CN113755075A - Ionic liquid functionalized carbon nanotube super-anticorrosion paint - Google Patents
Ionic liquid functionalized carbon nanotube super-anticorrosion paint Download PDFInfo
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- CN113755075A CN113755075A CN202111097862.7A CN202111097862A CN113755075A CN 113755075 A CN113755075 A CN 113755075A CN 202111097862 A CN202111097862 A CN 202111097862A CN 113755075 A CN113755075 A CN 113755075A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention provides an ionic liquid functionalized carbon nanotube super-anticorrosion coating, which comprises a main agent and a hardening agent; the mass ratio of the main agent to the hardening agent is 100: (20-35); the main agent contains 0.5-5 wt% of ionic liquid functionalized carbon nano tubes. According to the ionic liquid functionalized carbon nanotube super-anticorrosive coating, the ionic liquid functionalized carbon nanotube and metal powder are combined to achieve the purpose of overpass connection to form three-dimensional super-anticorrosive property, so that a coating film has good anticorrosive performance; the coating film has good compactness through the synergistic effect of the superfine metal powder and the fillers with different densities; the matching use of the auxiliary agent system enables the coating film to have a good appearance state. Particularly, the coating is matched with epoxy or polyurethane middle coating and polyurethane finish to form a three-coating matched coating, so that the corrosion resistance time and the service life of spraying equipment can be effectively prolonged, and the use cost of the equipment is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of super-anticorrosive coatings, and particularly relates to an ionic liquid functionalized carbon nanotube super-anticorrosive coating.
Background
The service life of the automobile, the engineering machinery, the off-road vehicle and other fields is greatly shortened because the operation is often more easily seriously corroded in the severe environment in the field for a long time. In order to solve the problem, an anticorrosive coating needs to be coated on the outer surface of the product to protect the product. However, the anticorrosive paint in the prior art has poor anticorrosive performance, and still cannot meet the anticorrosive requirements of mechanical products such as automobiles, engineering machinery, off-road vehicles and the like, so that the use cost of the products is high.
With the appearance of new materials and the maturity of application, the paint industry has also developed a lot, and the development of the effect of the super-anticorrosion paint becomes possible. Carbon-based materials such as carbon nanotubes have the advantages of high electrical conductivity, good stability, large specific surface area, low cost and the like, and thus have a huge research space in the automobile industry, particularly in the research of anticorrosive coatings in the fields of heavy trucks, engineering machinery and off-road vehicles. In order to improve the structure, interface and conductivity of the carbon nanotube, researchers have made a lot of researches in the directions of element doping (such as N, P, S doping), defect site construction and the like so as to improve the performance of the carbon nanotube, and further enable the anti-corrosion property of the coating or a matched coating to meet the index requirements of super-corrosion resistance. Even so, the super anticorrosive coatings in the prior art still can not satisfy the anticorrosive requirement of the equipment in the severe environment for a long time, and the anticorrosive effect still needs to be improved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the ionic liquid functionalized carbon nanotube super-anticorrosive coating which has excellent anticorrosive performance, can effectively prolong the service life of spraying equipment, and is more favorable for realizing the long-term operation of the spraying equipment in a severe environment.
An ionic liquid functionalized carbon nanotube super-anticorrosion coating comprises a main agent and a hardening agent; the mass ratio of the main agent to the hardening agent is 100: (20-35); the main agent contains 0.5-5 wt% of ionic liquid functionalized carbon nano tubes.
Ionic liquids are organic salts consisting of anions and cations, which are liquid at room temperature or at lower temperatures (generally below 100 ℃). Compared with traditional organic solvents and common saline solutions, the ionic liquid has many unique physicochemical properties, such as non-volatility or extremely low volatility, high thermal stability, good conductivity, wide electrochemical window and the like. In addition, the ionic liquid has designability, and the property of the ionic liquid can be changed by changing the matching of anions and cations, or corresponding functional groups are introduced on the anions and cations to realize specific functions.
The carbon nano tube is modified in situ by adopting the ionic liquid, and the modified carbon nano tube has the characteristics of the ionic liquid and the carbon nano tube, and has higher efficient electric conduction capability and high oxidation-reduction potential. Therefore, the anodic oxidation of the metal ions in the coating can be rapidly promoted to be passivated, and the corrosion rate of the metal ions in the medium can be effectively slowed down. Moreover, the anion of the ionic liquid with hydrophilicity can not only effectively improve the compatibility of the carbon nano tube and the coating, but also lead the carbon nano tube to be uniformly dispersed in the coating.
Because the surface of the metal powder such as zinc powder is provided with a layer of oxide film, the oxide film forms hydroxyl on the lower surface in the presence of water and is negatively charged, so that the ionic liquid cation can act with the oxide film, the aggregation of the metal powder is effectively reduced, and the metal powder is uniformly dispersed. That is to say, the ionic liquid can promote the carbon nano tubes with the anticorrosion capacity and the metal powder to be more uniformly dispersed in the coating, so that the coating is more compact, and the rust spots caused by uneven distribution of the anticorrosion filler of the coating are avoided. In addition, anions with nucleophilicity of the ionic liquid can effectively adsorb carbon dioxide on the surface of the coating, and acid corrosion is reduced.
The functionalized carbon nanotube super-anticorrosive coating based on the ionic liquid can achieve a more excellent anticorrosive effect, greatly prolongs the service life of equipment, is suitable for equipment operating in severe environments for a long time, such as heavy trucks, engineering machinery, off-road vehicles and the like, and has potential application value.
Preferably, the mass ratio of the main agent to the hardening agent is 100: (20-33).
Preferably, the ionic liquid functionalized carbon nanotube is an imidazole acetate ionic liquid functionalized carbon nanotube, and the structural formula is as follows:
the ionic liquid functionalized carbon nanotube synthesized by the invention is obtained by modifying and grafting amino on the carbon nanotube, alkylating and grafting imidazole bromide ionic liquid, and finally carrying out ion exchange reaction.
Preferably, the preparation method of the ionic liquid functionalized carbon nanotube comprises the following steps:
(1) the aminated carbon nanotube and 1, 3-dibromopropane react in a solvent A, and after the reaction is finished, the alkyl bromide functionalized carbon nanotube is obtained by post-treatment;
(2) reacting the alkyl bromide functionalized carbon nano tube with methylimidazole in a solvent B, and after the reaction is finished, carrying out post-treatment to obtain an imidazole bromide ionic liquid functionalized carbon nano tube;
(3) and carrying out anion exchange reaction on the imidazole bromine particle liquid functionalized carbon nano tube and potassium acetate in a solvent C, and after the reaction is finished, carrying out post-treatment to obtain the ionic liquid functionalized carbon nano tube.
The aminated carbon nanotube can be prepared by a commercial product or a self-prepared product, and for example, the aminated carbon nanotube can be prepared by the following method: treating the carbon nano tube by using mixed solution of concentrated sulfuric acid and concentrated nitric acid to obtain an-OH carbon nano tube; then reacting with 3-aminopropyl triethoxysilane to obtain the aminated carbon nanotube.
As a further preferred method, the preparation process of the aminated carbon nanotube is as follows:
a. the preparation method comprises the following steps of (1) ultrasonically dispersing a carbon nano tube in a mixed solution of concentrated sulfuric acid and concentrated nitric acid for 20-40 min, carrying out thermal reflux reaction at 110-160 ℃ for 40-80 min, and carrying out post-treatment after the reaction is finished to obtain an-OH carbon nano tube;
b. and (3) refluxing the-OH carbon nanotube and 3-Aminopropyltriethoxysilane (APTES) in water at 100-130 ℃ for 20-30 hours in an air atmosphere to obtain the aminated carbon nanotube.
Preferably, in the step (1), the mass ratio of the aminated carbon nanotube to 1, 3-dibromopropane is 1: (0.8 to 1.3); the reaction temperature is 40-60 ℃; the solvent A is one or more of acetonitrile, toluene and ethyl acetate.
The solvent a is further preferably acetonitrile.
More preferably, in the step (1), the mass ratio of the aminated carbon nanotube to 1, 3-dibromopropane is 1: 1; the reaction temperature was 50 ℃.
Preferably, in the step (2), the mass ratio of the alkyl bromide functionalized carbon nanotube to the methylimidazole is 1: (1-1.5); the reaction temperature is 60-80 ℃; the solvent B is one or more of acetonitrile, toluene and ethyl acetate.
The solvent B is more preferably acetonitrile.
More preferably, in the step (2), the mass ratio of the alkyl bromide functionalized carbon nanotube to the methylimidazole is 1: 1.2; the reaction temperature was 70 ℃.
Preferably, in the step (3), the anion exchange reaction is carried out at normal temperature; the solvent C is one or the mixture of ethanol and methanol.
The solvent C is more preferably ethanol.
Specifically, the preparation method of the ionic liquid functionalized carbon nanotube comprises the following steps:
step 1, taking a carbon nano tube, placing the carbon nano tube in a mixed solution of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic dispersion for 20-40 min, and performing thermal reflux reaction at 110-160 ℃ for 40-80 min; after the reaction is finished, washing the product for multiple times by using secondary water until the product is neutral, filtering and drying to obtain the-OH carbon nano tube;
and then dispersing the-OH carbon nanotubes in water, adding 3-Aminopropyltriethoxysilane (APTES), and refluxing in an air atmosphere at 100-130 ℃ for 20-30 hours to obtain the aminated carbon nanotubes, wherein the aminated carbon nanotubes are shown in figure 1.
Step 2-NH2Dispersing carbon nanotubes (aminated carbon nanotubes) in acetonitrile, adding 1, 3-dibromopropane, performing reflux reaction at 40-60 ℃ for 20-30 hours, washing with ethyl acetate and water respectively, and drying to obtain alkyl bromide functionalized carbon nanotubes;
and then dispersing the alkyl bromide functionalized carbon nanotube in acetonitrile, adding methylimidazole, carrying out reflux reaction at the temperature of 60-80 ℃ for 20-30 hours, washing with ethyl acetate and water after the reaction is finished, and drying to obtain the imidazole bromide ionic liquid functionalized carbon nanotube, as shown in figure 2.
And 3, carrying out anion exchange on the imidazole bromine ionic liquid functionalized carbon nano tube and potassium acetate in an ethanol solution, stirring at normal temperature overnight, carrying out suction filtration, washing with water for three times, and drying to obtain the ionic liquid functionalized carbon nano tube, wherein the ionic liquid functionalized carbon nano tube is shown in figure 3.
Preferably, the main agent comprises the following components in parts by weight based on 100 parts of the total amount of the main agent:
more preferably, the metal powder is one or more of zinc powder, zinc phosphate and micaceous iron;
the pigment is one or more of carbon black, titanium dioxide, phthalocyanine blue and iron oxide red;
the filler is one or more of talcum powder, precipitated barium sulfate, heavy calcium carbonate and mica powder;
the solvent I is one or more of dimethylbenzene, heavy aromatic hydrocarbon, butyl acetate, methyl isobutyl ketone, n-butyl alcohol and the like.
As a further preference, the solvent I comprises the following components in parts by weight based on 100 parts by weight of the total weight of the solvent I:
still more preferably, the filler is one or a mixture of talc and precipitated barium sulfate.
Still more preferably, the metal powder is zinc powder.
More preferably, the particle size of the metal powder is 500-1250 meshes; the particle size of the filler is 800-2000 meshes.
More preferably, the particle size of the metal powder is 800 meshes; the particle size of the filler is 1250 meshes.
As a further preference, the auxiliary agent comprises one or more of a dispersing agent, a wetting agent, a defoaming agent, a leveling agent and a dust-proof agent, and the weight parts of each auxiliary agent in the main agent are as follows:
further preferably, the dispersant is one or more of BYK-163, EFKA4050 and TEGO 630;
the wetting agent is one or more of BYK-378, EFKA5065 and TEGO 2100;
the defoaming agent is one or more of BYK-054, EFKA2722 and TEGO 900;
the leveling agent is one or more of BYK-323, EFKA3600 and TEGO 1484;
the dustproof agent is one or more of wax, bentonite and silicon dioxide.
Wherein BYK stands for Pico Chemicals, EFKA stands for Effka; TEGO stands for Digaku chemical company.
Preferably, the preparation process of the main agent comprises the following steps:
pulping: adding epoxy resin into a material mixing basin, slowly adding a part of solvent, dispersant, defoamer, wetting agent, pigment, filler, anti-settling agent, ionic liquid functionalized carbon nanotube and the like under a stirring state, adjusting the viscosity to be suitable for grinding by using the solvent, grinding for 3-4 times by using a sand mill until the fineness is below 30 mu m, and detecting the solid content of the paint paste.
Preparing paint: adding metal powder according to the formula amount under the stirring state of the paint paste, uniformly dispersing under the high-speed stirring state to the fineness of below 50 mu m, stirring and adjusting to medium and low speed, slowly adding a flatting agent and a solvent to adjust the viscosity of the paint liquid to 70-80S, filtering, packaging and warehousing after the detection performance is qualified.
As a further preference, the hardener comprises the following components in parts by weight, based on 100 parts by weight of the total weight of the hardener:
60-80 parts of fatty amine
0.2 to 0.5 part of stabilizer
19.5-39.8 parts of a solvent II.
Still more preferably, the fatty amine is one or more of MG-5221, NP3110, TE-80;
the stabilizer is TI;
the solvent II is one or more of dimethylbenzene, heavy aromatic hydrocarbon, butyl acetate and n-butyl alcohol.
As a further preferable scheme, the solvent II comprises the following components in parts by weight based on 100 parts by weight of the total weight of the solvent II:
60-80 parts of dimethylbenzene
20-40 parts of n-butyl alcohol.
Preferably, the ionic liquid functionalized carbon nanotube super-anticorrosion paint is used as a primer. Can be used together with the conventional epoxy or polyurethane middle coating and polyurethane finishing coat.
Preferably, the preparation process of the hardener comprises the following steps:
adding the fatty amine into a material mixing basin according to the formula, slowly adding the solvent under the stirring state, slowly adding the stabilizer under the stirring state after uniformly stirring, uniformly stirring the whole body, filtering, packaging and warehousing after the detection performance is qualified.
When the ionic liquid functionalized carbon nanotube super-anticorrosive coating is used, the main agent and the hardening agent which are respectively packaged are mixed according to a proportion, the viscosity is adjusted to the construction viscosity by using a matched diluent, and then coating construction can be carried out.
The ionic liquid functionalized carbon nanotube super-anticorrosion paint disclosed by the invention is prepared from epoxy resin, fatty amine matched pigment, filler, ionic liquid functionalized carbon nanotube, a dispersing agent, a wetting agent, a defoaming agent, a leveling agent, an anti-settling agent and other materials, and can achieve an excellent super-anticorrosion effect in the using process. The product can be used in the fields of heavy trucks, engineering machinery, off-road vehicles and the like with severe working environments.
The ionic liquid functionalized super-anticorrosion paint disclosed by the invention has a good anticorrosion property of a coating film due to the fact that the ionic liquid functionalized carbon nano tube and the metal powder form a cross-over structure, and the requirement of super-anticorrosion property of products such as heavy trucks, engineering machinery, off-road vehicles and the like is met through the use of the paint product disclosed by the invention. The matching use of the auxiliary agent matching system improves the surface state of the coating film, so that the coating film has good appearance. The coating thickness of the ionic liquid functionalized carbon nanotube super-anticorrosion paint is 70-90 mu m, and the ionic liquid functionalized carbon nanotube super-anticorrosion paint is suitable for super-anticorrosion requirements in the fields of heavy trucks, engineering machinery, off-road vehicles and the like.
Compared with the prior art, the invention has the beneficial effects that:
according to the ionic liquid functionalized carbon nanotube super-anticorrosion coating, the functionalized carbon nanotube has stronger electrochemical anticorrosion capacity, and the functionalized ionic liquid cations can also act with metal powder with negative electricity on the surface through electrostatic force, so that the dispersibility of the metal powder is improved, and the uniformity and compactness of the coating are further improved. Namely, the three-dimensional super-corrosion resistance formed by the overpass is achieved through the synergistic effect of the ionic liquid functionalized carbon nano tube and the metal powder, so that the coating has good corrosion resistance; the coating film has good compactness through the synergistic effect of the superfine metal powder and a plurality of fillers with different densities; the matching use of the auxiliary agent system enables the coating film to have a good appearance state. Particularly, the coating is matched with epoxy or polyurethane middle coating and polyurethane finish to form a three-coating matched coating, so that the corrosion resistance time and the service life of spraying equipment can be effectively prolonged, and the use cost of the equipment is greatly reduced.
Drawings
FIG. 1 is a schematic diagram of a process for synthesizing aminated carbon nanotubes according to one embodiment of the present invention;
FIG. 2 is a schematic diagram of a process for synthesizing imidazole bromide ionic liquid functionalized carbon nanotubes according to an embodiment of the present invention;
fig. 3 is a schematic diagram of a synthesis process of imidazole acetate ionic liquid functionalized carbon nanotubes in an embodiment of the present invention.
Detailed Description
For the purposes of simplicity and clarity, the invention will be further described with reference to preferred embodiments.
Specifically, the following are mentioned: of the raw materials used in the following examples, dispersants: BYK-163, EFKA4050, TEGO 630; wetting agent: EFKA5065, TEGO 2100; defoaming agent: BYK-054, TEGO 900; leveling agent: BYK-323 and EFKA 3600. Wherein: BYK stands for Picker chemical, EFKA stands for Effa; TEGO stands for Digaku chemical company. Other resins, pigments, hardeners, etc. are commercially available. That is, the starting materials for preparing the present invention are commercially available. The parts referred by the invention can be grams and kilograms, which are mainly selected according to the actual requirements of production.
Epoxy resin: sanmu SM601
Carbon black MA 100: mitsubishi of Japan
Bentonite 828: haimines 828
Fatty amine MG-5221: jiangsu Ma ancient chemical MG-5221
Fatty amine TE-80: changzhou mountain peak chemical engineering TE-80
Stabilizer TI: guangzhou Yingrui TI
Example 1
(1) Preparing the ionic liquid functionalized carbon nanotube:
modification of carbon nanotubes: weighing 1.00g of carbon nano tube in a mixed solution of 15mL of concentrated sulfuric acid and 15mL of concentrated nitric acid, carrying out ultrasonic dispersion for 30min, and then carrying out thermal reflux reaction at 140 ℃ for 60 min. Washing the product with secondary water for many times until the product is neutral, filtering and drying to obtain the-OH carbon nano tube. Subsequently, 1.00g of the OH-modified carbon nanotubes were dispersed in 20mL of secondary water, and after adding 1.00g of 3-Aminopropyltriethoxysilane (APTES), they were refluxed in an air atmosphere at 110 ℃ for 24 hours to obtain amino-modified carbon nanotubes, as shown in FIG. 1.
Preparing imidazole bromide ionic liquid functionalized carbon nanotubes: dispersing 1.00g of-NH 2 carbon nano-tube in 100mL of acetonitrile, simultaneously adding 1.00g of 1, 3-dibromopropane, carrying out reflux reaction at 50 ℃ for 24 hours, washing with ethyl acetate and water respectively, and drying to obtain the alkyl bromide functionalized carbon nano-tube. And then dispersing 1.00g of alkyl bromide functionalized carbon nanotube in 100mL of acetonitrile, adding 1.20g of methylimidazole, carrying out reflux reaction at 70 ℃ for 24 hours, washing with ethyl acetate and water, and drying to obtain the imidazole bromide ionic liquid functionalized carbon nanotube, wherein the reaction product is shown in figure 2.
Preparing imidazole acetate ionic liquid functionalized carbon nano tube: and (3) carrying out anion exchange on 1.00g of imidazole bromide ionic liquid functionalized carbon nanotube and potassium acetate in 100mL of ethanol solution, stirring at normal temperature overnight, carrying out suction filtration, washing with water for three times, and drying to obtain the target imidazole acetate ionic liquid functionalized carbon nanotube, wherein the target imidazole acetate ionic liquid functionalized carbon nanotube is shown in figure 3.
(2) Preparation of super anticorrosive paint
The process comprises the following steps:
a main agent: mixing (adding epoxy resin, solvent I, a dispersing agent, a wetting agent and a defoaming agent) → stirring → adding pigment, filler and a dustproof agent, and the prepared imidazole acetate ionic liquid functionalized carbon nanotube → grinding until the fineness is qualified (the fineness is less than 30 μm) → paint mixing (adding metal powder and dispersing at a high speed until the fineness is qualified (the fineness is less than 50 μm), then adding a leveling agent and a solvent) → adjusting the viscosity to 70-80S, and adding a solid content → detection performance → filtering and packaging qualified products.
Hardening agent: ingredients (adding fatty amine and solvent II) → stirring evenly → slowly adding stabilizer under stirring → detecting performance → filtering and packaging qualified products.
The main raw materials are proportioned as follows:
a main agent: hardening agent is 100: 20
The main agent comprises the following components by weight of 1000g of the total weight of the main agent:
wherein, the solvent I comprises the following components:
the ionic liquid functionalized carbon nanotube is the prepared imidazole acetate ionic liquid functionalized carbon nanotube.
Hardener total weight 200g, hardener:
wherein the solvent II comprises the following components:
3.7 parts of dimethylbenzene
And 1.74 parts of n-butanol.
Example 2
The process comprises the following steps: same as example 1
The main raw materials are proportioned as follows:
a main agent: hardening agent 100:25
The main agent comprises the following components in percentage by weight of 1000g of the total weight of the main agent:
wherein, the solvent I:
the ionic liquid functionalized carbon nanotube was the imidazolium acetate ionic liquid functionalized carbon nanotube prepared in example 1.
The composition of the hardener was as follows, based on 250g total weight of hardener:
wherein, the solvent II:
7.0 parts of xylene
And 1.9 parts of n-butanol.
Example 3
The process comprises the following steps: same as example 1
The main raw materials are proportioned as follows:
a main agent: hardening agent 100:30
The main agent comprises the following components in percentage by weight of 1000g of the total weight of the main agent:
wherein, the solvent I:
the ionic liquid functionalized carbon nanotube was the imidazolium acetate ionic liquid functionalized carbon nanotube prepared in example 1.
The composition of the hardener was as follows, based on 300g total weight of hardener:
wherein, the solvent II:
6.0 parts of dimethylbenzene
3.9 parts of n-butanol.
The preparation method of the ionic liquid functionalized carbon nanotube super anticorrosive coating in the embodiments 1 to 3 comprises the following steps:
(1) preparing a main agent:
pulping: adding epoxy resin into a material mixing basin, slowly adding a part of solvent I, a dispersing agent, a defoaming agent, a wetting agent, pigment, a filler, an anti-settling agent, an ionic liquid functionalized carbon nano tube and the like under a stirring state, adjusting the viscosity to be suitable for grinding by using the solvent I, grinding for 3-4 times by using a sand mill until the fineness is below 30 mu m, and detecting the solid content of the paint paste.
Preparing paint: adding metal powder according to the formula amount under the stirring state of the paint paste, uniformly dispersing under the high-speed stirring state to the fineness of below 50 mu m, stirring and adjusting to medium and low speed, slowly adding a flatting agent and a solvent I to adjust the viscosity of the paint liquid to 70-80S, filtering, packaging and warehousing after the detection performance is qualified.
(2) Preparing a hardening agent: adding the fatty amine into a material mixing basin according to the formula, slowly adding the solvent II under the stirring state, slowly adding the stabilizer under the stirring state after uniformly stirring, uniformly stirring the whole body, filtering, packaging and warehousing after the detection performance is qualified.
(3) The use of the ionic liquid functionalized carbon nanotube super-anticorrosion coating comprises the following steps: when in use, the main agent and the hardening agent which are respectively packaged are mixed according to the proportion, and the viscosity is adjusted to the construction viscosity by using a matched diluent, so that the coating construction can be carried out, and the coating film has excellent anti-corrosion performance.
And (3) comparison test:
conventional spraying of existing loaders is used as a comparison group:
the method comprises the following steps: the loader can achieve the coating effect by matching three coatings in a conventional state, and comprises matching of epoxy zinc-rich primer, epoxy or polyurethane middle coating and polyurethane finish.
The method comprises the following steps:
1. and performing shot blasting and sand blasting treatment on the loader workpiece to reach a corresponding grade.
2. And spraying the epoxy zinc-rich primer on the treated loader workpiece, mixing the components according to the proportion of the epoxy zinc-rich primer, uniformly stirring, and spraying the base material.
3. And baking the sprayed loader workpiece to dry the coating.
4. And (3) spraying the epoxy or polyurethane primer surfacer on the loader workpiece which is qualified and completely dried in the spraying of the primer surfacer, wherein the epoxy primer surfacer is adopted in the embodiment, and the components are mixed according to the proportion of the epoxy primer surfacer, uniformly stirred and then sprayed.
5. And baking the sprayed loader workpiece to dry the matched coating.
6. And (3) spraying polyurethane finish on the loader workpiece which is qualified and completely dried in the process of spraying the middle coating, mixing the components according to the proportion of the polyurethane finish, uniformly stirring, and then performing spraying construction.
7. And baking the sprayed loader workpiece to dry the matched coating.
8. And (4) detecting the performance of the matched coating on the completely dried loader workpiece.
The detection result of the three-coating film is as follows:
the coating is alkali resistant, and does not wrinkle, crack or change color slightly after 24 hours;
the coating has acid resistance, and does not wrinkle, crack or change color slightly after 24 hours;
the coating has neutral salt fog resistance, does not bubble, rust or crack within 1000h, gradually bubbles, rust and other problems within more than 1000h, and is seriously aggravated within 48 h;
the coating has aging resistance, 1000h delta E is less than or equal to 3.0, and the light loss rate is less than or equal to 30 percent.
Some manufacturers change the epoxy zinc-rich primer into a common epoxy primer or omit the coating of epoxy or polyurethane middle paint, so that the coating film has greatly reduced corrosion resistance although the cost is saved.
The loader adopts the spraying of the coating mode of the ionic liquid functionalized carbon nanotube super-anticorrosion coating as an experimental group:
the method comprises the following steps: the three coatings are matched to achieve the anti-corrosion performance, and are matched with the ionic liquid functionalized carbon nanotube super-anticorrosive coating (prepared in example 1), the epoxy intermediate coating and the polyurethane finish.
The method comprises the following steps:
1. and performing shot blasting and sand blasting treatment on the loader workpiece to reach a corresponding grade.
2. And spraying the ionic liquid functionalized carbon nanotube super-anticorrosive paint on the treated loader workpiece, mixing the components according to the proportion of the ionic liquid functionalized carbon nanotube super-anticorrosive paint, uniformly stirring, and spraying the base material.
3. And baking the sprayed loader workpiece to dry the coating.
4. The loader workpiece which is qualified and completely dried by spraying the ionic liquid functionalized carbon nanotube super-anticorrosive paint is subjected to epoxy primer surfacer (the same epoxy primer surfacer as the comparison group is adopted in the embodiment) construction, and the components are mixed according to the proportion of the epoxy primer surfacer and are uniformly stirred for spraying construction.
5. And baking the sprayed loader workpiece to dry the matched coating.
6. And (3) spraying polyurethane finish on the loader workpiece which is qualified and completely dried in the process of spraying the middle coating, mixing the components according to the proportion of the polyurethane finish coating which is the same as that of the comparison group, uniformly stirring, and then performing spraying construction.
7. And baking the sprayed loader workpiece to dry the matched coating.
8. And (4) detecting the performance of the matched coating on the completely dried loader workpiece.
The detection result of the ionic liquid functionalized carbon nanotube super-anticorrosion paint matched with the three-coating film is as follows:
the coating is alkali resistant, and does not wrinkle, crack or change color slightly after 24 hours;
the coating has acid resistance, and does not wrinkle, crack or change color slightly after 24 hours;
the coating is resistant to neutral salt fog, and does not bubble, rust or crack after 3600 h;
the coating has aging resistance, 1000h delta E is less than or equal to 3.0, and the light loss rate is less than or equal to 30 percent.
Conclusion of the comparative experiment:
(1) the ionic liquid functionalized carbon nanotube super-anticorrosive coating has the advantages of smooth matching coating, excellent coating state and no obstacle in integral matching coating.
(2) Compared with the salt spray resistance of a comparison group, the salt spray resistance of a coating (experimental group) coated by the ionic liquid functionalized carbon nanotube super-anticorrosion paint coating is greatly improved, so that the protection of the coating on a workpiece is greatly improved, the purposes of super-anticorrosion standard and long-acting protection are achieved, and the coated object can be protected for a long time in a severe working environment.
Example 4 (practical use)
The separately packaged base and hardener prepared in example 1 were mixed in a ratio of 100: 20 parts by weight of the components are mixed and are regulated to construction viscosity by a diluent, and the mixture is uniformly stirred to carry out spraying construction.
The method generally adopts a high-pressure airless spraying method:
(1) spraying the ionic liquid functionalized carbon nanotube super-anticorrosive paint onto a loader body workpiece qualified by shot blasting and sand blasting, wherein the spraying thickness is 80 mu m, and the baked coating is as follows:
the appearance is smooth and fine;
film hardness: not less than 2H;
the adhesive force of a coating film (2 mm by a lattice drawing method) is less than or equal to grade 1;
drawing: not less than 6 MPa.
(2) Spraying epoxy primer surfacer on a loader body coated with the ionic liquid functionalized carbon nanotube super-anticorrosive paint, wherein the coating thickness is 50 mu m, and forming a matched coating after baking:
the appearance of the coating film is smooth and fine;
the hardness of the coating film is more than or equal to 2H;
the adhesive force (2 mm by a lattice cutting method) of the matched coating is less than or equal to 1 grade.
(3) Spraying and coating polyurethane finish on a loader body coated with the ionic liquid functionalized carbon nanotube super-anticorrosive coating and the epoxy intermediate coating, wherein the coating thickness is 35 mu m, and the coating is a matching coating after baking:
the appearance of the coating film is smooth and fine;
the hardness of the coating film is more than or equal to 2H;
the adhesive force (2 mm by a lattice cutting method) of the matched coating is less than or equal to 1 grade;
the acid resistance of the matched coating (0.05mol/L, H)2SO4) No wrinkling, no cracking and slight color change after 24 hours;
the matched coating is alkali-resistant (0.1mol/L, NaOH) and does not wrinkle, crack or change color slightly for 24 hours;
the oil resistance (93# gasoline) of the matched coating is 8h, and the paint film does not wrinkle, crack or change color slightly;
the matched coating has diesel oil resistance for 240 hours, does not wrinkle, does not crack and slightly discolors;
the matching coating is good in moisture and heat resistance for 240 h;
and (3) high and low temperature test of the matched coating: 30 cycles, the paint film is intact (2 mm grid cutting) for grade 1;
the matched coating has neutral salt spray resistance (5% salt spray) for 3600h, and does not foam, rust or fall off;
the aging resistance of the matched coating is 1000h, delta E is less than or equal to 3.0, and the light loss rate is less than or equal to 30%.
The performance test data show that the ionic liquid functional carbon nanotube super-anticorrosion matched coating film sprayed by the method achieves the long-acting protection effect on the loader body. The loader coated with the ionic liquid functionalized carbon nanotube super-anticorrosion matching coating can adapt to extremely severe working environment, and the service life of the loader is greatly prolonged.
Although the present invention has been described in detail with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. And the invention is not limited to the embodiments of the examples given in the description.
Claims (10)
1. An ionic liquid functionalized carbon nanotube super-anticorrosion coating comprises a main agent and a hardening agent; the adhesive is characterized in that the mass ratio of the main agent to the hardening agent is 100: (20-35); the main agent contains 0.5-5 wt% of ionic liquid functionalized carbon nano tubes.
2. The ionic liquid functionalized carbon nanotube super anticorrosive coating according to claim 1, wherein the ionic liquid functionalized carbon nanotube is an imidazoleacetate ionic liquid functionalized carbon nanotube, and the structural formula is as follows:
3. the ionic liquid functionalized carbon nanotube super anticorrosive coating according to claim 1, wherein the preparation method of the ionic liquid functionalized carbon nanotube comprises the following steps:
(1) the aminated carbon nanotube and 1, 3-dibromopropane react in a solvent A, and after the reaction is finished, the alkyl bromide functionalized carbon nanotube is obtained by post-treatment;
(2) reacting the alkyl bromide functionalized carbon nano tube with methylimidazole in a solvent B, and after the reaction is finished, carrying out post-treatment to obtain an imidazole bromide ionic liquid functionalized carbon nano tube;
(3) and carrying out anion exchange reaction on the imidazole bromine particle liquid functionalized carbon nano tube and potassium acetate in a solvent C, and after the reaction is finished, carrying out post-treatment to obtain the ionic liquid functionalized carbon nano tube.
4. The ionic liquid functionalized carbon nanotube super anticorrosive coating according to claim 3, wherein in the step (1), the mass ratio of the aminated carbon nanotube to the 1, 3-dibromopropane is 1: (0.8 to 1.3); the reaction temperature is 40-60 ℃; the solvent A is one or more of acetonitrile, toluene and ethyl acetate.
5. The ionic liquid functionalized carbon nanotube super anticorrosive coating according to claim 3, wherein in the step (2), the mass ratio of the alkyl bromide functionalized carbon nanotube to the methylimidazole is 1: (1-1.5); the reaction temperature is 60-80 ℃; the solvent B is one or more of acetonitrile, toluene and ethyl acetate.
6. The ionic liquid functionalized carbon nanotube super anticorrosive paint according to claim 3, wherein in the step (3), potassium acetate is excessive in the anion exchange reaction; the anion exchange reaction is carried out at normal temperature; the solvent C is one or the mixture of ethanol and methanol.
7. The ionic liquid functionalized carbon nanotube super anticorrosive paint according to claim 1, wherein the main agent comprises the following components in parts by weight, based on 100 parts of the total amount of the main agent:
the hardener comprises the following components in parts by weight, based on 100 parts by weight of the total weight of the hardener:
60-80 parts of fatty amine
0.2 to 0.5 part of stabilizer
19.5-39.8 parts of a solvent II.
8. The ionic liquid functionalized carbon nanotube super anticorrosive paint of claim 7, wherein the metal powder is one or more of zinc powder, zinc phosphate and micaceous iron;
the pigment is one or more of carbon black, titanium dioxide, phthalocyanine blue and iron oxide red;
the filler is one or more of talcum powder, precipitated barium sulfate, heavy calcium carbonate and mica powder;
the solvent I is one or more of dimethylbenzene, heavy aromatic hydrocarbon, butyl acetate, methyl isobutyl ketone and n-butyl alcohol;
the fatty amine is one or more of MG-5221, NP3110 and TE-80;
the stabilizer is TI;
the solvent II is one or more of dimethylbenzene, heavy aromatic hydrocarbon, butyl acetate and n-butyl alcohol.
9. The ionic liquid functionalized carbon nanotube super anticorrosive paint according to claim 7, wherein the particle size of the metal powder is 500-1250 mesh; the particle size of the filler is 800-2500 meshes.
10. The ionic liquid functionalized carbon nanotube super anticorrosive paint according to claim 7, wherein the auxiliary agent comprises one or more of a dispersant, a wetting agent, a defoamer, a leveling agent and a dustproof agent, and the weight parts of each auxiliary agent in the main agent are as follows:
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