Figure 3 (a) Schematic diagram of degradation and
hydrolysis of PMx By . Reproduced with permission.[44]
Copyright 2019 American Chemical Society. (b) Hydrolysis and degradation
of copolymer. Reproduced with permission.[46] Copyright 2019
American Chemical Society. (c) Schematic diagram of the preparation and
degradation process of
HPMx E. (d) Mass loss of
HPMx E after immersion in ASW at 25 °C. Reproduced with
permission.[47] Copyright 2021 Royal Society of Chemistry. (e)
Schematic diagram of degradation and hydrolysis of PTAx . (f)
Fluorescence images of P. sp. on PTA5 surface with and without a
3-day pre-hydrolysis. Reproduced with permission.[51] Copyright 2021
American Chemical Society.
We synthesized hyperbranched degradable copolymer (HPMx E) with
via RROP of MDO, vinyl acetate (VAc) and diethylene glycol divinyl ether
(DEGDVE) (Figure 3c).[47] Since the vinyl monomers
and MDO are close in reactivity ester bonds can randomly distribute
along polymer chain, so that the degradation happens everywhere on the
surface. The coating had high adhesion strength after crosslinking under
UV. Figure 3d shows that mass loss of the coating increased with the
ester units. The coating with 44 mol% ester units had the highest mass
loss after a 14-day immersion in ASW, much higher than the coating
without ester units (0.4 mg·cm−2). The final
degradation product could dissolve in seawater, so it has limited impact
on the marine environment. Antibacterial assay demonstrates that the
copolymers with 50 mol% DEGDVE had good antibacterial ability. That is
due to the presence of DEGDVE, forming a hydration layer with water and
hindering bacterial adhesion.
We also prepared a hyperbranched copolymer via reversible addition
fragmentation chain transfer (RAFT) polymerization of MMA, TCB and
divinyl-functional PCL (PCL-vi2).[48] Owing to the
hyperbranched structure, the hyperbranched PCL had a crystallinity lower
than liner PCL. The fragmentation of branching points would make the
final degradation product smaller. The existence of TCB further improved
the hydrophilicity, self-renewal capacity and effectively inhibited the
adhesion of fouling organism. Thanks to the continuous degradation of
PCL and the hydrolysis of TCB, the self-renewal performance and
long-term antifouling ability of coating were guaranteed even in static
marine environments.
We studied the effect of branching points structure on self-renewal and
antifouling properties of hyperbranched copolymer. Three kind of divinyl
monomers including methacrylic anhydride (MAAH), N, N′-adipic
bis(diacetone acrylamide hydrazone) (DAA2H), and
ethylene glycol dimethacrylate (EGDMA) were
used.[49] It shows the degradation rate and mass
loss of the polymer increased with the branching point content. For the
same branching point content, the more breakable sites in branching
points, the greater the mass loss
(EGDMA<MAAH<DAA2H). Namely, the
degradation rate of the hyperbranched copolymer can be regulated by
varying the content or structure of branching points. Antibacterial and
anti-diatom assays demonstrate that the coatings have excellent
antifouling performance due to branching points degradation and
zwitterions produced by hydrolysis. We synthesized vinyl-functional
4-bromo-2-(4-chlorophenyl)-5-trifluoromethyl-1H-pyrrole-3-carbonitrile
(Econea -vi) as antifouling group, and introduced it to
hyperbranched polymer via RAFT polymerization.[50]With the function of contact killing, the grafted Econea could
effectively inhibit biofouling. On the other hand, Econea could
be released and degrade in seawater through the breaking the copolymer
chain.
Based on previous research, we proposed a strategy called the
”kill-resist-renew-trinity”.[51] For this purpose,
we synthesized a dual-functional monomer with TCB and TCPM, and
copolymerized it with MAAH to prepared a hyperbranched polymer
(PTAx ) with fouling killing, resisting and releasing functions
(Figure 3e). Even before hydrolysis, TCPM with contact killing property
provided the coating antibacterial ability. After hydrolysis, TCPM was
released from the coating to further improve antifouling performance.
Meanwhile, it generated zwitterion inhibiting the adhesion of bacteria.
The dynamic surface could remove the dead bacteria attached to the
surface. As shown in Figure 3f, the hyperbranched polymer with fouling
killing, resisting and releasing functions had excellent anti-biofouling
performance. Moreover, the hyperbranched copolymer would eventually
degrade into small molecules without formation of microplastics.
4. Conclusions
In conclusion, Dynamic Surface Antifouling (DSAF) provides a general
strategy to defeat marine biofouling. We have developed main chain
degradable polymer based antifouling materials. They exhibit good
anti-biofouling performances and mechanical properties both on static
and dynamic conditions. The surface erosion of degradable polymers has
linear kinetics, the service life can be regulated by the coating
thickness, and the release of the antifoulants can be well controlled.
The main chain degradation yields low molecular weight molecules instead
of microplastics, so the polymer materials are relatively eco-friendly.
By adjusting the molecular structure of the polymer, the antifouling
performance, service life and the mechanical properties can be
regulated. DSAF materials are promising in marine antifouling.
Acknowledgement
The financial support of the National Key Research and Development
Program of China (2022YFB3806403), National Natural Science Foundation
of China (52273073, U2241286, and 52003082), Guangdong Basic and Applied
Basic Research Foundation (2023B1515020025), the China Postdoctoral
Science Foundation (2022M721179) and Ministry of Science and Technology
of China is acknowledged.
References
- Tian, L. M.; Yin, Y.; Bing, W.; Jin, E. Antifouling Technology Trends
in Marine Environmental Protection. J Bionic Eng.2021 , 18, 239-263.
- Daniel. J. B.; Chin, S. L.; Serena, L. T.; Hu, X. P.; Pang, J. J.
Macrofouling Induced Localized Corrosion of Stainless Steel in
Singapore Seawater. Corros. Sci. 2017 , 129.
- Rao, T. S.; Kora, A. J.; Chandramohan, P.; Panigrahi, B. S.;
Narasimhan, S. V. Biofouling and Microbial Corrosion Problem in the
Thermo-fluid Heat Exchanger and Cooling Water System of a Nuclear Test
Reactor. Biofouling 2009 , 25, 581-591.
- Fitridge, I.; Dempster, T.; Guenther, J.; de Nys, R. The Impact and
Control of Biofouling in Marine Aquaculture: A Review.Biofouling 2012 , 28, 649-69.
- Richard, F. P.; Katherine, A. D.; Emma, L. J. The Influence of
Antifouling Practices on Marine Invasions. Biofouling2009 , 25, 633-644.
- Pan, J. S.; Ai, X. Q.; Ma, C. F.; Zhang, G. Z. Degradable Vinyl
Polymers for Combating Marine Biofouling. Acc. Chem. Res.2022 , 11, 1586–1598.
- Evans, S. M.; Birchenough, A. C.; Brancato, M. S. The TBT Ban: Out of
the Trying Pan into the Fire. Mar. Pollut. Bull. 2000 ,
40, 204-211.
- Hu, P.; Xie, Q. Y.; Ma, C. F.; Zhang, G. Z. Silicone-Based
Fouling-Release Coatings for Marine Antifouling. Langmuir2020 , 36, 2170-2183.
- Ma, C. F.; Zhou, H.; Wu, B.; Zhang, G. Z. Preparation of Polyurethane
with Zwitterionic Side Chains and Their Protein Resistance. ACS
Appl. Mater. Interfaces 2011 , 3, 455-461.
- Hu, P.; Xie, R.; Xie, Q. Y.; Ma, C. F.; Zhang, G. Z. Simultaneous
Realization of Antifouling, Self-healing, and Strong Substrate
Adhesion via a Bioinspired Self-stratification Strategy. Chem.
Eng. J 2022 , 449, 137875.
- Jin, H. C.; Tian, L. M.; Bing, W.; Zhao, J.; Ren, L. Q. Bioinspired
Marine Antifouling Coatings: Status, Prospects, and Future.Prog. Mater. Sci. 2022 , 124, 100889.
- Gaylarde, C. C.; Neto, J. A. B.; da Fonseca, E. M. Paint Fragments as
Polluting Microplastics: A Brief Review. Mar. Pollut. Bull.2021 , 162, 111847.
- Xie, Q. Y.; Pan, J. S.; Ma, C. F.; Zhang, G. Z. Dynamic Surface
Antifouling: Mechanism and Systems. Soft Matter2019 ,15, 1087-1107.
- Qi, M.; Song, Q. L.; Zhao, J. P.; Ma, C. F.; Zhang, G. Z.; Gong, X. J.
Three-Dimensional Bacterial Behavior near Dynamic Surfaces Formed by
Degradable Polymers. Langmuir 2017 , 33, 13098-13104.
- Qi, M.; Gong, X. J.; Wu, B.; Zhang, G. Z. Landing Dynamics of Swimming
Bacteria on a Polymeric Surface: Effect of Surface Properties.Langmuir 2017 , 33, 3525-3533.
- Hoffman, M. D.; Zucker, L. I.; Brown, P. J. B.; Kysela, D. T.; Brun,
Y. V.; Jacobson, S. C. Timescales and Frequencies of Reversible and
Irreversible Adhesion Events of Single Bacterial Cells. Anal.
Chem 2015 , 87, 12032-12039.
- Tamada, J. A.; LangerProc, Erosion kinetics of hydrolytically
degradable polymers. R. Natl. Acad. Sci. 1993 , 90,
552-556.
- Göpferich, A. Polymer Bulk Erosion. Macromolecules1997 , 30, 2598-2604.
- Nair, L. S.; Laurencin, C. T. Biodegradable Polymers as Biomaterials.Prog. Polym. Sci. 2007 , 32, 762-798.
- Gross, R. A.; Kalra, B. Biodegradable Polymers for the Environment.Science 2002 , 297, 803-807.
- Ma, C. F.; Xu, L. G.; Xu, W. T.; Zhang, G. Z. Degradable Polyurethane
for Marine Anti-biofouling. J. Mater. Chem. B 2013 , 1,
3099-3016.
- Chen, S. S.; Ma, C. F.; Zhang, G. Z. Biodegradable Polymer as
Controlled Release System of Organic Antifoulant to Prevent Marine
Biofouling. Prog. Org. Coat. 2017 , 104, 58-63.
- Ma, C. F.; Zhang, W. P.; Zhang, G. Z.; Qian, P. Y. Environmentally
Friendly Antifouling Coatings Based on Biodegradable Polymer and
Natural Antifoulant. ACS Sustainable Chem. Eng 2017 ,
5, 6304-6309.
- Ding, W.; Ma, C. F.; Zhang, W. P.; Chiang, H.; Tam, C.; Xu, Y.; Zhang,
G. Z.; Qian, P. Y. Anti-Biofilm Effect of a Butenolide/Polymer Coating
and Metatranscriptomic Analyses. Biofouling 2018 , 34,
111-122.
- Zhang, X. Y.; Xu, X. Y.; Peng, J.; Ma, C. F.; Nong, X. H.; Bao, J.;
Zhang, G. Z.; Qi, S. H. J. Antifouling Potentials of Eight
Deep-sea-derived Fungi from the South China Sea. Ind. Microbiol.
Biot. 2014 , 41, 741-748.
- Yao, J. H.; Chen, S. S.; Ma, C. F.; Zhang, G. Z. Marine
Anti-biofouling System with Poly-(ε-caprolactone)/clay Composite as
carrier of organic antifoulant. J. Mater. Chem. B2014 , 2, 5100-5106.
- Chen, S. S.; Ma, C. F.; Zhang, G. Z. Biodegradable polymers for marine
antibiofouling: Poly(ε-caprolactone)/poly(butylene succinate) blend as
controlled release system of organic antifoulant. Polymer2016 , 90, 215-221.
- Ma, J. L.; Ma, C. F.; Yang, Y.; Xu, W. T.; Zhang, G. Z. Biodegradable
Polyurethane Carrying Antifoulants for Inhibition of Marine
Biofouling. Ind. Eng. Chem. Res. 2014 , 53,
12753-12759.
- Ma, J. L.; Ma, C. F.; Zhang, G. Z. Degradable Polymer with Protein
Resistance in a Marine Environment. Langmuir 2015 , 31,
6471-6478.
- Xu, W. T.; Ma, C. F.; Ma, J. L.; Gan, T. S.; Zhang, G. Z. Marine
Biofouling Resistance of Polyurethane with Biodegradation and
Hydrolyzation. ACS Appl. Mater. Interfaces 2014, 6, 4017-4024.
- Ma, C. F.; Xu, W. T.; Pan, J. S.; Xie, Q. Y.; Zhang, G. Z. Degradable
Polymers for Marine Antibiofouling: Optimizing Structure to Improve
Performance. Ind. Eng. Chem. Res. 2016 , 55,
11495-11501.
- Pan, J. S.; Xie, Q. Y.; Chiang, H.; Peng, Q. M.; Qian, P. Y.; Ma, C.
F.; Zhang, G. Z. “From the Nature for the Nature”: An Eco-friendly
Antifouling Coating Consisting of Poly(lactic acid)-based Polyurethane
and Natural Antifoulant. ACS Sustainable Chem. Eng.2019 , 8, 1671-1678.
- Ai, X. Q.; Xie, Q. Y.; Ma, C. F.; Zhang, G. Z. Fouling Release Coating
Consisting of Hyperbranched Poly(ε-caprolactone)/Siloxane Elastomer.ACS Appl. Polym. Mater. 2020 , 2, 1429−1437.
- Xie, R.; Ai, X. Q.; Xie, Q. Y.; Ma, C. F.; Zhang, G. Z. Non-Silicone
Elastic Coating with Fouling Resistance and Fouling Release Abilities
Based on Degradable Hyperbranched Polymer. Prog. Org. Coat2023 ,175, 107350.
- Zhang, G. Z. Hybrid Copolymerization. Acta Polymerica Sinica2018 , 6, 668-673.
- Zhang, G. Z.; Ma, C. F. Method for preparing main chain scission-type
polysilyl (meth)acrylate resin and application thereof. US
Patent. 9,701,794 B2 , 2017 .
- Yang, H. J.; Xu, J. b.; Pispas, S.; Zhang, G. Z. Hybrid
Copolymerization of ε-Caprolactone and Methyl Methacrylate.Macromolecules 2012 , 45, 3312-3317.
- Yang, H. J.; Xu, J. b.; Pispas, S.; Zhang, G. Z. One-Step Synthesis of
Hyperbranched Biodegradable Polymer. RSC Adv. 2013 , 3,
6853-6858.
- Xu, J. B.; Yang, H. J.; Zhang, G. Z. Synthesis of Poly(ε
-caprolactone-co-methacrylic acid) Copolymer via Phosphazene-Catalyzed
Hybrid Copolymerization Macromol. Chem. Phys. 2013 ,
214, 378-385.
- Xu, J. B.; Fan, X. L.; Yang, J. X.; Ma, C. F.; Ye, X. D.; Zhang, G. Z.
Poly(l-lactide-co-2-(2-methoxyethoxy)ethyl methacrylate): A
Biodegradable Polymer with Protein Resistance. Colloid Surface
B 2014 , 116, 531-536.
- Dai, G. X.; Xie, Q. Y.; Chen, S. S.; Ma, C. F.; Zhang, G. Z.
Biodegradable Poly(ester)-Poly(methyl methacrylate) Copolymer for
Marine Anti-biofouling. Prog. Org. Coat. 2018 , 124,
55-60.
- Zhou, X.; Xie, Q. Y.; Ma, C. F.; Chen, Z. J.; Zhang, G. Z. Inhibition
of Marine Biofouling by Use of Degradable and Hydrolyzable Silyl
Acrylate Copolymer. Ind. Eng. Chem. Res. 2015 , 54,
9559-9565.
- Xie, Q. Y.; Ma, C. F.; Zhang, G. Z.; Bressy,C. Poly(ester)–Poly(silyl
methacrylate) Copolymers: Synthesis and Hydrolytic Degradation
Kinetics. Polym. Chem. 2018 , 9, 1448-1454.
- Dai, G. X.; Xie, Q. Y.; Ma, C. F.; Zhang, G. Z. Biodegradable
Poly(ester-co-acrylate) with Antifoulant Pendant Groups for Marine
Anti-biofouling. ACS Appl. Mater. Interfaces 2019 , 11,
11947-11953.
- Xie, Q. Y.; Xie, Q. N.; Pan, J. S.; Ma, C. F.; Zhang, G. Z.
Biodegradable Polymer with Hydrolysis-Induced Zwitterions for
Antibiofouling. ACS Appl. Mater. Interfaces 2018 , 10,
11213-11220.
- Dai, G. X.; Xie, Q. Y.; Ai, X. Q.; Ma, C. F.; Zhang, G. Z.
Self-generating and Self-Renewing Zwitterionic Polymer Surfaces for
Marine Anti-Biofouling. ACS Appl. Mater. Interfaces2019 , 11, 41750-41757.
- Ai, X. Q.; Pan, J. S.; Xie, Q. Y.; Ma, C. F.; Zhang, G. Z. UV-Curable
Hyperbranched Poly(ester-co-vinyl) by Radical Ring-Opening
Copolymerization for Antifouling Coatings. Polym. Chem.2021 , 12, 4524-4531.
- Mei, L. Q.; Ai, X. Q.; Ma, C. F.; Zhang, G. Z. Surface-fragmenting
Hyperbranched Copolymers with Hydrolysis-generating Zwitterions for
Antifouling Coatings. J. Mater. Chem. B 2020 , 8,
5434-5440.
- Pan, J. S.; Mei, L. Q.; Zhou, H.; Zhang, C.; Xie, Q. Y.; Ma, C. F.
Self-regenerating Zwitterionic Hyperbranched Polymer with Tunable
Degradation for Anti-Biofouling Coatings. Prog. Org. Coat.2022 , 163, 106674.
- Ai, X. Q.; Mei, L. Q.; Ma, C. F.; Zhang, G. Z. Degradable
Hyperbranched Polymer with Fouling Resistance for Antifouling
Coatings. Prog. Org. Coat. 2021 , 153, 106141.
- Dai, G. X.; Ai, X. Q.; Mei, L. Q.; Ma, C. F.; Zhang, G. Z.
Kill-Resist-Renew Trinity: Hyperbranched Polymer with
Self-regenerating Attack and Defense for Antifouling Coatings.ACS Appl. Mater. Interfaces 2021 , 13, 13735-13743.