Synthesis Of Zinc/Silyl-based Acrylate Copolymers For Antifouling Application

With the outlook of national blue ocean strategy and the rapid development of marine economy,the mineral resources,biological resources and energy resources in the depths of ocean are explored and utilized step by step.However,marine biofouling,which defined as diverse organisms adhered to the surface of underwater artificial facilities(e.g.ships and offshore platforms),has resulted in a series of problems that long plagued human beings.Undoubtedly,the antifouling coating is one of the most cost-effective methods to prevent against biofoulings.In this paper,the crosslinked zinc acrylate copolymers,zinc/silyl acrylate copolymers and silyl acrylate copolymers were synthesized by free radical polymerization and atom transfer radical polymerization for the environmentally friendly self-polishing antifouling application.By regulating and controlling the hydrolyzed monomer structure,content and molecular weight of copolymer,the self-polishing anti-fouling coatings could achieve controllable hydrolysis rate,stable erosion rate and long-term effective antifouling performance.The main research contents are as follows:In order to obtain crosslinked zinc acrylate random copolymers,the synthesised bifunctional zinc acrylate monomer was copolymerized with other acrylate monomers to obtain crosslinked zinc acrylate random copolymers,and then made of self-polishing antifouling coating.The results showed that the success synthesis of crosslinked zinc acrylate self-polishing copolymers with Zn-O bond was obained,which was characterized by FT-IR,~1H NMR and thermal analysis.The antifouling paint based on them had good storage stability by continuous monitoring its viscosity.The erosion performance of the antifouling coating was evaluated by the self-made dynamic simulation experiment.It was found that the erosion performance of the self-polishing coating was not only related to the hydrolyzable resin,but also to the other components in the coating formulation.The coating with higher content of the zinc acrylate monomer had faster erosion rate.The field tests showed that:the copper type antifouling paint,which was prepared by crosslinked zinc acrylate copolymer with 20 wt%zinc acrylate monomer and copper-based biocides showed at least 9-months antifouling perormance in the South China Sea and 15-months in the Yellow Sea by static raft test.The copper-free antifouling paints were prepared by the crosslinked zinc acrylate copolymer with16 wt%zinc acrylate monomer and various booster biocides.The coating,that has the antifoulant ratio of ZnPT and Tralopyril about 5:5,showed the best antifouling performance in the South China Sea and at least 9-months in the South of Singapore Sea.The zinc/sily acrylate copolymers were synthesised with the zinc acrylate monomer and tri(isopropyl)silyl acrylate as the hydrolyzable monomers,and the methyl methacrylate and ethyl acrylate as the comonomers.The ratio of the hydrolyzable monomers was regulated to improve the static anti-fouling properties of the silyl acrylate copolymer-based coatings.The static hydrolysis weightlessness test showed that the copolymers with higher content of zinc acrylate monomer had faster hydrolysis rate.The inhibition and attachment test of the ditom Phaeodactylum tricornutum Bohlin showed that the inhibitory effect of the polymers on the growth of P.tricornutum was more obvious with the increase of the zinc acrylate monomer content.The results indicated that the copper type self-polishing coatings prepared by the combination of zinc/sily acrylate copolymers and biocides achieved at least 15-months antifouling performance in the Yellow Sea of China.The silyl acrylate copolymers were synthesised with tri(isopropyl)silyl acrylate,methyl methacrylate,and 2-methoxyethyl acrylate as monomers,2-bromoisobutyryl bromide as initiator,cuprous bromide and bipyridyl bromide as catalyst by atom transfer active polymerization.The molecular weight distribution of obtained silyl acrylate copolymers was approximately 1.5.The results demonstrated that the silyl acrylate copolymers had no significant effect on the growth of Escherichia coli and Staphylococcus aureus,but the amount of ditom Nitzschia closterium f.minutissima adhered to the surface is less copmpared to the blank glass due to the hydrolysis of the polymers.When the cross-linked zinc acrylate resin-based copper and copper-free anti-fouling paints was applied for the ship trial,at least one year of the actual anti-fouling effect was obtained in the sea near Dalian.