A complex of methodical approaches for investigating structural changes under the influence of temperature are presented on the basis of modern coxacepts of the domain structure of block copolymers. Effects oJ formation of structure due to phase segregation, crystallization processes and those of thermal homogenization have been considered in connection with the deformational properties of polymers. One and the same polymer appears to ha~e quite different phase structures and properties when obtained by altering its thermal conditions. Thermomechanical analysis is shown to be a most efficient technique for investigating the changes in the phase structure of a wide series of polyether(ester)urethanes and -urethaneureas.
In the previous work of Kargin and Slonimskii and that of Kargin and Sogolov who studied the behavior of polymers over a wide range of temperature, it was shown that the shape of thermomechanical curves depends on magnitude of molecular weight of the polymers. As a result of investigation of theory and actual experimental studies in which polyisobutylene was employed, it was demonstrated that molecular weight could be estimated on the basis of thermomechanical properties. This suggested a relationship between the magnitude of molecular weight M found from the thermomechanical curves and that which was determined from glass temperatures Tg and fluid temperatures Tf. For practical use of this relationship, it is necessary to know the magnitude of the segments and two empirical constants. These values can be found by calculation of molecular weights of three different fractions of the polymer. This can be accomplished experimentally by any independent method. Once these magnitudes are determined, it is necessary to find, by means of the thermomechanical curve, the values Tg and Tf, in order to calculate the molecular weight of any sample of the same polymer. Because of the low degree of accuracy of determination of these values, and because of the peculiar differences, the reliability of the calculated molecular weight cannot be great, especially since the equation utilizes the logarithm of the molecular weight figure and not the molecular weight itself. Apparently the graphic solution is simpler than analytical methods: by means of the data of thermomechanical studies for various fractions of known molecular weights it is possible to graph the dependence of M or log Mon Tf−Tg. From what has been said, it is evident that we may use the demonstrated method only for polymers of high elasticity, and furthermore, only for those fractions in which Tf−Tg is greater than zero.
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