技术领域Technical Field
本发明涉及防污涂层技术领域，尤其涉及一种海洋船舶防污涂层及其制备方法。The present invention relates to the technical field of antifouling coatings, and in particular to an antifouling coating for marine vessels and a preparation method thereof.
背景技术Background Art
随着全球航运业的蓬勃发展,船舶海洋污损问题日益严峻。海洋污损不仅加速了船体和海洋设施的老化和腐蚀,也显著增加了航行阻力和燃料消耗,进而导致温室气体排放和环境污染问题加剧。因此,研制高效、长效、环境友好的船舶防污涂层技术,对于航运业的可持续发展至关重要。With the booming development of the global shipping industry, the problem of marine fouling of ships is becoming increasingly serious. Marine fouling not only accelerates the aging and corrosion of hulls and marine facilities, but also significantly increases navigation resistance and fuel consumption, which in turn leads to increased greenhouse gas emissions and environmental pollution. Therefore, the development of efficient, long-lasting and environmentally friendly ship antifouling coating technology is crucial to the sustainable development of the shipping industry.
传统的船舶防污涂层主要包括自抛光型涂层和防污剂释放型涂层。自抛光型涂层通过水解、溶解等方式逐渐剥离,从而带走表面附着的污损物。然而,这类涂层存在着持效期短、涂层损耗快等问题,且剥离的涂层碎片可能造成二次污染。防污剂释放型涂层则通过向海水中缓慢释放有机锡、铜等杀菌剂,抑制微生物在涂层表面附着。但是,这些有毒防污剂的大量使用,对海洋生态系统构成了严重威胁。因此,开发高效环保的新型防污涂层体系,成为当前船舶防污领域的重要挑战和发展方向。Traditional ship antifouling coatings mainly include self-polishing coatings and antifouling agent-releasing coatings. Self-polishing coatings are gradually peeled off by hydrolysis, dissolution, etc., thereby removing the fouling attached to the surface. However, this type of coating has problems such as short effective period and rapid coating loss, and the peeled coating fragments may cause secondary pollution. Antifouling agent-releasing coatings inhibit the attachment of microorganisms to the coating surface by slowly releasing fungicides such as organic tin and copper into seawater. However, the large-scale use of these toxic antifouling agents poses a serious threat to the marine ecosystem. Therefore, the development of a new type of efficient and environmentally friendly antifouling coating system has become an important challenge and development direction in the current field of ship antifouling.
近年来,不含有毒防污剂的新型环保防污涂层得到了广泛关注。其中,低表面能疏水防污涂层和仿生防污涂层成为研究热点。疏水防污涂层通过降低表面能,减少污损物与涂层的粘附作用力,使污损物难以在涂层表面吸附。但是,目前的疏水防污涂层普遍存在耐久性差、抗冲击和耐磨性能低等缺陷,在实际海洋环境中的防污效果往往难以长期维持。仿生防污涂层借鉴了天然生物表面的多级微纳米结构,通过形成超疏水表面,达到防污目的。然而,复杂精细的仿生微纳米结构在大面积涂层制备过程中容易被破坏,且成本较高,限制了其实际应用。In recent years, new environmentally friendly antifouling coatings that do not contain toxic antifouling agents have received widespread attention. Among them, low surface energy hydrophobic antifouling coatings and bionic antifouling coatings have become research hotspots. Hydrophobic antifouling coatings reduce the surface energy and the adhesion force between fouling and coatings, making it difficult for fouling to adsorb on the coating surface. However, current hydrophobic antifouling coatings generally have defects such as poor durability, low impact resistance and low wear resistance, and the antifouling effect in actual marine environments is often difficult to maintain for a long time. Bionic antifouling coatings draw on the multi-level micro-nano structure of natural biological surfaces and achieve the purpose of antifouling by forming a super-hydrophobic surface. However, the complex and delicate bionic micro-nano structure is easily destroyed during the preparation of large-area coatings, and the high cost limits its practical application.
除上述问题外,现有船舶防污涂层还普遍存在着以下技术障碍:In addition to the above problems, the existing ship antifouling coatings also generally have the following technical obstacles:
1.防污机制单一,难以应对复杂多变的海洋污损环境。例如,单纯依靠超疏水表面的自清洁效应,难以完全抵御海洋强腐蚀环境和严酷水流冲刷条件。1. The anti-fouling mechanism is single and it is difficult to cope with the complex and changeable marine fouling environment. For example, relying solely on the self-cleaning effect of the super-hydrophobic surface is difficult to completely resist the strong marine corrosive environment and harsh water flow conditions.
2.缺乏长效智能防污能力。传统的防污涂层很难在涂层全生命周期内持续提供有效的防污保护,尤其是后期往往出现药剂失活、涂层老化等问题,导致防污性能显著下降。2. Lack of long-term intelligent antifouling capabilities. Traditional antifouling coatings are difficult to provide effective antifouling protection throughout the coating's life cycle, especially in the later stages when problems such as agent inactivation and coating aging often occur, resulting in a significant decrease in antifouling performance.
3.涂层损伤修复能力差。海洋环境中的机械碰撞、紫外线照射等因素易引起涂层开裂、剥落等损伤,现有涂层很难自发修复这些缺陷,只能依赖人工检修,费时费力。3. Poor coating damage repair ability. Mechanical collision, ultraviolet radiation and other factors in the marine environment can easily cause coating cracking, peeling and other damage. It is difficult for existing coatings to spontaneously repair these defects and can only rely on manual maintenance, which is time-consuming and labor-intensive.
4.环境适应性不足。由于海水盐度、温度、pH等要素的时空差异,导致不同海域的污损特征差别很大。而目前的涂层配方和性能往往难以兼顾适应多种类型的海洋环境。4. Insufficient environmental adaptability. Due to the temporal and spatial differences in seawater salinity, temperature, pH and other factors, the fouling characteristics in different sea areas vary greatly. However, the current coating formula and performance are often difficult to adapt to various types of marine environments.
针对上述技术问题,本发明提出了一种海洋船舶防污涂层及其制备方法。In view of the above technical problems, the present invention proposes an antifouling coating for marine vessels and a preparation method thereof.
发明内容Summary of the invention
为了克服现有技术的不足,本发明的目的是提供一种海洋船舶防污涂层及其制备方法。In order to overcome the deficiencies of the prior art, the present invention aims to provide an antifouling coating for marine vessels and a preparation method thereof.
本发明的目的在于提供一种海洋船舶防污涂层,包括以下组分:包括以下重量份的各组分:The object of the present invention is to provide an antifouling coating for marine vessels, comprising the following components: comprising the following components in parts by weight:
低表面能氟硅改性环氧树脂40-60份；40-60 parts of low surface energy fluorine-silicon modified epoxy resin;
氨基改性纳米二氧化钛10-30份；10-30 parts of amino-modified nano titanium dioxide;
氨基改性纳米二氧化硅5-10份；5-10 parts of amino-modified nano-silicon dioxide;
季铵盐型聚合物胶囊5-15份；5-15 parts of quaternary ammonium salt polymer capsules;
有机锡聚合物微球5-10份；5-10 parts of organotin polymer microspheres;
硫醇封端超支化大分子1-5份。1-5 parts of thiol-terminated hyperbranched macromolecules.
具体地，所述低表面能氟硅改性环氧树脂的制备方法为:将1-5重量份十二烷基苯磺酸钠作为乳化剂溶于60-100重量份去离子水中,得乳化剂溶液A；将1-3重量份十六醇作为助稳定剂、0.2-0.8重量份过氧化苯甲酰作为引发剂、1-5重量份乙烯基含量为0.01-0.06摩尔％的乙烯基硅树脂、1-5重量份甲基丙烯酸六氟丁酯作为含氟单体和5-10重量份双酚A型环氧树脂E-44溶于20-40重量份由苯乙烯和丙烯酸丁酯组成的乙烯基混合单体中,得单体溶液B；将乳化剂溶液A和单体溶液B混合,搅拌分散,转速200-400r/min,时间20-40min；然后超声乳化,频率15-40KHz,功率100-300W,时间20-40min；即得微滴单体乳液；将微滴单体乳液加热至60-80℃,通入惰性气体并搅拌聚合3-8h,转速200-400r/min；聚合结束后冷却至室温,即得低表面能氟硅改性环氧树脂。Specifically, the preparation method of the low surface energy fluorine-silicon modified epoxy resin is as follows: 1-5 parts by weight of sodium dodecylbenzene sulfonate as an emulsifier is dissolved in 60-100 parts by weight of deionized water to obtain an emulsifier solution A; 1-3 parts by weight of hexadecanol as a stabilizer, 0.2-0.8 parts by weight of benzoyl peroxide as an initiator, 1-5 parts by weight of a vinyl silicone resin having a vinyl content of 0.01-0.06 mol%, 1-5 parts by weight of hexafluorobutyl methacrylate as a fluorine-containing monomer and 5-10 parts by weight of bisphenol A type epoxy resin E-44 are dissolved in 20-40 parts by weight of styrene. The monomer solution B is obtained from a vinyl mixed monomer composed of ethylene and butyl acrylate; the emulsifier solution A and the monomer solution B are mixed, stirred and dispersed at a speed of 200-400r/min and a time of 20-40min; then ultrasonic emulsification is performed at a frequency of 15-40KHz, a power of 100-300W and a time of 20-40min; a droplet monomer emulsion is obtained; the droplet monomer emulsion is heated to 60-80°C, an inert gas is introduced and stirred for polymerization for 3-8h at a speed of 200-400r/min; after the polymerization is completed, it is cooled to room temperature to obtain a low surface energy fluorosilicone modified epoxy resin.
具体地，所述氨基改性纳米二氧化钛的制备方法为:Specifically, the preparation method of the amino-modified nano titanium dioxide is:
(1)取10g纳米二氧化钛粉体,加入到装有100mL无水乙醇的烧杯中,超声分散30min,得到均匀的二氧化钛乙醇悬浮液；(1) Take 10 g of nano-titanium dioxide powder, add it into a beaker containing 100 mL of anhydrous ethanol, and disperse it by ultrasonic for 30 min to obtain a uniform titanium dioxide ethanol suspension;
(2)取2mLγ-氨丙基三乙氧基硅烷,缓慢滴加到装有300mL去离子水的三口烧瓶中,于50℃下搅拌反应2h,得到均一透明的硅烷水解液；(2) Take 2 mL of γ-aminopropyltriethoxysilane and slowly add it dropwise into a three-necked flask containing 300 mL of deionized water. Stir and react at 50° C. for 2 h to obtain a uniform and transparent silane hydrolyzate.
(3)将步骤(1)中的二氧化钛乙醇悬浮液缓慢滴加到步骤(2)的硅烷水解液中,升温至80℃,回流反应6h；(3) slowly adding the titanium dioxide ethanol suspension in step (1) to the silane hydrolyzate in step (2), heating to 80° C., and reflux for 6 h;
(4)反应结束后,将所得白色悬浮液离心分离,去离子水洗涤3次,无水乙醇洗涤1次,于60℃真空干燥4h,研磨过120目筛,即得氨基改性纳米二氧化钛粉体。(4) After the reaction is completed, the obtained white suspension is centrifuged, washed with deionized water three times, washed with anhydrous ethanol once, dried under vacuum at 60°C for 4 h, and ground through a 120-mesh sieve to obtain amino-modified nano-titanium dioxide powder.
具体地，所述氨基改性纳米二氧化硅的制备方法为:Specifically, the preparation method of the amino-modified nano-silica is:
(1)取5g纳米二氧化硅气凝胶,加入到装有60mL无水乙醇的烧杯中,搅拌分散均匀,超声20min,得到均一稳定的二氧化硅乙醇分散液；(1) Take 5 g of nano-silica aerogel and add it to a beaker containing 60 mL of anhydrous ethanol, stir and disperse it evenly, and ultrasonicate it for 20 min to obtain a uniform and stable silica ethanol dispersion;
(2)取3mLγ-氨丙基三乙氧基硅烷,溶解于450mL去离子水中,于室温下搅拌30min,得到硅烷水解液；(2) Take 3 mL of γ-aminopropyltriethoxysilane, dissolve it in 450 mL of deionized water, and stir it at room temperature for 30 minutes to obtain a silane hydrolyzate;
(3)在剧烈搅拌下,将步骤(1)中的二氧化硅乙醇分散液逐滴加入到步骤(2)的硅烷水解液中,滴加完毕后升温至90℃,继续反应10h；(3) under vigorous stirring, the silicon dioxide ethanol dispersion in step (1) is added dropwise to the silane hydrolyzate in step (2), and after the addition is complete, the temperature is raised to 90° C. and the reaction is continued for 10 hours;
(4)反应结束后,静置冷却至室温,抽滤,去离子水洗涤滤饼至中性,于70℃真空干燥6h,研磨过200目筛,即得氨基改性纳米二氧化硅粉体。(4) After the reaction is completed, the mixture is allowed to stand and cool to room temperature, filtered, and the filter cake is washed with deionized water until it is neutral. The filter cake is vacuum dried at 70° C. for 6 h, and ground through a 200-mesh sieve to obtain amino-modified nano-silica powder.
具体地，所述季铵盐型聚合物胶囊的制备方法为:(1)将1-5g聚甲基丙烯酸甲酯和1-5g十六烷基三甲基溴化铵溶解于50-100mL水中；(2)将上述溶液超声乳化,形成油包水型乳状液,超声频率20-50KHz,功率200-500W,时间10-30min，在乳化过程中缓慢滴加0.5-2g无水乙醇作为助乳化剂；(3)将乳状液置于50-80℃水浴中搅拌2-6h,转速300-600r/min,使水相蒸发；(4)将所得沉淀物抽滤并真空干燥,即得内含十六烷基三甲基溴化铵的聚甲基丙烯酸甲酯胶囊,平均粒径5-20μm。Specifically, the preparation method of the quaternary ammonium salt polymer capsule is as follows: (1) dissolving 1-5g of polymethyl methacrylate and 1-5g of hexadecyltrimethylammonium bromide in 50-100mL of water; (2) ultrasonically emulsifying the above solution to form an oil-in-water emulsion, with an ultrasonic frequency of 20-50KHz, a power of 200-500W, and a time of 10-30min, and slowly dropping 0.5-2g of anhydrous ethanol as an emulsifier during the emulsification process; (3) placing the emulsion in a 50-80°C water bath and stirring for 2-6h at a speed of 300-600r/min to evaporate the water phase; (4) filtering the obtained precipitate and vacuum drying it to obtain polymethyl methacrylate capsules containing hexadecyltrimethylammonium bromide, with an average particle size of 5-20μm.
具体地，所述有机锡聚合物微球的制备方法为:(1)将0.5-2mmol二丁基氯化锡和二苯基氯化锡按摩尔比1:1混合作为模板分子,4-8mmol甲基丙烯酸作为功能单体,5-20mmol三羟甲基丙烷三甲基丙烯酸酯作为交联剂,0.1-0.5mmol偶氮二异丁腈作为引发剂,溶于50-100mL由二氯甲烷和乙腈按体积比3:1混合形成的惰性溶剂中，加入0.01-0.05mmol2,2'-偶氮二(2,4-二甲基戊腈)作为分子导向剂；(2)通入N2排除氧气20-40min后,于50-70℃下聚合反应20-30h；(3)将所得块状聚合物研磨,过80-200目筛,用体积比为9:1的甲醇/乙酸溶液洗脱,除去模板分子；(4)将聚合物颗粒真空干燥,即得有机锡聚合物微球,粒径1-5μm。Specifically, the preparation method of the organotin polymer microspheres is as follows: (1) 0.5-2 mmol of dibutyltin chloride and diphenyltin chloride are mixed in a molar ratio of 1:1 as template molecules, 4-8 mmol of methacrylic acid is used as a functional monomer, 5-20 mmol of trimethylolpropane trimethacrylate is used as a crosslinking agent, and 0.1-0.5 mmol of azobisisobutyronitrile is used as an initiator, and the mixture is dissolved in 50-100 mL of an inert solvent formed by mixing dichloromethane and acetonitrile in a volume ratio of 3:1, and 0.01-0.05 mmol of 2,2'-azobis(2,4-dimethylvaleronitrile) is added as a molecular directing agent; (2) N2. After excluding oxygen for 20-40 minutes, the polymerization reaction is carried out at 50-70°C for 20-30 hours; (3) the obtained block polymer is ground, passed through an 80-200 mesh sieve, and eluted with a methanol/acetic acid solution with a volume ratio of 9:1 to remove the template molecules; (4) the polymer particles are vacuum dried to obtain organotin polymer microspheres with a particle size of 1-5 μm.
具体地，所述硫醇封端超支化大分子的制备方法为:(1)将0.1-0.5g三羟甲基丙烷三(3-巯基丙酸酯)作为三官能度硫醇单体溶于5-10mLN,N-二甲基甲酰胺中,加入0.01-0.05g对甲苯磺酸作为酯化催化剂，N2气氛下搅拌除氧20-40min；(2)加入0.05-0.3g 2-(丙烯酰氧基)-甲基丙烯酸乙酯作为二官能度丙烯酸酯单体,于40-60℃反应20-30h；(3)反应结束后加入过量无水乙醚,静置分层,取下层有机相；旋蒸除去溶剂后,滴加入过量无水乙醚中沉淀,抽滤；将沉淀物溶于二氯甲烷,再次滴加入无水乙醚沉淀,重复2-4次；将沉淀物真空干燥,即得端硫醇超支化聚合物,数均分子量5000-50000。Specifically, the preparation method of the thiol-terminated hyperbranched macromolecule is as follows: (1) dissolving 0.1-0.5 g of trimethylolpropane tris(3-mercaptopropionate) as a trifunctional thiol monomer in 5-10 mL of N,N-dimethylformamide, adding 0.01-0.05 g of p-toluenesulfonic acid as an esterification catalyst, and stirring and deoxygenating for 20-40 min under aN2 atmosphere; (2) adding 0.05-0.3 g of 2-(Acryloyloxy)-ethyl methacrylate is used as a difunctional acrylic ester monomer and reacted at 40-60°C for 20-30h; (3) after the reaction is completed, an excess of anhydrous ether is added, the mixture is allowed to stand for stratification, and the lower organic phase is taken; after the solvent is removed by rotary evaporation, the mixture is added dropwise to an excess of anhydrous ether for precipitation, and the mixture is filtered; the precipitate is dissolved in dichloromethane, anhydrous ether is added dropwise again for precipitation, and the mixture is repeated 2-4 times; the precipitate is dried in vacuum to obtain a terminal thiol hyperbranched polymer with a number average molecular weight of 5000-50000.
具体地，所述十六烷基三甲基溴化铵在季铵盐型聚合物胶囊中的含量为胶囊总重量的30-50％。Specifically, the content of hexadecyltrimethylammonium bromide in the quaternary ammonium salt polymer capsule is 30-50% of the total weight of the capsule.
一种海洋船舶防污涂层的制备方法，包括以下步骤：将40-60重量份氟硅改性环氧树脂、10-30重量份氨基改性纳米二氧化钛、5-10重量份氨基改性纳米二氧化硅、5-15重量份季铵盐型聚合物胶囊、5-10重量份有机锡聚合物微球和1-5重量份硫醇封端超支化大分子混合,加入二甲苯60-100份,球磨分散2-6小时,得到均一涂料；然后加入固化剂25-40份，所述固化剂为聚醚胺、二乙烯三胺、乙二胺、间二甲苯二胺、KH792、KH550中的一种或多种，然后采用喷涂或刷涂的方式涂覆到船体表面,涂层厚度控制在50-200μm,在常压、温度15-35℃的条件下固化24-48小时。A method for preparing an antifouling coating for marine ships comprises the following steps: mixing 40-60 parts by weight of fluorine-silicon modified epoxy resin, 10-30 parts by weight of amino-modified nano titanium dioxide, 5-10 parts by weight of amino-modified nano silicon dioxide, 5-15 parts by weight of quaternary ammonium salt polymer capsules, 5-10 parts by weight of organic tin polymer microspheres and 1-5 parts by weight of mercaptan-terminated hyperbranched macromolecules, adding 60-100 parts of xylene, and performing ball milling dispersion for 2-6 hours to obtain a uniform coating; then adding 25-40 parts of a curing agent, wherein the curing agent is one or more of polyetheramine, diethylenetriamine, ethylenediamine, meta-xylene diamine, KH792 and KH550, and then applying the coating to the surface of the hull by spraying or brushing, wherein the coating thickness is controlled to be 50-200 μm, and curing is performed for 24-48 hours at normal pressure and a temperature of 15-35° C.
与现有技术相比，本发明一种海洋船舶防污涂层及其制备方法及其制备方法能够达到以下有益效果：Compared with the prior art, the antifouling coating for marine vessels and the preparation method thereof of the present invention can achieve the following beneficial effects:
1.本发明巧妙地将表面能降低、表面微纳米结构优化和生物活性物质缓释三种不同的抗污作用机制集于一身,通过化学组分的精心设计实现了多机制间的协同增效。其中,氟硅改性环氧树脂基体中引入了低表面能的全氟烷基和聚硅氧烷结构,显著降低了涂层表面能,使其具有优异的疏水疏油性,抑制了海洋污染物的粘附。氨基改性纳米TiO2和氨基改性SiO2颗粒的引入不仅进一步降低了表面能,其各向异性的纳米棒/片状结构还构建了具有多级粗糙结构的涂层表面,形成了类似荷叶表面的"微纳米双重结构",阻断了污染物与涂层的接触,产生物理抗污效果。同时,季铵盐聚合物胶囊和有机锡聚合物微球分别可控释放抑菌剂和杀藻剂,通过化学方式持续抑制微生物在涂层表面的附着繁殖。上述物理抗污和化学抗污机制相互协同、互为补充,大大提升了涂层的综合防污效果,远超传统单一防污机制涂层。1. The present invention cleverly combines three different anti-fouling mechanisms, namely, surface energy reduction, surface micro-nanostructure optimization, and sustained release of bioactive substances, and achieves synergistic enhancement among multiple mechanisms through the careful design of chemical components. Among them, the low surface energy perfluoroalkyl and polysiloxane structures are introduced into the fluorosilicon modified epoxy resin matrix, which significantly reduces the surface energy of the coating, making it have excellent hydrophobicity and oleophobicity, and inhibiting the adhesion of marine pollutants. The introduction of amino-modified nano-TiO2 and amino-modifiedSiO2 particles not only further reduces the surface energy, but also constructs a coating surface with a multi-level rough structure due to its anisotropic nanorod/sheet structure, forming a "micro-nano dual structure" similar to the surface of a lotus leaf, blocking the contact between pollutants and the coating, and producing a physical anti-fouling effect. At the same time, quaternary ammonium salt polymer capsules and organotin polymer microspheres can controllably release antibacterial agents and algaecides, respectively, and continuously inhibit the attachment and reproduction of microorganisms on the coating surface by chemical means. The above-mentioned physical anti-fouling and chemical anti-fouling mechanisms work together and complement each other, greatly improving the comprehensive anti-fouling effect of the coating, far exceeding the traditional single anti-fouling mechanism coating.
2.传统含生物活性物质的防污涂层常存在活性物质释放不可控、效果不持久等问题。本发明创新性地采用了两种不同的缓释载体:季铵盐聚合物胶囊和有机锡聚合物微球,分别负责抑菌剂和杀藻剂的可控释放。胶囊和微球载体的化学结构和孔径分布差异,使得抑菌剂和杀藻剂呈现出不同的释放动力学特征,在涂层服役全过程中形成了早期快释-中期持续释放-后期缓释的多阶段智能释放模式,持续提供针对不同时期藻菌生长的精准抑制,最大限度地发挥生物活性物质的作用。同时,季铵盐阳离子表面活性剂分子中的疏水烷基链还可与聚合物胶囊壁产生疏水作用,而有机锡分子与有聚合物微球中的空穴间存在位阻匹配作用,这些分子间的特异性相互作用进一步提高了缓释载体对活性物质的包封性能,减缓了活性物质的释放速率,延长了缓释周期。2. Traditional antifouling coatings containing biologically active substances often have problems such as uncontrollable release of active substances and short-lasting effects. The present invention innovatively uses two different sustained-release carriers: quaternary ammonium salt polymer capsules and organotin polymer microspheres, which are responsible for the controlled release of antibacterial agents and algaecides, respectively. The differences in the chemical structure and pore size distribution of capsule and microsphere carriers make the antibacterial agents and algaecides present different release kinetic characteristics, forming a multi-stage intelligent release mode of early rapid release-mid-term sustained release-late sustained release during the entire service process of the coating, continuously providing precise inhibition of algae and fungi growth at different periods, and maximizing the role of biologically active substances. At the same time, the hydrophobic alkyl chains in the quaternary ammonium salt cationic surfactant molecules can also produce hydrophobic effects with the polymer capsule wall, and there is a steric matching effect between the organotin molecules and the holes in the polymer microspheres. The specific interactions between these molecules further improve the encapsulation performance of the sustained-release carrier for active substances, slow down the release rate of active substances, and extend the sustained-release period.
3.海洋环境恶劣,防污涂层长期服役难免出现局部损伤和老化,导致防污性能下降。本发明的一大创新点在于引入了硫醇封端超支化大分子作为自修复基元。这种超支化大分子兼具高度支化的骨架结构和硫醇活性末端基团,赋予了涂层多层次自修复能力。一方面,超支化大分子骨架的拓扑结构和空间位阻效应,可在涂层受到局部应力损伤时,通过大分子链段的重排和缠结实现结构层面的自修复；另一方面,硫醇基团可通过动态二硫键的断裂与重组修复化学键层面的缺陷。同时,在氧化还原条件变化时,硫醇基团还可发生可逆的氧化偶联和还原解离反应,进一步提高自修复体系的环境适应性。此外,有机锡聚合物微球和胶囊释放的三丁基锡离子和季铵盐离子还可与超支化分子中的硫醇基团配位,形成金属配位键或离子对作用,在一定程度上也有助于修复涂层微区损伤。这种覆盖分子、微观和宏观多个层次的自修复功能弥补了海洋防污涂层容易损伤老化的不足,大大延长了涂层的耐久性。3. The marine environment is harsh, and local damage and aging are inevitable in the long-term service of antifouling coatings, resulting in a decrease in antifouling performance. A major innovation of the present invention is the introduction of thiol-terminated hyperbranched macromolecules as self-repairing primitives. This hyperbranched macromolecule has both a highly branched skeleton structure and thiol-active terminal groups, which endows the coating with multi-level self-repairing capabilities. On the one hand, the topological structure and steric hindrance effect of the hyperbranched macromolecular skeleton can achieve self-repair at the structural level through the rearrangement and entanglement of the macromolecular segments when the coating is damaged by local stress; on the other hand, the thiol group can repair defects at the chemical bond level by breaking and reorganizing the dynamic disulfide bonds. At the same time, when the redox conditions change, the thiol group can also undergo reversible oxidative coupling and reductive dissociation reactions, further improving the environmental adaptability of the self-repairing system. In addition, the tributyltin ions and quaternary ammonium salt ions released by the organotin polymer microspheres and capsules can also coordinate with the thiol groups in the hyperbranched molecules to form metal coordination bonds or ion pairs, which to a certain extent also helps to repair the coating micro-area damage. This self-repairing function covering multiple levels of molecular, microscopic and macroscopic levels makes up for the shortcomings of marine antifouling coatings that are easily damaged and aged, and greatly extends the durability of the coating.
4.防污涂层配方复杂,组分间的相容性和稳定性控制一直是个难题。本发明在防污组分的筛选和基体匹配性设计方面进行了系统优化,实现了组分功能的最大化发挥和相容性矛盾的巧妙解决。例如,季铵盐抑菌剂分子中的长烷基疏水链可有效增容疏水性的氟硅改性环氧树脂,而亲水的季铵头基则可在涂层表面富集,形成抗菌亲水层,在提高抑菌活性的同时还能促进表面水膜形成,降低污损物粘附。有机锡离子与纳米二氧化硅，纳米二氧化钛表面可形成Sn-O配位键,不仅有助于提高有机锡分子的包封率,还能拓展杀藻剂分子在涂层基体中的分散性。超支化大分子中的亲水基团如羟基、羧基等还可与无机纳米粒子表面产生氢键作用,在增强无机-有机杂化界面结合力的同时,也为纳米粒子在涂层基体中的均匀分散创造了条件。总之,本发明在防污组分的化学结构匹配性设计上独具匠心,最大程度地协调了各组分间的相容性,强化了界面作用,实现了1+1＞2的协同增效。4. The formula of antifouling coating is complex, and the compatibility and stability control between components has always been a difficult problem. The present invention has carried out systematic optimization in the screening of antifouling components and the design of matrix matching, realizing the maximization of component functions and the ingenious solution of compatibility contradictions. For example, the long alkyl hydrophobic chain in the quaternary ammonium salt antibacterial agent molecule can effectively increase the capacity of hydrophobic fluorosilicone modified epoxy resin, while the hydrophilic quaternary ammonium head group can be enriched on the coating surface to form an antibacterial hydrophilic layer, which can promote the formation of surface water film while improving the antibacterial activity and reduce the adhesion of foulants. Organic tin ions can form Sn-O coordination bonds with the surface of nano-silicon dioxide and nano-titanium dioxide, which not only helps to improve the encapsulation rate of organic tin molecules, but also expands the dispersibility of algaecide molecules in the coating matrix. The hydrophilic groups in the hyperbranched macromolecules, such as hydroxyl and carboxyl groups, can also produce hydrogen bonds with the surface of inorganic nanoparticles, which not only enhances the binding force of the inorganic-organic hybrid interface, but also creates conditions for the uniform dispersion of nanoparticles in the coating matrix. In short, the present invention is ingenious in the design of chemical structure matching of antifouling components, coordinates the compatibility between the components to the greatest extent, strengthens the interface effect, and achieves a synergistic effect of 1+1>2.
5.防污涂层制备过程涉及复杂的物理化学反应,各制备步骤的匹配与协同至关重要。本发明在涂层材料的制备工艺设计方面进行了系统的优化创新,实现了制备过程的协同高效。首先,在氟硅改性环氧树脂的合成中,先在体系中引入硅氧烷偶联剂,通过其与环氧基团的开环反应以化学键合的方式引入聚硅氧烷侧链,再进行后续的氟改性反应,避免了游离态的氟硅改性剂分子破坏体系稳定性。在季铵盐聚合物胶囊的合成中,优选采用简单高效的一步法乳液聚合工艺,在反应过程中同时引入季铵盐表面活性剂和聚合单体,季铵盐分子在起乳化剂作用的同时还参与聚合反应,最终通过自组装形成内层包覆季铵盐分子的聚合物胶囊结构,避免了繁琐的多步骤制备。而在有机锡聚合物微球的制备过程中,独特的原位聚合包埋工艺也巧妙地将包封、成球集于一步,优化了微球的微观结构和表面性能,提高了包封率。此外,将不同组分采用溶液共混法进行复合也能实现组分在分子水平的均匀分散,简化了制备流程。5. The preparation process of antifouling coating involves complex physical and chemical reactions, and the matching and coordination of each preparation step are crucial. The present invention has carried out systematic optimization and innovation in the design of the preparation process of the coating material, and achieved the coordinated and efficient preparation process. First, in the synthesis of fluorine-silicon modified epoxy resin, a siloxane coupling agent is first introduced into the system, and the polysiloxane side chain is introduced in a chemically bonded manner through the ring-opening reaction with the epoxy group, and then a subsequent fluorine modification reaction is carried out, thereby avoiding the free fluorine-silicon modifier molecules from destroying the stability of the system. In the synthesis of quaternary ammonium salt polymer capsules, a simple and efficient one-step emulsion polymerization process is preferably adopted, and quaternary ammonium salt surfactants and polymerization monomers are introduced simultaneously during the reaction process. The quaternary ammonium salt molecules not only act as emulsifiers but also participate in the polymerization reaction, and finally form a polymer capsule structure with an inner layer coated with quaternary ammonium salt molecules through self-assembly, thereby avoiding cumbersome multi-step preparation. In the preparation process of organotin polymer microspheres, the unique in-situ polymerization embedding process also cleverly combines encapsulation and sphering in one step, optimizes the microstructure and surface properties of the microspheres, and improves the encapsulation rate. In addition, compounding different components using the solution blending method can also achieve uniform dispersion of the components at the molecular level, simplifying the preparation process.
综上所述,本发明的长效自修复防污涂层体系在机理创新、功能集成和制备工艺优化等方面实现了历史性突破,各功能组分和作用机制间的精准协同是实现涂层性能跨越式提升的根本。同时,这种以化学反应机理和材料组成结构为基础,兼顾分子设计、界面优化和宏观加工的多层次协同创新范式,为复杂体系的构效关系研究和功能材料的设计开发提供了新的思路。In summary, the long-lasting self-repairing antifouling coating system of the present invention has achieved a historic breakthrough in mechanism innovation, functional integration and preparation process optimization. The precise coordination between the functional components and the action mechanism is the fundamental to achieve a leap-forward improvement in coating performance. At the same time, this multi-level collaborative innovation paradigm based on chemical reaction mechanism and material composition structure, taking into account molecular design, interface optimization and macro-processing, provides new ideas for the study of structure-activity relationship of complex systems and the design and development of functional materials.
具体实施方式DETAILED DESCRIPTION
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明具体实施例对本发明技术方案进行清楚、完整地描述。显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the specific embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
实施例1Example 1
一种海洋船舶防污涂层,其组成为:An antifouling coating for marine vessels, comprising:
低表面能氟硅改性环氧树脂40重量份；40 parts by weight of low surface energy fluorine-silicon modified epoxy resin;
氨基改性纳米二氧化钛20重量份；20 parts by weight of amino-modified nano titanium dioxide;
氨基改性纳米二氧化硅5重量份；5 parts by weight of amino-modified nano-silicon dioxide;
季铵盐型聚合物胶囊10重量份；10 parts by weight of quaternary ammonium salt polymer capsules;
有机锡聚合物微球5重量份；5 parts by weight of organotin polymer microspheres;
硫醇封端超支化大分子3重量份。3 parts by weight of thiol-terminated hyperbranched macromolecules.
各组分的制备方法如下:The preparation methods of each component are as follows:
(1)低表面能氟硅改性环氧树脂的制备:(1) Preparation of low surface energy fluorine-silicon modified epoxy resin:
在250ml四口烧瓶中,加入十二烷基苯磺酸钠1重量份、去离子水80重量份,搅拌溶解,得乳化剂溶液A；在另一烧瓶中,加入十六醇1重量份、过氧化苯甲酰0.2重量份、乙烯基含量0.015摩尔％的乙烯基硅树脂2重量份、甲基丙烯酸六氟丁酯2重量份、双酚A型环氧树脂E-448重量份,再加入苯乙烯15重量份和丙烯酸丁酯15重量份,搅拌溶解,得单体溶液B。将溶液A和B混合,搅拌(300r/min,30min),超声乳化(20KHz,200W,30min),即得微滴单体乳液。将乳液加热至70℃,通入N2并搅拌聚合(300r/min,5h)。冷却至室温,即得氟硅改性环氧树脂。In a 250ml four-necked flask, add 1 part by weight of sodium dodecylbenzene sulfonate and 80 parts by weight of deionized water, stir and dissolve to obtain emulsifier solution A; in another flask, add 1 part by weight of hexadecanol, 0.2 parts by weight of benzoyl peroxide, 2 parts by weight of vinyl silicone resin with a vinyl content of 0.015 mol%, 2 parts by weight of hexafluorobutyl methacrylate, 8 parts by weight of bisphenol A epoxy resin E-44, and then add 15 parts by weight of styrene and 15 parts by weight of butyl acrylate, stir and dissolve to obtain monomer solution B. Mix solutions A and B, stir (300r/min, 30min), and ultrasonically emulsify (20KHz, 200W, 30min) to obtain a micro-droplet monomer emulsion. Heat the emulsion to 70°C, introduceN2 and stir to polymerize (300r/min, 5h). Cool to room temperature to obtain a fluorosilicone modified epoxy resin.
氨基改性纳米二氧化钛的制备方法为:The preparation method of amino-modified nano titanium dioxide is:
(1)取10g纳米二氧化钛粉体,加入到装有100mL无水乙醇的烧杯中,超声分散30min,得到均匀的二氧化钛乙醇悬浮液；(1) Take 10 g of nano-titanium dioxide powder, add it into a beaker containing 100 mL of anhydrous ethanol, and disperse it by ultrasonic for 30 min to obtain a uniform titanium dioxide ethanol suspension;
(2)取2mLγ-氨丙基三乙氧基硅烷,缓慢滴加到装有300mL去离子水的三口烧瓶中,于50℃下搅拌反应2h,得到均一透明的硅烷水解液；(2) Take 2 mL of γ-aminopropyltriethoxysilane and slowly add it dropwise into a three-necked flask containing 300 mL of deionized water. Stir and react at 50° C. for 2 h to obtain a uniform and transparent silane hydrolyzate.
(3)将步骤(1)中的二氧化钛乙醇悬浮液缓慢滴加到步骤(2)的硅烷水解液中,升温至80℃,回流反应6h；(3) slowly adding the titanium dioxide ethanol suspension in step (1) to the silane hydrolyzate in step (2), heating to 80° C., and reflux for 6 h;
(4)反应结束后,将所得白色悬浮液离心分离,去离子水洗涤3次,无水乙醇洗涤1次,于60℃真空干燥4h,研磨过120目筛,即得氨基改性纳米二氧化钛粉体。(4) After the reaction is completed, the obtained white suspension is centrifuged, washed with deionized water three times, washed with anhydrous ethanol once, dried under vacuum at 60°C for 4 h, and ground through a 120-mesh sieve to obtain amino-modified nano-titanium dioxide powder.
氨基改性纳米二氧化硅的制备方法为:The preparation method of amino-modified nano-silica is:
(1)取5g纳米二氧化硅气凝胶,加入到装有60mL无水乙醇的烧杯中,搅拌分散均匀,超声20min,得到均一稳定的二氧化硅乙醇分散液；(1) Take 5 g of nano-silica aerogel and add it to a beaker containing 60 mL of anhydrous ethanol, stir and disperse it evenly, and ultrasonicate it for 20 min to obtain a uniform and stable silica ethanol dispersion;
(2)取3mLγ-氨丙基三乙氧基硅烷,溶解于450mL去离子水中,于室温下搅拌30min,得到硅烷水解液；(2) Take 3 mL of γ-aminopropyltriethoxysilane, dissolve it in 450 mL of deionized water, and stir it at room temperature for 30 minutes to obtain a silane hydrolyzate;
(3)在剧烈搅拌下,将步骤(1)中的二氧化硅乙醇分散液逐滴加入到步骤(2)的硅烷水解液中,滴加完毕后升温至90℃,继续反应10h；(3) under vigorous stirring, the silicon dioxide ethanol dispersion in step (1) is added dropwise to the silane hydrolyzate in step (2), and after the addition is complete, the temperature is raised to 90° C. and the reaction is continued for 10 hours;
(4)反应结束后,静置冷却至室温,抽滤,去离子水洗涤滤饼至中性,于70℃真空干燥6h,研磨过200目筛,即得氨基改性纳米二氧化硅粉体。(4) After the reaction is completed, the mixture is allowed to stand and cool to room temperature, filtered, and the filter cake is washed with deionized water until it is neutral. The filter cake is vacuum dried at 70° C. for 6 h, and ground through a 200-mesh sieve to obtain amino-modified nano-silica powder.
(2)季铵盐型聚合物胶囊的制备:(2) Preparation of quaternary ammonium salt polymer capsules:
在烧瓶中加入聚甲基丙烯酸甲酯3g、十六烷基三甲基溴化铵3g、水75mL,超声乳化(30KHz,300W,20min),同时滴加无水乙醇1g。将乳液置于65℃水浴中搅拌(400r/min,4h)。抽滤沉淀物,去离子水洗涤3次,真空干燥,得聚合物微胶囊15g,粒径10μm。Add 3g of polymethyl methacrylate, 3g of hexadecyltrimethylammonium bromide, and 75mL of water into a flask, and perform ultrasonic emulsification (30KHz, 300W, 20min), while dropping 1g of anhydrous ethanol. Place the emulsion in a 65℃ water bath and stir (400r/min, 4h). Filter the precipitate, wash it with deionized water 3 times, and vacuum dry it to obtain 15g of polymer microcapsules with a particle size of 10μm.
(3)有机锡聚合物微球的制备:(3) Preparation of organotin polymer microspheres:
在250mL三口烧瓶中,依次加入二丁基氯化锡1mmol、二苯基氯化锡1mmol、甲基丙烯酸6mmol、三羟甲基丙烷三甲基丙烯酸酯15mmol、偶氮二异丁腈0.3mmol、2,2'-偶氮二(2,4-二甲基戊腈)0.03mmol、二氯甲烷45mL和乙腈15mL。通N230min后,60℃下聚合24h。将块状聚合物研磨,过100目筛,用甲醇/乙酸(9:1)洗脱,真空干燥,得有机锡聚合物微球9g,粒径3μm。In a 250mL three-necked flask, add 1mmol of dibutyltin chloride, 1mmol of diphenyltin chloride, 6mmol of methacrylic acid, 15mmol of trimethylolpropane trimethacrylate, 0.3mmol of azobisisobutyronitrile, 0.03mmol of 2,2'-azobis(2,4-dimethylvaleronitrile), 45mL of dichloromethane and 15mL of acetonitrile in sequence. After passing N2 for 30min, polymerize at 60℃ for 24h. Grind the block polymer, pass through a 100-mesh sieve, elute with methanol/acetic acid (9:1), and vacuum dry to obtain 9g of organotin polymer microspheres with a particle size of 3μm.
(4)硫醇封端超支化大分子的制备:(4) Preparation of thiol-terminated hyperbranched macromolecules:
在100mL四口烧瓶中,加入三羟甲基丙烷三(3-巯基丙酸酯)0.3g、N,N-二甲基甲酰胺8mL、对甲苯磺酸0.03g,N2气氛下搅拌30min。加入2-(丙烯酰氧基)-甲基丙烯酸乙酯0.2g,50℃下反应24h。加入无水乙醚60mL,静置分层,取下层有机相,旋蒸除溶剂。将粗产物溶解于二氯甲烷10mL中,滴加到无水乙醚100mL中沉淀,抽滤。重复沉淀-溶解过程3次,真空干燥,得白色粉末1.2g,数均分子量25000。In a 100mL four-necked flask, add 0.3g of trimethylolpropane tris(3-mercaptopropionate), 8mL of N,N-dimethylformamide, and 0.03g of p-toluenesulfonic acid, and stir for 30min under N2 atmosphere. Add 0.2g of ethyl 2-(acryloyloxy)-methacrylate, and react at 50℃ for 24h. Add 60mL of anhydrous ether, let stand for stratification, take the lower organic phase, and evaporate the solvent. Dissolve the crude product in 10mL of dichloromethane, add dropwise to 100mL of anhydrous ether for precipitation, and filter. Repeat the precipitation-dissolution process 3 times, vacuum dry, and obtain 1.2g of white powder with a number average molecular weight of 25000.
涂层的制备方法:Coating preparation method:
将上述制得的氟硅改性环氧树脂40份、氨基改性纳米二氧化钛20份、氨基改性纳米二氧化硅5份、季铵盐型聚合物胶囊10份、有机锡聚合物微球5份和硫醇封端超支化大分子3份混合,加入二甲苯80份,球磨分散(300r/min,2h),即得涂料，然后加入固化剂25，所述固化剂为二乙烯三胺。将涂料喷涂于船体表面,厚度80μm,于35℃固化30h。40 parts of the above-prepared fluorine-silicon modified epoxy resin, 20 parts of amino-modified nano titanium dioxide, 5 parts of amino-modified nano silicon dioxide, 10 parts of quaternary ammonium salt polymer capsules, 5 parts of organotin polymer microspheres and 3 parts of thiol-terminated hyperbranched macromolecules were mixed, 80 parts of xylene were added, and ball milling was performed (300r/min, 2h) to obtain the coating, and then a curing agent 25 was added, wherein the curing agent was diethylenetriamine. The coating was sprayed on the hull surface with a thickness of 80μm and cured at 35°C for 30h.
实施例2Example 2
一种海洋船舶防污涂层,其组成为:An antifouling coating for marine vessels, comprising:
低表面能氟硅改性环氧树脂60重量份；60 parts by weight of low surface energy fluorine-silicon modified epoxy resin;
氨基改性纳米二氧化钛10重量份；10 parts by weight of amino-modified nano titanium dioxide;
氨基改性纳米二氧化硅10重量份；10 parts by weight of amino-modified nano-silicon dioxide;
季铵盐型聚合物胶囊5重量份；5 parts by weight of quaternary ammonium salt polymer capsules;
有机锡聚合物微球10重量份；10 parts by weight of organotin polymer microspheres;
硫醇封端超支化大分子1重量份。1 part by weight of thiol-terminated hyperbranched macromolecules.
各组分的制备方法如下:The preparation methods of each component are as follows:
(1)低表面能氟硅改性环氧树脂的制备:(1) Preparation of low surface energy fluorine-silicon modified epoxy resin:
在500ml四口烧瓶中,加入十二烷基苯磺酸钠5重量份、去离子水100重量份,搅拌溶解,得乳化剂溶液A；在另一烧瓶中,加入十六醇3重量份、过氧化苯甲酰0.8重量份、乙烯基含量0.06摩尔％的乙烯基硅树脂5重量份、甲基丙烯酸六氟丁酯5重量份、双酚A型环氧树脂E-4410重量份,再加入苯乙烯10重量份和丙烯酸丁酯30重量份,搅拌溶解,得单体溶液B。将溶液A和B混合,搅拌(400r/min,40min),超声乳化(40KHz,300W,40min),即得微滴单体乳液。将乳液加热至80℃,通入Ar并搅拌聚合(400r/min,8h)。冷却至室温,即得氟硅改性环氧树脂。In a 500ml four-necked flask, add 5 parts by weight of sodium dodecylbenzene sulfonate and 100 parts by weight of deionized water, stir and dissolve to obtain emulsifier solution A; in another flask, add 3 parts by weight of hexadecanol, 0.8 parts by weight of benzoyl peroxide, 5 parts by weight of vinyl silicone resin with a vinyl content of 0.06 mol%, 5 parts by weight of hexafluorobutyl methacrylate, 10 parts by weight of bisphenol A epoxy resin E-44, and then add 10 parts by weight of styrene and 30 parts by weight of butyl acrylate, stir and dissolve to obtain monomer solution B. Mix solutions A and B, stir (400r/min, 40min), and ultrasonically emulsify (40KHz, 300W, 40min) to obtain a droplet monomer emulsion. Heat the emulsion to 80°C, pass Ar and stir to polymerize (400r/min, 8h). Cool to room temperature to obtain a fluorine-silicon modified epoxy resin.
(2)季铵盐型聚合物胶囊的制备:(2) Preparation of quaternary ammonium salt polymer capsules:
在烧瓶中加入聚甲基丙烯酸甲酯1g、十六烷基三甲基溴化铵1g、水50mL,超声乳化(50KHz,500W,10min),同时滴加无水乙醇0.5g。将乳液置于80℃水浴中搅拌(600r/min,2h)。抽滤沉淀物,去离子水洗涤2次,真空干燥,得聚合物微胶囊6g,粒径5μm。Add 1g of polymethyl methacrylate, 1g of hexadecyltrimethylammonium bromide, and 50mL of water into a flask, perform ultrasonic emulsification (50KHz, 500W, 10min), and simultaneously drop 0.5g of anhydrous ethanol. Place the emulsion in an 80℃ water bath and stir (600r/min, 2h). Filter the precipitate, wash it twice with deionized water, and vacuum dry it to obtain 6g of polymer microcapsules with a particle size of 5μm.
(3)有机锡聚合物微球的制备:(3) Preparation of organotin polymer microspheres:
在500mL三口烧瓶中,依次加入二丁基氯化锡2mmol、二苯基氯化锡2mmol、甲基丙烯酸8mmol、三羟甲基丙烷三甲基丙烯酸酯20mmol、偶氮二异丁腈0.5mmol、2,2'-偶氮二(2,4-二甲基戊腈)0.05mmol、二氯甲烷75mL和乙腈25mL。通N240min后,70℃下聚合30h。将块状聚合物研磨,过200目筛,用甲醇/乙酸(9:1)洗脱,真空干燥,得有机锡聚合物微球16g,粒径5μm。In a 500mL three-necked flask, add 2mmol of dibutyltin chloride, 2mmol of diphenyltin chloride, 8mmol of methacrylic acid, 20mmol of trimethylolpropane trimethacrylate, 0.5mmol of azobisisobutyronitrile, 0.05mmol of 2,2'-azobis(2,4-dimethylvaleronitrile), 75mL of dichloromethane and 25mL of acetonitrile in sequence. After passing N2 for 40min, polymerize at 70℃ for 30h. Grind the block polymer, pass through a 200-mesh sieve, elute with methanol/acetic acid (9:1), and vacuum dry to obtain 16g of organotin polymer microspheres with a particle size of 5μm.
(4)硫醇封端超支化大分子的制备:(4) Preparation of thiol-terminated hyperbranched macromolecules:
在250mL四口烧瓶中,加入三羟甲基丙烷三(3-巯基丙酸酯)0.1g、N,N-二甲基甲酰胺5mL、对甲苯磺酸0.01g,N2气氛下搅拌20min。加入2-(丙烯酰氧基)-甲基丙烯酸乙酯0.05g,40℃下反应20h。加入无水乙醚30mL,静置分层,取下层有机相,旋蒸除溶剂。将粗产物溶解于二氯甲烷5mL中,滴加到无水乙醚50mL中沉淀,抽滤。重复沉淀-溶解过程2次,真空干燥,得白色粉末0.4g,数均分子量5000。In a 250mL four-necked flask, add 0.1g of trimethylolpropane tris(3-mercaptopropionate), 5mL of N,N-dimethylformamide, and 0.01g of p-toluenesulfonic acid, and stir for 20min under N2 atmosphere. Add 0.05g of 2-(acryloyloxy)-ethyl methacrylate and react at 40℃ for 20h. Add 30mL of anhydrous ether, let stand for stratification, take the lower organic phase, and evaporate the solvent. Dissolve the crude product in 5mL of dichloromethane, add dropwise to 50mL of anhydrous ether for precipitation, and filter. Repeat the precipitation-dissolution process twice, vacuum dry, and obtain 0.4g of white powder with a number average molecular weight of 5000.
涂层的制备方法:Preparation method of coating:
将上述制得的氟硅改性环氧树脂60份、氨基改性纳米二氧化钛10份、氨基改性纳米二氧化硅10份、季铵盐型聚合物胶囊5份、有机锡聚合物微球10份和硫醇封端超支化大分子1份混合,加入二甲苯60份,球磨分散(500r/min,6h),即得涂料，然后加入固化剂40份，所述固化剂为间二甲苯二胺。将涂料刷涂于船体表面,厚度50μm,于15℃固化48h。Mix 60 parts of the above-prepared fluorine-silicon modified epoxy resin, 10 parts of amino-modified nano titanium dioxide, 10 parts of amino-modified nano silicon dioxide, 5 parts of quaternary ammonium salt polymer capsules, 10 parts of organic tin polymer microspheres and 1 part of thiol-terminated hyperbranched macromolecules, add 60 parts of xylene, and disperse by ball milling (500r/min, 6h) to obtain the coating, and then add 40 parts of curing agent, which is m-xylene diamine. Apply the coating to the surface of the hull with a thickness of 50μm and cure at 15°C for 48h.
实施例3Example 3
一种海洋船舶防污涂层,其组成为:An antifouling coating for marine vessels, comprising:
低表面能氟硅改性环氧树脂50重量份；50 parts by weight of low surface energy fluorine-silicon modified epoxy resin;
氨基改性纳米二氧化钛30重量份；30 parts by weight of amino-modified nano titanium dioxide;
氨基改性纳米二氧化硅8重量份；8 parts by weight of amino-modified nano-silicon dioxide;
季铵盐型聚合物胶囊15重量份；15 parts by weight of quaternary ammonium salt polymer capsules;
有机锡聚合物微球8重量份；8 parts by weight of organotin polymer microspheres;
硫醇封端超支化大分子5重量份。5 parts by weight of thiol-terminated hyperbranched macromolecules.
各组分的制备方法如下:The preparation methods of each component are as follows:
(1)低表面能氟硅改性环氧树脂的制备:(1) Preparation of low surface energy fluorine-silicon modified epoxy resin:
在1000ml四口烧瓶中,加入十二烷基苯磺酸钠3重量份、去离子水60重量份,搅拌溶解,得乳化剂溶液A；在另一烧瓶中,加入十六醇2重量份、过氧化苯甲酰0.5重量份、乙烯基含量0.04摩尔％的乙烯基硅树脂3重量份、甲基丙烯酸六氟丁酯4重量份、双酚A型环氧树脂E-446重量份,再加入苯乙烯25重量份和丙烯酸丁酯25重量份,搅拌溶解,得单体溶液B。将溶液A和B混合,搅拌(200r/min,20min),超声乳化(15KHz,100W,20min),即得微滴单体乳液。将乳液加热至60℃,通入N2并搅拌聚合(200r/min,3h)。冷却至室温,即得氟硅改性环氧树脂。In a 1000ml four-necked flask, add 3 parts by weight of sodium dodecylbenzene sulfonate and 60 parts by weight of deionized water, stir and dissolve to obtain emulsifier solution A; in another flask, add 2 parts by weight of hexadecanol, 0.5 parts by weight of benzoyl peroxide, 3 parts by weight of vinyl silicone resin with a vinyl content of 0.04 mol%, 4 parts by weight of hexafluorobutyl methacrylate, 6 parts by weight of bisphenol A epoxy resin E-44, and then add 25 parts by weight of styrene and 25 parts by weight of butyl acrylate, stir and dissolve to obtain monomer solution B. Mix solutions A and B, stir (200r/min, 20min), and ultrasonically emulsify (15KHz, 100W, 20min) to obtain a droplet monomer emulsion. Heat the emulsion to 60°C, introduceN2 and stir to polymerize (200r/min, 3h). Cool to room temperature to obtain a fluorosilicone modified epoxy resin.
(2)季铵盐型聚合物胶囊的制备:(2) Preparation of quaternary ammonium salt polymer capsules:
在烧瓶中加入聚甲基丙烯酸甲酯5g、十六烷基三甲基溴化铵5g、水100mL,超声乳化(20KHz,200W,30min),同时滴加无水乙醇2g。将乳液置于50℃水浴中搅拌(300r/min,6h)。抽滤沉淀物,去离子水洗涤3次,真空干燥,得聚合物微胶囊20g,粒径20μm。Add 5g of polymethyl methacrylate, 5g of hexadecyltrimethylammonium bromide, and 100mL of water into a flask, and perform ultrasonic emulsification (20KHz, 200W, 30min), while adding 2g of anhydrous ethanol. Place the emulsion in a 50℃ water bath and stir (300r/min, 6h). Filter the precipitate, wash it with deionized water 3 times, and vacuum dry it to obtain 20g of polymer microcapsules with a particle size of 20μm.
(3)有机锡聚合物微球的制备:(3) Preparation of organotin polymer microspheres:
在100mL三口烧瓶中,依次加入二丁基氯化锡0.5mmol、二苯基氯化锡0.5mmol、甲基丙烯酸5mmol、三羟甲基丙烷三甲基丙烯酸酯10mmol、偶氮二异丁腈0.1mmol、2,2'-偶氮二(2,4-二甲基戊腈)0.01mmol、二氯甲烷30mL和乙腈10mL。通N220min后,50℃下聚合20h。将块状聚合物研磨,过80目筛,用甲醇/乙酸(9:1)洗脱,真空干燥,得有机锡聚合物微球5g,粒径1μm。In a 100mL three-necked flask, add 0.5mmol of dibutyltin chloride, 0.5mmol of diphenyltin chloride, 5mmol of methacrylic acid, 10mmol of trimethylolpropane trimethacrylate, 0.1mmol of azobisisobutyronitrile, 0.01mmol of 2,2'-azobis(2,4-dimethylvaleronitrile), 30mL of dichloromethane and 10mL of acetonitrile in sequence. After passing N2 for 20min, polymerize at 50℃ for 20h. Grind the block polymer, pass through an 80-mesh sieve, elute with methanol/acetic acid (9:1), and vacuum dry to obtain 5g of organotin polymer microspheres with a particle size of 1μm.
(4)硫醇封端超支化大分子的制备:(4) Preparation of thiol-terminated hyperbranched macromolecules:
在100mL四口烧瓶中,加入三羟甲基丙烷三(3-巯基丙酸酯)0.5g、N,N-二甲基甲酰胺10mL、对甲苯磺酸0.05g,N2气氛下搅拌40min。加入2-(丙烯酰氧基)-甲基丙烯酸乙酯0.3g,60℃下反应30h。加入无水乙醚100mL,静置分层,取下层有机相,旋蒸除溶剂。将粗产物溶解于二氯甲烷20mL中,滴加到无水乙醚200mL中沉淀,抽滤。重复沉淀-溶解过程4次,真空干燥,得白色粉末2.4g,数均分子量50000。In a 100mL four-necked flask, add 0.5g of trimethylolpropane tris(3-mercaptopropionate), 10mL of N,N-dimethylformamide, and 0.05g of p-toluenesulfonic acid, and stir for 40min under N2 atmosphere. Add 0.3g of 2-(acryloyloxy)-ethyl methacrylate and react at 60℃ for 30h. Add 100mL of anhydrous ether, let stand for stratification, take the lower organic phase, and evaporate the solvent. Dissolve the crude product in 20mL of dichloromethane, add dropwise to 200mL of anhydrous ether for precipitation, and filter. Repeat the precipitation-dissolution process 4 times, vacuum dry, and obtain 2.4g of white powder with a number average molecular weight of 50,000.
涂层的制备方法:Preparation method of coating:
将上述制得的氟硅改性环氧树脂50份、氨基改性纳米二氧化钛30份、氨基改性纳米二氧化硅8份、季铵盐型聚合物胶囊15份、有机锡聚合物微球8份和硫醇封端超支化大分子5份混合,加入二甲苯100份,球磨分散(500r/min,4h),即得涂料，然后加入固化剂30份，所述固化剂为KH550。将涂料喷涂于船体表面,厚度200μm,于25℃固化24h。Mix 50 parts of the above-prepared fluorine-silicon modified epoxy resin, 30 parts of amino-modified nano titanium dioxide, 8 parts of amino-modified nano silicon dioxide, 15 parts of quaternary ammonium salt polymer capsules, 8 parts of organotin polymer microspheres and 5 parts of thiol-terminated hyperbranched macromolecules, add 100 parts of xylene, and ball mill dispersion (500r/min, 4h) to obtain the coating, and then add 30 parts of curing agent, the curing agent is KH550. Spray the coating on the hull surface with a thickness of 200μm and cure at 25°C for 24h.
对比例1Comparative Example 1
一种海洋船舶防污涂层,其组成为:An antifouling coating for marine vessels, comprising:
环氧树脂40重量份；40 parts by weight of epoxy resin;
氨基改性纳米二氧化钛20重量份；20 parts by weight of amino-modified nano titanium dioxide;
氨基改性纳米二氧化硅5重量份；5 parts by weight of amino-modified nano-silicon dioxide;
季铵盐型聚合物胶囊10重量份；10 parts by weight of quaternary ammonium salt polymer capsules;
有机锡聚合物微球5重量份；5 parts by weight of organotin polymer microspheres;
硫醇封端超支化大分子3重量份。3 parts by weight of thiol-terminated hyperbranched macromolecules.
其中,环氧树脂选用市售的液体双酚A型环氧树脂E-51,其余组分的制备方法与实施例1相同。The epoxy resin is commercially available liquid bisphenol A epoxy resin E-51, and the preparation methods of the remaining components are the same as those in Example 1.
涂层的制备方法:Preparation method of coating:
将上述组分按给定配比混合,加入二甲苯80份,球磨分散(300r/min,2h),即得涂料，然后加入固化剂25，所述固化剂为二乙烯三胺。将涂料喷涂于船体表面,厚度80μm,于35℃固化30h。The above components were mixed in a given ratio, 80 parts of xylene were added, and the coating was dispersed by ball milling (300r/min, 2h), and then a curing agent 25 was added, wherein the curing agent was diethylenetriamine. The coating was sprayed on the surface of the hull with a thickness of 80μm and cured at 35°C for 30h.
对比例2Comparative Example 2
一种海洋船舶防污涂层,其组成为:An antifouling coating for marine vessels, comprising:
低表面能氟硅改性环氧树脂60重量份；60 parts by weight of low surface energy fluorine-silicon modified epoxy resin;
氨基改性纳米二氧化钛10重量份；10 parts by weight of amino-modified nano titanium dioxide;
氨基改性纳米二氧化硅10重量份；10 parts by weight of amino-modified nano-silicon dioxide;
十六烷基三甲基溴化铵5重量份(替代实施例2中的季铵盐型聚合物胶囊)；5 parts by weight of cetyltrimethylammonium bromide (replacing the quaternary ammonium salt polymer capsules in Example 2);
有机锡聚合物微球10重量份；10 parts by weight of organotin polymer microspheres;
硫醇封端超支化大分子1重量份。1 part by weight of thiol-terminated hyperbranched macromolecules.
其中,十六烷基三甲基溴化铵为市售试剂,未经包覆,其余组分的制备方法与实施例2相同。Among them, hexadecyltrimethylammonium bromide is a commercially available reagent and is not coated. The preparation methods of the remaining components are the same as those in Example 2.
涂层的制备方法:Preparation method of coating:
将上述组分按给定配比混合,加入二甲苯60份,球磨分散(500r/min,6h),即得涂料。将涂料刷涂于船体表面,厚度50μm,于15℃固化48h。The above components were mixed in a given ratio, 60 parts of xylene were added, and the coating was dispersed by ball milling (500r/min, 6h). The coating was applied to the hull surface with a thickness of 50μm and cured at 15℃ for 48h.
对比例3Comparative Example 3
一种海洋船舶防污涂层,其组成为:An antifouling coating for marine vessels, comprising:
低表面能氟硅改性环氧树脂50重量份；50 parts by weight of low surface energy fluorine-silicon modified epoxy resin;
氨基改性纳米二氧化钛30重量份；30 parts by weight of amino-modified nano titanium dioxide;
氨基改性纳米二氧化硅8重量份；8 parts by weight of amino-modified nano-silicon dioxide;
季铵盐型聚合物胶囊15重量份；15 parts by weight of quaternary ammonium salt polymer capsules;
三丁基锡8重量份(替代实施例3中的有机锡聚合物微球)；8 parts by weight of tributyltin (replacing the organotin polymer microspheres in Example 3);
硫醇封端超支化大分子5重量份。5 parts by weight of thiol-terminated hyperbranched macromolecules.
其中,三丁基锡为常规有机锡化合物,其余组分的制备方法与实施例3相同。Among them, tributyltin is a conventional organic tin compound, and the preparation methods of the remaining components are the same as in Example 3.
涂层的制备方法:Preparation method of coating:
将上述组分按给定配比混合,加入二甲苯100份,球磨分散(500r/min,4h),即得涂料，然后加入固化剂30份，所述固化剂为KH550。将涂料喷涂于船体表面,厚度200μm,于25℃固化24h。The above components were mixed in a given ratio, 100 parts of xylene were added, and the coating was obtained by ball milling (500r/min, 4h), and then 30 parts of curing agent were added, and the curing agent was KH550. The coating was sprayed on the hull surface with a thickness of 200μm and cured at 25℃ for 24h.
对比例4Comparative Example 4
一种海洋船舶防污涂层,其组成为:An antifouling coating for marine vessels, comprising:
低表面能氟硅改性环氧树脂40重量份；40 parts by weight of low surface energy fluorine-silicon modified epoxy resin;
氨基改性纳米二氧化钛20重量份；20 parts by weight of amino-modified nano titanium dioxide;
氨基改性纳米二氧化硅5重量份；5 parts by weight of amino-modified nano-silicon dioxide;
季铵盐型聚合物胶囊10重量份；10 parts by weight of quaternary ammonium salt polymer capsules;
有机锡聚合物微球5重量份。5 parts by weight of organotin polymer microspheres.
其余组分的制备方法与实施例1相同。The preparation methods of the remaining components are the same as in Example 1.
涂层的制备方法:Preparation method of coating:
将上述组分按给定配比混合,加入二甲苯80份,球磨分散(300r/min,2h),即得涂料。将涂料喷涂于船体表面,厚度80μm,于35℃固化30h。The above components were mixed in a given ratio, 80 parts of xylene were added, and the coating was dispersed by ball milling (300r/min, 2h). The coating was sprayed on the hull surface with a thickness of 80μm and cured at 35℃ for 30h.
在以上4个对比例中,对比例1通过普通环氧树脂替代低表面能氟硅改性环氧树脂,旨在突出氟硅改性对提高涂层表面疏水性和抗污性能的关键作用；对比例2用游离态的十六烷基三甲基溴化铵替代季铵盐聚合物胶囊,意在说明胶囊包覆结构对提高季铵盐抗菌剂缓释性能和长效性的重要意义；对比例3用普通三丁基锡化合物替代有机锡聚合物微球,目的是验证分子微球结构对提升有机基锡防污剂缓释性能和减少生态毒性的显著效果；对比例4则通过移除硫醇封端超支化大分子,来证明该组分在赋予涂层自修复功能、改善长期防污性能方面的不可或缺性。In the above four comparative examples, comparative example 1 replaces the low surface energy fluorine-silicon modified epoxy resin with ordinary epoxy resin, aiming to highlight the key role of fluorine-silicon modification in improving the surface hydrophobicity and anti-fouling performance of the coating; comparative example 2 replaces the quaternary ammonium salt polymer capsule with free hexadecyltrimethylammonium bromide, intending to illustrate the importance of the capsule coating structure in improving the sustained release performance and long-term effectiveness of quaternary ammonium salt antibacterial agents; comparative example 3 replaces the organotin polymer microspheres with ordinary tributyltin compounds, aiming to verify the significant effect of the molecular microsphere structure on improving the sustained release performance of organotin antifouling agents and reducing ecological toxicity; comparative example 4 removes the thiol-terminated hyperbranched macromolecules to prove the indispensability of this component in giving the coating self-repairing function and improving long-term antifouling performance.
根据作用机制协同分析,本发明涂层体系的关键创新点在于:According to the synergistic analysis of the mechanism of action, the key innovation of the coating system of the present invention is:
1.通过引入低表面能氟硅改性环氧树脂和纳米TiO2/SiO2复合填料,构建了具有优异疏水自清洁性能和机械强度的涂层基体；1. By introducing low surface energy fluorine-silicon modified epoxy resin and nano-TiO2 /SiO2 composite filler, a coating matrix with excellent hydrophobic self-cleaning properties and mechanical strength was constructed;
2.采用季铵盐聚合物胶囊和有机锡聚合物微球分别装载抑菌剂和杀藻剂,实现了对微生物和藻类的可控缓释抑制,大幅提升了涂层的长效防污性能；2. Quaternary ammonium salt polymer capsules and organotin polymer microspheres are used to load antibacterial agents and algaecides respectively, achieving controlled and slow-release inhibition of microorganisms and algae, greatly improving the long-term antifouling performance of the coating;
3.引入硫醇封端超支化分子作为自修复基元,通过其特殊的支化结构和动态键合作用,赋予了涂层多层次自修复能力,有效修复表面微观缺陷,延长使用寿命。3. The introduction of thiol-terminated hyperbranched molecules as self-repairing elements, through their special branched structure and dynamic bonding, endows the coating with multi-level self-repairing capabilities, effectively repairs surface microscopic defects and extends its service life.
针对以上创新点,建立以下材料性能评估模型和测试方法:In view of the above innovations, the following material performance evaluation model and test method are established:
1.涂层表面疏水性和自清洁性能评估1. Evaluation of coating surface hydrophobicity and self-cleaning performance
实验条件:采用接触角测量仪和人工污染液,在25℃、60％RH环境中进行测试。Experimental conditions: The test was conducted in an environment of 25°C and 60% RH using a contact angle meter and artificial contamination liquid.
实验步骤:Experimental steps:
(1)将涂层样品固定于样品台,用量程注射器滴加5μL去离子水于表面,水滴静置30s后测量其接触角；重复5次,取平均值；(1) Fix the coating sample on the sample stage, add 5 μL of deionized water to the surface with a range syringe, and measure its contact angle after the water drop is left to stand for 30 seconds; repeat 5 times and take the average value;
(2)取20μL人工污染液(由油性染料、有机硅油等组成)滴于涂层表面,静置2h后,用去离子水冲洗1min,目测污渍去除情况,并用色差仪测量污渍残留量。(2) Take 20 μL of artificial contamination liquid (composed of oily dyes, silicone oil, etc.) and drop it on the coating surface. After standing for 2 hours, rinse with deionized water for 1 minute. Visually inspect the stain removal and measure the amount of stain residue using a colorimeter.
表1Table 1
2.涂层长效防污性能评估2. Evaluation of long-term antifouling performance of coatings
实验条件:采用旋转式动态海洋污损模拟试验装置,在25℃、pH 8.2的人工海水中进行60天浸泡试验。Experimental conditions: A rotating dynamic marine fouling simulation test device was used to conduct a 60-day immersion test in artificial seawater at 25°C and pH 8.2.
实验步骤:Experimental steps:
(1)将涂层样品固定于转轴上,浸没于装有藻菌混合培养液的人工海水中,转速600rpm,每天光照12h；(1) The coating sample was fixed on a rotating shaft and immersed in artificial seawater containing a mixed culture of algae and fungi at a speed of 600 rpm and under light for 12 h per day;
(2)分别于第10天、30天、45天和60天取出样品,用清水冲洗,自然晾干,称重并拍照记录；(2) Take out the samples on the 10th, 30th, 45th and 60th days, rinse them with clean water, dry them naturally, weigh them and take photos for record;
(3)采用扫描电镜(SEM)观察样品表面微生物和藻类的附着情况,并用ATP荧光法定量检测样品表面的生物量。(3) Scanning electron microscopy (SEM) was used to observe the attachment of microorganisms and algae on the sample surface, and the ATP fluorescence method was used to quantitatively detect the biomass on the sample surface.
表2Table 2
3.涂层力学性能和自修复性能评估3. Evaluation of coating mechanical properties and self-healing properties
实验条件:采用划痕实验和冲蚀实验,在室温下进行。Experimental conditions: Scratch test and erosion test were carried out at room temperature.
实验步骤:Experimental steps:
(1)划痕实验:用锋利的刀片在涂层表面垂直划出10条宽度约50μm、长度1cm的划痕,然后放入60℃烘箱中保持12h；分别于划痕前、划痕后以及自修复后采用光学显微镜观察划痕形貌变化,并测量划痕宽度；(1) Scratch test: Use a sharp blade to vertically scratch 10 scratches with a width of about 50 μm and a length of 1 cm on the coating surface, and then place it in a 60°C oven for 12 h; use an optical microscope to observe the scratch morphology changes before scratching, after scratching, and after self-repairing, and measure the scratch width;
(2)冲蚀实验:将涂层样品固定于旋转装置上,在转速1000rpm下进行砂砾冲蚀2h,记录涂层的失重率；然后静置72h,再称重计算自修复前后的质量变化。(2) Erosion experiment: The coating sample was fixed on a rotating device and subjected to gravel erosion at a rotation speed of 1000 rpm for 2 h, and the weight loss rate of the coating was recorded; then it was allowed to stand for 72 h and weighed again to calculate the mass change before and after self-repair.
表3Table 3
结果分析与讨论:Results and discussion:
(1)根据表1的数据，从涂层表面疏水性和自清洁性能数据可以看出,实施例1-3的涂层表面水接触角均在155°以上,远高于对比例,表明氟硅改性环氧树脂显著提高了涂层表面的疏水性。同时,实施例1-3的人工污渍残留量也远低于对比例,证明了氟硅改性和纳米复合填料协同构建的微纳米结构涂层具有优异的自清洁性能。(1) According to the data in Table 1, it can be seen from the data of the hydrophobicity and self-cleaning performance of the coating surface that the water contact angles of the coating surfaces of Examples 1-3 are all above 155°, which are much higher than those of the comparative example, indicating that the fluorine-silicon modified epoxy resin significantly improves the hydrophobicity of the coating surface. At the same time, the amount of artificial stains remaining in Examples 1-3 is also much lower than that of the comparative example, proving that the micro-nanostructured coating synergistically constructed by fluorine-silicon modification and nanocomposite fillers has excellent self-cleaning performance.
(2)根据表2的数据，从涂层长效防污性能评价结果来看,实施例1-3在整个60天试验周期内的生物附着量始终保持在较低水平,而对比例则呈现出大幅增长的趋势。这表明季铵盐聚合物胶囊和有机锡微球能够通过可控缓释机制,在涂层表面形成持久稳定的抑菌抗藻屏障。相比之下,对比例2和3中游离态的季铵盐和有机锡分子的快速溶出流失,导致其防污效能迅速衰减。(2) According to the data in Table 2, from the evaluation results of the long-term antifouling performance of the coating, the amount of biological attachment in Examples 1-3 remained at a low level throughout the 60-day test period, while the comparative example showed a trend of substantial growth. This shows that the quaternary ammonium salt polymer capsules and organotin microspheres can form a long-lasting and stable antibacterial and anti-algae barrier on the coating surface through a controlled sustained release mechanism. In contrast, the rapid dissolution and loss of free quaternary ammonium salts and organotin molecules in Comparative Examples 2 and 3 caused their antifouling performance to decay rapidly.
(3)根据表3的数据，在涂层力学性能和自修复性能方面,实施例1-3经划痕试验后其划痕宽度平均缩小70％以上,而对比例仅为20-50％,说明硫醇封端超支化分子构建的动态键合网络和支化结构空间效应,赋予了涂层显著的自修复能力。同时,实施例1-3在冲蚀试验中的失重率以及自修复后的剩余失重率也明显低于对比例,再次证实了自修复基元和微纳米复合结构在提升涂层机械强度、韧性和自修复性能方面的协同增效作用。其中,实施例3综合性能最佳,有望成为本发明的优选方案。(3) According to the data in Table 3, in terms of mechanical properties and self-healing properties of the coating, the scratch width of Examples 1-3 after the scratch test was reduced by an average of more than 70%, while the comparative example was only 20-50%, indicating that the dynamic bonding network and branched structure spatial effect constructed by the thiol-terminated hyperbranched molecules endowed the coating with significant self-healing ability. At the same time, the weight loss rate of Examples 1-3 in the erosion test and the remaining weight loss rate after self-healing were also significantly lower than those of the comparative example, which once again confirmed the synergistic effect of the self-healing element and the micro-nano composite structure in improving the mechanical strength, toughness and self-healing properties of the coating. Among them, Example 3 has the best comprehensive performance and is expected to become the preferred solution of the present invention.
综合以上实验数据和机理分析,可以得出如下结论:Based on the above experimental data and mechanism analysis, the following conclusions can be drawn:
1.本发明涂层体系巧妙地将表面化学(低表面能氟硅改性)、界面化学(季铵盐胶囊和有机锡聚合物微球)以及超分子化学(超支化动态键合网络)多个不同层次的多靶点协同机制集于一身,多管齐下,构建了一种全方位提升船舶防污性能的创新方案。1. The coating system of the present invention cleverly integrates multiple target synergistic mechanisms at different levels of surface chemistry (low surface energy fluorine-silicon modification), interface chemistry (quaternary ammonium salt capsules and organic tin polymer microspheres) and supramolecular chemistry (hyperbranched dynamic bonding network), and constructs an innovative solution to comprehensively improve the antifouling performance of ships through a multi-pronged approach.
2.与传统的单一防污机制不同,本发明的协同机制不仅从源头上阻止了污染物在涂层表面的粘附富集(超疏水自清洁),还通过化学手段可控缓释抑制微生物繁殖(季铵盐胶囊和有机锡聚合物微球),以及从微观损伤处快速自我修复(超支化动态化学键合),真正实现了涂层全生命周期的长效防护。2. Different from the traditional single anti-fouling mechanism, the synergistic mechanism of the present invention not only prevents the adhesion and accumulation of pollutants on the coating surface from the source (superhydrophobic self-cleaning), but also inhibits the reproduction of microorganisms through controlled slow release by chemical means (quaternary ammonium salt capsules and organic tin polymer microspheres), as well as rapid self-repair from microscopic damage (hyperbranched dynamic chemical bonding), truly realizing long-term protection throughout the entire life cycle of the coating.
3.更为重要的是,本发明的多靶点协同机制并非简单的"1+1＞2"的叠加效应,而是通过精心设计的化学组分和结构,在分子、微观和宏观多个层次实现了不同功能单元的相互促进、相得益彰。例如疏水涂层表面有利于缓释胶囊和有机锡聚合物微球的均匀分散,并减缓水解降解；而纳米复合填料不仅增强了基体强度,也为自修复基元提供了更多的针定位点,促进了其动态键合网络的构筑。3. More importantly, the multi-target synergistic mechanism of the present invention is not a simple superposition effect of "1+1>2", but through the carefully designed chemical components and structures, different functional units are mutually promoted and complement each other at the molecular, microscopic and macroscopic levels. For example, the hydrophobic coating surface is conducive to the uniform dispersion of sustained-release capsules and organotin polymer microspheres, and slows down hydrolysis degradation; while the nanocomposite filler not only enhances the strength of the matrix, but also provides more pin positioning points for the self-repairing element, promoting the construction of its dynamic bonding network.
4.此外,本发明的协同机制还体现在防污基元与其他组分的相容性方面。引入的季铵盐阳离子表面活性剂不仅是高效抑菌剂,也能作为乳化剂促进其他组分的分散；而超支化大分子在提供自修复功能的同时,也可作为增容剂提高基体的柔韧性和耐冲击性。这些"一石二鸟"的协同效应不仅简化了涂层配方,也有助于降低生产成本。4. In addition, the synergistic mechanism of the present invention is also reflected in the compatibility of the antifouling element with other components. The introduced quaternary ammonium salt cationic surfactant is not only a highly effective antibacterial agent, but also can be used as an emulsifier to promote the dispersion of other components; while the hyperbranched macromolecules provide self-repairing function, they can also be used as a compatibilizer to improve the flexibility and impact resistance of the matrix. These "killing two birds with one stone" synergistic effects not only simplify the coating formula, but also help reduce production costs.
5.最后还需指出,本发明充分体现了仿生学思想和绿色环保理念。疏水自清洁表面借鉴了荷叶等天然植物的微纳米结构,有机锡聚合物微球的包埋固载减少了锡的环境释放量,季铵盐和超支化基元也均为低毒易降解的有机物。因此,本发明是一种高效、长效、环境友好的海洋防污涂层新材料。5. Finally, it should be pointed out that the present invention fully embodies the bionics and green environmental protection concepts. The hydrophobic self-cleaning surface draws on the micro-nano structure of natural plants such as lotus leaves. The embedding and immobilization of organic tin polymer microspheres reduces the environmental release of tin. The quaternary ammonium salt and hyperbranched motif are also low-toxic and easily degradable organic substances. Therefore, the present invention is a new marine antifouling coating material with high efficiency, long-lasting effect and environmental friendliness.
综上所述,本发明的多靶点协同防污涂层体系,在机理创新、功能集成和环境友好等方面实现了重大突破,展现了涂层化学、材料学与生物学交叉融合的巨大潜力,不仅可望从根本上解决海洋船舶等设施的污损问题,也为仿生智能材料的开发提供了新的思路,具有广阔的应用前景。In summary, the multi-target synergistic antifouling coating system of the present invention has achieved major breakthroughs in mechanism innovation, functional integration and environmental friendliness, and has demonstrated the great potential for the cross-integration of coating chemistry, materials science and biology. It is not only expected to fundamentally solve the fouling problem of marine vessels and other facilities, but also provides new ideas for the development of bionic intelligent materials and has broad application prospects.
以上所述仅为本发明的实施例而已，并不用于限制本发明。对于本领域技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原理之内所作的任何修改、等同替换、改进等，均应包含在本发明的权利要求范围之内。The above description is only an embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
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| CN202410657134.4ACN118460058B (en) | 2024-05-25 | 2024-05-25 | Marine ship antifouling coating and preparation method thereof |
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| CN120587093A (en)* | 2025-08-08 | 2025-09-05 | 咸阳圣亚机电设备有限公司 | High-cleanliness rust-proof surface treatment process for double-H control shell |
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| CN106397655A (en)* | 2016-09-08 | 2017-02-15 | 中国农业科学院农业质量标准与检测技术研究所 | Organotin molecularly imprinted polymer microsphere, solid phase extraction column and use of solid phase extraction column |
| CN110358396A (en)* | 2019-08-09 | 2019-10-22 | 江苏海晟涂料有限公司 | A kind of long-acting controlled release marine antifouling coating |
| CN111378081A (en)* | 2020-03-31 | 2020-07-07 | 陕西立高涂料有限公司 | Preparation method of fluorosilicone modified epoxy resin emulsion for anticorrosive paint |
| CN112169012A (en)* | 2020-09-29 | 2021-01-05 | 江南大学 | A kind of self-healing hot-melt biomedical adhesive and preparation method thereof |
| US20230212419A1 (en)* | 2021-01-29 | 2023-07-06 | Quzhou Research Institute of Zhejiang University | Preparation method for ultraviolet-responsive coumarin controlled-release and self-repairing anti-fouling paint |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106397655A (en)* | 2016-09-08 | 2017-02-15 | 中国农业科学院农业质量标准与检测技术研究所 | Organotin molecularly imprinted polymer microsphere, solid phase extraction column and use of solid phase extraction column |
| CN110358396A (en)* | 2019-08-09 | 2019-10-22 | 江苏海晟涂料有限公司 | A kind of long-acting controlled release marine antifouling coating |
| CN111378081A (en)* | 2020-03-31 | 2020-07-07 | 陕西立高涂料有限公司 | Preparation method of fluorosilicone modified epoxy resin emulsion for anticorrosive paint |
| CN112169012A (en)* | 2020-09-29 | 2021-01-05 | 江南大学 | A kind of self-healing hot-melt biomedical adhesive and preparation method thereof |
| US20230212419A1 (en)* | 2021-01-29 | 2023-07-06 | Quzhou Research Institute of Zhejiang University | Preparation method for ultraviolet-responsive coumarin controlled-release and self-repairing anti-fouling paint |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN120587093A (en)* | 2025-08-08 | 2025-09-05 | 咸阳圣亚机电设备有限公司 | High-cleanliness rust-proof surface treatment process for double-H control shell |
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