Preparation Of Fluorinated Acrylate Polymer Coatings And Its Anti-biofouling Properties

The economic and energy loss caused by the adhesion of marine organisms has always been troubling. Fluorine-containing polymers are widely used in the field of functional coatings due to they have many advantages, such as excellent film-forming ability, low surface energy, strong hydrophobic, high heat resistance and goode chemical stability, etc.In this paper, two fluorine-containing coatings, Poly（ADMH-co-DFMA-co- MMA） and SiO₂/Poly（ADMH-co-DFMA-co-MMA）, were prepared by using 3-allyl-5,5-dimethylhydantion（ADMH） as sterilization functional monomer, 1H,1H,7H- dodecafluoroheptyl methacrylate（DFMA） as hydrophobic monomer with low surface energy, methyl methacrylate（MMA） as the supporting monomer, AOT as emulsifier and AIBN as initiator. The stability of inverse microemulsion system and the chemical and physical properties were investigated. Furthermore, the anti-biofouling properties of the two coatings were evaluted.Poly（ADMH-co-DFMA-co-MMA） coating was synthesized via inverse microemulsion method. Ternary phase diagram and inverse microemulsion region were studied. Chemical structure of Poly（ADMH-co-DFMA-co-MMA） were characterized by FTIR, NMR and XPS, and the functional monomer ADMH, DFMA and supportive monomer MMA were all confirmed to sucessfully participate in the co-polymerization. In the meantime, The effects of the amount of DFMA and ADMH on the surface hydrophobicity of copolymer were discussed by the different ratio of V（DFMA） /V（MMA）. The results indicated that the surface hydrophobicity of copolymer was increased with the increasing of DFMA content. when the V（DFMA） /V（MMA）= 1:1, the contact angle（CA） stopped increasing, and the dosage of the ADMH had little effect on CA. Moreover, Thermogravimetric analysis showed that the decomposition temperature was above 300 degrees, which showed that the copolymer had good heat resistance.The number of colonies of e.coli was observed by the coating contact with Escherichia coli. The results showed that the effect sterilization enhanced with increasing amount of ADMH, and the sterilization rate reached 90.57% when ADMH concentration was 5 mmoL. However, with the further increase of the amount of ADMH, the bactericidal effect has declined., and it found that the CA of the coating is closely related to the antifouling performance. Through 2 months of dynamic simulation of the sea trial, The coating-air（C-A） side with a high degree of hydrophobicity had almost no Asterocapsa adhesion,on the conctrary, coating-glass（C-G） interface was stacking with algae.SiO₂/Poly（ADMH-co-DFMA-co-MMA） copolymer coating was prepared via Sol-gel method and in situ polymerization. The morphology of composite latex particles was observed by transmission electron microscope（TEM）, it illustrated that the particle diameter was monodisperse in the range of 50-100 nm, and some nano scale bulges were observed by scanning electron microscope（SEM）. Moreover, structure of the polymeric coating was characterized by FTIR, NMR and XPS. The results demonstrated that the monomers and SiO₂ nanoparticals all joined into co-polymerization and recombination. Additionally, The effects of the amount of DFMA on the surface hydrophobicity of copolymers with different fluorinated chain length were discussed. It showed that the CA of C-A and C-G interface were both increased with the increasing of the amount of DFMA. when V（DFMA） /V（MMA）= 1:1, the CA is no longer increased.Antibacterial experiment of coating showed that the bactericidal effect was improved with the increase of ADMH content. When ADMH concentration was 5 mmoL, the sterilization rate can reach as high as 95.9%. Dynamic simulation hanging test showed that C-G interface was covered with biomass, C-A side almost no fouling organism, it indicated that the C- A has good antifouling property.Compared P（ADMH-co-DFMA-co-MMA） with SiO₂/Poly（ADMH-co- DFMA-co-MMA）, the content of fluorine in C-A and C-G interface were higher than that of the silica introduced. The introduction of SiO₂ is benficial to improve the thermal stability of the copolymer coating and to build the surface roughness of the coating, which wetting condition is consistent with the Cassie model. on the other hand, the hydrophobicity and self cleaning effect of the coating surface are enhanced to a certain extent by the bulges structure of nano/micro on the surface of composite.