Saturated hydrocarbon elastomers, peroxide

Saturated hydrocarbon polymers are also crosslinked by the action of organic peroxides, though branching reduces the efficiency. Polyethylene is crosslinked by dicumyl peroxide at an efficiency of about 1.0, saturated EPR gives an efficiency of about 0.4, while butyl rubber cannot be cured at all. For polyethylene, the reaction scheme is similar to that of the unsaturated elastomers. 

Peroxyl radical reaction with the polymer. This is a generally much slower process, which is structure dependent. In saturated hydrocarbon polymers, e g. polyethylene (PE) and polypropylene (PP), it is exclusively a hydrogen atom abstraction. In this case. Per is a hydroperoxide group (POOH). The corresponding rate constant is very low = 10 -10 l.mor. s at ambient temperature (see Table 12.7). In polyenic elastomers, e g. polybutadiene (PBD) and polyisoprene (PIP), step 3 can also be an addition to double bonds. In this case. Per is a peroxide bridge (POOP). The corresponding rate constant is also very low typically = 10 -10 l.mor. s at ambient temperature for an intramolecular addition (see Table 12.7). 

The properties of these elastomers are widely different. All require vulcanization. In general, sulfur is used only for unsaturated polymers, peroxides, quinones, metallic oxides, or cliisocyauates effect vulcanization with saturated types. Many are special-puipose rubbers, some can be used in tires when loaded with carbon black, others have high resistance to attack by heat and hydrocarbon oils and thus are superior to natural rubber for steam hose, gasoline and oil-loading hose. Most are available in latex form. See also Elastomers. 

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