IV. The Micellar Theory of the Structure of Rubber

Abstract

Abstract The molecular weight data reported in Part II depend on the assumption that the values obtained by extrapolating osmotic pressure measurements to infinite dilution represent true molecular weights. This point of view has been strongly criticized, particularly by Pummerer and his coworkers, according to whom rubber normally exists in solution in the form of micelles comprising more or less well-defined aggregates containing a considerable number of chemical molecules. The- osmotic “molecular weight” is then regarded as the weight of an average micelle. If they exist, these micelles may be important in determining both the chemical and physical behavior of rubber, for we should clearly expect the bonds by which the chemical molecules are bound into micelles to be weaker than those within the molecules. It may be noted that it has been shown elsewhere that the physical properties of a series of rubber fractions are closely related to their osmotic and viscosity molecular weights. Since, according to the micellar theory, these fractions can differ only in micelle size, their mechanical behavior must, from this viewpoint, be determined by the size of the micelles, which must therefore remain intact during mechanical deformation of the rubber. It is the object of the present paper to examine in more detail the basis of the micellar theory, and especially to offer an interpretation of the results of the East method, on which Pummerer's arguments are mainly based.