WO2020108552A1 - 一种石墨烯防腐涂料 - Google Patents

一种石墨烯防腐涂料 Download PDF

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Publication number
WO2020108552A1
WO2020108552A1 PCT/CN2019/121478 CN2019121478W WO2020108552A1 WO 2020108552 A1 WO2020108552 A1 WO 2020108552A1 CN 2019121478 W CN2019121478 W CN 2019121478W WO 2020108552 A1 WO2020108552 A1 WO 2020108552A1
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Prior art keywords
graphene
paint
coating
surface treatment
anticorrosive paint
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PCT/CN2019/121478
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English (en)
French (fr)
Inventor
王克
杨扬
陈桥
川崎学
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Toray Advanced Materials Research Laboratories China Co Ltd
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Toray Advanced Materials Research Laboratories China Co Ltd
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Priority to US17/292,745 priority Critical patent/US12024648B2/en
Priority to EP19891395.6A priority patent/EP3889224A4/en
Priority to CN201980075555.3A priority patent/CN113039251B/zh
Priority to JP2021526315A priority patent/JP7424376B2/ja
Publication of WO2020108552A1 publication Critical patent/WO2020108552A1/zh
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/106—Anti-corrosive paints containing metal dust containing Zn
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the invention belongs to the field of chemical coatings, and particularly relates to a high-performance anticorrosive coating with only a low content of modified graphene.
  • Graphene has been discovered in 2004 by Konstantin Novoselov and Andre Geim of the University of Manchester in the UK using micromechanical peeling (Novoselov, KS & Geim, AKet al. Electric field effect in atomically thin carbon films.Science,306,666-669,2004), its excellent mechanical, electrical and thermal properties have attracted the attention of material scientists.
  • Graphene is a planar two-dimensional thin film material composed of carbon atoms with sp 2 hybrid orbital hexagonal honeycomb lattice and only one carbon atom thickness. It is a zero-dimensional fullerene, one-dimensional carbon nanotube and three-dimensional graphite. The basic unit.
  • graphene can not only improve the mechanical properties and anti-corrosion performance of the anti-corrosion coating itself, but also cause pores in the paint film, and form a corrosion circuit with the corrosive medium and the base metal plate to accelerate corrosion.
  • high-quality graphene itself is expensive, how to control the amount of graphene added, improve the dispersibility of graphene, and obtain high-performance graphene anticorrosive coatings is a difficult point at this stage.
  • Patent Document 1 discloses a graphene anti-corrosion coating.
  • graphene is added to the traditional zinc-rich coating to utilize the high strength and high barrier of graphene Characteristics such as improved adhesion, hardness and barrier properties of the paint, and extended the salt spray resistance time of the paint.
  • this method does not perform surface treatment on graphene. Due to its own characteristics, graphene is prone to agglomeration and is difficult to disperse evenly in the epoxy resin as the substrate. In this case, the addition of graphene may form agglomeration in the coating. Particles, causing void defects in the paint, affect its performance.
  • Patent Document 2 proposes a scheme for treating graphene with TEMPO catalytic oxidation and using the graphene as an anticorrosive coating.
  • the modified graphene has a good dispersion effect in the coating, and the anticorrosive time of the coating has Improve to a certain extent.
  • the content of graphene used in its examples is relatively high, and the amount of graphene added in several groups of examples even exceeds 1 wt%.
  • the price of graphene on the market is currently high. Such an amount of addition will significantly increase the anticorrosive coating. cost.
  • Patent Literature 1 CN 105623471A
  • Patent Literature 2 CN 107739566A
  • the present inventors have found through in-depth research that the graphene is modified by using a surface treatment agent, and the modified graphene is added to the anticorrosive coating using epoxy resin as a base material at a low content. It can introduce the chemical bonding force between graphene and epoxy resin, so as to improve the dispersion of graphene in anticorrosive coatings, enhance the density of the coating, and obtain low cost and barrier properties, electrical conductivity, mechanical strength, anticorrosion and other aspects Graphene anticorrosive coating with excellent performance.
  • the present invention specifically provides a graphene anticorrosive coating, which includes epoxy resin and graphene, the graphene is graphene modified by a surface treatment agent, and the amount of graphene added is only 0.01- 0.2wt%.
  • the so-called total solid paint mass is the mass of the coating film after the coating has dried.
  • the epoxy resin used as the base material in the anticorrosive paint of the present invention is not particularly limited as long as it is an epoxy resin commonly used in anticorrosive paint.
  • One or more of epoxy resins E-51, E-44, E-20, E-12, and E-06 are preferred.
  • the graphene anticorrosive coating of the present invention includes the above epoxy resin and modified graphene.
  • the graphene is graphene modified by a surface treatment agent, and the content of graphene is only 0.01-0.2 wt% relative to the total mass of the coating solid. If the amount of graphene added is less than 0.01 wt%, the content is too low to be sufficient to exert the barrier effect of graphene, nor can it form a conductive path in the coating system to increase the utilization rate of zinc powder. If the amount of graphene added exceeds 0.2 wt%, too high content will make graphene easy to agglomerate, locally concentrate in the coating system, and form pores, which will lead to a decrease in the overall performance of the coating.
  • the amount of graphene added is preferably 0.02 wt% or more, and more preferably 0.03 wt% or more. Meanwhile, the amount of graphene added is preferably 0.1 wt% or less, and more preferably 0.05 wt% or less.
  • Graphene used in the present invention is not particularly limited as long as its sheet diameter size in terms of D50 is within a range that does not impair the effects of the present invention, and is preferably 30 ⁇ m or less.
  • the thickness of the graphene used in the present invention is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 2-12 nm.
  • the thickness of graphene can be measured by an atomic force microscope (AFM), using a J scanner Si 3 N 4 needle to scan in a contact mode at a frequency of 1.0-2.4 Hz.
  • Graphene test pretreatment method using N-methylpyrrolidone (NMP) as a solvent, graphene is dispersed therein, formulated into a 0.002 wt% dispersion liquid, dropped on mica flakes, dried and subjected to AFM measurement.
  • NMP N-methylpyrrolidone
  • the graphene used in the present invention is not particularly limited as long as its sheet diameter to size ratio represented by D90/D50 is within a range that does not impair the effects of the present invention, and is preferably 2 or less.
  • the graphene size D50 and D90 of graphene are measured by the volume reference mode of the particle size distribution test.
  • the above-mentioned modified graphene is obtained by reducing the graphite oxide after treatment with a surface treatment agent.
  • the surface of the modified graphene contains functional groups that can react with the epoxy groups in the epoxy resin. After the reaction, a carbon-nitrogen chemical bond is formed between the graphene and the epoxy resin, which improves the binding force between the graphene and the resin.
  • the characteristic peak of the carbon-nitrogen chemical bond structure can be observed in the infrared spectrum in the range of 1000-1300 cm -1 .
  • a surface treatment agent containing a nitrogen element in order to obtain better effects, it is preferable to use a surface treatment agent containing a nitrogen element.
  • the surface treatment agent may be one or more of arylaminos, pyrazolones, and catechols.
  • the arylamino surface treatment agent can be exemplified by o-chloroaniline, p-chloroaniline, o-toluidine, acetanilide, 2-aminobenzylamine, p-methoxyaniline, 2-nitroaniline, 2-phenethylamine
  • o-chloroaniline p-chloroaniline
  • o-toluidine acetanilide
  • 2-aminobenzylamine p-methoxyaniline
  • 2-nitroaniline 2-phenethylamine
  • hydrochloride 4,4'-diaminodiphenylmethane
  • 2-aminobenzylamine, 2-phenethylamine hydrochloride and 4,4'-diaminodiphenylmethane preferably 2-aminobenzylamine, 2-phenethylamine hydrochloride and 4,4'-diaminodiphenylmethane.
  • the pyrazolone surface treatment agent can be exemplified by 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, bispyrazolone, picric acid, 1-phenyl- One or more of 3-methyl-5-pyrazolone, preferably bispyrazolone.
  • the catechol surface treatment agent can be exemplified by catechol borane, catechol violet, 3,5-di-tert-butyl-1,2-dihydroxybenzene, 4-nitrocatechol, hydrochloric acid
  • catechol borane catechol borane
  • catechol violet 3,5-di-tert-butyl-1,2-dihydroxybenzene
  • 4-nitrocatechol hydrochloric acid
  • dopamine preferably dopamine hydrochloride.
  • the method for modifying the surface of graphene can be carried out by using a high-temperature reflux reaction, a normal temperature and normal pressure blending reaction, and the like.
  • a thermal reduction method or a method using hydrazine hydrate, dithionite and the like as a reducing agent can be used for reduction, and preferably dithionite is used as the reduction Method of reduction.
  • dithionite is used as the reduction Method of reduction.
  • the modified graphene of the present invention preferably has an oxygen element/carbon element atomic ratio of 0.05-0.4, and further preferably has a lower limit of 0.1 and a preferred upper limit of 0.25.
  • the O/C ratio is too low, the physical properties tend to be close to graphene, and the dispersibility is poor; when the O/C ratio is too high, the resistivity of the modified graphene tends to be too high, and the zinc powder cannot be fully utilized.
  • the salt spray resistance time cannot achieve particularly excellent results.
  • the nitrogen element/carbon element atomic ratio in the modified graphene of the present invention is preferably 0.01-0.05, further preferably, the lower limit is 0.015, and the upper limit is preferably Is 0.03.
  • the N/C ratio is too low, the functional groups that tend to graft cannot achieve the expected dispersion effect; when the N/C ratio is too high, too many functional groups are grafted, which tends to cause crosslinking between modified graphenes, Dispersion decreased.
  • the O/C ratio and N/C ratio can be measured by X-ray photoelectron spectroscopy (XPS).
  • the method of preparing graphene may be as described below, but is not limited thereto.
  • the amount of surface treatment agent should be controlled between 0.01-0.5 times the mass of graphite oxide.
  • certain functional groups are grown on the surface of the graphene to produce sufficient bonding and dispersion effects.
  • the amount of the surface treatment agent must be more than 0.01 times of the treated graphite oxide. If the surface treatment agent is used excessively, it will lead to excessive grafting of functional groups, which will make the graphene after surface treatment have a tendency to crosslink, and self-aggregation will occur, affecting the dispersion effect.
  • the method for preparing the graphene anticorrosive coating may be a slurry directly added with modified graphene, or a modified graphene powder and a corresponding dispersant.
  • a method for preparing the above graphene anticorrosive coating it is preferable to directly add the modified graphene slurry.
  • a curing agent in addition to the above epoxy resin and modified graphene, a curing agent may be contained.
  • the curing agent is not particularly limited as long as it is a curing agent commonly used in anticorrosive coatings. Specifically, one or more of amine curing agents, acid anhydride curing agents, resin curing agents, and imidazole curing agents can be used.
  • the solvent used for the coating may be one or more of toluene, xylene, trimethylbenzene, n-butanol, and water.
  • the graphene anticorrosive paint of the present invention may further contain other additives.
  • the other auxiliary agents may be exemplified by dispersants, defoamers, wetting agents, anti-flash rust agents, thickeners, thixotropic agents, and the like, and these auxiliary agents may be used alone or in combination of two or more.
  • the invention overcomes the problem that graphene itself easily agglomerates due to the high specific surface.
  • a surface treatment agent By modifying the graphene with a surface treatment agent, it has good dispersibility in the substrate and avoids the agglomeration of graphene, thereby Achieve high barrier effect.
  • the improvement of the barrier performance can be directly reflected in the oxygen transmission rate of the paint film.
  • the better the barrier performance the lower the oxygen transmission rate of the paint film.
  • the oxygen transmission rate of the graphene paint film of the present invention can reach 0.35g /m 2 ⁇ h or less.
  • the film thickness of the graphene paint in the present invention refers to the thickness of the paint after the paint is sprayed on the substrate and dried.
  • gloss test is used as a characterization method, which indirectly reflects the dispersibility of graphene in the paint. If graphene has good dispersibility in it, it will be very low because the graphene sheets are distributed evenly and light reflects on the paint with little reflection.
  • the gloss of the graphene paint film of the present invention can reach 3 degrees or less.
  • the present invention proposes a graphene anticorrosive coating.
  • a chemical bond force is introduced between graphene and epoxy resin, and the modification force is improved by using the bonding force between modified graphene and epoxy resin.
  • high-performance graphene anticorrosive coatings can be obtained through simple steps and low cost methods, and the application prospect is more clear.
  • the anti-corrosion coating can be widely used in many occasions such as ships, containers, oil tanks and so on.
  • the graphene coating prepared by this method has low cost and excellent conductivity, and can also be applied to anti-static and other fields.
  • the base material of the coating is one or more of epoxy resins E-51, E-44, E-20, E-12, and E-06.
  • the method for preparing graphene may be as follows, but it is not limited thereto.
  • the modified graphene used in the present invention can be obtained by surface-treating the graphene obtained by the chemical reduction method.
  • the commonly used graphene is mainly divided into three categories: CVD graphene, physical exfoliation graphene, chemical exfoliation graphene.
  • CVD graphene can be a single layer, but the surface has no functional groups, it is difficult to perform surface treatment, and the dispersibility is poor. At the same time, it is expensive and not suitable for large-scale applications.
  • the physical peeling method is easy to prepare graphene, but the thickness is difficult to make thin, and the properties are close to natural graphite.
  • the surface of the chemically peeled graphene contains functional groups, which can be surface-treated as required, or it can be made very thin, so this experiment chooses to use the chemically peeled graphene.
  • the raw graphite oxide is made from natural graphite by Hummers method. Natural graphite was purchased from Qingdao Haida Graphite Co., Ltd. Model LC-180. Finely adjust the thickness of graphite oxide by controlling the amount of oxidant added in the oxidation process; adjust the diameter and size distribution of graphite oxide through the micronization treatment at the late stage of the reaction. Micronization here refers to ultrasound and various treatments with micronization means. The obtained graphite oxide was treated with a surface treatment agent.
  • modified graphite oxide was obtained.
  • the modified graphite oxide is reduced by using a reducing agent to obtain modified graphene (slurry, concentration 2%). The reduction is performed at normal temperature and pressure, and the reaction time is 1.5 hours.
  • Table 1 List of modified graphene (slurry, concentration 2%)
  • Test method After zeroing the thickness gauge, place the dried paint film sample under the instrument probe for measurement. Select 10 different areas on the paint film sample and take the average value.
  • Test method The dried paint is tested using a Fourier transform infrared spectrometer, and the presence or absence of functional groups and chemical bonds is determined according to the characteristic absorption peak in the infrared spectrum.
  • Test method apply paint to the steel plate, and after the paint film is dried, fully open the bending tester, select shaft rods of different diameters, insert the sample plate, so that the paint surface faces the seat plate. Close the instrument at a steady speed within 1-2s to bend the test plate 180° around the axis. The flexibility of the paint film is indicated by the minimum shaft diameter that does not cause the paint film to crack.
  • Test method Place the dried paint film under the impact tester, drop it on the test board with a weight of fixed mass, and indicate the impact resistance of the paint film by the maximum height that does not cause damage to the paint film.
  • Resistivity Tester (DESCO EMI19787 United States)
  • Test method coat the coating on an insulator material (such as PET), and after the coating is dried into a paint film, use a resistivity tester to test the surface resistance of the coating.
  • an insulator material such as PET
  • the gloss measurement of the coating is based on the surface reflection of light relative to the reference standard of polished glass. The amount of light reflected on the surface depends on the angle of incidence and the nature of the surface. Glossiness is classified as matte, semi- or high-gloss. In order to determine the most suitable measurement angle, start the measurement with a gloss meter set at an incident angle of 90°. If the test result is between 10-70, the coating is called “semi-gloss” and should be measured using a 60° angle. If the result is less than 10, the product is "low gloss” and should be measured at an angle of 85°. If it is greater than 70, the product is called “high gloss” and should be measured using an angle of 20°.
  • Test method The paint is made into a film, and the gas permeability test is performed on the gas permeability tester using the differential pressure method according to JIS K7126-A standard.
  • the test coating film is fixed in the middle of the test chamber to divide the chamber into an upper chamber and a lower chamber with a constant pressure difference therebetween. Gas molecules will penetrate the sample from the high-pressure chamber into the low-pressure chamber, then monitor the pressure change of the low-pressure chamber, and the gas transmission rate is calculated by the system.
  • Salt spray resistance Neutral salt spray test chamber (HAIDA HD-E808-120 China)
  • Test method According to the national standard GB/T1771-2007, apply the paint to the steel plate after sandblasting treatment. After the paint is dried, the surface is scratched and tested in a neutral salt spray test box. The time when the paint blisters, falls off or scratches rust marks exceeds 2mm indicates the salt spray resistance of the paint.
  • the homogenizer was used for dispersion for 10 minutes to obtain graphene anticorrosive coating.
  • Example 1 Except that no modified graphene was added, the same operation as in Example 1 was performed to obtain a graphene anticorrosive paint as shown in Table 2-1.
  • Example 1 Except that the modified graphene was changed to graphene without surface treatment, the same operation as in Example 1 was performed to obtain a graphene anticorrosive paint as shown in Table 2-1.
  • Example 1 Change the modified graphene content of the coating in Example 1 as shown in Table 2-1 and Table 2-2, and perform the same operation as in Example 1 to obtain the graphene shown in Table 2-1 and Table 2-2 Anticorrosive paint.
  • Example 1 The modified graphene in Example 1 is changed as shown in Table 3-1, Table 3-2, and Table 3-3, and the same operations as in Example 1 are performed to obtain Table 3-1, Table 3-2, and The graphene anticorrosive coating shown in Table 3-3.
  • Example 1 The modified graphene of Example 1 was changed as shown in Table 4, and the same operation as Example 1 was performed to obtain the graphene anticorrosive paint shown in Table 4.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Abstract

一种石墨烯防腐涂料，包含环氧树脂和经表面改性的石墨烯，石墨烯添加量为涂料固体总质量的0.01-0.2wt%，通过对石墨烯进行表面处理，提高石墨烯在涂料中的分散性，增强涂料的致密性。

Description

一种石墨烯防腐涂料 技术领域
本发明属于化工涂料领域，具体涉及一种仅具有低含量改性石墨烯的高性能的防腐涂料。
背景技术
现如今腐蚀生锈对人们的生活产生大量的不便，造成大量的能源和资源的损失浪费，每年给各国带来巨额的经济损失。据美国、日本、加拿大等国公布的报告，每年仅因腐蚀所造成的直接经济损失就大约占了国民经济总产值的1％-4％，腐蚀生锈的钢铁约占年产量的20％，而在中国，每年金属腐蚀造成的经济损失约占国民生产总值的4％，腐蚀损失甚至超过了火灾、风灾和地震造成损失的总和。如此惊人的损耗，使得人们对于高性能防腐涂料的迫切需求日益增加。
石墨烯自2004年由英国曼彻斯特大学的康斯坦丁·诺沃肖洛夫和安德烈·盖姆在实验室用微机械剥离法发现以来(Novoselov,K.S.&Geim,A.K.et al.Electric field effect in atomically thin carbon films.Science,306,666-669,2004)，其优异的力学、电学、热学性能受到材料科学家的关注。石墨烯是一种由碳原子以sp 2杂化轨道组成六角形呈蜂巢晶格、只有一个碳原子厚度的平面二维薄膜材料，是构建零维富勒烯、一维碳纳米管和三维石墨的基础单元。石墨烯是迄今为止最薄的纳米材料，因其优异的力学性能(拉伸强度130GPa、杨氏模量高达1TPa)和突出的导电性能(电导率10S·m -1)、超高径厚比等，在涂料等领域的应用正逐渐引起大众的关注。但将石墨烯作为填料加入到防腐涂料中时，由于其高比表面积和不溶于水、不溶于油的特性，很难实现良好的分散。如果分散效果不好，形成团聚，石墨烯不仅不能改善防腐涂料本身的机械性能和防腐性能，反而会使得涂料的漆膜产生孔隙，且与腐蚀介质、 基材金属板形成腐蚀电路，加速腐蚀。另外，高品质石墨烯本身价格昂贵，如何控制石墨烯的添加量，提高石墨烯地分散性，获得高性能石墨烯防腐涂料是现阶段的一个难点。
专利文献1公开了一种石墨烯防腐涂料，其为了改变传统方法制备的涂料耐盐雾时间过低的缺点，向传统的富锌涂料中添加石墨烯，利用石墨烯自身的高强度、高阻隔性等特点提高了涂料的附着力、硬度和阻隔性能，延长了涂料的耐盐雾时间。但该方法并没有对石墨烯进行表面处理，石墨烯由于自身特性极易发生团聚且在作为基材的环氧树脂中难以分散均匀，如此情况下，石墨烯的添加可能会在涂料中形成团聚颗粒，造成涂料的空洞缺陷，影响其本身的性能。
专利文献2中，提出了一种用TEMPO催化氧化处理石墨烯，并将该石墨烯用于防腐涂料的方案，改性后的石墨烯在涂料中有良好的分散效果，涂料的防腐时间有了一定程度的提高。但其实施例中使用的石墨烯含量偏高，有几组实施例中石墨烯的添加量甚至超过了1wt％，目前市场上石墨烯的价格偏高，如此的添加量会明显增加防腐涂料的成本。
现有技术文献
专利文献
专利文献1：CN 105623471A
专利文献2：CN 107739566A
发明内容
本发明人为了解决上述问题，经过深入研究发现，通过采用表面处理剂对石墨烯进行改性，并将上述改性的石墨烯以低含量添加至以环氧树脂作为基材的防腐涂料中，能够在石墨烯和环氧树脂之间引入化学键结合力，从而提高石墨烯在防腐涂料中的分散性，增强涂料的致密性，得到低成本且阻隔性、导电性、机械强度、防腐性等方面性能优异的石墨烯防腐涂料。即，本 发明具体提供一种石墨烯防腐涂料，其包括环氧树脂和石墨烯，所述石墨烯是经表面处理剂改性的石墨烯，石墨烯添加量仅仅为涂料固体总质量的0.01-0.2wt％。所谓涂料固体总质量为涂料干燥后涂膜的质量。
<环氧树脂>
本发明的防腐涂料中作为基材采用的环氧树脂只要是在防腐涂料中常用的环氧树脂即可，没有特别限定。优选环氧树脂E-51、E-44、E-20、E-12、E-06中的一种或多种。
<改性石墨烯>
本发明的石墨烯防腐涂料中，包括上述环氧树脂和改性石墨烯。所述石墨烯是经过表面处理剂改性的石墨烯，相对于所述涂料固体总质量，石墨烯的含量仅仅为0.01-0.2wt％。如果石墨烯的添加量小于0.01wt％，含量过低，不足以发挥石墨烯的阻隔效果，也不能在涂料体系中形成提高锌粉使用率的导电通路。如果石墨烯的添加量超过0.2wt％，含量过高会使得石墨烯容易团聚，在涂料体系中局部集中，形成孔隙从而导致涂料整体性能下降。
石墨烯的添加量优选为0.02wt％以上，进一步优选为0.03wt％以上。同时，石墨烯的添加量优选为0.1wt％以下，进一步优选为0.05wt％以下。
本发明中使用的石墨烯，以D50计的其片径尺寸只要在不损害本发明的效果的范围内则没有特别限定，优选为30μm以下。
本发明中使用的石墨烯，其厚度的范围只要在不损害本发明的效果的范围内则没有特别限定，优选为2-12nm。石墨烯的厚度可由原子力显微镜(AFM)进行测量，使用J scanner Si 3N 4针头以1.0-2.4Hz的频率在接触模式下扫描。石墨烯测试前处理方法：使用N-甲基吡咯烷酮(NMP)作为溶剂，将石墨烯分散其中，配制成0.002wt％的分散液，滴在云母片上，干燥后进行AFM测定。
本发明中使用的石墨烯，以D90/D50表示的其片径尺寸比只要在不损害本发明的效果的范围内则没有特别限定，优选为2以下。石墨烯的片径尺寸D50和D90通过粒度分布测试的体积基准模式进行测量。
本发明中，上述改性石墨烯是由氧化石墨经表面处理剂处理后再进行还原得到的。改性石墨烯表面含有与环氧树脂中的环氧基团可反应的官能团，反应后在石墨烯与环氧树脂间产生碳氮化学键结合，提高了石墨烯和树脂之间的结合力。在红外谱图中1000-1300cm -1范围内可以观察到该碳氮化学键结构的特征峰。
本发明中，为了能得到更好的效果，优选使用含氮元素的表面处理剂。
具体地，作为所述表面处理剂，可列举为芳基氨基类、吡唑啉酮类、儿茶酚类中的一种或多种。
所述芳基氨基类表面处理剂可列举为邻氯苯胺、对氯苯胺、邻甲苯胺、乙酰苯胺、2-氨基苄胺、对甲氧基苯胺、2-硝基苯胺、2-苯乙胺盐酸盐、4,4'-二氨基二苯甲烷中的一种或多种，优选2-氨基苄胺、2-苯乙胺盐酸盐和4,4'-二氨基二苯甲烷。
所述吡唑啉酮类表面处理剂可列举为1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮、双吡唑酮、苦酮酸、1-苯基-3-甲基-5-吡唑啉酮中的一种或多种，优选双吡唑酮。
所述儿茶酚类表面处理剂可列举为儿茶酚硼烷、邻苯二酚紫、3,5-二叔丁基-1,2-苯二酚、4-硝基儿茶酚、盐酸多巴胺中的一种或多种，优选盐酸多巴胺。
本发明中，石墨烯表面改性的方法可以采用高温回流反应、常温常压共混反应等进行。
进一步地，作为表面处理剂处理后的氧化石墨的还原，可以采用热还原的方法或者以水合肼、连二亚硫酸盐等作为还原剂的方法等进行还原，优选采用连二亚硫酸盐作为还原剂的方法还原。其中，为防止石墨烯片层卷曲、团聚或脱落，优选在0-50℃的低温条件使得上述还原反应温和进行。
从操作性、成本、分散性、导电性的方面考虑，优选本发明的改性石墨烯中氧元素/碳元素原子比为0.05-0.4，进一步，优选下限为0.1，优选上限为 0.25。O/C比过低时，倾向于物理性能与石墨烯接近，分散性较差；O/C比过高时，倾向于改性石墨烯的电阻率过高，锌粉无法充分利用，涂料的耐盐雾时间无法达到特别优秀的效果。
从表面处理剂的接枝率、改性石墨烯的分散性的方面考虑，优选本发明的改性石墨烯中氮元素/碳元素原子比为0.01-0.05，进一步，优选下限为0.015，优选上限为0.03。N/C比过低时，倾向于接枝的官能团达不到预计分散效果；N/C比过高时，接枝过多的官能团，倾向于使改性石墨烯之间产生交联，导致分散性下降。O/C比和N/C比可通过X射线光电子能谱分析(XPS)进行测量。
本发明中，制备石墨烯的方法可以是以下所述这样，但不限于此。制备上述改性石墨烯时，表面处理剂的用量需控制在氧化石墨质量的0.01-0.5倍之间。为了保证表面处理剂能够发挥效果，在石墨烯表面生长上一定的官能团，产生足够的键合作用及分散效果，表面处理剂的用量需在处理的氧化石墨的0.01倍以上。如果表面处理剂使用过量，会导致接枝过量的官能团，会使得表面处理后的石墨烯有交联的倾向，发生自团聚，影响分散效果。同时过量的官能团会提高石墨烯的电阻从而影响导电性，会影响到锌粉的利用率。从经济角度和后处理的难易度上讲，也不宜使用过多的表面处理剂。经过实验检讨，最终将表面处理剂的用量限定在氧化石墨质量的0.5倍以内。表面处理剂用量最终可以通过X射线光电子能谱分析(XPS)测得的原子比进行表征。
本发明中，制备石墨烯防腐涂料的方法可以为直接加入改性石墨烯的浆料，或者加入改性石墨烯粉体和相应的分散剂。作为上述石墨烯防腐涂料的制备方法，优选直接加入改性石墨烯浆料。其原因是与粉体相比，浆料中的改性石墨烯已经处于良好分散的状态，与涂料中环氧树脂的相容性非常好，因此这种添加方法相较于粉体添加更有利于改性石墨烯在环氧树脂基材中的分散，不容易出现粉体添加时环氧树脂基材中可能出现的团聚现象，同时避 免粉体添加时引入过多的分散剂而破坏涂料体系的整体性能。因此添加石墨烯浆料更能得到高性能的石墨烯防腐涂料。
<固化剂>
本发明中，除了上述环氧树脂和改性石墨烯之外，还可以含有固化剂。所述固化剂没有特别限定，只要是防腐涂料中常用的固化剂即可。具体可以选用胺类固化剂、酸酐类固化剂、树脂类固化剂、咪唑类固化剂中的一种或者多种。
<溶剂>
本发明中，作为涂料所使用的溶剂，可列举为甲苯、二甲苯、三甲苯、正丁醇、水中的一种或多种。
<其他助剂>
本发明的石墨烯防腐涂料中，还可以含有其它助剂。所述其它助剂可列举为分散剂、消泡剂、润湿剂、防闪锈剂、增稠剂、触变剂等，且这些助剂可以单独使用或组合2种以上使用。
本发明克服了石墨烯自身由于高比表面从而很容易发生团聚的问题，通过采用表面处理剂对石墨烯进行改性使其在基材中具有良好的分散性，避免了石墨烯的团聚，从而实现高阻隔的效果。阻隔性能的提高可以直接反映在涂料漆膜的氧气透过率上，阻隔性能越好，漆膜的氧气透过率越低，本发明的石墨烯涂料漆膜的氧气透过率可以达到0.35g/m 2·h以下。本发明中的石墨烯涂料的膜厚是指将涂料喷涂在基板上干燥后的涂料的厚度。本发明中为了表征石墨烯在涂料中的分散效果，采用光泽度测试作为表征方法，间接反映石墨烯在涂料中的分散性。若石墨烯在其中分散性良好的话，会因为石墨烯片层分布得很均匀、光线照射在涂料上反射很少，因此光泽度会非常低。本发明的石墨烯涂料漆膜的光泽度可以达到3度以下。
本发明提出了一种石墨烯防腐涂料，通过对石墨烯进行表面处理，在石墨烯与环氧树脂之间引入化学键作用力，利用改性石墨烯与环氧树脂之间的 结合力提高改性石墨烯在作为涂料基材的环氧树脂中的分散性。根据本发明，可通过简单步骤、低成本的方法得到高性能的石墨烯防腐涂料，应用前景更为明确。该防腐涂料可广泛应用于船舶、集装箱、油罐等众多场合。通过该方法制备得到的石墨烯涂料成本低廉，导电性优越，也可以应用于防静电等领域。
具体实施方式
以下通过实施例对本发明进行进一步说明，但这些实施例仅在于举例说明，不对本发明的范围做出界定。
1.原料
(1)环氧树脂
涂料的基材为环氧树脂E-51、E-44、E-20、E-12、E-06中的一种或多种。
(2)改性石墨烯
本发明中，制备石墨烯的方法可以是下述这样，但不仅限于此。本发明使用的改性石墨烯可通过对化学还原法得到的石墨烯进行表面处理得到。通常使用的石墨烯主要分为3类：CVD法石墨烯、物理剥离法石墨烯、化学剥离法石墨烯。其中CVD石墨烯可以做到单层，但是表面没有官能团，很难进行表面处理，分散性差，同时价格昂贵，不适合大规模应用。物理剥离法石墨烯制备方法简便，但是厚度很难做薄，性质接近于天然石墨。化学剥离石墨烯表面含有官能团，可以按需求进行表面处理，也可以做到很薄，因此本实验选择使用化学剥离法石墨烯。其中原料的氧化石墨由天然石墨经Hummers法自制得到。天然石墨购买自青岛海达石墨有限公司，型号为LC-180。通过控制氧化过程中氧化剂的添加量微调氧化石墨的厚度；通过反应后期的微细化处理调整氧化石墨的片径尺寸和尺寸分布，这里的微细化处理指超声以及具有微细化处理功能的多种处理手段。将得到的氧化石墨使用表面处理剂进行处理，表面处理在常温常压下进行，反应3小时后，得到改 性氧化石墨。使用还原剂对改性氧化石墨进行还原得到改性石墨烯(浆料，浓度2％)，还原在常温常压下进行，反应时间1.5小时。
利用不同的表面处理剂和还原剂得到不同参数的改性石墨烯，性能如下表1所示。其中D50/D90由粒度分布测试的体积基准模式进行测量，厚度经原子力显微镜(AFM)进行测量，O/C比、N/C比经X射线光电子能谱分析(XPS)测量。
表1：改性石墨烯列表(浆料，浓度2％)
Figure PCTCN2019121478-appb-000001
Figure PCTCN2019121478-appb-000002
2-氨基苄胺：国药集团化学试剂有限公司，直接使用。
双吡唑酮：国药集团化学试剂有限公司，直接使用。
盐酸多巴胺：国药集团化学试剂有限公司，直接使用。
2-苯乙胺盐酸盐：国药集团化学试剂有限公司，直接使用。
4,4'-二氨基二苯甲烷：上海阿拉丁试剂有限公司，直接使用。
双(3-甲基-1-苯基-5-吡唑啉酮)：上海阿拉丁试剂有限公司，直接使用。
3-(2,3-环氧丙氧)丙基三甲氧基硅烷(KH-560)：上海阿拉丁试剂有限公司，直接使用。
(3)还原剂
连二亚硫酸钠：国药集团化学试剂有限公司，直接使用。
水合肼：国药集团化学试剂有限公司，直接使用。
氢碘酸：国药集团化学试剂有限公司，直接使用。
(4)其他助剂：膨润土、重晶石、氧化铁红、锌粉，国药集团化学试剂有限公司，直接使用；分散剂(硅酸盐类分散剂：DISPERBYK-103)、消泡剂(有机硅类消泡剂：BYK-015)、润湿剂(聚酯改性有机硅润湿剂：DISPERBYK-142)、防闪锈剂(有机锌螯合物类防闪锈剂：FA-179)，均购自昆山玳权精细化工科技有限公司，直接使用。
2.本发明的实施例和比较例中相关性能的测定方法：
A.石墨烯防腐涂料中的石墨烯含量：通过下式计算得到。
Figure PCTCN2019121478-appb-000003
B.石墨烯涂层厚度：漆膜测厚仪(TIME TT220中国)
测试方法：将测厚仪归零后，把干燥后漆膜样品置于仪器探头下进行测定即可。在漆膜样品上选择不同区域测定10次，取其平均值。
C.键能结合：红外光谱分析(SHIMADZU AIM-9000日本)
测试方法：将干燥后的涂料使用傅里叶变换红外光谱仪进行测试，根据红外谱图中的特征吸收峰判断是否有官能团、化学键的产生或消失。
D.柔韧性：弯曲试验仪(LEPU FA-YZQ-II中国)
测试方法：将涂料涂敷在钢板上，漆膜干燥后，将弯曲试验仪完全打开，选取不同直径的轴棒，插入样板，使涂料面朝座板。在1-2s内以平稳的速度合上仪器，使试板绕轴弯曲180°。通过不引起漆膜开裂的最小轴棒直径表示漆膜的柔韧性。
E.耐冲击性：冲击试验器(DALAI QCJ-120中国)
测试方法：将干燥的漆膜放置于冲击试验器下方，以固定质量的重锤落于试板上，通过不引起漆膜破坏的最大高度表示漆膜的耐冲击性。
F.电阻率：电阻率测试仪(DESCO EMI19787美国)
测试方法：将涂料涂覆在绝缘体材料(如PET)上，待涂料干燥成漆膜后，用电阻率测试仪测试涂料的表面电阻值。
G.光泽度：光泽仪(SPEEDRE SDR600中国)
测试方法：涂料的光泽度测量是基于光的表面反射相对于抛光玻璃参考标准，在表面上反射的光量依赖于入射角度和表面的性质。光泽度被归类为无光泽，半或高光泽。为了确定最合适的测量角度，用设定在入射90°角光泽度仪开始测量。如果测试结果是在10-70，该涂层被称为“半光泽度”，并应使用60°角进行测量。如果结果是小于10，该产品是“低光泽度”，并应使用85°的角度进行测量。如果大于70，该产品被称为“高光泽度”，并应使用20°的角度进行测量。
H.氧气透过率：气体渗透测试仪(Labthink CLASSIC 216中国)
测试方法：将涂料制成膜状，根据JIS K7126-A标准，使用压差法在气体渗透测试仪上进行气体渗透性测试。将测试涂膜固定在测试室的中间，以将室分隔成上室和下室，其间具有恒定压差。气体分子将从高压室穿透样品进入低压室，然后监测低压室的压力变化，并由系统计算气体传输速率。
I.耐盐雾性：中性盐雾试验箱(HAIDA HD-E808-120中国)
测试方法：按照国标GB/T 1771-2007将涂料涂在经过喷砂处理的钢板上面，涂料干燥后在表面进行划痕，在中性盐雾试验箱中不间断测试。用涂料起泡、脱落或划痕锈痕超过2mm的时间表示涂料的耐盐雾性。
实施例1
称取13g的固化剂，往其中加入20g水、0.1g润湿剂和0.2g分散剂，开始搅拌；
搅拌20min后，往体系里加入0.1g分散剂、0.1g消泡剂、0.3g膨润土，继续搅拌15min；
加入7g滑石粉，搅拌5min后加入4g重晶石、7g氧化铁红和0.2g消泡剂，搅拌15min。
加入0.2g防闪锈剂，搅拌分散15min。
加入0.03g改性石墨烯，分散20min；
加入215.2g锌粉、40g水，保证体系的润湿；
加入60g环氧树脂，分散15min。
为保证分散性，用均质机进行分散10min，得到石墨烯防腐涂料。
用200目过滤网对体系进行过滤后，将完成的涂料喷涂在喷砂钢板上，测试涂料的各方面性能，具体性能如表2-1所示。
对比例1
除不添加改性石墨烯以外，与实施例1进行相同的操作得到如表2-1所示的石墨烯防腐涂料。
对比例2
除将改性石墨烯变更为未经表面处理的石墨烯以外，与实施例1进行相同的操作得到如表2-1所示的石墨烯防腐涂料。
实施例2-6，对比例3-5
如表2-1和表2-2所示改变实施例1中涂料的改性石墨烯含量，与实施例1进行相同的操作得到如表2-1和表2-2中所示的石墨烯防腐涂料。
实施例7-24
将实施例1中的改性石墨烯如表3-1、表3-2和表3-3所示变更外，进行与实施例1相同的操作得到如表3-1、表3-2和表3-3所示的石墨烯防腐涂料。
实施例25-30
将实施例1的改性石墨烯如表4所示变更外，进行与实施例1相同的操作，得到如表4所示的石墨烯防腐涂料。
表2-1
Figure PCTCN2019121478-appb-000004
Figure PCTCN2019121478-appb-000005
表2-2
Figure PCTCN2019121478-appb-000006
Figure PCTCN2019121478-appb-000007
如表2-1和表2-2所示，结合实施例1-6对比例1-5可知，在一定范围内，添加改性石墨烯能大幅提升涂料的性能，但超过范围后，石墨烯含量过高，可能发生团聚现象，使得其在涂料中的分散性降低，此时团聚可能会造成涂料局部缺陷的产生，因此石墨烯的大量添加反而会降低涂料的性能。当涂料添加改性石墨烯后，耐冲击性、韧性提升、生成结合键、氧气透过率、光泽度下降，耐盐雾时间上升，即综合性能上升。
表3-1
Figure PCTCN2019121478-appb-000008
Figure PCTCN2019121478-appb-000009
表3-2
Figure PCTCN2019121478-appb-000010
Figure PCTCN2019121478-appb-000011
表3-3
Figure PCTCN2019121478-appb-000012
Figure PCTCN2019121478-appb-000013
如表2-1、表2-2、表3-1、表3-2、表3-3所示，结合实施例1、7-12，在一定的范围内O/C比越低，改性石墨烯的导电性越高，涂料整体的导电性因此也提高，有助于提高锌粉的利用率，延长防腐时间。结合实施例1、13-18可知，在一定的范围内N/C比高，表明表面处理剂的接枝率较高，石墨烯的分散性会相对较好，石墨烯涂料的综合性能也比较好。
表4
Figure PCTCN2019121478-appb-000014
Figure PCTCN2019121478-appb-000015
如表2-1、表2-2和表4所示，结合实施例1、25-30、对比例2，芳基氨基类、吡唑啉酮类、儿茶酚类作为表面处理剂，处理不同物理参数的氧化石墨、经不同方法还原得到的改性石墨烯都能提升涂料的性能，且相较于未进行表面处理的石墨烯提升效果明显。

Claims (10)

  1. 一种石墨烯防腐涂料，其特征在于：所述涂料包含环氧树脂和经表面处理剂改性的石墨烯，所述石墨烯添加量为涂料固体总质量的0.01-0.2wt％。
  2. 根据权利要求1所述的石墨烯防腐涂料，其特征在于：所述石墨烯添加量为涂料固体总质量的0.01-0.05wt％。
  3. 根据权利要求1所述的石墨烯防腐涂料，其特征在于：所述石墨烯中的氧元素/碳元素原子比(O/C比)为0.05-0.40。
  4. 根据权利要求1所述的石墨烯防腐涂料，其特征在于：所述石墨烯中的氮元素/碳元素原子比(N/C比)为0.01-0.05。
  5. 根据权利要求1所述的石墨烯防腐涂料，其特征在于：所述石墨烯的厚度为2-12nm。
  6. 根据权利要求1所述的石墨烯防腐涂料，其特征在于：所述表面处理剂为芳基氨基类、吡唑啉酮类、儿茶酚类中的一种或多种。
  7. 根据权利要求1所述的石墨烯防腐涂料，其特征在于：所述表面处理剂为邻氯苯胺、对氯苯胺、邻甲苯胺、乙酰苯胺、2-氨基苄胺、对甲氧基苯胺、2-硝基苯胺、2-苯乙胺盐酸盐、4,4'-二氨基二苯甲烷、1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮、双吡唑酮、苦酮酸、1-苯基-3-甲基-5-吡唑啉酮、儿茶酚硼烷、邻苯二酚紫、3,5-二叔丁基-1,2-苯二酚、4-硝基儿茶酚、盐酸多巴胺中的一种或多种。
  8. 根据权利要求1所述的石墨烯防腐涂料，其特征在于：所述表面处理剂为2-氨基苄胺、2-苯乙胺盐酸盐、4,4'-二氨基二苯甲烷、双吡唑酮、盐酸多巴胺中的一种或多种。
  9. 根据权利要求1所述的石墨烯防腐涂料，其特征在于：所述涂料的漆膜的光泽度为3以下。
  10. 根据权利要求1所述的石墨烯防腐涂料，其特征在于：所述涂料的漆膜的氧气透过率为0.35g/m 2·h以下。
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US12024648B2 (en) 2024-07-02
JP2022519146A (ja) 2022-03-22
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