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CN112251063B - Preparation method and application of composite anticorrosive paint - Google Patents

Preparation method and application of composite anticorrosive paint Download PDF

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CN112251063B
CN112251063B CN202011110225.4A CN202011110225A CN112251063B CN 112251063 B CN112251063 B CN 112251063B CN 202011110225 A CN202011110225 A CN 202011110225A CN 112251063 B CN112251063 B CN 112251063B
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wax
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weight
silicon dioxide
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CN112251063A (en
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裴亚利
朱晓辉
贾德荣
陈海海
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Beijing Aerospace Sai De Science & Technology Development Co ltd
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Beijing Aerospace Sai De Science & Technology Development Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • C09D5/082Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084Inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/321Phosphates
    • C08K2003/325Calcium, strontium or barium phosphate

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention discloses a preparation method and application of a composite anticorrosive paint, belonging to the field of pigments, wherein the step 1): preparing a composite anticorrosive pigment, adopting sodium silicate and sulfuric acid as raw materials, reacting at normal temperature and normal pressure to synthesize low-water-pore low-oil-absorption silicon dioxide, then sequentially adding a supersaturated calcium hydroxide solution, a phosphoric acid solution and calcium chloride into the system, uniformly stirring, finally coating with a wax emulsion, washing, drying and crushing to prepare the anticorrosive pigment with the average particle size of less than 5 mu m; and 2, mixing 65-75 parts by weight of epoxy resin, 12-15 parts by weight of butyl acetate, 8-12 parts by weight of composite anticorrosive pigment, 5.5 parts by weight of drying agent and 0.5 part by weight of iron oxide red to prepare the anticorrosive paint. The preparation method disclosed by the invention breaks through a single anticorrosion mechanism at normal temperature and normal pressure in the whole process, is designed by comprehensively considering multiple aspects of forming a compact layer, calcium ion exchange and metal chelating, is low in production cost, and the prepared anticorrosive pigment is excellent in salt spray resistance.

Description

Preparation method and application of composite anticorrosive paint
Technical Field
The invention mainly relates to the field of anticorrosive pigments, in particular to a preparation method and application of a composite anticorrosive paint.
Background
Nowadays, the problem of metal corrosion is more and more emphasized, the loss caused by metal corrosion is very large every year, and the marine salt spray corrosion is the problem which needs to be solved at present. The salt spray corrosion at sea is mainly an electrochemical effect, and chlorine ions have the greatest influence. The long-time contact with salt fog air can catalyze electrode reaction to cause the metal to lose electrons, oxygen and water in the air or water drops accelerate cathode reaction under the action of electrolyte salt, and in the electrochemical reaction, chloride ions not only serve as a member of electrolyte, but also serve as pioneers to break through a metal oxide layer to expel oxygen to generate soluble chloride, so that pores are formed. Based on the process, various corrosion prevention methods are carried out. Corrosion protection is currently involved in a number of areas including metallurgy, biology, paints, etc. and is principally based on corrosion inhibitors, metal passivation layers, sacrificial types such as zinc powder, and more recently on calcium ion exchange.
However, the existing anticorrosion technology mostly adopts a single anticorrosion substrate, so that the performance of the pigment is limited.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method and application of a composite anticorrosive paint, the anticorrosive paint of the invention can break through a single anticorrosive mechanism, is designed by comprehensively considering a plurality of aspects of compact layer formation, calcium ion exchange and metal chelating, has low production cost, and has excellent salt spray resistance.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
on one hand, the preparation method of the composite anticorrosive paint is provided, and comprises the following steps:
step 1): preparing a composite anticorrosive pigment, adopting sodium silicate and sulfuric acid as raw materials, reacting at normal temperature and normal pressure to synthesize low-water-pore low-oil-absorption silicon dioxide, then sequentially adding a supersaturated calcium hydroxide solution, a phosphoric acid solution and calcium chloride into the system, uniformly stirring, finally coating with a wax emulsion, washing, drying and crushing to prepare the anticorrosive pigment with the average particle size of less than 5 mu m;
and 2, mixing 65-75 parts by weight of epoxy resin, 12-15 parts by weight of butyl acetate, 8-12 parts by weight of composite anticorrosive pigment, 5.5 parts by weight of drying agent and 0.5 part by weight of iron oxide red to prepare the anticorrosive paint. The preferred amounts of addition are: 70 parts of epoxy resin, 14 parts of butyl acetate, 10 parts of composite anticorrosive pigment, 5.5 parts of drying agent and 0.5 part of iron oxide red.
The pore volume and oil absorption of the anticorrosive pigment prepared by the invention are key control indexes of low oil absorption silica, and the specific surface area, the calcium adsorption capacity and the silica content are key control indexes of anticorrosive calcium ions and calcium phosphate. The calcium adsorption was measured by EDTA complexometric titration, but the acidifying agent was changed from hydrochloric acid to acetic acid due to the presence of calcium phosphate in the pigment. The calcium phosphate content is indirectly reflected by the silica content (dry basis).
The content of calcium phosphate is indirectly reflected by the dry content of silica means that: during the measurement of the dry content of silica, calcium phosphate and calcium fluoride were not decomposed by evaporation due to hydrofluoric acid and high temperature, and remained in the platinum crucible. The silicon dioxide content calculation formula can be used for reasoning, and the more calcium phosphate, the smaller the measured silicon dioxide content; conversely, the larger.
According to the invention, the low-water-pore low-oil-absorption silicon dioxide is synthesized at normal temperature, the calcium ion exchange anticorrosion effect is exerted, phosphate radicals and a metal base material form a compact to play an isolation anticorrosion effect by introducing the phosphate radicals and the wax emulsion, the wax emulsion coating greatly improves the calcium ion adsorption amount of the silicon dioxide, and the prepared anticorrosion pigment has the characteristics of low pore volume and low oil absorption, has low viscosity after being added into paint, and avoids the problem that the pigment cannot be added due to overlarge construction viscosity.
The low water pore low oil absorption silica prepared by the method has the same refractive index with most of resins, is porous and easy to adsorb, has stable chemical properties, and can be used as a delustering agent, a thixotropic agent and the like. The low-porosity and low-oil-absorption silica prepared by the invention has the characteristics of low pore volume and high specific surface area, so that the silica has the properties of strong adsorbability, low viscosity, high bulk density and the like, and on one hand, the low-porosity and low-oil-absorption silica can prevent foaming in later paint application, and on the other hand, the upper limit of the addition amount generated by viscosity is improved, so that more anticorrosive pigments can be added under the condition of low viscosity.
Further, the specific steps of step 1) are as follows:
1) preparing low water pore and low oil absorption silicon dioxide: adding the prepared 20-40 wt% of dilute sulfuric acid solution into a reaction container, starting stirring, slowly adding the prepared dilute sodium silicate solution under a stirring state until the pH value is close to 6, and stirring for a period of time to prepare the low-water-hole low-oil-absorption silicon dioxide; the content of silicon dioxide in the dilute sodium silicate solution is 5 to 25 weight percent; the mass ratio of sulfuric acid in the dilute sulfuric acid solution to silicon dioxide in the sodium silicate solution is 1: (2-2.2);
2) performing composite treatment: preparing supersaturated lime water from calcium oxide and water according to the mass ratio of 1: 6-10; adding the prepared supersaturated limewater into the system in the step 1), stirring for fifteen minutes at the pH of 12-14, adding a phosphoric acid liquid with the concentration of 20-40 wt%, adjusting the pH to about 9.5-10.5, adding a calcium chloride solid, and uniformly stirring; the mass ratio of the calcium oxide, phosphoric acid in phosphoric acid liquid, calcium chloride and silicon dioxide in sodium silicate solution is (0.3-0.5): (0.055-0.1): (0.55-0.8): (2-2.2);
3) coating with wax liquid, heating the system in the step 2) to 70-90 ℃, adding wax emulsion, stirring and preserving heat for 3 hours, wherein the concentration of wax in the wax emulsion is 12 wt%, and the mass ratio of the wax in the wax liquid to silicon dioxide in the sodium silicate solution is (0.15-0.25): (2-2.2); then washing, drying and crushing to obtain the anticorrosive pigment.
Further, in the step 1), in the step 2), the concentration of phosphoric acid in the phosphoric acid liquid is 30 wt%, and the pH value is 8-9.
Further, in the step 3), the wax in the wax emulsion is one or more of polyethylene wax, oxidized polyethylene wax, paraffin wax and palm wax.
Further, in the steps 1), 2) and 3), the mass ratio of sulfuric acid in the dilute sulfuric acid solution, silicon dioxide in the sodium silicate solution, calcium oxide in the saturated limewater, phosphoric acid in the phosphoric acid liquid, calcium chloride and wax in the wax emulsion is 1: (2-2.2): (0.2-0.35): (0.055-0.7): (0.5-0.8): (0.11-0.23).
Further, in the step 3), washing and washing are carried out until the electric conductivity is less than 300 mu S/cm, the drying temperature is 250-300 ℃, the crushing mode is super jet crushing, and the average particle size after crushing is less than 5 mu m.
On the other hand, the application of the composite anticorrosive paint prepared by the preparation method is provided, and the composite anticorrosive paint is applied to a substrate to form a coating.
The amount of calcium oxide and phosphoric acid added in the present invention directly affects the amount of effective preservative substance. Pore volume and oil absorption are key control indexes of low oil absorption silica, and specific surface area, calcium adsorption capacity and silica content are key control indexes of corrosion-resistant calcium ions and calcium phosphate. The calcium adsorption was measured by EDTA complexometric titration, but the acidifying agent was changed from hydrochloric acid to acetic acid due to the presence of calcium phosphate in the pigment. The calcium phosphate content is indirectly reflected by the silica content (dry basis).
Compared with the prior art, the composite anticorrosive pigment with excellent salt spray resistance and low price is prepared by adopting normal-temperature reaction and selecting cheap raw materials and auxiliary agents in the whole process, utilizing various anticorrosive mechanisms such as calcium ion exchange and phosphate radical ion chelation, and adding wax emulsion to improve the calcium ion adsorption degree and increase the paint anti-settling property.
After adopting such design, the invention has at least the following advantages:
the preparation method disclosed by the invention breaks through a single anticorrosion mechanism at normal temperature and normal pressure in the whole process, is designed by comprehensively considering multiple aspects of forming a compact layer, calcium ion exchange and metal chelating, is low in production cost, and the prepared anticorrosive pigment is excellent in salt spray resistance. The low-water-pore low-oil-absorption silicon dioxide is synthesized at normal temperature, the calcium ion exchange anticorrosion effect is exerted, the wax emulsion is wrapped by introducing phosphate ions and the wax emulsion, the calcium ion adsorption capacity of the silicon dioxide is greatly improved, the prepared anticorrosive pigment has the characteristics of low pore volume and low oil absorption, the viscosity is lower after the anticorrosive pigment is added into paint, and the problem that the pigment cannot be added due to overlarge construction viscosity is solved.
Detailed Description
The present invention is further illustrated by the following examples, but the present invention is not limited to the following examples, and any products similar or equivalent to the present invention, which are obtained by the teaching of the present invention, are within the scope of protection.
Example 1:
1) preparing low water pore and low oil absorption silicon dioxide: adding 500g of 30% dilute sulfuric acid solution into a reaction vessel, starting stirring, and slowly adding sodium silicate solution (modulus 3.1-3.4, SiO) under stirring2% by weight (10%) about 3.1kg over a period of 30min, at a pH of about 6, and stirring for 15 minutes to obtain the low hydroscopic low oil absorbing silica.
2) Introduction of calcium phosphate and calcium ion source: 450g of supersaturated calcium hydroxide solution (calcium oxide: water: 1:8) was added to the system, and stirred for 20 minutes, and then a dilute phosphoric acid solution (30% concentration) was slowly added thereto, and at this time, pH was adjusted to 8 to 9, and then 120g of calcium chloride solid was added thereto, and stirred for 20 minutes.
3) Coating and crushing wax liquid: the temperature of the system in the step two is raised to 80 ℃, about 250g of oxidized polyethylene wax emulsion (the wax content is about 12%) is slowly added, and the mixture is stirred for 3 hours under the condition of heat preservation. Washing until the electric conductivity is less than 300 mu S/cm, drying at 260 ℃, and carrying out super jet milling until the average particle size is less than 5 mu m to obtain the anticorrosive pigment 1.
Example 2:
1) preparing low water pore and low oil absorption silicon dioxide: adding 1.2kg of 20% dilute sulfuric acid solution into a reaction vessel, stirring, and slowly adding sodium silicate solution (modulus 3.1-3.4, SiO) under stirring2% by weight (5%) about 9.9kg, the addition time is 50min, the pH is about 6, and the mixture is stirred and placed for 1.5h, thus obtaining the low-hydroscopic low-oil absorption silica.
2) Introduction of calcium phosphate and calcium ion source: 640g of supersaturated calcium hydroxide solution (calcium oxide: water: 1:7) was added to the system, and stirred for 30 minutes, then a dilute phosphoric acid solution (30% concentration) was slowly added thereto, and about 56g of the solution was added, at which time the pH was 8 to 9, and 190g of calcium chloride solid was added, and stirred for 30 minutes.
3) Coating and crushing wax liquid: the temperature of the system in the step two is raised to 90 ℃, about 416g of oxidized polyethylene wax emulsion (the wax content is about 12%) is slowly added, and the mixture is stirred for 3 hours under the condition of heat preservation. Washing until the electric conductivity is less than 300 mu S/cm, drying at 260 ℃, and carrying out super jet milling until the average particle size is less than 5 mu m to obtain the anticorrosive pigment 2.
Example 3:
1) preparing low water pore and low oil absorption silicon dioxide: adding 300g of 40% dilute sulfuric acid solution into a reaction vessel, starting stirring, and slowly adding sodium silicate solution (modulus 3.1-3.4, SiO) under stirring2% by weight (20%) about 1.3kg over a period of 20min, at a pH of about 6, and stirring for 15 minutes to obtain the low hydroscopic low oil absorbing silica.
2) Introduction of calcium phosphate and calcium ion source: 410g of supersaturated calcium hydroxide solution (calcium oxide: water: 1:9) was added to the system, and the mixture was stirred for 20 minutes, then about 23g of dilute phosphoric acid solution (30% concentration) was slowly added thereto, at which time the pH was 8 to 9, and then 95g of calcium chloride solid was added thereto, and the mixture was stirred for 20 minutes.
3) Coating and crushing wax liquid: and heating the system in the second step to 85 ℃, slowly adding about 208g of oxidized polyethylene wax emulsion (the wax content is about 12 percent), and stirring for 3 hours under the condition of heat preservation. Washing until the electric conductivity is less than 300 mu S/cm, drying at 260 ℃, and carrying out super jet milling until the average particle size is less than 5 mu m to obtain the anticorrosive pigment 3.
Example 4:
1) preparing low water pore and low oil absorption silicon dioxide: adding 500g of 30% dilute sulfuric acid solution into a reaction vessel, starting stirring, and slowly adding sodium silicate solution (modulus 3.1-3.4, SiO) under stirring2% by weight (10%) of about 3kg, and stirring at a pH of about 6 for 15 minutes for 30min to obtain a low hydroscopic low oil absorbing silica.
2) Introduction of calcium phosphate and calcium ion source: 240g of supersaturated calcium hydroxide solution (calcium oxide: water: 1:7) was added to the system, and the mixture was stirred for 20 minutes, then about 30g of dilute phosphoric acid solution (30% concentration) was slowly added thereto, at which time the pH was 8 to 9, and then 115g of calcium chloride solid was added thereto, and the mixture was stirred for 20 minutes.
3) Coating and crushing wax liquid: the temperature of the system in the step two is raised to 80 ℃, about 233g of oxidized polyethylene wax emulsion (the wax content is about 12 percent) is slowly added, and the mixture is stirred for 3 hours under the condition of heat preservation. Washing until the electric conductivity is less than 300 mu S/cm, drying at 260 ℃, and carrying out super jet milling until the average particle size is less than 5 mu m to obtain the anticorrosive pigment 4.
Example 5:
1) preparing low water pore and low oil absorption silicon dioxide: adding 710g of 30% dilute sulfuric acid solution into a reaction vessel, starting stirring, and slowly adding sodium silicate solution (modulus 3.1-3.4, SiO) under stirring2% by weight (10%) about 4.4kg over a 35min addition period at a pH of about 6 and stirring for 15 minutes to provide the low hydroscopic low oil absorbing silica.
Step two, introducing calcium phosphate and a calcium ion source: 552g of a supersaturated calcium hydroxide solution (calcium oxide: water: 1:7) was added to the system, and the mixture was stirred for 20 minutes, then about 46g of a dilute phosphoric acid solution (30% concentration) was slowly added thereto, at which time the pH was 8 to 9, and then 100g of a calcium chloride solid was added thereto, and the mixture was stirred for 20 minutes.
2) Coating and crushing wax liquid: the temperature of the system in the step two is raised to 80 ℃, about 350g of oxidized polyethylene wax emulsion (the wax content is about 12 percent) is slowly added, and the mixture is stirred for 3 hours under the condition of heat preservation. Washing until the electric conductivity is less than 300 mu S/cm, drying at 260 ℃, and carrying out super jet milling until the average particle size is less than 5 mu m to obtain the anticorrosive pigment 5.
Example 6:
1) preparing low water pore and low oil absorption silicon dioxide: adding 450g of 30% dilute sulfuric acid solution into a reaction vessel, starting stirring, and slowly adding sodium silicate solution (modulus 3.1-3.4, SiO) under stirring2% by weight (10%) of about 2.75kg over a period of 30min, at a pH of about 6, and stirring for 15 minutes to obtain the low hydroscopic low oil absorbing silica.
2) Introduction of calcium phosphate and calcium ion source: 387g of supersaturated calcium hydroxide solution (calcium oxide: water: 1:8) was added to the system, and stirred for 20 minutes, and then diluted phosphoric acid solution (30% concentration) was slowly added thereto at a pH of 8 to 9 of about 28g, and then 110g of calcium chloride solid was added thereto, and stirred for 15 minutes.
3) Coating and crushing wax liquid: the temperature of the system in the step two is raised to 90 ℃, about 125g of oxidized polyethylene wax emulsion (the wax content is about 12%) is slowly added, and the mixture is stirred for 3 hours under the condition of heat preservation. Washing until the electric conductivity is less than 300 mu S/cm, drying at 260 ℃, and carrying out super jet milling until the average particle size is less than 5 mu m to obtain the anticorrosive pigment 6.
Comparative example 1:
the difference from example 1 is that no phosphoric acid is added.
Comparative example 2:
the difference from example 1 is that no wax emulsion is added.
Test examples
The paint is prepared by using the composite anticorrosive pigment prepared in the above examples or comparative examples: the epoxy ester primer is used as a main body, butyl acetate is used as a diluent, a composite anticorrosive pigment, a drying agent and a small amount of iron oxide red are added to prepare a coating, the adding proportion of each component is 70:14:10:5.5:0.5, the coating is filtered by 80 meshes, the coating is sprayed on a common low-carbon steel sheet (70mm to 150mm) according to GB1765-1979 national standard, the coating is put into a room-temperature drying box for 30min and then is put into a 120-DEG oven for drying; and (5) grinding with No. 400 water sand paper, and drying at 120 ℃. Spraying second paint, drying by the same method, sealing edges, and making the film thickness be 40 +/-5 μm.
Table 1 Properties of products prepared from composite anticorrosive pigments of examples 1-6 and comparative examples 1 and 2
Figure BDA0002728361000000081
As can be seen from Table 1, the products prepared in the embodiments 1-6 of the present invention have the characteristics of low pore volume and low oil absorption, and have low coating viscosity and excellent neutral salt spray resistance. The products prepared by the comparative examples 1 and 2 have high pore volume, oil absorption and viscosity and poor neutral salt spray resistance, and further show that the phosphoric acid and wax emulsion of the invention has obvious influence on the performance of the products.
The main components of the anticorrosive pigment prepared by the invention are low-water-pore low-oil-absorption silicon dioxide, and calcium phosphate, oxidized polyethylene wax and adsorbed calcium ions are used as the secondary components. The composite pigment plays a role in resisting salt fog by forming a compact layer, chelating phosphate ions and exchanging partial calcium ions, and has excellent salt fog resistance.
Compared with the prior art, the composite anticorrosive pigment with excellent salt spray resistance and low price is prepared by adopting normal-temperature reaction and selecting cheap raw materials and auxiliary agents in the whole process, utilizing various anticorrosive mechanisms such as calcium ion exchange and phosphate radical ion chelation, and adding wax emulsion to improve the calcium ion adsorption degree and increase the paint anti-settling property.
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 present invention in any way, and it will be apparent to those skilled in the art that the above description of the present invention can be applied to various modifications, equivalent variations or modifications without departing from the spirit and scope of the present invention.

Claims (5)

1. The preparation method of the composite anticorrosive paint is characterized by comprising the following steps:
step 1: preparing a composite anticorrosive pigment, adopting sodium silicate and sulfuric acid as raw materials, reacting at normal temperature and normal pressure to synthesize low-water-pore low-oil-absorption silicon dioxide, then sequentially adding a supersaturated calcium hydroxide solution, a phosphoric acid solution and calcium chloride into the system, stirring and uniformly mixing, finally heating the system to 70-90 ℃, coating with a wax emulsion, washing, drying and crushing to prepare the anticorrosive pigment with the average particle size of less than 5 mu m; the method specifically comprises the following steps:
1) preparing low water pore and low oil absorption silicon dioxide: adding the prepared 20-40 wt% of dilute sulfuric acid solution into a reaction container, starting stirring, slowly adding the prepared dilute sodium silicate solution under a stirring state until the pH value is close to 6, and stirring for a period of time to prepare the low-water-hole low-oil-absorption silicon dioxide; the content of silicon dioxide in the dilute sodium silicate solution is 5 to 25 weight percent; the mass ratio of sulfuric acid in the dilute sulfuric acid solution to silicon dioxide in the sodium silicate solution is 1: (2-2.2);
2) performing composite treatment: preparing supersaturated lime water from calcium oxide and water according to the mass ratio of 1: 6-10; adding the prepared supersaturated limewater into the system in the step 1), stirring for fifteen minutes at the pH of 12-14, adding a phosphoric acid solution with the concentration of 20-40 wt%, adjusting the pH to 9.5-10.5, adding a calcium chloride solid, and uniformly stirring; the mass ratio of the calcium oxide, phosphoric acid in a phosphoric acid solution, calcium chloride and silicon dioxide in a sodium silicate solution is (0.3-0.5): (0.055-0.1): (0.55-0.8): (2-2.2);
3) coating with wax liquid, heating the system in the step 2) to 70-90 ℃, adding wax emulsion, stirring and preserving heat for 3 hours, wherein the concentration of wax in the wax emulsion is 12 wt%, and the mass ratio of the wax in the wax liquid to silicon dioxide in the sodium silicate solution is (0.15-0.25): (2-2.2); then washing, drying and crushing to obtain the anticorrosive pigment;
in the steps 1), 2) and 3), the mass ratio of sulfuric acid in the dilute sulfuric acid solution, silicon dioxide in the sodium silicate solution, calcium oxide in the saturated lime water, phosphoric acid in the phosphoric acid solution, calcium chloride and wax in the wax emulsion is 1: (2-2.2): (0.3-0.5): (0.055-0.1): (0.55-0.8): (0.15 to 0.25);
and 2, mixing 65-75 parts by weight of epoxy resin, 12-15 parts by weight of butyl acetate, 8-12 parts by weight of composite anticorrosive pigment, 5.5 parts by weight of drying agent and 0.5 part by weight of iron oxide red to prepare the anticorrosive paint.
2. The preparation method of the composite anticorrosive paint according to claim 1, wherein in the step 2, the addition amount of each component is as follows: 70 parts of epoxy resin, 14 parts of butyl acetate, 10 parts of composite anticorrosive pigment, 5.5 parts of drying agent and 0.5 part of iron oxide red.
3. The preparation method of the composite anticorrosive paint according to claim 1 or 2, wherein in the step 2), the concentration of phosphoric acid in the phosphoric acid solution is 30 wt%, and the pH value is 8-9.
4. The preparation method of the composite anticorrosive paint according to claim 1 or 2, wherein in the step 3), the wax in the wax emulsion is one or more of polyethylene wax, oxidized polyethylene wax, paraffin wax and palm wax.
5. The preparation method of the composite anticorrosive paint according to any one of claims 1 or 2, characterized in that in the step 3), the paint is washed until the conductivity is less than 300 μ S/cm, the drying temperature is 250-300 ℃, the pulverization is carried out by super jet pulverization, and the average particle size after pulverization is less than 5 μm.
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