CN112663400A - Copper-based metal product gas-phase antirust paper and preparation method thereof - Google Patents
Copper-based metal product gas-phase antirust paper and preparation method thereof Download PDFInfo
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Abstract
An air phase antirust paper for copper-based metal products and a preparation method thereof. The composite gas-phase slow-release layer comprises the following components in percentage by mass: 10-25% sodium benzoate; 10-20% potassium sorbate; 5-15% of C8-10 acid; 30-55% of benzotriazole; 10-30% of an oleamide borate compound; 10-35% fumed silica. The compound vapor phase corrosion inhibitor is fully fused and interacted under the regulation of a nonionic surfactant oleic acid amide boric acid ester compound; the fumed silica can be used as a support body of the vapor composite corrosion inhibitor, so that the specific surface area of the fumed silica is greatly improved, the fumed silica can be fully volatilized to the metal surface to form a protective film, and the vapor antirust performance can be better exerted through the synergistic effect.
Description
The technical field is as follows:
the invention relates to the field of nontoxic gas-phase antirust paper products suitable for copper special products, in particular to gas-phase antirust paper for copper-based metal products and a preparation method thereof.
Background art:
the gas phase rust prevention technology is one of the important methods of non-contact rust prevention at present. It uses vapor phase Corrosion Inhibitor (VCI) to automatically volatilize gas at normal temperature to form a layer of protective film on the metal surface, thus inhibiting the generation of electrochemical reaction, and simultaneously blocking the Corrosion of some substances (such as water, oxygen and other acidic gases) which accelerate the Corrosion of the metal to the metal surface, thereby slowing down or preventing the Corrosion to the metal surface. Common packaging use forms are gas-phase rust preventive powder: placing a certain amount of vapor phase inhibitor in a packaging container or a sealed space; antirust paper: coating a vapor phase inhibitor on the base paper; gas-phase antirust film: the corrosion inhibitor is added to the plastic film. In the three using modes, the gas phase corrosion inhibitor continuously and slowly volatilizes through sublimation to form corrosion inhibitor gas, and the gas phase corrosion inhibitor gas diffuses to the surface of the metal and is communicated with the surface of the metal to form a molecular film through chemical bonds or adsorption, so that the corrosion on the surface of the metal is effectively inhibited.
The gas-phase antirust paper has a long history of being used for surface protection packaging of metal products, has the characteristics of non-contact antirust no dead angle, environmental friendliness, convenient use, cleanness and the like compared with the traditional antirust oil and water-soluble antirust liquid, and has been widely applied to the antirust corrosion of the production, transportation, storage and other links of metals and products thereof in recent years. In the effective chemical components used as the gas phase corrosion inhibitor at present, the nitroso-based corrosion inhibitor still occupies a great proportion, but researches have clearly shown that nitroso and secondary amine are easily converted into a strong carcinogen nitrosamine in organisms, and the waste gas phase antirust paper after being used can cause great pollution to the environment. On the other hand, part of the vapor phase corrosion inhibitor has a deliquescence phenomenon, can reduce the mechanical strength of the antirust packaging paper in the storage process, and is easily damaged by edges and corners of steel materials in the use process. Although researchers use a large amount of industrial modified zeolite to improve the performance of the anti-rust paper, the production of the industrial modified zeolite is harmful to the health of operators and pollutes the environment, and fire accidents easily occur, so that the safe production has potential risks. Furthermore, the use of industrially modified zeolites does not impose any particular requirements on their particle size, and they do not function as large as possible as a support for the dispersed vapor phase corrosion inhibitor. In addition, at present, the components in the formula of the gaseous corrosion inhibitor in most of the gaseous rust-proof paper are simply mixed physically or dissolved and mixed, and are connected with each other without proper surface active molecules, so that the components of the gaseous corrosion inhibitor cannot be completely fused with each other, and the gaseous rust-proof function of the gaseous corrosion inhibitor can be fully exerted. The gas phase antirust paper for some multi-metals cannot play a good role in a single metal product.
Therefore, the development and production of the gas phase anti-rust paper which has excellent anti-rust effect on the copper-based metal products, is environment-friendly and is simple and convenient to operate has important significance for solving the rust problem of the metal products in the storage and transportation process.
The nonionic surfactant can well link the components of the vapor phase corrosion inhibitor together, promote the mutual fusion of the components and fully exert the vapor phase corrosion inhibition performance of the components; meanwhile, the surface tension of the liquid can be greatly reduced, the wettability is enhanced, and the components of the vapor phase corrosion inhibitor are firmly and uniformly attached to the vapor phase anti-rust paper. The oleic acid amide boric acid ester prepared by using unsaturated acid, alcohol amine and boric acid which are abundant in natural resources as raw materials has a hydrophobic group and also contains a plurality of hydrophilic groups such as hydroxyl, amide and the like, so that the oleic acid amide boric acid ester has high surface activity and strong wetting capability, and has a dissolution promotion effect on organic gas phase molecules containing amino groups. More importantly, the amino and borate contained in the oleic acid amide boric acid ester molecule can be used as an extreme pressure lubricant, a dispersion stabilizer, an adsorbent, an antirust agent and a wetting agent. However, their use as additives in gas-phase anti-rust paper technology has not been reported.
The invention content is as follows:
the invention aims to solve the defects in the prior art and provides vapor phase antirust paper for copper-based metal and a preparation method thereof. Solves the problems of poor performance and environment generation of the gas phase antirust paper in use.
In order to solve the problems, the invention adopts the following technical scheme:
the gas-phase antirust paper for the copper-based metal product is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 10-25% sodium benzoate; 10-20% potassium sorbate; 5-15% of C8-10 acid; 30-55% of benzotriazole; 10-30% of an oleamide borate compound; 10-35% fumed silica;
the oleic acid amide boric acid ester compound is prepared from the following raw materials in parts by weight: 25-36 parts of oleic acid; 10-15 parts by weight of maleic anhydride; 36-42 parts of diethanolamine; catalyst PB is 0.04-0.06 weight portion; 1-3 parts by weight of KOH; 5-8 parts of boric acid; 1-2 parts of toluene; 24-31 parts of deionized water;
the preparation method of the oleamide borate compound comprises the following steps:
adding oleic acid into a four-neck flask filled with nitrogen, adding a catalyst PB, heating to 140-150 ℃ in the nitrogen atmosphere, slowly adding maleic anhydride in batches under the stirring condition to ensure that no white mist overflows from the reaction bottle mouth, heating to 180-200 ℃, and carrying out heat preservation reaction for 3-5 hours; cooling the temperature of the reaction liquid to 160-;
the preparation method of the gas-phase antirust paper for the copper-based metal product comprises the following steps:
(a) adding a certain volume of deionized water into a reactor, heating to 40-60 ℃, sequentially adding sodium benzoate, potassium sorbate, C8-10 acid and benzotriazole which are components of the gas phase corrosion inhibitor according to mass percentage, and stirring and reacting until the components are completely dissolved after each component is added;
(b) adding the required amount of oleamide borate compound into the solution obtained in the step (a), stirring and reacting for half an hour at 40-60 ℃, and adjusting the pH to 8-9 by butyric acid or isobutanol amine;
(c) adding the required amount of fumed silica into the solution obtained in the step (b), stirring and reacting for 0.5-1 hour at 40-60 ℃ to fully and uniformly mix the reaction liquid, and naturally cooling to room temperature for later use;
(d) uniformly coating the dispersion liquid formed in the step (c) on fiber base paper, wherein the coating weight of the dispersion liquid on the fiber base paper is controlled to be 12 +/-2 g/cm2；
The volume of deionized water in step (a) is such that the mass percentage of the gas phase slow release component in the dispersion formed in step (c) is between 15 and 40%.
Compared with the prior art, the invention has the outstanding characteristics and beneficial effects that:
the compound gas-phase corrosion inhibitor is dissolved in an aqueous medium step by step, all components are fully fused by utilizing the multifunctional oleic acid amide boric acid ester surfactant with extreme pressure lubrication, stable dispersion, adsorption, rust prevention, wetting and the like, and then the gas-phase silicon dioxide is dispersed in the surfactant to be used as a nano supporting substrate, so that the dispersibility and the gas-phase volatilization performance of the gas-phase corrosion inhibitor in the anti-rust paper are improved, and a good gas-phase rust prevention effect is exerted. The invention does not relate to toxic or environment harmful substances, and belongs to an environment-friendly antirust product.
The specific implementation mode is as follows:
the present invention will be further understood in detail with reference to the following examples, but it should be understood that the scope of the present invention is limited only by the following examples. Various alterations and modifications made by those skilled in the art and conventional means without departing from the spirit of the invention are intended to be included within the scope of the invention.
Example 1:
the gas-phase antirust paper for the copper-based metal product is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 20% sodium benzoate; 23% potassium sorbate; 10% of C8-10 acid; 15% of benzotriazole; 15% of an oleamide borate compound; 17% fumed silica;
the preparation method of the oleamide borate compound comprises the following steps:
accurately weighing 30 g of purified oleic acid, adding the purified oleic acid into a four-neck flask filled with nitrogen, adding 0.05 g of catalyst PB, heating to 140 ℃ under the nitrogen atmosphere, slowly adding 15 g of maleic anhydride in batches under the stirring condition to ensure that no white mist overflows from the mouth of the reaction bottle, heating to 190 ℃, and carrying out heat preservation reaction for 3 hours; cooling the temperature of the reaction liquid to 150 ℃, slowly adding 18 g of diethanolamine, 1.5 g of KOH and 18 g of diethanolamine in batches, heating to 170 ℃ for reaction for 3 hours, slowly adding 4 g of diethanolamine for amination for 0.5 hour, naturally cooling to 100 ℃, gradually adding 5.5 g of boric acid and 3 ml of toluene under the stirring condition, continuously heating to 125 ℃, reacting until no water is evaporated out, finishing the reaction, naturally cooling to below 100 ℃, and adding deionized water according to the proportion to obtain the oleamide borate compound antirust agent;
the preparation method of the gas-phase antirust paper for the copper-based metal product comprises the following steps:
(a) adding a certain volume of deionized water into a reactor, heating to 40-60 ℃, sequentially adding sodium benzoate, potassium sorbate, C8-10 acid and benzotriazole which are components of the gas phase corrosion inhibitor according to mass percentage, and stirring and reacting until the components are completely dissolved after each component is added;
(b) adding the required amount of oleamide borate compound into the solution obtained in the step (a), stirring and reacting for half an hour at 50 ℃, and adjusting the pH to be between 8 and 9 by butyric acid or isobutanol amine;
(c) adding the required amount of fumed silica into the solution obtained in the step (b), stirring and reacting for 0.5 hour at 50 ℃ to fully and uniformly mix the reaction liquid, and naturally cooling to room temperature for later use;
(d) uniformly coating the dispersion liquid formed in the step (c) on fiber base paper, wherein the coating weight of the dispersion liquid on the fiber base paper is controlled to be 12 +/-2 g/cm2；
The volume of deionized water in step (a) is such that the mass percent of the gas phase extended release component in the dispersion formed in step (c) is 25%.
Example 2:
the gas-phase antirust paper for the copper-based metal product is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 18% sodium benzoate; 30% potassium sorbate; 12% of C8-10 acid; 14% of benzotriazole; 13% of an oleamide borate compound; 13% fumed silica;
the other steps are the same as in example 1.
Example 3:
the gas-phase antirust paper for the copper-based metal product is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 18% sodium benzoate; 20% potassium sorbate; 15% of C8-10 acid; 17% of benzotriazole; 15% of an oleamide borate compound; 15% fumed silica;
the other steps are the same as in example 1.
Example 4:
the gas-phase antirust paper for the copper-based metal product is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 28% sodium benzoate; 15% potassium sorbate; 10% of C8-10 acid; 12% of benzotriazole; 25% of an oleamide borate compound; 10% fumed silica;
the other steps are the same as in example 1.
Comparative example 1:
the gas-phase antirust paper for the copper-based metal product is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 26% sodium benzoate; 25% potassium sorbate; 15% of C8-10 acid; 16% benzotriazole; 18% fumed silica;
the other steps are the same as in example 1.
Comparative example 2:
the gas-phase antirust paper for the copper-based metal product is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 26% sodium benzoate; 25% potassium sorbate; 20% of C8-10 acid; 16% benzotriazole; 13% of an oleamide borate compound;
the other steps are the same as in example 1.
Example 5 application effect test example
The gas phase rust preventive paper products obtained in examples 1, 2, 3 and 4 and comparative examples 1 and 2 were subjected to gas phase rust preventive treatment on copper-based metal products and compared in terms of rust preventive properties, and the test standards were referred to GB/T19532-2004, and the test results are shown in Table 1:
the comparative test results in table 1 show that the rust inhibitive effect of the gas phase rust inhibitive paper of the present invention on copper based metals is better than that of comparative example 1 which does not contain oleamide borate additive and comparative example 2 which does not contain fumed silica nano support carrier, wherein the effect of example 2 is the best and is the preferred embodiment of the present invention. The gas-phase antirust paper has the selling price lower than one half of that of foreign similar products, has no toxic or side effect, does not pollute the environment, meets the requirements of national environmental protection standards, and can completely replace imported products. The analysis suggests that the gas phase corrosion inhibition mechanism of the compounds is as follows: on one hand, the compounded vapor phase corrosion inhibitor is fully fused and interacted under the regulation of the nonionic surfactant of oleamide boric acid ester; on the other hand, the fumed silica is used as a support body of the fumed composite corrosion inhibitor, so that the specific surface area of the fumed silica is greatly improved, the fumed silica can be fully volatilized to the surface of metal, and the fumed rust-proof performance can be better exerted through the synergistic effect, wherein boric acid ester is contained in the molecules of the corrosion inhibitor; and N and O atoms in the molecule both contain lone-pair electrons, can form a coordination bond with a d electron empty orbit of Fe, and generate chemical adsorption; and the corrosion inhibition effect of organic salt in the compound corrosion inhibitor is added, so that the compound corrosion inhibitor forms a firm adsorption film on the metal surface to inhibit the contact of oxygen and water on the metal surface, and a good antirust effect is exerted.
Claims (1)
1. The gas-phase antirust paper for the special metal copper product is characterized by comprising a composite gas-phase slow-release layer and a raw paper layer, wherein the composite gas-phase slow-release layer comprises the following components in percentage by mass: 10-25% sodium benzoate; 10-20% potassium sorbate; 5-15% of C8-10 acid; 30-55% of benzotriazole; 10-30% of an oleamide borate compound; 10-35% fumed silica;
the oleic acid amide boric acid ester compound is prepared from the following raw materials in parts by weight: 25-36 parts of oleic acid; 10-15 parts by weight of maleic anhydride; 36-42 parts of diethanolamine; catalyst PB is 0.04-0.06 weight portion; 1-3 parts by weight of KOH; 5-8 parts of boric acid; 1-2 parts of toluene; 24-31 parts of deionized water;
the preparation method of the oleamide borate compound comprises the following steps:
adding oleic acid into a four-neck flask filled with nitrogen, adding a catalyst PB, heating to 140-150 ℃ in the nitrogen atmosphere, slowly adding maleic anhydride in batches under the stirring condition to ensure that no white mist overflows from the reaction bottle mouth, heating to 180-200 ℃, and carrying out heat preservation reaction for 3-5 hours; cooling the temperature of the reaction liquid to 160-;
the preparation method of the gas-phase antirust paper for the special copper product comprises the following steps:
(a) adding a certain volume of deionized water into a reactor, heating to 40-60 ℃, sequentially adding sodium benzoate, potassium sorbate, C8-10 acid and benzotriazole which are components of the gas phase corrosion inhibitor according to mass percentage, and stirring and reacting until the components are completely dissolved after each component is added;
(b) adding the required amount of oleamide borate compound into the solution obtained in the step (a), stirring and reacting for half an hour at 40-60 ℃, and adjusting the pH to 8-9 by butyric acid or isobutanol amine;
(c) adding the required amount of fumed silica into the solution obtained in the step (b), stirring and reacting for 0.5-1 hour at 40-60 ℃ to fully and uniformly mix the reaction liquid, and naturally cooling to room temperature for later use;
(d) uniformly coating the dispersion liquid formed in the step (c) on fiber base paper, wherein the coating weight of the dispersion liquid on the fiber base paper is controlled to be 10 +/-2 g/cm2；
The volume of deionized water in step (a) is such that the mass percentage of the gas phase slow release component in the dispersion formed in step (c) is between 15 and 40%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116536969A (en) * | 2023-06-16 | 2023-08-04 | 苏州启阳新材料科技股份有限公司 | Aqueous silicone oil gas-phase antirust emulsion for paper products |
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| JPH03227497A (en) * | 1990-01-31 | 1991-10-08 | Kanzaki Paper Mfg Co Ltd | Production of non-water-absorptive antirust paper |
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| CN106676534A (en) * | 2017-01-07 | 2017-05-17 | 青岛鑫盈鑫包装材料有限公司 | Mercaptobenzothiazole gas-phase rust-proof fiberboard and preparation method thereof |
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2020
- 2020-12-21 CN CN202011514748.5A patent/CN112663400A/en not_active Withdrawn
Patent Citations (5)
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|---|---|---|---|---|
| JPH03227497A (en) * | 1990-01-31 | 1991-10-08 | Kanzaki Paper Mfg Co Ltd | Production of non-water-absorptive antirust paper |
| CN105316687A (en) * | 2014-07-01 | 2016-02-10 | 蒋寿悟 | Improved gas-phase antirust agent and preparation method thereof |
| CN106676534A (en) * | 2017-01-07 | 2017-05-17 | 青岛鑫盈鑫包装材料有限公司 | Mercaptobenzothiazole gas-phase rust-proof fiberboard and preparation method thereof |
| CN110499512A (en) * | 2019-09-11 | 2019-11-26 | 王二坡 | One kind being applicable in environmentally friendly gaseous recombination corrosion inhibitor of more metals and preparation method thereof |
| CN111206250A (en) * | 2020-01-20 | 2020-05-29 | 青岛科技大学 | Mixed amide type water-based gas-phase antirust concentrated solution and preparation and use methods thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116536969A (en) * | 2023-06-16 | 2023-08-04 | 苏州启阳新材料科技股份有限公司 | Aqueous silicone oil gas-phase antirust emulsion for paper products |
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