Ashless rust preventive composition containing mixed acid polyamine and method of making

Abstract

The application discloses a mixed acid polyamine-containing ashless rust inhibitor composition, which is composed of the following components in percentage by mass: ashless rust inhibitor 60-80%, film forming agent 0.5-20%, antioxidant 1-3%, non-ferrous metal corrosion inhibitor 0.1-0.5%, and the balance is base oil; the application also discloses a preparation method of the mixed acid polyamine-containing ashless rust inhibitor composition; the application further discloses an ashless rust inhibitor; the ashless rust inhibitor has the characteristics of excellent rust-proof performance, especially excellent salt spray resistance and damp heat resistance, good solubility in petroleum solvents and lubricating oil base oil, and can be used to prepare various rust-proof oils.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of rust-proof oil, and particularly relates to a rust inhibitor composition containing mixed acid polyamine, a preparation method of the rust inhibitor composition containing mixed acid polyamine, and a rust inhibitor. BACKGROUND

[0002] Commonly used oil-soluble rust inhibitors mainly include sulfonates, carboxylic acids and their derivatives, esters, organic phosphates, organic amines, and heterocyclic compounds. Among them, sulfonates are one of the most widely used rust inhibitors, which have good rust resistance and excellent water displacement property, but are usually used in combination with other rust inhibitors to form a rust inhibitor composition. Such a rust inhibitor composition usually contains metals and has a high ash content, which cannot meet the requirements of some specific applications, such as rust prevention for workpieces before heat treatment, and rust prevention for low-ash or ash-free hydraulic oils.

[0003] Currently, commonly used oil-soluble ash-free rust inhibitors include organic carboxylic acids / esters, organic amines, nitrogen-containing compounds, and heterocyclic compounds.

[0004] It is known that compounds containing both carboxylic acid groups and hydroxyl groups can be used as ash-free rust inhibitors. For example, a patent application published on October 11, 1983, with the application publication number US4409411, discloses a process for the hydrogenation of benzene and Group IVA metal hydride catalysts therefor, which contains an ashless rust inhibitor of alkyl succinic acid polyol ester for rust prevention in fuel oils and lubricating oils. Another patent application published on October 8, 1991, with the application publication number US5055230A, discloses an inhibitor composition containing hydroxyl, ester, and carboxylic acid groups, which can be used in water-based or oil-based products.

[0005] When using an ash-free rust inhibitor alone to prepare rust-proof oil, the rust prevention performance is limited, and it is usually necessary to use it in combination with other rust inhibitors containing metals, such as dinonylnaphthalene sulfonate. Although the rust prevention performance is improved, it still does not meet the requirement of ash-free.

[0006] A patent application published on August 25, 2020, with the application publication number CN111575088, discloses an ash-free rust inhibitor composition, which is composed of 5-30% base oil, 30-90% organic carboxylic acid rust inhibitor, and 5-40% gemini imidazoline derivative. The rust inhibitor composition has good oil solubility, small dosage, excellent rust prevention performance, low acid value, and good emulsion resistance. The rust inhibitor composition mainly meets the rust prevention requirements of industrial lubricating oils, but cannot meet the requirements of rust-proof oil.

[0007] Content of the invention

[0008] The present application aims to provide ashless rust inhibitor composition containing mixed acid polyamine, which has rust-proof performance, especially excellent salt spray resistance and damp heat resistance, good solubility in petroleum solvents and lubricating oil base oil, and the characteristics of being able to modulate various rust-proof oils.

[0009] The second object of the present application is to provide a preparation method of ashless rust inhibitor composition containing mixed acid polyamine.

[0010] The third object of the present application is to provide ashless rust inhibitor.

[0011] The first technical solution adopted by the present application is ashless rust inhibitor composition containing mixed acid polyamine, which is composed of the following raw material components in mass percentage: ashless rust inhibitor 60% to 80%, film forming agent 0.5% to 20%, antioxidant 1% to 3%, non-ferrous metal corrosion inhibitor 0.1% to 0.5%, and the balance is base oil.

[0012] The first technical solution of the present application is also characterized in that:

[0013] The film forming agent is at least one of vaseline, paraffin, oxidized paraffin, oil-soluble asphalt, ethylene-propylene copolymer, methacrylate copolymer, polyisobutylene, hydrogenated styrene diene copolymer or lanolin, or two or more of them mixed in any ratio.

[0014] The non-ferrous metal corrosion inhibitor is at least one of benzene triazole derivative or thiadiazole derivative, or two or more of them mixed in any ratio.

[0015] The antioxidant is at least one of phenolic antioxidant or amine antioxidant, or two or more of them mixed in any ratio.

[0016] The base oil is at least one of industrial white oil, mineral oil or synthetic oil or reclaimed oil, or two or more of them mixed in any ratio.

[0017] The ashless rust inhibitor is prepared by the following method:

[0018] Step 1: the following components are weighed according to mass percentage: non-polar solvent S 26.8% to 45.7%, dinonyl naphthalene sulfonic acid 8% to 20.7%, dodecenyl succinic acid 3.2% to 19.7%, polyene polyamine 8.2% to 12.7%, deionized water 1.2% to 2.5%, methanol 1.3% to 3%, methyl methacrylate 0.4% to 0.9%, and the balance is base oil.

[0019] Step 2: in non-polar solvent S, mix dinonyl naphthalene sulfonic acid and dodecenyl succinic acid to obtain mixed acid A.

[0020] Step 3: mix the polyene polyamine with the mixed acid A obtained in step 1, add deionized water and methanol, and react at 70±5℃ until the solution PH is neutral to obtain solvent B.

[0021] Step 4: add methyl methacrylate and base oil to the solvent B obtained in step 2, distill at 145±5℃ until most of the solvent and its azeotrope with water are replaced by the base oil, and distill under reduced pressure at 2±1kPa until no obvious distillate is produced.

[0022] The non-polar solvent S is one of n-heptane, dioxane or toluene, or a combination of two or more in any proportion; the polyene polyamine is one of diethylene triamine, triethylene tetramine or tetraethylene pentamine, or a combination of two or more in any proportion; and the base oil is one of industrial white oil, mineral oil, hydrogenated oil or PAO base oil, or a combination of two or more in any proportion.

[0023] The second technical solution adopted by the present application is a preparation method of ashless rust inhibitor composition containing mixed acid polyamine, which is specifically implemented according to the following steps:

[0024] Step 1: weigh the following components according to the mass percentage: select ashless rust inhibitor 60%~80%, film forming agent 0.5%~20%, antioxidant 1%~3%, non-ferrous metal corrosion inhibitor 0.1%~0.5%, and the rest is base oil.

[0025] Step 2: heat and stir the base oil at 60℃~70℃, add the film forming agent and the antioxidant, heat to 80℃~100℃, continue to stir for 1~2 hours, and then cool to 60℃~70℃ after complete dissolution to obtain solution A.

[0026] Step 3: add the ashless rust inhibitor and the non-ferrous metal corrosion inhibitor to the solution A obtained in step 2 in sequence, and stir at 60℃~70℃ for 1~2 hours to obtain the ashless rust inhibitor composition.

[0027] The second technical solution of the present application is also characterized in that:

[0028] The stirring rate in steps 2 and 3 is 200-800rpm.

[0029] The third technical solution adopted by the present application is an ashless rust inhibitor prepared by the following method:

[0030] Step 1: weigh the following components according to the mass percentage: non-polar solvent S 26.8%~45.7%, dinonyl naphthalene sulfonic acid 8%~20.7%, dodecenyl succinic acid 3.2%~19.7%, polyene polyamine 8.2%~12.7%, deionized water 1.2%~2.5%, methanol 1.3%~3%, methyl methacrylate 0.4%~0.9%, and the rest is base oil.

[0031] Step 2: Mix dinonyl naphthalene sulfonic acid and dodecenyl succinic acid in a non-polar solvent S to obtain mixed acid A.

[0032] Step 3: Mix polyene polyamine with mixed acid A obtained in Step 1, add deionized water and methanol, and react at 70±5℃ until the solution PH value is neutral to obtain solvent B.

[0033] Step 4: Add methyl methacrylate and base oil to solvent B obtained in Step 2, heat to 145±5℃ and distill until most of the solvent and its azeotrope with water are replaced by the base oil, and distill under reduced pressure at 2±1kPa until no obvious distillate is produced.

[0034] The non-polar solvent S is one of n-heptane, dioxane or toluene, or a combination of two or more in any proportion; the polyene polyamine is one of diethylene triamine, triethylene tetramine or tetraethylene pentamine, or a combination of two or more in any proportion; and the base oil is one of industrial white oil, mineral oil, hydrogenated oil or PAO base oil, or a combination of two or more in any proportion.

[0035] The beneficial effects of the present application are:

[0036] The ashless rust inhibitor composition containing mixed acid polyamine, the ashless rust inhibitor in the ashless rust inhibitor composition containing mixed acid polyamine and the preparation method of the ashless rust inhibitor composition containing mixed acid polyamine, wherein the ashless rust inhibitor composition containing mixed acid polyamine does not contain metal ions, has good rust prevention performance, especially excellent salt spray resistance and wet heat resistance, generates gaseous oxides after high temperature ignition, does not leave stains on the workpiece surface, is particularly suitable for rust prevention of workpieces before heat treatment, and can also be used for ashless hydraulic oil; at the same time, the ashless rust inhibitor composition containing mixed acid polyamine has good solubility in petroleum solvents and lubricating oil base oils, and can be used to adjust the properties of various rust-proof oils. DETAILED DESCRIPTION

[0037] The present application will be described in detail below in conjunction with specific embodiments.

[0038] The first technical solution of the present application is to provide an ashless rust inhibitor composition containing mixed acid polyamine, which is composed of the following raw materials in mass percentage: 60% to 80% of ashless rust inhibitor, 0.5% to 20% of film forming agent, 1% to 3% of antioxidant, 0.1% to 0.5% of non-ferrous metal corrosion inhibitor, and the balance of base oil.

[0039] The film forming agent is at least one of vaseline, paraffin, oxidized paraffin, oil-soluble asphalt, ethylene-propylene copolymer, methyl methacrylate copolymer, polyisobutylene, hydrogenated styrene-diene copolymer or lanolin, or two or more of them mixed in any ratio. The addition of the film forming agent can adjust the photosensitive liquid to make the photosensitive liquid easy to be coated and leveled, improve the adhesion of the photosensitive layer and the plate base, and the photochemical reaction speed of the photosensitive layer, and is beneficial to the formation of a fixed film layer of the photosensitive liquid on the plate base. The film forming agent has the same solubility as the photosensitive substance.

[0040] The non-ferrous metal corrosion inhibitor is at least one of benzene triazole derivative or thiadiazole derivative, or two or more of them mixed in any ratio. In the present application, the chemical substance or compound with a concentration of 0.1% to 0.5% and other substances can prevent or slow down the corrosion of the material.

[0041] The antioxidant is at least one of phenolic antioxidant or amine antioxidant, or two or more of them mixed in any ratio. The addition of the antioxidant can delay or inhibit the progress of the polymer oxidation process, thereby preventing the aging of the polymer and prolonging its service life. The dosage of the antioxidant should be appropriate, generally less than 10%. In the present application, the amount of the antioxidant is selected to be 1% to 3% of the total composition, which can maximize the rust prevention period without ash.

[0042] The base oil is at least one of industrial white oil, mineral oil, synthetic oil or reclaimed oil, or two or more of them mixed in any ratio.

[0043] The ashless rust inhibitor is prepared by the following method:

[0044] Step 1: The following components are weighed according to the mass percentage: non-polar solvent S 26.8% to 45.7%, dinonyl naphthalene sulfonic acid 8% to 20.7%, dodecenyl succinic acid 3.2% to 19.7%, polyene polyamine 8.2% to 12.7%, deionized water 1.2% to 2.5%, methanol 1.3% to 3%, methyl methacrylate 0.4% to 0.9%, and the balance is base oil;

[0045] Step 2: In the non-polar solvent S, mix the dinonyl naphthalene sulfonic acid and the dodecenyl succinic acid to obtain a mixed acid A;

[0046] Step 3: Mix the polyene polyamine with the mixed acid A obtained in Step 1, add deionized water and methanol, and react at 70±5℃ until the solution PH value is neutral, to obtain a solvent B;

[0047] Step 4: Add methyl methacrylate and base oil to the solvent B obtained in Step 2, heat to 145±5℃ and distill until most of the solvent and its azeotrope with water are replaced by the base oil, and then reduce the pressure to 2±1kPa and distill until no obvious distillate is produced.

[0048] The non-polar solvent S is one of n-heptane, dioxane or toluene or a combination of two or more thereof in any ratio; the polyene polyamine is one of diethylene triamine, triethylene tetramine or tetraethylene pentamine or a combination of two or more thereof in any ratio; and the base oil is one of industrial white oil, mineral oil, hydrogenated oil or PAO base oil or a combination of two or more thereof in any ratio.

[0049] The second technical solution of the present application is to provide a preparation method of the ashless rust inhibitor composition containing mixed acid polyamine, which is specifically implemented according to the following steps:

[0050] Step 1: the following components are weighed according to the mass percentage: 60% to 80% of ashless rust inhibitor, 0.5% to 20% of film forming agent, 1% to 3% of antioxidant, 0.1% to 0.5% of non-ferrous metal corrosion inhibitor, and the rest is base oil.

[0051] Step 2: the base oil is heated and stirred at 60°C to 70°C, the stirring rate is 200-800 rpm, the film forming agent and the antioxidant are added, the temperature is raised to 80°C to 100°C, the stirring is continued for 1 to 2 hours, the stirring rate is 200-800 rpm, after all the components are dissolved, the temperature is lowered to 60°C to 70°C, and solution A is obtained.

[0052] Step 3: the ashless rust inhibitor and the non-ferrous metal corrosion inhibitor prepared in step 2 are added to solution A in sequence, and stirred at 60°C to 70°C for 1 to 2 hours, and the stirring rate is 200-800 rpm, to obtain the ashless rust inhibitor composition containing mixed acid polyamine.

[0053] The ashless rust inhibitor composition containing mixed acid polyamine prepared by this method has excellent rust prevention function, excellent salt spray resistance and excellent wet heat resistance, is suitable for rust prevention of workpieces before heat treatment due to its ashless performance, has good solubility in petroleum solvents and lubricating oil base oil, and can be used to prepare various rust prevention oils.

[0054] The third technical solution of the present application is an ashless rust inhibitor prepared by the following method:

[0055] Step 1: the following components are weighed according to the mass percentage: 26.8% to 45.7% of non-polar solvent S, 8% to 20.7% of dinonyl naphthalene sulfonic acid, 3.2% to 19.7% of dodecenyl succinic acid, 8.2% to 12.7% of polyene polyamine, 1.2% to 2.5% of deionized water, 1.3% to 3% of methanol, 0.4% to 0.9% of methyl methacrylate, and the rest is base oil.

[0056] Step 2: in the non-polar solvent S, the dinonyl naphthalene sulfonic acid and the dodecenyl succinic acid are mixed to obtain mixed acid A.

[0057] Step 3: Mix polyene polyamine with mixed acid A obtained in Step 1, add deionized water and methanol, react at 70±5℃ until the solution PH value is neutral, to obtain solvent B.

[0058] Step 4: Add methyl methacrylate and base oil to solvent B obtained in Step 2, heat to 145±5℃ distillation until most of the solvent and its azeotrope with water are replaced by base oil, distill under reduced pressure at 2±1kPa until no obvious distillate is produced.

[0059] Wherein, the non-polar solvent S is one of n-heptane, dioxane or toluene or a combination of two or more in any proportion; the polyene polyamine is one of diethylene triamine, triethylene tetramine or tetraethylene pentamine or a combination of two or more in any proportion; the base oil is one of industrial white oil, mineral oil, hydrogenated oil or PAO base oil or a combination of two or more in any proportion.

[0060] Example 1

[0061] The preparation scheme of ashless rust inhibitor composition containing mixed acid polyamine is as follows:

[0062] Table 1 Raw material ratio for preparing amine-containing ashless rust inhibitor composition in Example 1

[0063]

[0064]

[0065] The preparation method of amine-containing ashless rust inhibitor composition is specifically implemented according to the following steps:

[0066] Step 1: According to the above table data, each raw material is weighed; wherein, the ashless rust inhibitor preparation method is as follows: 57g of n-heptane is added to a 250ml three-necked flask equipped with a reflux condenser, 37g of dinonyl naphthalene sulfonic acid and 5.7g of dodecenyl succinic acid are added to the flask in turn, and stirring is started; 14.6g of triethylene tetramine is slowly added to the flask, and the feeding is completed within 10 minutes; then 3.2g of methanol and 2.7g of deionized water are added to the flask; slowly heat to 70±5℃, react for 1-2 hours until the solution PH value is neutral; then add 1.0g of methyl methacrylate and 57g of mineral base oil 150SN to the system, slowly heat to 145±5℃ distillation until most of the solvent and its azeotrope with water are replaced by base oil; finally, distill under reduced pressure at 2±1kPa until no obvious distillate is produced, to obtain ashless rust inhibitor.

[0067] Step 2: PCL 150N base oil was heated and stirred at 60°C with a stirring rate of 200-800 rpm, and oxidized paraffin wax and 2,6-di-tert-butyl-p-cresol were added. The temperature was raised to 80°C, and the mixture was stirred for 1-2 hours at a stirring rate of 200-800 rpm. After complete dissolution, the temperature was lowered to 60°C.

[0068] Step 3: The ashless rust inhibitor composition AR1 containing amine groups was obtained by sequentially adding ashless rust inhibitor and benzotriazole derivative to the solution obtained in Step 2, and stirring for 2 hours at a stirring rate of 200-800 rpm.

[0069] Example 2

[0070] The ashless rust inhibitor composition containing mixed acid polyamine was prepared according to the following scheme:

[0071] Table 2 Raw material ratio for preparing the ashless rust inhibitor composition containing amine groups in Example 2

[0072]

[0073]

[0074] The ashless rust inhibitor composition containing amine groups was prepared according to the following steps:

[0075] Step 1: The raw materials were weighed according to the data in the above table. The ashless rust inhibitor was prepared according to the following method: 42 g of toluene was added to a 250 ml three-necked flask equipped with a reflux condenser, and 9.2 g of dinonyl naphthalene sulfonic acid and 22.7 g of dodecenyl succinic acid were sequentially added to the flask while stirring. 9.5 g of tetraethylenepentamine was slowly added to the flask over a period of 10 minutes. Then, 1.6 g of methanol and 1.4 g of deionized water were added to the flask. The temperature was slowly raised to 70±5°C, and the reaction was carried out for 1-2 hours until the solution pH was neutral. Then, 0.5 g of methyl methacrylate and 28 g of Liaohe No. 10 base oil were added to the system, and the temperature was slowly raised to 145±5°C for distillation until most of the solvent and its azeotrope with water were replaced by the base oil. Finally, the system was distilled under reduced pressure at 2±1 kPa until no obvious distillate was produced, and the ashless rust inhibitor was obtained.

[0076] Step 2: PCL 150N base oil was heated and stirred at 60°C with a stirring rate of 200-800 rpm, and oxidized paraffin wax and 2,6-di-tert-butyl-p-cresol were added. The temperature was raised to 80°C, and the mixture was stirred for 1-2 hours at a stirring rate of 200-800 rpm. After complete dissolution, the temperature was lowered to 60°C.

[0077] Step 3: The ashless rust inhibitor composition AR2 containing amine groups was obtained by sequentially adding ashless rust inhibitor and benzotriazole derivative to the solution obtained in Step 2, and stirring for 2 hours at a stirring rate of 200-800 rpm.

[0078] Example 3

[0079] Table 3 Raw material ratio for preparing amine group-containing ashless rust inhibitor composition in Example 3

[0080]

[0081]

[0082] The method for preparing the amine group-containing ashless rust inhibitor composition is specifically implemented according to the following steps:

[0083] Step 1: The raw materials are weighed according to the data in the above table respectively; wherein, the ashless rust inhibitor is prepared according to the following method: 58 g of dioxane is added to a 250 ml three-necked flask equipped with a reflux condenser, 23 g of dinonyl naphthalene sulfonic acid and 14 g of dodecenyl succinic acid are added into the flask in turn, and stirring is started; 21 g of diethylenetriamine is slowly added into the flask, and the feeding is completed within 10 minutes; then, 6.4 g of methanol and 5.4 g of deionized water are added into the flask; the temperature is slowly raised to 70±5℃, and the reaction is carried out for 1-2 hours until the solution PH value is neutral; then, 2 g of methyl methacrylate and 86 g of hydrogenated base oil 150N are added into the system, and the temperature is slowly raised to 145±5℃ for distillation until most of the solvent and its azeotrope with water are replaced by the base oil; finally, the distillation is carried out under reduced pressure at 2±1 kPa until no obvious distillate is produced, and the ashless rust inhibitor is obtained.

[0084] Step 2: The PCL 150N base oil is heated and stirred at 70℃, the stirring rate is 200-800 rpm, lanolin and dialkyldiphenylamine are added, the temperature is raised to 100℃, and the stirring is carried out for 1-2 hours, the stirring rate is 200-800 rpm, and after complete dissolution, the temperature is lowered to 70℃.

[0085] Step 3: The ashless rust inhibitor and the thiadiazole derivative are sequentially added into the solution obtained in Step 2, and stirred for 2 hours, the stirring rate is 200-800 rpm, and the amine group-containing ashless rust inhibitor composition AR3 is obtained.

[0086] Example 4

[0087] Table 4 Raw material ratio for preparing amine group-containing ashless rust inhibitor composition in Example 4

[0088]

[0089]

[0090] The method for preparing the amine group-containing ashless rust inhibitor composition is specifically implemented according to the following steps:

[0091] Step 1: Weigh each raw material according to the data in the table above. The specific preparation method of the ashless rust inhibitor is as follows: Add 56g of n-heptane to a 250ml three-necked flask equipped with a reflux condenser. Add 27.6g of dinonylnaphthalenesulfonic acid and 11.4g of dodecenylsuccinic acid to the flask in sequence and start stirring. Slowly add a mixture of 16.7g of triethylenetetramine and tetraethylenepentamine to the flask, and complete the addition within 10 minutes. Then add 3.2g of methanol and 2.7g of deionized water to the flask. Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH of the solution is neutral. Then add 1g of methyl methacrylate and 56g of hydrogenated base oil Yubase 4 to the system. Slowly raise the temperature to 145±5℃ and distill until most of the solvent and its azeotrope with water are replaced by the base oil. Finally, distill under reduced pressure at 2±1kPa until no obvious distillate is produced, thus obtaining the ashless rust inhibitor.

[0092] Step 2: Heat and stir PCL 150N base oil at 70°C at a stirring speed of 200-800 rpm. Add polyisobutylene and 2,6-di-tert-butyl-p-cresol, heat to 90°C, and stir for 1-2 hours at a stirring speed of 200-800 rpm. After complete dissolution, cool to 70°C.

[0093] Step 3: Add the ashless rust inhibitor and the thiadiazole derivative to the solution obtained in Step 2 in sequence, stir for 2 hours at a stirring speed of 200-800 rpm, and the amine-containing ashless rust inhibitor composition AR4 is obtained.

[0094] Example 5

[0095] Table 5. Raw material ratio for the preparation of the amine-containing ashless rust inhibitor composition in Example 5.

[0096] Component Mass fraction, % Ashless rust preventive 70 Petroleum jelly 10 Benzotriazole derivative 0.5 Dialkyldiphenylamine 3 PCL 150N base oil 16.5

[0097] The preparation method of the amine-containing ashless rust inhibitor composition is carried out according to the following steps:

[0098] Step 1: The raw materials were weighed according to the data in the table above; among them, the ashless rust inhibitor was prepared as follows: 48 g of dioxane was added to a 250 ml three-necked flask equipped with a reflux condenser, 18.4 g of dinonyl naphthalene sulfonic acid, 17.0 g of dodecenyl succinic acid were added into the flask in turn, and the stirring was started; 12.5 g of a mixture of triethylene tetramine and diethylene triamine was slowly added into the flask, and the feeding was completed within 10 minutes; then 3.2 g of methanol and 2.7 g of deionized water were added into the flask; the temperature was slowly raised to 70±5℃, and the reaction was carried out for 1-2 hours until the solution pH value was neutral; then 1 g of methyl methacrylate and 21 g of industrial white oil W1-100 were added into the system, and the temperature was slowly raised to 145±5℃ for distillation until most of the solvent and its azeotrope with water were replaced by base oil; finally, the system was distilled under reduced pressure at 2±1 kPa until no obvious distillate was produced, and the ashless rust inhibitor was obtained.

[0099] Step 2: The PCL 150N base oil was heated and stirred at 60℃, the stirring rate was 200-800 rpm, the vaseline and the dialkyldiphenylamine were added, the temperature was raised to 80℃, and the stirring was carried out for 1-2 hours, the stirring rate was 200-800 rpm, and after the complete dissolution, the temperature was lowered to 60℃.

[0100] Step 3: The ashless rust inhibitor and the benzotriazole derivative were added into the solution obtained in step 2 in turn, and the stirring was carried out for 2 hours, the stirring rate was 200-800 rpm, and the ashless rust inhibitor composition containing amine group AR5 was obtained.

[0101] Example 6

[0102] Table 6 Raw material ratio for preparing the ashless rust inhibitor composition containing amine group in Example 6

[0103] Component Mass fraction, % Ashless rust preventive 60 Methacrylate copolymer 0.5 Benzotriazole derivative 0.1 Dialkyldiphenylamine 1 PCL 150N base oil 38.4

[0104] The method for preparing the ashless rust inhibitor composition containing amine group was carried out according to the following steps:

[0105] Step 1: The raw materials were weighed according to the data in the table above; among them, the ashless rust inhibitor was prepared as follows: 52 g of toluene was added to a 250 ml three-necked flask equipped with a reflux condenser, 23 g of dinonyl naphthalene sulfonic acid, 14.2 g of dodecenyl succinic acid were added to the flask in turn, and stirring was started; a mixture of 14.6 g of diethylenetriamine, triethylenetetramine and tetraethylenepentamine was slowly added to the flask, and the addition was completed within 10 minutes; then 3.2 g of methanol and 2.7 g of deionized water were added to the flask; slowly heated to 70±5℃, reacted for 1-2 hours, until the solution PH value was neutral; then 1 g of methyl methacrylate and 35 g of constant force No. 10 base oil were added to the system, slowly heated to 145±5℃ and distilled until most of the solvent and its azeotrope with water were replaced by base oil; finally, vacuum distillation was carried out at 2±1 kPa until no obvious distillate was produced, and the ashless rust inhibitor was obtained.

[0106] Step 2: The PCL 150N base oil was heated and stirred at 60℃, the stirring rate was 200-800 rpm, the methacrylate copolymer and the dialkyldiphenylamine were added, the temperature was raised to 80℃, and the stirring was carried out for 1-2 hours, the stirring rate was 200-800 rpm, and after the complete dissolution, the temperature was lowered to 60℃.

[0107] Step 3: The ashless rust inhibitor and the benzotriazole derivative were added to the solution obtained in step 2 in turn, and stirred for 2 hours, the stirring rate was 200-800 rpm, and the amine-containing ashless rust inhibitor composition AR6 was obtained.

[0108] Comparative Example 1

[0109] The implementation is the same as Example 1, except that calcium dinonyl naphthalene sulfonate is used instead of ashless rust inhibitor. A rust inhibitor composition AR1-1 is obtained, which is an ash-containing rust inhibitor composition.

[0110] Comparative Example 2

[0111] The implementation is the same as Example 1, except that BASF L12 is used instead of ashless rust inhibitor. An ashless rust inhibitor composition AR1-2 is obtained.

[0112] The performance test is the same as the test method in the example.

[0113] Performance test:

[0114] The amine-containing ashless rust inhibitor compositions AR1-AR6 obtained in Examples 1-6 were tested for performance, and the complexing agent composition was dissolved in Liaohe No. 10 base oil at a mass fraction of 15%. The method for evaluating the rust prevention performance is as follows: the wet heat test adopts GB / T 2361 method; the salt spray test adopts SH / T0081 method; the performance test of Comparative Examples 1 and 2 is the same as the test method in Examples 1-6.

[0115] Table 7 Experimental results of examples and comparative examples

[0116]

[0117]

[0118] Table 7 lists the analysis results of examples 1-6 and comparative examples 1-2. It can be seen from Table 7 that the rust resistance, humidity resistance and salt spray resistance of the ash-free rust inhibitor composition containing mixed acid polyamine of the present application are similar to the performance of the ash-containing rust inhibitor composition of comparative example 1, and are superior to the salt spray resistance and humidity resistance of comparative example 2; the ash-free rust inhibitor composition containing mixed acid polyamine of the present application is suitable for rust prevention of workpieces before heat treatment due to its strong rust prevention performance and ash-free nature, and the rust prevention period is not less than 3 years, and is also used for ash-free hydraulic oil; and has good solubility in petroleum solvents and lubricating oil base oils, and can be used to prepare various rust-proof oils.

Claims

1. A composition of ashless rust inhibitor containing mixed acid polyamines, characterized in that, The composition is based on the following raw material components by weight percentage: 60%–80% ashless rust inhibitor, 0.5%–20% film-forming agent, 1%–3% antioxidant, 0.1%–0.5% non-ferrous metal corrosion inhibitor, with the balance being base oil; The ashless rust inhibitor is prepared by the following method: Step 1: Weigh the following components by mass percentage: nonpolar solvent S 26.8%–45.7%, dinonylnaphthalenesulfonic acid 8%–20.7%, dodecenylsuccinic acid 3.2%–19.7%, polyene polyamine 8.2%–12.7%, deionized water 1.2%–2.5%, methanol 1.3%–3%, methyl methacrylate 0.4%–0.9%, with the remainder being base oil; Step 2: In a nonpolar solvent S, dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid are mixed to obtain mixed acid A; Step 3: Mix the polyene polyamine with the mixed acid A obtained in Step 1, add deionized water and methanol, and react at 70±5℃ until the pH of the solution is neutral to obtain mixed solution B; Step 4: Add methyl methacrylate and base oil to the mixture B obtained in Step 3, heat to 145±5℃ and distill until most of the solvent and its azeotrope with water are replaced by the base oil, and distill under reduced pressure at 2±1kPa until no obvious distillate is produced.

2. The ashless rust inhibitor composition containing mixed acid polyamines according to claim 1, characterized in that, The film-forming agent is one or more of the following: petrolatum, paraffin wax, oxidized paraffin wax, oil-soluble asphalt, ethylene-propylene copolymer, methacrylate copolymer, polyisobutylene, hydrogenated styrene diene copolymer, or lanolin, mixed in any proportion.

3. The ashless rust inhibitor composition containing mixed acid polyamines according to claim 1, characterized in that, The non-ferrous metal corrosion inhibitor is one or more of benzotriazole derivatives or thiadiazole derivatives mixed in any proportion.

4. The ashless rust inhibitor composition containing mixed acid polyamines according to claim 1, characterized in that, The antioxidant is one or more of phenolic antioxidants or amine antioxidants, mixed in any proportion.

5. The ashless rust inhibitor composition containing mixed acid polyamines according to claim 1, characterized in that, The base oil is one or more of mineral oil, synthetic oil or recycled oil mixed in any proportion.

6. The ashless rust inhibitor composition containing mixed acid polyamines according to claim 1, characterized in that, The nonpolar solvent S is one or more of n-heptane, dioxane, or toluene in any proportion; the polyene polyamine is one or more of diethylenetriamine, triethylenetetramine, or tetraethylenepentamine in any proportion; and the base oil is one or more of mineral oil or PAO base oil in any proportion.

7. The ashless rust inhibitor composition containing mixed acid polyamines according to claim 1, characterized in that, The base oil is a hydrogenated oil, and the base oil is an industrial white oil.

8. The ashless rust inhibitor composition containing mixed acid polyamines according to claim 1, characterized in that, The base oil is industrial white oil.

9. The method for preparing the ashless rust inhibitor composition containing mixed acid polyamines according to any one of claims 1-8, characterized in that, The specific steps are as follows: Step 1: Weigh the following components by mass percentage: 60%–80% ashless rust inhibitor, 0.5%–20% film-forming agent, 1%–3% antioxidant, 0.1%–0.5% non-ferrous metal corrosion inhibitor, with the remainder being base oil; Step 2: Heat and stir the base oil at 60℃~70℃, add the film-forming agent and antioxidant, raise the temperature to 80℃~100℃, continue stirring for 1~2 hours, and after it is completely dissolved, cool it to 60℃~70℃ to obtain solution A; Step 3: Add ashless rust inhibitor and non-ferrous metal corrosion inhibitor sequentially to solution A obtained in step 2, and stir at 60℃~70℃ for 1~2 hours to obtain the ashless rust inhibitor composition containing mixed acid polyamine.

10. The preparation method according to claim 9, characterized in that, The stirring rate in steps 2 and 3 is 200-800 rpm.

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