氟化聚合物/双微胶囊自修复防污涂层的研究
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摘要
针对水下涂层材料在使用过程中产生的微裂纹难以及时修复和海洋生物污损问题,设计开发了一种氟化聚合物/双微胶囊的环氧树脂复合涂层(PFG/Dual-MCs/ER),该复合涂层具有微裂纹自修复和抗生物黏附的双重功能.采用原位乳液聚合法制备了包裹环氧树脂和稀释剂的聚脲醛微胶囊(ER-MCs),采用溶剂蒸发法制备了包裹水下环氧固化剂的聚甲基丙烯酸甲酯微胶囊(UEH-MCs),采用自由基聚合法制备了甲基丙烯酸六氟丁酯(HFBM)与甲基丙烯酸缩水甘油酯(GMA)的无规共聚物(PFG).将两种微胶囊包埋在环氧树脂涂层中并在表面接枝上PFG,制备出PFG/Dual-MCs/ER复合涂层.表征了微胶囊和PFG的结构组成,并检测了涂层的自修复和抗蛋白黏附性能.结果表明,PFG/Dual-MCs/ER复合涂层具有较好的自修复能力,表面接枝PFG使涂层表面对牛血清白蛋白的吸附明显减少.因此,这种兼具自修复和抗蛋白黏附性能,易于制备的PFG/Dual-MCs/ER复合涂层在海洋设施防护领域具有较好的应用前景.
A dual-function coating with self-healing and antibiofouling properties was prepared by combining two kinds of microcapsules in epoxy coating and surface grafting with fluorinated polymer to resolve the problems of microcracking and marine biofouling of underwater coating materials. A microcapsule,named ER-MCs,with a poly(urea-formaldehyde)shell,entrapped in a mixture of epoxy resin(E44)and n-butyl glycidyl ether was prepared using in-situ emulsion polymerization.Another microcapsule,named UEH-MCs,with a polymethyl methacrylate shell,entrapped in an underwater epoxy hardener(UEH)was prepared using a solvent evaporation technique.A fluorinated polymer(PFG)was synthesized by conventional free radical polymerization using hexafluorobutyl methacrylate and glycidyl methacrylate as monomers.The two microcapsules were entrapped in the epoxy resin to form a self-healing Dual-MCs/ER coating and whereas PFG/Dual-MCs/ER coating was obtained by casting PFG solution on the incomplete cured surface of the Dual-MCs/ER.The structures of microcapsules and PFG were characterized and self-healing and anti-protein-fouling properties were detected.The results showed that the PFG/DualMCs/ER composite coating featured a desirable self-healing capability whereas the grafting of PFG on the surface of Dual-MCs/ER coating significantly reducd the adsorption of bovine serum albumin on the coating surface. Therefore,given its easy fabrication,the PFG/Dual-MCs/ER composite coating,which possesses self-healing and anti-protein-fouling properties,features a promising application in the field of marine facility protection.
A dual-function coating with self-healing and antibiofouling properties was prepared by combining two kinds of microcapsules in epoxy coating and surface grafting with fluorinated polymer to resolve the problems of microcracking and marine biofouling of underwater coating materials. A microcapsule,named ER-MCs,with a poly(urea-formaldehyde)shell,entrapped in a mixture of epoxy resin(E44)and n-butyl glycidyl ether was prepared using in-situ emulsion polymerization.Another microcapsule,named UEH-MCs,with a polymethyl methacrylate shell,entrapped in an underwater epoxy hardener(UEH)was prepared using a solvent evaporation technique.A fluorinated polymer(PFG)was synthesized by conventional free radical polymerization using hexafluorobutyl methacrylate and glycidyl methacrylate as monomers.The two microcapsules were entrapped in the epoxy resin to form a self-healing Dual-MCs/ER coating and whereas PFG/Dual-MCs/ER coating was obtained by casting PFG solution on the incomplete cured surface of the Dual-MCs/ER.The structures of microcapsules and PFG were characterized and self-healing and anti-protein-fouling properties were detected.The results showed that the PFG/DualMCs/ER composite coating featured a desirable self-healing capability whereas the grafting of PFG on the surface of Dual-MCs/ER coating significantly reducd the adsorption of bovine serum albumin on the coating surface. Therefore,given its easy fabrication,the PFG/Dual-MCs/ER composite coating,which possesses self-healing and anti-protein-fouling properties,features a promising application in the field of marine facility protection.
引文
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[2]Selim M S,Shenashen M A,El-Safty S A,et al.Recent progress in marine foul-release polymeric nanocomposite coatings[J].Progress in Materials Science,2017,87:1-32.
[3]Kim S,Gim T,Jeong Y,et al.Facile construction of robust multilayered PEG films on polydopamine-coated solid substrates for marine antifouling applications[J].ACS Appl Mater Interfaces,2017,10(9):7626-7631.
[4]Mieszkin S,Callow M E,Callow J A.Interactions between microbial biofilms and marine fouling algae:Amini review[J].Biofouling,2013,29(9):1097-1113.
[5]Lejars M,Margaillan A,Bressy C.Fouling release coatings:A nontoxic alternative to biocidal antifouling coatings[J].Chemical Reviews,2012,112(8):4347-4390.
[6]Herold D A,Keil K,Bruns D E.Oxidation of polyethylene glycols by alcohol dehydrogenase[J].Biochemical Pharmacology,1989,38(1):73-76.
[7]Schmidt D L,Brady R F,Lam K,et al.Contact angle hysteresis,adhesion,and marine biofouling[J].Langmuir the ACS Journal of Surfaces&Colloids,2004,20(7):2830-2836.
[8]Kuroki H,Tokarev I,Nykypanchuk D,et al.Stimuliresponsive materials with self-healing antifouling Surface via 3D polymer grafting[J].Advanced Functional Materials,2013,23(36):4593-4600.
[9]Andersson H M,Keller M W,Moore J S,et al.Selfhealing polymers and composites[J].Springer Netherlands,2007,100(2):19-44.
[10]White S R,Sottos N R,Geubelle P H,et al.Autonomic healing of polymer composites[J].Nature,2001,409(6822):794.
[11]Kamphaus J M,Rule J D,Moore J S,et al.A new self-healing epoxy with tungsten(VI)chloride catalyst[J].Journal of the Royal Society Interface,2008,5(18):95-103.
[12]Wu G,An J,Tang X Z,et al.A versatile approach towards multifunctional robust microcapsules with tunable,restorable,and solvent-proof superhydrophobicity for self-healing and self-cleaning coatings[J].Advanced Functional Materials,2014,24(43):6751-6761.
[13]Jin H,Mangun C L,Griffin A S,et al.Microcapsules:Thermally stable autonomic healing in epoxy using a dual-microcapsule system[J].Advanced Materials,2014,26(2):282-287.
[14]Wang X,Liu D,Li W,et al.Microencapsulation of cholesteric liquid crystal by combined method of solvent evaporation and photopolymerization[J].Molecular Crystals&Liquid Crystals,2013,571(1):57-66.
[15]Zhang L,Tang M,Zhang J,et al.One simple and stable coating of mixed-charge copolymers on poly(vinyl chloride)films to improve antifouling efficiency[J].Journal of Applied Polymer Science,2017,134(12):1-10.
[16]Zhang Y,Qi Y H,Zhang Z P,et al.Synthesis of fluorinated acrylate polymer and preparation and properties of antifouling coating[J].Journal of Coatings Technology&Research,2015,12(1):215-223.