Abstract
Poly(ethyl ethylene phosphonate)-based methacrylic copolymers containing polysiloxane methacrylate (SiMA) co-units are proposed as surface-active additives as alternative solutions to the more investigated polyzwitterionic and polyethylene glycol counterparts for the fabrication of novel PDMS-based coatings for marine antifouling applications. In particular, the same hydrophobic SiMA macromonomer was copolymerized with a methacrylate carrying a poly(ethyl ethylene phosphonate) (PEtEPMA), a phosphorylcholine (MPC), and a poly(ethylene glycol) (PEGMA) side chain to obtain non-water soluble copolymers with similar mole content of the different hydrophilic units. The hydrolysis of poly(ethyl ethylene phosphonate)-based polymers was also studied in conditions similar to those of the marine environment to investigate their potential as erodible films. Copolymers of the three classes were blended into a condensation cure PDMS matrix in two different loadings (10 and 20 wt%) to prepare the top-coat of three-layer films to be subjected to wettability analysis and bioassays with marine model organisms. Water contact angle measurements showed that all of the films underwent surface reconstruction upon prolonged immersion in water, becoming much more hydrophilic. Interestingly, the extent of surface modification appeared to be affected by the type of hydrophilic units, showing a tendency to increase according to the order PEGMA < MPC < PEtEPMA. Biological tests showed that Ficopomatus enigmaticus release was maximized on the most hydrophilic film containing 10 wt% of the PEtEP-based copolymer. Moreover, coatings with a 10 wt% loading of the copolymer performed better than those containing 20 wt% for the removal of both Ficopomatus and Navicula, independent from the copolymer nature.
Highlights
The macromonomer poly(ethyl ethylene phosphonate) methacrylate (PEtEPMA) was obtained by terminating the polymerization with an excess of 2-isocyanatoethyl methacrylate (Scheme 1)
The results suggest that, despite the random structure of the copolymers, the chemically incompatible polyphosphonate (or polyzwitterion or poly(ethylene glycol)) and polysiloxane side chains were able to self-assemble in separated microdomains characterized by the thermal behavior of the corresponding homopolymers
PEtEPMA-based films derived therefrom were proven to be more susceptible to surface reconstruction after prolonged exposure to water than the corresponding MPC and poly(ethylene glycol) methyl ether methacrylate (PEGMA)-based coatings
Summary
Along with hydrophilicity, thermo-responsiveness, biocompatibility, potential biodegradability, possibility to introduce a functional group in the chain end, and similarity to biomacromolecules such as nucleic acids, are some of the many aspects that make polyphosphonates very appealing for biological and biomedical applications [7]. They have been studied as drug nanocarriers [8], or in protein-polymer conjugation [9]
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