Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a microencapsulation curing agent and a water-based inorganic zinc-rich anticorrosive coating based on the microencapsulation curing agent, aiming at improving the curing rate of a coating and solving the problem of poor early water resistance of the coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly discloses a microencapsulated curing agent which is characterized in that: the microencapsulated curing agent is a curing agent coated in a silica shell layer.
Preferably, the curing agent is sodium fluoborate or sodium fluosilicate. The reason why the sodium fluoborate or the sodium fluosilicate is adopted as the curing agent is as follows: the curing agent for silicate water glass is more, such as inorganic acid, borate, carbonate, metal oxide, chloride, fluorosilicate, fluoroborate, etc., but soluble compounds are decomposed too fast in silicate solution with high pH value, so that gelation is easy to occur, the coating is ineffective, so that the curing agent is not suitable for being used in the coating, and the curing effect of the metal oxide is poor. In comparison, the capability of decomposing and releasing acid of the sodium fluoborate or the sodium fluosilicate is mild, but from the actual coating effect, the decomposition rate is too fast, and the agglomeration is easy to occur on the surface of the sodium fluoborate or the sodium fluosilicate, so that coarse particle precipitation is generated, the uniformity and the stability of the coating are further damaged, and the influence on the performance of a final coating is great. The microencapsulation coating is used for further slowing down the decomposition and release of sodium fluoborate or sodium fluosilicate in aqueous silicate solution and improving the compatibility and dispersibility in the aqueous silicate solution. Sodium fluoborate or sodium fluosilicate is selected as a microencapsulated curing agent because of a better curing effect after being coated.
The reason why the microencapsulated curing agent of the present invention employs silicon dioxide as the shell layer is that: the invention discovers that the selected shell material needs to have good compatibility with silicate solution of the water-based inorganic anticorrosive coating so as to ensure that the coated curing agent can be uniformly dispersed in the coating. The invention discovers in experimental investigation that various common shell materials including high molecular (such as polyethylene, polypropylene, polystyrene, polyurethane, chitosan and the like) and inorganic (such as carbon base, titanium dioxide and the like) can not achieve the required effect. In addition, the compactness of the polymer coating is higher, and the barrier property is good, so that the permeation and the diffusion of the curing agent are not facilitated. The silicon dioxide has excellent hydrophilicity, chemical stability and colloid stability, has good compatibility with silicate solution of the water-based inorganic anticorrosive coating, is beneficial to uniform dispersion of the wrapped curing agent in the coating, inhibits the precipitation of agglomerated large particles, and has stable and controllable quality of the obtained coating. Meanwhile, the silicon dioxide shell layer is easy to control and synthesize, and is convenient for industrial production. Therefore, the invention selects silicon dioxide as shell material.
Preferably, the mass of the silica shell layer accounts for 2-15% of the mass of the curing agent. The loading of silica can affect the slow release of the curing agent and thus the curing effect of the coating.
The invention also discloses a preparation method of the microencapsulated curing agent, which comprises the following steps:
step 1, adding absolute ethyl alcohol into a curing agent to prepare curing agent slurry;
step 2, heating the curing agent slurry to a reaction temperature, and then keeping the constant temperature;
step 3, adding deionized water and a dispersing surfactant into the curing agent slurry while stirring;
step 4, adding ammonia water and tetraethoxysilane into the curing agent slurry while stirring, and reacting at constant temperature to hydrolyze and condense the tetraethoxysilane under the catalysis of the ammonia water; and centrifuging, washing and drying the suspension after reaction to obtain the microencapsulated curing agent.
Preferably, in step 1, the mass concentration of the curing agent slurry is 0.1% to 30%.
Preferably, in the step 2, the reaction temperature is 40 to 70 ℃.
Preferably, in the step 3, the dispersing surfactant is Cetyl Trimethyl Ammonium Bromide (CTAB) or polyvinylpyrrolidone (PVP), the dosage of the dispersing surfactant is 0.1-10% of the mass of the curing agent, and the volume ratio of the deionized water to the absolute ethyl alcohol is 0.1-1: 6.
Preferably, in the step 4, the mass concentration of the ammonia water is 10-28%, the volume ratio of the ammonia water to the absolute ethyl alcohol is 1: 100-700, and the mass ratio of the tetraethoxysilane to the curing agent is 1g: 2-15.
Preferably, in the step 4, the isothermal reaction time is 1 to 24 hours.
The invention further discloses a water-based inorganic zinc-rich anticorrosive paint which is characterized in that: the microencapsulation curing agent is added into the water-based inorganic zinc-rich anticorrosive coating.
Preferably, the water-based inorganic zinc-rich coating is prepared by uniformly mixing a liquid component and a solid component in a mass ratio of 1: 2-3;
the liquid component comprises the following raw materials in percentage by mass:
the solid component comprises the following raw materials in percentage by mass:
90-97% of zinc powder,
3-10% of a microencapsulation curing agent.
Preferably, the method comprises the following steps: the high-modulus silicate mixed solution is a mixed aqueous solution of at least two of lithium silicate, sodium silicate and potassium silicate with the modulus of 3.0-5.0, and the concentration of the solution is 25% -40%; the solution stabilizer is a silane coupling agent; the aqueous auxiliary agent is at least two of a wetting dispersant, a thickening agent, a flatting agent, a defoaming agent and a titanate coupling agent; the zinc powder is 325-800 meshes of active zinc powder.
The invention has the beneficial effects that:
1. the microencapsulated curing agent provided by the invention is a sodium fluoborate or sodium fluosilicate curing agent coated in a silicon dioxide shell layer, and has the advantages of two aspects: the silica shell layer has good compatibility with silicate solution, which is beneficial to the uniform dispersion of the wrapped curing agent in the coating, and the obtained coating has stable and controllable quality; by adjusting the load of the silicon dioxide, the slow release of the curing agent can be realized, the performance of the silicate adhesive is not influenced, the curing rate is improved, and the technical problem of poor early water resistance of the coating is solved.
2. The microencapsulation curing agent is added into the water-based inorganic anticorrosive coating provided by the invention, so that the curing rate is improved, and the obtained coating has better early water resistance.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, but it is to be understood that the description is intended to illustrate further advantageous features of the invention and is not intended to limit or restrict the scope of the appended claims.
Example 1
This example first prepares the microencapsulated curing agent as follows:
step 1, adding 5g of sodium fluoborate into 300mL of absolute ethyl alcohol to prepare curing agent slurry with the mass concentration of 2%.
And 2, heating the curing agent slurry to 45 ℃, and then keeping the constant temperature.
And 3, adding 15mL of deionized water and 0.2g of CTAB into the curing agent slurry while stirring.
Step 4, adding 3mL of ammonia water with the mass concentration of 15% into the curing agent slurry while stirring, then slowly dropwise adding 2g of Tetraethoxysilane (TEOS), stirring at constant temperature for reaction for 10 hours after dropwise adding is finished, and performing hydrolytic polycondensation on the tetraethoxysilane under the catalysis of the ammonia water; and centrifuging the reacted suspension, washing with absolute ethyl alcohol, and drying to obtain the microencapsulated curing agent, wherein the mass of the silicon dioxide shell layer accounts for 11.5% of the mass of the curing agent.
Sodium Fluoroborate (SFB) used in the present example and microencapsulated curing agent (SiO) obtained by coating silica shell layer2@ SFB) is shown in FIG. 1. From fig. 1, it can be seen that after the sodium fluoborate is wrapped by the silica, the diffraction peak of the XRD pattern still appears as the diffraction peak of the sodium fluoborate, but the diffraction intensity of the main intensity peak is obviously reduced due to the wrapping of the silica. It can also be seen that the silica shell synthesized under the synthesis conditions is amorphous.
FIGS. 2 and 3 are Scanning Electron Microscope (SEM) images of the sodium fluoroborate used in the present example and the microencapsulated curing agent obtained by coating the silica shell layer. As shown in FIG. 2, the sodium fluoroborate is in the form of a strip before being coated, and has a distinct right-angled edge. And the sodium fluoborate coated by the silicon dioxide (as shown in figure 3) has obvious change of the overall shape of the particles, the shape becomes round, and the appearance of the right-angle edge does not appear. However, from the single particles which are not completely wrapped, the characteristic right-angled edge morphology of the sodium fluoborate can be clearly seen, and the effective wrapping of the sodium fluoborate by the silicon dioxide is proved.
The above characterization data illustrates that encapsulation of the curing agent sodium fluoroborate with silica microencapsulation has been achieved using this synthetic method.
Based on the microencapsulated curing agent, the present example also prepares the aqueous inorganic zinc-rich anticorrosive coating according to the following method:
to 94g of 500 mesh active zinc powder, 6g of the microencapsulated curing agent prepared in this example was added to obtain a solid component.
Respectively weighing 60g of potassium silicate solution and 60g of lithium silicate solution with the modulus of 4.0 and the solid content of 26%, dispersing uniformly under stirring, slowly adding 15g of deionized water and 3g of triethoxysilane under medium-speed stirring, finally adding 1g of wetting dispersant BYK-190 and 1g of defoamer BYK-019, stirring for 40 minutes, and uniformly mixing to obtain a liquid component.
And uniformly mixing the liquid component and the solid component according to the mass ratio of 1:2.5 to obtain the required water-based inorganic zinc-rich anticorrosive paint.
Comparative experiments to increase the cure rate of the coating and early water resistance were as follows: the aqueous inorganic zinc-rich coating added with the microencapsulated curing agent of the embodiment and the coating without any curing agent (the other components and the proportion are the same) are respectively coated on a sample plate with standard size after polishing and derusting, and after curing for 72 hours according to the general preparation method of paint film GB/T1727-1992, the coating without the curing agent is found to be broken and fall off after being soaked in 3.5 wt% saline water for 20 days according to the requirement of the determination method of GB/T9274-1988 paint and varnish liquid-resistant medium, and the coating added with the microencapsulated curing agent of the embodiment is intact after being soaked for 20 days. Therefore, the microencapsulated curing agent of the embodiment can shorten the curing time and solve the problem of poor early water resistance of the coating.
Example 2
This example first prepares the microencapsulated curing agent as follows:
step 1, adding 10g of sodium fluosilicate into 400mL of absolute ethyl alcohol to prepare curing agent slurry with the mass concentration of 3%.
And 2, heating the curing agent slurry to 50 ℃, and then keeping the constant temperature.
And 3, adding 10mL of deionized water and 0.3g of CTAB into the curing agent slurry while stirring.
Step 4, adding 2mL of ammonia water with the mass concentration of 28% into the curing agent slurry while stirring, then dropwise adding 3g of Tetraethoxysilane (TEOS), stirring at constant temperature for reaction for 5 hours after the completion of the addition, and performing hydrolytic polycondensation on the tetraethoxysilane under the catalysis of the ammonia water; and centrifuging the reacted suspension, washing with absolute ethyl alcohol, and drying to obtain the microencapsulated curing agent, wherein the mass of the silicon dioxide shell layer accounts for 8.7% of the mass of the curing agent.
Sodium Fluorosilicate (SFS) used in this example and microencapsulated curing agent (SiO) obtained by coating silica shell2@ SFS) is shown in fig. 4. As can be seen from fig. 4, after the sodium fluorosilicate is coated with the silica, the diffraction peak of the XRD pattern still appears as the diffraction peak of the sodium fluorosilicate, but the decrease of the diffraction intensity of the main strong peak is more obvious, which is also due to the coating of the silica. It can also be seen that the silica shell synthesized under the synthesis conditions is amorphous.
FIGS. 5 and 6 are Scanning Electron Microscope (SEM) images of the sodium fluorosilicate used in the present example and the microencapsulated curing agent obtained after coating with a silica shell layer, respectively. As shown in fig. 5, the morphology of the sodium fluorosilicate before coating was amorphous granular, and the surface of the granules was smooth. The sodium fluorosilicate (as shown in fig. 6) coated with silica has no obvious change in the overall shape of the particles, but the surfaces of the particles become unsmooth, and a large number of silica micro-particles are distributed on the particles, which proves that the sodium fluorosilicate is coated by the silica microspheres.
The above characterization data illustrates that encapsulation of the curing agent sodium fluorosilicate with silica microencapsulation has been achieved using this synthetic method.
Based on the microencapsulated curing agent, the present example also prepares the aqueous inorganic zinc-rich anticorrosive coating according to the following method:
to 93g of 500 mesh active zinc powder, 7g of the microencapsulated curing agent prepared in this example was added to obtain a solid component.
Respectively weighing 40g of potassium silicate solution with the modulus of 3.8 and the solid content of 30 percent, 40g of lithium silicate solution and 40g of sodium silicate solution, slowly adding 20g of deionized water and 4g of triethoxysilane in a stirring state at a medium speed, finally adding 1.5g of titanate coupling agent and 2g of flatting agent BYK-349, stirring for 30 minutes, and uniformly mixing to obtain the liquid component.
And uniformly mixing the liquid component and the solid component according to the mass ratio of 1:3.0 to obtain the required water-based inorganic zinc-rich coating.
The microencapsulated curing agent is added to solve the problems of slow curing and poor early water resistance of the coating, and the comparative experiment is as follows: : the aqueous inorganic zinc-rich coating added with the microencapsulated curing agent of the embodiment and the coating without any curing agent (the other components and the proportion are the same) are respectively coated on a sample plate with standard size after polishing and derusting, and after curing for 72 hours according to GB/T1727-1992 general preparation method of paint film, the coating without the microencapsulated curing agent is found to be broken and fall off after being soaked in 3.5 wt% saline water for 20 days according to the requirement of GB/T9274 + 1988 determination of liquid-resistant medium of paint and varnish, and the coating added with the microencapsulated curing agent of the embodiment is not damaged after being soaked for 20 days. Therefore, the microencapsulated curing agent of the embodiment can shorten the curing time and solve the problem of poor early water resistance of the coating.
Example 3
In this example, a microencapsulated curing agent and an aqueous inorganic zinc-rich anticorrosive coating were prepared in the same manner as in example 1, except that: the amount of tetraethyl orthosilicate (TEOS) is changed to 0.1g, and the mass of the silicon dioxide shell layer accounts for 0.6 percent of the mass of the curing agent. The prepared coating can generate more agglomerated large-particle solids after being mixed and stirred for a period of time, which indicates that the coating amount of a silicon dioxide shell layer is less, so that the curing agent is released quickly, and the coating fails due to agglomeration.
Example 4
In this example, a microencapsulated curing agent and an aqueous inorganic zinc-rich anticorrosive coating were prepared in the same manner as in example 1, except that: the amount of tetraethyl orthosilicate (TEOS) is changed to 0.4g, and the mass of the silicon dioxide shell layer accounts for 2.4% of the mass of the curing agent. The prepared coating is respectively coated on a sample plate with standard size after polishing and rust removal, and after curing for 72 hours according to GB/T1727-1992 general preparation method of paint films, and then soaking in 3.5 wt% saline water for 20 days according to the requirements of GB/T9274-1988 determination of color paint and varnish liquid-resistant medium, the coating is found to be intact, which indicates that the microencapsulated curing agent prepared with the silicon dioxide shell coating amount of 2.4% meets the curing requirement.
Example 5
In this example, a microencapsulated curing agent and an aqueous inorganic zinc-rich anticorrosive coating were prepared in the same manner as in example 1, except that: the amount of tetraethyl orthosilicate (TEOS) is changed to 2.5g, and the mass of the silicon dioxide shell layer accounts for 14.4% of the mass of the curing agent. The prepared coating is respectively coated on a sample plate with standard size after polishing and rust removal, and after curing for 72 hours according to GB/T1727-1992 general preparation method of paint films, and then soaking in 3.5 wt% saline water for 20 days according to the requirements of GB/T9274-1988 determination of color paint and varnish liquid-resistant medium, the coating is found to be intact, which indicates that the microencapsulated curing agent prepared with 14.4% of coating amount of a silicon dioxide shell layer meets the curing requirement.
Example 6
In this example, a microencapsulated curing agent and an aqueous inorganic zinc-rich anticorrosive coating were prepared in the same manner as in example 1, except that: the amount of tetraethyl orthosilicate (TEOS) is changed to 3g, and the mass of the silicon dioxide shell layer accounts for 17.3% of the mass of the curing agent. The prepared coating is respectively coated on a sample plate with standard size after polishing and rust removal, and after curing for 72 hours according to GB/T1727-1992 general preparation method of paint films, and then soaking in 3.5 wt% saline water for 20 days according to the requirements of GB/T9274-1988 determination of color paint and varnish liquid-resistant medium, the coating is found to be dispersed and fall off, which indicates that the microencapsulated curing agent prepared with the silicon dioxide shell coating amount of 17.3% cannot meet the curing requirement.
Example 7
In this example, a microencapsulated curing agent and an aqueous inorganic zinc-rich anticorrosive coating were prepared in the same manner as in example 2, except that: the amount of tetraethyl orthosilicate (TEOS) is changed to 0.2g, and the mass of the silicon dioxide shell layer accounts for 0.6 percent of the mass of the curing agent. The prepared coating can generate more white large-particle solids after being mixed and stirred for a period of time, which indicates that the coating amount of the silicon dioxide shell is less, so that the curing agent is released quickly, and the coating is agglomerated and fails.
Example 8
In this example, a microencapsulated curing agent and an aqueous inorganic zinc-rich anticorrosive coating were prepared in the same manner as in example 2, except that: the amount of tetraethyl orthosilicate (TEOS) is changed to 0.8g, and the mass of the silicon dioxide shell layer accounts for 2.4% of the mass of the curing agent. The prepared coating is respectively coated on a sample plate with standard size after polishing and rust removal, and after curing for 72 hours according to GB/T1727-1992 general preparation method of paint films, and then soaking in 3.5 wt% saline water for 20 days according to the requirements of GB/T9274-1988 determination of color paint and varnish liquid-resistant medium, the coating is found to be intact, which indicates that the microencapsulated curing agent prepared with the silicon dioxide shell coating amount of 2.4% meets the curing requirement.
Example 9
In this example, a microencapsulated curing agent and an aqueous inorganic zinc-rich anticorrosive coating were prepared in the same manner as in example 2, except that: the amount of tetraethyl orthosilicate (TEOS) is changed to 5g, and the mass of the silicon dioxide shell layer accounts for 14.4% of the mass of the curing agent. The prepared coating is respectively coated on a sample plate with standard size after polishing and rust removal, and after curing for 72 hours according to GB/T1727-1992 general preparation method of paint films, and then soaking in 3.5 wt% saline water for 20 days according to the requirements of GB/T9274-1988 determination of color paint and varnish liquid-resistant medium, the coating is found to be intact, which indicates that the microencapsulated curing agent prepared with 14.4% of coating amount of a silicon dioxide shell layer meets the curing requirement.
Example 10
In this example, a microencapsulated curing agent and an aqueous inorganic zinc-rich anticorrosive coating were prepared in the same manner as in example 2, except that: the amount of tetraethyl orthosilicate (TEOS) is changed to 6g, and the mass of the silicon dioxide shell layer accounts for 17.3% of the mass of the curing agent. The prepared coating is respectively coated on a sample plate with standard size after polishing and rust removal, and after curing for 72 hours according to GB/T1727-1992 general preparation method of paint films, and then soaking in 3.5 wt% saline water for 20 days according to the requirements of GB/T9274-1988 determination of color paint and varnish liquid-resistant medium, the coating is found to be dispersed and fall off, which indicates that the microencapsulated curing agent prepared with the silicon dioxide shell coating amount of 17.3% cannot meet the curing requirement.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.