How 4-(7-Octen-1-yl)-N,N-diphenylaniline co-units induce strong melt memory effects in isotactic polypropylene random copolymers

The random incorporation of comonomer units in isotactic polypropylene usually disrupts the chemical regularity of the macromolecular chain, thereby remarkably affecting the crystallization and melting processes. We study the influence of a novel comonomer 4-(7-Octen-1-yl)-N,N-diphenylaniline (ODPA), in the concentration range of 1.1–6.8 mol%, on the crystallization and self-nucleation behavior of isotactic polypropylene copolymers. Non-isothermal and isothermal differential scanning calorimetry experiments demonstrated that crystallization kinetics are significantly retarded upon comonomer incorporation as the ODPA co-units are excluded to the amorphous regions. Furthermore, ODPA comonomer incorporation leads to a sharp increase in nucleation density; thus, spherulitic superstructures become significantly smaller. Remarkably, the ODPA co-units induce a strong melt memory effect that can persist even above the equilibrium melting temperature for copolymers with 4.4–6.8 mol% ODPA. The width of Domain IIa (exclusive melt-memory domain), an indicator of the self-nucleation strength, starts to increase sharply once the content of ODPA exceeds 1.8 mol%. In contrast, the width of Domain IIb (self-seeding domain) remains constant. We attribute the self-nucleation effect in these ODPA copolymers to the aggregation of co-units in the interlamellar amorphous regions that hinder, upon melting, the motion of the chain sequences that were initially packed within the crystal lattice. In this way, to reach the isotropic melt state, the sample must be heated to much higher temperatures than its apparent or even equilibrium melting point, depending on the comonomer content. Consequently, nucleation upon cooling from the self-nucleated melt becomes easier and faster.