Synthesis of bottlebrush copolymers based on poly(dimethylsiloxane) for surface active additives

Abstract

Abstract Bottlebrush polymers have been used as surface-active additives for chemically-identical linear polymers because they spontaneously accumulate at surfaces through an entropy-mediated process. In this work, we design functional bottlebrush polymer additives with mixed side-chain chemistries that can deliver unique surface properties. Bottlebrush polymers with poly(dimethylsiloxane) (PDMS) side-chains and bottlebrush copolymers with PDMS and poly(lactic acid) (PLA) side-chains are synthesized using ring opening metathesis polymerization. Contact angle goniometry, X-ray photoelectron spectroscopy (XPS), and microscopy demonstrate a spontaneous accumulation of these additives at the film surface without lateral phase segregation. Bottlebrush polymers were found to enrich the film surface more strongly than linear block copolymers of PDMS-b-PLA, and the surface contact angle was tunable by varying the composition and quantity of added bottlebrush copolymer. Significantly, bottlebrush additives segregate rapidly, during film casting. This work demonstrates that low-surface energy bottlebrush copolymer additives can be used to introduce new surface properties in polymer films.