Multifunctional nanocomposite coating material, its preparation method and application

Abstract

The application provides a multifunctional nanocomposite coating material, a preparation method and application thereof. The coating material comprises a first functional component, a second functional component, a third functional component, a fourth functional component and an auxiliary agent; wherein the first functional component is nano titanium oxide and / or nano zinc oxide, the second functional component is a zinc-containing phosphate, the third functional component is nano titanium oxide and / or nano silicon oxide; and the fourth functional component is an organic fluorine resin.

Description

Technical Field

[0001] This invention provides a composite material, particularly an antibacterial, anti-corrosion, and wear-resistant coating material for use as a coating, its preparation method, and its application. Background Technology

[0002] Water injection is a crucial method for increasing oilfield production, but corrosion of injection wells remains a persistent problem. The complex quality of injection water and the constantly changing external environment have led to corrosion and scaling in most oilfield injection wells in my country, severely impacting actual production progress and efficiency, and limiting oil output. Analysis of relevant statistical data reveals that corrosion in most Chinese oilfield injection wells is influenced by numerous factors, including free CO2, H2S, sulfate-reducing bacteria (SRB), dissolved oxygen, sulfides, suspended particles, iron content, temperature, flow rate, and pressure. Organic coatings in injection wells often face damage due to scraping and other factors, and existing coatings often cannot simultaneously fulfill multiple functions such as corrosion prevention, antibacterial and antifouling properties, and wear resistance. Summary of the Invention

[0003] One aspect of the present invention provides a multifunctional nanocomposite coating material, comprising a first functional component, a second functional component, a third functional component, a fourth functional component, and an additive; wherein the first functional component is nano-titanium oxide and / or nano-zinc oxide, the second functional component is a zinc-containing phosphate, the third functional component is nano-titanium oxide iron oxide red and / or nano-silica, and the fourth functional component is an organic fluorine resin.

[0004] In one specific embodiment, the average particle size of the first functional component, the second functional component, and the third functional component is independently 10 to 100 nm.

[0005] In one specific embodiment, the organofluorine resin is at least one of tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-ethylene ether copolymer, and polyvinylidene fluoride.

[0006] In one specific embodiment, the phosphate is zinc phosphate.

[0007] In one specific embodiment, the additives include solvents, dispersants, film-forming agents, and curing agents.

[0008] In one specific embodiment, the solvent is at least one selected from xylene, acetone, and cyclohexanone.

[0009] In one specific embodiment, the dispersant is at least one selected from sodium dodecyl sulfate, sodium tetradecyl sulfate, and sodium hexadecyl sulfate.

[0010] In one specific embodiment, the film-forming agent is polymethylphenylsiloxane and / or dimethylsiloxane. For example, the relative molecular weight of polymethylphenylsiloxane is 126 to 166; the relative molecular weight of dimethylsiloxane is 222 to 444.

[0011] In one specific embodiment, the curing agent is at least one selected from monoisocyanate, diisocyanate, and triisocyanate.

[0012] In one specific embodiment, based on the total mass of the material as 100%, the content of the first functional component is 0.8% to 3%, the content of the second functional component is 0.5% to 3%, the content of the third functional component is 1.5% to 4%, and the content of the fourth functional component is 35% to 50%.

[0013] In one specific embodiment, based on the total mass of the material as 100%, the solvent content is 1% to 20%, the dispersant content is 2% to 4%, the film-forming agent content is 2% to 4%, and the curing agent content is 32% to 39%.

[0014] The second invention provides a method for preparing the material as described in any one of the first inventions, comprising the following steps:

[0015] 1) The first functional component is mixed with the first dispersant and the first solvent and dispersed uniformly to obtain the first dispersion;

[0016] 2) Mix the second functional component with the second dispersant and the second solvent, and disperse them uniformly to obtain the second dispersion;

[0017] 3) Mix the third functional component with the third dispersant and the third solvent, and disperse them uniformly to obtain the third dispersion;

[0018] 4) Mix the first dispersion, the second dispersion, the third dispersion, the fourth functional component, and the fourth solvent, and disperse them evenly to obtain the fourth dispersion;

[0019] 5) Mix the curing agent, the fourth dispersion, the film-forming agent, and optionally the fifth solvent, and disperse them uniformly to obtain the multifunctional nanocomposite coating material.

[0020] In one specific embodiment, in step 1), uniform dispersion is achieved by grinding in a ball mill.

[0021] In one specific implementation, in steps 2) and 3), dispersion is carried out independently for 8 to 15 minutes at a rotational speed of 200 to 500 rpm.

[0022] In one embodiment, the first dispersant, the second dispersant, and the third dispersant are independently at least one of sodium dodecyl sulfate, sodium tetradecyl sulfate, and sodium hexadecyl sulfate.

[0023] In one specific embodiment, the first solvent, the second solvent, the third solvent, the fourth solvent, and the fifth solvent are independently at least one of xylene, acetone, and cyclohexanone.

[0024] The third invention provides the use of the material according to any one of the inventions or the material prepared by the method according to the second invention as a coating.

[0025] In one specific embodiment, the coating is used for at least one of antibacterial, anti-corrosion, and wear-resistant purposes. The beneficial effects of the invention are:

[0026] The material of this invention enables the coating to possess multiple properties simultaneously, including corrosion resistance, antibacterial properties, corrosion prevention, wear resistance, and high temperature resistance. Furthermore, all of these properties are improved compared to existing technologies, thereby enhancing the applicability of the coating material in the operating conditions of oilfield water injection systems. Attached Figure Description

[0027] Figure 1 The antibacterial rate, corrosion resistance, and amount of triboelectric weight loss of Examples 1 to 3, Comparative Examples 1 to 3, and blank are shown. Detailed Implementation

[0028] The present invention will be further described below with reference to the embodiments. However, the embodiments of the present invention are merely illustrative examples and should not be construed as limiting the present invention under any circumstances.

[0029] Example 1

[0030] The total mass of the composite coating material is 100% as follows: 50% tetrafluoroethylene-ethylene copolymer, 3% nano-TiO2 with an average particle size of 20nm, 3% nano-zinc phosphate with an average particle size of 20nm, 4% nano-silica with an average particle size of 20nm, 4% dispersant sodium dodecyl sulfate, 3.0% film-forming agent polymethylphenylsiloxane, 32% curing agent triisocyanate, and 1% solvent xylene.

[0031] The preparation method is as follows:

[0032] 1) Place TiO2, dispersant and solvent into a ball mill and grind with agate balls for 24 hours to uniformly disperse TiO2; prepare nano TiO2 dispersion;

[0033] 2) Place the nano zinc phosphate, dispersant and solvent into a ball mill and grind with agate balls for 24 hours to uniformly disperse the nano zinc phosphate; thus, prepare a nano zinc phosphate dispersion.

[0034] 3) Place nano-silica, dispersant and solvent into a ball mill and grind with agate balls for 24 hours to uniformly disperse the nano-silica; prepare nano-silica dispersion.

[0035] 4) Add tetrafluoroethylene-ethylene copolymer, solvent, nano TiO2 dispersion, nano zinc phosphate dispersion and nano silica dispersion to a high-speed disperser, and disperse at 600 rpm for 20 min to obtain functional dispersion.

[0036] 5) Add the functional dispersion, curing agent triisocyanate and film-forming agent polymethylphenylsiloxane to the mixing tank, add the remaining solvent (if any), and disperse at 500 rpm for 20 min to obtain the composite coating material.

[0037] Example 2

[0038] Based on the total mass of the composite coating material as 100%, the composition is as follows: 42% tetrafluoroethylene-ethylene ether copolymer, 0.8% nano-TiO2 with an average particle size of 20 nm, 0.5% nano-zinc phosphate with an average particle size of 20 nm, 1.3% nano-iron oxide red with an average particle size of 20 nm, 2.1% sodium tetradecyl sulfate dispersant, 2.6% dimethylsiloxane film-forming agent, 39% monoisocyanate curing agent, and 11.7% cyclohexanone solvent.

[0039] The preparation method is as follows:

[0040] 1) TiO2, dispersant and solvent are placed in a ball mill and ground with agate balls for 24 hours to uniformly disperse TiO2; nano TiO2 dispersion is obtained.

[0041] 2) Place the nano zinc phosphate, dispersant and solvent into a ball mill and grind with agate balls for 24 hours to uniformly disperse the nano zinc phosphate; thus, prepare a nano zinc phosphate dispersion.

[0042] 3) Place the nano iron oxide red, dispersant and solvent into a ball mill and grind with agate balls for 24 hours to uniformly disperse the nano iron oxide red; thus, prepare a nano iron oxide red dispersion.

[0043] 4) Add tetrafluoroethylene-ethylene ether copolymer, solvent, nano TiO2 dispersion, nano zinc phosphate dispersion and nano iron oxide red dispersion to a high-speed disperser, and disperse at 450 rpm for 40 min to obtain functional dispersion.

[0044] 5) Add the functional dispersion, curing agent monoisocyanate and film-forming agent dimethylsiloxane to the stirred tank, add the remaining amount of cyclohexanone (if any), and disperse at 400 rpm for 15 min to obtain the composite coating material.

[0045] Example 3

[0046] The total mass of the composite coating material is 100%, consisting of 35% polyvinylidene fluoride, 1.0% nano-ZnO with an average particle size of 20nm, 0.6% nano-zinc phosphate with an average particle size of 20nm, 1.5% nano-silica with an average particle size of 20nm, 3% sodium tetradecyl sulfate as dispersant, 4.1% dimethylsiloxane as film-forming agent, 35% triisocyanate as curing agent, and 19.8% acetone as solvent.

[0047] The preparation method is as follows:

[0048] 1) Place ZnO2, dispersant and solvent into a ball mill and grind with agate balls for 24 hours to uniformly disperse ZnO2; prepare nano ZnO2 dispersion;

[0049] 2) Place the nano zinc phosphate, dispersant and solvent into a ball mill and grind with agate balls for 24 hours to uniformly disperse the nano zinc phosphate; thus, prepare a nano zinc phosphate dispersion.

[0050] 3) Place nano-silica, dispersant and solvent into a ball mill and grind with agate balls for 24 hours to uniformly disperse the nano-silica; prepare nano-silica dispersion.

[0051] 4) Add polyvinylidene fluoride, solvent, nano ZnO2 dispersion, nano zinc phosphate dispersion and nano silica dispersion to high-speed dispersion, and disperse at 400 rpm for 40 min to obtain functional dispersion.

[0052] 5) Add the functional dispersion, curing agent triisocyanate and film-forming agent dimethylsiloxane to the mixing tank, add the remaining acetone (if any), and disperse at 350 rpm for 30 min using a high-speed dispersant to obtain the composite coating material.

[0053] Comparative Example 1

[0054] Based on the total mass of the composite coating material as 100%, the composition is as follows: tetrafluoroethylene-ethylene ether 42%, nano-TiO2 with an average particle size of 20 nm 0.8%, nano-silica with an average particle size of 20 nm 1.3%, dispersant sodium tetradecyl sulfate 2.1%, film-forming agent dimethylsiloxane 2.6%, curing agent monoisocyanate 39%, and solvent cyclohexanone 12.2%.

[0055] Everything else is the same as in Example 2.

[0056] Comparative Example 2

[0057] Based on the total mass of the composite coating material as 100%, the composition is as follows: 42% tetrafluoroethylene-ethylene, 0.8% zinc phosphate with an average particle size of 20nm, 1.3% silicon dioxide with an average particle size of 20nm, 2.1% sodium tetradecyl sulfate dispersant, 3.0% polymethylphenylsiloxane film-forming agent, 32% triisocyanate curing agent, and 12.2% xylene solvent.

[0058] Everything else is the same as in Example 1.

[0059] Comparative Example 3

[0060] Based on the total mass of the composite coating material as 100%, the composition is as follows: 42% tetrafluoroethylene-ethylene copolymer, 0.8% nano zinc phosphate with an average particle size of 20 nm, 0.9% nano titanium dioxide with an average particle size of 20 nm, 2.1% sodium tetradecyl sulfate dispersant, 2.6% polymethyl phenylsiloxane film-forming agent, 39% triisocyanate curing agent, and 12.6% xylene solvent.

[0061] Everything else is the same as in Example 1.

[0062] The performance of the composite coating materials prepared in the above embodiments and comparative examples was evaluated using a dynamic high-temperature and high-pressure reactor, as follows:

[0063] 1) Each composite coating material was coated onto an N80 test plate, cured at 25°C, and then cured in a desiccator for 3 days to obtain coating samples. Three replicate coating samples were prepared for each composite coating material. The N80 test plate without composite coating material was used as a blank sample.

[0064] 2) A dynamic high-temperature and high-pressure reactor was used to simulate the environment of an oilfield water injection well, namely, an ambient temperature of 60℃, a CO2 partial pressure of 1MPa, a water salinity of 18530mg / L, and a flow rate of 1m / s. Each coating sample or blank sample was placed in the dynamic high-temperature and high-pressure reactor.

[0065] 3) The experimental period was 15 days. After the samples were removed, corrosion resistance was measured using an electrochemical workstation to analyze corrosion resistance, and friction weight loss was measured using a friction testing machine to analyze wear resistance. Results are shown below. Figure 1 .

[0066] The antibacterial properties of the composite coating materials prepared in the above embodiments and comparative examples were tested using the atmospheric pressure method, as follows:

[0067] 1) After curing at 25℃, the samples were cured in a desiccator for 3 days to obtain the coating samples. Three replicate coating samples were prepared for each composite coating material. The uncoated sample was used as a blank control.

[0068] 2) Add 100 μl of a 1×10⁻⁶ solution to each coated sample or blank sample. 6E. coli culture medium at CFU / ml (culture medium formula: yeast extract 1.0 g / L, sodium lactate 3.5 g / L, sodium citrate 5.0 g / L, magnesium sulfate (MgSO4) 2.0 g / L, calcium sulfate (CaSO4·2H2O) 1.0 g / L, ammonium chloride (NH4Cl) 1.0 g / L, dipotassium hydrogen phosphate (K2HPO4) 0.5 g / L, ferrous ammonium sulfate (Fe(NH4)2(SO4)2) 1.0 g / L, deionized water) was placed in an incubator at 37℃ and allowed to stand for 12 hours. Then, the E. coli culture medium dropped onto each coated sample or blank sample was rinsed with 9.9 ml (i.e., diluted 100 times) of sterilized culture medium and collected. The collected E. coli culture medium was tested for bacterial content using the serial dilution method in bacterial vials. The bacterial count on the surface of each coated sample was Cc (CFU / ml), and the bacterial content in the blank sample was measured as Cb (CFU / ml).

[0069] 3) Calculation of antibacterial rate: (C b -C c ) / C b The results are shown below. Figure 1 .

[0070] While the present invention has been described with reference to specific embodiments, those skilled in the art will understand that various changes can be made without departing from the true spirit and scope of the invention. Furthermore, numerous modifications can be made to the subject, spirit, and scope of the invention to suit specific situations, materials, material compositions, and methods. All such modifications are included within the scope of the claims of the present invention.

Claims

1. Use of a multifunctional nanocomposite coating material in the working condition of an oilfield water injection system, the multifunctional nanocomposite coating material comprising a first functional component, a second functional component, a third functional component, a fourth functional component, and an auxiliary agent; wherein the first functional component is nano titanium oxide and / or nano zinc oxide, the second functional component is a zinc-containing phosphate, the third functional component is nano red iron oxide and / or nano silicon oxide; the fourth functional component is an organic fluorine resin; the average particle size of the first functional component, the second functional component, and the third functional component is independently 10-100 nm; the content of the first functional component is 0.8%-3%, the content of the second functional component is 0.5%-3%, the content of the third functional component is 1.5%-4%, and the content of the fourth functional component is 35%-50%, based on the total mass of the multifunctional nanocomposite coating material being 100%.

2. Use according to claim 1, characterized in that, the organic fluorine resin is a tetrafluoroethylene-vinyl ether copolymer.

3. Use according to claim 1, characterized in that, the auxiliary agent comprises a solvent, a dispersant, a film-forming agent, and a curing agent.

4. Use according to claim 3, characterized in that, the solvent is at least one of xylene, acetone, and cyclohexanone.

5. Use according to claim 3, characterized in that, the dispersant is at least one of sodium dodecyl sulfate, sodium tetradecyl sulfate, and sodium hexadecyl sulfate.

6. Use according to claim 3, characterized in that, the film-forming agent is polymethylphenylsiloxane and / or dimethylsiloxane.

7. Use according to claim 3, characterized in that, the curing agent is diisocyanate or triisocyanate.

8. Use according to any one of claims 3 to 7, characterized in that, the content of the solvent is 1%-20%, the content of the dispersant is 2%-4%, the content of the film-forming agent is 2%-4%, and the content of the curing agent is 32%-39%, based on the total mass of the multifunctional nanocomposite coating material being 100%.

9. Use according to any one of claims 3 to 7, characterized in that, the multifunctional nanocomposite coating material is prepared according to the following steps: 1) mixing the first functional component with a first dispersant and a first solvent, uniformly dispersing to obtain a first dispersion liquid; 2) mixing the second functional component with a second dispersant and a second solvent, uniformly dispersing to obtain a second dispersion liquid; 3) mixing the third functional component with a third dispersant and a third solvent, uniformly dispersing to obtain a third dispersion liquid; 4) mixing the first dispersion liquid, the second dispersion liquid, the third dispersion liquid, the fourth functional component, a fourth solvent, uniformly dispersing to obtain a fourth dispersion liquid; 5) mixing the curing agent, the fourth dispersion liquid, the film-forming agent, and a fifth solvent, uniformly dispersing to obtain the multifunctional nanocomposite coating material.

10. Use according to claim 9, characterized in that, in step 1), the dispersion is uniformly achieved by grinding in a ball mill; and / or in steps 2) and 3), independently by dispersing at a rotation speed of 200-500 rpm for 8-15 minutes; and / or the first dispersant, the second dispersant, and the third dispersant are independently at least one of sodium dodecyl sulfate, sodium tetradecyl sulfate, and sodium hexadecyl sulfate; and / or the first solvent, the second solvent, the third solvent, the fourth solvent, and the fifth solvent are independently at least one of xylene, acetone, and cyclohexanone.

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