Linear Free Energy Relationship Involving the Properties of Prevulcanization Inhibitors
Abstract The utilization of σ* constants for substituted phenyl groups converted from the known Hammett σ constants of the phenyl substituents is useful in assessing the linear free energy relationship (LFER) of the properties of various inhibitors. The inhibitors include thioketals, sulfenamides and N,N′thiobis(substituted formanilides). In the LFER of the rate of reaction between thioketals with 2-mercaptobenzothiazole, the rate is fastest when the thio group of the thioketal is attached to a substituted phenyl with the highest positive σ constant. The σ constant of alkyl groups is negative, and an alkylthio group gives a thioketal with a slower reaction rate. The LFER applies to the 13C NMR shift of the quaternary carbon of the thioketals with alkylthio groups. The slope of the linear relation is positive. However, changes in the 13C NMR shift of the arylthio derivatives are relatively small in spite of a wide variation in σ* constant. The LFER applies to the scorch delaying activities of all structural types of inhibitors in stocks accelerated by various benzothiazoles. In the linear relationship of scorch delay versus σ* constant in each type of inhibitor, the slope is negative. Variables with negative σ* constants give longer delay and those with more positive σ* constants give shorter delay. An exception is in the very fast curing MSSM/DPG stock where the thioketals from acetoacetanilide with arylthio groups give longer delay than the alkylthio compounds. In the TBBS-accelerated stock, the slopes of the linear relation of the carbamate sulfenamides, N,N′-thiobisformanilides and thioketals of cyanoacetanilides are about equal. However, the level of scorch delay obtained with the sulfenamides is significantly higher than the other two, which are equal in inhibition level. The inhibition action of N,N′-thiobisformanilides without alkylthio or arylthio groups is probably due to the formation of labile formanilide polysulfide intermediates.