Coating knowledge: Research Progress of organosilicon low surface energy marine antifouling coatings

Core tips: Qin Ruirui, Hu Shengxiang, Gong Xiangyi (Zhengzhou Zhongyuan application technology research and Development Co., Ltd., Zhengzhou 450007) Abstract: the antifouling mechanism of organosilicon marine antifouling coating is summarized, the research progress of organosilicon marine antifouling coating, acrylic resin, epoxy resin and polyurethane modified organosilicon marine antifouling coating is summarized, and the organosilicon marine antifouling coating is prospected Direction of development Key words: antifouling, coating, ocean, organosilicon, modification, low surface energy, classification no of silicon oil in Chinese Library: tq324.2 + 1 document identification code: adoi: 10.11941/j.issn.1009-436 Which is the price of Dajin diatom mud Recommended brief introduction: which is the price of Dajin diatom mud? How to buy genuine diatom mud? Guangdong diatom mud agent suggests placing a basin of cold water in the air conditioning room, so that the diatom mud wall can breathe effectively The feature of the breathing wall is obvious When the indoor air is dry, the diatom mud wall will release the absorbed water quickly Put it out to help regulate the indoor dry humidity It is suggested to place a basin of cold water in the air conditioning room, so that the wall of diatom mud can breathe effectively The feature of the wall that can breathe is obvious When the indoor air is relatively dry, the wall of diatom mud will absorb the water Home of coatings: Qin Ruirui, Hu Shengxiang, Gong Xiangyi (Zhengzhou Zhongyuan applied technology research and Development Co., Ltd., Zhengzhou 450007) Abstract: the antifouling mechanism of organosilicon marine antifouling coating is summarized, including organosilicon marine antifouling coating, acrylic resin, epoxy resin and polyurethane The research progress of modified organosilicon marine antifouling coatings and the development trend of organosilicon marine antifouling coatings are prospected Key words: antifouling, coating, marine, organosilicon, modification, low surface energy, classification no of silicon oil in Chinese Library: tq324.2 + 1 document identification code: adoi: 10.11941/j.issn.1009-4369.2015.01.016 The marine antifouling coating is applied to the surface of the underwater part of the hull Its function is to reduce the pollution of marine organisms on the hull surface, keep the hull smooth, reduce the fuel consumption, and extend the service life of the ship The antifouling coating containing organotin insecticide appeared in the middle of the 20th century has good antifouling effect, but it has been completely banned in 2008 due to its serious harm to the marine environment [1] Although other insecticides (such as copper oxide and combined insecticides) can be used instead of organotin insecticides to make antifouling coatings, the environmental harm of such antifouling coatings is no less than organotin coatings Therefore, the development of new antifouling coatings with low surface energy and complete environmental friendliness is of great significance for the safety of marine transportation, especially for the protection of the marine environment, and has become a hot spot in the research of marine antifouling coatings at home and abroad in recent years [2] At present, low surface energy antifouling coatings are mainly based on organosilicon polymer or fluoropolymer [3] In fact, due to the high price and difficult preparation of fluoropolymer, there are few commercial products at present The marine antifouling coating based on organosilicon polymer has become a hot spot in the research, development and production of internationally renowned coating manufacturers [4] 1 The antifouling mechanism of organosilicon marine antifouling coating r.f Brady studied the antifouling principle of the coating It is found that the surface energy of the coating is the main factor affecting the biological adhesion When the surface energy is between 22-25mj / m2, the amount of biological adhesion is the least, and there is a certain relationship between the surface energy and the elastic modulus The lower the elastic modulus of the coating, the better the flexibility, the less likely the cracks or cracks of the hull or bottom coating are to crack, and the more likely the dirt is to fall off in the way of peeling [5] This method is one of the three ways (peeling, plane shearing and non plane shearing) for the removal of marine fouling from the coating surface, which requires the least energy [6] In addition, the molecular structure, film thickness, polarity, molecular mobility and other factors also have some influence on the antifouling effect Organosilicon polymer has low surface energy (21.2mj / m2) and low elastic modulus (0.002gpa), which makes organosilicon marine antifouling coating have strong self-cleaning ability, and it is difficult for marine pollutants to adhere to it; even if there is adhesion, it can be easily removed by water washing or decontamination equipment If vinyl, hydroxyl or other reactive groups are introduced into the organosilicon polymer molecules, coupled with coupling agents, auxiliaries, fillers, etc., the strength of the coating and adhesion with the substrate can also be enhanced At present, organosilicon marine antifouling coatings are mainly divided into organosilicon polymer based coatings and organic resin modified organosilicon polymer based coatings The following are respectively introduced 2 Organosilicon marine antifouling coating pure organosilicon marine antifouling coating is applied to the hull surface In the process of ship traveling, silicone oil or other additives slowly infiltrate from the coating body to the coating surface, making the surface appear smooth oil layer, and the dirt adheres to it, which is easy to be removed under the action of water flow or decontamination equipment, so as to achieve the purpose of antifouling and easy cleaning In 1972, W.J Mueller obtained the first patent of organosilicon marine antifouling coating The coating is based on silicone rubber and other additives [7] Then there are several related patents [8-10] The antifouling effect of the early coatings is not as good as that of the traditional coatings Later, there were several reports on organosilicon marine antifouling coatings [11] Although these coatings have a certain antifouling effect, they are not suitable for practical application due to their poor workability, long curing time, poor repainting performance and weak adhesion with the hull However, a new direction for the research of organosilicon marine antifouling coatings is pointed out Since 1990s, organosilicon marine antifouling coatings have developed rapidly 50 W Roy prepared organosilicon marine antifouling coating with self-made silicone resin with vinyl and hydrogen as base material and some additives After six months of application of the coating on the hull with the silicates primer, it shows a good antifouling effect and the coating can maintain a good integrity [12] Y Yonehara et al Used a series of self-made organosilicon polymers with different structures containing vinyl or / and hydroxyl sealing end as base materials, different proportions of silicone oil as additives, adding solvents, fillers, etc., to prepare marine antifouling coatings without pesticides Compared with the traditional vinyl chloride resin antifouling coating (the insecticides used are triphenyltin fluoride and red Fe2O3; Cu2O, red Fe2O3 and Bao; triphenyltin fluoride, Cu2O and red Fe2O3) for 12 months, the actual hanging plate experiment was carried out The results show that the surface tension of organosilicon marine antifouling coating is significantly lower than that of traditional marine antifouling coating, and the antifouling effect is also better than that of traditional antifouling coating [13] K Masato et al Synthesized hydroxyl terminated polysiloxane with different viscosity, added silicone oil containing vinyl or ketosilane coupling agent, boric acid organic catalyst and different groups (methyl, phenyl, etc.) to prepare silicone marine antifouling coating Four months later, there was no attachment of marine organisms on the surface of the coating, while there were many sludge, shellfish and vegetation on the surface of the coating without silicone oil [14] S Takafumi synthesized silicone oil with polyether chain, long chain alkyl and / or aryl groups of different molar mass (250-100000g / mol), which was added to RTV silicone resin in different proportion, to prepare antifouling coating for underwater use In use, the surface tension of the coating is reduced by the slow seepage of silicone oil to the surface, so as to have the antifouling effect Compared with the traditional vinyl chloroisobutyl ether copolymer antifouling coating, the antifouling effect of the coating can reach more than 2 years, while the traditional antifouling coating has different degrees of pollution when it is used for up to 1 year [15] J stein of General Electric Company of the United States synthesized polysiloxane with silanol, carbonyl, dialkyloxy and trialkoxy end sealing respectively, added silica (SiO2) or calcium carbonate as filler, and added catalyst, coupling agent and other auxiliaries to prepare Condensation Type RTV marine antifouling coating The results of real sea hanging plate test show that 91% ~ 99% of the coating surface is not polluted by marine organisms after 12 months of underwater [16-18] T Sakamoto of shinyue company, Japan, takes RTV silicone resin containing at least two silicon hydroxyl groups or other hydrolyzable groups as the base material, ionic liquid as the auxiliary agent, and silane with silicon hydroxyl groups or other hydrolyzable groups as the preparation of underwater antifouling coating The results of the real sea hanging plate test show that the coating still has good antifouling performance in the water for more than 12 months [19-20] Wang Ke et al Synthesized dimethylsilicone oil and dimethyldiphenylsilicone oil and added them to organosilicon marine antifouling coating The effect of silicone oil on the antifouling performance of coating was explained by the morphology of silicone oil on the coating surface and SEM photos The actual sea hanging plate confirmed that the antifouling performance of the antifouling coating added with silicone oil, especially phenyl silicone oil, has been greatly improved Even if there is a fouling marine organism attached, it can easily fall off without affecting the stability of the coating in the sea water [21] Because the organosilicon marine antifouling coating based on pure organosilicon polymer is easy to prepare, commercial products have been formed at present, such as hempasil77500 series of Hempel company in Denmark, international intersleep of akzonobe company in the Netherlands, Captain BIOX of Kansai company in Japan, Sealion of Jotun company in Norway, etc Although these products have excellent performance, they have lower antifouling effect and higher price compared with traditional antifouling coatings The antifouling function of pure organosilicon marine antifouling coating is to penetrate the coating body to the surface through silicone oil or other additives, so that the dirt attached to the oil surface is easy to fall off, so as to play a antifouling role Therefore, the disadvantages of this kind of coating are also obvious The outstanding problem is that silicone oil or other additives will be released in 2-3 years, which will make the coating lose the antifouling property Moreover, the coating has poor recoating property and is not easy to repair Therefore, there are still many problems to be solved Home of coatings is specialized in coatings, diatom mud, paint coating, coating technology, fire retardant coating news and coating, diatom mud, paint coating, coating technology, fire retardant coating decoration knowledge and decoration renderings,