Abstract
It has been shown that the age resistance of elastomeric vulcanizates is influenced to a very marked degree by residues formed in situ in the vulcanizate during the curing process. By a dual process of removal of these residues and incorporation of selected ingredients subsequent to vulcanization, it has been shown that age resistance (as measured by accelerated oven-aging tests at 212° F) in rubbers cured by sulfur and/or sulfur bearing accelerators, is a prime function of these residues and nearly independent of the stability of the network structure. An extremely active inhibitor is formed in situ during vulcanization of SBR and natural rubber using thiuram accelerators. This inhibitor can be used to “reinhibit” acetone-extracted accelerator-cured rubber. When added to sulfur/accelerator, peroxide, or radiation-cured vulcanizates, it improves their age resistance, but only in the case of the sulfur/accelerator cured rubber is this improvement better than with conventional inhibitors. This leads to the conclusion that the efficiency with which an inhibitor protects a vulcanizate varies widely, and conversely it appears that certain types of network structures are more readily protected or that certain inhibitors can function more efficiently in the protection of certain structures than others. In the case of natural rubber cured with TMTD (zinc oxide present), the bulk of the accelerator residue is ZnDMDC, and this residue has been shown to function as a very efficient antioxidant when incorporated into acetone-extracted, accelerator-cured vulcanizate. It is no more effective than conventional inhibitors, however, when incorporated into an acetone-extracted, sulfur/accelerator-cured vulcanizate. Finally, it has been shown that acetone extraction of the various vulcanizates may lead to improvement or worsening of their age resistance, depending upon the nature of the residues resulting from the curing process.
Carbon Black Network Structure in Natural Rubber Vulcanizates