Study On Synthesis And Properties Of Antifouling Fluorine-containing Polymethacrylates

Marine biofouling has become a worldwide problem in the maritime industry for both vesselsand industrial equipment. Serious adverse impact from biofouling has been recognized includingimpairment of the operation efficiency of ships and other oceanographic equipment or instruments,increased fuel consumption and corrosion. Although the self-polishing coatings based ontributyltin (TBT) or cuprous oxide are effective on removing or reducing biofouling over the lastfew decades because of slow release of tin, copper or other toxins in time, their use has beenrestricted through legislation due to environmental concerns, emission of gases such as COχ, SOχand NOχinto the atmosphere, and incursion of invasive species into marine habitats. It is thushighly desirable to develop high efficient, broad-spectrum, environment-friendly coatings withanti-biofouling properties.The research aims to develop a new type of antifouling polymer by utilizing organic fluorinemonomer with excellent antifouling performance and strong sticky dopamine monomer. In the text,novel methacrylate copolymers containing catechol and trifluoromethyl pendant side groups weresynthesized by free radical polymerization of N-(3,4-dihydroxyphenyl)ethyl methacrylamide(DMA) and2,2,2-trifluoroethyl methacrylate (TFME) with,′-azobisisobutyronitrile (AIBN) asinitiator. A series of copolymers with different content of TFME ranging from3%to95%wereobtained by changing the molar ratio of DMA to TFME from25:1to1:25. Fourier transforminfrared(FT-IR) spectroscopy, gel permeation chromatography(GPC), thermal gravimetric analysis(TGA), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) wereused to characterize the copolymers, which showed high glass transition temperatures and goodthermostability. Moreover, the formed polymer film displayed a good antifouling property and acertain degree of hardness due to trifluoromethyl pendant side groups existed in the polymer. Theobtained copolymer with high molecular weight could adhere to surfaces of glass, plastics andmetals using catechol groups as multivalent H-bonding anchors. Chemical resistance test indicated that the films prepared from the polymers had excellent water resistance, a strong resistance toalkali and salt water. A relative high water contact angle among the prepared polymers is121°.Furthermore, the copolymer exerts the excellent water resistance with low bibulous rate as a resultof the existence of fluorine atoms. The better polymer DF1-1was selected to carry out theanti-fouling performance test, which indicated that the polymer coating has a good antifoulingeffect.In addition, the synthesized copolymer is modified with introduction EG9ME to increase thetoughness of the polymer and film-forming property. And the poly(DMA-co-EG9ME) with strongviscosity has also been designed to add into coating formula so as to improve the film formationability of paintings. The starting materials used for the synthesis of polymer are low cost andeasily available. More importantly, the copolymers are easy to degrade and environmentallyfriendly as a result of short trifluoromethyl pendant side groups. The polymer reveals a goodantifouling performance, which is expected to be used for marine coatings in order to prevent thepollution of marine life.