阅读说明：本技术 一种防锈冲压油及其制备方法 (Antirust stamping oil and preparation method thereof ) 是由 陶洪南 于 2021-07-02 设计创作，主要内容包括：本发明涉及一种防锈冲压油及其制备方法,属于金属成型加工技术领域。本发明的冲压油将防锈添加剂和防锈协同促进剂共同使用,将植酸钙复配到曼尼希碱中后,植酸根离子与金属阳极溶解形成的亚铁离子静电吸引结合成沉淀物,其附着在曼尼希碱未作用到的区域,增加了金属表面的饱和吸附量,进一步阻止了电子穿透膜向溶液的扩散,因此,这种复配防锈更有效地抑制阳极金属溶解和阴极析氢反应的发生,并且植酸钙对曼尼希碱的防锈蚀性能表现出了较好的协同效应,防锈性能显著提高,应用前景广阔。(The invention relates to antirust stamping oil and a preparation method thereof, belonging to the technical field of metal forming processing. According to the punching oil disclosed by the invention, the antirust additive and the antirust synergistic accelerator are used together, after calcium phytate is compounded into the Mannich base, the phytic acid ions and ferrous ions formed by dissolving the metal anode are subjected to electrostatic attraction to form precipitates which are attached to an area where the Mannich base does not act, so that the saturated adsorption quantity of the metal surface is increased, and the diffusion of an electron penetrating film to a solution is further prevented, therefore, the compounding antirust is more effective in inhibiting the dissolution of the metal anode and the hydrogen evolution reaction of a cathode, the antirust performance of the calcium phytate on the Mannich base shows a good synergistic effect, the antirust performance is remarkably improved, and the application prospect is wide.)

1. An antirust stamping oil is characterized in that: the composite material comprises the following raw materials in parts by weight:

80-84 parts of white oil;

5-9 parts of soybean oil;

3.5-3.9 parts of an antirust additive;

0.3-0.7 parts of barium dinonyl naphthalene sulfonate;

0.5 to 0.9 parts of dodecenylsuccinic acid;

0.3-0.7 parts of barium petroleum sulfonate;

1.2-1.6 parts of span 80;

0.9-1.3 parts of carbon nano tubes;

the antirust additive is prepared by mixing aniline, absolute ethyl alcohol, hydrochloric acid, formaldehyde and acetophenone for reaction.

2. The rust-proof stamping oil as claimed in claim 1, wherein: the antirust protective agent also comprises 2.9-3.3 parts by weight of an antirust synergistic accelerator;

the rust-proof synergistic accelerator is prepared by reacting rice bran, distilled water, hydrochloric acid, activated carbon, saturated lime water and a sodium hydroxide solution.

3. The rust-proof punching oil as claimed in claim 2, characterized in that: the composite material comprises the following raw materials in parts by weight:

82 parts of white oil;

7 parts of soybean oil;

3.7 parts of an antirust additive;

3.1 parts of an antirust synergistic accelerator;

0.5 part of barium dinonylnaphthalenesulfonate;

0.7 part of dodecenylsuccinic acid;

0.5 part of barium petroleum sulfonate;

1.4 parts of span 80;

1.1 parts of carbon nanotubes.

4. A preparation method of antirust stamping oil is characterized by comprising the following specific preparation steps:

(1) weighing white oil, soybean oil, an antirust additive, an antirust synergistic accelerator, barium dinonylnaphthalene sulfonate, dodecenylsuccinic acid, barium petroleum sulfonate, span 80 and carbon nanotubes;

(2) adding white oil and soybean oil into a mixing and stirring reaction kettle, starting a stirring pump for stirring, adding an antirust additive, an antirust synergistic accelerator, barium dinonylnaphthalene sulfonate, dodecenylsuccinic acid, barium petroleum sulfonate and carbon nano tubes while stirring, stirring for 15-20 min at normal temperature and normal pressure, finally adding span 80, continuously stirring for 8-10 min at normal temperature and normal pressure, and discharging to obtain the antirust punching oil.

5. The method for preparing the antirust punching oil according to claim 4, wherein the preparation step of the antirust additive is as follows:

(1) mixing aniline and absolute ethyl alcohol according to a volume ratio of 6:5, putting the mixture into a three-neck flask provided with a reflux condenser and a stirrer, stirring, dropwise adding hydrochloric acid with the concentration of 0.5mol/L, the volume of which is 2 times that of the aniline, heating the three-neck flask in a water bath, heating to 80-85 ℃, and refluxing for 1.0-1.5 h to obtain a reflux liquid;

(2) mixing formaldehyde and acetophenone according to a mass ratio of 1: 2 to obtain a mixed dispersion liquid, cooling the reflux liquid to 60-65 ℃, mixing the reflux liquid and the mixed dispersion liquid according to a volume ratio of 2:1, cooling to room temperature, adjusting the stirring speed to 450-500 r/min, and stirring and dispersing for 2-3 h to obtain the antirust additive.

6. The method for preparing the antirust punching oil according to claim 4, wherein the preparation step of the antirust synergistic accelerator is as follows:

(1) weighing rice bran, crushing to obtain a rice bran crushed material, mixing the rice bran crushed material and distilled water according to a material-liquid ratio of 1:10 to obtain a mixed solution, putting the mixed solution into a reaction kettle, adjusting the pH of the mixed solution to 3 by using hydrochloric acid with the concentration of 0.2mol/L, stirring and reacting for 2-3 hours at the temperature of 40-50 ℃ by using a magnetic stirrer, and performing suction filtration to obtain a filtrate;

(2) adding active carbon with the mass of 5% of the filtrate into the filtrate, heating to 80-85 ℃, standing for 30-40 min, decoloring and filtering the active carbon to obtain a decolored filtrate, firstly adjusting the pH of the decolored filtrate to 6 with saturated lime water, then adjusting the pH to be neutral with sodium hydroxide solution, standing for layering for 2-3 h, and filtering and separating to obtain filter residues, thus obtaining the antirust synergistic promoter.

Technical Field

The invention relates to antirust stamping oil and a preparation method thereof, belonging to the technical field of metal forming processing.

Background

At present, the lubricating performance of the commercially available stamping oil can basically meet the use requirements of users, but a light petroleum solvent containing aromatic hydrocarbon is usually adopted, the light petroleum solvent containing aromatic hydrocarbon has a large smell, and causes adverse stimulation and influence on operators and personnel contacting the substance for a long time, certain health hidden dangers exist, and environmental pollution of a stamping workshop is caused; besides, there are three problems to be solved urgently in the performance of the common stamping oil in the market:

firstly, the product has poor rust resistance and wet-heat resistance, the outdoor exposure test time is short, and the rust resistance requirement of the stamping part under the medium-term and long-term storage condition cannot be met;

secondly, in order to meet the lubricating performance requirement of stamping, additives with high viscosity, strong adhesion and high flash point, such as medium-long chain chlorinated paraffin, a vulcanizing agent and the like, are added into the product, a large amount of halogenated hydrocarbon solvent, aromatic hydrocarbon and other organic solvents are needed for cleaning, and the organic solvents bring secondary pollution and are very unfavorable for the working environment and operators;

and thirdly, most of the components in the formula contain toxic and harmful substances such as chlorine, sulfur, heavy metals and the like, so that the health of human bodies and the environmental safety are harmed.

In view of the above-mentioned defects, the present designer actively makes research and innovation to create an antirust stamping oil and a preparation method thereof, so that the antirust stamping oil has industrial utilization value.

Disclosure of Invention

In order to solve the technical problems, the invention aims to provide the antirust stamping oil and the preparation method thereof.

The invention relates to antirust stamping oil which comprises the following raw materials in parts by weight:

80-84 parts of white oil;

5-9 parts of soybean oil;

3.5-3.9 parts of an antirust additive;

0.3-0.7 parts of barium dinonyl naphthalene sulfonate;

0.5 to 0.9 parts of dodecenylsuccinic acid;

0.3-0.7 parts of barium petroleum sulfonate;

1.2-1.6 parts of span 80;

0.9-1.3 parts of carbon nano tubes;

the antirust additive is prepared by mixing aniline, absolute ethyl alcohol, hydrochloric acid, formaldehyde and acetophenone for reaction. Firstly, mixing aniline and absolute ethyl alcohol, then acidifying, heating and refluxing to obtain a reflux liquid; adding a mixed solution of formaldehyde and acetophenone into the reflux liquid, stirring and dispersing to obtain an antirust additive, wherein the antirust additive component is a Mannich base, after quaternization, the antirust additive takes a nitrogen atom with larger electronegativity as a central polar group, the polar group has strong hydrophilicity, and after the antirust additive contacts the metal surface, the antirust additive has physical adsorption with the metal to form an adsorption layer;

further, the antirust protective coating also comprises 2.9-3.3 parts by weight of an antirust synergistic accelerator;

the rust-proof synergistic accelerator is prepared by reacting rice bran, distilled water, hydrochloric acid, activated carbon, saturated lime water and a sodium hydroxide solution. The invention takes rice bran rich in phytic acid as raw material, lixiviates with hydrochloric acid to obtain filtrate, and then precipitates and separates with saturated lime water to obtain calcium phytate component, wherein the phytic acid ion in the calcium phytate contains phosphate group, which is a metal multidentate chelating agent, so that when the calcium phytate is complexed with metal ion in punching oil and metal surface, a layer of compact monomolecular protective film is easily formed on the metal surface, which can effectively prevent oxygen and the like from entering the metal surface, the corrosion current is led out by the conductive layer and the passivated metal film due to the monomolecular hole electron conductive layer formed on the treated metal surface, thereby achieving the anti-rust effect, in addition, the calcium ion in the calcium phytate also forms an insoluble complex, which can be used as cathode inhibitor to inhibit the cathode electrochemical reaction, play the role of protecting the matrix, improve the anti-rust effect, is nontoxic and harmless to human body, has no pollution to the environment, the price cost is low, and the environment-friendly requirement is met, so that the antirust effect of the stamping oil prepared by the method is greatly improved;

more importantly, the antirust additive and the antirust synergistic accelerator are used together, after calcium phytate is compounded into the Mannich base, the phytate ions and ferrous ions formed by dissolution of a metal anode are combined into a precipitate through electrostatic attraction, the precipitate is attached to an area where the Mannich base does not act, the saturated adsorption quantity of the metal surface is increased, and the diffusion of an electron penetrating film to a solution is further prevented, so that the compounding antirust can more effectively inhibit the dissolution of the anode metal and the occurrence of a hydrogen evolution reaction of a cathode, the antirust performance of the calcium phytate to the Mannich base shows a good synergistic effect, and the antirust performance is remarkably improved;

further, the paint comprises the following raw materials in parts by weight:

82 parts of white oil;

7 parts of soybean oil;

3.7 parts of an antirust additive;

3.1 parts of an antirust synergistic accelerator;

0.5 part of barium dinonylnaphthalenesulfonate;

0.7 part of dodecenylsuccinic acid;

0.5 part of barium petroleum sulfonate;

1.4 parts of span 80;

1.1 parts of carbon nanotubes. The formula proportion of the antirust punching oil has an optimal value, and the antirust performance of the antirust punching oil can be optimal only under the condition of the proportion.

A preparation method of antirust stamping oil comprises the following specific preparation steps:

(1) weighing white oil, soybean oil, an antirust additive, an antirust synergistic accelerator, barium dinonylnaphthalene sulfonate, dodecenylsuccinic acid, barium petroleum sulfonate, span 80 and carbon nanotubes;

(2) adding white oil and soybean oil into a mixing and stirring reaction kettle, starting a stirring pump for stirring, adding an antirust additive, an antirust synergistic accelerator, barium dinonylnaphthalene sulfonate, dodecenylsuccinic acid, barium petroleum sulfonate and carbon nano tubes while stirring, stirring for 15-20 min at normal temperature and normal pressure, finally adding span 80, continuously stirring for 8-10 min at normal temperature and normal pressure, and discharging to obtain the antirust punching oil.

Further, the preparation steps of the antirust additive are as follows:

(1) mixing aniline and absolute ethyl alcohol according to a volume ratio of 6:5, putting the mixture into a three-neck flask provided with a reflux condenser and a stirrer, stirring, dropwise adding hydrochloric acid with the concentration of 0.5mol/L, the volume of which is 2 times that of the aniline, heating the three-neck flask in a water bath, heating to 80-85 ℃, and refluxing for 1.0-1.5 h to obtain a reflux liquid;

(2) mixing formaldehyde and acetophenone according to a mass ratio of 1: 2 to obtain a mixed dispersion liquid, cooling the reflux liquid to 60-65 ℃, mixing the reflux liquid and the mixed dispersion liquid according to a volume ratio of 2:1, cooling to room temperature, adjusting the stirring speed to 450-500 r/min, and stirring and dispersing for 2-3 h to obtain the antirust additive.

Further, the preparation method of the rust-proof synergistic accelerator comprises the following steps:

(1) weighing rice bran, crushing to obtain a rice bran crushed material, mixing the rice bran crushed material and distilled water according to a material-liquid ratio of 1:10 to obtain a mixed solution, putting the mixed solution into a reaction kettle, adjusting the pH of the mixed solution to 3 by using hydrochloric acid with the concentration of 0.2mol/L, stirring and reacting for 2-3 hours at the temperature of 40-50 ℃ by using a magnetic stirrer, and performing suction filtration to obtain a filtrate;

(2) adding active carbon with the mass of 5% of the filtrate into the filtrate, heating to 80-85 ℃, standing for 30-40 min, decoloring and filtering the active carbon to obtain a decolored filtrate, firstly adjusting the pH of the decolored filtrate to 6 with saturated lime water, then adjusting the pH to be neutral with sodium hydroxide solution, standing for layering for 2-3 h, and filtering and separating to obtain filter residues, thus obtaining the antirust synergistic promoter.

By the scheme, the invention at least has the following advantages:

(1) firstly, mixing aniline and absolute ethyl alcohol, then acidifying, heating and refluxing to obtain a reflux liquid; adding a mixed solution of formaldehyde and acetophenone into the reflux liquid, stirring and dispersing to obtain an antirust additive, wherein the antirust additive component is a Mannich base, after quaternization, the antirust additive takes a nitrogen atom with larger electronegativity as a central polar group, the polar group has strong hydrophilicity, and after the antirust additive contacts the metal surface, the antirust additive has physical adsorption with the metal to form an adsorption layer;

(2) the invention takes rice bran rich in phytic acid as raw material, lixiviates with hydrochloric acid to obtain filtrate, and then precipitates and separates with saturated lime water to obtain calcium phytate component, wherein the phytic acid ion in the calcium phytate contains phosphate group, which is a metal multidentate chelating agent, so that when the calcium phytate is complexed with metal ion in punching oil and metal surface, a layer of compact monomolecular protective film is easily formed on the metal surface, which can effectively prevent oxygen and the like from entering the metal surface, the corrosion current is led out by the conductive layer and the passivated metal film due to the monomolecular hole electron conductive layer formed on the treated metal surface, thereby achieving the anti-rust effect, in addition, the calcium ion in the calcium phytate also forms an insoluble complex, which can be used as cathode inhibitor to inhibit the cathode electrochemical reaction, play a role in protecting the matrix, improve the anti-rust effect, is nontoxic and harmless to human body, the stamping oil has no pollution to the environment, has low price and cost, meets the requirement of environmental protection, and greatly improves the antirust effect of the stamping oil prepared by the invention;

(3) more importantly, the antirust additive and the antirust synergistic accelerator are used together, after calcium phytate is compounded into the Mannich base, the phytate ions and ferrous ions formed by dissolution of a metal anode are combined into a precipitate through electrostatic attraction, the precipitate is attached to an area where the Mannich base does not act, the saturated adsorption quantity of the metal surface is increased, and the diffusion of an electron penetrating film to a solution is further prevented, so that the compounding antirust can more effectively inhibit the dissolution of the anode metal and the occurrence of a hydrogen evolution reaction of a cathode, the antirust performance of the calcium phytate to the Mannich base shows a good synergistic effect, and the antirust performance is remarkably improved;

(4) according to the invention, soybean oil rich in unsaturated fatty acid is added into stamping oil as base oil, after the antirust stamping oil acts on the surface of metal, the barrier absorption capacity of the antirust stamping oil on oxygen in the air is strong, the soybean oil can be chelated with part of oxidized metal divalent ions, the adhesion of the antirust stamping oil to the metal is improved, the oxidized unsaturated fatty acid can be slowly reduced by the metal ions to form virtuous cycle, so that the antirust stamping oil can keep stronger reduction performance all the time, and the antirust period of the antirust stamping oil is prolonged.

The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.

Detailed Description

The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

(1) Mixing aniline and absolute ethyl alcohol according to a volume ratio of 6:5, putting the mixture into a three-neck flask provided with a reflux condenser and a stirrer, stirring, dropwise adding hydrochloric acid with the concentration of 0.5mol/L, the volume of which is 2 times that of the aniline, heating the three-neck flask in a water bath, heating to 80-85 ℃, and refluxing for 1.0-1.5 h to obtain a reflux liquid; firstly, mixing aniline and absolute ethyl alcohol, then acidifying, heating and refluxing to obtain a reflux liquid;

(2) mixing formaldehyde and acetophenone according to a mass ratio of 1: 2 to obtain a mixed dispersion liquid, cooling the reflux liquid to 60-65 ℃, mixing the reflux liquid and the mixed dispersion liquid according to a volume ratio of 2:1, cooling to room temperature, adjusting the stirring speed to 450-500 r/min, and stirring and dispersing for 2-3 h to obtain an antirust additive; adding a mixed solution of formaldehyde and acetophenone into the reflux liquid, stirring and dispersing to obtain an antirust additive, wherein the antirust additive component is a Mannich base, after quaternization, the antirust additive takes a nitrogen atom with larger electronegativity as a central polar group, the polar group has strong hydrophilicity, and after the antirust additive contacts the metal surface, the antirust additive has physical adsorption with the metal to form an adsorption layer;

(3) weighing rice bran, crushing to obtain a rice bran crushed material, mixing the rice bran crushed material and distilled water according to a material-liquid ratio of 1:10 to obtain a mixed solution, putting the mixed solution into a reaction kettle, adjusting the pH of the mixed solution to 3 by using hydrochloric acid with the concentration of 0.2mol/L, stirring and reacting for 2-3 hours at the temperature of 40-50 ℃ by using a magnetic stirrer, and performing suction filtration to obtain a filtrate; firstly, rice bran rich in phytic acid is taken as a raw material, and hydrochloric acid is adopted for leaching to obtain filtrate;

(4) adding activated carbon with the mass of 5% of the filtrate into the filtrate, heating to 80-85 ℃, standing for 30-40 min, decoloring and filtering the activated carbon to obtain a decolored filtrate, firstly adjusting the pH of the decolored filtrate to 6 with saturated lime water, then adjusting the pH to be neutral with a sodium hydroxide solution, standing for layering for 2-3 h, and filtering and separating to obtain filter residues, thus obtaining the antirust synergistic promoter; then precipitating and separating by saturated lime water to obtain a calcium phytate component, wherein the phytic acid radical ion in the calcium phytate contains a phosphate group, and the phytic acid radical ion is a metal multidentate chelating agent, therefore, when the calcium phytate is complexed with metal ions in the stamping oil and on the metal surface, a layer of compact monomolecular protective film is easily formed on the metal surface, oxygen and the like can be effectively prevented from entering the metal surface, the corrosion current is led out by the conduction of the conductive layer and the passivated metal film due to the monomolecular hole electron conductive layer formed on the treated metal surface, thereby achieving the antirust effect, in addition, calcium ions in the calcium phytate also form an insoluble complex which can be used as a cathode inhibitor to inhibit cathode electrochemical reaction, play a role in protecting a matrix and improve the antirust effect, and is nontoxic, the stamping oil has the advantages of no harm to human bodies, no pollution to the environment, low price and cost, and accordance with the environmental protection requirement, so that the antirust effect of the stamping oil prepared by the invention is greatly improved;

more importantly, the antirust additive and the antirust synergistic accelerator are used together, after calcium phytate is compounded into the Mannich base, the phytate ions and ferrous ions formed by dissolution of a metal anode are combined into a precipitate through electrostatic attraction, the precipitate is attached to an area where the Mannich base does not act, the saturated adsorption quantity of the metal surface is increased, and the diffusion of an electron penetrating film to a solution is further prevented, so that the compounding antirust can more effectively inhibit the dissolution of the anode metal and the occurrence of a hydrogen evolution reaction of a cathode, the antirust performance of the calcium phytate to the Mannich base shows a good synergistic effect, and the antirust performance is remarkably improved;

(5) weighing 80-84 parts of white oil, 5-9 parts of soybean oil, 3.5-3.9 parts of an antirust additive, 2.9-3.3 parts of an antirust synergistic accelerator, 0.3-0.7 part of barium dinonylnaphthalene sulfonate, 0.5-0.9 part of dodecenylsuccinic acid, 0.3-0.7 part of barium petroleum sulfonate, 1.2-1.6 parts of span 80 and 0.9-1.3 parts of a carbon nano tube;

(6) adding white oil and soybean oil into a mixing and stirring reaction kettle, starting a stirring pump for stirring, adding an antirust additive, an antirust synergistic accelerator, barium dinonylnaphthalene sulfonate, dodecenylsuccinic acid, barium petroleum sulfonate and carbon nano tubes while stirring, stirring for 15-20 min at normal temperature and normal pressure, finally adding span 80, continuously stirring for 8-10 min at normal temperature and normal pressure, and discharging to obtain the antirust punching oil. According to the invention, soybean oil rich in unsaturated fatty acid is added into stamping oil as base oil, after the antirust stamping oil acts on the surface of metal, the barrier absorption capacity of the antirust stamping oil on oxygen in the air is strong, the soybean oil can be chelated with part of oxidized metal divalent ions, the adhesion of the antirust stamping oil to the metal is improved, the oxidized unsaturated fatty acid can be slowly reduced by the metal ions to form virtuous cycle, so that the antirust stamping oil can keep stronger reduction performance all the time, and the antirust period of the antirust stamping oil is prolonged.

Examples

Example 1

Mixing aniline and absolute ethyl alcohol according to a volume ratio of 6:5, putting the mixture into a three-neck flask provided with a reflux condenser and a stirrer, stirring, dropwise adding hydrochloric acid with the concentration of 0.5mol/L, the volume of which is 2 times that of the aniline, heating the three-neck flask in a water bath to 85 ℃, and refluxing for 1.5h to obtain a reflux liquid; mixing formaldehyde and acetophenone according to a mass ratio of 1: 2 to obtain a mixed dispersion liquid, cooling the reflux liquid to 65 ℃, mixing the reflux liquid and the mixed dispersion liquid according to a volume ratio of 2:1, cooling to room temperature, adjusting the stirring speed to 500r/min, and stirring and dispersing for 3 hours to obtain the antirust additive; weighing rice bran, crushing to obtain a rice bran crushed product, mixing the rice bran crushed product and distilled water according to a material-liquid ratio of 1:10 to obtain a mixed solution, putting the mixed solution into a reaction kettle, adjusting the pH of the mixed solution to 3 by using hydrochloric acid with the concentration of 0.2mol/L, stirring and reacting for 3 hours at 50 ℃ by using a magnetic stirrer, and performing suction filtration to obtain a filtrate; adding active carbon with the mass of 5% of the filtrate into the filtrate, heating to 85 ℃, standing for 40min, decoloring and filtering the active carbon to obtain a decolored filtrate, firstly adjusting the pH of the decolored filtrate to 6 with saturated lime water, then adjusting the pH to be neutral with sodium hydroxide solution, standing for layering for 3h, filtering and separating to obtain filter residue, thus obtaining the antirust synergistic accelerator; weighing 80 parts of white oil, 5 parts of soybean oil, 3.5 parts of an antirust additive, 2.9 parts of an antirust synergistic accelerator, 0.3 part of barium dinonylnaphthalene sulfonate, 0.5 part of dodecenylsuccinic acid, 0.3 part of barium petroleum sulfonate, 1.2 parts of span 80 and 0.9 part of carbon nano tube in parts by weight; adding white oil and soybean oil into a mixing and stirring reaction kettle, starting a stirring pump to stir, adding an antirust additive, an antirust synergistic accelerator, barium dinonylnaphthalene sulfonate, dodecenylsuccinic acid, barium petroleum sulfonate and carbon nanotubes while stirring, stirring for 20min at normal temperature and normal pressure, finally adding span 80, continuously stirring for 10min at normal temperature and normal pressure, and discharging to obtain the antirust punching oil.

Example 2

Mixing aniline and absolute ethyl alcohol according to a volume ratio of 6:5, putting the mixture into a three-neck flask provided with a reflux condenser and a stirrer, stirring, dropwise adding hydrochloric acid with the concentration of 0.5mol/L, the volume of which is 2 times that of the aniline, heating the three-neck flask in a water bath to 85 ℃, and refluxing for 1.5h to obtain a reflux liquid; mixing formaldehyde and acetophenone according to a mass ratio of 1: 2 to obtain a mixed dispersion liquid, cooling the reflux liquid to 65 ℃, mixing the reflux liquid and the mixed dispersion liquid according to a volume ratio of 2:1, cooling to room temperature, adjusting the stirring speed to 500r/min, and stirring and dispersing for 3 hours to obtain the antirust additive; weighing rice bran, crushing to obtain a rice bran crushed product, mixing the rice bran crushed product and distilled water according to a material-liquid ratio of 1:10 to obtain a mixed solution, putting the mixed solution into a reaction kettle, adjusting the pH of the mixed solution to 3 by using hydrochloric acid with the concentration of 0.2mol/L, stirring and reacting for 3 hours at 50 ℃ by using a magnetic stirrer, and performing suction filtration to obtain a filtrate; adding active carbon with the mass of 5% of the filtrate into the filtrate, heating to 85 ℃, standing for 40min, decoloring and filtering the active carbon to obtain a decolored filtrate, firstly adjusting the pH of the decolored filtrate to 6 with saturated lime water, then adjusting the pH to be neutral with sodium hydroxide solution, standing for layering for 3h, filtering and separating to obtain filter residue, thus obtaining the antirust synergistic accelerator; weighing 81 parts of white oil, 6 parts of soybean oil, 3.6 parts of an antirust additive, 3.0 parts of an antirust synergistic accelerator, 0.4 part of barium dinonylnaphthalene sulfonate, 0.6 part of dodecenylsuccinic acid, 0.4 part of barium petroleum sulfonate, 1.3 parts of span 80 and 1.0 part of carbon nano tube in parts by weight; adding white oil and soybean oil into a mixing and stirring reaction kettle, starting a stirring pump to stir, adding an antirust additive, an antirust synergistic accelerator, barium dinonylnaphthalene sulfonate, dodecenylsuccinic acid, barium petroleum sulfonate and carbon nanotubes while stirring, stirring for 20min at normal temperature and normal pressure, finally adding span 80, continuously stirring for 10min at normal temperature and normal pressure, and discharging to obtain the antirust punching oil.

Example 3

Mixing aniline and absolute ethyl alcohol according to a volume ratio of 6:5, putting the mixture into a three-neck flask provided with a reflux condenser and a stirrer, stirring, dropwise adding hydrochloric acid with the concentration of 0.5mol/L, the volume of which is 2 times that of the aniline, heating the three-neck flask in a water bath to 85 ℃, and refluxing for 1.5h to obtain a reflux liquid; mixing formaldehyde and acetophenone according to a mass ratio of 1: 2 to obtain a mixed dispersion liquid, cooling the reflux liquid to 65 ℃, mixing the reflux liquid and the mixed dispersion liquid according to a volume ratio of 2:1, cooling to room temperature, adjusting the stirring speed to 500r/min, and stirring and dispersing for 3 hours to obtain the antirust additive; weighing rice bran, crushing to obtain a rice bran crushed product, mixing the rice bran crushed product and distilled water according to a material-liquid ratio of 1:10 to obtain a mixed solution, putting the mixed solution into a reaction kettle, adjusting the pH of the mixed solution to 3 by using hydrochloric acid with the concentration of 0.2mol/L, stirring and reacting for 3 hours at 50 ℃ by using a magnetic stirrer, and performing suction filtration to obtain a filtrate; adding active carbon with the mass of 5% of the filtrate into the filtrate, heating to 85 ℃, standing for 40min, decoloring and filtering the active carbon to obtain a decolored filtrate, firstly adjusting the pH of the decolored filtrate to 6 with saturated lime water, then adjusting the pH to be neutral with sodium hydroxide solution, standing for layering for 3h, filtering and separating to obtain filter residue, thus obtaining the antirust synergistic accelerator; weighing 82 parts of white oil, 7 parts of soybean oil, 3.7 parts of an antirust additive, 3.1 parts of an antirust synergistic accelerator, 0.5 part of barium dinonylnaphthalene sulfonate, 0.7 part of dodecenylsuccinic acid, 0.5 part of barium petroleum sulfonate, 1.4 parts of span 80 and 1.1 parts of carbon nano tubes in parts by weight; adding white oil and soybean oil into a mixing and stirring reaction kettle, starting a stirring pump to stir, adding an antirust additive, an antirust synergistic accelerator, barium dinonylnaphthalene sulfonate, dodecenylsuccinic acid, barium petroleum sulfonate and carbon nanotubes while stirring, stirring for 20min at normal temperature and normal pressure, finally adding span 80, continuously stirring for 10min at normal temperature and normal pressure, and discharging to obtain the antirust punching oil.

Example 4

Mixing aniline and absolute ethyl alcohol according to a volume ratio of 6:5, putting the mixture into a three-neck flask provided with a reflux condenser and a stirrer, stirring, dropwise adding hydrochloric acid with the concentration of 0.5mol/L, the volume of which is 2 times that of the aniline, heating the three-neck flask in a water bath to 85 ℃, and refluxing for 1.5h to obtain a reflux liquid; mixing formaldehyde and acetophenone according to a mass ratio of 1: 2 to obtain a mixed dispersion liquid, cooling the reflux liquid to 65 ℃, mixing the reflux liquid and the mixed dispersion liquid according to a volume ratio of 2:1, cooling to room temperature, adjusting the stirring speed to 500r/min, and stirring and dispersing for 3 hours to obtain the antirust additive; weighing rice bran, crushing to obtain a rice bran crushed product, mixing the rice bran crushed product and distilled water according to a material-liquid ratio of 1:10 to obtain a mixed solution, putting the mixed solution into a reaction kettle, adjusting the pH of the mixed solution to 3 by using hydrochloric acid with the concentration of 0.2mol/L, stirring and reacting for 3 hours at 50 ℃ by using a magnetic stirrer, and performing suction filtration to obtain a filtrate; adding active carbon with the mass of 5% of the filtrate into the filtrate, heating to 85 ℃, standing for 40min, decoloring and filtering the active carbon to obtain a decolored filtrate, firstly adjusting the pH of the decolored filtrate to 6 with saturated lime water, then adjusting the pH to be neutral with sodium hydroxide solution, standing for layering for 3h, filtering and separating to obtain filter residue, thus obtaining the antirust synergistic accelerator; weighing 83 parts of white oil, 8 parts of soybean oil, 3.8 parts of an antirust additive, 3.2 parts of an antirust synergistic accelerator, 0.6 part of barium dinonylnaphthalene sulfonate, 0.8 part of dodecenylsuccinic acid, 0.6 part of barium petroleum sulfonate, 1.5 parts of span 80 and 1.2 parts of carbon nano tubes in parts by weight; adding white oil and soybean oil into a mixing and stirring reaction kettle, starting a stirring pump to stir, adding an antirust additive, an antirust synergistic accelerator, barium dinonylnaphthalene sulfonate, dodecenylsuccinic acid, barium petroleum sulfonate and carbon nanotubes while stirring, stirring for 20min at normal temperature and normal pressure, finally adding span 80, continuously stirring for 10min at normal temperature and normal pressure, and discharging to obtain the antirust punching oil.

Example 5

Mixing aniline and absolute ethyl alcohol according to a volume ratio of 6:5, putting the mixture into a three-neck flask provided with a reflux condenser and a stirrer, stirring, dropwise adding hydrochloric acid with the concentration of 0.5mol/L, the volume of which is 2 times that of the aniline, heating the three-neck flask in a water bath to 85 ℃, and refluxing for 1.5h to obtain a reflux liquid; mixing formaldehyde and acetophenone according to a mass ratio of 1: 2 to obtain a mixed dispersion liquid, cooling the reflux liquid to 65 ℃, mixing the reflux liquid and the mixed dispersion liquid according to a volume ratio of 2:1, cooling to room temperature, adjusting the stirring speed to 500r/min, and stirring and dispersing for 3 hours to obtain the antirust additive; weighing rice bran, crushing to obtain a rice bran crushed product, mixing the rice bran crushed product and distilled water according to a material-liquid ratio of 1:10 to obtain a mixed solution, putting the mixed solution into a reaction kettle, adjusting the pH of the mixed solution to 3 by using hydrochloric acid with the concentration of 0.2mol/L, stirring and reacting for 3 hours at 50 ℃ by using a magnetic stirrer, and performing suction filtration to obtain a filtrate; adding active carbon with the mass of 5% of the filtrate into the filtrate, heating to 85 ℃, standing for 40min, decoloring and filtering the active carbon to obtain a decolored filtrate, firstly adjusting the pH of the decolored filtrate to 6 with saturated lime water, then adjusting the pH to be neutral with sodium hydroxide solution, standing for layering for 3h, filtering and separating to obtain filter residue, thus obtaining the antirust synergistic accelerator; weighing 84 parts of white oil, 9 parts of soybean oil, 3.9 parts of an antirust additive, 3.3 parts of an antirust synergistic accelerator, 0.7 part of barium dinonylnaphthalene sulfonate, 0.9 part of dodecenylsuccinic acid, 0.7 part of barium petroleum sulfonate, 1.6 parts of span 80 and 1.3 parts of carbon nano tubes in parts by weight; adding white oil and soybean oil into a mixing and stirring reaction kettle, starting a stirring pump to stir, adding an antirust additive, an antirust synergistic accelerator, barium dinonylnaphthalene sulfonate, dodecenylsuccinic acid, barium petroleum sulfonate and carbon nanotubes while stirring, stirring for 20min at normal temperature and normal pressure, finally adding span 80, continuously stirring for 10min at normal temperature and normal pressure, and discharging to obtain the antirust punching oil.

Example 6: in example 6, the rust inhibitive additive of the present invention was not added, and other conditions and component ratios were the same as in example 1 of the present invention;

example 7: in example 7, the rust inhibitive synergistic accelerator of the present invention was not added, and other conditions and component ratios were the same as in example 1 of the present invention;

example 8: in example 8, the soybean oil of the present invention was not added, and other conditions and component ratios were the same as those in example 1 of the present invention;

example 9: in example 9, the carbon nanotubes of the present invention were not added, and other conditions and component ratios were the same as those in example 1 of the present invention;

comparative example 1: sodium tungstate with similar properties to calcium phytate is adopted to replace the calcium phytate to prepare the antirust punching oil, and other conditions and components are the same as those in the example 1 of the invention;

performance test

The performance of the rust-proof stamping oil prepared in the embodiments 1 to 9 and the comparative example 1 is respectively detected, and the detection results are shown in table 1:

detection method/test method

The rust resistance test method comprises the following steps: the detection method adopts a liquid phase corrosion (GB/T11143) and a humidity chamber experiment (GB/T2361), wherein the detection result in the liquid phase corrosion (GB/T11143) is represented by corrosion degree and is divided into three degrees, namely: slight rusting: no more than 6 rust spots, each no more than 1mm in diameter;

moderate rusting: the corrosion is more than 6 points, but less than 5 percent of the surface area of the test steel bar;

severe rusting: the corrosion area exceeds 5 percent of the area of the test steel bar;

wherein, the detection result in the wet box test (GB/T2361) is expressed by corrosion degree, and is divided into 6 grades which are respectively:

level 0: area of rust product coverage (%): 0

Level 1: area of rust product coverage (%): 0.05

And 2, stage: area of rust product coverage (%): 0.5

And 3, level: area of rust product coverage (%): 1

4, level: area of rust product coverage (%): 8

And 5, stage: area of rust product coverage (%): 40-50;

TABLE 1 Performance test results

The test data in the table above are analyzed, and the experimental data in examples 1 to 5 are compared, so that it can be seen that the test data in examples 1 to 3 are better and better, but the corrosion degree is increased from example 4 to example 5, wherein the rust-proof performance of the product in example 3 is the best, because the formula ratio of the rust-proof stamping oil of the present invention has the best value, only under the condition of the ratio of example 3, the rust-proof performance of the stamping oil of the present invention can reach the best, and then the performance test data of examples 1 and 6 of the present invention are compared, so that it can be seen that the rust-proof performance of the final stamping oil is remarkably reduced because the rust-proof additive of the present invention is not added in example 6, and other conditions and component ratios are the same as those in example 1 of the present invention, thereby it can be confirmed that the rust-proof additive component of the present invention is a mannich base, and after quaternization, the antirust additive takes nitrogen atoms with larger electronegativity as a central polar group, the polar group has strong hydrophilicity, and has physical adsorption with metal to form an adsorption layer after contacting the metal surface, meanwhile, the nonpolar group forms a hydrophobic film in the direction away from the metal, the charge state of the metal surface is changed, the activation energy of the rusting reaction of the corrosion candle is increased, the rusting reaction is difficult to carry out, and the antirust effect is preliminarily achieved;

comparing the performance test data of the example 1 and the example 7 of the present invention, it can be seen that the rust inhibiting synergistic accelerator of the present invention is not added in the example 7, and other conditions and component ratios are the same as those in the example 1 of the present invention, which results in a significant decrease in the rust inhibiting performance of the final punching oil, and thus it can be confirmed that the present invention uses rice bran rich in phytic acid as a raw material, leaches the rice bran with hydrochloric acid to obtain a filtrate, and then precipitates and separates the filtrate with saturated lime water to obtain a calcium phytate component, wherein the phytate ion in the calcium phytate contains phosphate group, which is a metal multidentate chelating agent, so that when the calcium phytate is complexed with metal ions in the punching oil and on the metal surface, a dense monomolecular protective film is easily formed on the metal surface, oxygen and oxygen can be effectively prevented from entering the metal surface, and the treated metal surface can lead out corrosion current due to the formed monomolecular hole electron conductive layer, and the conductive layer and the passivated metal film, in addition, calcium ions in the calcium phytate also form an insoluble complex which can be used as a cathode inhibitor to inhibit cathode electrochemical reaction, so that the matrix is protected, the antirust effect is improved, and the stamping oil is non-toxic, harmless to a human body, free of pollution to the environment, low in price and low in cost, meets the environmental protection requirement, and greatly improves the antirust effect;

comparing the performance detection data of the example 1 and the example 8 of the invention, it can be seen that in the example 8, because the soybean oil of the invention is not added, and other conditions and component proportions are the same as those in the example 1 of the invention, the rust-proof performance of the final punching oil is reduced, so that the invention can be confirmed that the soybean oil rich in unsaturated fatty acid is added into the punching oil as the base oil, after the rust-proof punching oil acts on the metal surface, the blocking and absorbing capacity for oxygen in the air is strong, and the soybean oil can be chelated with part of oxidized metal divalent ions, so as to improve the adhesive force of the rust-proof punching oil to the metal, and the oxidized unsaturated fatty acid can be slowly reduced by the metal ions to form a good cycle, so that the rust-proof oil always maintains strong reducing performance, thereby prolonging the rust-proof period of the rust-proof punching oil;

comparing the performance test data of the example 1 and the example 9 of the present invention, it can be seen that the rust inhibitive performance of the final punching oil is reduced because the carbon nanotubes of the present invention are not added in the example 9, and other conditions and component ratios are the same as those in the example 1 of the present invention, and thus it can be confirmed that the present invention further adds the carbon nanotubes, and the addition thereof is helpful to improve the self-corrosion potential of the metal matrix and reduce the corrosion current, and improves the corrosion inhibitive performance of the steel bar, thereby improving the rust inhibitive performance thereof.

Comparing the performance detection data of the example 1 and the comparative example 1, it can be seen that the comparative example 1 adopts sodium tungstate with similar property to calcium phytate to replace calcium phytate to prepare the antirust punching oil, and other conditions and components are the same as those in the example 1, so that the antirust performance of the final punching oil is reduced, thereby confirming that the antirust additive and the antirust synergistic accelerator are used together, after calcium phytate is compounded into mannich base, the phytic acid ions and ferrous ions formed by dissolving the metal anode are electrostatically attracted and combined into precipitates which are attached to the area where the mannich base does not act, the saturated adsorption quantity of the metal surface is increased, and the diffusion of electrons to the solution through the film is further prevented, therefore, the compounded antirust more effectively inhibits the dissolution of the anode metal and the hydrogen evolution reaction of the cathode, and the mannich corrosion performance of the calcium phytate shows better synergistic effect, the antirust performance is obviously improved.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.