阅读说明：本技术 一种缓释型气相防锈剂及其制备方法 (Slow-release gas-phase antirust agent and preparation method thereof ) 是由 姜锐 谭振洲 常羽坤 李伟哲 窦志刚 徐欣轶 沈萍 闫宏飞 于 2021-09-23 设计创作，主要内容包括：本发明公开的一种缓释型气相防锈剂及其制备方法,其中,缓释型气相防锈剂包括芯材和壁材,芯材由下述原料按重量份配成：苯甲酸盐60-64份、钼酸盐17-20份、有机类铜缓蚀剂19-23份、酒石酸钠0.8-1.2份、肉桂酸钠0.5-1份；壁材包裹在芯材外,与芯材形成核壳结构；壁材为海藻酸钠、聚甲基丙烯酸甲酯、乙基纤维素、醋酸纤维素、大豆分离蛋白、乳清蛋白、壳聚糖、阿拉伯胶、明胶中的一种或几种混合物。本发明提供的缓释型气相防锈剂通过芯材的表面包裹一层壁材,延缓和降低芯材中的气相防锈剂的释放速度,进而实现气相防锈剂的缓慢释放及控制释放,以满足防锈剂对金属部件及设备设施在长周期贮运过程中的防锈防护需求。(The invention discloses a slow-release gas-phase antirust agent and a preparation method thereof, wherein the slow-release gas-phase antirust agent comprises a core material and a wall material, wherein the core material is prepared from the following raw materials in parts by weight: 60-64 parts of benzoate, 17-20 parts of molybdate, 19-23 parts of organic copper corrosion inhibitor, 0.8-1.2 parts of sodium tartrate and 0.5-1 part of sodium cinnamate; the wall material is wrapped outside the core material and forms a core-shell structure with the core material; the wall material is one or more of sodium alginate, polymethyl methacrylate, ethyl cellulose, cellulose acetate, soy protein isolate, lactalbumin, chitosan, acacia and gelatin. The slow-release gas-phase antirust agent provided by the invention has the advantages that the surface of the core material is coated with the wall material, so that the release speed of the gas-phase antirust agent in the core material is delayed and reduced, the slow release and the controlled release of the gas-phase antirust agent are further realized, and the antirust protection requirements of the antirust agent on metal parts and equipment facilities in the long-period storage and transportation process are met.)

1. A slow-release gas-phase rust inhibitor is characterized by comprising:

the core material is prepared from the following raw materials in parts by weight: 60-64 parts of benzoate, 17-20 parts of molybdate, 19-23 parts of organic copper corrosion inhibitor, 0.8-1.2 parts of sodium tartrate and 0.5-1 part of sodium cinnamate;

the wall material is wrapped outside the core material and forms a core-shell structure with the core material; the wall material is one or a mixture of more of Sodium Alginate (SA), polymethyl methacrylate (PMMA), Ethyl Cellulose (EC), cellulose acetate, soy protein isolate, whey protein, chitosan, Arabic gum and gelatin.

2. The slow-release gas-phase antirust agent according to claim 1, wherein the benzoate is one or a mixture of sodium benzoate, potassium benzoate, ammonium benzoate and monoethanolamine benzoate.

3. The slow release gas phase rust inhibitor of claim 1, wherein the molybdate is one or more of sodium molybdate, potassium molybdate, lithium molybdate and ammonium molybdate.

4. The sustained-release gas-phase antirust agent according to claim 1, wherein the organic copper corrosion inhibitor is at least one of benzotriazole, tolyltriazole and 4-hydroxybenzotriazole.

5. The slow-release gas-phase rust inhibitor according to claim 1, wherein the gas-phase rust inhibitor has an average particle diameter of 3 to 50 μm.

6. The slow-release gas-phase rust inhibitor according to claim 1, wherein the wall material forms a semipermeable shell outside the core material.

7. The slow-release gas-phase rust inhibitor according to claim 6, wherein the core material is released from the wall material by means of dissolution or permeation or diffusion.

8. The preparation method of the slow-release gas-phase antirust agent is characterized by comprising the following steps of:

(1) preparation of wall material solution: swelling and dispersing the wall material raw material in a water bath at 50-60 ℃ by using a proper amount of water to prepare a wall material solution with the concentration of 1.5-3%;

(2) preparation of core material solution: adding proper amount of water into 60-64 parts of benzoate, 17-20 parts of molybdate, 19-23 parts of organic copper corrosion inhibitor, 0.8-1.2 parts of sodium tartrate and 0.5-1 part of sodium cinnamate in parts by weight, dissolving and uniformly mixing in a water bath at 70-90 ℃ to prepare a core material solution;

(3) mixing: adding the core material solution into the wall material solution according to the ratio of the wall material solution to the core material solution (8-11): 1, and then stirring for 1-2 hours until the solution is uniformly mixed;

(4) and (3) preparing a finished product: and (4) treating the mixed solution obtained in the step (3) by adopting a spray drying method to finish the preparation of the gas-phase antirust agent.

9. The preparation method of the slow-release gas-phase antirust agent according to claim 8, wherein the air inlet temperature of the spray drying method is controlled to be 175-205 ℃, the compressed air flow is 500-800L/h, the feed flow is 3-6 ml/min, and the air outlet temperature is controlled to be 75-95 ℃.

Technical Field

The invention relates to the field of antirust packaging materials, in particular to a slow-release gas-phase antirust agent and a preparation method thereof.

Background

Since metal and metal products are easily corroded by the atmosphere during the manufacturing, transporting and storing processes, which affects the appearance and performance, even causes scrap, it is necessary to protect the metal and its products from rust protection under the conditions of long manufacturing, transporting and storing time or high humidity and high temperature.

The principle of the vapor phase rust inhibitor is that the vapor phase rust inhibitor can be directly gasified (sublimated) at normal temperature and normal pressure, reaches a saturated state in a closed ring mirror, and molecules of the vapor phase rust inhibitor are absorbed on the surface of metal to form a molecular protective film to prevent the metal from being corroded.

The gas phase rust inhibitor volatilizes faster in the package, especially at an overhigh temperature, has a faster volatilization speed, cannot realize a slow release effect, influences the service life of the gas phase rust inhibitor, even causes the gas phase rust inhibitor to lose effectiveness in the continuous use process, and thus greatly shortens the protection effect period of the gas phase rust inhibitor on metal products, thereby causing the loss of the protected metal products due to corrosion, especially the long-period rust prevention process of the metal products under the high-temperature and high-humidity environment condition.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a slow-release gas-phase antirust agent and a preparation method thereof.

The invention provides a slow-release gas-phase antirust agent, which comprises the following components in part by weight:

the core material is prepared from the following raw materials in parts by weight: 60-64 parts of benzoate, 17-20 parts of molybdate, 19-23 parts of organic copper corrosion inhibitor, 0.8-1.2 parts of sodium tartrate and 0.5-1 part of sodium cinnamate;

the wall material is wrapped outside the core material and forms a core-shell structure with the core material; the wall material is one or a mixture of more of Sodium Alginate (SA), polymethyl methacrylate (PMMA), Ethyl Cellulose (EC), cellulose acetate, soy protein isolate, whey protein, chitosan, Arabic gum and gelatin.

Further, the benzoate is one or a mixture of more of sodium benzoate, potassium benzoate, ammonium benzoate and monoethanolamine benzoate.

Further, the molybdate is one or a mixture of sodium molybdate, potassium molybdate, lithium molybdate and ammonium molybdate.

Furthermore, the organic copper corrosion inhibitor is at least one of benzotriazole, methylbenzotriazole and 4-hydroxybenzotriazole.

Further, the average particle size of the gas phase antirust agent is 3-50 μm.

Furthermore, the wall material forms a semi-permeable shell outside the core material.

Further, the core material is released from the wall material by means of dissolution or permeation or diffusion.

The invention also provides a preparation method of the slow-release gas-phase antirust agent, which comprises the following steps:

(1) preparation of wall material solution: swelling and dispersing the wall material raw material in a water bath at 50-60 ℃ by using a proper amount of water to prepare a wall material solution with the concentration of 1.5-3%;

(2) preparation of core material solution: adding proper amount of water into 60-64 parts of benzoate, 17-20 parts of molybdate, 19-23 parts of organic copper corrosion inhibitor, 0.8-1.2 parts of sodium tartrate and 0.5-1 part of sodium cinnamate in parts by weight, dissolving and uniformly mixing in a water bath at 70-90 ℃ to prepare a core material solution;

(3) mixing: adding the core material solution into the wall material solution according to the ratio of the wall material solution to the core material solution (8-11): 1, and then stirring for 1-2 hours until the solution is uniformly mixed;

(4) and (3) preparing a finished product: and (4) treating the mixed solution obtained in the step (3) by adopting a spray drying method to finish the preparation of the gas-phase antirust agent.

Furthermore, the air inlet temperature of the spray drying method is controlled to be 175-205 ℃, the compressed air flow is 500-800L/h, the feed flow is 3-6 ml/min, and the air outlet temperature is controlled to be 75-95 ℃.

The slow-release gas-phase antirust agent provided by the invention does not contain nitrite antirust components, has excellent adsorption performance, can form a protective layer on the surface of metal after gasification, has good gas-phase antirust performance on various metals such as steel, copper and the like, and is particularly suitable for the rust prevention of metal surfaces which are difficult to touch such as deep holes, slender pipes, bends, gaps and the like; meanwhile, the surface of the core material is coated with a layer of wall material, so that the wall material delays and reduces the release speed of the gas-phase antirust agent in the core material, and further the slow release and controlled release of the gas-phase antirust agent are realized, and the antirust protection requirements of the gas-phase antirust agent on metal parts and equipment facilities in the long-period storage and transportation process are met.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The invention provides a slow-release gas-phase antirust agent which comprises a core material and a wall material, wherein the core material is prepared from the following raw materials in parts by weight: 60-64 parts of benzoate, 17-20 parts of molybdate, 19-23 parts of organic copper corrosion inhibitor, 0.8-1.2 parts of sodium tartrate and 0.5-1 part of sodium cinnamate; the wall material is wrapped outside the core material and forms a core-shell structure with the core material; the wall material is one or more of Sodium Alginate (SA), polymethyl methacrylate (PMMA), Ethyl Cellulose (EC), cellulose acetate, soybean protein isolate, lactalbumin, chitosan, Arabic gum and gelatin.

According to the slow-release type gas phase antirust agent provided by the invention, the surface of the core material is coated with the wall material, so that the wall material is used for coating the gas phase antirust agent to form a core-shell structure, the gas phase antirust agent is relatively isolated from the external environment, the influence of the external environment on the gas phase antirust agent is reduced to a certain extent, meanwhile, the volatilization speed of the gas phase antirust agent in the long-period antirust process can be reduced, the wall material realizes the slow-release effect on the gas phase antirust agent, the purpose of prolonging the protection period of the gas phase antirust agent on metal products is achieved, and the antirust protection requirements of metal components and equipment facilities in the long-period storage and transportation process are met.

In a word, the slow-release gas-phase antirust agent provided by the invention does not contain nitrite antirust components, has excellent adsorption performance, can form a protective layer on the surface of metal after gasification, has good gas-phase antirust performance on various metals such as steel, copper and the like, and is particularly suitable for the rust prevention of metal surfaces which are difficult to touch such as deep holes, slender pipes, bends, gaps and the like; meanwhile, the surface of the core material is coated with a layer of wall material, so that the wall material delays and reduces the release speed of the gas-phase antirust agent in the core material, and further the slow release and controlled release of the gas-phase antirust agent are realized, and the antirust protection requirements of the gas-phase antirust agent on metal parts and equipment facilities in the long-period storage and transportation process are met.

In some embodiments, the benzoate salt is one or more mixtures of sodium benzoate, potassium benzoate, ammonium benzoate, monoethanolamine benzoate.

In some embodiments, the molybdate is one or more of sodium molybdate, potassium molybdate, lithium molybdate, and ammonium molybdate.

In some embodiments, the organic copper corrosion inhibitor is at least one of benzotriazole, methylbenzotriazole and 4-hydroxybenzotriazole.

In some embodiments, the gas phase rust inhibitor has an average particle diameter of 3 to 50 μm.

In some embodiments, the wall material forms a semi-permeable shell outside the core material, so that the gas phase antirust agent in the core material can be released through the semi-permeable shell, and the release speed of the gas phase antirust agent in the core material is delayed and reduced.

In some embodiments, the core material is released from the wall material by means of dissolution or permeation or diffusion.

The invention provides a preparation method of a slow-release gas-phase antirust agent, which comprises the following steps:

(1) preparation of wall material solution: swelling and dispersing the wall material raw material in a water bath at 50-60 ℃ by using a proper amount of water to prepare a wall material solution with the concentration of 1.5-3%;

(2) preparation of core material solution: adding proper amount of water into 60-64 parts of benzoate, 17-20 parts of molybdate, 19-23 parts of organic copper corrosion inhibitor, 0.8-1.2 parts of sodium tartrate and 0.5-1 part of sodium cinnamate in parts by weight, dissolving and uniformly mixing in a water bath at 70-90 ℃ to prepare a core material solution;

(3) mixing: adding the core material solution into the wall material solution according to the ratio of the wall material solution to the core material solution (8-11): 1, and then stirring for 1-2 hours until the solution is uniformly mixed;

(4) and (3) preparing a finished product: and (4) treating the mixed solution obtained in the step (3) by adopting a spray drying method to finish the preparation of the gas-phase antirust agent.

In some embodiments, the air inlet temperature of the spray drying method is controlled to be 175-205 ℃, the compressed air flow is 500-800L/h, the feed flow is 3-6 ml/min, and the air outlet temperature is controlled to be 75-95 ℃.

The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.

Embodiments 1 to 3 of the present invention provide a slow-release gas-phase antirust agent, which is composed of an external wall material and an internal core material, wherein the core material is wrapped by the wall material to form a core-shell structure. The microencapsulated gas phase rust inhibitor has an average particle diameter of 3 to 50 μm.

Example 1

The slow-release gas-phase antirust agent comprises a core material and a wall material, wherein the core material is prepared from the following raw materials in parts by weight: 61 parts of benzoate, 18 parts of molybdate, 20 parts of organic copper corrosion inhibitor, 1 part of sodium tartrate and 0.6 part of sodium cinnamate; the wall material is wrapped outside the core material and forms a core-shell structure with the core material; the wall material is a mixture of Sodium Alginate (SA) and soybean protein isolate in a mass ratio of 1: 1.

A preparation method of a slow-release gas-phase antirust agent comprises the following steps:

(1) preparation of wall material solution: weighing 4.5g of polymethyl methacrylate (PMMA) and 4.5g of soybean protein isolate, and swelling and dispersing the materials in a water bath at 50-60 ℃ by using a proper amount of water to prepare a wall material solution with the concentration of 2%;

(2) preparation of core material solution: adding 61 parts by weight of benzoate, 18 parts by weight of molybdate, 20 parts by weight of organic copper corrosion inhibitor, 1 part by weight of sodium tartrate and 0.6 part by weight of sodium cinnamate into a proper amount of water, dissolving in a water bath at 70-90 ℃, and uniformly mixing to prepare a core material solution;

(3) mixing: adding the core material solution into the wall material solution according to the ratio of the wall material solution to the core material solution of 9:1, and then stirring for 1-2 hours until the solutions are uniformly mixed;

(4) and (3) preparing a finished product: and (4) treating the mixed solution obtained in the step (3) by adopting a spray drying method, wherein the air inlet temperature is controlled at 180 ℃, the compressed air flow is 500L/h, the feed flow is 3ml/min, and the air outlet temperature is controlled at 80 ℃, so that the preparation of the gas-phase antirust agent is completed.

Example 2

The slow-release gas-phase antirust agent comprises a core material and a wall material, wherein the core material is prepared from the following raw materials in parts by weight: 62 parts of benzoate, 19 parts of molybdate, 21 parts of organic copper corrosion inhibitor, 0.8 part of sodium tartrate and 0.7 part of sodium cinnamate; the wall material is wrapped outside the core material and forms a core-shell structure with the core material; the wall material is a mixture of chitosan, Arabic gum and Ethyl Cellulose (EC) according to the mass ratio of 5:5: 1.

A preparation method of a slow-release gas-phase antirust agent comprises the following steps:

(1) preparation of wall material solution: weighing 5g of chitosan, 5g of Arabic gum and 1g of Ethyl Cellulose (EC), and swelling and dispersing the chitosan, the Arabic gum and the EC with a proper amount of water in a water bath at 50-60 ℃ to prepare a wall material solution with the concentration of 2.5%;

(2) preparation of core material solution: adding appropriate amount of water into 62 parts of benzoate, 19 parts of molybdate, 21 parts of organic copper corrosion inhibitor, 0.8 part of sodium tartrate and 0.7 part of sodium cinnamate in parts by weight, dissolving and uniformly mixing in a water bath at 70-90 ℃ to prepare a core material solution;

(3) mixing: adding the core material solution into the wall material solution according to the proportion of the wall material solution to the core material solution being 10:1, and then stirring for 1-2 hours until the solutions are uniformly mixed;

(4) and (3) preparing a finished product: and (4) treating the mixed solution obtained in the step (3) by adopting a spray drying method, wherein the air inlet temperature is controlled at 190 ℃, the compressed air flow is 700L/h, the feed flow is 5ml/min, and the air outlet temperature is controlled at 85 ℃, so that the preparation of the gas-phase antirust agent is completed.

Example 3

The slow-release gas-phase antirust agent comprises a core material and a wall material, wherein the core material is prepared from the following raw materials in parts by weight: 60 parts of benzoate, 17 parts of molybdate, 23 parts of organic copper corrosion inhibitor, 1.1 parts of sodium tartrate and 0.8 part of sodium cinnamate; the wall material is wrapped outside the core material and forms a core-shell structure with the core material; the wall material is a mixture of chitosan and gelatin according to the mass ratio of 2: 1.

A preparation method of a slow-release gas-phase antirust agent comprises the following steps:

(1) preparation of wall material solution: weighing 6g of chitosan and 3g of gelatin, and swelling and dispersing the chitosan and the gelatin in water bath at 50-60 ℃ by using a proper amount of water to prepare a wall material solution with the concentration of 3%;

(2) preparation of core material solution: adding proper amount of water into 60 parts of benzoate, 17 parts of molybdate, 23 parts of organic copper corrosion inhibitor, 1.1 parts of sodium tartrate and 0.8 part of sodium cinnamate in parts by weight, dissolving and uniformly mixing in water bath at 70-90 ℃ to prepare a core material solution;

(3) mixing: adding the core material solution into the wall material solution according to the proportion of the wall material solution to the core material solution being 11:1, and then stirring for 1-2 hours until the solutions are uniformly mixed;

(4) and (3) preparing a finished product: and (4) treating the mixed solution obtained in the step (3) by adopting a spray drying method, wherein the air inlet temperature is controlled at 200 ℃, the compressed air flow is 800L/h, the feed flow is 6ml/min, and the air outlet temperature is controlled at 90 ℃, so that the preparation of the gas-phase antirust agent is completed.

The target products prepared in examples 1, 2 and 3 were subjected to a gas phase corrosion inhibition ability test, a gas phase corrosion inhibition ability test after accelerated consumption, a compatibility test and a contact corrosion test. The gas-phase corrosion inhibition capacity test and the gas-phase corrosion inhibition capacity test after accelerated consumption are tested according to GB/T16267-2008 packaging material test method gas-phase corrosion inhibition capacity, the compatibility test is tested according to GB/T16265-. The specific test results are shown in table 1.

TABLE 1

The test results show that the examples 1, 2 and 3 have excellent gas phase corrosion inhibition capability, have the same excellent gas phase corrosion inhibition capability after accelerated consumption, have no contact corrosion with steel, red copper and aluminum, and have good compatibility with the red copper and the aluminum.

In conclusion, examples 1, 2 and 3 have good rust-proof performance for both ferrous metals and nonferrous metals, and the microencapsulated gas phase rust inhibitor has good slow-release effect.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.