【作者】 曲园园；

【导师】 张淑芬；

【作者基本信息】 大连理工大学 ， 应用化学， 2012， 博士

【摘要】 本文针对现有舰船防污涂料的VOC排放和有毒防污剂渗出对大气及海洋环境的污染问题,设计合成了一类新型的有机硅改性丙烯酸酯自乳化乳液,应用于防污涂料的成膜物,并对新型防污剂环氧甲萘醌(ME)在防污涂料中的应用进行了研究,得到一种新型的零VOC排放的乳液型舰船防污涂料。为了克服传统的由非反应型乳化剂制备的乳液漆膜耐水性差的缺点,本文采用反应型乳化剂烯丙基丙基磺基琥珀酸双酯钠盐(M-10S)和烯丙基辛基酚聚氧乙烯醚(AE-200)制备了新型有机硅改性丙烯酸酯自乳化乳液。采用红外光谱、差热分析、透射电镜和纳米粒度仪分别对有机硅改性丙烯酸酯的结构、玻璃化转变温度、乳液粒子形貌及大小进行分析表征。当甲基丙烯酸甲酯(MMA)的添加量为13.0wt%(物料总量)、丙烯酸丁酯(BA)添加量为13.0wt%(物料总量)、乙烯基三乙氧基硅烷(VTES)添加量为5.0wt%(物料总量)、质量比为1：1的M-10S和AE-200复合乳化剂添加量为0.7wt%(物料总量)、引发剂过硫酸铵(APS)添加量为0.3wt%(物料总量)、反应温度为80℃、反应时间为3h时,所制备的有机硅改性丙烯酸酯自乳化乳液最小数均粒径达到62.4nm。乳液漆膜性能优异,可以满足防污涂料成膜物使用要求。论文对维生素K3系列产品的防污效果进行了研究,确定了采用无毒、价廉的环氧甲萘醌(ME)作为主防污剂,并对与其匹配的防污助剂进行了研究。同时,为了使防污涂料中主防污剂ME释放可控,采用聚丙烯酸酯为囊壁对防污剂环氧甲萘醌(ME)进行微胶囊包覆,从而控制ME的释放速率,延长涂料使用寿命。研究了囊壁材最优组成、制备工艺对微胶囊平均粒径的影响；采用透射电镜(TEM)对微胶囊形貌进行表征。结果表明,所有的ME都被微胶囊化,ME微胶囊囊壁材最优组成为MMAwt％:BAwt％:AA(丙烯酸)wt%=26：45：29；采用分步加料法和复合乳化剂体系(OP-10wt％:SDS wt％=1:1)制备的微胶囊平均粒径为338.4nm。当囊芯材和囊壁材的质量比1：7时,涂料中ME渗出最平稳。论文以制备的新型有机硅改性丙烯酸酯自乳化乳液作为成膜物,以微胶囊化的环氧甲萘醌(ME)为主防污剂制备了新型水性防污涂料,对涂料漆膜的机械性能和防污性能进行了详细研究。结果表明,漆膜附着力为1级,抗冲击超过50cm·kg；当囊芯材和囊壁材的质量比为1：7的ME微胶囊的添加量为36.6wt%、吡啶硫酮锌的添加量为0.5wt%、纳米ZnO的添加量为2.0wt%、纳米TiO2的添加量为0.5wt%时,涂料的防污效果最佳。涂膜防污期可达3-4年。该涂料以水为分散介质,使用无毒高效的防污剂,达到无毒和零VOC排放的效果。另外,本文针对网箱养殖用防污涂料使用期短,及网绳的特殊柔韧性,设计合成了一类新型养殖网箱用防污涂料。该涂料以松香为成膜物,VOC豁免溶剂丙酮为溶剂,通过添加环保型防污剂ME和壬酸香草酰胺(PAV)以及增塑剂,制备了海水养殖用网箱防污涂料,讨论了增塑剂的选择和防污剂ME和PAV用量对漆膜防污效果的影响,检测了漆膜的急性毒性。防污效果海上对比实验结果表明,以邻苯二甲酸二辛酯和氯化石蜡复合物为增塑剂(邻苯二甲酸二辛酯：氯化石蜡=1：1)、PAV用量5.0wt%(物料总量)、ME用量2.5wt%(物料总量)时,3个月后海上挂样网片基本无增重,防污期可达10个月以上。急性毒性检测结果表明,制备的网箱防污涂料实际无毒。更多还原

【Abstract】 Now, most antifouling coatings still suffered from many problems, especially the atmospheric and marine pollution caused by VOCs emission and toxic biocides release. As concerning such disadvantages of antifouling coating, a novel silicone-acrylate self-emulsifying emulsion which can be used as film former of antifouling coating was designed and investigated, and the application of novel biocide-2,3-epoxy-2-methyl-1,4-naphthoquinone (ME) in the anfiouling coating was also studied. A high efficient, novel antifouling coating without VOCs emission was successfully formulated.Generally, the unpolymerizable emulsifiers in traditional emulsion show very poor water resistance property which is fatal to the antifouling coating. To conquer such problem, in this paper, a novel silicone-acrylate emulsion was synthesized using polymerizable emulsifiers4-propyl-1-(1-propenyl) sulfosuccinate (M-10S) and allyl octylphenyl polyoxyethylene glycol ether (AE-200). The emulsion was characterized by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and transmission electron microscopy micrograph (TEM). The optimal polymerization condition is13.0wt%MMA,13.0wt%BA,5.0wt%VTES,0.7wt%compound emulsifier-M-10S:AE-200=1:1(wt/wt),0.3wt%ammonium persulfate (APS),80℃of polymerization temperature,3h of reaction time. The Z-average particle size of the emulsion is62.4nm. The performances of the film prepared from the emulsion were excellent. This novel silicone-acrylate emulision met the commercial standards of film-forming polymer for antifouling coating.Antifouling performances of Vitamin K3products were studied in this paper, and ME was employed as main antifoulant. In the mean time, the antifouling additives matching with ME were also studied. In order to control the release of main antifoulant-ME from the coating film, and prepare the antifouling coating with long service life, polyacrylate emulsion was applied as wall material to microcapsulate ME. Shell material component and the effect of the preparation procedure on the microcapsule particle size were studied. TEM was used to characterize ME microcapsules. The results showed that ME was successfully microencapsulated and the average particle size was only338.4nm by multistep feeding in the presence of emulsifiers-OP-10:SDS=1:1(wt/wt). The optimal shell material component is MMA:BA:AA=26:45:29(wt:wt:wt). When the core/shell mass ratio of microcapsules was1:7, the release rate of ME from the coating was steady.In this paper, a waterborne antifouling coating for ship hull protection was prepared by employing novel synthesized silicone-acrylate emulsion as film former and ME microcapsules as main antifoulant. Physical and mechanical properties, antifouling performance were tested. The adhesion of the coating film reaches1grade and the impact resistance is over50cm·kg, The optimal recipe of the waterborne antifouling coating is36.6wt%ME microcapsules,0.5wt%Zinc pyrithione,2.0wt%nano-sized ZnO and0.5wt%nano-sized TiO2. The antifouling activity of the coating film is excellent. The service life of the coating film can last for3-4years. By the application of water as dispersion medium and environmental friendly antifouling agents, there is no VOCs emission from the environmental friendly coating.Based on the short service life of the antifouling coating used on marine cage, and the special flexibility of the netting, a novel antifouling coating was studied and prepared with rosin, acetone, ME, pelargonic acid vanillyamide (PAV) and plasticizer. The observation on treated netting hung up for3months in the sea showed that the antifouling efficiency of the coating made with plasticizers-dinormal octyl phthalate:chlorcosane=1:1(wt/wt) in the presence of5.0wt%PAV and2.5wt%ME was excellent, and there was no weight gain of the netting. The service life of the coatin film can last at least10months. Meanwhile the coating film was environmental friendly.更多还原