Crystallization phenomena in some polyester — urethanes

A density balance has been used to measure the crystallization isotherms of poly(ethylene adipate) and copolymers which were prepared by extending the polyester with four different diisocyanates. The occurrence of extensive secondary crystallization processes precluded satisfactory interpretation in terms of the Avrami theory and further analysis could only be based on the half-time for crystallization. This parameter has the advantage that it is determined directly and is independent of any theoretical analysis. The presence of very small concentrations of diisocyanate units can have a profound effect on the rate of crystallization if they are very different structurally from the parent polyester, e.g. a molar concentration of about 5% of 2,4-tolylene diisocyanate increases the half-time by a factor of 20 whereas the same concentration of hexamethylene diisocyanate has an insignificant effect. The temperature dependence of the half-times is discussed in relation to several theories of crystallization.