Abstract
The high degree of dehydrogenation effected by tert.-butoxy radicals at the α-methylenic groups of olefins enables these radicals to be used for the carbon-to-carbon cross-linking of unsaturated carbon chains, and especially of the polyisoprenic chains of natural rubber. Such cross-linking amounts to a vulcanization process in which the connecting links between chain molecules are just C—C bonds, which may be expected to have appropriate attributes. An examination has first been made of the cross-linking produced by tert.- butoxy radicals (from di-tert.-butyl peroxide) at 140° between the short iso-prenic chains in 1-methylcyclohexene, 4-methylhept-3-ene, 2,6-dimethylocta-2, 6-diene, and digeranyl. Cross-linking proceeds efficiently in each case, and the points of union in these isoprene units which become directly joined are not confined to original α-methylenic carbon atoms. Where the reagent radicals are in considerable deficit, e.g., one per two or three of the isoprene units present, those olefin molecules which are attacked become linked together mostly by single unions to form aggregates containing two, three or four molecules; but in the tetraisoprenic olefins the extent to which more than one union is formed between some of the directly linked molecules becomes appreciable. In natural rubber, cross-linking occurs smoothly and to nearly the full extent corresponding to the (in practice restricted) proportion of peroxidic reagent employed. Good vulcanizates can be so obtained in which the tensile stength is found to increase towards a maximum and then to decline rapidly as the degree of cross-linking steadily increases. Thus to obtain vulcanizates of the optimum physical characteristics, the degree of cross-linking must be suitably chosen. The role of the peroxidic reagent is almost entirely non-additive and non-degradative.
Modulus of Natural Rubber Crosslinked by Dicumyl Peroxide. I. Experimental Observations