CN111073737A - Anti-rust oil without containing heavy metal - Google Patents
Anti-rust oil without containing heavy metal Download PDFInfo
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- CN111073737A CN111073737A CN201911209635.1A CN201911209635A CN111073737A CN 111073737 A CN111073737 A CN 111073737A CN 201911209635 A CN201911209635 A CN 201911209635A CN 111073737 A CN111073737 A CN 111073737A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation
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- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/16—Naphthenic acids
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/401—Fatty vegetable or animal oils used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
- C10M2215/222—Triazines
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
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Abstract
The invention discloses an anti-rust oil without heavy metal, which comprises the following components in percentage by weight: 1-15% of first antirust agent, 1-10% of second antirust agent, 5-15% of film-forming agent, 0.1-5% of antioxidant, 0.1-5% of preservative, 0.01-2% of defoaming agent, 0.01-2% of essence and the balance of modified vegetable oil. The anti-rust oil disclosed by the invention does not contain heavy metals, and the modified vegetable oil is adopted to replace mineral oil as base oil, so that the anti-rust oil is biodegradable and environment-friendly; the modified vegetable oil is not easy to oxidize, and the anti-rust oil has good stability and long service life; the two-component antirust agent with mutual synergistic effect is used, so that the antirust performance is good.
Description
Technical Field
The invention relates to the technical field of anti-rust oil, and particularly relates to environment-friendly heavy metal-free modified plant anti-rust oil.
Background
The existing antirust oil generally contains mineral oil and heavy metals. In recent years, waste rust preventive oil enters the natural environment for various reasons, so that the pollution of the rust preventive oil and the environmental health problem are gradually concerned, and the development of environment-friendly rust preventive oil has become a global consensus.
On the premise of increasing the petroleum consumption and reducing the reserves in the world, people are prompted to search mineral oil substitutes for producing the anti-rust oil. The vegetable oil is used for preparing the rust preventive oil, which becomes the choice of people. Compared with mineral oil, the vegetable oil has better biodegradability, and is green and environment-friendly antirust oil. However, the vegetable oil has some defects, such as the chemical structure of the vegetable oil contains more unsaturated components, the oxidation resistance is poor, the vegetable oil is easy to smell and deteriorate, and the service life of the anti-rust oil is influenced.
In addition, a heavy metal rust preventive agent such as barium petroleum sulfonate, barium dinonylnaphthalene sulfonate and the like is generally contained in a commonly used rust preventive oil. Heavy metal pollution is different from pollution of other organic compounds, and heavy metals have enrichment property and are difficult to degrade in the environment. Heavy metals are widely distributed in the atmosphere, water, soil, and organisms, and soil is often the repository and ultimate destination of heavy metals. When the environment changes, the heavy metal forms in the soil are transformed and released to cause pollution. Since heavy metals are not biodegradable and bioaccumulative, they can directly threaten higher organisms including humans.
Based on the above problems, there is a need to develop an antirust oil with good antirust performance, long service life and environmental protection.
Disclosure of Invention
The existing antirust oil has the following defects: (1) the heavy metal pollution is caused by adopting the antirust agent containing the heavy metal; (2) mineral oil is adopted as base oil, so that biodegradation is not easy to occur, and the treatment difficulty is high; (3) the plant anti-rust oil has more unsaturated components, poor oxidation resistance, easy odor generation and deterioration and short service life. The invention aims to provide the plant anti-rust oil which is environment-friendly, free of heavy metal, long in service life and good in anti-rust performance, so as to solve the technical problems.
The invention provides anti-rust oil without heavy metal, which comprises the following components in percentage by weight:
the preparation method of the anti-rust oil without heavy metal comprises the following steps:
(1) adding a first antirust agent, a second antirust agent, a film forming agent, an antioxidant and a preservative into the modified vegetable oil in parts by weight, heating at the temperature of 90-110 ℃, and stirring at the speed of 300-500 rpm for 20-30 min to prepare a uniform mixture;
(2) and (2) adding a defoaming agent and essence into the uniform mixture obtained in the step (1), and then performing ultrasonic oscillation for 10-20 min.
Preferably, the method for preparing a heavy metal-free rust preventive oil of the present invention comprises the steps of:
(1) adding a first antirust agent, a second antirust agent, a film forming agent, an antioxidant and a preservative into the modified vegetable oil in parts by weight, heating at 90 ℃, and stirring at the speed of 300rpm for 30min to prepare a uniform mixture;
(2) and (2) adding a defoaming agent and essence into the uniform mixture obtained in the step (1), and then carrying out ultrasonic oscillation for 20 min. Thus obtaining the anti-rust oil without heavy metal.
The anti-rust oil without heavy metal is prepared by using modified vegetable oil as base oil, specifically organic silicon modified vegetable oil, which can be any one or a mixture of more than two of rapeseed oil, soybean oil, cottonseed oil and palm oil through organic silicon modification. The preparation process of the organic silicon modified vegetable oil at least comprises ester exchange reaction, epoxidation reaction and ring opening reaction.
The preparation method of the organic silicon modified vegetable oil comprises the following steps:
(1) adding 100 parts by mass of vegetable oil into a reactor, gradually adding 20-30 parts by mass of 6-8% potassium hydroxide methanol solution, carrying out ester exchange reaction at 60-70 ℃ for 1-3h, washing to be neutral after the reaction is finished, removing water and drying to obtain fatty acid methyl ester;
(2) adding a mixture of 100-150 parts of acetic acid and a strong acid cation exchange resin catalyst into the fatty acid methyl ester obtained in the step (1) by mass at the temperature of 60-70 ℃, then gradually adding a hydrogen peroxide solution, wherein the molar ratio of H2O2 to acetic acid is 1-1.5:1, preserving heat for 4 hours to carry out epoxidation reaction, washing to be neutral after the reaction is finished, removing water and drying to obtain epoxy vegetable oil;
(3) dropwise adding 30-50 parts of acetic acid into the epoxy vegetable oil obtained in the step (1) by mass at the temperature of 50-60 ℃, preserving heat for 1-3 hours after dropwise adding for ring-opening reaction, washing to be neutral after the reaction is finished, removing water and drying to obtain vegetable oleyl alcohol;
(4) dropwise adding vegetable oil alcohol and triethylamine into the diethyl ether solution of the trimethyl silicon chloride under the conditions of ice water bath and nitrogen protection, then reacting for 2 hours at the temperature of 30-60 ℃, washing to be neutral after the reaction is finished, evaporating to remove the solvent and drying in vacuum to obtain the organic silicon modified vegetable oil; the molar ratio of the trimethyl silicon chloride to the vegetable oil alcohol is 1: 1.
preferably, the preparation method of the organic silicon modified vegetable oil comprises the following steps:
(1) adding 100 parts by mass of vegetable oil into a reactor, gradually adding 25 parts by mass of 8% potassium hydroxide methanol solution, carrying out ester exchange reaction at 70 ℃ for 2h, washing to be neutral after the reaction is finished, removing water and drying to obtain fatty acid methyl ester;
(2) adding 120 parts of a mixture of acetic acid and a strongly acidic cation exchange resin catalyst to 100 parts by mass of the fatty acid methyl ester obtained in step (1) at a temperature of 60 ℃ and gradually adding a hydrogen peroxide solution in which H is2O2Keeping the molar ratio of the obtained product to acetic acid at 1.2:1 for 4 hours to carry out epoxidation reaction, washing to be neutral after the reaction is finished, removing water and drying to obtain epoxy vegetable oil;
(3) dropwise adding 50 parts of acetic acid into 100 parts by mass of the epoxy vegetable oil obtained in the step (1) at the temperature of 60 ℃, preserving heat for 3 hours after dropwise adding for ring-opening reaction, washing to be neutral after the reaction is finished, removing water and drying to obtain vegetable oil alcohol;
(4) dropwise adding vegetable oil alcohol and triethylamine into the diethyl ether solution of the trimethyl silicon chloride under the conditions of ice water bath and nitrogen protection, then reacting for 2 hours at the temperature of 40 ℃, washing to be neutral after the reaction is finished, evaporating to remove the solvent and drying in vacuum to obtain the organic silicon modified vegetable oil; the molar ratio of the trimethyl silicon chloride to the vegetable oil alcohol is 1: 1.
the content of unsaturated components in the vegetable oil after ester exchange reaction, epoxidation reaction, ring opening reaction and organic silicon modification is obviously reduced, so that the oxidation resistance is obviously improved, the stability of the anti-rust oil is improved, and the service life of the anti-rust oil is prolonged.
On the other hand, compared with the vegetable oil which is not modified, the vegetable oil which is modified by the organic silicon can form an oil film on the friction surface to play a role in lubricating stably all the time, and the stable friction force and friction coefficient are kept, so that the organic silicon modified vegetable oil is improved to have a better lubricating effect.
The first antirust agent is one or a mixture of more than two of N-oleoyl amino acid octadecylamine salt, calcium petroleum sulfonate, sodium petroleum sulfonate, dodecene succinic acid amine, oxidized petroleum ester calcium soap, dodecene succinic acid ester, heptadecene imidazoline alkenyl succinic acid salt and zinc naphthenate in any proportion.
The second antirust agent is a metal antirust agent containing modified thiadiazole.
The first antirust agent used in the invention is a more conventional antirust agent in the prior art, and most of the antirust agents are non-heavy metal petroleum sulfonate, non-heavy metal organic salts and organic acids, but the antirust performance of the antirust agent is poorer than that of a heavy metal antirust agent, such as barium petroleum sulfonate.
The modified thiadiazole is used as a second antirust agent, and is prepared according to the following process: mixing octadecyl acid and thionyl chloride, stirring uniformly, performing reflux reaction for 100-200min, distilling under reduced pressure, adding an alkaline solution of aspartic acid, adjusting the pH value to 8-9, stirring at room temperature for reaction for 120-200min, cooling, adjusting the pH value to acidity, separating liquid, and washing to obtain a material A; mixing 2-mercapto-5-methyl-1, 3, 4-thiadiazole with a sulfuric acid aqueous solution, adding a material A at 35-40 ℃, reacting at 45-55 ℃ for 100-200min, cooling, adding water, filtering, dissolving a filter cake with a sodium hydroxide aqueous solution, adjusting the pH value to 2-3, filtering, washing, drying, and recrystallizing to obtain a material B; adding the material B into dimethylbenzene, adding triethanolamine at 60-70 ℃, stirring and reacting for 2-4h at 100-105 ℃, and cooling, evaporating and drying after the reaction is finished to obtain the modified thiadiazole.
The rust preventive oil prepared by mixing and mutually matching the first rust inhibitor and the second rust inhibitor used by the invention can play a role in synergy in multiple aspects, obviously improves the rust preventive performance of the rust inhibitor, prolongs the rust preventive time of the rust inhibitor, and prolongs the rust preventive time by more than 3 months compared with the rust preventive oil which is singly used and contains the same first rust inhibitor.
Preferably, the first rust inhibitor of the present invention is calcium petroleum sulfonate.
The film forming agent is any one or a mixture of more than two of lanolin, lanolin fatty acid pentaerythritol ester, polyvinyl butyral film forming resin, acrylic resin polyurethane copolymer resin and butadiene resin in any proportion. The optimized film forming agent is lanolin and lanolin fatty acid pentaerythritol ester, the film forming agent can be stably and uniformly distributed in the anti-rust oil taking modified vegetable oil as base oil, the film forming property is excellent, and the anti-rust oil can uniformly and stably cover the metal surface.
The anti-rust oil without heavy metal comprises at least one antioxidant of 2, 6-di-tert-butyl-4-methylphenol, diphenylamine, octyl butyl diphenylamine and phenolic ester type antioxidants. In the using process, under the influence of factors such as air, metal and the like, the rust preventive oil can be oxidized into low molecular compounds such as alcohol, carboxylic acid, ketone and the like, and further condensation can occur to form polymers, so that the rust preventive performance is poor, even mechanical parts can be corroded, and the service life is shortened. Therefore, an antioxidant which can retard or inhibit the oxidation of the rust preventive oil must be added to the rust preventive oil to prolong the working life of the rust preventive oil. The preferred antioxidant of the invention is 2, 6-di-tert-butyl-4-methylphenol, diphenylamine and octyl butyl diphenylamine, which can effectively prevent the rust preventive oil from being oxidized into low molecular compounds such as alcohol, carboxylic acid, ketone and the like, thereby improving the antioxidant capacity of the rust preventive oil and ensuring that the rust preventive oil has good antioxidant performance and stability.
The heavy metal-free antirust oil has the preservative 1,3, 5-tri (2-hydroxyethyl) -hexahydro-triazine or 1, 2-benzisothiazol-3-one.
The anti-rust oil without heavy metal can also contain a small amount of nano activated carbon of 0.01-0.5 percent, can inhibit the oxidation process of the anti-rust oil and can absorb decomposition products which generate unpleasant odor in the anti-rust oil.
The heavy metal-free anti-rust oil disclosed by the invention has the advantages that the defoaming agent can be one or more of organic silicon, polyether or amide; silicone-based defoaming agents are preferred.
The essence of the rust preventive oil containing no heavy metal of the present invention may be a conventional essence, preferably lemon essence, which can improve the taste of the rust preventive oil.
Compared with the prior art, the invention has the following beneficial effects:
(1) the rust preventive oil does not contain heavy metal and has no heavy metal pollution;
(2) the modified vegetable oil is adopted as the base oil, so that the oil is biodegradable, non-renewable energy sources are saved, and the oil is green and environment-friendly;
(3) the modified vegetable oil is not easy to oxidize, good in stability and long in service life;
(4) the two-component antirust agent with mutual synergistic effect is used, so that the antirust performance is good;
(5) the rust-proof period can reach more than two years, and the maximum neutral salt spray test can reach 196 hours.
Detailed Description
In order to clearly and completely describe the technical solutions in the embodiments of the present invention, it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples 1 to 10A rust preventive oil free from heavy metals was prepared by using the respective components in the mass percentages shown in Table 1 below.
TABLE 1 weight percentages of respective components of the heavy metal-free rust preventive oils of examples 1 to 10
Example 1
The present invention provides a heavy metal-free rust preventive oil comprising the components in the weight percentages according to example 1 in Table 1 above.
Preparation of organic silicon modified vegetable oil
The preparation method of the organic silicon modified vegetable oil comprises the following steps:
(1) adding 100 parts by mass of vegetable oil into a reactor, gradually adding 25 parts by mass of 8% potassium hydroxide methanol solution, carrying out ester exchange reaction at 70 ℃ for 2h, washing to be neutral after the reaction is finished, removing water and drying to obtain fatty acid methyl ester;
(2) adding 120 parts of a mixture of acetic acid and a strong-acid cation exchange resin catalyst into the fatty acid methyl ester obtained in the step (1) by mass at the temperature of 60 ℃, gradually adding a hydrogen peroxide solution, keeping the temperature for 4 hours for epoxidation, washing to be neutral after the reaction is finished, removing water and drying to obtain epoxy vegetable oil, wherein the molar ratio of H2O2 to acetic acid is 1.2: 1;
(3) dropwise adding 50 parts of acetic acid into 100 parts by mass of the epoxy vegetable oil obtained in the step (1) at the temperature of 60 ℃, preserving heat for 3 hours after dropwise adding for ring-opening reaction, washing to be neutral after the reaction is finished, removing water and drying to obtain vegetable oil alcohol;
(4) dropwise adding vegetable oil alcohol and triethylamine into the diethyl ether solution of the trimethyl silicon chloride under the conditions of ice water bath and nitrogen protection, then reacting for 2 hours at the temperature of 40 ℃, washing to be neutral after the reaction is finished, evaporating to remove the solvent and drying in vacuum to obtain the organic silicon modified vegetable oil; the molar ratio of the trimethyl silicon chloride to the vegetable oil alcohol is 1: 1.
secondly, preparing modified thiadiazole
The second antirust agent modified thiadiazole is prepared according to the following process:
(1) mixing octadecyl acid and thionyl chloride, stirring uniformly, performing reflux reaction for 100-200min, distilling under reduced pressure, adding an alkaline solution of aspartic acid, adjusting the pH value to 8-9, stirring at room temperature for reaction for 120-200min, cooling, adjusting the pH value to acidity, separating liquid, and washing to obtain a material A;
(2) mixing 2-mercapto-5-methyl-1, 3, 4-thiadiazole with a sulfuric acid aqueous solution, adding a material A at 35-40 ℃, reacting at 45-55 ℃ for 100-200min, cooling, adding water, filtering, dissolving a filter cake with a sodium hydroxide aqueous solution, adjusting the pH value to 2-3, filtering, washing, drying, and recrystallizing to obtain a material B;
(3) adding the material B into dimethylbenzene, adding triethanolamine at 60-70 ℃, stirring and reacting for 2-4h at 100-105 ℃, and cooling, evaporating and drying after the reaction is finished to obtain the modified thiadiazole.
Thirdly, preparing the rust preventive oil
The preparation method of the anti-rust oil without heavy metal comprises the following steps:
(1) adding a first antirust agent, a second antirust agent, a film forming agent, an antioxidant and a preservative into the modified vegetable oil in parts by weight, heating at 90 ℃, and stirring at the speed of 300rpm for 30min to prepare a uniform mixture;
(2) and (2) adding a defoaming agent and essence into the uniform mixture obtained in the step (1), and then carrying out ultrasonic oscillation for 20 min. Thus obtaining the anti-rust oil without heavy metal.
Examples 2 to 10
The heavy metal-free rust preventive oil of each of examples 2 to 10, comprising the components in the weight percentages of examples 2 to 10 in Table 1 above, was used, and the method for producing the silicone-modified vegetable oil, the method for producing the modified thiadiazole, and the method for producing the heavy metal-free rust preventive oil were the same as those of example 1.
The method and procedure for measuring physical properties of the heavy metal-free rust preventive oils of examples 1 to 10, and the evaluations were carried out in accordance with the standards such as GB/T510, SH/T0215, GB/T2361, etc., and the results are shown in Table 2.
TABLE 2 evaluation results of physical Properties and anticorrosive ability of the heavy metal-free anticorrosive oils of examples 1 to 10
The rust preventive oils containing no heavy metal prepared according to the different formulations of examples 1 to 10 exhibited good physical properties and rust preventive properties, particularly rust preventive properties; can meet the antirust effect on metal in daily working conditions.
In conclusion, the anti-rust oil without heavy metal provided by the invention has the advantages that the components do not contain heavy metal, and no heavy metal pollution is caused; the modified vegetable oil is adopted to replace mineral oil as base oil, so that the oil is biodegradable and environment-friendly; the modified vegetable oil is not easy to oxidize, and the anti-rust oil has good stability and long service life; the two-component antirust agent with mutual synergistic effect has the characteristic of good antirust performance. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The anti-rust oil without heavy metal is characterized by comprising the following components in percentage by weight: 1-15% of first antirust agent, 1-10% of second antirust agent, 5-15% of film-forming agent, 0.1-5% of antioxidant, 0.1-5% of preservative, 0.01-2% of defoaming agent, 0.01-2% of essence and the balance of modified vegetable oil.
2. The heavy metal-free rust preventive oil as claimed in claim 1, wherein the modified vegetable oil is an organosilicon-modified vegetable oil obtained by modifying with an organosilicon any one or a mixture of two or more of rapeseed oil, soybean oil, cottonseed oil and palm oil.
3. The heavy metal-free rust preventive oil as claimed in claim 2, wherein the silicone-modified vegetable oil is prepared by a process further comprising at least a transesterification reaction, an epoxidation reaction and a ring-opening reaction.
4. The heavy metal-free rust preventive oil as claimed in claim 1, wherein the first rust preventive agent is any one of or a mixture of two or more of octadecylamine N-oleoyl aminate, calcium petroleum sulfonate, amine dodecenyl succinate, calcium soap of oxidized petroleum fat, dodecenyl succinic acid, dodecenyl succinate, heptadecenyl imidazolinyl succinate, and zinc naphthenate in any proportion.
5. The heavy metal-free rust preventive oil as claimed in claim 1, wherein the second rust preventive agent is a modified thiadiazole-containing agent.
6. The heavy metal-free rust preventive oil as claimed in claim 1, wherein the film-forming agent is any one of lanolin, lanolin fatty acid pentaerythritol ester, polyvinyl butyral film-forming resin, acrylic resin, urethane copolymer resin and butadiene resin, or a mixture of two or more thereof in any proportion.
7. The heavy metal-free rust preventive oil as claimed in claim 1, wherein the antioxidant is at least one of 2, 6-di-t-butyl-4-methylphenol, diphenylamine, octylbutyldiphenylamine, and phenol ester type antioxidants.
8. The heavy metal-free rust preventive oil as claimed in claim 1, wherein the preservative is 1,3, 5-tris (2-hydroxyethyl) -hexahydro-triazine or 1, 2-benzisothiazol-3-one.
9. The heavy metal-free rust preventive oil as claimed in claim 1, wherein the modified vegetable oil is prepared by a process comprising the steps of:
(1) adding 100 parts by mass of vegetable oil into a reactor, gradually adding 20-30 parts by mass of 6-8% potassium hydroxide methanol solution, carrying out ester exchange reaction at 60-70 ℃ for 1-3h, washing to be neutral after the reaction is finished, removing water and drying to obtain fatty acid methyl ester;
(2) adding a mixture of 100-150 parts by mass of acetic acid and a strongly acidic cation exchange resin catalyst to 100 parts by mass of the fatty acid methyl ester obtained in step (1) at a temperature of 60-70 ℃, and gradually adding a hydrogen peroxide solution in which H is2O2Keeping the molar ratio of the obtained product to acetic acid at 1-1.5:1, keeping the temperature for 4 hours to perform epoxidation reaction, washing the obtained product to be neutral after the reaction is finished, removing water and drying the obtained product to obtain epoxy vegetable oil;
(3) dropwise adding 30-50 parts of acetic acid into the epoxy vegetable oil obtained in the step (1) by mass at the temperature of 50-60 ℃, preserving heat for 1-3 hours after dropwise adding for ring-opening reaction, washing to be neutral after the reaction is finished, removing water and drying to obtain vegetable oleyl alcohol;
(4) dropwise adding vegetable oil alcohol and triethylamine into the diethyl ether solution of the trimethyl silicon chloride under the conditions of ice water bath and nitrogen protection, then reacting for 2 hours at the temperature of 30-60 ℃, washing to be neutral after the reaction is finished, evaporating to remove the solvent and drying in vacuum to obtain the organic silicon modified vegetable oil; the molar ratio of the trimethyl silicon chloride to the vegetable oil alcohol is 1: 1.
10. a process for producing a rust preventive oil free from heavy metal as claimed in any one of claims 1 to 9, characterized by comprising the steps of:
(1) adding a first antirust agent, a second antirust agent, a film forming agent, an antioxidant and a preservative into the modified vegetable oil in parts by weight, heating at the temperature of 90-110 ℃, and stirring at the speed of 300-500 rpm for 20-30 min to prepare a uniform mixture;
(2) and (2) adding a defoaming agent and essence into the uniform mixture obtained in the step (1), and then performing ultrasonic oscillation for 10-20 min.
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