Release of Polymeric Biocides from Synthetic Matrices for Marine Biofouling Applications

Abstract

Marine biofouling is a natural phenomenon representing one of the greatest problems in marine technology (navigation, aquaculture nets, etc). To circumvent these problems, antifouling paints or coatings, i.e. matrices containing biocidal species, are used to protect the submerged surfaces and objects. Polymers containing quaternary phosphonium or quaternary ammonium groups are promising biocidal materials. Such a biocidal polymeric material is the polymeric salt PSSAmC16 formed between the polystyrene sulfonate anion and the cetyltrimethylammonium cation. When embedded into a paint or a polymeric matrix, the cation of PSSAmC16 is gradually dissolved in the surrounding water through an ion exchange mechanism, offering the biocidal protection of the surface. In the present work, the release of PSSAmC16 from the synthetic polymeric matrix poly(methyl methacrylate), PMMA, was evaluated, as a function of the contact time with the surrounding aqueous environment. The PSSAmC16 content in the matrix varied from 0 up to 40 % (wt/wt), while aqueous NaCl solutions with a salt concentration up to 2M were investigated. The release of the polymeric biocidal was quantified through Total Organic Carbon (TOC) and Total Nitrogen (TN) measurements. Both methods reveal that the major part of the polymeric biocidal is released within a few days, while release increases with the PSSAmC16 content and it is enhanced by the salinity.

Evaluation of the release characteristics of covalently attached or electrostatically bound biocidal polymers utilizing SERS and UV-Vis absorption

“…From these results, the overall quantity of the released material, namely the sum of the masses of its components found in solution, is determined at 2.8 mg. This quantity is ~70% of the PSSAmC16 content (4 mg) of the PMMA film, in a very good agreement with the results found through Total Organic Carbon and Total Nitrogen determination for the release of PSSAmC16 for similar release studies [18]. The projection of the concentration to the moles of PSSAmC16 released after a few weeks of immersion reveals a number of 0.80·10 -6 moles of styrene sulfonate units of PSS detected by the UV-Vis measurements vis-à-vis to the number of 0.70·10 -6 moles of AmC16 cations probed by SERS measurements.…”

“…While the solubility of PSSAmC16 in pure water is limited, the polymer is soluble in aqueous 0.5 M NaCl solution [18]. So, the UV-Vis spectra of PSSAmC16 and CTAB in this seawater simulant were evaluated ( Figure 3).…”

Evaluation of Antimicrobial Efficiency of New Polymers Comprised by Covalently Attached and/or Electrostatically Bound Bacteriostatic Species, Based on Quaternary Ammonium Compounds

“…The homopolymers poly(cetyltrimethylammonium 4-styrene sulfonate) (PSSAmC 16 ) and poly(hexadecyltributylphosphonium 4-styrene sulfonate) (PSSPhC 16 ) were synthesized through electrostatic interaction between PSSNa and the surfactants cetyltrimethylammonium bromide (CTAB) or hexadecyltributylphosphonium bromide (HTPB), respectively [18,36]. The quaternization of the homopolymer poly(vinyl benzyl chloride) (PVBC), with N,N-dimethylhexadecylamine (HAM), took place after the polymerization of vinyl benzyl chloride through free radical polymerization (FRP) in CHCl 3 using AIBN as initiator.…”

Polymeric Coatings Based on Water-Soluble Trimethylammonium Copolymers for Antifouling Applications

“…The behavior of the coated nets in aqueous environment was investigated, prior to the fouling tests under accelerated fouling conditions [29]. Small pieces of the coated nets were immersed in pure water or 3.5%(w/v) NaCl solutions and the evolution of Total Organic Carbon (TOC) and Total Nitrogen (TN) was monitored with immersion time.…”