Statistical Lengths of Rubberlike Hydrocarbon Molecules
Abstract It has been known for some time that the pure hydrocarbons of balata (or gutta-percha) and natural rubber have the same chemical composition and chemical properties. Both balata and rubber appear to be polymers of isoprene, (C5H8)n, with the same degree of unsaturation. Their physical properties are sufficiently different, however, to make it clear that their structures must differ in some important respect. Since the molecules contain numerous double bonds, it has been suggested that rubber and balata are geometric isomers. Every fourth bond in a rubber or balata molecule is a double bond, so it follows that the possibilities for geometric isomerism are considerable. It was proposed by Meyer and Mark that natural rubber hydrocarbon has a structure for which the molecular chain is cis with respect to all of the double bonds. Balata (or gutta-percha) is then supposed to have a trans-structure throughout, this view having been verified by Fuller and Bunn. It is the purpose of the present paper to consider, from the point of view of recent theories of rubber elasticity, to what extent these structures explain the differences in physical properties. The method to be employed involves calculation of the root mean square lengths of the cis- and trans-structures, which, when compared to their maximum lengths, should give an indication of their extensibilities. In 1932 Eyring treated the problem of the average square length of a hydrocarbon chain. In the present paper a different derivation of Eyring's equation is given (for illustrative purposes), after which this derivation will be extended to the rubberlike molecules with double bonds.