Antibacterial and antifouling performance of bisphenol-A/Poly(ethylene glycol) binary epoxy coatings containing bromine-benzyl-disubstituted polyaniline
Introduction
Biofouling remains an important issue for the surface applications such as in public utilities, medical devices and the marine industries [1,2]. Biofouling can cause health problems, disable the surface functions and even result in accidents. Biofouling undergoes four processes which are of the conditioning film, primary colonization, secondary colonization and tertiary colonization [3]. Corresponding to different biofouling stages, strategies such as fouling release, fouling resistance and antimicrobial could be applied to prevent fouling process [4,5]. However, fouling will eventually colonize the surface. In this situation, functional antifoulants can inhibit or kill fouling organisms, preventing the formation of biofilms. Thus, to prepare excellent antifouling coatings which can function before and after the fouling settles, the coating matrix materials and the functional antifoulants are of great importance and should be well designed in consideration of their physical and chemical properties.
Matrix materials such as epoxy coatings, fluorine-based coatings, silicone-based coatings, polyurethane coatings, polyacrylate coatings, and PEG-based coatings have been investigated for antifouling applications [[6], [7], [8], [9], [10]]. The excellent antifouling performance of the low-surface-energy materials such as epoxy coatings, fluorine-based coatings and silicone-based coatings can be attributed to the fouling release effect which makes it easy to sweep fouling away from the coating surfaces [[11], [12], [13]]. In addition, hydrolysable polymers such as polyurethane and polyacrylate are applied in self-polishing coatings and possess good antifouling performance [[14], [15], [16]]. Besides, PEG-based coatings have excellent antifouling performance which can be ascribed to the steric repulsion force of the hydration shell formed by the H-bond-induced water molecules nearby the PEG chains [4,17]. To improve antifouling performance, composite matrixes combining low-surface-energy materials and PEG-based materials were also prepared [[18], [19], [20], [21]]. Composite matrixes undergo microphase separation giving rise to both hydrophobic and hydrophilic phases, which can benefit antifouling performance against more fouling species. Furthermore, microphase separation can expose more antifoulant particle area to sterilize biofouling [22,23]. Besides, composite matrixes combining low-surface-energy materials and PEG-based materials can make up the weak mechanical strength of PEG-based coatings. Bisphenol-A epoxy have been widely applied to protect surfaces for their advantages such as high strength, good adhesion and excellent scratch [24]. Thus, bisphenol-A epoxy and PEG-epoxy can be applied together as excellent coating matrix materials to improve the mechanical strength and antifouling performance.
Antifoulants are considerably important for the long-term antifouling performance. There are many kinds of materials which can be used as antifoulants including natural products, metals or metal oxide, organic micromolecule and polymers [[25], [26], [27], [28]]. Natural products such as chitosan, plant polyphenols and butenolide were studied and applied in antifouling, while the cost-effective mass production of natural products restricts their applications in antifouling [[29], [30], [31], [32]]. Metal and metal oxide nanomaterials (such as tributyltin, cuprous oxide, zinc oxide, silver) are most widely used antifoulants and possess effective antifouling performance. However, some of these antifoulants have been banned or discouraged due to their high toxicity [[33], [34], [35], [36]]. Organic micromolecule (such as quaternary ammonium cation and biguanide) have high antibacterial efficiency [37]. The disadvantage of organic micromolecule antifoulants is their penetrative property. Recently, polyaniline and its derivates have drawn much attention in antifouling taking advantage of their nonvolatile and impermeable properties [[38], [39], [40]]. However, owing to its cation antibacterial mechanism, PANI cannot be used in the environment with the pH higher than 3 [41]. Besides, to prepare high sterilization surface, antifoulants should be enriched on the surface and sterilization functional groups should orient toward the outside of the surfaces. Thus, PANI should be modified with effective antibacterial groups and hydrophobic groups for better antifouling performance. PANI derivatives such as bromine-substituted PANI and quaternary ammonium polycations can be easily prepared and possess high antibacterial activity [[41], [42], [43]]. By benzyl substitution, benzyl-substituted PANI (BP) can be prepared with lots of hydrophobic benzyl groups which can move or orient toward the surface promoted by hydrophilic segments [44]. Thus, bromine-benzyl-disubstituted PANI (BBP) was further prepared as a multifunctional antifoulant.
Herein, bisphenol-A/Poly(ethylene glycol) binary epoxy coatings (BAE/PEGE) containing BBP were prepared which combined fouling release effect of BAE segments, fouling resistance effect of PEG segments and the sterilization activity of BBP. Phase separation degree can be controlled by adjusting the ratio of PEG in coatings. PEG segments in the coatings can swell to expose more functional sites of BBP nanoparticles toward the surface while high strength of the coatings can be remained due to the bisphenol-A epoxy segments. In addition, BBP has lots of hydrophobic benzyl groups and can be propelled to move or orient toward the surface. Besides, BBP has the structure of both amine and benzyl groups, which can improve the compatibility of hydrophilic PEG segments with other hydrophobic segments. The as-prepared coatings showed high antibacterial and antifouling performance and can be easily applied on many substrates.
Section snippets
Materials
Aniline, ammonium (APS), sulfuric acid (98%), ammonium hydroxide (25%), benzyl chloride, N-Methyl pyrrolidone (NMP), ethyl alcohol and ethyl acetate were purchased from Jiangtian Chemical Reagent Co. Ltd. (Tianjin, China). Potassium bromide and potassium bromate were purchased from Guangfu Chemical Reagent Co. Ltd. (Tianjin, China). The bisphenol-A epoxy (BAE, 0.41–0.47 eq/100 g) was provided by Tianjin Yanhai Co. Ltd., China. Polyethylene glycol epoxy (PEGE, Mn = 400) was obtained from Heowns
Characterizations of PANI, BP and BBP
Fig. 2 presents the SEM images of PANI, BP and BBP. PANI has the morphology of nanofibers while BP and BBP are nanoparticles. The nanofibers morphology of PANI was damaged during benzylation and bromination process.
The FT-IR spectrum was performed to characterize the polymer structure. Fig. 3a shows the similar FT-IR spectrums for PANI, BP and BBP. A broad absorption at 3200–3430 cm−1 corresponds to NH and NH2 groups with hydrogen bonds. The band at 3030 cm−1 can be attributed to the stretching
Conclusions
In this work, PANI, BP and BBP were successfully prepared and characterized. Benzyl groups substituted in the amine groups of PANI endow BP with high hydrophobic property. In addition, bromine groups substituted in benzene rings of PANI enable BBP high antibacterial performance. The sterilization ratio of BBP suspension with a concentration of 4 mg/mL is up to 100% against E. coli and B. subtilis. Coatings with different amount PEGE and BBP nanoparticles were prepared. BBP nanoparticles with
Acknowledgments
This work was supported by Public Science and Technology Research Funds Projects of Ocean (No. 201405013-5), Tianjin Research Program of Basic Research and Frontier Technology (No. 15JCQNJC43400), SKL-ChE-17T01.
References (52)
- et al.
Modified tannin extracted from black wattle tree as an environmentally friendly antifouling pigment
Ind. Crop. Prod.
(2015) - et al.
Polymer brush coatings for combating marine biofouling
Prog. Polym. Sci.
(2014) - et al.
Triple antifouling strategies for reverse osmosis membrane biofouling control
J. Membr. Sci.
(2018) - et al.
UV-curable enzymatic antibacterial waterborne polyurethane coating
Biochem. Eng. J.
(2016) - et al.
Effect of Polyethylene glycol methyl ether blend humic acid on poly (vinylidene fluoride-co-hexafluropropylene) PVDF-HFP membranes: pH responsiveness and antifouling behavior with optimization approach
Polym. Test.
(2017) - et al.
Surface studies on superhydrophobic and oleophobic polydimethylsiloxane–silica nanocomposite coating system
Appl. Surf. Sci.
(2012) - et al.
Enhancing the permeation flux and antifouling performance of polyamide nanofiltration membrane by incorporation of PEG-POSS nanoparticles
J. Membr. Sci.
(2017) - et al.
New pegylated hyperbranched polyester as chemical modifier of epoxy resins in UV cationic photocuring
React. Funct. Polym.
(2011) - et al.
Investigation of corrosion protection performance of epoxy coatings modified by polyaniline/clay nanocomposites on steel surfaces
Prog. Org. Coat.
(2014) - et al.
A review of the recent advances in antimicrobial coatings for urinary catheters
Acta Biomater.
(2017)
Pigmented edible bean coats as natural sources of polyphenols with antioxidant and antibacterial effects
LWT-Food Sci. Technol.
Study on antibacterial activity of chemically synthesized PANI-Ag-Au nanocomposite
Appl. Surf. Sci.
Bifunctional CuO/TiO 2 nanocomposite as nanofiller for improved corrosion resistance and antibacterial protection
Prog. Org. Coat.
Antibacterial activity and mechanism of chitosan with ultra high molecular weight
Carbohydr. Polym.
Morphological, electrical & antibacterial properties of trilayered Cs/PAA/PPy bionanocomposites hydrogel based on Fe3O4-NPs
Carbohydr. Polym.
TBT is still a matter of concern in Peru
Chemosphere
Covalent bonding of AgNPs to 304 stainless steel by reduction in situ for antifouling applications
Appl. Surf. Sci.
Synthesis of chitosan capped copper oxide nanoleaves using high intensity (30 kHz) ultrasound sonication and their application in antifouling coatings
Ultrason. Sonochem.
Synthesis and characterization of the NiFe2O4@TEOS-TPS@Ag nanocomposite and investigation of its antibacterial activity
Appl. Surf. Sci.
Antibacterial cotton fibers treated with silver nanoparticles and quaternary ammonium salts
Carbohydr. Polym.
Colloidal polyaniline dispersions: antibacterial activity, cytotoxicity and neutrophil oxidative burst
Colloids Surf. B Biointerfaces
Functionalized polyanilines disrupt Pseudomonas aeruginosa and Staphylococcus aureus biofilms
Colloids Surf., B
Improved antibacterial, antifouling and corrosion protective performance of epoxy coatings with poly(m -aminophenol)
Prog. Org. Coat.
Poly(ethylene glycol)-grafted silica nanoparticles for highly hydrophilic acrylic-based polyurethane coatings
Prog. Org. Coat.
The improvement of free-radical scavenging capacity of the phosphate medium electrosynthesized polyaniline
Electrochim. Acta
Antifouling ultrafiltration membranes by selective swelling of polystyrene/poly(ethylene oxide) block copolymers
J. Membr. Sci.
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