Mesoporous organic silicon nano container with spiral structure as well as preparation method and application of mesoporous organic silicon nano container
By preparing helical mesoporous organosilicon nanorods loaded with corrosion inhibitors and combining them with epoxy resin, the problems of easy damage and porosity in epoxy coatings were solved, achieving a more effective metal rust prevention effect.
Patent Information
- Application Number
- CN202511280864.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-09
- Publication Date
- 2025-11-28
AI Technical Summary
Existing epoxy coatings are prone to damage and voids on metal surfaces, resulting in reduced rust prevention. Mesoporous nanomaterials also have shortcomings in terms of corrosion inhibitor release and loading.
Using helical mesoporous organosilicon nanorods as a carrier, corrosion inhibitors are loaded and combined with epoxy resin to form an anti-rust epoxy coating. The slow release capability of the helical structure is used to improve the anti-rust performance of the coating.
It significantly improves the rust prevention and self-healing properties of epoxy coatings, providing longer-lasting rust protection for metals, and is suitable for steel and copper materials.
Smart Images
Figure CN121022159A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of metal rust prevention, and particularly relates to a mesoporous organosilicon nanocapsule with a spiral structure, a preparation method thereof and application thereof in metal rust prevention. BACKGROUND
[0002] A rust-proof coating is a simple method for forming a protective barrier on the surface of a metal to block corrosive media, and is widely used in the rust prevention of metal materials such as steel and copper. As a typical rust-proof coating, an epoxy coating can form a dense and tightly adhered film on the surface of a steel material, effectively isolating the corrosion of oxygen, water and other chemical substances, thereby providing good rust-proof performance. However, due to the volume shrinkage or release of volatile substances during the curing process of the epoxy resin, internal stress and voids are easily generated, which weakens the rust-proof effect. In view of the problem of easy damage and voids of the coating, an effective strategy is to construct a coating with a rust-proof self-repairing function, thereby avoiding the corrosion of corrosive media through the coating to corrode the metal material. It has been reported that mesoporous nanomaterials can adsorb and store corrosion inhibitors due to their internal pore structure; when the coating is damaged, the nanocapsule can repair the coating defects by releasing the corrosion inhibitor, thereby slowing down or preventing the corrosion reaction.
[0003] Mesoporous materials have adjustable pore size, high specific surface area, large pore volume and excellent biocompatibility, and have wide application value in adsorption separation, energy storage, catalysis and drug loading. Mesoporous silica is one of the materials that has been widely studied, especially mesoporous organosilicon nanorods with a spiral structure, which not only have a large pore volume and an ordered mesoporous structure, but also have a high specific surface area and a large pore volume, which can significantly improve the loading capacity of the mesoporous nanorod for corrosion inhibitors, and the organosilicon skeleton structure can improve the compatibility of the nanocapsule with the corrosion inhibitor and the dispersion ability in the epoxy resin. The mesoporous nanorod also has the advantages of easy molding, controllable material and morphology, and the spiral structure of the nanocapsule can improve the slow release ability of the nanocapsule for the corrosion inhibitor, thereby achieving persistent protection of the metal material. In addition, benzotriazole, dopamine hydrochloride, methyl imidazole and 2-mercaptobenzothiazole can form an inhibition interface at the defects of the epoxy coating, thereby improving the overall stability and corrosion resistance of the epoxy coating. The present application provides a mesoporous organosilicon nanorod with a spiral structure, which can further improve the stability and rust-proof performance of the epoxy coating by loading the corrosion inhibitor and combining with the epoxy resin, and has important significance in the field of coating rust prevention of steel and copper materials. SUMMARY
[0004] The present application aims to provide a mesoporous organosilicon nanocapsule with a spiral structure, a preparation method thereof and application thereof.
[0005] The preparation method of the mesoporous organosilicon nanocapsule with a spiral structure provided by the present application comprises the following specific steps:
[0006] (1) A certain amount of structure-directing agent is added to water, and a uniform transparent solution A is formed after stirring for a period of time under water bath heating;
[0007] (2) A basic catalyst is added to the above solution, and solution B is obtained after uniform mixing and continued stirring for a period of time;
[0008] (3) A certain volume of organosilane is placed in a constant pressure dropping funnel and slowly added to solution B, and a mesoporous organosilicon nanorod with a spiral structure is obtained after heating and stirring for a period of time and centrifugal washing;
[0009] Step (4) The corrosion inhibitor is dissolved in dichloromethane, a certain amount of mesoporous organosilicon nanorod is added, and a nanocapsule loaded with corrosion inhibitor with a spiral structure is obtained after uniform mixing and rotary evaporation under reduced pressure.
[0010] Preferably, in step (1), the structure-directing agent is selected from one or more of cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide, and cetyltrimethylammonium iodide; further preferably, CTAB; the concentration of the structure-directing agent is 6-6.5 g / L; preferably, the concentration is 6.3 g / L; and the water bath temperature is 35-45℃.
[0011] Preferably, in step (2), the basic catalyst is selected from one or more of ammonia, triethylamine, diethylamine, and tripropylamine; further preferably, ammonia; the volume of the ammonia is 4-6 mL; and the stirring time is 10-30 min.
[0012] Preferably, in step (3), the organosilane is selected from one or more of tetraethyl orthosilicate (TEOS), (3-mercaptopropyl)trimethoxysilane (MPTS), vinyltrimethoxysilane (VTMS), phenyltrimethoxysilane (PTMS), and 1,2-bis(triethoxysilyl)ethane (BTEE); further preferably, TEOS; the slow dropping time is 20-30 min; the heating temperature is 35-45℃; the stirring time is 6-24 h; and the mass ratio of the organosilane reagent to the structure-directing agent is (8-10):1, preferably 8:1.
[0013] Preferably, in step (4), the corrosion inhibitor includes benzotriazole, dopamine hydrochloride, methyl imidazole, and 2-mercaptobenzothiazole, and the mass percentage of the corrosion inhibitor mixture is 10-30% based on the mass of the mesoporous organosilicon nanorod with a spiral structure.
[0014] Further, the mass ratio of the four corrosion inhibitors is preferably 3:1:2:1;
[0015] The application also provides a spiral structure mesoporous organosilicon nanometer container prepared by the preparation method.
[0016] The application also provides application of the spiral structure mesoporous organosilicon nanometer container in metal rust prevention. Specifically, the spiral structure mesoporous organosilicon nanometer container is dispersed in epoxy resin in a certain proportion to form a rust-proof epoxy coating, and then is coated on the surface of metal to form an epoxy rust-proof coating after drying at room temperature.
[0017] Preferably, the addition amount of the nanometer container accounts for 0.5-5% of the mass of the epoxy resin; and the coating method is spin coating.
[0018] Compared with the prior art, the application has the following beneficial effects:
[0019] Since the mesoporous nanorod has an organosilicon skeleton, it is not only beneficial to improve the compatibility of the nanometer container to the organic corrosion inhibitor and accelerate the loading of the corrosion inhibitor, but also can improve the compatibility and dispersion stability of the nanometer container in the epoxy resin, so as to facilitate the uniform dispersion of the mesoporous nanometer container in the epoxy coating.
[0020] The spiral structure mesoporous organosilicon nanorod synthesized in the application has an ordered mesoporous structure and a large pore volume, can load more corrosion inhibitors, and the spiral structure can improve the slow-release performance of the nanometer container at defects or pores of the epoxy coating, so as to form a corrosion inhibitor film on the surface of metal, prevent corrosion media such as oxygen, moisture and harmful ions from contacting the surface of metal, and effectively inhibit the metal corrosion process.
[0021] The rust-proof epoxy coating provided by the application obviously improves the rust-proof and self-repairing performance of the epoxy coating by adding the spiral structure mesoporous nanometer container as a key filler to the epoxy resin, provides longer and more stable rust-proof performance for metal equipment, and has a wide application prospect in the field of metal rust prevention. BRIEF DESCRIPTION OF DRAWINGS
[0022] Figure 1 The SEM and TEM photos of the spiral structure mesoporous organosilicon nanorod in Example 1 of the application.
[0023] Figure 2 The SEM and TEM photos of the spiral structure nanometer container loaded with corrosion inhibitors in Example 1 of the application.
[0024] Figure 3 The SEM and TEM photos of the spiral structure mesoporous organosilicon nanorod in Example 2 of the application.
[0025] Figure 4 The SEM and TEM photos of the spiral structure mesoporous organosilicon nanorod in Example 3 of the application.
[0026] Figure 5 SEM and TEM photos of the spiral structure mesoporous organosilica nanorods in the present application comparative example 1.
[0027] Figure 6 SEM and TEM photos of the spiral structure mesoporous organosilica nanorods in the present application comparative example 2.
[0028] Figure 7 SEM and TEM photos of the spiral structure mesoporous organosilica nanorods in the present application comparative example 3.
[0029] Figure 8 SEM and TEM photos of the spiral structure mesoporous organosilica nanorods in the present application comparative example 4. DETAILED DESCRIPTION
[0030] The present application provides a spiral structure mesoporous organosilica nanocapsule, which comprises a mesoporous nanocapsule taking mesoporous organosilica nanorods as a carrier and taking a corrosion inhibitor as a loading object, and is added into an epoxy resin as a key filler to form an epoxy rust-proof coating on the surface of a metal material.
[0031] The present application will be further described in conjunction with the accompanying drawings and specific embodiments. However, the protection scope of the present application is not limited to these embodiments. Any changes or equivalent replacements without departing from the concept of the present application are included in the protection scope of the present application.
[0032] Example 1: Preparation of a spiral structure mesoporous organosilica nanocapsule and a rust-proof coating, and the specific steps are as follows:
[0033] (1) 1 g of hexadecyl trimethyl ammonium bromide (CTAB) was dispersed in 160 mL of water, and stirring was started at a stirring speed of 200 rpm, and the water bath temperature was set to 35°C. After stirring for 0.5 h, a uniform transparent solution A was formed;
[0034] (2) 6 mL of ammonia water was added as a catalyst into solution A, and after uniform mixing, solution B was obtained, and then stirring was continued at 35°C for 10 min;
[0035] (3) 5 mL of tetraethyl orthosilicate (TEOS) was placed in a constant pressure dropping funnel, and was slowly added into solution B, and the dropping time was 25 min, and then stirring was continued under the condition of a 35°C water bath for 12 h, and centrifugal separation was performed, and spiral structure mesoporous organosilica nanorods 1 (see Figure 1 ) were obtained;
[0036] (4) 0.3 g benzotriazole, 0.1 g dopamine hydrochloride, 0.2 g methyl imidazole and 0.1 g 2-mercaptobenzothiazole were dissolved in 20 mL dichloromethane, 3 g of the helical mesoporous organosilica nanorods were added, and after mixing, rotary evaporation was carried out at 40°C under reduced pressure to obtain the helical nanoreservoirs loaded with corrosion inhibitors (see Figure 2 );
[0037] (5) 0.1 g of the helical nanoreservoirs loaded with corrosion inhibitors were dispersed in 10 g of epoxy resin, and after mixing, the surface of the iron sheet was coated by spin coating, and after drying, an epoxy rust-proof coating was formed.
[0038] Example 2: Preparation of helical mesoporous organosilica nanoreservoirs and rust-proof coating, the specific steps are as follows:
[0039] (1) 1 g of cetyltrimethylammonium bromide (CTAB) was dispersed in 160 mL of water, stirring was started at a stirring speed of 200 rpm, the water bath temperature was set to 35°C, and after stirring for 0.5 h, a uniform transparent solution A was formed;
[0040] (2) 4 mL of ammonia was added as a catalyst to solution A, and after mixing, solution B was obtained, and then stirring was continued at 35°C for 10 min;
[0041] (3) 5 mL of tetraethyl orthosilicate (TEOS) was placed in a constant pressure dropping funnel and slowly added to solution B, the dropping time was 25 min, and then stirring was continued at a water bath temperature of 35°C for 12 h, and centrifugal separation was carried out to obtain helical mesoporous organosilica nanorods 2 (see Figure 3 );
[0042] (4) 0.3 g benzotriazole, 0.1 g dopamine hydrochloride, 0.2 g methyl imidazole and 0.1 g 2-mercaptobenzothiazole were dissolved in 20 mL dichloromethane, 3 g of the helical mesoporous organosilica nanorods were added, and after mixing, rotary evaporation was carried out at 40°C under reduced pressure to obtain the helical nanoreservoirs loaded with corrosion inhibitors;
[0043] (5) 0.1 g of the helical nanoreservoirs loaded with corrosion inhibitors were dispersed in 10 g of epoxy resin, and after mixing, the surface of the iron sheet was coated by spin coating, and after drying, an epoxy rust-proof coating was formed.
[0044] Example 3: Preparation of helical mesoporous organosilica nanoreservoirs and rust-proof coating, the specific steps are as follows:
[0045] (1) 1 g of cetyltrimethylammonium bromide (CTAB) was dispersed in 160 mL of water, stirring was started at a stirring speed of 200 rpm, the water bath temperature was set to 45°C, and after stirring for 0.5 h, a uniform transparent solution A was formed;
[0046] (2) Add 6 mL of ammonia water as a catalyst to solution A, mix well to obtain solution B, and then continue stirring at 45°C for 10 min.
[0047] (3) Place 5 mL of tetraethyl orthosilicate (TEOS) in a constant pressure dropping funnel and slowly add it dropwise to solution B over a period of 25 min. Then, continue stirring the reaction for 12 h under a 45 °C water bath. After centrifugation, obtain helical mesoporous organosilicon nanorods 3( Figure 4 );
[0048] (4) Dissolve 0.3g benzotriazole, 0.1g dopamine hydrochloride, 0.2g methylimidazole and 0.1g 2-mercaptobenzothiazole in 20mL of dichloromethane, add 3g of helical mesoporous organosilicon nanorods, mix evenly and then evaporate under reduced pressure at 40℃ to obtain a helical nanocontainer loaded with corrosion inhibitor.
[0049] (5) Disperse 0.1g of a spiral-structured nanocontainer loaded with corrosion inhibitor in 10g of epoxy resin, mix evenly, and then apply it to the iron sheet surface by spin coating. After drying, an epoxy anti-rust coating is formed.
[0050] Comparative Example 1: The only difference from Example 1 is that step (2) is different.
[0051] Specifically, 8 mL of ammonia water was added to solution A as a catalyst, and after mixing evenly, solution B was obtained. Then, the mixture was stirred at 45°C for 10 min.
[0052] The final result is to obtain mesoporous organosilicon nanorods with small pitch and surface-intercalated nanoparticles, such as... Figure 5 As shown, excessive alkaline catalyst makes it difficult to prepare uniform helical mesoporous organosilicon nanorods.
[0053] Comparative Example 2: The only difference from Example 1 is that step (2) is different.
[0054] Specifically, 10 mL of ammonia water was added to solution A as a catalyst, and after mixing evenly, solution B was obtained. Then, the mixture was stirred at 45°C for 10 min.
[0055] The final result is a mesoporous silica rod with slightly raised ends, such as... Figure 6 As shown, an excess of alkaline catalyst cannot prepare uniform helical mesoporous organosilicon nanorods.
[0056] Comparative Example 3: The only difference from Example 1 is that step (2) is different.
[0057] Specifically, 2 mL of ammonia water is added as a catalyst into solution A, and after mixing evenly, solution B is obtained, and then stirring is continued at 45°C for 10 min;
[0058] The final result is to obtain a cylindrical short rod with some small particles, as shown in Figure 7 As shown, insufficient addition of the basic catalyst makes it difficult to prepare uniform mesoporous organosilica nanorods with a spiral structure.
[0059] Comparative Example 4: The only difference compared with Example 1 is that step (2) is different.
[0060] Specifically, 1 mL of ammonia water is added as a catalyst into solution A, and after mixing evenly, solution B is obtained, and then stirring is continued at 45°C for 10 min;
[0061] The final result is to obtain irregular small particles with a size of about 30 nm with some adhesion, as shown in Figure 8 As shown, too low concentration of the basic catalyst makes it difficult to prepare uniform mesoporous organosilica nanorods with a spiral structure.
[0062] The present application further carries out salt spray box accelerated corrosion experiments of different materials for Example 1, Example 2, Example 3, and Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4. Specifically, based on the mesoporous organosilica nanovessels prepared in the corresponding examples and comparative examples, after being combined with epoxy resin, they are respectively coated on the surface of steel and brass to form an epoxy coating, and the salt spray box accelerated corrosion experiment is carried out, and the results are shown in Table 1. The experiment shows that the epoxy coating prepared based on the mesoporous organosilica nanovessels with a spiral structure has better contact rust prevention effect, and can be widely applied to the rust prevention of metal parts in mechanical equipment.
[0063] Table 1 Salt spray box accelerated corrosion experiment
[0064]
[0065] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled persons in the art, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.
Claims
1. A method for preparing a helical mesoporous organosilicon nanocontainer, characterized in that, The specific steps are as follows: (1) Add the structure-directing agent to water and stir under water bath heating to form a homogeneous and transparent solution A; (2) Add the alkaline catalyst to the above solution A, mix well and continue stirring to obtain solution B; (3) Place the organosilane in a constant pressure dropping funnel and slowly add it to solution B. Heat and stir, centrifuge and wash to obtain helical mesoporous organosilicon nanorods. (4) Dissolve the corrosion inhibitor in dichloromethane, then add mesoporous organosilicon nanorods, mix evenly, and evaporate under reduced pressure to obtain a spiral-structured nanocontainer loaded with corrosion inhibitor.
2. The preparation method according to claim 1, characterized in that, The structure directing agent in step (1) is selected from hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, and hexadecyltrimethylammonium iodide; the concentration of the structure directing agent is 6-6.5 g / L; and the water bath temperature is 35-45 ℃.
3. The preparation method according to claim 1, characterized in that, The alkaline catalyst in step (2) is selected from ammonia, triethylamine, diethylamine, and tripropylamine; the stirring time is 10-30 min.
4. The preparation method according to claim 1, characterized in that, The organosilane mentioned in step (3) is selected from tetraethyl orthosilicate, (3-mercaptopropyl)trimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, and 1,2-bis(triethoxysilyl)ethane; the slow dropwise addition time is 20-30 min; the heating temperature is 35-45 ℃; the stirring time is 6-24 h; and the mass ratio of the organosilane reagent to the structure directing agent is (8-10):
1.
5. The preparation method according to claim 1, characterized in that, The corrosion inhibitors mentioned in step (4) are four types: benzotriazole, dopamine hydrochloride, methylimidazole, and 2-mercaptobenzothiazole; the mass percentage of the corrosion inhibitors is 10-30% based on the mass of the helical mesoporous organosilicon nanorods.
6. The preparation method according to claim 5, characterized in that, The mass ratio of the four corrosion inhibitors benzotriazole, dopamine hydrochloride, methylimidazole and 2-mercaptobenzothiazole in step (4) is 3:1:2:
1.
7. A helical mesoporous organosilicon nanocontainer, obtained by the preparation method according to any one of claims 1-6.
8. The application of the helical structure mesoporous organosilicon nanocontainer according to claim 7 in metal rust prevention.
9. The application according to claim 7, characterized in that, A helical mesoporous organosilicon nanocapacitor is dispersed in epoxy resin to form an anti-rust epoxy coating; then it is applied to a metal surface and dried at room temperature to form an epoxy anti-rust coating.
10. The application according to claim 9, characterized in that, The amount of the nanocontainer added is 0.5-5% of the mass of the epoxy resin; the coating method is spin coating.