Green Strength in Emulsion SBR

Abstract

The present study and that published previously show that crosslinks based on quaternary ammonium halide salts introduced into emulsion SBR-type polymers confer green strength on blends with other compatible rubbers. The crosslink density employed did not exceed 1 link per 3000 combined monomer groups, equivalent to two links per weight-average polymer chain. Judging by the positive slopes of stress-strain curves, green strength obtained in this manner will persist up to at least 50°C. The crosslinks can be broken by mechanical shear and will re-form under resting conditions during times ranging from days at room temperature to minutes at 150°C. Prolonged mechanical shear in laboratory mixing equipment causes progressive loss of modulus and reduction in the slope of the stress-strain curves of compounds containing these labile crosslinks. Similar effects are observed in corresponding control compounds containing no labile crosslinks, but the initial advantage of the crosslinked compounds is progressively reduced and may be lost if shearing is sufficiently prolonged. Available evidence suggests that the principal cause of loss of modulus through shear is selective breakdown of the high molecular weight fraction of the base polymer. The breakdown of the longer chains, which are those most likely initially to carry three or more crosslinks, eliminates most of the network structure responsible for enhanced modulus. Whether chemical effects contribute to loss of modulus remains to be determined, but the evidence suggests that any such effects will be of lesser importance. Because the shear encountered in small laboratory mixing devices differs from that in full-scale factory equipment and stress-strain curves may not reliably predict green-stock behavior, the significance of the present findings can only be determined by factory trials. It is evident, however, that for the most efficient utilization of high green-strength SBR, exposure of the crosslinked SBR component to mechanical shear during mixing should be held to a minimum. On the other hand, to achieve smooth sheets or profiles at the forming stage, the final compound should be subjected briefly to a high degree of shear at as low a temperature as practicable, to break the labile crosslinks in the stock. Green strength will be recovered during subsequent rest periods. The present study suggests that these conditions should be readily achieved in a calendering operation, such as normally used for preparing carcass plies. However, to a greater extent than in most polymer developments, the final proving ground for applications for this new modification of SBR must be full-scale factory trials.

Covalent Cross-Linking of Polymers through Ionene Formation and Their Thermal De-Cross-Linking

“…These polymers were considered physically cross-linked elastomers because of ion pair interactions. There are also reports dealing with the cross-linking of polymers via ionene covalent bridges . One of them was concerned with a rubber that contained about two ionene bridges per polymer chain and could de-cross-link under mechanical shear and re-cross-link under resting conditions, due to reversible dequaternization 5d…”