Amphiphilic zwitterionic-PDMS-based surface-modifying additives to tune fouling-release of siloxane-polyurethane marine coatings

[Display omitted] •PDMS-poly(SBMA) Amphiphilic additives via controlled free radical polymerization.•Amphiphilic additives incorporated into marine hydrophobic coating.•Amphiphilic additives improved release of barnacles & U. linza from coating.•Novel, amphiphilic, surface-modifying additives for marine coatings. Amphiphilic coatings have shown promising performance for marine applications to deter and limit biofouling. Hydrophobic marine coatings are unable to deter marine organisms that prefer hydrophobic surfaces for settlements, thus a series of amphiphilic additives were prepared and introduced to a hydrophobic system to attain surface amphiphilicity and improved performance without changing the base matrix. In this work, we report the successful synthesis of amphiphilic additives where highly incompatible blocks of hydrophobic polydimethylsiloxane (PDMS) and hydrophilic poly(sulfobetaine methacrylate) (poly(SBMA)) were connected, using ARGET ATRP (activators regenerated by electron transfer atom transfer radical polymerization) controlled radical polymerization technique. The surface characterization confirmed the presence of self-migrated amphiphilic additives to the surface of hydrophobic coating systems, and biological assessments indicated that the additives desirably improved fouling-release performance of the base hydrophobic system against macroalgal spores (Ulva linza) and barnacles (Amphibalanus amphitrite) while these additives had no detrimental effect on ability of the base matrix to release bacteria (Cellulophaga lytica), diatoms (Navicula incerta), and mussels (Geukensia demissa). Furthermore, this study not only reported the outstanding contribution of poly(SBMA)-PDMS additives towards contending with marine biofouling as well as the facile preparation of amphiphilic additives, but also concluded that several factors should be considered in the design of these additives for tailoring hydrophobic coatings: 1) PDMS block with a molecular weight of 1000 M¯n is preferred over higher molecular weights of PDMS; 2) hydrophilic portion between a range of 50% to 80% provides the desired amphiphilicity on a surface; and 3) poly(SBMA) block size does not necessarily impact the effectiveness of an additive.