Electrophilic addition of brominated poly(isobutylene-co-4-methylstyrene) to olefins catalyzed by zinc salts: a model study

The chemical reactivity of a new elastomer based on brominated poly(isobutylene-co-4-methylstyrene) in electrophilic additions to olefins has been investigated using model compounds as well as appropriate polymers. The reactions catalyzed by zinc salts are influenced by the solubility as well as the composition of the catalyst. While the reactivity of zinc bromide is limited by its low solubility in nonpolar medium, zinc oxide and zinc stearate can afford excellent results once an induction period has elapsed. The induction period likely corresponds to the formation of more reactive zinc based moieties through interchange reactions with the benzylic bromide groups. The mechanism of the addition process involves initial formation of carbocationic complexes with the zinc salts, followed by addition to the double bonds of the olefins. The products resulting from these additions have been characterized by NMR as well as gas chromatography-mass spectrometry. A comparison of potential crosslinking processes involving olefin addition or electrophilic aromatic substitution reactions shows that the former process is preferred. The findings of this study are directly applicable to the co-curing of elastomers based on brominated poly-(isobutylene-co-4-methylstyrene) with polyolefins.