Self-Nucleation in Stereodefective Isotactic Polypropylene: The Impact of Stereodefects on the Melt Memory

The memory of crystals in the melt of stereodefective samples of isotactic polypropylene (iPP), characterized by different concentrations of rr stereodefects from 0.49 to 10.5 mol %, was analyzed. Experiments of self-nucleation and annealing have demonstrated that high contents of rr stereodefects, largely incorporated in the crystals of iPP, produce a significant memory of crystals in the melt that persists up to high temperatures well above the melting temperature. For low stereodefect concentrations (lower than 2–3 mol %), the memory of the crystals is erased at temperatures (T_s,DI‑DII) only few degrees above the end of the melting endotherm (T_m,end), whereas for contents of rr defects higher than 3–4 mol %, the memory of crystals persists even upon heating at temperatures much above the end of the endothermic signal. The width of the heterogeneous melt Domain II, in terms of range of temperatures in the melt in which the memory exists and self-nucleation takes place, and the difference between the temperature at which the isotropic melt begins T_s,DI‑DII and the end of the melting endotherm T_m,end increase with the increase of defects concentration. The higher the amount of stereodefects and the lower the melting temperature of iPP, the higher the temperature at which the self-nuclei must be heated to cancel the memory of crystals. These results indicate that a significant memory of iPP crystals exists in the melt not only in copolymers of iPP with noncrystallizable comonomeric units but also for iPPs containing small defects largely incorporated in the crystals. During crystallization of these stereodefective iPPs, the selection of the crystallizable segments of suitable length, which has been considered responsible for the formation of the heterogeneous melt and self-nuclei, should be less demanding thanks to the incorporation of stereodefects in the crystallizable sequences. However, upon successive heating to melt at low temperatures these highly irregular produced crystals, the diffusion and homogenization of all long and short sequences is in any case not easy, also considering the low temperature, and portions of partitioned sequences are left in the melt acting as efficient self-nuclei upon cooling and crystallization from the melt. The melt-memory attributed to these self-nuclei and the process of self-nucleation induce crystallization of the γ form, while crystallization from the isotropic melt induces crystallization of the α form, also in the case of samples with high concentrations of stereodefects that should crystallize in the γ form.