Elastomer Structures and ‘Cold Crystallization’

In a great number of applications an ideal elastomer should satisfy, to a certain extent, both of the following requirements: (1) nearly instantaneous crystallization upon application of strain (strain induced crystallization) and (2) slow or no crystallization when cooled at the temperature of maximum crystallization rate (cold induced crystallization). A noteworthy case of (2) is elastomer crystallization in a strained state. The connection between the points (1) and (2) has not been clearly understood up to now, but it is known that some crystallizable elastomers fulfil the requirements of both (1) and (2) better than others. From an experimental point of view, cold induced crystallization kinetics are substantially easier to measure than those of very fast strain induced crystallization. The phenomenon of cold induced crystallization in natural rubber, NR, has been known since the very beginning of elastomer technology and the tendency of natural rubber to crystallize by cooling has been overcome by crosslinking it with sulphur (vulcanization) without impairing its ability to crystallize by stretching (Goodyear, 1836). The synthesis of cis-polyisoprenes (IR) and cis-polybutadiene (BR) of different microstructural purity (different cis content) gave the possibility of changing the crystallization rate. It has also been reported that the very fast cold crystallization of trans-polypentenamer (TPA) could be reduced by lowering the trans content. The same fact had been observed earlier for trans-polychloroprene. There is a general agreement in postulating that the reduction of the crystallization rate, obtained either by cross-linking or by chain regularity reduction, can be linked with the lowering of the melting point. In both cases the low level of structural defects introduced in the chains does not affect the glass transition temperature in such a way as to vary the crystallization rate. The aim of this paper is to emphasize the importance of the variations of the glass transition temperature and melting point on the elastomeric cold crystallization rate and the way these may be used in planning new elastomer structures.