially no combined sulfur from the persulfate, and it appears that the true initiator is the RS free radical formed by reaction of the thiol with potassium persulfate. Dodecanethiol used as a polymerization modifier or chain transfer agent is combined in a greater amount than the one thiol per polymer molecule expected on the basis of simple chain transfer. High molecular-weight fractions contained 3–4 thiol sulfur atoms per polymer molecule and the results suggest that thiol addition to the double bonds of the polymer had occurred.