Preparation And Properties Of Acrylate Fluorinated Boron Polymer Based Antifouling Coatings

From ancient times till today,marine biofouling has existed in people's marine activities for a long time,which seriously hinders the development of marine resources and the development of marine economy.At present,the application of marine antifouling coating is one of the most economical and effective antifouling strategies.However,traditional antifouling coatings contain heavy metal ions,which seriously affect the marine ecological environment.In order to overcome the above shortcomings of the traditional antifouling coatings,non-metal acrylate boron polymers?ABPs?and acrylate boron fluorinated polymers?ABFPs?are synthesized.The self-healing acrylate boron fluorinated polymer coatings?SABFPs?,ultrathin carbon nitride/acrylate boron fluorinated polymer coatings?UCAS?and titanium dioxide-carbon nitride/acrylate boron fluorinated polymer coatings?TCNCs?are prepared by acrylate boron fluorinated polymers and functional fillers,and their chemical structure,wettability properties,antifouling properties are studied,The research contents are as follows:In this paper,non-metal ABPs are designed and synthesized via free radical polymerization and proton-exchange reaction.The exfoliation of the diphenylpyridine borane side chain of ABPs endows the polymers with self-polishing properties,and the self-polishing rates are in the range of 5 mg/?cm²·d??73.3 mg/?cm²·d?,while the high self-polishing rates make the polymer films unfavorable for Nitzschia closterium to attach.After 12 months'real sea test,no obvious large fouling organisms are found on the coating surfaces of the copper free antifouling coatings prepared by 10 wt%econea except a small amount of sludge.In order to improve the antifouling performance of the polymers,amphiphilic ABFPs were synthesized by introduce the fluoroacrylate side chains into the molecular structure of the ABPs.Due to the introduction of fluoroacrylate monomers,the self polishing rates of ABFPs decline to 2 mg/?cm²·d??57 mg/?cm²·d?.The surfaces of the coatings are clean,bright and free of any fouling biological adhesion after 90 days'real sea test because of the self-polishing and amphiphilic properties of the polymers and the release of antifouling agent.In this paper,different content of perfluoropolyether lubricating oil are added to ABFPs to prepare the SABFPs.More lubricant oil and higher temperature lead to the faster self-healing speed.When the addition of lubricating oil is 9 wt%,the self-healing process of the damaged coating can be completed at 20? within 80 min.The friction coefficient of the coating can be reduced more than 75% by adding 1 wt%lubricating oil.SABFPs possess good storage stability of lubricating oil,the friction coefficient of most coatings are still below 0.6 after the accelerated evaporation of lubricating oil at 70? for 40 h.The self-polishing property of polymer matrix and the existence of lubricating oil on the coating surfaces contribute to the clean surfaces of SABFPs after 60 days'real sea test in Bohai Sea area.Carbon nitride was synthesized by high-temperature calcination and the UCAs are prepared by adding different content of ultra-thin carbon nitride?ultrathin g-C₃N₄?into ABFPs.The optimum addition of ultra-thin carbon nitride is 7 wt%.When the content of ultra-thin carbon nitride exceeds 7 wt%,there will be obvious agglomeration on the coating surfaces.The chemical oxygen demand?COD?of UCAs coating is 3.2 mg/L after 21 days'immersion in artificial seawater.The self-polishing effect of polymer matrix and the reactive oxygen species produced from ultra-thin carbon nitride can not only hinder the adhesion of algae,but also have a certain driving effect on mussels.The adhesion rate of mussels is 20%within 76 hours,and after 124 hours,the adhesion rate of mussels decrease to 0%.In order to overcome the low separation efficiency of the photogenerated electron-electron holes,titanium dioxide-carbon nitride composite is prepared and added to the ABFPs to prepare TCNCs.The test results show that when the content of titanium dioxide-carbon nitride composite is 7 wt%,the coating surfaces are smooth without agglomeration.The thickness change of the coating is 4.4?m/d,and no diatom cells are found on the surfaces of TCNCs.Compared to the UCAs,the band gap decreases to 2.43 eV from 2.69 eV,while the photoluminescence intensity at 400 nm decreases along with the increased photocatalytic efficiency.The adhesion rate of mussels is 0%within 72 hours due to the self-polishing of polymer matrix and the reactive oxygen species produced by titanium dioxide-carbon nitride.