Crystallization of Cis-Polyisoprenes in a Capillary Rheometer. II. The Effects of Experimental Parameters and Molecular Structure
Abstract Cis-polyisoprenes are readily crystallized under the pressure and orientation forces existing in a capillary rheometer. The ease at which crystallization can be effected is a complex function of the interrelationships existing among the temperature, the molecular weight, stereoregularity, and the dimensions of the capillary. For a given cis-polyisoprene and capillary, crystallization occurs more readily as the molecular weight is increased. Decreasing the diameter of the capillary and/or increasing the length of the capillary enhances the ease at which a given cis-polyisoprene can be crystallized. Using the optimum conditions presently available, natural rubber has been crystallized at 146° C. The ease at which crystallization is effected decreases drastically as the cis-1,4 content of the polyisoprene is reduced. Trans-1,4 and 3,4 are similarly effective in retarding the crystallization process and their effects are proportional to their concentrations in the molecular chains. However, polyisoprenes which will not crystallize under static conditions at −20° C are readily crystallized in the capillary rheometer at much higher temperatures.