Properties of solution‐grown crystals of fractions of isotactic polypropylene with different degrees of stereoregularity

Abstract

AbstractSolution‐grown crystals of fractions of isotactic polypropylene (IPP) with different degrees of stereoregularity have been obtained by isothermal crystallization from α‐chloronaphthalene, using a self‐seeding technique. Electron micrographs of samples, crystallized under the same undercooling, show that, with decreasing fraction of isotactic pentads, the perfect rectangular shape of the single crystal is lost and the presence of more complex morphologies is increasingly observed. The equilibrium dissolution temperature Td of IPP fractions, from polymers prepared with a titanium based catalyst, decreases linearly with decreasing percentage of isotactic pentads. An extrapolated value of 171°C is obtained for the equilibrium dissolution temperature of a crystal of IPP with 100% isotactic pentads, i.e., an IPP crystal free of configurational defects. The melting temperature T′m and the apparent enthalpy of fusion ΔH of crystallized and annealed crystal aggregates have been determined by differential calorimetry. The equilibrium melting temperature Tm also depends greatly upon the isotactic pentad concentration. For 100% concentration the extrapolated value of Tm is 181°C. Tm decreases about 1°C per 1% decrease in the isotactic pentad population. The observed equilibrium melting and dissolution temperature depression does not follow the predictions of the Flory equation for copolymer crystallization. In fact, the effect of decreasing probability of isotactic sequence propagation is to depress Td and Tm much more rapidly. The apparent enthalpy of fusion of both solution‐grown crystals and melt‐recrystallized samples decreases with an increase in the number of configurational impurities along the chain. For the most stereoregular fraction the average length of isotactic stereoblocks has been compared with the lamellar thickness of solution‐grown lath‐shaped single crystals.