Many synthetic polymers used to form polymer-brush films feature a main backbone with functional, oligomeric side chains. While the structure of such graft polymers mimics biomacromolecules to an extent, it lacks the monodispersity and structural purity present in nature. Here we demonstrate that side-chain heterogeneity within graft polymers significantly influences hydration and the occurrence of hydrophobic interactions in the subsequently formed brushes and consequently impacts fundamental interfacial properties. This is demonstrated for the case of poly(methacrylate)s (PMAs) presenting oligomeric side chains of different length (n) and dispersity. A precise tuning of brush structure was achieved by first synthesizing oligo(2-ethyl-2-oxazoline) methacrylates (OEOXMAs) by cationic ring-opening polymerization (CROP), subsequently purifying them into discrete macromonomers with distinct values of n by column chromatography, and finally obtaining poly[oligo(2-ethyl-2-oxazoline) methacrylate]s (POEOXMAs) by reversible addition–fragmentation chain-transfer (RAFT) polymerization. Assembly of POEOXMA on Au surfaces yielded graft polymer brushes with different side-chain dispersities and lengths, whose properties were thoroughly investigated by a combination of variable angle spectroscopic ellipsometry (VASE), quartz crystal microbalance with dissipation (QCMD), and atomic force microscopy (AFM) methods. Side-chain dispersity, or dispersity within brushes, leads to assemblies that are more hydrated, less adhesive, and more lubricious and biopassive compared to analogous films obtained from graft polymers characterized by a homogeneous structure.

Amphiphilic methacrylate copolymers (Si-co-EF) containing polysiloxane (Si) and mixed poly(oxyethylene)–perfluorohexyl (EF) side chains were synthesized with different compositions and used together with polysiloxane-functionalized nanoparticles as additives of condensation cured nanocomposite poly(siloxane) films. The mechanical properties of the nanocomposite films were consistent with the elastomeric behavior of the poly(siloxane) matrix without significant detriment from either the copolymer or the nanoparticles. Films were found to be markedly hydrophobic and liphophobic, with both properties being maximized at an intermediate content of EF units. The high enrichment in fluorine at the film surface was proven by angle-resolved X-ray photoelectron spectroscopy (AR-XPS). Long-term marine antifouling performance was evaluated in field immersion trials of test panels for up to 10 months of immersion. Both nanoparticles and amphiphilic copolymer were found to be highly effective in reducing the colonization of foulants, especially hard macrofoulants, when compared with control panels. Lowest percentage of surface coverage was 20% after 10 months of immersion (films with 4 wt% copolymer and 0.5 wt% nanoparticles), which was further decreased to less than 10% after exposure to a water jet for 10 s. The enhanced antifouling properties of coatings containing both nanoparticles and copolymer were confirmed by laboratory assays against the polychaete Ficopomatus enigmaticus and the diatom Navicula salinicola.

Poly(dimethylsiloxane) (PDMS) elastomer coatings containing an amphiphilic hydrolyzable diblock copolymer additive were prepared and their potential as marine antifouling and antiadhesion materials was tested. The block copolymer additive consisted of a PDMS first block and a random poly(trialkylsilyl methacrylate (TRSiMA, R = butyl, isopropyl)-co-poly(ethyleneglycol) methacrylate (PEGMA) copolymer second block. PDMS-b-TRSiMA block copolymer additives without PEGMA units were also used as additives. The amphiphilic character of the coating surface was assessed in water using the captive air bubble technique for measurements of static and dynamic contact angles. The attachment of macro- and microorganisms on the coatings was evaluated by field tests and by performing adhesion tests to the barnacle Amphibalanus amphitrite and the green alga Ulva rigida. All the additive-based PDMS coatings showed better antiadhesion properties to A. amphitrite larvae than to U. rigida spores. Field tests provided meaningful information on the antifouling and fouling release activity of coatings over an immersion period of 23 months.