Antibiofouling Hybrid Dendritic Boltorn/Star PEG Thiol-ene Cross-Linked Networks

A series of thiol-ene generated amphiphilic crosslinked networks was prepared by reaction of alkene-modified Boltorn polyesters (Boltorn-ene) with varying weight percent of 4-armed poly(ethylene glycol) (PEG) tetrathiol (0-25 wt %) and varying equivalents of pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) (0-64 wt %). These materials were designed to present complex surface topographies and morphologies, with heterogeneity of surface composition and properties and robust mechanical properties, to serve as nontoxic antibiofouling coatings that are amenable to large-scale production for application in the marine environment. Therefore, a two-dimensional matrix of materials compositions was prepared to study the physical and mechanical properties, over which the compositions spanned from 0 to 25 wt % PEG tetrathiol and 0-64 wt % PETMP (the overall thiol/alkene (SH/ene) ratios ranged from 0.00 to 1.00 equiv), with both cross-linker weight percentages calculated with respect to the weight of Boltorn-ene. The Boltorn-ene components were prepared through the esterification of commercially available Boltorn H30 with 3-butenoic acid. The subsequent cross-linking of the Boltorn-PEG-PETMP films was monitored using IR spectroscopy, where it was found that near-complete consumption of both thiol and alkene groups occurred when the stoichiometry was ca. 48 wt % PETMP (0.75 equiv SH/ene, independent of PEG amount). The thermal properties of the films showed an increase in T-g with an increase in 4-armed PEG-tetrathiol wt %, regardless of the PETMP concentration. Investigation of the bulk mechanical properties in dry and wet states found that the Young's modulus was the greatest at 48 wt % PETMP (0.7.5 equiv of SH/ene). The ultimate tensile strength increased when PETMP was constant and the PEG concentration was increased: The Young's modulus was slightly lower for wet films at constant PEG or constant PETMP amounts, than for the dry samples. The nanoscopic surface features were probed using atomic force microscopy (AFM), where it was observed that the surface of the amphiphilic films became increasingly rough with increasing PEG wt %. On the basis of the physicochemical data from the diverse sample matrix, a focused compositional profile was then investigated further to determine the antifouling performance of the cross-linked Boltorn-PEG-PETMP networks. For these studies, a low, constant PETMP concentration of 16 wt % was maintained with variation in the PEG wt % (0-35 wt %). Antifouling and fouling-release activities were tested against the marine alga Ulva. Spore settlement densities were low on these films, compared to that on standards of polydimethylsiloxane and glass.