A kind of corrosion-resistant graphene modified epoxy resin floor paint and preparation method thereof

Abstract

The invention discloses a corrosion-resistant graphene-modified epoxy resin floor paint and a preparation method thereof. The preparation method comprises, by weight, adding 0.5 to 5 parts of modified graphene oxide to 30 to 60 parts of a curing agent to obtain a mixture; mixing the mixture, 80 to 120 parts of a waterborne epoxy resin, 20 to 30 parts of a pigment filler, 1 to 2 parts of a leveling agent, 0.5 to 1 part of a defoaming agent, and 0.5 to 1 part of a dispersant to obtain the corrosion-resistant graphene-modified epoxy resin floor paint. The invention adds modified graphene oxide to the epoxy resin floor paint to obtain the corrosion-resistant graphene-modified epoxy resin floor paint, and the corrosion-resistant graphene-modified epoxy resin floor paint coating also has a strong anti-corrosion ion protection effect when immersed in seawater for a long time; at the same time, the mechanical properties of the corrosion-resistant graphene-modified epoxy resin floor paint coating can be regulated by adjusting the amount of modified graphene oxide added.

Description

Technical Field

[0001] The invention relates to the technical field of epoxy floor paints, and in particular to a corrosion-resistant graphene-modified epoxy resin floor paint and a preparation method thereof. Background Art

[0002] Epoxy resin floor paint is a high-performance coating product composed of epoxy resin, curing agent and solvent. It has wear resistance, water resistance and corrosion resistance, and can be used in floor decoration of various places, such as factories, garages, hospitals, schools, stadiums, shopping malls, etc.

[0003] Adding functional additives to conventional epoxy floor paint can improve its performance and applicability, so that it can be used in environments with special requirements. Corrosion-resistant epoxy resin floor paint is widely used in chemical plants, electronics plants, machinery manufacturing plants, pharmaceutical plants, laboratories and other places where the ground is required to have high corrosion resistance. Using this floor paint can effectively extend the service life of the ground and improve the safety and cleanliness of the working environment. CN108546494A discloses an acid-resistant graphene water-based epoxy floor paint and a preparation method thereof, wherein graphene is dispersed in a curing agent and then stirred with water-based epoxy resin, filler, dispersant, defoamer and leveling agent to prepare the same. This method can improve the acid corrosion resistance of water-based epoxy floor paint. However, the inorganic material graphene has the disadvantage of poor compatibility with the organic components of floor paint, and its mechanical strength and long-term stability may be affected.

[0004] Therefore, it is necessary to modify graphene to improve the long-term corrosion resistance of epoxy resin floor paint. Summary of the invention

[0005] In order to solve the technical problems existing in the prior art, the present invention provides a method for preparing a corrosion-resistant graphene-modified epoxy resin floor paint, which comprises, by weight:

[0006] Adding 0.5 to 5 parts of modified graphene oxide to 30 to 60 parts of a curing agent to obtain a mixture;

[0007] The mixture, 80 to 120 parts of waterborne epoxy resin, 20 to 30 parts of pigments and fillers, 1 to 2 parts of leveling agents, 0.5 to 1 parts of defoaming agents, and 0.5 to 1 parts of dispersants are mixed to obtain corrosion-resistant graphene-modified epoxy resin floor paint.

[0008] Graphene oxide, because of its large surface area and excellent barrier properties, can be used to prepare high-performance polymer coatings with enhanced mechanical, thermal and anti-corrosion properties, which can prevent the diffusion of ions, water and oxygen. In recent years, the addition of functionalized graphene oxide to polymer coatings to improve the anti-corrosion properties of coatings has been reported by many researchers. The results show that the incorporation of graphene oxide is beneficial to improve the corrosion and barrier properties of coatings. However, the surface of graphene oxide is rich in polar functional groups, such as hydroxyl, carboxyl and epoxide, which leads to poor dispersibility in organic systems and accelerates the penetration of water molecules in water-based coatings. It also allows electrolytes to move along the nanosheets, which makes it difficult for graphene oxide-based coatings to meet the long-term corrosion protection requirements. Polyaniline has been widely used in various fields due to its excellent conductivity, redox characteristics, environmental stability, non-toxicity, and easy modification. Polyaniline has a certain passivation effect and has a good anti-corrosion effect on metal materials. Polyaniline can be grown on the surface of graphene oxide by in-situ polymerization. The inert properties of graphene oxide also improve the poor barrier properties of polyaniline and enhance the passivation properties of polyaniline. Polyaniline can also enhance the hydrophobicity of graphene oxide. The synergistic effect of polyaniline and reduced graphene oxide is used to achieve a composite coating with excellent corrosion resistance, which has great potential. In addition, metal oxides are widely reported as nanofillers in epoxy coatings to enhance their barrier properties. Therefore, after the polyaniline / graphene oxide composite material is prepared by in-situ polymerization, the copper oxide nanoparticles are further modified on its surface by a hydrothermal method to prepare modified graphene oxide.

[0009] Furthermore, the preparation method of the modified graphene oxide comprises, by weight:

[0010] S1, dispersing 0.1 to 1 parts of graphene oxide in 30 to 60 parts of water to obtain a graphene oxide dispersion, and dispersing aniline in an acidic solution to obtain an aniline dispersion;

[0011] S2, mixing the graphene oxide dispersion and the aniline dispersion, and then adding 20 to 30 parts of an aqueous solution of ammonium persulfate to react to obtain a polyaniline / graphene oxide composite material;

[0012] S3, dispersing 1 to 2 parts of polyaniline / graphene oxide composite material and 2 to 5 parts of soluble copper salt in 50 to 100 parts of water, adjusting the pH and then performing a hydrothermal reaction to obtain modified graphene oxide.

[0013] Furthermore, the concentration of the ammonium persulfate aqueous solution in S2 is 1 to 3 mol / L.

[0014] Furthermore, the acidic solution in S1 is a 1-3 mol / L hydrochloric acid or phosphoric acid aqueous solution.

[0015] Furthermore, the soluble copper salt in S3 is at least one of copper nitrate pentahydrate, copper sulfate pentahydrate, and copper chloride dihydrate.

[0016] Furthermore, the pH in S3 is adjusted to 10-12.

[0017] Furthermore, the hydrothermal reaction in S3 is maintained at 150-180° C. for 5-20 hours.

[0018] Furthermore, the curing agent is an aromatic amine curing agent.

[0019] The pigment filler is at least one of quartz powder, talcum powder, titanium dioxide or barium sulfate.

[0020] The leveling agent is a modified polyether siloxane type leveling agent.

[0021] The defoaming agent is a silicone defoaming agent.

[0022] The dispersant is at least one of sodium polycarboxylate, potassium polyacrylate and sodium polyacrylate.

[0023] Furthermore, the particle size of the pigment and filler is 300-500 mesh.

[0024] The present invention also provides a corrosion-resistant graphene-modified epoxy resin floor paint, which is prepared by the above-mentioned preparation method.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The present invention adds modified graphene oxide to epoxy resin floor paint to obtain corrosion-resistant graphene modified epoxy resin floor paint. The corrosion-resistant graphene modified epoxy resin floor paint coating also has a strong anti-corrosion ion protection effect when immersed in seawater for a long time; and the mechanical properties of the corrosion-resistant graphene modified epoxy resin floor paint coating can be regulated by adjusting the addition amount of the modified graphene oxide. DETAILED DESCRIPTION

[0027] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0028] The following will be combined with the specific embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] Introduction of some raw materials used in the embodiments of the present invention:

[0030] Waterborne epoxy resin, bisphenol A epoxy resin E51 was purchased from Shandong Kepler Biotechnology Co., Ltd.;

[0031] Aromatic amine curing agent, brand CYDHD-113, purchased from Henan Huineng Resin Co., Ltd.;

[0032] Modified polyether siloxane leveling agent, model BYK-333, purchased from BYK, Germany;

[0033] Silicone defoamer, model BYK-A530, purchased from BYK, Germany;

[0034] Polycarboxylic acid sodium salt, model CN-5040, was purchased from Beijing Dongfang Chennuo Chemical Technology Co., Ltd.

[0035] Other raw materials not mentioned are common raw materials in the art.

[0036] Example 1

[0037] A method for preparing a corrosion-resistant graphene-modified epoxy resin floor paint, comprising the following steps:

[0038] Step 1, weighing 0.1kg modified graphene oxide, 5kg aromatic amine curing agent, 10kg water-based epoxy resin, 2kg 300-mesh quartz powder, 0.1kg modified polyether siloxane leveling agent, 0.1kg silicone defoamer, and 0.05kg polycarboxylate sodium salt;

[0039] Step 2, adding the modified graphene oxide to the aromatic amine curing agent and stirring at a speed of 300 rpm for 30 minutes to obtain a mixture;

[0040] Step 3: Mix the mixture obtained in step 2, water-based epoxy resin, 300-mesh quartz powder, modified polyether siloxane leveling agent, silicone defoamer, and sodium polycarboxylate, and stir at a speed of 500 rpm for 30 minutes to obtain a corrosion-resistant graphene-modified epoxy resin floor paint.

[0041] The preparation method of modified graphene oxide is:

[0042] S1. Disperse 0.05 kg of graphene oxide in 5 kg of water under ultrasound at 100 kHz for 30 min to obtain a graphene oxide dispersion; disperse 0.01 kg of aniline in 2 mol / L phosphoric acid aqueous solution and stir at a speed of 500 rpm for 30 min to obtain an aniline dispersion;

[0043] S2, stirring the graphene oxide dispersion and the aniline dispersion at a speed of 300 rpm for 10 min, then adding 2 kg of 2 mol / L ammonium persulfate aqueous solution to react, maintaining the temperature at 5 ° C, stirring at a speed of 300 rpm for 1 h, filtering and collecting the insoluble matter, washing, and drying to obtain a polyaniline / graphene oxide composite material;

[0044] S3. Disperse 0.1 kg of polyaniline / graphene oxide composite material and 0.5 kg of copper nitrate pentahydrate in 5 kg of water at a speed of 300 rpm and stir for 20 min, adjust the pH to 10, transfer to a hydrothermal reactor and perform hydrothermal reaction at 180° C. for 8 h, filter and collect insoluble matter, wash, and dry to obtain modified graphene oxide.

[0045] Example 2

[0046] A method for preparing a corrosion-resistant graphene-modified epoxy resin floor paint, comprising the following steps:

[0047] Step 1, weighing 0.2kg modified graphene oxide, 5kg aromatic amine curing agent, 10kg water-based epoxy resin, 2kg 300-mesh quartz powder, 0.1kg modified polyether siloxane leveling agent, 0.1kg silicone defoamer, and 0.05kg polycarboxylate sodium salt;

[0048] Step 2, adding the modified graphene oxide to the aromatic amine curing agent and stirring at a speed of 300 rpm for 30 minutes to obtain a mixture;

[0049] Step 3: Mix the mixture obtained in step 2, water-based epoxy resin, 300-mesh quartz powder, modified polyether siloxane leveling agent, silicone defoamer, and sodium polycarboxylate, and stir at a speed of 500 rpm for 30 minutes to obtain a corrosion-resistant graphene-modified epoxy resin floor paint.

[0050] Wherein, the preparation method of modified graphene oxide is the same as that in Example 1.

[0051] Example 3

[0052] A method for preparing a corrosion-resistant graphene-modified epoxy resin floor paint, comprising the following steps:

[0053] Step 1, weighing 0.3kg modified graphene oxide, 5kg aromatic amine curing agent, 10kg water-based epoxy resin, 2kg 300-mesh quartz powder, 0.1kg modified polyether siloxane leveling agent, 0.1kg silicone defoamer, and 0.05kg polycarboxylate sodium salt;

[0054] Step 2, adding the modified graphene oxide to the aromatic amine curing agent and stirring at a speed of 300 rpm for 30 minutes to obtain a mixture;

[0055] Step 3: Mix the mixture obtained in step 2, water-based epoxy resin, 300-mesh quartz powder, modified polyether siloxane leveling agent, silicone defoamer, and sodium polycarboxylate, and stir at a speed of 500 rpm for 30 minutes to obtain a corrosion-resistant graphene-modified epoxy resin floor paint.

[0056] Wherein, the preparation method of modified graphene oxide is the same as that in Example 1.

[0057] Example 4

[0058] A method for preparing a corrosion-resistant graphene-modified epoxy resin floor paint, comprising the following steps:

[0059] Step 1, weighing 0.5kg modified graphene oxide, 5kg aromatic amine curing agent, 10kg water-based epoxy resin, 2kg 300-mesh quartz powder, 0.1kg modified polyether siloxane leveling agent, 0.1kg silicone defoamer, and 0.05kg polycarboxylate sodium salt;

[0060] Step 2, adding the modified graphene oxide to the aromatic amine curing agent and stirring at a speed of 300 rpm for 30 minutes to obtain a mixture;

[0061] Step 3: Mix the mixture obtained in step 2, water-based epoxy resin, 300-mesh quartz powder, modified polyether siloxane leveling agent, silicone defoamer, and sodium polycarboxylate, and stir at a speed of 500 rpm for 30 minutes to obtain a corrosion-resistant graphene-modified epoxy resin floor paint.

[0062] Wherein, the preparation method of modified graphene oxide is the same as that in Example 1.

[0063] Comparative Example

[0064] A method for preparing a corrosion-resistant graphene-modified epoxy resin floor paint, comprising the following steps:

[0065] Step 1, weighing 0.3kg of polyaniline / graphene oxide composite material, 5kg of aromatic amine curing agent, 10kg of water-based epoxy resin, 2kg of 300-mesh quartz powder, 0.1kg of modified polyether siloxane leveling agent, 0.1kg of silicone defoaming agent, and 0.05kg of polycarboxylic acid sodium salt;

[0066] Step 2, adding the polyaniline / graphene oxide composite material to the aromatic amine curing agent and stirring at a rotation speed of 300 rpm for 30 minutes to obtain a mixture;

[0067] Step 3: Mix the mixture obtained in step 2, water-based epoxy resin, 300-mesh quartz powder, modified polyether siloxane leveling agent, silicone defoamer, and sodium polycarboxylate, and stir at a speed of 500 rpm for 30 minutes to obtain a corrosion-resistant graphene-modified epoxy resin floor paint.

[0068] The preparation method of the polyaniline / graphene oxide composite material is as follows:

[0069] S1. Disperse 0.05 kg of graphene oxide in 5 kg of water under ultrasound at 100 kHz for 30 min to obtain a graphene oxide dispersion; disperse 0.01 kg of aniline in 2 mol / L phosphoric acid aqueous solution and stir at a speed of 500 rpm for 30 min to obtain an aniline dispersion;

[0070] S2. The graphene oxide dispersion and the aniline dispersion were stirred at a speed of 300 rpm for 10 min, and then 2 kg of 2 mol / L ammonium persulfate aqueous solution was added for reaction. The temperature was maintained at 5° C. and the speed was 300 rpm for stirring for 1 h. The insoluble matter was collected by filtration, washed, and dried to obtain a polyaniline / graphene oxide composite material.

[0071] Test Case

[0072] The corrosion-resistant graphene-modified epoxy resin floor paint was prepared by the embodiment of the present invention and the comparative example, and was applied to a steel plate with a thickness of 1 mm, a length of 15 mm, and a width of 10 mm to form a 100 μm coating after curing. With reference to GB / T50589-2010 Technical Specification for Epoxy Self-Leveling Floor Engineering, impact resistance, compressive strength and hardness tests were carried out, and with reference to ASTMD3359-09, adhesion was evaluated by a tape test, and the results are shown in Table 1.

[0073] Table 1

[0074]

[0075]

[0076] From the results in Table 1, it can be seen that the corrosion-resistant graphene-modified epoxy resin floor paint coatings prepared in Examples 1 to 4 of the present invention have good impact resistance. The proportion of modified graphene in Examples 1 to 4 increases successively, and the compressive strength, hardness and adhesion all show a trend of first increasing and then decreasing with the increase of the proportion of modified graphene. This is because too much content of modified graphene will produce agglomeration and thus affect the mechanical properties of the coating. Nano copper oxide in modified graphene can effectively improve the mechanical properties of the coating.

[0077] The corrosion-resistant graphene-modified epoxy resin floor paint was prepared using the embodiments of the present invention and the comparative examples, and was applied to a steel plate with a thickness of 1 mm, a length of 15 mm, and a width of 10 mm to form a 100 μm coating after curing. The coating was then immersed in natural seawater for 480 h and the adhesion was tested again. The results are shown in Table 2.

[0078] Table 2

[0079]

[0080] It can be seen from the results in Table 2 that the modified graphene obtained by preparing copper oxide nanoparticles on the polyaniline / graphene oxide composite material can be added to the water-based epoxy resin to significantly improve the adhesion in the corrosive medium, which indicates that it is not easily corroded by the corrosive medium. The corrosion resistance of epoxy coatings is mainly affected by the crosslinking density and protective performance. The electrolyte in the corrosive medium will cause holes and cracks on the coating surface under long-term action. Therefore, one of the most important aspects affecting the anti-corrosion effect of the coating is adhesion. The adhesion retention rate of Examples 1 to 3 of the present invention is good and can meet the needs of long-term corrosion resistance.

[0081] The corrosion-resistant graphene-modified epoxy resin floor paint prepared in the examples of the present invention and the comparative examples was applied to a steel plate with a thickness of 1 mm, a length of 15 mm, and a width of 10 mm, and then cured to form a 100 μm coating. The charge transfer resistance (R ct ), and the results are shown in Table 3.

[0082] Table 3

[0083]

[0084] R ct It can reflect the ease with which ions pass through the coating. The impermeability of the coating increases with R ct The results in Table 3 correspond to those in Table 2, which also illustrate that it is difficult for ions in the corrosive medium to enter the corrosion-resistant graphene-modified epoxy resin floor paint prepared by the present invention, and at the same time, long-term corrosion resistance can be guaranteed.

Claims

1. A method for preparing a corrosion-resistant graphene-modified epoxy resin floor paint, characterized in that: In parts by mass, it includes: Adding 0.5 to 5 parts of modified graphene oxide to 30 to 60 parts of a curing agent to obtain a mixture; The mixture, 80-120 parts of waterborne epoxy resin, 20-30 parts of pigments and fillers, 1-2 parts of leveling agents, 0.5-1 parts of defoamers, and 0.5-1 parts of dispersants are mixed to obtain a corrosion-resistant graphene-modified epoxy resin floor paint; The preparation method of the modified graphene oxide comprises, by weight, S1, dispersing 0.1-1 parts of graphene oxide in 30-60 parts of water to obtain a graphene oxide dispersion, and dispersing 1-2 parts of aniline in 30-60 parts of an acidic solution to obtain an aniline dispersion; S2, mixing the graphene oxide dispersion and the aniline dispersion, and then adding 20 to 30 parts of an aqueous solution of ammonium persulfate to react to obtain a polyaniline / graphene oxide composite material; S3, dispersing 1-2 parts of the polyaniline / graphene oxide composite material and 2-5 parts of a soluble copper salt in 50-100 parts of water, adjusting the pH, and performing a hydrothermal reaction to obtain modified graphene oxide; The pH in S3 is adjusted to 10-12, and the hydrothermal reaction is maintained at 150-180°C for 5-20 hours.

2. The preparation method of the corrosion-resistant graphene-modified epoxy resin floor paint according to claim 1, characterized in that, The concentration of the ammonium persulfate aqueous solution in S2 is 1~3 mol / L.

3. The preparation method of the corrosion-resistant graphene-modified epoxy resin floor paint according to claim 1, characterized in that, The acidic solution in S1 is 1~3 mol / L hydrochloric acid or phosphoric acid aqueous solution.

4. The preparation method of the corrosion-resistant graphene-modified epoxy resin floor paint according to claim 1, characterized in that, The soluble copper salt in S3 is at least one of copper nitrate pentahydrate, copper sulfate pentahydrate, and copper chloride dihydrate.

5. The preparation method of the corrosion-resistant graphene-modified epoxy resin floor paint according to any one of claims 1 to 4, characterized in that, The curing agent is an aromatic amine curing agent; The pigment filler is at least one of quartz powder, talcum powder, titanium dioxide or barium sulfate; The leveling agent is a modified polyether siloxane type leveling agent; The defoamer is a silicone defoamer; The dispersant is at least one of sodium polycarboxylate, potassium polyacrylate and sodium polyacrylate.

6. The method for preparing the corrosion-resistant graphene-modified epoxy resin floor paint according to claim 5, characterized in that: The particle size of the pigment and filler is 300-500 mesh.

7. A corrosion-resistant graphene-modified epoxy resin floor paint, characterized in that: The corrosion-resistant graphene-modified epoxy resin floor paint is prepared by the preparation method of any one of claims 1 to 6.

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