New progress has been made in the research of key basic materials of marine anti-fouling coatings at South China University of Technology

Marine pollution is a global problem, involving energy, environment, national defense and other major national needs, and maritime power, Belt and Road, military-civilian integration and other major national strategies. It is an inescapable and necessary problem for marine development and marine industry. At present, anti-fouling coatings are the most convenient, effective and economical strategy to prevent and control marine pollution, as one of the most important varieties of marine coatings, is the key to the core competitiveness of marine coatings enterprise products . Its core technology - polymer resin, not only as a coating substation and anti-fouling agent carrier, but also directly affect the performance of the coating and control the release of anti-fouling agent, determine its anti-fouling, environmental protection, service life and so on, is the most critical marine anti-fouling coatings in the basic material.
self-polishing anti-fouling coatings based on zinc polypropylene, copper or silane are the dominant anti-fouling technology, with anti-fouling periods of up to 3-5 years. However, the existing self-polishing anti-fouling coatings are mainly applicable to ocean-going ships, and their performance has certain requirements for the duration and speed of the voyage. This is because the existing self-polishing resin structure contains only hydrolysable side-base, resulting in its surface self-renewal depends on strong water flushing, static anti-fouling capacity is not ideal. In addition, the existing self-polishing resin side-based chemical structure has a great impact on it, and its main chain non-degradability leads to hydrolytic resin long-term presence in the marine environment, which is not conducive to marine ecology. More importantly, the existing self-polishing resin technology has long been monopolized by foreign multinational companies. The above problems greatly restrict the development and industrialization of anti-fouling technology of ships in China.
South China University of Technology marine engineering materials team has long been engaged in environmentally friendly marine anti-fouling system related research. In recent years, a series of work has been carried out around polymer resin, a key basic material in marine anti-fouling coatings. For the first time in the world, the team prepared a main chain-degradable self-polishing resin (DSPC): polyester-co-methyl acrylic silane. The resin not only has the hydrolytic side foundation of the traditional self-polishing resin, but also has the degradable main chain structure, which can effectively coordinate the hydrolytic properties of the side foundation and the solubility of the polymer, and successfully breaks through the limitations of poor regulation of the polishing rate of the existing technology and weak static anti-fouling ability. In particular, the resin can be degraded into small molecules through the main chain without causing marine microplastic pollution (Ind. Eng. Chem. Res. 2015, 54, 9559)。 The resin technology has the advantages of environmental and ecological friendliness and excellent anti-fouling performance, and is an important innovation of traditional self-polishing resin.
Then, in collaboration with the MAPIEM Laboratory at the University of Toulon in France, the team developed a series of degraded, hydrolytic-rate-adjustable main chain degradation self-polishing resins to suit different use situations, and discussed the polymerization, degradation and hydrodegradation dynamics of resins, laying the theoretical foundation for the wide application of DSPC (Polym. Chem. 2018,DOI: 10.1039/C8PY00052B)。
Figure 1. Roadmap for the synthesis of polyester-polymethyl acrylates co-polymers
Recently, they also introduced hydrolytic-convertible sex ion preludes into the system, preparing a main chain degradation self-polished two-sex ion anti-fouling resin, which, in addition to the above advantages, can also produce super-hydrophobic ion surfaces through surface hydrolytic reactions. And its native sex ion surface can be constantly updated through the degradation of the main chain, i.e. the formation of a dynamic surface with deface resistance, with excellent anti-fouling performance (ACS Appl. Mater. Interfaces, 2018,DOI: 10.1021/acsami.8b00962)。 In addition, the team expanded into this area by introducing a biodegradable main chain structure into copper polypropyl acrylic and zinc polyacrylic acid to prepare a variety of new self-polishing resins.
Figure 2. The main chain degradation type self-polished sex ion anti-fouling resin and its anti-fouling experiment
it is known that the above series of main chain degradation self-polishing resin has applied for 12 Chinese invention patents (authorization 6), PCT international patent 2. More recently, the technology has been granted a U.S. patent (US 9701794 B2), breaking a long-standing technology monopoly in the field in developed countries such as the United States, the European Union, and Japan. At present, we have successfully realized the ton test, and in a number of ships to carry out real-ship experiments, anti-fouling effect is excellent. The above-mentioned work successfully breaks through the existing synthesis and application technology of self-polishing anti-fouling resin, which has a driving effect and important economic significance for the development of high-performance anti-fouling coatings with independent intellectual property rights and the acceleration of the development of anti-fouling technology in China's ships.
3. Licensed U.S. Patent and Main Chain Degradation Self-Polishing Anti-fouling Coatings Marine Experiments
Refer:
1) Zhou X, Xie QY, Ma CF, Chen ZJ, Zhang GZ. Inhibition of marine biofouling by use of degradableand hydrolysable silyl acrylate copolymer. Ind. Eng. Chem. Res. 2015, 54, 9559-9565.
2) Xie QY, Ma CF, ZhangGZ, Bressy C. Poly(ester)-poly(silyl methacrylate) copolymers: synthesis andhydrolytic degradation kinetics. Polym. Chem. 2018, DOI:10.1039/C8PY00052B.
3) Xie QY,Xie QN, Pan JS, Ma CF, Zhang GZ. Biodegradable polymer with hydrolysis induced zwitterionsfor antibiofouling. ACS Appl. Mater.Interfaces, 2018, DOI:10.1021/acsami.8b00962.
4) Zhang GZ, Ma CF. Method for preparing main chain scission-type polysilyl (meth)acrylateresin and application thereof. US patent 9701794 B2.
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