WO2022041429A1

WO2022041429A1 - Anti-fouling gel particles containing rare earth/anti-fouling agent and preparation method therefor

Info

Publication number: WO2022041429A1
Application number: PCT/CN2020/123188
Authority: WO
Inventors: 张初镱; 谢志鹏; 邓冰锋; 黄从树
Original assignee: 中国船舶重工集团公司第七二五研究所
Priority date: 2020-08-24
Filing date: 2020-10-23
Publication date: 2022-03-03
Also published as: CN112175434A; CN112175434B

Abstract

Anti-fouling gel particles containing a rare earth/anti-fouling agent and a preparation method therefor, which belongs to the technical field of chemical materials. Firstly, white carbon black is prepared as a carrier by using a sol-gel method; the white carbon black is modified with a silane coupling agent, and a rare earth cerium solution is then added thereto to obtain a rare earth antimicrobial white carbon black with a good dispersity; and then the rare earth antimicrobial white carbon black and an anti-fouling agent are co-coated by means of a free radical copolymerization method, such that the prepared anti-fouling gel has double anti-fouling mechanisms of both a hydrophilic property for preventing bacterial adhesion and an anti-fouling agent for sterilization. The addition of the rare earth substance, on the one hand, can greatly improve the anti-fouling efficiency of the anti-fouling agent, and on the other hand, because the surface of the rare earth antimicrobial white carbon black is rich in a large number of hydroxyl groups, can form intramolecular or/and intermolecular hydrogen bonds with amide groups, such that the mechanical properties of the anti-fouling gel particles can be significantly enhanced and a long-lasting anti-fouling effect can be achieved. The anti-fouling gel particles containing the rare earth/anti-fouling agent have a simple preparation process and a rich source of raw materials, and can effectively reduce production costs.

Description

一种含稀土/防污剂的防污凝胶粒子及其制备方法A kind of antifouling gel particle containing rare earth/antifouling agent and preparation method thereof

技术领域technical field

本发明属于化工材料技术领域，具体地说，本发明涉及一种含稀土/防污剂的防污凝胶粒子及其制备方法。The invention belongs to the technical field of chemical materials, and in particular, the invention relates to an antifouling gel particle containing rare earth/antifouling agent and a preparation method thereof.

背景技术Background technique

我国海域辽阔，在广袤的海洋环境中生活着超过1700多类4000多种的生物，其中大多数都会成为污损生物。若不采取有效的防治措施，海洋中的船舶、桥梁、石油钻井平台、管道等设施都很容易被海洋生物附着。海洋生物污损会增加船舶的航行阻力，降低航速，增加燃料消耗，加速材料腐蚀，影响了我国武器装备的战斗力，不但会增加维护频率及成本支出，还会增加温室气体排放，影响气候变化等。目前解决污损问题最具广谱性和有效性的方法，是在海洋装备表面涂覆防污涂料，现用防污涂料主要为含氧化亚铜自抛光防污涂料，其工作原理为依靠氧化亚铜防污剂渗出，毒杀、抑制海生物污损生长，并且含氧化亚铜的防污涂料效果较久，但经研究表明，防污涂料释放的氧化亚铜最终降解产物为碱式碳酸铜，它往往会超过海水中的溶解度，从而在海港中大量积聚，将给海洋环境造成了严重的潜在危害，严重破坏海洋生态平衡，欧洲及美国部分地区已经开始限制它们的使用范围和使用量，这样间接限制了某些武器装备功能的有效发挥。因此，开发一种低毒高效的新型环保长效防污涂料是新一代武器装备发展的迫切需求。my country has a vast sea area, and there are more than 1,700 species of more than 4,000 species living in the vast marine environment, most of which will become fouling creatures. If no effective control measures are taken, ships, bridges, oil drilling platforms, pipelines and other facilities in the ocean are easily attached by marine organisms. Marine biofouling will increase the navigation resistance of ships, reduce speed, increase fuel consumption, accelerate material corrosion, and affect the combat effectiveness of my country's weapons and equipment. It will not only increase maintenance frequency and cost expenditure, but also increase greenhouse gas emissions and affect climate change. . At present, the most broad-spectrum and effective method to solve the problem of fouling is to apply antifouling paint on the surface of marine equipment. The antifouling paint currently used is mainly self-polishing antifouling paint containing cuprous oxide. Its working principle is to rely on oxidation The cuprous antifouling agent oozes out, poisons and inhibits the fouling growth of marine organisms, and the antifouling paint containing cuprous oxide has a longer effect, but research shows that the final degradation product of cuprous oxide released by the antifouling paint is basic Copper carbonate, which often exceeds the solubility in seawater and accumulates in large quantities in seaports, will cause serious potential harm to the marine environment and seriously damage the marine ecological balance. Parts of Europe and the United States have begun to limit their scope and use. This indirectly limits the effective play of the functions of certain weapons and equipment. Therefore, it is an urgent need for the development of a new generation of weapons and equipment to develop a new type of low-toxicity and high-efficiency environmentally friendly long-acting antifouling coating.

其中亲水性高分子三维网络构成的水凝胶材料，由于其超吸水性，可在表面形成一层很薄的水化层，有效阻止蛋白质等在其表面的吸附，同时水膜的高弹性形变作用，在海水摆动下会在一定范围内形成机械摇摆，从而进一步降低其污损生物粘附作用，为我们环境友好型防污涂料拓宽了思路。而稀土元素由于其特殊的电子层结构，易与水、空气等体系发生催化反应，产生O ₂和·OH活性氧自由基，将水中的分子电离，从而增加水中负离子的浓度，这种负离子具有较优异的抗菌功能。此外，稀土离子有强烈的渗透到生物体内的独特特性，能有效击穿细胞膜，促进抑菌物质快速达到细胞内部，使细胞蛋白质变性而完成灭菌，从而与抗菌物质产生协同效应，将其与防污剂进行复配时，可大大减少防污剂的用量及提高防污效率，其中铈是地壳中含量最高的稀土元素，具有良好的开发前景。近年来随着有机锡的禁用，吡啶系防污剂由于具有较好的防污效果，且在海水中见光易分解的特点，在国内自抛光防污涂料中外作为复配防污剂组分已被大量使用，但在水凝胶类型的防污涂料中报道较少，且均为添加稀土物质，调高防污效率。 Among them, the hydrogel material composed of a three-dimensional network of hydrophilic macromolecules can form a thin hydration layer on the surface due to its super water absorption, which can effectively prevent the adsorption of proteins on its surface. At the same time, the high elasticity of the water film Deformation, mechanical swing will be formed within a certain range under the swing of seawater, thereby further reducing its fouling bioadhesion, which broadens the idea of our environment-friendly antifouling coatings. Due to its special electronic layer structure, rare earth elements are easy to catalyze reactions with water, air and other systems to generate O ₂ and OH active oxygen radicals, which ionize molecules in water, thereby increasing the concentration of negative ions in water. This negative ion has Excellent antibacterial function. In addition, rare earth ions have the unique characteristics of strong penetration into the body, which can effectively penetrate the cell membrane, promote the rapid arrival of antibacterial substances into the cell, denature the cell proteins and complete the sterilization, thereby producing a synergistic effect with the antibacterial substances. When the antifouling agent is compounded, the dosage of the antifouling agent can be greatly reduced and the antifouling efficiency can be improved. Among them, cerium is the rare earth element with the highest content in the earth's crust, and has a good development prospect. In recent years, with the ban of organotin, pyridine-based antifouling agents are used as compound antifouling agent components in domestic self-polishing antifouling coatings due to their good antifouling effect and easy decomposition in seawater. It has been widely used, but it is rarely reported in hydrogel type antifouling coatings, and rare earth substances are added to increase the antifouling efficiency.

例如，中国专利申请号为201510236375.2，申请公开日为2015年8月26日的专利申请文件公开了一种新型水凝胶防污涂层制备方法。该专利将PVA凝胶放入含KPS的AAm溶液中进行浸泡，得到PVA/PAAm双网络结构的水凝胶，干燥成微粉后与环氧树脂进行混合，制备成水凝胶防污涂层，具有一定的防污效果，但水凝胶未进行强化处理，影响了水凝胶本身的力学性能，制备成防污涂料后无法起到长久的防污效果，在10个月时已经失效。For example, the Chinese patent application number is 201510236375.2, and the patent application document with the application publication date on August 26, 2015 discloses a novel hydrogel antifouling coating preparation method. In this patent, the PVA gel is soaked in an AAm solution containing KPS to obtain a hydrogel with a PVA/PAAm double network structure, which is dried into micropowder and mixed with epoxy resin to prepare a hydrogel antifouling coating. It has a certain antifouling effect, but the hydrogel has not been strengthened, which affects the mechanical properties of the hydrogel itself. After being prepared into an antifouling coating, it cannot have a long-term antifouling effect, and it has failed after 10 months.

又如，中国专利申请号为201811215424.4，申请公开日为2019年2月22日的专利申请文件公开了一种缓释硅油的水凝胶及其在海洋防污涂料中的应用。该专利采用丙烯酰胺、N-羟甲基丙烯酰胺和N-异丙基丙烯酰胺共聚，通过酰胺基和羟基形成分子内或/和分子间氢键，增强水凝胶的刚性，但由于N-羟甲基丙烯酰胺不超过10％，且其自带羟基不足，对水凝胶强度增强有限；且该涂层在浅海浸泡6个月后防污性能下降均超过8％，表明通过缓释硅油增强防污性能的方法具有一定的局限性。For another example, the Chinese patent application number is 201811215424.4, and the patent application document with the application publication date on February 22, 2019 discloses a slow-release silicone oil hydrogel and its application in marine antifouling coatings. This patent uses acrylamide, N-methylol acrylamide and N-isopropylacrylamide to copolymerize, and forms intramolecular or/and intermolecular hydrogen bonds through amide groups and hydroxyl groups to enhance the rigidity of the hydrogel, but due to N- Methylol acrylamide does not exceed 10%, and its own hydroxyl group is insufficient, and the strength enhancement of hydrogel is limited; and the antifouling performance of the coating decreased by more than 8% after being immersed in shallow sea for 6 months, indicating that the slow-release silicone oil Methods to enhance antifouling performance have certain limitations.

再如，中国专利申请号为201710809362.9，申请公开日为2018年2月2日的专利申请文件公开了基于硅酮水凝胶树脂和天然防污剂的环境友好型防污材料。该专利以烯丙基聚乙二醇或乙二醇单烯丙基醚和含氢硅油为起始原料，加热进行氢硅化反应，然后加入与二甲苯中充分溶胀溶解的丁基橡胶，继续反应制成硅酮水凝胶树脂，在其中加入天然防污剂，固化后得到防污材料，但是，由于合成过程中加入丁基橡胶，虽然提高了防污涂料的强度，但同时降低了材料的亲水特性，且防污剂不释放，无法起到很好的防污效果，6个月实海挂板已经有海生物附着。For another example, the Chinese patent application number is 201710809362.9, and the patent application document with the application publication date on February 2, 2018 discloses an environmentally friendly antifouling material based on a silicone hydrogel resin and a natural antifouling agent. This patent uses allyl polyethylene glycol or ethylene glycol monoallyl ether and hydrogen-containing silicone oil as starting materials, heats for hydrosilation reaction, then adds butyl rubber that is fully swollen and dissolved in xylene, and continues the reaction A silicone hydrogel resin is made into which a natural antifouling agent is added, and an antifouling material is obtained after curing. However, due to the addition of butyl rubber during the synthesis process, although the strength of the antifouling coating is improved, it also reduces the strength of the material. Hydrophilic properties, and the antifouling agent is not released, so it cannot play a good antifouling effect. The actual sea hanging board has been attached to sea creatures for 6 months.

因此，开发一种高效的防污材料，是目前亟需解决的问题。Therefore, the development of an efficient antifouling material is an urgent problem to be solved at present.

发明内容SUMMARY OF THE INVENTION

1.要解决的问题1. The problem to be solved

针对现有防污材料无法达到长久防污效果的问题，本发明的目的在于提供一种含稀土/防污剂的防污凝胶粒子，采用硅烷偶联剂改性白炭黑后负载稀土和抗菌离子，与防污剂形成协同防污效果，减少防污剂用量，提高防污效率，并与亲水性凝胶形成双重防污机制，有效提高涂层防污效果。Aiming at the problem that the existing antifouling materials cannot achieve a long-term antifouling effect, the purpose of the present invention is to provide an antifouling gel particle containing rare earth/antifouling agent, which is modified with a silane coupling agent and then loaded with rare earth and antifouling gel particles. Antibacterial ions form a synergistic antifouling effect with the antifouling agent, reduce the amount of the antifouling agent, improve the antifouling efficiency, and form a dual antifouling mechanism with the hydrophilic gel to effectively improve the antifouling effect of the coating.

本发明还提供一种含稀土/防污剂的防污凝胶粒子的制备方法，其目的在于制备上述防污凝胶粒子。The present invention also provides a method for preparing antifouling gel particles containing rare earth/antifouling agent, the purpose of which is to prepare the above antifouling gel particles.

2.技术方案2. Technical solutions

为了解决上述问题，本发明所采用的技术方案如下：In order to solve the above problems, the technical scheme adopted in the present invention is as follows:

一种含稀土/防污剂的防污凝胶粒子，包括防污剂，还包括稀土抗菌白炭黑粒子和亲水性凝胶，所述的亲水性凝胶包覆稀土抗菌白炭黑粒子和防污剂，其中，所述的稀土抗菌白炭黑粒子以白炭黑为载体，通过偶联剂改性后，负载稀土促进物和抗菌离子，所述稀土促进物为含稀土元素的物质。An antifouling gel particle containing rare earth/antifouling agent, including antifouling agent, rare earth antibacterial silica particles and hydrophilic gel, wherein the hydrophilic gel coats rare earth antibacterial silica Particles and antifouling agent, wherein, the rare earth antibacterial silica particles use silica as a carrier, and after being modified by a coupling agent, a rare earth promoter and antibacterial ions are loaded, and the rare earth promoter is a rare earth element-containing substance.

进一步地，所述的防污剂为吡啶系防污剂，所述的亲水性凝胶以丙烯酰胺聚合物和丙烯酸聚合物为骨架，所述的稀土促进物为稀土铈溶液或钇溶液，所述稀土钇溶液包括硝酸钇。Further, the antifouling agent is a pyridine antifouling agent, the hydrophilic gel takes acrylamide polymer and acrylic acid polymer as skeleton, and the rare earth promoter is rare earth cerium solution or yttrium solution, The rare earth yttrium solution includes yttrium nitrate.

进一步地，所述的抗菌离子为硫酸锌溶液、硫酸铝溶液、硫酸铬溶液中的一种或几种的混合物。Further, the antibacterial ion is one or a mixture of zinc sulfate solution, aluminum sulfate solution, and chromium sulfate solution.

进一步地，所述的稀土抗菌白炭黑粒子的制备工艺步骤为：Further, the preparation process steps of the rare earth antibacterial silica particles are:

(1)溶胶凝胶预反应：将一定量烷氧基硅烷、浓氨水和少量去离子水依次加入反应器中，调节搅拌速度为200～400r/min，升温至50～60℃条件下反应2～3h；(1) Sol-gel pre-reaction: Add a certain amount of alkoxysilane, concentrated ammonia water and a small amount of deionized water into the reactor in turn, adjust the stirring speed to 200-400 r/min, and heat up to 50-60 °C for reaction 2 ~3h;

(2)硅烷偶联剂改性：向步骤(1)的反应中加入硅烷偶联剂，于40～60℃下继续反应4～6h，充分反应后，加入适量去离子水，再滴加盐酸溶液中和至中性；(2) Modification of silane coupling agent: add a silane coupling agent to the reaction in step (1), continue the reaction at 40-60° C. for 4-6 h, after sufficient reaction, add an appropriate amount of deionized water, and then dropwise add hydrochloric acid The solution is neutralized to neutral;

(3)稀土抗菌物质负载：向步骤(2)的反应中添加稀土铈溶液，反应5～10min后加入抗菌离子溶液，继续反应2～3h；(3) Rare earth antibacterial substance loading: adding rare earth cerium solution to the reaction in step (2), adding antibacterial ion solution after 5-10 minutes of reaction, and continuing the reaction for 2-3 hours;

(4)洗涤和烘干：将步骤(3)得到的沉淀充分洗涤并干燥后研磨得到稀土抗菌白炭黑粒子。(4) washing and drying: the precipitate obtained in step (3) is fully washed and dried, and then ground to obtain rare earth antibacterial silica particles.

进一步地，所述稀土抗菌白炭黑粒子制备工艺中各原料的质量份数为：Further, the mass fraction of each raw material in the preparation process of the rare earth antibacterial silica particles is:

进一步地，所述的浓氨水浓度为25％；所述的烷氧基硅烷以乙醇为溶剂且浓度为10～15％；所述的硅烷偶联剂以乙醇为溶剂且浓度为40～50％，所述的硅烷偶联剂包括KH550、KH560和KH570中的一种或几种的混合物；所述的稀土铈溶液为硝酸铈、硝酸镧中的一种或两种的混合物，所述稀土铈溶液的浓度为0.03～0.07mol/L；所述的抗菌离子溶液的浓度为0.5～1mol/L。Further, the concentration of the concentrated ammonia water is 25%; the alkoxysilane uses ethanol as the solvent and the concentration is 10-15%; the silane coupling agent uses ethanol as the solvent and the concentration is 40-50% , the silane coupling agent includes one or more mixtures of KH550, KH560 and KH570; the rare earth cerium solution is one or two mixtures of cerium nitrate and lanthanum nitrate, and the rare earth cerium The concentration of the solution is 0.03-0.07 mol/L; the concentration of the antibacterial ion solution is 0.5-1 mol/L.

即所述的稀土抗菌白炭黑粒子的制备工艺步骤为：That is, the preparation process steps of the rare earth antibacterial silica particles are:

a.溶胶凝胶预反应a. Sol-gel pre-reaction

将一定量烷氧基硅烷(10～15％)、浓氨水(25％)和少量去离子水依次加入反应器中，调节搅拌速度为200～400r/min，升温至50～60℃条件下反应2～3h。A certain amount of alkoxysilane (10-15%), concentrated ammonia (25%) and a small amount of deionized water were added to the reactor in turn, and the stirring speed was adjusted to 200-400r/min, and the temperature was raised to 50-60 ℃. 2 to 3 hours.

b.硅烷偶联剂改性b. Modification of silane coupling agent

向步骤a的反应中加入硅烷偶联剂(40～50％)，继续反应4～6h，充分反应后，加入适量去离子水，再滴加盐酸溶液中和至中性。Add a silane coupling agent (40-50%) to the reaction in step a, continue the reaction for 4-6 hours, after sufficient reaction, add an appropriate amount of deionized water, and then dropwise add hydrochloric acid solution to neutralize to neutrality.

c.稀土抗菌物质负载c. Rare earth antibacterial substance loading

加入稀土溶液(0.03～0.07mol/L)，反应5～10min后加入抗菌离子溶液(0.5～1mol/L)，继续反应2～3h。Add rare earth solution (0.03～0.07mol/L), add antibacterial ion solution (0.5～1mol/L) after reacting for 5～10min, continue to react for 2～3h.

d.洗涤和烘干d. Washing and drying

反应结束后采用抽滤法获得沉淀，并用去离子水洗涤2～3次。然后将沉淀物在120℃真空干燥2h，然后放入高能球磨机中研磨8h，即获得稀土抗菌白炭黑粒子。After the reaction, the precipitate was obtained by suction filtration, and washed with deionized water for 2 to 3 times. Then, the precipitate was vacuum-dried at 120°C for 2 hours, and then put into a high-energy ball mill for grinding for 8 hours to obtain rare earth antibacterial silica particles.

一种含稀土/防污剂的防污凝胶粒子的制备方法，步骤为：在去离子水为反应溶剂下，将丙烯酰胺类单体、丙烯酸基类单体、防污剂和稀土抗菌白炭黑粒子在化学交联剂、引发剂和催化剂的作用下发生自由基共聚反应，将自由基共聚反应的产物洗涤、烘干后研磨，得到防污凝胶粒子。A preparation method of antifouling gel particles containing rare earth/antifouling agent. The carbon black particles undergo a free radical copolymerization reaction under the action of a chemical crosslinking agent, an initiator and a catalyst, and the product of the free radical copolymerization reaction is washed, dried and ground to obtain antifouling gel particles.

进一步地，其步骤为：Further, the steps are:

S1、自由基共聚亲水凝胶合成：向反应釜中加入10～20份的丙烯酰胺类单体，10～20份的丙烯酸基类单体，3～5份防污剂，3～5份稀土抗菌白炭黑粒子，0.1～0.5份的化学交联剂，0.1～0.5份引发剂，50～70份的去离子水，搅拌升温至60～80℃，10分钟后向反应釜中加入0.1～0.5份的催化剂，继续搅拌2～3h后停止搅拌，在10～20℃条件下静置继续反应1小时；S1. Synthesis of free-radical copolymerization hydrophilic gel: add 10-20 parts of acrylamide monomers, 10-20 parts of acrylic monomers, 3-5 parts of antifouling agent, 3-5 parts of antifouling agent into the reaction kettle Rare earth antibacterial silica particles, 0.1-0.5 parts of chemical cross-linking agent, 0.1-0.5 parts of initiator, 50-70 parts of deionized water, stir and heat up to 60-80 ℃, after 10 minutes, add 0.1 ～0.5 part of catalyst, continue stirring for 2～3 hours, stop stirring, and continue to react for 1 hour under the condition of 10～20℃;

S2、洗涤和烘干：将步骤S1制备的产物，挤压成小块状，并用去离子水洗涤2～3次，置于烘箱中烘干，然后放入高能球磨机中研磨8h，即得到所需的防污凝胶粒子。S2, washing and drying: the product prepared in step S1 is extruded into small pieces, washed with deionized water for 2 to 3 times, dried in an oven, and then put into a high-energy ball mill for grinding for 8 hours to obtain the obtained Antifouling gel particles required.

进一步地，所述的丙烯酰胺类单体为丙烯酰胺、N-异丙基丙烯酰胺、N-二乙基丙烯酰胺中的一种或几种；所述的丙烯酸基类单体为丙烯酸、甲基丙烯酸羟丙酯、甲基丙烯酸羟乙酯中的一种或几种；所述的防污剂为吡啶系防污剂，吡啶系防污剂为吡啶硫酮锌、吡啶硫酮铜、吡啶三苯基硼中的一种或几种。Further, the acrylamide-based monomers are one or more of acrylamide, N-isopropylacrylamide, and N-diethylacrylamide; the acrylic-based monomers are acrylic acid, methyl methacrylate One or more of hydroxypropyl acrylate and hydroxyethyl methacrylate; the antifouling agent is a pyridine antifouling agent, and the pyridine antifouling agent is zinc pyrithione, copper pyrithione, pyridine One or more of triphenylboron.

进一步地，所述的化学交联剂为双甲基丙烯酸乙二醇酯、N,N-亚甲基双丙烯酰胺、双甲基丙烯酸低聚乙二醇酯中的一种或几种，化学交联剂起到主交联的目的；所述的引发剂为过硫酸钾、过硫酸铵中的一种或两种；所述的催化剂为四甲基乙二胺、四甲基己二胺中的一种或两种。Further, the chemical cross-linking agent is one or more of ethylene glycol bismethacrylate, N,N-methylenebisacrylamide, and oligoethylene glycol bismethacrylate. The crosslinking agent serves the purpose of main crosslinking; the initiator is one or both of potassium persulfate and ammonium persulfate; the catalyst is tetramethylethylenediamine, tetramethylhexamethylenediamine one or both of them.

一种上述含稀土/防污剂的防污凝胶粒子在制备船舶防污涂料上的应用。An application of the above rare earth/antifouling agent-containing antifouling gel particles in the preparation of marine antifouling paint.

3.有益效果3. Beneficial effects

相比于现有技术，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:

(1)本发明的防污凝胶粒子采用水凝胶包覆负载稀土抗菌白炭黑粒子及防污剂，实现双重防污机制；稀土抗菌白炭黑粒子是指制备的白炭黑通过硅烷偶联剂改性，白炭黑分散性更好，改性后接入的有机官能团，能增强药物的负载量，负载稀土物质和抗菌离子；水凝胶材料，由于其超吸水性，可在表面形成一层很薄的水化层，有效阻止污损生物在其表面的吸附，当其一旦附着，可通过稀土物质及防污剂释放，快速起到杀菌作用，形成双重防污机制的“双保险效果”；(1) The antifouling gel particles of the present invention use hydrogels to coat and load rare earth antibacterial silica particles and antifouling agents to achieve dual antifouling mechanisms; Coupling agent modification, the dispersibility of silica is better, and the organic functional groups added after modification can enhance the loading of drugs, load rare earth substances and antibacterial ions; hydrogel materials, due to their super water absorption, can be used in A very thin hydration layer is formed on the surface, which can effectively prevent the adsorption of fouling organisms on its surface. Once it is attached, it can be released by rare earth substances and antifouling agents, which can quickly play a bactericidal effect and form a dual antifouling mechanism. Double insurance effect";

(2)本发明的防污凝胶粒子引入稀土元素，提高防污剂防污效率，稀土离子有强烈的渗透到生物体内的独特特性，能有效击穿细胞膜，促进抑菌物质快速达到细胞内部，使细胞蛋白质变性而完成灭菌，从而与抗菌物质产生协同效应，提高防污剂防污效率；本发明使用稀土铈，也可以采用其他的稀土材料进行制备，但一方面稀土铈是地壳中丰度最高的稀土材料，原材料相对易得；(2) Rare earth elements are introduced into the antifouling gel particles of the present invention to improve the antifouling efficiency of the antifouling agent. The rare earth ions have the unique characteristic of strongly permeating into the living body, which can effectively penetrate the cell membrane and promote the rapid arrival of antibacterial substances inside the cell. , denaturation of cell proteins to complete sterilization, thereby producing a synergistic effect with antibacterial substances, and improving the antifouling efficiency of antifouling agents; the present invention uses rare earth cerium, and other rare earth materials can also be used for preparation, but on the one hand rare earth cerium is in the earth's crust. The most abundant rare earth materials, the raw materials are relatively easy to obtain;

(3)本发明的防污凝胶粒子采用白炭黑作为功能交联剂，增强亲水性水凝胶的机械性能，白炭黑表面富含多大量羟基等功能集团，可以形成氢键作用，起到增强作用，可作为官能团交联剂，在亲水性水凝胶体系中作为骨架的支撑点和交联点，加固水凝胶的大分子骨架强度，从而增强亲水性水凝胶的机械性能；(3) The antifouling gel particles of the present invention use white carbon black as a functional cross-linking agent to enhance the mechanical properties of the hydrophilic hydrogel. The surface of the white carbon black is rich in functional groups such as a large number of hydroxyl groups, which can form hydrogen bonds. , plays a reinforcing role, can be used as a functional group cross-linking agent, as a support point and cross-linking point of the skeleton in the hydrophilic hydrogel system, strengthen the macromolecular skeleton strength of the hydrogel, thereby enhancing the hydrophilic hydrogel mechanical properties;

(4)本发明研制了一种含稀土/防污剂的防污凝胶粒子及其制备方法，首先以白炭黑作为载体，通过加入稀土铈溶液，采用溶胶-凝胶法获得具有稀土抗菌粒子，值得注意的是，由于白炭黑具有一定的多孔结构，但其本身尺寸就较小，为微纳级别，直接添加稀土元素会影响负载效果，稀土铈的酸性溶液为液体状态，有助于负载吸附；再通过自由基共聚法用亲水性凝胶将其与吡啶系防污剂共包覆，制备的防污凝胶兼具亲水特性抗菌附着及防污剂杀菌双重防污机制，稀土物质的加入，一方面可大大提高吡啶系防污剂的防污效率，另一方面由于稀土抗菌白炭黑表面富含大量羟基等功能集团，可与酰胺基形成分子内或/和分子间氢键，增强防污凝胶粒子的力学性能，即显著增强防污凝胶粒子的刚性，达到持久防污效果；而且材料制备工艺简单，原料来源丰富，可有效降低生产成本，具有较好的市场竞争力，和潜在应用价值；(4) The present invention has developed an antifouling gel particle containing rare earth/antifouling agent and a preparation method thereof. First, white carbon black is used as a carrier, and a rare earth cerium solution is added, and a sol-gel method is used to obtain rare earth antibacterial Particles, it is worth noting that because silica has a certain porous structure, but its own size is small, at the micro-nano level, the direct addition of rare earth elements will affect the loading effect. The acidic solution of rare earth cerium is in a liquid state, which helps Then, it is co-coated with a pyridine-based antifouling agent with a hydrophilic gel by a free radical copolymerization method, and the prepared antifouling gel has both hydrophilic properties, antibacterial adhesion, and antifouling agent sterilization dual antifouling mechanisms. On the one hand, the addition of rare earth substances can greatly improve the antifouling efficiency of pyridine-based antifouling agents; It can enhance the mechanical properties of the antifouling gel particles, that is, significantly enhance the rigidity of the antifouling gel particles, and achieve a lasting antifouling effect; and the material preparation process is simple and the source of raw materials is rich, which can effectively reduce the production cost, and has good performance. market competitiveness and potential application value;

(5)本发明的亲水性水凝胶材料，由于其超吸水性，可在表面形成一层水化层，有效阻止蛋白质等在其表面的吸附，同时水膜的高弹性形变作用，在海水摆动下形成一定的机械摇摆，可进一步降低污损生物粘附作用，为环境友好型防污涂料拓宽了思路，而稀土元素由于特殊的电子层结构，可与抗菌物质产生协同效应，可有效提高防污效率。(5) The hydrophilic hydrogel material of the present invention can form a layer of hydration layer on the surface due to its super water absorption, which can effectively prevent the adsorption of proteins and the like on its surface. A certain mechanical sway is formed under the swing of seawater, which can further reduce the fouling bioadhesion and broaden the ideas for environmentally friendly antifouling coatings. Due to the special electronic layer structure, rare earth elements can produce synergistic effects with antibacterial substances, which can effectively Improve antifouling efficiency.

附图说明Description of drawings

图1为防污凝胶浅海浸泡12个月效果图。Figure 1 shows the effect of antifouling gel immersion in shallow sea for 12 months.

具体实施方式detailed description

下面结合具体实施例对本发明进一步进行描述，实施例中各物质的添加量均为质量份数。The present invention will be further described below with reference to specific examples, and the addition amounts of each substance in the examples are all parts by mass.

表1 实施例中防污凝胶粒子各原料配方Each raw material formula of antifouling gel particles in the embodiment of table 1

实施例1Example 1

本实施例中的一种含稀土/防污剂的防污凝胶粒子，其制备方法如下：其中制备方法中各原料种类及添加量如表1所示：A kind of antifouling gel particle containing rare earth/antifouling agent in the present embodiment, its preparation method is as follows: wherein in the preparation method, each raw material kind and addition are as shown in table 1:

(1)稀土抗菌白炭黑粒子的制备工艺(1) Preparation process of rare earth antibacterial silica particles

a.溶胶凝胶预反应a. Sol-gel pre-reaction

将20份四甲氧基硅烷、3份浓氨水和1份少量去离子水依次加入反应器中，调节搅拌速度为200r/min，升温至50℃条件下反应3h。20 parts of tetramethoxysilane, 3 parts of concentrated ammonia water and 1 part of deionized water were successively added to the reactor, the stirring speed was adjusted to 200 r/min, and the temperature was raised to 50 °C for 3 h.

b.偶联剂改性b. Coupling agent modification

加入20份KH550硅烷偶联剂，继续反应6h，加入6份去离子水，再滴加盐酸溶液中和至中性。Add 20 parts of KH550 silane coupling agent, continue to react for 6 hours, add 6 parts of deionized water, and then dropwise add hydrochloric acid solution to neutralize to neutrality.

c.抗菌物质负载c. Antimicrobial load

加入15份0.05mol/L的硝酸铈溶液，反应8min后加入10份0.8mol/L的硫酸铝溶液，以及15份0.5mol/L的硫酸锌溶液，继续反应2.5h。15 parts of 0.05mol/L cerium nitrate solution were added, and after 8 minutes of reaction, 10 parts of 0.8mol/L aluminum sulfate solution and 15 parts of 0.5mol/L zinc sulfate solution were added, and the reaction was continued for 2.5h.

d.洗涤和烘干d. Washing and drying

反应结束后采用抽滤法获得沉淀，并用去离子水洗涤2～3次。然后将沉淀物在120℃真空干燥2h，然后放入高能球磨机中研磨8h，即获得本实施例的稀土抗菌白炭黑粒子。After the reaction, the precipitate was obtained by suction filtration, and washed with deionized water for 2 to 3 times. Then, the precipitate was vacuum-dried at 120° C. for 2 hours, and then put into a high-energy ball mill for grinding for 8 hours, to obtain the rare earth antibacterial silica particles of this example.

(2)防污凝胶粒子制备工艺(2) Preparation process of antifouling gel particles

S1、自由基共聚亲水凝胶合成：向反应釜中加入20份丙烯酰胺，10份丙烯酸，2份吡啶硫酮铜，3份吡啶硫酮锌，3份上述稀土抗菌白炭黑粒子，0.1份的双甲基丙烯酸乙二醇酯，0.1份的过硫酸铵，61.7份的去离子水，搅拌升温至70℃，10分钟后向反应釜中加入0.1份的四甲基己二胺，继续搅拌2.5h后停止搅拌，在15℃条件下静置继续反应1小时；S1. Synthesis of free-radical copolymerized hydrophilic gel: add 20 parts of acrylamide, 10 parts of acrylic acid, 2 parts of copper pyrithione, 3 parts of zinc pyrithione, 3 parts of the above-mentioned rare earth antibacterial silica particles, 0.1 Part of ethylene glycol dimethacrylate, 0.1 part of ammonium persulfate, 61.7 parts of deionized water, stirring and warming up to 70 ° C, adding 0.1 part of tetramethylhexamethylene diamine to the reaction kettle after 10 minutes, continue After stirring for 2.5 hours, the stirring was stopped, and the reaction was continued for 1 hour under the condition of 15°C;

S2、洗涤和烘干：将步骤S1制备的产物，挤压成小块状，并用去离子水洗涤2～3次，置于烘箱中烘干，然后放入高能球磨机中研磨8h，即得到本实施例所需的防污凝胶粒子。S2, washing and drying: the product prepared in step S1 is extruded into small pieces, washed with deionized water for 2 to 3 times, dried in an oven, and then put into a high-energy ball mill for grinding for 8 hours to obtain the present invention. Antifouling Gel Particles Desired for Examples.

实施例2Example 2

本实施例中的一种含稀土/防污剂的防污凝胶粒子，其制备方法如下：其中制备方法中各原料种类及添加量如表1所示：A kind of antifouling gel particle containing rare earth/antifouling agent in the present embodiment, its preparation method is as follows: wherein in the preparation method, various raw material types and addition amounts are shown in Table 1:

a.溶胶凝胶预反应a. Sol-gel pre-reaction

将25份四乙氧基硅烷、4份浓氨水和1份少量去离子水依次加入反应器中，调节搅拌速度为250r/min，升温至55℃条件下反应2.5h。25 parts of tetraethoxysilane, 4 parts of concentrated ammonia water and 1 part of deionized water were successively added to the reactor, the stirring speed was adjusted to 250r/min, and the temperature was raised to 55°C for 2.5h reaction.

b.偶联剂改性b. Coupling agent modification

加入5份KH550、10份KH560和10份KH570硅烷偶联剂，加入5份去离子水，于55℃下反应5h，滴加盐酸溶液中和至中性。Add 5 parts of KH550, 10 parts of KH560 and 10 parts of KH570 silane coupling agent, add 5 parts of deionized water, react at 55°C for 5 hours, and dropwise add hydrochloric acid solution to neutralize to neutrality.

c.稀土抗菌物质负载c. Rare earth antibacterial substance loading

加入10份0.03mol/L的硫酸铈溶液，10份0.07mol/L的硝酸镧溶液，反应5min后加入20份0.5mol/L的硫酸锌溶液，继续反应2h。Add 10 parts of 0.03mol/L cerium sulfate solution and 10 parts of 0.07mol/L lanthanum nitrate solution, after 5 minutes of reaction, add 20 parts of 0.5mol/L zinc sulfate solution, and continue the reaction for 2h.

d.洗涤和烘干d. Washing and drying

S1、自由基共聚亲水凝胶合成：向反应釜中加入15份的N-异丙基丙烯酰胺，15份的甲基丙烯酸羟乙酯，2份的吡啶硫酮锌，2份的吡啶三苯基硼，5份上述稀土抗菌白炭黑粒子，0.3份的N,N-亚甲基双丙烯酰胺，0.2份过硫酸钾，0.1份的过硫酸铵，60.1份的去离子水，搅拌升温至60～80℃，10分钟后向反应釜中加入0.3份的四甲基乙二胺，继续搅拌2～3h后停止搅拌，在10～20℃条件下静置继续反应1小时；S1. Synthesis of free radical copolymerization hydrophilic gel: add 15 parts of N-isopropylacrylamide, 15 parts of hydroxyethyl methacrylate, 2 parts of zinc pyrithione, 2 parts of pyridine triacetate to the reaction kettle Phenyl boron, 5 parts of the above rare earth antibacterial silica particles, 0.3 parts of N,N-methylenebisacrylamide, 0.2 parts of potassium persulfate, 0.1 parts of ammonium persulfate, 60.1 parts of deionized water, stirring and heating to 60～80℃, add 0.3 part of tetramethylethylenediamine to the reaction kettle after 10 minutes, continue stirring for 2～3h, stop stirring, and let stand at 10～20℃ and continue to react for 1 hour;

实施例3Example 3

a.溶胶凝胶预反应a. Sol-gel pre-reaction

将15份四乙氧基硅烷、15份四甲氧基硅烷、5份浓氨水和1份少量去离子水依次加入反应器中，调节搅拌速度为300r/min，升温至60℃条件下反应2h。15 parts of tetraethoxysilane, 15 parts of tetramethoxysilane, 5 parts of concentrated ammonia water and 1 part of deionized water were added to the reactor in turn, the stirring speed was adjusted to 300r/min, and the temperature was raised to 60 °C and reacted for 2h .

b.偶联剂改性b. Coupling agent modification

加入10份KH550、10份KH560和10份KH570硅烷偶联剂，继续反应反应4h，加入4份去离子水，滴加盐酸溶液中和至中性。Add 10 parts of KH550, 10 parts of KH560 and 10 parts of KH570 silane coupling agent, continue the reaction for 4 hours, add 4 parts of deionized water, and dropwise add hydrochloric acid solution to neutralize to neutrality.

c.稀土抗菌物质负载c. Rare earth antibacterial substance loading

加入10份0.07mol/L的硝酸铈溶液、10份0.07mol/L的硝酸镧溶液、5份0.07mol/L的硝酸钇溶液反应10min后加入10份1mol/L的硫酸锌溶液、5份1mol/L的硫酸铬溶液，继续反应3h。Add 10 parts of 0.07mol/L cerium nitrate solution, 10 parts of 0.07mol/L lanthanum nitrate solution, and 5 parts of 0.07mol/L yttrium nitrate solution to react for 10min, then add 10 parts of 1mol/L zinc sulfate solution, 5 parts of 1mol/L zinc sulfate solution /L of chromium sulfate solution, continue to react for 3h.

d.洗涤和烘干d. Washing and drying

S1、自由基共聚亲水凝胶合成：向反应釜中加入10份的N-二乙基丙烯酰胺，20份的甲基丙烯酸羟丙酯，2份的吡啶硫酮铜，1份的吡啶三苯基硼，4份上述稀土抗菌白炭黑粒子，0.3份的N,N-亚甲基双丙烯酰胺，0.2份的双甲基丙烯酸低聚乙二醇酯，0.2份过硫酸钾，0.3份过硫酸铵，59.5份的去离子水，搅拌升温至80℃，10分钟后向反应釜中加入0.3份四甲氧乙二胺和0.2份的四甲氧己二胺，继续搅拌3h后停止搅拌，在20℃条件下静置继续反应1小时；S1, free radical copolymerization hydrophilic gel synthesis: add 10 parts of N-diethylacrylamide, 20 parts of hydroxypropyl methacrylate, 2 parts of copper pyrithione, 1 part of pyridine triacetate into the reactor Phenylboron, 4 parts of the above rare earth antibacterial silica particles, 0.3 parts of N,N-methylenebisacrylamide, 0.2 parts of oligoethylene glycol bismethacrylate, 0.2 parts of potassium persulfate, 0.3 parts of Ammonium persulfate, 59.5 parts of deionized water, stirred and heated to 80°C, 0.3 parts of tetramethoxyethylenediamine and 0.2 parts of tetramethoxyhexanediamine were added to the reaction kettle after 10 minutes, and the stirring was stopped after continuing to stir for 3h , stand at 20°C and continue to react for 1 hour;

性能测试Performance Testing

(1)稀土抗菌白炭黑粒子抑菌效果(1) Bacteriostatic effect of rare earth antibacterial silica particles

测试实施例1～3的稀土抗菌白炭黑粒子的抑菌效果，测试方法如下所示：在无菌环境下把灭菌后的琼脂培养基在净化工作台上缓慢的倒入到培养皿里并平放待凝固使用。用生理盐水将大肠杆菌稀释到所需浓度，用移液枪吸取100μL稀释后的菌液到试管里，再添加0.1g需检测的样品，在恒温(37℃)培养摇床上震荡30min，使其混合均匀。结束后，吸取适量上层液体滴加到培养基上，用涂布棒将液体均匀涂板。把培养皿在恒温(37℃)培养箱里放置18～24h。经培养后，通过菌落计数法计算各样品抑菌率，测试数据如下表2：The antibacterial effect of the rare earth antibacterial silica particles of Examples 1 to 3 was tested, and the test method was as follows: in a sterile environment, slowly pour the sterilized agar medium into a petri dish on a purification workbench And lay flat for solidification. Dilute Escherichia coli to the required concentration with physiological saline, use a pipette to draw 100 μL of the diluted bacterial solution into the test tube, add 0.1 g of the sample to be tested, and shake it on a constant temperature (37°C) culture shaker for 30 minutes to make it well mixed. After the end, draw an appropriate amount of the upper layer liquid dropwise onto the medium, and use a coating rod to spread the liquid evenly on the plate. Place the petri dish in a constant temperature (37°C) incubator for 18-24h. After culturing, the antibacterial rate of each sample was calculated by the colony counting method, and the test data were as follows in Table 2:

表2 白炭黑抑菌效率Table 2 Bacteriostatic efficiency of silica

对照组1为无负载离子白炭黑，对照组2为通过单独添加硫酸锌溶液0.7mol/L制备的含锌白炭黑，对照组3为通过单独添加稀土铈浓度0.05mol/L制备的含稀土白炭黑，以及实施例1！3所制备的稀土抗菌白炭黑粒子，从上表可以发现，单独添加稀土铈的白炭黑抑菌效果不明显，单独添加抗菌离子锌的白炭黑抑菌效率可达74.9％，而实施例1～3通过同时添加稀土铈和抗菌离子制备的稀土抗菌粒子抑菌效率相较对照组具有较大提高，最高可达86.9％。Control group 1 is unsupported ionic silica, control group 2 is zinc-containing silica prepared by adding 0.7mol/L zinc sulfate solution alone, and control group 3 is prepared by adding rare earth cerium concentration 0.05mol/L alone. Rare earth white carbon black, and rare earth antibacterial white carbon black particles prepared in Examples 1 and 3, it can be found from the above table that the antibacterial effect of the white carbon black added with rare earth cerium alone is not obvious, and the white carbon black with antibacterial ion zinc added alone The antibacterial efficiency can reach 74.9%, while the antibacterial efficiency of rare earth antibacterial particles prepared by simultaneously adding rare earth cerium and antibacterial ions in Examples 1 to 3 is greatly improved compared with the control group, up to 86.9%.

(2)防污凝胶力学性能(2) Mechanical properties of antifouling gel

测试实施例1～3中添加了稀土抗菌粒子后所发明的防污凝胶力学性能变化，测试方法采用GB/T 528-2009《硫化橡胶或热塑性橡胶拉伸应力应变性能的测定》进行测试，试验结果如下表3：The mechanical properties of the antifouling gels invented after adding rare earth antibacterial particles in test examples 1 to 3 were changed. The results are as follows in Table 3:

表3 防污凝胶力学性能变化Table 3 Changes in mechanical properties of antifouling gel

对照组4为合成的亲水凝胶，制备方法为：向反应釜中加入10份的N-二乙基丙烯酰胺，20份的甲基丙烯酸羟丙酯，2份的吡啶硫酮铜，1份的吡啶三苯基硼，0.3份的N,N-亚甲基双丙烯酰胺，0.2份的双甲基丙烯酸低聚乙二醇酯，0.3份过硫酸铵，67份的去离子水，搅拌升温至80℃，10分钟后向反应釜中加入0.1～0.5份的催化剂，继续搅拌3h后停止搅拌，在20℃条件下静置继续反应1小时。实施例1中添加稀土抗菌白炭黑粒子3份，实施例2中添加稀土抗菌白炭黑粒子5份，实施例3中添加稀土抗菌白炭黑粒子4份，从上表可以发现，通过添加稀土铈抗菌白炭黑粒子，亲水凝胶的拉伸强度和断裂伸长率均有显著的增强。Control group 4 is a synthetic hydrophilic gel, and the preparation method is as follows: adding 10 parts of N-diethylacrylamide, 20 parts of hydroxypropyl methacrylate, 2 parts of copper pyrithione to the reaction kettle, and 1 part of parts of triphenylboron pyridine, 0.3 parts of N,N-methylenebisacrylamide, 0.2 parts of oligoethylene glycol bismethacrylate, 0.3 parts of ammonium persulfate, 67 parts of deionized water, stirring The temperature was raised to 80°C, 0.1-0.5 parts of catalyst was added to the reaction kettle after 10 minutes, the stirring was continued for 3 hours, and then the stirring was stopped, and the reaction was continued at 20°C for 1 hour. In Example 1, 3 parts of rare earth antibacterial silica particles were added, 5 parts of rare earth antibacterial silica particles were added in Example 2, and 4 parts of rare earth antibacterial silica particles were added in Example 3. It can be found from the above table that by adding Rare earth cerium antibacterial silica particles, the tensile strength and elongation at break of the hydrophilic gel are significantly enhanced.

(3)防污凝胶防污性能(3) Antifouling performance of antifouling gel

测试所发明防污凝胶的实海防污性能，测试方法采用《防污漆样板浅海浸泡试验方法》进行，参照实施例2中的配方，通过混合水溶液，进行喷涂制板，在厦门大漓浦屿进行实海挂板试验实海浸泡12个月后如图1所示，从图1中可以发现，防污凝胶表面无任何污损生物附着，漆膜完整，无起泡、开裂、脱落等现象，说明所发明防污凝胶具有优良的防污性能。The antifouling performance of the antifouling gel invented by the invention was tested. The test method was carried out using the "Antifouling paint sample shallow sea immersion test method". With reference to the formula in Example 2, by mixing the aqueous solution, spraying and making the board were carried out. After immersion in the real sea for 12 months in Puyu, it is shown in Figure 1. It can be found from Figure 1 that there is no fouling biological adhesion on the surface of the antifouling gel, the paint film is complete, and there is no blistering, cracking, The phenomenon of falling off, etc., shows that the antifouling gel of the invention has excellent antifouling performance.

Claims

一种含稀土/防污剂的防污凝胶粒子，包括防污剂，其特征在于：还包括稀土抗菌白炭黑粒子和亲水性凝胶，所述的亲水性凝胶包覆稀土抗菌白炭黑粒子和防污剂，其中，所述的稀土抗菌白炭黑粒子以白炭黑为载体，并且负载稀土促进物和抗菌离子。An antifouling gel particle containing rare earth/antifouling agent, comprising an antifouling agent, and characterized in that it also includes rare earth antibacterial silica particles and a hydrophilic gel, wherein the hydrophilic gel coats the rare earth Antibacterial white carbon black particles and antifouling agent, wherein, the rare earth antibacterial white carbon black particles use white carbon black as a carrier, and are loaded with rare earth promoters and antibacterial ions.
根据权利要求1所述的一种含稀土/防污剂的防污凝胶粒子，其特征在于：所述的防污剂为吡啶系防污剂，所述的亲水性凝胶以丙烯酰胺聚合物和丙烯酸聚合物为骨架，所述的稀土促进物为稀土铈溶液。The rare earth/antifouling agent-containing antifouling gel particle according to claim 1, wherein the antifouling agent is a pyridine antifouling agent, and the hydrophilic gel is acrylamide The polymer and the acrylic polymer are the skeleton, and the rare earth promoter is a rare earth cerium solution.
根据权利要求1所述的一种含稀土/防污剂的防污凝胶粒子，其特征在于：所述的抗菌离子为硫酸锌溶液、硫酸铝溶液、硫酸铬溶液中的一种或几种的混合物。The antifouling gel particle containing rare earth/antifouling agent according to claim 1, wherein the antibacterial ion is one or more of zinc sulfate solution, aluminum sulfate solution, and chromium sulfate solution mixture.
根据权利要求1所述的一种含稀土/防污剂的防污凝胶粒子，其特征在于：所述的稀土抗菌白炭黑粒子的制备工艺步骤为：The antifouling gel particle containing rare earth/antifouling agent according to claim 1, characterized in that: the preparation process steps of the rare earth antibacterial silica particles are:

(1)溶胶凝胶预反应：将烷氧基硅烷、浓氨水和去离子水依次加入反应器中搅拌，调节搅拌速度为200～400r/min，升温至50～60℃条件下反应2～3h；(1) Sol-gel pre-reaction: Add alkoxysilane, concentrated ammonia water and deionized water to the reactor and stir in sequence, adjust the stirring speed to 200-400 r/min, and react at 50-60 °C for 2-3 hours ;

(2)硅烷偶联剂改性：向步骤(1)的反应中加入硅烷偶联剂，于40～60℃下反应4～6h，充分反应后，加入适量去离子水，再滴加盐酸溶液中和至中性；(2) Modification of silane coupling agent: add silane coupling agent to the reaction of step (1), react at 40-60° C. for 4-6 h, after sufficient reaction, add an appropriate amount of deionized water, and then add hydrochloric acid solution dropwise neutral to neutral;

(3)稀土抗菌物质负载：向步骤(2)的反应中添加稀土铈溶液，反应5～10min后加入抗菌离子，继续反应2～3h；(3) Rare earth antibacterial substance loading: adding rare earth cerium solution to the reaction in step (2), adding antibacterial ions after the reaction for 5 to 10 minutes, and continuing the reaction for 2 to 3 hours;

(4)洗涤和烘干：将步骤(3)得到的沉淀充分洗涤并干燥后研磨得到稀土抗菌白炭黑粒子。(4) washing and drying: the precipitate obtained in step (3) is fully washed and dried, and then ground to obtain rare earth antibacterial silica particles.
根据权利要求4所述的一种含稀土/防污剂的防污凝胶粒子，其特征在于：所述稀土抗菌白炭黑粒子制备工艺中各原料的质量份数为：The antifouling gel particle containing rare earth/antifouling agent according to claim 4, wherein the mass fraction of each raw material in the preparation process of the rare earth antibacterial silica particle is:

其中，所述的浓氨水浓度为25％；所述的烷氧基硅烷以乙醇为溶剂且浓度为10～15％；所述的硅烷偶联剂以乙醇为溶剂且浓度为40～50％，所述的硅烷偶联剂包括KH550、KH560和KH570中的一种或几种的混合物；所述的稀土铈溶液包括硝酸铈、硫酸铈中的一种或两种的混合物；所述稀土铈溶液的浓度为0.03～0.07mol/L；所述的抗菌离子溶液的浓度为0.5～1mol/L。Wherein, the concentration of the concentrated ammonia water is 25%; the alkoxysilane uses ethanol as the solvent and the concentration is 10-15%; the silane coupling agent uses ethanol as the solvent and the concentration is 40-50%, The silane coupling agent includes a mixture of one or more of KH550, KH560 and KH570; the rare earth cerium solution includes one or a mixture of cerium nitrate and cerium sulfate; the rare earth cerium solution The concentration of the antibacterial ion solution is 0.03-0.07 mol/L; the concentration of the antibacterial ion solution is 0.5-1 mol/L.
一种含稀土/防污剂的防污凝胶粒子的制备方法，其特征在于：步骤为：在去离子水为反应溶剂下，将丙烯酰胺类单体、丙烯酸基类单体、防污剂和稀土抗菌白炭黑粒子在化学交联剂、引发剂和催化剂的作用下发生自由基共聚反应，将自由基共聚反应的产物洗涤、烘干后研磨，得到防污凝胶粒子。A preparation method of antifouling gel particles containing rare earth/antifouling agent, characterized in that the steps are: in deionized water as a reaction solvent, mixing acrylamide monomers, acrylic monomers, antifouling agents A free radical copolymerization reaction occurs with rare earth antibacterial silica particles under the action of a chemical crosslinking agent, an initiator and a catalyst, and the product of the free radical copolymerization reaction is washed, dried and ground to obtain antifouling gel particles.
根据权利要求6所述的一种含稀土/防污剂的防污凝胶粒子的制备方法，其特征在于：其步骤为：The method for preparing antifouling gel particles containing rare earth/antifouling agent according to claim 6, wherein the steps are:

S1、自由基共聚亲水凝胶合成：向反应釜中加入10～20份的丙烯酰胺类单体，10～20份的丙烯酸基类单体，3～5份防污剂，3～5份稀土抗菌白炭黑粒子，0.1～0.5份的化学交联剂，0.1～0.5份引发剂，50～70份的去离子水，搅拌升温至60～80℃，10分钟后向反应釜中加入0.1～0.5份的催化剂，继续搅拌2～3h后停止搅拌，在10～20℃条件下静置继续反应1小时；S1. Synthesis of free-radical copolymerization hydrophilic gel: add 10-20 parts of acrylamide monomers, 10-20 parts of acrylic monomers, 3-5 parts of antifouling agent, 3-5 parts of antifouling agent into the reaction kettle Rare earth antibacterial silica particles, 0.1-0.5 parts of chemical cross-linking agent, 0.1-0.5 parts of initiator, 50-70 parts of deionized water, stir and heat up to 60-80 ℃, after 10 minutes, add 0.1 ～0.5 part of catalyst, continue stirring for 2～3h, stop stirring, and continue to react for 1 hour under the condition of 10～20℃;

S2、洗涤和烘干：将步骤S1制备的产物，挤压成小块状，并用去离子水洗涤2～3次，置于烘箱中烘干，然后放入高能球磨机中研磨8h，即得到所需的防污凝胶粒子。S2, washing and drying: the product prepared in step S1 is extruded into small pieces, washed with deionized water for 2 to 3 times, dried in an oven, and then put into a high-energy ball mill for grinding for 8 hours to obtain the obtained Antifouling gel particles required.
根据权利要求6或7所述的一种含稀土/防污剂的防污凝胶粒子的制备方法，其特征在于：所述的丙烯酰胺类单体为丙烯酰胺、N-异丙基丙烯酰胺、N-二乙基丙烯酰胺中的一种或几种；所述的丙烯酸基类单体为丙烯酸、甲基丙烯酸羟丙酯、甲基丙烯酸羟乙酯中的一种或几种；所述的防污剂为吡啶系防污剂，吡啶系防污剂为吡啶硫酮锌、吡啶硫酮铜、吡啶三苯基硼中的一种或几种。The method for preparing antifouling gel particles containing rare earth/antifouling agent according to claim 6 or 7, wherein the acrylamide monomers are acrylamide, N-isopropylacrylamide , one or more of N-diethylacrylamide; the acrylic-based monomer is one or more of acrylic acid, hydroxypropyl methacrylate, and hydroxyethyl methacrylate; the The antifouling agent is a pyridine antifouling agent, and the pyridine antifouling agent is one or more of zinc pyrithione, copper pyrithione and pyridinetriphenylboron.
根据权利要求8所述的一种含稀土/防污剂的防污凝胶粒子的制备方法，其特征在于：所述的化学交联剂为双甲基丙烯酸乙二醇酯、N,N-亚甲基双丙烯酰胺、双甲基丙烯酸低聚乙二醇酯中的一种或几种；所述的引发剂为过硫酸钾、过硫酸铵中的一种或两种；所述的催化剂为四甲基乙二胺、四甲基己二胺中的一种或两种。The method for preparing antifouling gel particles containing rare earth/antifouling agent according to claim 8, wherein the chemical crosslinking agent is ethylene glycol bismethacrylate, N,N- One or more of methylene bisacrylamide and bis-methacrylic acid oligoethylene glycol ester; the initiator is one or both of potassium persulfate and ammonium persulfate; the catalyst It is one or both of tetramethylethylenediamine and tetramethylhexamethylenediamine.
一种权利要求1～5所述含稀土/防污剂的防污凝胶粒子在制备船舶防污涂料上的应用。An application of the rare earth/antifouling agent-containing antifouling gel particles of claims 1 to 5 in the preparation of marine antifouling coatings.