Correlation Analysis of Curing Agents

The linear correlation of the pKa to the σ* constants of the substituted phenylthio group indicates the validity of the σ* being equal to the sum of the Hammett's constant of these substituent groups and the σ* of the phenyl group (0.6). The inhibitory activity of the compound LSR depends on the reactivity of BtSSR with BtSH and the general stability of the mixed disulfides which form during the curing process. For BtSSR as accelerators, the Hammett's rule applies to scorch delay time versus σ* constant as the variable with negative slope in the LFER. In benzothiazole-2-sulfenamides, the 13C NMR chemical shift of the carbon at the 2-position of the benzothiazolyl group (C8) is consistently greater than the chemical shift at the carbon adjacent to the amino nitrogen (CN) in the same molecule. It indicates that the electronic distribution at the S-N bond is consistently more positive at the S atom and more negative at the amino nitrogen. The 13C NMR chemical shift at C8 is inversely proportional to the σ* constant of the amino substituents. A wider range of amino substituents is applicable for the correlation analysis with 13C chemical shifts than σ* constants as the variable. When benzothiazole-2-sulfenamides are used as accelerators, two linear relationships with slopes of opposite signs are obtained for the N-substituted phenyl and the N-alkyl sulfenamides, respectively, in the relationship of the scorch delay to the 13C8 chemical shift or the σ* constant. Longer scorch delay was obtained with the pertinent electron-withdrawing phenyl or the sterically hindered alkyl substituents. The more basic amino derivatives give a faster acceleration rate and a higher crosslink efficiency. A significant linear correlation was obtained for scorch delay versus Hammett's σ constant of the phenyl substituents of the N,N′-dithiobisformanilides as vulcanizing agents.