Elsevier

Progress in Organic Coatings

Volume 124, November 2018, Pages 61-70
Progress in Organic Coatings

Antibacterial and antifouling performance of bisphenol-A/Poly(ethylene glycol) binary epoxy coatings containing bromine-benzyl-disubstituted polyaniline

https://doi.org/10.1016/j.porgcoat.2018.08.010Get rights and content

Highlights

  • Benzyl-substituted PANI was prepared and exhibited high hydrophobicity.

  • Bromine-benzyl-disubstituted PANI was prepared and had high sterilization activity.

  • Coating phase structures can be adjusted by varying the PEGE ratio.

  • Coatings with PEGE and BBP nanoparticles have improved antibacterial and antifouling performance.

Abstract

Polyaniline (PANI), benzyl-substituted polyaniline (BP) and bromine-benzyl-disubstituted polyaniline(BBP) were prepared and characterized by scanning electron microscope (SEM), Fourier transform infrared (FT-IR), UV–vis absorption spectra, wettability test and thermogravimetric Analysis (TGA). It is noted that BBP nanoparticles has high antibacterial activity against both Gram-negative E. coil and Gram-positive B. subtilis while PANI and BP do not have obvious antibacterial activity. The bisphenol-A/Poly(ethylene glycol) binary epoxy coatings (BAE/PEGE) containing BBP were prepared using cardanol-based phenalkamine as curing agent. The prepared coatings were evaluated by wettability test, optical microscope, AFM, SEM, TGA, antibacterial and antifouling tests. The results demonstrate that the prepared coatings with PEGE and BBP exhibits improved antibacterial and antifouling performance comparing with pure bisphenol-A epoxy coating. The combination of fouling release effect of BAE, fouling resistance function of PEG and sterilization function of BBP is a promising strategy to improve the antibacterial and antifouling performance of prepared coating surfaces.

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.

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