CN105802441A - Water-borne graphene composite coating, and water-borne graphene composite paint and preparation method thereof - Google Patents
Water-borne graphene composite coating, and water-borne graphene composite paint and preparation method thereof Download PDFInfo
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Abstract
本发明提供了一种水性石墨烯复合涂料，其由水性树脂、石墨烯、苯胺低聚物衍生物、水及涂料助剂组成，在水性石墨烯复合涂料中所述石墨烯所占的质量百分数为0.01％～4％，该石墨烯通过与苯胺低聚物衍生物形成π‑π键而均匀分散于所述水性树脂中。本发明还提供了一种水性石墨烯复合涂料的制备方法和水性石墨烯复合涂层。
The invention provides a water-based graphene composite coating, which is composed of water-based resin, graphene, aniline oligomer derivatives, water and coating additives, and the mass percentage of graphene in the water-based graphene composite coating 0.01%-4%, the graphene is uniformly dispersed in the water-based resin by forming π-π bonds with aniline oligomer derivatives. The invention also provides a preparation method of the water-based graphene composite coating and the water-based graphene composite coating.
Description
技术领域technical field
本发明涉及一种防腐涂料和防腐涂层，尤其涉及一种基于石墨烯的水性石墨烯复合涂层、水性石墨烯复合涂料及其制备方法。The invention relates to an anti-corrosion coating and an anti-corrosion coating, in particular to a graphene-based water-based graphene composite coating, a water-based graphene composite coating and a preparation method thereof.
背景技术Background technique
防腐涂料，是指可对金属等起到防腐蚀的作用的油漆涂料。近几年国家一直在对地球十分之七的海洋加大投资力度，防腐涂料已成为涂料领域的重要的生力军，防腐涂料发挥着越来越大的作用，发展前景可观。Anti-corrosion coatings refer to paints and coatings that can prevent corrosion of metals. In recent years, the country has been increasing investment in seven-tenths of the earth's oceans. Anti-corrosion coatings have become an important new force in the field of coatings. Anti-corrosion coatings are playing an increasingly important role and have promising development prospects.
水性涂料是指水作为涂料的溶剂。在使用时，涂料以分子团聚体分散在水中，依靠分子团聚体相互靠拢，界面分子渗透，分子团聚体融合，待水挥发后最终形成涂层。水性涂料由于不采用有机溶剂，而是采用水作为溶剂，因而较环保而受到大众青睐。Water-based paint refers to water as the solvent of the paint. When in use, the paint is dispersed in water as molecular aggregates, relying on the molecular aggregates to move closer to each other, the interface molecules penetrate, the molecular aggregates fuse, and finally form a coating after the water volatilizes. Water-based paints are favored by the public because they do not use organic solvents, but use water as a solvent, which is more environmentally friendly.
然而，水性涂料很难形成均一性、结构致密性的膜结构，从而制约了水性涂料的性能。同时，在成膜过程中，由于亲水基团的残留造成涂层亲水性提高，对水汽扩散屏蔽能力降低，涂层抗湿粘结能力降低。除此之外，水性树脂难以实现对填料和颜料颗粒的高度浸润和分散，导致其难形成高质量的防腐涂料。However, it is difficult for water-based coatings to form a uniform and dense film structure, which restricts the performance of water-based coatings. At the same time, in the process of film formation, due to the residual hydrophilic groups, the hydrophilicity of the coating is improved, the ability to shield water vapor diffusion is reduced, and the coating's ability to resist moisture adhesion is reduced. In addition, it is difficult for water-based resins to achieve a high degree of infiltration and dispersion of fillers and pigment particles, making it difficult to form high-quality anti-corrosion coatings.
发明内容Contents of the invention
针对现有技术的不足，本发明的主要目的在于提供一种水性石墨烯复合涂层、水性石墨烯复合涂料及其制备方法，所述水性石墨烯复合涂料中石墨烯均匀分散于水性树脂中，所制水性石墨烯复合涂料与金属基体结合力大、有机挥发物排放低，所制得的水性石墨烯复合涂层具有良好的防水渗透性和耐盐雾性以及较强的防护能力，可作为重防腐涂料应用于船舶、桥梁等相对苛刻腐蚀环境中。For the deficiencies in the prior art, the main purpose of the present invention is to provide a kind of water-based graphene composite coating, water-based graphene composite coating and preparation method thereof, graphene is uniformly dispersed in the water-based resin in the described water-based graphene composite coating, The prepared water-based graphene composite coating has a strong binding force with the metal substrate and low emission of organic volatiles. The prepared water-based graphene composite coating has good waterproof permeability, salt spray resistance and strong protection ability, and can be used as Heavy-duty anti-corrosion coatings are used in relatively harsh corrosive environments such as ships and bridges.
本发明提供一种水性石墨烯复合涂料，其由水性树脂、石墨烯、苯胺低聚物衍生物、水及涂料助剂组成，在水性石墨烯复合涂料中所述石墨烯所占的质量百分数为0.01％～4％，该石墨烯通过与苯胺低聚物衍生物形成π-π键而均匀分散于水中。The invention provides a kind of water-based graphene composite coating, which is made up of water-based resin, graphene, aniline oligomer derivatives, water and coating additives, and the mass percent that graphene accounts for in the water-based graphene composite coating is: 0.01%-4%, the graphene is uniformly dispersed in water by forming π-π bonds with aniline oligomer derivatives.
其中，所述苯胺低聚物衍生物与石墨烯的质量比为1:10～10:1。Wherein, the mass ratio of the aniline oligomer derivative to graphene is 1:10˜10:1.
其中，所述石墨烯的直径为5μm～50μm。Wherein, the diameter of the graphene is 5 μm˜50 μm.
其中，所述苯胺低聚物衍生物为带有功能团的苯胺低聚物，所述功能团包括羧基、烷基、磺酸基、磷酸基、环氧基团、聚乙二醇基团和/或聚乙烯醇基团，所述苯胺低聚物为苯胺三聚体、苯胺四聚体、苯胺五聚体、苯胺六聚体中的一种或组合。Wherein, the aniline oligomer derivatives are aniline oligomers with functional groups, and the functional groups include carboxyl groups, alkyl groups, sulfonic acid groups, phosphoric acid groups, epoxy groups, polyethylene glycol groups and /or polyvinyl alcohol group, the aniline oligomer is one or a combination of aniline trimer, aniline tetramer, aniline pentamer, aniline hexamer.
其中，所述水性树脂为水性环氧树脂、水性丙烯酸树脂、水性聚氨酯树脂、水性丙烯酸聚氨酯树脂和水性氨基树脂中的一种或组合。Wherein, the water-based resin is one or a combination of water-based epoxy resin, water-based acrylic resin, water-based polyurethane resin, water-based acrylic polyurethane resin and water-based amino resin.
其中，所述涂料助剂包括防沉剂、消泡剂和流平剂，所述防沉剂为气相二氧化硅、聚酰胺蜡和有机膨润土中的一种或组合，所述消泡剂为二甲基硅油、醚酯化合物、改性矿物油、聚氧乙基甘油醚、小分子金属有机物和改性有机硅聚合物中的一种或组合，所述流平剂为乙二醇丁醚、醋丁纤维素、聚丙烯酸酯类、硅油、羟甲基纤维素、聚二甲基硅烷、聚甲基苯基硅氧烷和改性有机硅化合物中的一种或组合。Wherein, the coating additive includes anti-settling agent, defoamer and leveling agent, and the anti-settling agent is one or a combination of fumed silica, polyamide wax and organic bentonite, and the defoamer is One or a combination of simethicone oil, ether ester compound, modified mineral oil, polyoxyethyl glycerol ether, small molecular metal organic compound and modified silicone polymer, and the leveling agent is butyl glycol ether , Acetate butyl cellulose, polyacrylates, silicone oil, hydroxymethyl cellulose, polydimethylsilane, polymethylphenylsiloxane and modified organosilicon compounds, or one or a combination thereof.
本发明还提供一种水性石墨烯复合涂料的制备方法，其包括以下步骤：将等摩尔量的苯胺低聚物衍生物和碱溶解于水，得到混合物A；向所述混合物A中加入石墨烯，使苯胺低聚物衍生物与石墨烯混合均匀并在苯胺低聚物衍生物与石墨烯之间形成π-π键得到石墨烯分散液；提供一水性树脂，向所述水性树脂中加入所述石墨烯分散液并混合均匀，得到混合物B；向所述混合物B中加入涂料助剂，得到水性石墨烯复合涂料，其中，在所述水性石墨烯复合涂料中所述石墨烯所占的质量百分数为0.01％～4％。The present invention also provides a method for preparing a water-based graphene composite coating, which comprises the following steps: dissolving equimolar amounts of aniline oligomer derivatives and alkali in water to obtain a mixture A; adding graphene to the mixture A , make the aniline oligomer derivatives and graphene mix uniformly and form π-π bonds between the aniline oligomer derivatives and graphene to obtain a graphene dispersion; provide an aqueous resin, add the Described graphene dispersion liquid and mix homogeneously, obtain mixture B; Add coating aid in described mixture B, obtain water-based graphene composite coating, wherein, the mass that graphene accounts for in described water-based graphene composite coating The percentage is 0.01% to 4%.
其中，所述碱为氢氧化钠、三乙胺、氢氧化钾和氨水中的一种。Wherein, the alkali is one of sodium hydroxide, triethylamine, potassium hydroxide and ammonia water.
本发明还提供一种水性石墨烯复合涂层，其由水性树脂、石墨烯、苯胺低聚物衍生物及涂料助剂组成，在水性石墨烯复合涂层中所述石墨烯所占的质量百分数为0.01％～4％，该石墨烯通过与苯胺低聚物衍生物形成π-π键而均匀分散于所述水性树脂中。The present invention also provides a water-based graphene composite coating, which is composed of water-based resin, graphene, aniline oligomer derivatives and coating additives, and the mass percentage of graphene in the water-based graphene composite coating 0.01%-4%, the graphene is uniformly dispersed in the water-based resin by forming π-π bonds with aniline oligomer derivatives.
其中，在水性石墨烯复合涂层中所述水性树脂所占的质量百分数为80％～95％，所述苯胺低聚物衍生物所占的质量百分数为0.01％～5％，所述涂料助剂所占的质量百分数为1％～10％。Wherein, the mass percentage of the water-based resin in the water-based graphene composite coating is 80% to 95%, and the mass percentage of the aniline oligomer derivative is 0.01% to 5%. The mass percentage of agent is 1%～10%.
相较于现有技术，本发明提供的水性石墨烯复合涂料中，通过对石墨烯的表面经过苯胺低聚物衍生物的改性修饰，极大提高了石墨烯的分散性和化学稳定性，使得所述石墨烯均匀分散于所述水性树脂中，而石墨烯具有良好的疏水性能，故在应用过程中，可有效抑制水分子在形成的水性石墨烯复合涂层的表面吸附。同时，石墨烯具有二维片层结构，其在涂料中均匀分散，当形成水性石墨烯复合涂层后，石墨烯可层层叠加，形成致密的隔绝层，因而小分子腐蚀介质(水分子、氯离子等)很难通过这层致密的隔绝层，起到了突出的物理隔绝作用。即，所制得的水性石墨烯复合涂层具有良好的耐水渗透性和耐盐雾性以及较强的防护能力，从而水性石墨烯复合涂层具有优异的防腐效果。并且，所述水性石墨烯复合涂料不含有机溶剂，不会带来有机挥发物排放，绿色环保。本发明提供的水性石墨烯复合涂料的制备方法，通过制备工艺创新，可得到具有较好分散性和化学稳定性的水性石墨烯复合涂料，制备工艺简单，成本低廉，利于产业化。Compared with the prior art, in the water-based graphene composite coating provided by the present invention, the dispersibility and chemical stability of graphene are greatly improved by modifying the surface of graphene through aniline oligomer derivatives, The graphene is uniformly dispersed in the water-based resin, and the graphene has good hydrophobic properties, so in the application process, the adsorption of water molecules on the surface of the formed water-based graphene composite coating can be effectively inhibited. At the same time, graphene has a two-dimensional sheet structure, which is uniformly dispersed in the coating. After forming a water-based graphene composite coating, graphene can be stacked layer by layer to form a dense insulating layer, so small molecules corrode the medium (water molecules, Chloride ions, etc.) are difficult to pass through this dense insulating layer, which plays a prominent role in physical isolation. That is, the prepared water-based graphene composite coating has good water penetration resistance, salt spray resistance and strong protection ability, so the water-based graphene composite coating has an excellent anti-corrosion effect. Moreover, the water-based graphene composite coating does not contain organic solvents, does not cause organic volatile emissions, and is environmentally friendly. The preparation method of the water-based graphene composite coating provided by the present invention can obtain the water-based graphene composite coating with good dispersibility and chemical stability through the innovation of the preparation process. The preparation process is simple, the cost is low, and it is beneficial to industrialization.
附图说明Description of drawings
图1为实施例1所述石墨烯分散液(右)和未经处理的石墨烯经水分散后(左)的照片。Fig. 1 is the photo of the graphene dispersion (right) described in Example 1 and untreated graphene after water dispersion (left).
图2为实施例1所述石墨烯分散液的透射电镜照片。Fig. 2 is the transmission electron micrograph of the graphene dispersion liquid described in embodiment 1.
图3a为对比例1水性环氧树脂涂层经盐雾实验500小时后的表面形貌照片。Figure 3a is a photo of the surface morphology of the water-based epoxy resin coating of Comparative Example 1 after a salt spray test for 500 hours.
图3b为实施例1所得的水性石墨烯复合涂层经盐雾实验500小时后的表面形貌照片。Figure 3b is a photo of the surface morphology of the water-based graphene composite coating obtained in Example 1 after a salt spray test for 500 hours.
图4为实施例1所得的水性石墨烯复合涂层(对应b曲线)和对比例1水性环氧树脂涂层(对应a曲线)在3.5wt％NaCl溶液中浸泡48小时后的自腐蚀电位曲线。Fig. 4 is the self-corrosion potential curve after soaking in 3.5wt%NaCl solution for 48 hours of the aqueous graphene composite coating (corresponding to b curve) of embodiment 1 gained and comparative example 1 aqueous epoxy resin coating (corresponding to a curve) .
图5a为对比例1水性环氧树脂涂层在3.5wt％NaCl溶液中浸泡48小时内的交流阻抗谱的阻抗复平面图。Figure 5a is an impedance complex plane view of the AC impedance spectrum of the water-based epoxy resin coating of Comparative Example 1 soaked in 3.5wt% NaCl solution for 48 hours.
图5b为对比例1水性环氧树脂涂层在3.5wt％NaCl溶液中浸泡48小时内的交流阻抗谱的波特图。Figure 5b is a Bode plot of the AC impedance spectrum of the waterborne epoxy resin coating of Comparative Example 1 soaked in 3.5wt% NaCl solution for 48 hours.
图5c为实施例1所得的水性石墨烯复合涂层在3.5wt％NaCl溶液中浸泡48小时内的交流阻抗谱的阻抗复平面图。Fig. 5c is an impedance complex plane view of the AC impedance spectrum of the aqueous graphene composite coating obtained in Example 1 soaked in 3.5 wt% NaCl solution for 48 hours.
图5d为实施例1所得的水性石墨烯复合涂层在3.5wt％NaCl溶液中浸泡48小时内的交流阻抗谱的波特图。Figure 5d is a Bode plot of the AC impedance spectrum of the aqueous graphene composite coating obtained in Example 1 soaked in 3.5wt% NaCl solution for 48 hours.
图6为实施例1所得的水性石墨烯复合涂层(对应实线)与对比例1水性环氧树脂涂层(对应虚线)在3.5wt％NaCl溶液中浸泡48小时内的极化曲线。Fig. 6 is the polarization curve of the water-based graphene composite coating obtained in Example 1 (corresponding to the solid line) and the water-based epoxy resin coating (corresponding to the dotted line) of Comparative Example 1 soaked in 3.5wt% NaCl solution for 48 hours.
图7为实施例1所得的水性石墨烯复合涂层(对应b曲线)与对比例1水性环氧树脂涂层(对应a曲线)在3.5wt％NaCl溶液中浸泡48小时内的lgQc-t1/2曲线及线性回归方程(其中，Qc为涂层的电容，t为测试时间)。Fig. 7 is the lgQ c -t of the aqueous graphene composite coating (corresponding to b curve) and comparative example 1 aqueous epoxy resin coating (corresponding to a curve) soaked in 3.5wt%NaCl solution in 48 hours of embodiment 1 1/2 curve and linear regression equation (where, Q c is the capacitance of the coating, t is the test time).
图8a为对比例1水性环氧树脂涂层的表面的接触角照片。Figure 8a is a photo of the contact angle of the surface of the waterborne epoxy resin coating of Comparative Example 1.
图8b为实施例1所得的水性石墨烯复合涂层的表面的接触角照片。Fig. 8 b is the photo of the contact angle of the surface of the aqueous graphene composite coating obtained in Example 1.
具体实施方式detailed description
以下将结合附图对本发明提供的水性石墨烯复合涂层、水性石墨烯复合涂料及其制备方法作进一步说明。The water-based graphene composite coating provided by the present invention, the water-based graphene composite coating and the preparation method thereof will be further described below in conjunction with the accompanying drawings.
本发明实施例提供一种水性石墨烯复合涂料的制备方法。该方法包括如下步骤：The embodiment of the present invention provides a method for preparing a water-based graphene composite coating. The method comprises the steps of:
工序(1)：将等摩尔量的苯胺低聚物衍生物和碱溶解于水，得到混合物A。加碱的目的是为了使苯胺低聚物衍生物能够更好的溶于水。加等摩尔量是使苯胺低聚物衍生物结构中带有的羧酸，或者别的酸的基团能够和碱完全中和。所述碱为氢氧化钠、三乙胺、氢氧化钾和氨水中的一种。Step (1): equimolar amounts of aniline oligomer derivatives and alkali are dissolved in water to obtain a mixture A. The purpose of adding alkali is to make the aniline oligomer derivatives more soluble in water. Adding an equimolar amount is to make the carboxylic acid contained in the structure of the aniline oligomer derivative, or other acid groups, completely neutralize with the alkali. The alkali is one of sodium hydroxide, triethylamine, potassium hydroxide and ammonia water.
将苯胺低聚物衍生物和碱分散于水中，使苯胺低聚物衍生物充分溶解。所述苯胺低聚物衍生物用于修饰改性所述石墨烯。所述苯胺低聚物衍生物为带有功能团的苯胺低聚物，所述功能团包括羧基、烷基、磺酸基、磷酸基、环氧基团、聚乙二醇基团和/或聚乙烯醇基团。优选地，所述苯胺低聚物为苯胺三聚体、苯胺四聚体、苯胺五聚体、苯胺六聚体中的一种或组合。The aniline oligomer derivative and alkali are dispersed in water to fully dissolve the aniline oligomer derivative. The aniline oligomer derivatives are used to modify the graphene. The aniline oligomer derivatives are aniline oligomers with functional groups, and the functional groups include carboxyl groups, alkyl groups, sulfonic acid groups, phosphoric acid groups, epoxy groups, polyethylene glycol groups and/or polyvinyl alcohol group. Preferably, the aniline oligomer is one or a combination of aniline trimer, aniline tetramer, aniline pentamer, aniline hexamer.
所述苯胺低聚物或其衍生物可具有如下结构式：The aniline oligomer or derivative thereof may have the following structural formula:
(M主要为钠离子，钾离子，季铵盐等)。(M is mainly sodium ion, potassium ion, quaternary ammonium salt, etc.).
工序(2)：在所述混合物A中加入石墨烯，使苯胺低聚物衍生物与石墨烯混合均匀并在苯胺低聚物衍生物与石墨烯之间形成π-π键得到石墨烯分散液。具体的，由于所述苯胺低聚物衍生物中的苯环和石墨烯结构相近，因而所述苯胺低聚物衍生物可与石墨烯之间形成π-π键而实现与石墨烯均匀混合。需要指出的是，利用苯胺低聚物衍生物与石墨烯之间形成π-π键，这种方式不同于化学接枝改性，其并不破坏石墨烯本身的结构，也不同于物理性包覆石墨烯的高分子，其并不牺牲石墨烯的性能。也就是说，通过苯胺低聚物衍生物修饰改性石墨烯，其仅使石墨烯的分散性和稳定性更好，而并不破坏石墨烯的结构，也不降低石墨烯原有的性能。Step (2): adding graphene to the mixture A, mixing the aniline oligomer derivative and graphene uniformly and forming a π-π bond between the aniline oligomer derivative and graphene to obtain a graphene dispersion . Specifically, since the benzene ring in the aniline oligomer derivative is similar in structure to graphene, the aniline oligomer derivative can form a π-π bond with graphene to achieve uniform mixing with graphene. It should be pointed out that the formation of π-π bonds between aniline oligomer derivatives and graphene is different from chemical grafting modification, which does not destroy the structure of graphene itself, and is also different from physical encapsulation. Graphene-coated polymers without sacrificing the properties of graphene. That is to say, modifying graphene with aniline oligomer derivatives only improves the dispersibility and stability of graphene without destroying the structure of graphene or reducing the original properties of graphene.
可以理解，可通过高速搅拌、超声、球磨和/或砂磨的分散方法使石墨烯均匀分散，进一步使石墨烯与苯胺低聚物衍生物混合均匀。It can be understood that the graphene can be uniformly dispersed by high-speed stirring, ultrasonic, ball milling and/or sand milling dispersion methods, and further the graphene and aniline oligomer derivatives can be mixed uniformly.
所述石墨烯包括石墨烯纳米片、石墨烯微米片、石墨烯纳米带、少层石墨烯(2-5层)、多层石墨烯(2-9层)、石墨烯量子点以及这些石墨烯类材料的衍生物)。所述石墨烯材料的定义可参见文献“Allin the graphene family–A recommended nomenclature fortwo-dimensional carbon materials”。所述石墨烯材料还可以选自厚度≤20nm，更优选地，厚度≤10nm的材料。在本实施例中，该石墨烯材料的厚度优选≤3nm，石墨烯材料越薄，柔韧性越好，越容易加工。所述石墨烯材料的的制备方法不限，采用本领域技术人员熟知的石墨烯产品或用常规的制备方法制备即可。本发明的石墨烯材料优选宁波墨西科技有限公司提供的石墨烯产品。石墨烯材料可以选自化学氧化法如Brodie法、Hummers法或Staudenmaier法中的任意一种方法制备的氧化石墨烯经热膨胀制得的石墨烯材料。也可以选用机械剥离、液相剥离或电化学剥离制备的石墨烯材料。所述石墨烯的直径为5μm～50μm。Described graphene comprises graphene nanosheet, graphene microsheet, graphene nanobelt, few-layer graphene (2-5 layer), multi-layer graphene (2-9 layer), graphene quantum dot and these graphene derivatives of similar materials). The definition of the graphene material can be found in the document "Allin the graphene family—A recommended nomenclature for two-dimensional carbon materials". The graphene material can also be selected from materials with a thickness≤20nm, more preferably, a thickness≤10nm. In this embodiment, the thickness of the graphene material is preferably ≤3nm, and the thinner the graphene material, the better the flexibility and the easier it is to process. The preparation method of the graphene material is not limited, and it can be prepared by using graphene products well known to those skilled in the art or by conventional preparation methods. The graphene material of the present invention is preferably a graphene product provided by Ningbo Moxi Technology Co., Ltd. The graphene material can be selected from graphene materials prepared by thermal expansion of graphene oxide prepared by any one of chemical oxidation methods such as Brodie method, Hummers method or Staudenmaier method. Graphene materials prepared by mechanical exfoliation, liquid phase exfoliation or electrochemical exfoliation can also be selected. The graphene has a diameter of 5 μm˜50 μm.
所述苯胺低聚物衍生物与石墨烯的质量比为1:10～10:1。优选地，所述苯胺低聚物衍生物与石墨烯的质量比为2:1～1:1。The mass ratio of the aniline oligomer derivatives to graphene is 1:10˜10:1. Preferably, the mass ratio of the aniline oligomer derivative to graphene is 2:1˜1:1.
工序(3)：提供一水性树脂，向所述水性树脂中加入所述石墨烯分散液并混合均匀，得到混合物B。可通过高速搅拌、超声、球磨和/或砂磨的分散方法使石墨烯分散液均匀分散于水性树脂中，进一步使石墨烯均匀分散于水性树脂中。所述水性树脂为水性环氧树脂、水性丙烯酸树脂、水性聚氨酯树脂、水性丙烯酸聚氨酯树脂和水性氨基树脂中的一种或组合。Step (3): providing a water-based resin, adding the graphene dispersion into the water-based resin and mixing uniformly to obtain a mixture B. The graphene dispersion can be uniformly dispersed in the water-based resin by high-speed stirring, ultrasonic, ball milling and/or sand-milling dispersion methods, and the graphene can be further uniformly dispersed in the water-based resin. The water-based resin is one or a combination of water-based epoxy resin, water-based acrylic resin, water-based polyurethane resin, water-based acrylic polyurethane resin and water-based amino resin.
工序(4)：向所述混合物B中加入涂料助剂，得到水性石墨烯复合涂料。所述涂料助剂包括防沉剂、消泡剂和流平剂。所述防沉剂为气相二氧化硅、聚酰胺蜡和有机膨润土中的一种或组合。所述消泡剂为二甲基硅油、醚酯化合物、改性矿物油、聚氧乙基甘油醚、小分子金属有机物和改性有机硅聚合物中的一种或组合。所述流平剂为乙二醇丁醚、醋丁纤维素、聚丙烯酸酯类、硅油、羟甲基纤维素、聚二甲基硅烷、聚甲基苯基硅氧烷和改性有机硅化合物中的一种或组合。可以理解，所述水性石墨烯复合涂料还可包括固化剂。所述固化剂可为水性聚酰胺，用于加速所述水性石墨烯复合涂料固化过程。Step (4): adding a coating additive to the mixture B to obtain a water-based graphene composite coating. The coating additives include anti-settling agents, defoamers and leveling agents. The anti-settling agent is one or a combination of fumed silica, polyamide wax and organic bentonite. The defoaming agent is one or a combination of simethicone, ether ester compound, modified mineral oil, polyoxyethyl glyceryl ether, small molecule metal organic compound and modified silicone polymer. The leveling agent is ethylene glycol butyl ether, cellulose acetate, polyacrylate, silicone oil, hydroxymethyl cellulose, polydimethylsilane, polymethylphenylsiloxane and modified organosilicon compound one or a combination of. It can be understood that the water-based graphene composite coating can also include a curing agent. The curing agent can be water-based polyamide, which is used to accelerate the curing process of the water-based graphene composite coating.
得到的水性石墨烯复合涂料中所述石墨烯所占的质量百分数为0.01％～4％，优选为，0.2％～1.0％。The mass percentage of the graphene in the obtained water-based graphene composite paint is 0.01%-4%, preferably 0.2%-1.0%.
本发明还提供一种采用上述方法制备的水性石墨烯复合涂料。该水性石墨烯复合涂料由水性树脂、石墨烯、苯胺低聚物衍生物、水及涂料助剂组成。在水性石墨烯复合涂料中所述石墨烯所占的质量百分数为0.01％～4％。优选的，在所述水性石墨烯复合涂料中所述石墨烯所占的质量百分数为0.2％～1.0％。该石墨烯通过与苯胺低聚物衍生物形成π-π键而均匀分散于所述水性树脂中。The present invention also provides a water-based graphene composite coating prepared by the method. The water-based graphene composite coating is composed of water-based resin, graphene, aniline oligomer derivatives, water and coating additives. The mass percentage of the graphene in the water-based graphene composite coating is 0.01% to 4%. Preferably, the mass percentage of the graphene in the water-based graphene composite coating is 0.2%-1.0%. The graphene is uniformly dispersed in the water-based resin by forming π-π bonds with aniline oligomer derivatives.
本发明还提供一种采用上述水性石墨烯复合涂料制备的得到的水性石墨烯复合涂层。具体的，将上述水性石墨烯复合涂料通过刮涂、辊涂等手段涂覆于基体上，待所述水性石墨烯复合涂料中的水挥发后而形成水性石墨烯复合涂层。所述水性石墨烯复合涂层由水性树脂、石墨烯、苯胺低聚物衍生物及涂料助剂组成。在水性石墨烯复合涂层中所述石墨烯所占的质量百分数为0.01％～4％。该石墨烯通过与苯胺低聚物衍生物形成π-π键而均匀分散于所述水性树脂中。在水性石墨烯复合涂层中所述水性树脂所占的质量百分数为80％～95％，所述苯胺低聚物衍生物所占的质量百分数为0.01％～5％，所述涂料助剂所占的质量百分数为1％～10％。The present invention also provides a water-based graphene composite coating prepared by using the above-mentioned water-based graphene composite coating. Specifically, the above-mentioned water-based graphene composite coating is coated on the substrate by scraping, roller coating and other means, and the water-based graphene composite coating is formed after the water in the water-based graphene composite coating is volatilized. The water-based graphene composite coating is composed of water-based resin, graphene, aniline oligomer derivatives and coating additives. The mass percentage of the graphene in the water-based graphene composite coating is 0.01% to 4%. The graphene is uniformly dispersed in the water-based resin by forming π-π bonds with aniline oligomer derivatives. The mass percentage of the water-based resin in the water-based graphene composite coating is 80% to 95%, the mass percentage of the aniline oligomer derivative is 0.01% to 5%, and the coating additives are The mass percentage is 1% to 10%.
本发明提供的水性石墨烯复合涂料中，通过对石墨烯的表面经过苯胺低聚物衍生物的改性修饰，极大提高了石墨烯的分散性和化学稳定性，使得所述石墨烯均匀分散于所述水性树脂中，而石墨烯具有良好的疏水性能，故在应用过程中，可有效抑制水分子在形成的水性石墨烯复合涂层的表面吸附。同时，石墨烯具有二维片层结构，其在涂料中均匀分散，当形成水性石墨烯复合涂层后，石墨烯可层层叠加，形成致密的隔绝层，因而小分子腐蚀介质(水分子、氯离子等)很难通过这层致密的隔绝层，起到了突出的物理隔绝作用。即，所制得的水性石墨烯复合涂层具有良好的耐水渗透性和耐盐雾性以及较强的防护能力，从而水性石墨烯复合涂层具有优异的防腐效果。并且，所述水性石墨烯复合涂料不含有机溶剂，不会带来有机挥发物排放，绿色环保。本发明提供的水性石墨烯复合涂料的制备方法，通过制备工艺创新，可得到具有较好分散性和化学稳定性的水性石墨烯复合涂料，制备工艺简单，成本低廉，利于产业化。In the water-based graphene composite coating provided by the present invention, the dispersibility and chemical stability of graphene are greatly improved by modifying the surface of graphene through aniline oligomer derivatives, so that the graphene is evenly dispersed In the water-based resin, graphene has good hydrophobic properties, so in the application process, it can effectively inhibit the adsorption of water molecules on the surface of the formed water-based graphene composite coating. At the same time, graphene has a two-dimensional sheet structure, which is uniformly dispersed in the coating. After forming a water-based graphene composite coating, graphene can be stacked layer by layer to form a dense insulating layer, so small molecules corrode the medium (water molecules, Chloride ions, etc.) are difficult to pass through this dense insulating layer, which plays a prominent role in physical isolation. That is, the prepared water-based graphene composite coating has good water penetration resistance, salt spray resistance and strong protection ability, so the water-based graphene composite coating has an excellent anti-corrosion effect. Moreover, the water-based graphene composite coating does not contain organic solvents, does not cause organic volatile emissions, and is environmentally friendly. The preparation method of the water-based graphene composite coating provided by the present invention can obtain the water-based graphene composite coating with good dispersibility and chemical stability through the innovation of the preparation process. The preparation process is simple, the cost is low, and it is beneficial to industrialization.
为进一步描述本发明，下面为所述水性石墨烯复合涂料、水性石墨烯复合涂层的制备方法，在不同参数下的具体实施例：For further describing the present invention, below is the preparation method of described water-based graphene composite coating, water-based graphene composite coating, the specific embodiment under different parameters:
实施例1：Example 1:
称取苯胺三聚体1.24g溶于50ml THF中，再加入1.04g丁二酸酐，反应3小时，用石油醚沉淀，得到苯胺三聚体羧基衍生物。Weigh 1.24 g of aniline trimer and dissolve it in 50 ml of THF, then add 1.04 g of succinic anhydride, react for 3 hours, and precipitate with petroleum ether to obtain aniline trimer carboxyl derivative.
称取2.0g苯胺三聚体羧基衍生物和0.33g NaOH固体溶于10mL水中，得到混合物A。向所述混合物A中加入2g石墨烯(购自宁波墨西科技有限公司)，超声分散1小时，得到石墨烯分散液。石墨烯经苯胺三聚体羧基衍生物修饰后在水中的含量达到0.2g/mL。所述石墨烯分散液与未经处理的石墨烯经水分散后的对比效果见图1。所述石墨烯分散液的电子透射电镜照片见图2。由图1和图2可见，石墨烯经过苯胺三聚体羧基衍生物修饰后可均匀分散于水中，所述石墨烯分散液中石墨烯呈片状结构。Weigh 2.0g of aniline trimer carboxyl derivative and 0.33g of NaOH solid and dissolve in 10mL of water to obtain mixture A. 2 g of graphene (purchased from Ningbo Moxi Technology Co., Ltd.) was added to the mixture A, and ultrasonically dispersed for 1 hour to obtain a graphene dispersion. The content of graphene in water reached 0.2g/mL after modified by aniline trimer carboxyl derivative. The comparative effect of the graphene dispersion and untreated graphene after water dispersion is shown in Figure 1. The transmission electron micrograph of the graphene dispersion is shown in Figure 2. It can be seen from Figures 1 and 2 that graphene can be uniformly dispersed in water after being modified by aniline trimer carboxyl derivatives, and graphene in the graphene dispersion liquid has a sheet-like structure.
将所述石墨烯分散液加到45g水性环氧树脂中(购自西北永新集团有限公司)，并混合均匀，得到混合物B。向所述混合物B中依次加入1g流平剂、2g消泡剂、2.67g防沉剂和45g水性聚酰胺固化剂，搅拌均匀，即得到水性石墨烯复合涂料。The graphene dispersion was added to 45g of water-based epoxy resin (purchased from Northwest Yongxin Group Co., Ltd.), and mixed uniformly to obtain mixture B. Add 1g leveling agent, 2g defoamer, 2.67g anti-settling agent and 45g water-based polyamide curing agent to the mixture B in sequence, and stir evenly to obtain the water-based graphene composite coating.
将得到的水性石墨烯复合涂料涂覆于一碳钢基体上，待水挥发后，得到水性石墨烯复合涂层。The obtained water-based graphene composite coating is coated on a carbon steel substrate, and after the water volatilizes, the water-based graphene composite coating is obtained.
为了对比实验效果，还制备了对比例1水性环氧树脂涂层。对比例1中所述水性环氧树脂涂层的制备方法同实施例1，不同的是，没有加入石墨烯分散液。In order to compare the experimental effects, a water-based epoxy resin coating of Comparative Example 1 was also prepared. The preparation method of the waterborne epoxy resin coating described in Comparative Example 1 is the same as in Example 1, except that no graphene dispersion is added.
对实施例1所述水性石墨烯复合涂层以及对比例1的水性环氧树脂涂层进行耐盐雾性能的测试。具体的，将所述水性石墨烯复合涂层与对比例1水性环氧树脂涂层分别置于盐雾试验箱中，500小时后取出，并在室温下干燥后进行拍照(见图3a和图3b)。由图3a和图3b可见，水性环氧树脂涂层的表面有明显的腐蚀坑出现，而水性石墨烯复合涂层的表面没有明显的腐蚀现象发生。The water-based graphene composite coating described in Example 1 and the water-based epoxy resin coating of Comparative Example 1 were tested for salt spray resistance. Specifically, the water-based graphene composite coating and the water-based epoxy resin coating of Comparative Example 1 are respectively placed in a salt spray test chamber, taken out after 500 hours, and taken pictures after drying at room temperature (see Fig. 3a and Fig. 3b). It can be seen from Figure 3a and Figure 3b that there are obvious corrosion pits on the surface of the waterborne epoxy resin coating, but no obvious corrosion phenomenon occurs on the surface of the waterborne graphene composite coating.
对实施例1所述水性石墨烯复合涂层以及对比例1的水性环氧树脂涂层进行防腐性能的测试。具体的，将所述水性石墨烯复合涂层与对比例1的水性环氧树脂涂层分别在3.5wt％NaCl溶液(以模拟海水)中浸泡8天，然后采用上海晨华CHI660E电化学工作站，以开路电位、交流阻抗和动电位极化曲线测试技术分析石墨烯对水性石墨烯复合涂层的作用机理。具体的，以带有鲁金毛细管的饱和甘汞电极为参比电极，铂片电极为对电极，石墨烯涂层/碳钢电极为工作电极，在模拟海水溶液中浸泡使开路电位(OCP)稳定后，在OCP下以正弦波扰动幅值30mV，频率范围为100000Hz～0.01Hz进行电阻抗(EIS)扫描。极化曲线的扫描速度为0.5mV/s，扫描范围为-200～200mVvs.OCP。测试OCP结果见图4，交流阻抗结果见图5a至图5d，极化曲线结果见图6。由图4、图5a至图5d、图6可知，所述水性石墨烯复合涂层比环氧树脂涂层的阻抗大；在浸泡48小时后，水性石墨烯复合涂层的自腐蚀电流密度为130nA·cm-2，而水性环氧树脂涂层的自腐蚀电流密度为38nA·cm-2。这说明经过苯胺低聚物衍生物的改性修饰的石墨烯可均匀分散于水性树脂中，从而得到的水性石墨烯复合涂层的开路电位正移，阻抗增大，自腐蚀电流密度降低，进而大大提高了水性石墨烯复合涂层的防腐性能。The water-based graphene composite coating described in Example 1 and the water-based epoxy resin coating of Comparative Example 1 were tested for anti-corrosion performance. Specifically, soak the water-based graphene composite coating and the water-based epoxy resin coating of Comparative Example 1 in 3.5wt% NaCl solution (to simulate seawater) for 8 days, and then use Shanghai Chenhua CHI660E electrochemical workstation, The mechanism of action of graphene on waterborne graphene composite coatings was analyzed by open circuit potential, AC impedance and potentiodynamic polarization curve testing techniques. Specifically, a saturated calomel electrode with a Lukin capillary is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and a graphene-coated/carbon steel electrode is used as a working electrode. After stabilization, electrical impedance (EIS) scanning was performed under OCP with a sine wave disturbance amplitude of 30 mV and a frequency range of 100000 Hz to 0.01 Hz. The scanning speed of the polarization curve is 0.5mV/s, and the scanning range is -200～200mVvs.OCP. The test OCP results are shown in Figure 4, the AC impedance results are shown in Figures 5a to 5d, and the polarization curve results are shown in Figure 6. From Fig. 4, Fig. 5a to Fig. 5d, Fig. 6, it can be seen that the impedance of the water-based graphene composite coating is larger than that of the epoxy resin coating; after soaking for 48 hours, the self-corrosion current density of the water-based graphene composite coating is 130nA·cm -2 , while the self-corrosion current density of the waterborne epoxy resin coating is 38nA·cm -2 . This shows that the modified graphene modified by aniline oligomer derivatives can be uniformly dispersed in the water-based resin, so that the open circuit potential of the obtained water-based graphene composite coating is positively shifted, the impedance is increased, and the self-corrosion current density is reduced. The anti-corrosion performance of the water-based graphene composite coating is greatly improved.
对实施例1所述水性石墨烯复合涂层以及对比例1水性环氧树脂涂层进行耐水渗透性能的测试。具体的，通过对交流阻抗值进行拟合，以lgQc(Qc为涂层电容)对t1/2作图，得到图7。通过线性拟合，可以分别得到水性环氧树脂涂层和水性石墨烯复合涂层的线性回归方程，进而计算得到水性环氧树脂涂层和水性石墨烯复合涂层的扩散系数分别为5.56×10-9cm2/h和1.61×10-11cm2/h。这说明经过苯胺低聚物衍生物的改性修饰的石墨烯可均匀分散于水性树脂中，从而减缓了水分子在水性石墨烯复合涂层中的扩散速度。The water-based graphene composite coating described in Example 1 and the water-based epoxy resin coating of Comparative Example 1 were tested for water penetration resistance. Specifically, by fitting the AC impedance value, plot lgQ c (Qc is coating capacitance) against t 1/2 to obtain FIG. 7 . Through linear fitting, the linear regression equations of the waterborne epoxy resin coating and the waterborne graphene composite coating can be obtained respectively, and then the diffusion coefficients of the waterborne epoxy resin coating and the waterborne graphene composite coating are calculated to be 5.56×10 -9 cm 2 /h and 1.61×10 -11 cm 2 /h. This shows that the modified graphene modified by aniline oligomer derivatives can be uniformly dispersed in the water-based resin, thereby slowing down the diffusion speed of water molecules in the water-based graphene composite coating.
对实施例1所述水性石墨烯复合涂层以及对比例1水性环氧树脂涂层进行接触角的测试(见图8)。结果为：所述水性石墨烯复合涂层的接触角为95.38°；所述水性环氧树脂涂层的接触角为87.32°。这说明经过苯胺低聚物衍生物的改性修饰的石墨烯可均匀分散于水性树脂中，从而使所述水性环氧树脂涂层的接触角增大，进而增加了所述水性环氧树脂涂层的疏水性能。The water-based graphene composite coating described in Example 1 and the water-based epoxy resin coating of Comparative Example 1 were tested for contact angle (see Figure 8). The result is: the contact angle of the waterborne graphene composite coating is 95.38°; the contact angle of the waterborne epoxy resin coating is 87.32°. This shows that the modified graphene modified by aniline oligomer derivatives can be uniformly dispersed in the water-based resin, thereby increasing the contact angle of the water-based epoxy resin coating, and then increasing the water-based epoxy resin coating. Hydrophobic properties of the layer.
实施例2：Example 2:
称取1.5g实施例所制的苯胺三聚体羧基衍生物和0.33g NaOH固体溶于10mL水中，得到混合物A。向所述混合物A中加入1.5g石墨烯，超声分散1小时，得到石墨烯分散液。石墨烯经苯胺三聚体羧基衍生物修饰后在水中的含量达到0.15g/mL。Weigh 1.5 g of the aniline trimer carboxyl derivative prepared in the example and dissolve 0.33 g of NaOH solid in 10 mL of water to obtain mixture A. Add 1.5 g of graphene to the mixture A, and ultrasonically disperse for 1 hour to obtain a graphene dispersion. The content of graphene in water reached 0.15g/mL after modified by aniline trimer carboxyl derivative.
将所述石墨烯分散液加到92g水性聚氨酯树脂中(购自西北永新集团有限公司)，并混合均匀，得到混合物B。向所述混合物B中依次加入1.67g流平剂、1g消泡剂、2g防沉剂，搅拌均匀，即得到水性石墨烯复合涂料。The graphene dispersion was added to 92g of water-based polyurethane resin (purchased from Northwest Yongxin Group Co., Ltd.), and mixed uniformly to obtain mixture B. Add 1.67g of leveling agent, 1g of defoamer, and 2g of anti-sedimentation agent in sequence to the mixture B, and stir evenly to obtain a water-based graphene composite coating.
实施例3：Example 3:
称取2g实施例1所制的苯胺三聚体羧基衍生物和0.33g NaOH固体溶于10mL水中，得到混合物A。向所述混合物A中加入2g石墨烯，超声分散1小时，得到石墨烯分散液。石墨烯经苯胺三聚体羧基衍生物修饰后在水中的含量达到0.2g/mL。Weigh 2 g of the aniline trimer carboxyl derivative prepared in Example 1 and 0.33 g of NaOH solid and dissolve them in 10 mL of water to obtain mixture A. Add 2 g of graphene to the mixture A, and ultrasonically disperse for 1 hour to obtain a graphene dispersion. The content of graphene in water reached 0.2g/mL after modified by aniline trimer carboxyl derivative.
将所述石墨烯分散液加到91g水性丙烯酸树脂中(购自山东潍坊富乐新材料有限公司)，并混合均匀，得到混合物B。向所述混合物B中依次加入1.67g流平剂、2g消泡剂、2g防沉剂，搅拌均匀，即到水性石墨烯复合涂料。The graphene dispersion was added to 91 g of water-based acrylic resin (purchased from Shandong Weifang Fule New Material Co., Ltd.), and mixed uniformly to obtain a mixture B. Add 1.67g of leveling agent, 2g of defoamer, and 2g of anti-sedimentation agent in sequence to the mixture B, and stir evenly, that is, to the water-based graphene composite coating.
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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