Preparation and Antifouling Properties of N-Methylol Acrylamide (NMA)-Modified Acrylic Resins

doi:10.11902/1005.4537.2024.115

Journal of Chinese Society for Corrosion and protection

2025, Vol. 45

Issue (3): 747-756 DOI: 10.11902/1005.4537.2024.115

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Preparation and Antifouling Properties of N-Methylol Acrylamide (NMA)-Modified Acrylic Resins

TIAN Qiumei, NI Chunhua, LUO Yunpeng, WANG Yanjian, XU Hao, LI Xia, YU Liangmin, YAN Xuefeng(

)

Key Laboratory of Marine Chemistry Theory and Technology of Ministry of Education, Ocean University of China, Qingdao 266100, China

Cite this article:

TIAN Qiumei, NI Chunhua, LUO Yunpeng, WANG Yanjian, XU Hao, LI Xia, YU Liangmin, YAN Xuefeng. Preparation and Antifouling Properties of N-Methylol Acrylamide (NMA)-Modified Acrylic Resins. Journal of Chinese Society for Corrosion and protection, 2025, 45(3): 747-756.

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Abstract

A novel self-renewable coating RZn-NMA-X with self-crosslinking properties and antifouling performance was prepared by introducing N-Methylol acrylamide (NMA) into a self-polishing acrylic resin. The coating formed by the combination of a self-polishing resin with a hydrophilic crosslinking network referred to as RZn-NMA-X, exhibited a stable hydrolysis rate and stable film-forming surface in seawater in a 60 d static soaking test. The laboratory bioassay and 150 d marine field test showed that the RZn-NMA-X polymer has good antifouling properties with an optimal content of 5%NMA. In conclusion, the incorporation of an appropriate amount of NMA not only enhances the antifouling performance of the coating, but also provides assurance for its gradual polishing and resistance to biofouling due to its favorable surface characteristics, which is beneficial for enhancing the longevity of marine antifouling in coating applications. The preparation method suggested in this study is straightforward, and the raw materials are affordable and readily available, making it suitable for large-scale production in antifouling applications.

Key words: acrylic resin self-polishing self-crosslinking antifouling N-Methylol acrylamide (NMA)

Received: 07 April 2024 32134.14.1005.4537.2024.115

ZTFLH:

TG174

Fund: National Natural Science Foundation of China(U22A20112);Natural Science Foundation of Hainan Province(522CXTD520);Key Research and Development Project of Shandong Province(2022CXGC020401)

Corresponding Authors: YAN Xuefeng, E-mail: yanxuefeng@ouc.edu.cn

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	Articles by authors
	TIAN Qiumei
	NI Chunhua
	LUO Yunpeng
	WANG Yanjian
	XU Hao
	LI Xia
	YU Liangmin
	YAN Xuefeng

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https://www.jcscp.org/EN/10.11902/1005.4537.2024.115 OR https://www.jcscp.org/EN/Y2025/V45/I3/747

Fig.1 Synthetic route (a) and synthetic process (b) of RZn-NMA-X polymers

Table 1 Experimental formulations of RZn-NMA-X polymers

Fig.2 Wavelength scan (a) and standard curve (b) of N. closterium

Table 2 Basic indexes of RZn-NMA-X resin

Fig.3 FTIR spectra of NMA-containing acrylic polymers

Fig.4 Adhesions of RZn-NMA-X polymer coatings

Fig.5 Mass losses of RZn-NMA-X polymer coatings during immersion in seawater for 60 d (a), and changes of contact angle for the coatings before and after 50 d soaking (b)

Fig.6 Digital images (a), laser confocal topographies (b), and laser confocal 3D topographies and corresponding surface roughnesses (c) of RZn-NMA-X polymer with the coatings after soaking for different time

Fig.7 Antibacterial effects (a) and percent inhibitions (b) of RZn-NMA-X polymer coatings against Pseudoalteromonas sp.

Fig.8 Growth inhibition curves of RZn-NMA-X on N. closterium

Fig.9 Attachments of fouling organisms on the control (a1-d1), RZn-NMA-0 (a2-d2)， RZn-NMA-5 (a3-d3), RZn-NMA-10(a4-d4) and RZn-NMA-15 (a5-d5) polymer coatings after soaking for 30 d (a), 60 d (b), 90 d (c) and 150 d (d) in the seawater of Jiaozhou Bay

Table 3 Anti-fouling scoring results of the test panel after immersion for 150 d

Fig.10 Antifouling mechanism of RZn-NMA-X polymer coating

[1]	Jin H C, Tian L M, Bing W, et al. Bioinspired marine antifouling coatings: Status, prospects, and future [J]. Prog. Mater. Sci., 2022, 124: 100889
[2]	Ferreira O, Rijo P, Gomes J F, et al. Biofouling inhibition with grafted econea biocide: Toward a nonreleasing eco-friendly multiresistant antifouling coating [J]. ACS Sustainable Chem. Eng., 2020, 8: 12
[3]	Yebra D M, Kiil S, Dam-Johansen K. Antifouling technology-past, present and future steps towards efficient and environmentally friendly antifouling coatings [J]. Prog. Org. Coat., 2004, 50: 75
[4]	Maan A M C, Hofman A H, de Vos W M, et al. Recent developments and practical feasibility of polymer-based antifouling coatings [J]. Adv. Funct. Mater., 2020, 30: 2000936
[5]	Schultz M P, Bendick J A, Holm E R, et al. Economic impact of biofouling on a naval surface ship [J]. Biofouling, 2011, 27: 87
[6]	Dafforn K A, Lewis J A, Johnston E L. Antifouling strategies: History and regulation, ecological impacts and mitigation [J]. Mar. Pollut. Bull., 2011, 62: 453
[7]	Lejars M, Margaillan A, Bressy C. Fouling release coatings: A nontoxic alternative to biocidal antifouling coatings [J]. Chem. Rev., 2012, 112: 4347
[8]	Nurioglu A G, Esteves A C C, de With G. Non-toxic, non-biocide-release antifouling coatings based on molecular structure design for marine applications [J]. J. Mater. Chem. B, 2015, 3: 6547
[9]	Ke N, Ni Y Y, He J Q, et al. Research progress of metal corrosion caused by extracellular polymeric substances of microorganisms [J]. J. Chin. Soc. Corros. Prot., 2024, 44: 278
	柯楠, 倪莹莹, 何嘉淇等. 微生物胞外聚合物引起的金属腐蚀的研究进展 [J]. 中国腐蚀与防护学报, 2024, 44: 278
[10]	Hu J Z, Shangguan J Y, Deng P C, et al. Effect of barnacle adhesion on corrosion behavior of Q235 steel [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 1145
	胡杰珍, 上官桔钰, 邓培昌等. 基于阵列电极技术研究藤壶附着对Q235钢腐蚀行为的影响 [J]. 中国腐蚀与防护学报, 2023, 43: 1145
[11]	Ma S D, Chen X, Tai Y, et al. Ecological study on fouling organisms in a marine environmental test station situated at Sanya bay [J]. J. Chin. Soc. Corros. Prot., 2024, 44: 38
	马士德, 陈新, 邰余等. 三亚海洋环境试验站污损生物生态研究 [J]. 中国腐蚀与防护学报, 2024, 44: 38
[12]	Almeida E, Diamantino T C, de Sousa O. Marine paints: The particular case of antifouling paints [J]. Prog. Org. Coat., 2007, 59: 2
[13]	Amara I, Miled W, Slama R B, et al. Antifouling processes and toxicity effects of antifouling paints on marine environment. A review [J]. Environ. Toxicol. Pharmacol., 2018, 57: 115
[14]	Callow J A, Callow M E. Trends in the development of environmentally friendly fouling-resistant marine coatings [J]. Nat. Commun., 2011, 2: 244
[15]	Banerjee I, Pangule R C, Kane R S. Antifouling coatings: Recent developments in the design of surfaces that prevent fouling by proteins, bacteria, and marine organisms [J]. Adv. Mater., 2011, 23: 690
[16]	Sha J N, Chen R R, Yu J, et al. Dynamic multi-level microstructured antifouling surfaces by combining quaternary ammonium modified go with self-polishing copolymers [J]. Carbon, 2023, 201: 1038
[17]	Chen R R, Li Y K, Tang L, et al. Synthesis of zinc-based acrylate copolymers and their marine antifouling application [J]. RSC Adv., 2017, 7: 40020
[18]	Xu W T, Ma C F, Ma J L, et al. Marine biofouling resistance of polyurethane with biodegradation and hydrolyzation [J]. ACS Appl. Mater. Interfaces, 2014, 6: 4017
[19]	Li N, Xu Z, Zheng S, et al. Superamphiphilic TiO₂ composite surface for protein antifouling [J]. Adv. Mater., 2021, 33: 2003559
[20]	Huang Z X, Ghasemi H. Hydrophilic polymer-based anti-biofouling coatings: Preparation, mechanism, and durability [J]. Adv. Colloid Interface Sci., 2020, 284: 102264
[21]	Leng C, Hung H C, Sun S W, et al. Probing the surface hydration of nonfouling zwitterionic and peg materials in contact with proteins [J]. ACS Appl. Mater. Interfaces, 2015, 7: 16881
[22]	Wu J, Zhao C, Hu R D, et al. Probing the weak interaction of proteins with neutral and zwitterionic antifouling polymers [J]. Acta Biomater., 2014, 10: 751
[23]	Koschitzki F, Wanka R, Sobota L, et al. Amphiphilic dicyclopentenyl/carboxybetaine-containing copolymers for marine fouling-release applications [J]. ACS Appl. Mater. Interfaces, 2020, 12: 34148
[24]	Ye Q, He B L, Zhang Y, et al. Grafting robust thick zwitterionic polymer brushes via subsurface-initiated ring-opening metathesis polymerization for antimicrobial and anti-biofouling [J]. ACS Appl. Mater. Interfaces, 2019, 11: 39171
[25]	Guo S S, Jańczewski D, Zhu X Y, et al. Surface charge control for zwitterionic polymer brushes: Tailoring surface properties to antifouling applications [J]. J. Colloid Interface Sci., 2015, 452: 43
[26]	Kardela J H, Millichamp I S, Ferguson J, et al. Nonfreezable water and polymer swelling control the marine antifouling performance of polymers with limited hydrophilic content [J]. ACS Appl. Mater. Interfaces, 2019, 11: 29477
[27]	Dai G X, Xie Q Y, Chen S S, et al. Biodegradable poly(ester)-poly(methyl methacrylate) copolymer for marine anti-biofouling [J]. Prog. Org. Coat., 2018, 124: 55
[28]	Parvate S, Mahanwar P. Advances in self-crosslinking of acrylic emulsion: What we know and what we would like to know [J]. J. Dispers. Sci. Technol., 2019, 40: 519
[29]	Chen L J, Wu F Q, Li D S, et al. Preparation of self-crosslinked acrylate emulsion with high elasticity and its rheological properties [J]. J. Cent. South Univ. Technol., 2008, 15: 324
[30]	Wei L M, Hou Z Y. High performance polymer binders inspired by chemical finishing of textiles for silicon anodes in lithium ion batteries [J]. J. Mater. Chem. A, 2017, 5: 22156
[31]	Sun J Y, Lin X Y, Qiu Y H, et al. In situ polymerization of N-methylol acrylamide (NMA) for bamboo anti-mold modification [J]. Constr. Build. Mater., 2023, 363: 129887
[32]	Chen L J, Wu F Q. Preparation and characterization of novel self cross-linking fluorinated acrylic latex [J]. J. Appl. Polym. Sci., 2012, 123: 1997
[33]	Gu Y, Cheng L, Gu Z B, et al. Preparation, characterization and properties of starch-based adhesive for wood-based panels [J]. Int. J. Biol. Macromol., 2019, 134: 247
[34]	Zhou Y, Chen G B, Yan S G, et al. Epoxy composite coating with excellent anticorrosion and self-healing properties based on acrylate copolymers [J]. Prog. Org. Coat., 2022, 172: 107098
[35]	Wang X, Yang J, Liu Z X, et al. Antifouling property of Cu₂O-free self-polishing antifouling coatings based on amide derivatives inspired by capsaicin [J]. Langmuir, 2022, 38: 10244
[36]	Khotbehsara M M, Manalo A, Aravinthan T, et al. Effects of ultraviolet solar radiation on the properties of particulate-filled epoxy based polymer coating [J]. Polym. Degrad. Stab., 2020, 181: 109352
[37]	Ni C H, Feng K, Li X, et al. Study on the preparation and properties of new environmentally friendly antifouling acrylic metal salt resins containing indole derivative group [J]. Prog. Org. Coat., 2020, 148: 105824
[38]	Liu C, Xie Q Y, Ma C F, et al. Fouling release property of polydimethylsiloxane-based polyurea with improved adhesion to substrate [J]. Ind. Eng. Chem. Res., 2016, 55: 6671
[39]	Hu P. Preparation and properties of fouling resistant silicone-based marine antifouling coatings [D]. Guangzhou: South China University of Technology, 2022
	胡朋. 污损阻抗型有机硅基海洋防污涂层的制备与性能研究 [D]. 广州: 华南理工大学, 2022
[40]	Hu P, Xie Q Y, Ma C F, et al. Fouling resistant silicone coating with self-healing induced by metal coordination [J]. Chem. Eng. J., 2021, 406: 126870
[41]	Han X, Wu J H, Zhang X H, et al. Special issue on advanced corrosion-resistance materials and emerging applications. The progress on antifouling organic coating: From biocide to biomimetic surface [J]. J. Mater. Sci. Technol., 2021, 61: 46
[42]	Bressy C, Margaillan A, Faÿ F, et al. 18-Tin-free self-polishing marine antifouling coatings [A]. HellioC, YebraD. Advances in Marine Antifouling Coatings and Technologies [M]. Oxford: Woodhead, 2009: 445-491
[43]	Zhang J B, Liu Y Z, Wang X W, et al. Self-polishing emulsion platforms: Eco-friendly surface engineering of coatings toward water borne marine antifouling [J]. Prog. Org. Coat., 2020, 149: 105945
[44]	Jafarzadeh S, Rhim J W, Alias A K, et al. Application of antimicrobial active packaging film made of semolina flour, nano zinc oxide and nano-kaolin to maintain the quality of low-moisture mozzarella cheese during low-temperature storage [J]. J. Sci. Food Agric., 2019, 99: 2716
[45]	Mahamuni-Badiger P P, Patil P M, Badiger M V, et al. Biofilm formation to inhibition: Role of zinc oxide-based nanoparticles [J]. Mater. Sci. Eng., 2020, 108C: 110319
[46]	Wang X, Yu L M, Li F C, et al. Synthesis of amide derivatives containing capsaicin and their antioxidant and antibacterial activities [J]. J. Food Biochem., 2019, 43: e13061
[47]	Zhou W J, Wang Y J, Ni C H, et al. Preparation and evaluation of natural rosin-based zinc resins for marine antifouling [J]. Prog. Org. Coat., 2021, 157: 106270
[48]	Hepler P K. Calcium: A central regulator of plant growth and development [J]. Plant Cell, 2005, 17: 2142

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