Self-Organization of Graft Copolymers and Retortable iPP-Based Nanoporous Films Thereof

Abstract

Polyolefins might become inexpensive alternatives to the existing membranes based on polyethersulfone. Here, we disclose the production of retortable, well-defined polypropylene (PP)-based nanoporous films derived from amphiphilic graft copolymer precursors. The graft copolymers, containing a polypropylene backbone and polyester grafts, were obtained by grafting lactones, specifically δ-valerolactone and ε-caprolactone, from well-defined randomly functionalized poly(propylene-co-10-undecen-1-ol) as a macroinitiator. Depending on the composition, the graft copolymers self-assemble into droplet, cylindrical, lamellar, or interconnected two-phase morphologies. Functional mesoporous iPP-based films were fabricated by the selective degradation of the polyester blocks of the copolymers. Their structure and morphology were studied using atomic force microscopy (AFM), scanning electron microscopy (SEM), small-angle X-ray scattering (SAXS), and solid-state NMR, while the mesoporosity was assessed by nitrogen sorption experiments. The pore size of the films is strongly influenced not only by the volume fraction of the copolymer blocks but unexpectedly also by the topology (i.e., number of grafts) of the graft copolymer, as was confirmed by computational modeling studies using the dynamic density functional theory (DDFT) engine within the Culgi software. This work provides a conclusive answer on how the morphology of iPP-based graft copolymers is tuned by the copolymer composition and the amount and length of the grafted polyester blocks. Filtration tests and flux determination demonstrated that such structurally well-defined mesoporous products could be considered for the development of ultrafiltration membranes while the chemical resistance and sterilization tests revealed their robust performance and suitability for water purification applications.