阅读说明：本技术 具有抑菌特性的石墨烯基水性防腐涂料及其制备方法 (Graphene-based water-based anticorrosive paint with antibacterial property and preparation method thereof ) 是由 冯杰 王方强 刘曦 陈家慧 蔡钢 毛健 于 2020-07-23 设计创作，主要内容包括：本发明公开了具有抑菌特性的石墨烯基水性防腐涂料及其制备方法,涉及复合材料科学技术领域,解决了处理微生物腐蚀的效果却并不理想的问题。本发明包括(2)将一定量的氧化石墨烯粉末加入到150mL去离子水中,用细胞破碎机超声处理混合物20～60min,然后在该分散液中加入步骤(1)中所制备的氧化银颗粒,超声处理1～10min,连续搅拌3～8h,得到氧化银/氧化石墨烯复合物,过滤、冷冻干燥；(3)按0.1～2.0wt％的比例将(2)中制备产物添加到适量的丁苯胶乳(固含量48～52％)中,并搅拌1～5h,即可得到复合涂料。本发明表现出高效抑菌、防腐能力,可应对多种腐蚀类型。(The invention discloses a graphene-based water-based anticorrosive paint with antibacterial property and a preparation method thereof, relates to the technical field of composite material science, and solves the problem that the effect of treating microbial corrosion is not ideal. Adding a certain amount of graphene oxide powder into 150mL of deionized water, carrying out ultrasonic treatment on the mixture for 20-60 min by using a cell crusher, then adding the silver oxide particles prepared in the step (1) into the dispersion liquid, carrying out ultrasonic treatment for 1-10 min, continuously stirring for 3-8 h to obtain a silver oxide/graphene oxide compound, filtering, and freeze-drying; (3) and (3) adding the product prepared in the step (2) into a proper amount of styrene-butadiene latex (with the solid content of 48-52%) according to the proportion of 0.1-2.0 wt%, and stirring for 1-5 hours to obtain the composite coating. The invention has high-efficiency antibacterial and antiseptic abilities, and can cope with various corrosion types.)

1. The graphene-based water-based anticorrosive paint with antibacterial property is characterized by comprising a filler taking water as a solvent, wherein the filler comprises graphene oxide and functional silver oxide particles loaded on the surface of the graphene oxide;

the graphene oxide is used for playing a role in medium barrier.

2. The graphene-based waterborne anticorrosive coating with bacteriostatic properties according to claim 1, wherein the water is deionized water.

3. The preparation method of the anticorrosive paint is characterized by comprising the following steps:

s1, mixing 4-6 g of sodium persulfate, 0.3-0.9 g of sodium dodecyl benzene sulfonate and 150mL of deionized water to form a solution;

s2, gradually dropping a sodium hydroxide solution into the solution in the S1 until the pH value becomes alkaline;

s3, after the treatment of S2, heating the mixture in a water bath to 50-80 ℃, slowly dripping a silver nitrate solution under continuous stirring, and then continuously preserving the heat for 10-40 min to obtain a silver oxide particle precipitate;

s4, after pretreating silver oxide particles, adding the silver oxide particles into dispersion liquid of graphene oxide powder, carrying out ultrasonic treatment, then continuously stirring for 3-8 hours to obtain a silver oxide/graphene oxide compound, and filtering, freezing and drying;

and S5, adding the silver oxide/graphene oxide compound dried in the S4 into styrene-butadiene latex according to a certain proportion, and stirring for 1-5 hours to obtain the composite coating.

4. The method for preparing the anticorrosive paint according to claim 3, wherein the sodium hydroxide solution is 2.5mol/L sodium hydroxide solution until the pH value becomes alkaline, and the pH value is 12-14.

5. The preparation method of the anticorrosive paint according to claim 4, wherein the silver nitrate solution is 50mL and 0.4mol/L, and the time for dripping the silver nitrate solution is 15-25 min.

6. The preparation method of the anticorrosive paint according to claim 5, wherein the S4 pretreatment comprises the steps of precipitating, filtering, washing and freeze-drying the obtained silver oxide particles.

7. The preparation method of the anticorrosive paint according to claim 6, wherein the dispersion of the graphene oxide powder is prepared by the following steps:

adding graphene oxide powder into 150mL of deionized water, and carrying out ultrasonic treatment on the mixture for 20-60 min by using a cell crusher to obtain a dispersion liquid of the graphene oxide powder.

8. The preparation method of the anticorrosive paint according to claim 7, wherein the styrene-butadiene latex is styrene-butadiene latex with a solid content of 48-52%.

9. The method of claim 3, wherein the silver oxide is formed from AgO in a multi-valence state and Ag in a single valence state₂O, wherein the weight percentage of AgO is not less than 10%, and the multi-valence state comprises monovalent and trivalent.

10. The preparation method of the anticorrosive paint according to claim 3, wherein the weight percentage of the silver oxide in the silver oxide/graphene oxide compound is 5-40%, and the addition amount of the silver oxide/graphene oxide compound in the styrene-butadiene latex is 0.1-2.0 wt%.

Technical Field

The invention relates to the technical field of composite material science, in particular to a graphene-based water-based anticorrosive paint with antibacterial property and a preparation method thereof.

Background

The coating protection is the most common protection means in the practical use of metal materials, and directly separates the corrosion environment from the metal, thereby avoiding the occurrence of corrosion reaction. However, the materials are subject to various kinds of corrosion in different use environments, for example, in the environments of oceans, soils, oil fields and the like, metals and coatings need to not only deal with electrochemical corrosion reaction caused by oxygen and electrolyte solution, but also can be exposed to the propagation and breeding of various microorganisms on the surfaces of the metals and coatings, and finally the weight of parts is increased, and partial bacterial secretion is corrosive, so that the coatings and the metals are easily locally corroded and are more harmful.

As the derivative of graphene, graphene oxide also has a similar two-dimensional carbon structure, so that the graphene oxide has strong stability and good barrier effect on gas or liquid, and because a certain amount of functional groups are reserved in the graphene oxide, the graphene oxide has good dispersibility in water and polymer base materials, and the permeation resistance of the coating to corrosive media can be enhanced. Meanwhile, the graphene oxide is also an ideal template material of the nano particles, and the particles can be effectively distributed on the surface of the graphene oxide under the action of simple machinery, so that the loading object can exert the functional characteristics of the graphene oxide, and a new idea is provided for the application and design of the multifunctional graphene-based coating.

At present, in the design of graphene/polymer anticorrosive paint, more consideration is given to the use of graphene/polymer anticorrosive paint for treating the electrochemical corrosion problem (such as chinese patent applications CN201910565419.4 and CN201911264487.3), but the effect of treating the microbial corrosion is not ideal.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the effect of treating microbial corrosion is not ideal, and the invention provides the graphene-based water-based anticorrosive paint with antibacterial property and the preparation method thereof, which solve the problems. The invention aims to ensure that the polymer coating has high-efficiency antibacterial property while enhancing the anticorrosive property so as to meet various requirements of corrosive environment.

The invention is realized by the following technical scheme:

the graphene-based water-based anticorrosive paint with the antibacterial property comprises a filler taking water as a solvent, wherein the filler comprises graphene oxide and functional silver oxide particles loaded on the surface of the graphene oxide, the graphene oxide is used for playing a medium blocking role, and the water is deionized water.

The preparation method of the graphene-based water-based anticorrosive paint with antibacterial property comprises the following steps:

(1) mixing 4-6 g of sodium persulfate, 0.3-0.9 g of sodium dodecyl benzene sulfonate and 150mL of deionized water to form a solution. Gradually dripping sodium hydroxide solution (2.5mol/L) into the system until the pH value is 12-14, heating to 50-80 ℃ in a water bath, slowly dripping silver nitrate solution (50mL,0.4mol/L) for about 15-25 min under continuous stirring, then preserving heat for 10-40 min under the condition to obtain silver oxide particle precipitate, filtering, washing, and freeze-drying;

(2) adding a certain amount of graphene oxide powder into 150mL of deionized water, carrying out ultrasonic treatment on the mixture for 20-60 min by using a cell crusher, then adding the silver oxide particles prepared in the step (1) into the dispersion liquid, carrying out ultrasonic treatment for 1-10 min, continuously stirring for 3-8 h to obtain a silver oxide/graphene oxide compound, filtering, and freeze-drying;

(3) and (3) adding the product prepared in the step (2) into a proper amount of styrene-butadiene latex (with the solid content of 48-52%) according to the proportion of 0.1-2.0 wt%, and stirring for 1-5 hours to obtain the composite coating.

In the above step, the silver oxide is formed by AgO with multiple valence states (I, III) and Ag with single valence state (I)₂And O, wherein the weight percentage of AgO is not less than 10%, and the weight percentage of the silver oxide in the silver oxide/graphene oxide compound is controlled to be 5-40%.

The invention has the following advantages and beneficial effects:

(1) the graphene oxide contains a certain functional group, and can effectively load silver oxide particles, so that the agglomeration of the particles is avoided;

(2) the invention uses styrene-butadiene latex as the main coating component, silver oxide/graphene oxide compound as the functional filler, and the composite system can use water as the solvent;

(3) the composite coating of the invention has high-efficiency antibacterial and anticorrosive capability and can cope with various corrosion types.

Drawings

The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:

FIG. 1 is a flow chart of the present invention.

Detailed Description

Before any embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangements of components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive changes, are within the scope of the present invention.

The invention aims to ensure that the polymer coating has high-efficiency antibacterial property while enhancing the anticorrosive property so as to meet various requirements of corrosive environment.

The invention is realized by the following technical scheme:

the graphene-based water-based anticorrosive paint with the antibacterial property comprises a filler taking water as a solvent, wherein the filler comprises graphene oxide and functional silver oxide particles loaded on the surface of the graphene oxide, the graphene oxide is used for playing a medium blocking role, and the water is deionized water.

The preparation method of the anticorrosive paint, as shown in fig. 1, comprises the following steps:

s1, mixing 4-6 g of sodium persulfate, 0.3-0.9 g of sodium dodecyl benzene sulfonate and 150mL of deionized water to form a solution;

s2, gradually dropping a sodium hydroxide solution into the solution in the S1 until the pH value becomes alkaline;

s3, after the treatment of S2, heating the mixture in a water bath to 50-80 ℃, slowly dripping a silver nitrate solution under continuous stirring, and then continuously preserving the heat for 10-40 min to obtain a silver oxide particle precipitate;

s4, after pretreating silver oxide particles, adding the silver oxide particles into dispersion liquid of graphene oxide powder, carrying out ultrasonic treatment, then continuously stirring for 3-8 hours to obtain a silver oxide/graphene oxide compound, and filtering, freezing and drying;

and S5, adding the silver oxide/graphene oxide compound dried in the S4 into styrene-butadiene latex according to a certain proportion, and stirring for 1-5 hours to obtain the composite coating.

Further, the sodium hydroxide solution is 2.5mol/L of sodium hydroxide solution until the pH value becomes alkaline, and the pH value is 12-14.

Further, the silver nitrate solution is 50mL and is 0.4mol/L, and the time for dripping the silver nitrate solution is 15-25 min.

Further, the pretreatment of S4 comprises the steps of precipitating, filtering, washing and freeze-drying the obtained silver oxide particles.

Further, the preparation process of the dispersion liquid of the graphene oxide powder is as follows:

adding graphene oxide powder into 150mL of deionized water, and carrying out ultrasonic treatment on the mixture for 20-60 min by using a cell crusher to obtain a dispersion liquid of the graphene oxide powder.

Further, the styrene-butadiene latex is styrene-butadiene latex with the solid content of 48-52%.

Further, the silver oxide is composed of AgO in a multi-valence state and Ag in a single valence state₂O, wherein the weight percentage of AgO is not less than 10%, and the multi-valence state comprises monovalent and trivalent.

Further, the weight percentage of the silver oxide in the silver oxide/graphene oxide compound is 5-40%, and the addition amount of the silver oxide/graphene oxide compound in the styrene-butadiene latex is 0.1-2.0 wt%.