Elastomers antiozonants mechanism

Involvement of the Ozonized Rubber Moieties in Antiozonant Mechanism. The rubber chain relinking theory (30) is consistent in part with the self-healing film formation theory (37) a reaction between an antiozonant or some of its transformation products and ozonized elastomer is considered. Either scission of ozonized rubber is prevented in this way or severed parts of the rubber chain are recombined (i.e., relinked). A "self-healing" film resistant to ozonation is formed on the rubber surface. Such a film formed by the contribution of nonvolatile and flexible fragments of the rubber matrix should be more persistent than any film suggested in the protective film theory. 

The ozone concentration in the troposphere during the daytime is typically about 1 pphm (parts per hundred million parts of air by volume) [20], Values up to 100 pphm were measured in some photochemical smog areas. The molecular mechanism of the ozone aging of diene based elastomers was studied in detail and is well understood [19,21], Products or intermediates different from those arising in autoxidation or photo-oxidation of polymers were identified ozonides (3), zwitterions (4), diperoxides (5), polyperoxides (6), polymeric ozonides (7) and terminal aldehydes (8). Reactivity of aminic antiozonants (AOZ) with these species accounts for the protection of rubbers against atmospheric 03. AOZ must also possess antioxidant properties, because the free radical processes are concerted with ozonation due to the permanent presence of oxygen. 

Photo-oxidation proceeds relatively slowly. That is why elastomers made from chlo-roprene rubber exhibit considerably better resistance to ozone attack and weather influences than those made from NR, SBR, and NBR. Moreover, chloroprene rubbers respond well to anti-aging and antiozonant agents so that they can be recommended for use under difficult climatic conditions, e.g., in the tropics. By extrapolating mechanical property changes after several years of weathering in ozone-rich atmosphere, the current technology allows the prediction that chloroprene rubber products will exhibit sufficient strain for most static applications even after 50 years in service [697]. 

Many theories have been proposed to explain the mechanism of how antiozo-nants protect elastomeric articles from the effects of ozone. Most support the scavenger model, and indicate that an ideal antiozonant should be capable of migrating in a mbber matrix to the surface whenever the equilibrium of the antiozonant concentration in the compound is upset by the formation of ozonized antiozonant at the surface, but yet not freely migrate to the surface and volatilize out of the elastomer without first reacting with ozone at the surface. On the... 

In conclusion, the selection of the proper antidegradants for elastomeric compounds should be based upon a carefiil assessment of the elastomers used, the normal service requirements expected from these compounds, and the environment in which they are to perform. Only then, one can choose the ideal combination of antioxidants and antiozonants. It must be emphasized that the degradation of elastomers proceeds via several mechanisms, and as a result, it is essential to choose and use a combination of antidegradants which will inhibit aU of the described mechanisms of degradation that are expected to be encountered during a products service fife [28]. 

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