CN110591525A

CN110591525A - Water-based paint added with graphene and preparation method thereof

Info

Publication number: CN110591525A
Application number: CN201910913494.5A
Authority: CN
Inventors: 马利纳; 王洁; 楚会来; 胡中源
Original assignee: Hebei Chenyang Industry and Trade Group Co Ltd
Current assignee: Hebei Chenyang Industry and Trade Group Co Ltd
Priority date: 2019-09-25
Filing date: 2019-09-25
Publication date: 2019-12-20

Abstract

The invention relates to the field of water-based paint, in particular to water-based paint added with graphene and a preparation method thereof. The water-based paint comprises the following components: the paint comprises water-based epoxy modified alkyd resin, a dispersing agent, a leveling agent, a pH value regulator, a drier, an oil-resistant agent, a rheological additive, nano aluminum oxide, composite zinc phosphate, barium sulfate, a pigment, a graphene aqueous solution, a corrosion inhibitor, a thickening agent and deionized water. The coating is compounded by waterborne epoxy modified alkyd resin, graphene, nano-alumina and other components, so that the obtained coating has excellent corrosion resistance and weather resistance, and can be used as an anticorrosive coating for steel pipelines.

Description

Water-based paint added with graphene and preparation method thereof

Technical Field

The invention relates to the field of water-based paint, in particular to water-based paint added with graphene and a preparation method thereof.

Background

The buried pipeline is one of the important facilities for oil and gas transmission carrier and ground engineering, and is a link for connecting upstream resources with downstream users. Because the pipeline is buried underground for a long time, the penetrated terrain is complex, the soil quality is various, the factors such as external soil characteristics and terrain settlement can cause the steel buried pipeline to generate corrosion, perforation, leakage and other conditions to bring important losses, including direct losses such as component cost, repair cost, corrosion prevention cost and equipment replacement cost, and indirect losses such as product loss caused by production stop, corrosion leakage, corrosion product accumulation or corrosion damage and the like. Furthermore, the leakage of harmful substances caused by the corrosion of pipelines can cause serious environmental pollution, even disasters and endanger the personal safety. Therefore, strict external corrosion prevention measures are required for steel buried pipelines. The external anticorrosion measures usually adopted at present are mainly spraying anticorrosion paint, which can play a role in beautifying while isolating the erosion of harmful substances.

In the prior art, the steel pipeline is mainly sprayed with the oily anticorrosive paint, but with the coming of environmental protection policy, the water-based anticorrosive paint becomes a development trend. However, the existing water-based paint has poor corrosion resistance and is difficult to meet the high requirement of buried steel pipelines on corrosion resistance.

Disclosure of Invention

Aiming at the problem that the existing water-based paint is poor in corrosion resistance, the invention provides a water-based paint added with graphene.

The invention also provides a preparation method of the graphene-added water-based paint.

In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:

the graphene-added water-based paint comprises the following raw materials in parts by weight: 40-60 parts of water-based epoxy modified alkyd resin, 1-3 parts of dispersing agent, 2-4 parts of flatting agent, 0.5-2 parts of pH value regulator, 0.8-1.2 parts of drier, 0.5-1.5 parts of oil repellent agent, 0.5-2 parts of rheological additive, 1-5 parts of nano aluminum oxide, 10-15 parts of composite zinc phosphate, 5-10 parts of barium sulfate, 11-17 parts of pigment, 2-5 parts of graphene aqueous solution, 0.5-2 parts of corrosion inhibitor, 0.1-0.5 part of thickener and 10-25 parts of deionized water; the graphene aqueous solution contains 4-6% by mass of graphene and 1-1.5% by mass of silane coupling agent.

The waterborne epoxy modified alkyd resin used in the waterborne coating is a resin modified by epoxy, oleic acid and acrylic acid, has good salt spray resistance and water resistance, is quick to dry on the surface, has excellent adhesive force to steel pipelines, has good luster and good coating property to pigments and fillers, can enable a film to be bright and plump after being formed into a film, and has good appearance. Such as GS-5000B of Guangsheng chemical industry.

The graphene used in the coating is a good surfactant, which is beneficial to improving the wettability and the adhesive force of the water-based coating, and the flaky structure of the coating can enable the coating to have higher mechanical strength, improve the tensile strength of the coating after film formation, reduce the elongation, enable the coating to have good water resistance and acid and alkali resistance, remarkably improve the corrosion resistance of the coating, and enable the coating to play a better protection role when applied to a steel pipeline; the graphene has good antibacterial activity, can prevent the integrity of the coating film from being damaged by the infection of bacteria, and maintains the corrosion resistance and the antifouling property of the coating film; meanwhile, the graphene can also improve the heat insulation effect and the flame retardant effect of the coating film, so that the coating film has a certain effect on safety protection. Graphene powder produced using the Changlong graphite product is preferred.

After the silane coupling agent and graphene are prepared into a graphene aqueous solution with a specific concentration, the graphene in the obtained aqueous solution is not easy to agglomerate, has high stability, can be stored for a long time, is convenient to prepare and store in mass production, and can improve the strength of a coating film. The preparation method of the graphene aqueous solution comprises the following steps: and (3) placing the silane coupling agent and the graphene in deionized water, and carrying out ultrasonic treatment until the silane coupling agent and the graphene are uniformly dispersed.

The nano aluminum oxide used in the coating can increase the hardness and the friction resistance of a coating film of the coating, is beneficial to maintaining the integrity of the coating film, and further improves the corrosion resistance of the coating film.

The coating is compounded by waterborne epoxy modified alkyd resin, graphene, nano-alumina and other components, so that the obtained coating has excellent corrosion resistance and weather resistance, and can be used as an anticorrosive coating for steel pipelines.

Preferably, the water-based paint comprises the following raw materials in parts by weight: 52 parts of waterborne epoxy modified alkyd resin, 2.4 parts of dispersant, 3.5 parts of flatting agent, 1.4 parts of pH value regulator, 1.0 part of drier, 1.1 parts of oil-resistant agent, 1.5 parts of rheological additive, 3 parts of nano-alumina, 13 parts of composite zinc phosphate, 8 parts of barium sulfate, 13.5 parts of pigment, 3.5 parts of graphene aqueous solution, 1.6 parts of corrosion inhibitor, 0.38 part of thickener and 20 parts of deionized water.

Preferably, the drier is GS-101 in Guangshu chemical industry, and the drier is matched with waterborne epoxy modified alkyd resin, particularly GS-5000B in Guangshu chemical industry, has good solid drying property and can meet the requirement of pipeline coating.

Preferably, the oil-repellent agent is a polyether siloxane copolymer, such as digao 270, which has excellent anti-cratering effect and good recoatability, and also has the function of promoting the flow of the coating.

Preferably, the corrosion inhibitor is a mixture of glass fiber and thiourea corrosion inhibitor in a mass ratio of 1: 1.8-2.2. The acid resistance and the alkali resistance of the coating film are obviously improved by matching the two, and the anticorrosion effect of the water-based paint is obviously improved. Thiourea has weak reducibility and can react with a strong oxidant, and can be directly and spontaneously adsorbed on the surface of a steel pipeline to form a compact corrosion-inhibiting layer when the coating is coated, nano alumina in the formula forms a nano alumina film on the outer surface of the corrosion-inhibiting layer, and the nano alumina film is an epoxy resin coating film which is formed by other components in the water-based coating and takes graphene as a reinforcing framework. Although graphene has weak oxidation, graphene does not chemically react with thiourea due to the nano-alumina thin film between graphene and thiourea.

Preferably, the corrosion inhibitor is a mixture of glass fiber and thiourea corrosion inhibitor in a mass ratio of 1: 2.

Preferably, the silane coupling agent is gamma-glycidoxypropyltrimethoxysilane, preferably of the formula Y9669.

Preferably, the dispersant is a vinyl copolymer attached with a pigment anchoring group, such as 4474 of AFCONA, which has excellent pigment stabilizing performance and can improve the color uniformity of a coating film.

Preferably, the rheological additive is bentonite, so that thermal stability and thixotropy can be provided for the coating system, hard precipitation of pigment can be prevented, moisture shrinkage can be reduced, color separation and blooming phenomena can be minimized, and the appearance color of the coating is full. Such as hamming's bentonite LT.

Preferably, the fineness of the barium sulfate is 1500 meshes.

Preferably, the pigment is 10-15 parts of titanium dioxide and 1-2 parts of carbon black. Such as titanium dioxide R706 and carbon black MA 100.

Preferably, the leveling agent is an acrylic leveling agent, so that the leveling and flowing of the coating system can be improved, the gloss of a paint film can be improved, shrinkage cavities and fish eyes can be eliminated, orange peel and pinholes can be reduced, the surface quality of the paint film can be improved, and the corrosion resistance of the paint film can be prevented from being influenced by water permeating into the paint film. Such as French pioneer PW-336, does not contain VOC, does not influence the interlayer adhesion, has defoaming and defoaming effects, and can improve the substrate wettability.

Preferably, the thickener is an equal mass ratio mixture of the nonionic modified water-soluble polyurethane thickener and the hydrophobic modified associative thickener. The nonionic modified water-soluble polyurethane thickener has excellent Newtonian rheological property, flow and leveling property, stable performance in a wide pH range and microbial degradation prevention property, has strong association with the surface of emulsion particles of a coating, has higher thickening efficiency, and can ensure that a coating film has high fullness and high gloss. Such as Nippondi PS-202 without organic solvent. The hydrophobic modified associative thickener has the advantages of high thickening effect, excellent flowing, leveling and splashing resistance, good construction performance, high shear viscosity, brush retention and painting performance, good moving performance and covering power of a paint roller, reliable biological stability and capability of resisting the degradation of microorganisms and enzymes. Like AP-660 in Shanghai field, the paint does not contain harmful components such as organic solvents, organic tin, inorganic heavy metals and the like, is nontoxic and tasteless, is safe to use, and does not increase the content of organic volatile matters in the water-based paint.

The invention also provides a preparation method of the graphene-added water-based paint, which comprises the steps of weighing the raw materials according to the weight part ratio, sequentially adding the dispersing agent, the flatting agent, the pH regulator, the drier, the nano aluminum oxide, the composite zinc phosphate, the barium sulfate, the pigment, the graphene aqueous solution, the corrosion inhibitor and 40-60% formula amount of deionized water into the water-based epoxy modified alkyd resin under the stirring state, completely dispersing, shaking until the fineness is less than or equal to 25 mu m, adding the oil-resistant agent, the rheological aid, the thickening agent and the rest formula amount of deionized water, dispersing until the fineness is less than or equal to 25 mu m, and filtering with a 200-mesh sieve to obtain the graphene-added water-based paint.

The preparation method of the graphene-added water-based paint provided by the invention is simple to operate and is suitable for large-scale production operation.

Preferably, the stirring state is 800-1000 rpm.

Preferably, the oil repellent agent, rheology assistant, thickener and the remaining formulation amount of deionized water are added and dispersed at 600-800 rpm/min.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Examples

The embodiment of the invention provides a graphene-added water-based paint and a preparation method thereof, and the mass part ratio of raw materials in each embodiment is shown in table 1.

TABLE 1

The waterborne epoxy modified alkyd resin is GS-5000B of Guangshan chemical industry, the dispersing agent is 4474 of AFCONA, the flatting agent is French pioneer PW-336, the pH regulator is AMP-95 of Dow of America, the drier is GS-101 of Guangshan chemical industry, the anti-oiling agent is digao 270, the rheological additive is Haiming bentonite LT, the thickening agent is an equal mass ratio mixture of Ningbaidi PS-202 and AP-660 of Shanghai field Yuan chemical industry, the graphene in the graphene aqueous solution is graphene powder produced by Changlong graphite products, and the silane coupling agent is Meiji Y9669.

The preparation method of the water-based paint added with the graphene in the above embodiments comprises the following steps:

step 1, weighing the raw materials according to the weight parts in the table 1, sequentially adding a dispersing agent, a leveling agent, a pH regulator, a drier, nano-alumina, composite zinc phosphate, barium sulfate, titanium dioxide, carbon black, a graphene aqueous solution, a corrosion inhibitor and 40-60% formula amount of deionized water into waterborne epoxy modified alkyd resin in a dispersion tank under the stirring state of 800-1000 rpm/min, dispersing while adding, and dispersing for 15-20 min to obtain paint paste.

And 2, placing the paint slurry in an oscillation tank, and oscillating for 30min to ensure that the fineness is less than or equal to 25 mu m.

And 3, adding the paint slurry after oscillation into a dispersion tank, adding an oil-resistant agent, a rheological aid, a thickening agent and deionized water with the residual formula amount, completely dispersing at 600-800rpm/min until the fineness is less than or equal to 25 mu m, and filtering by using 200-mesh filter cloth to obtain the finished paint slurry.

Specific parameters in the preparation process of each example are shown in table 2:

TABLE 2

Comparative example

The comparative example provides a graphene-added water-based paint and a preparation method thereof, and the mass part ratio of raw materials in each comparative example is shown in table 3.

TABLE 3

The raw material sources and the preparation method in each proportion are the same as example 3, and the water-based alkyd resin in comparative example 1 is 1AK27B of the same chemical industry.

Examination example

The products of examples 1 to 5 and comparative examples 1 to 4 were subjected to physical property inspection.

The tensile strength refers to the structural compactness of the coating film and the impact resistance and puncture resistance. Tensile strength and elongation at break test: 1. the measured value of the waterproof coating tensile strength testing machine is between 15 and 85 percent of the measuring range, the indicating value precision is not lower than 1 percent, and the extension range is more than 500 mm; 2. electric heating air blast oven: the temperature control precision is +2 ℃; 3. a sheet punching machine and a dumbbell cutter meeting the GBT528 requirement; 4. a thickness meter: the diameter of the contact surface is 6mm, the unit area pressure is 0.02MPa, and the division value is 0.01mm.

And adopting a proper dumbbell type test according to national standards, drawing parallel lines with the distance of 25mm, measuring the thicknesses of three points in the middle and at two ends of the software marked line by using a thickness meter, and taking the arithmetic average value on the thickness of the software marked line as the thickness of the test piece. And adjusting the distance between the clamps of the tensile strength tester to be about 70mm, and clamping the test piece on the tensile strength tester.

And (3) calculating:

after standard curing for 7 days, the tensile strength and other physical properties of the products obtained in examples 1-5 and comparative examples 1-4 were examined, and the results of the examination of examples 1-5 are shown in Table 4, and the results of the examination of comparative examples 1-4 are shown in Table 5.

TABLE 4

Item	Example 1	Example 2	Example 3	Example 4	Example 5
						Hardness (not less than H)	H	H	2H	2H	2H
Adhesion (less than or equal to 1)	1	0	0	0	0
						Tensile Strength (MPa)	1.3	1.7	2.1	2.3	1.9
Elongation at Break (%)	98	120	141	165	152
						Water resistance (not less than 72h, 25 ℃ C.)	128h	175h	220h	360h	320h
Acid resistance (5% H)₂SO₄,≥72h)	135h	172h	189h	210h	203h
						Alkali resistance (5% NaOH, 72h)	141h	159h	176h	204h	187h

TABLE 5

As can be seen from the test results in tables 4 and 5, the graphene-added water-based paint prepared in examples 1 to 5 has good hardness, adhesion, tensile strength, elongation at break, water resistance, acid resistance and alkali resistance after being formed into a film, and is obviously superior to each proportion, which indicates that the graphene-added water-based paint provided by the invention has excellent corrosion resistance.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims

1. A graphene-added water-based paint is characterized in that: the material comprises the following raw materials in parts by weight: 40-60 parts of water-based epoxy modified alkyd resin, 1-3 parts of dispersing agent, 2-4 parts of flatting agent, 0.5-2 parts of pH value regulator, 0.8-1.2 parts of drier, 0.5-1.5 parts of oil repellent agent, 0.5-2 parts of rheological additive, 1-5 parts of nano aluminum oxide, 10-15 parts of composite zinc phosphate, 5-10 parts of barium sulfate, 11-17 parts of pigment, 2-5 parts of graphene aqueous solution, 0.5-2 parts of corrosion inhibitor, 0.1-0.5 part of thickener and 10-25 parts of deionized water; the graphene aqueous solution contains 4-6% by mass of graphene and 1-1.5% by mass of silane coupling agent.

2. The graphene-added water-based paint according to claim 1, characterized in that: the material comprises the following raw materials in parts by weight: 52 parts of waterborne epoxy modified alkyd resin, 2.4 parts of dispersant, 3.5 parts of flatting agent, 1.4 parts of pH value regulator, 1.0 part of drier, 1.1 parts of oil-resistant agent, 1.5 parts of rheological additive, 3 parts of nano-alumina, 13 parts of composite zinc phosphate, 8 parts of barium sulfate, 13.5 parts of pigment, 3.5 parts of graphene aqueous solution, 1.6 parts of corrosion inhibitor, 0.38 part of thickener and 20 parts of deionized water.

3. The graphene-added water-based paint according to claim 1, characterized in that: the drier is GS-101 in the Guangshu chemical industry.

4. The graphene-added water-based paint according to claim 1, characterized in that: the oil-resistant agent is polyether siloxane copolymer.

5. The graphene-added water-based paint according to claim 1, characterized in that: the corrosion inhibitor is a mixture of glass fiber and thiourea corrosion inhibitor in a mass ratio of 1: 1.8-2.2.

6. The graphene-added water-based paint according to claim 5, characterized in that: the corrosion inhibitor is a mixture of glass fiber and thiourea corrosion inhibitor in a mass ratio of 1: 2.

7. The graphene-added water-based paint according to claim 1, characterized in that: the silane coupling agent is gamma-glycidol ether oxygen propyl trimethoxy silane.

8. The graphene-added water-based paint according to claim 1, characterized in that: the dispersant is a vinyl copolymer attached with a pigment anchoring group; and/or

The rheological additive is bentonite; and/or

The fineness of the barium sulfate is 1500 meshes; and/or

The pigment comprises 10-15 parts of titanium dioxide and 1-2 parts of carbon black; and/or

The leveling agent is an acrylic acid leveling agent; and/or

The thickening agent is a mixture of nonionic modified water-soluble polyurethane thickening agent and hydrophobic modified associative thickening agent in equal mass ratio.

9. The method for preparing the graphene-added water-based paint according to any one of claims 1 to 8, characterized in that: weighing the raw materials according to the weight part ratio, sequentially adding the dispersing agent, the flatting agent, the pH regulator, the drier, the nano aluminum oxide, the composite zinc phosphate, the barium sulfate, the pigment, the graphene aqueous solution, the corrosion inhibitor and 40-60% formula amount of deionized water into the waterborne epoxy modified alkyd resin under the stirring state, completely dispersing, shaking until the fineness is less than or equal to 25 mu m, adding the oil-resistant agent, the rheological aid, the thickening agent and the rest formula amount of deionized water, dispersing until the fineness is less than or equal to 25 mu m, and filtering with 200 meshes; and (5) obtaining the product.

10. The method for preparing the graphene-added water-based paint according to claim 9, wherein: the stirring state is 800-1000 rpm; and/or

The oil-resistant agent, the rheological additive, the thickening agent and the deionized water with the rest formula amount are added and dispersed at 600-800 rpm/min.