Ash-free antirust agent and preparation method thereof

Abstract

The invention provides an ash-free antirust agent and a preparation method thereof. The preparation method comprises the following steps: in a non-polar solvent, mixing dinonyl naphthalene sulfonic acid and dodecenylsuccinic acid to obtain a mixed acid A; the preparation method comprises the following steps: mixing polyethylene polyamine and mixed acid A according to a molar ratio of (0.5-2.0): 1, and adding deionized water and methanol to react until the pH value of the solution is neutral; and adding methyl methacrylate and base oil into the reacted system, heating and distilling, and then carrying out reduced pressure distillation until no obvious distillate is generated, thereby obtaining the ash-free antirust agent. The invention also provides the ash-free antirust agent prepared by the method. The ashless antirust agent integrates the advantages of the dinonyl naphthalene sulfonic acid group and the dodecenyl succinic acid group on the molecular level, the antirust property is better, and the ashless antirust agent and the anti-wear reagent at extreme pressure have a very good synergistic effect.

Description

Technical Field

[0001] The invention relates to an ashless rust inhibitor and a preparation method thereof, belonging to the technical field of rust inhibitor preparation. Background Art

[0002] In order to meet the requirements of harsh working conditions, industrial oils are generally added with extreme pressure anti-wear agents containing active sulfur components. The introduction of active sulfur elements will corrode the copper and steel parts in the system, and because water will inevitably enter the oil during the working process, it will aggravate the corrosion of steel parts. Therefore, in order to better protect mechanical parts, a certain amount of rust inhibitors need to be added to the oil.

[0003] In addition, as the precision of parts and components increases, the requirements for oil filterability are also increasing. Ash-containing additives containing metal ions will affect the filterability of oil. Therefore, it is necessary to add ashless rust inhibitors to the oil. Currently, commonly used oil-soluble ashless rust inhibitors include organic carboxylic acids / esters, organic amines, nitrogen-containing compounds and heterocyclic compounds.

[0004] It is well known that compounds containing both carboxylic acid and hydroxyl functional groups can be used as ashless rust inhibitors. For example, patent US4409411 discloses the preparation of an alkyl succinic acid polyol ester ashless rust inhibitor for rust prevention of fuel oil and lubricating oil; patent US5055230 discloses an ashless rust inhibitor containing hydroxyl, ester and carboxylic acid groups, which can be used for water-based or oil-based products.

[0005] Patent US4165292 discloses the preparation of an ashless rust inhibitor of alkyl succinic acid amine, which is used for rust prevention of lubricating oil. Patent US5275749 discloses an ashless rust inhibitor of acylated aspartic acid derivatives. Patent US5254277 discloses an ashless rust inhibitor of bis(hydroxyethyl) animal fatty amine and its carboxylic acid ester, which is used for rust prevention of polyol esters.

[0006] In addition, due to competitive adsorption between each other, many rust inhibitors will have an adverse effect on the performance of extreme pressure anti-wear agents. Therefore, special attention should be paid to the compounding between rust inhibitors and extreme pressure anti-wear agents. However, there is currently a lack of rust inhibitors that can work well with extreme pressure anti-wear agents. Summary of the invention

[0007] In order to solve the above technical problems, the purpose of the present invention is to provide an ashless rust inhibitor and a preparation method thereof, wherein the ashless rust inhibitor has excellent rust prevention performance and has a good synergistic effect with an extreme pressure anti-wear agent.

[0008] To achieve the above object, the present invention first provides a method for preparing an ashless rust inhibitor, which comprises the following steps:

[0009] In a nonpolar solvent, dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid are mixed to obtain a mixed acid A;

[0010] The polyene polyamine and the mixed acid A are mixed in a molar ratio of 0.5-2.0:1, and deionized water and methanol are added to react until the pH value of the solution is neutral;

[0011] Methyl methacrylate and base oil are added to the system after the reaction, and the temperature is raised for distillation, and then the reduced pressure distillation is performed until no obvious distillate is produced, thereby obtaining the ashless rust inhibitor.

[0012] In the above preparation method, preferably, the molar ratio of dinonylnaphthalenesulfonic acid to dodecenylsuccinic acid is 1:4-4:1.

[0013] In the above preparation method, when calculating the molar ratio of polyene polyamine to mixed acid A, the molar amount of mixed acid A is based on the sum of the molar amounts of dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid.

[0014] In the above preparation method, preferably, the non-polar solvent includes one or a combination of two or more of n-heptane, dioxane, and toluene.

[0015] In the above preparation method, preferably, the polyene polyamine includes one or a combination of two or more of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

[0016] In the above preparation method, preferably, the molar ratio of the deionized water to the polyene polyamine is 0.5-1.5:1.

[0017] In the above preparation method, preferably, the molar ratio of methanol to polyene polyamine is 1.0-2.0: 1. The present invention attempts to replace methanol with anhydrous ethanol and n-butanol, but the desired effect of the present invention cannot be obtained.

[0018] In the above preparation method, preferably, the reaction after adding deionized water and methanol is carried out at a temperature of 70±5°C.

[0019] In the above preparation method, preferably, the molar ratio of methyl methacrylate to polyene polyamine is 0.05-0.15:1.

[0020] In the above preparation method, preferably, the base oil is added in an amount such that the ratio of the total mass of the mixed acid A and the polyene polyamine to the mass of the base oil is 40:60-70:30.

[0021] In the above preparation method, preferably, the base oil includes one or a combination of two or more of industrial white oil, mineral oil, hydrogenated oil, and PAO base oil.

[0022] In the above preparation method, preferably, the temperature of the temperature-raising distillation is 145±5°C.

[0023] In the above preparation method, preferably, the temperature-raising distillation is carried out until no obvious fraction is distilled out, at which point most of the non-polar solvent and its azeotrope with water are replaced by the base oil.

[0024] In the above preparation method, preferably, the pressure of the reduced pressure distillation is 2±1 kPa.

[0025] According to a specific embodiment of the present invention, preferably, the above-mentioned preparation method can be carried out according to the following specific steps: in a non-polar solvent, dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid are mixed in a molar ratio of 0.5-2.0:1 to obtain a mixed acid A; further, polyene polyamine is mixed with the mixed acid A in a molar ratio of 0.5-2.0:1, a small amount of deionized water and methanol are added, and the mixture is reacted at 70±5°C until the pH value of the solution is neutral; a small amount of methyl methacrylate and an appropriate amount of base oil are added to the system, and the temperature is raised to 145±5°C for distillation until most of the solvent and its azeotrope with water are replaced by the base oil; and then the ash-free rust inhibitor according to the present invention is obtained by reduced pressure distillation at 2±1kPa until no obvious distillate is produced.

[0026] The invention also provides an ashless rust inhibitor, which is prepared by the above preparation method.

[0027] The present invention also provides an oil product, wherein the oil product contains more than 0.02wt% of an ashless rust inhibitor and 0.01-0.03% of an extreme pressure anti-wear agent; the ashless rust inhibitor is the above-mentioned ashless rust inhibitor provided by the present invention.

[0028] The prior art does not involve an ashless rust inhibitor of a mixed acid amine of dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid.

[0029] The ashless rust inhibitor of the present invention is a single agent, the anion part of which is a mixed acid of dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid, and the cation part is polyene polyamine. The ashless rust inhibitor of the present invention integrates the advantages of dinonylnaphthalenesulfonic acid group and dodecenylsuccinic acid group at the molecular level, has better rust resistance, and has good synergistic effect with extreme pressure anti-wear agent. The present invention is characterized in that the reaction conditions are mild, the amination reaction is gel-free, the polyene polyamine can fully participate in the reaction, and no post-treatment is required, thereby achieving a 100% yield. DETAILED DESCRIPTION

[0030] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0031] Example 1

[0032] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0033] Add 57 g of n-heptane to a 250 ml three-necked flask equipped with a reflux condenser, add 37 g of dinonylnaphthalenesulfonic acid and 5.7 g of dodecenylsuccinic acid to the flask, and start stirring;

[0034] 14.6 g of triethylenetetramine was slowly added dropwise to the flask and the addition was completed within 10 minutes;

[0035] Then 3.2 g of methanol and 2.7 g of deionized water were added to the flask;

[0036] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0037] Then, 1.0 g of methyl methacrylate and 57 g of mineral base oil 150SN 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;

[0038] Finally, the product was distilled under reduced pressure at 2±1 kPa until no obvious distillate was produced, thereby obtaining the ashless rust inhibitor AAR-1.

[0039] Example 2

[0040] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0041] Add 42 g of toluene to a 250 ml three-necked flask equipped with a reflux condenser, add 9.2 g of dinonylnaphthalenesulfonic acid and 22.7 g of dodecenylsuccinic acid to the flask, and start stirring;

[0042] 9.5 g of tetraethylenepentamine was slowly added dropwise to the flask and the addition was completed within 10 minutes;

[0043] Then 1.6 g of methanol and 1.4 g of deionized water were added to the flask;

[0044] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0045] 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;

[0046] Finally, the product was distilled under reduced pressure at 2±1 kPa until no obvious distillate was produced, thereby obtaining the ashless rust inhibitor AAR-1.

[0047] Example 3

[0048] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0049] Add 58 g of dioxane to a 250 ml three-necked flask equipped with a reflux condenser, add 23 g of dinonylnaphthalenesulfonic acid and 14 g of dodecenylsuccinic acid to the flask, and start stirring;

[0050] 21 g of diethylenetriamine was slowly added dropwise to the flask and the addition was completed within 10 minutes;

[0051] Then, 6.4 g of methanol and 5.4 g of deionized water were added to the flask;

[0052] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0053] Then, 2 g of methyl methacrylate and 86 g of hydrogenated base oil 150N 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;

[0054] Finally, the product was distilled under reduced pressure at 2±1 kPa until no obvious distillate was produced, thereby obtaining the ashless rust inhibitor AAR-3.

[0055] Example 4

[0056] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0057] Add 56 g of n-heptane to a 250 ml three-necked flask equipped with a reflux condenser, add 27.6 g of dinonylnaphthalenesulfonic acid and 11.4 g of dodecenylsuccinic acid to the flask, and start stirring;

[0058] 16.7 g of a mixture of triethylenetetramine and tetraethylenepentamine was slowly added dropwise to the flask. The addition was completed within 10 minutes.

[0059] Then 3.2 g of methanol and 2.7 g of deionized water were added to the flask;

[0060] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0061] Then, 1 g of methyl methacrylate and 56 g of hydrogenated base oil Yubase 4 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;

[0062] Finally, the product was distilled under reduced pressure at 2±1 kPa until no obvious distillate was produced, thereby obtaining the ashless rust inhibitor AAR-4.

[0063] Example 5

[0064] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0065] Add 48 g of dioxane to a 250 ml three-necked flask equipped with a reflux condenser, add 18.4 g of dinonylnaphthalenesulfonic acid and 17.0 g of dodecenylsuccinic acid to the flask, and start stirring;

[0066] A mixture of 12.5 g of triethylenetetramine and diethylenetriamine was slowly added dropwise to the flask. The addition was completed within 10 minutes.

[0067] Then 3.2 g of methanol and 2.7 g of deionized water were added to the flask;

[0068] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0069] Then, 1 g of methyl methacrylate and 21 g of industrial white oil W1-100 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;

[0070] Finally, the product was distilled under reduced pressure at 2±1 kPa until no obvious distillate was produced, thereby obtaining the ashless rust inhibitor AAR-5.

[0071] Example 6

[0072] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0073] Add 52 g of toluene to a 250 ml three-necked flask equipped with a reflux condenser, add 23 g of dinonylnaphthalenesulfonic acid and 14.2 g of dodecenylsuccinic acid to the flask, and start stirring;

[0074] 14.6 g of a mixture of diethylenetriamine, triethylenetetramine and tetraethylenepentamine was slowly added dropwise to the flask. The addition was completed within 10 minutes.

[0075] Then 3.2 g of methanol and 2.7 g of deionized water were added to the flask;

[0076] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0077] Then, 1 g of methyl methacrylate and 35 g of Hengli 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;

[0078] Finally, the product was distilled under reduced pressure at 2±1 kPa until no obvious distillate was produced, thereby obtaining the ashless rust inhibitor AAR-6.

[0079] Comparative Example 1

[0080] This comparative example provides a method for preparing an ashless rust inhibitor. The specific steps are the same as those in Example 1, except that stearic acid is used, and the obtained ashless rust inhibitor is AAR-a.

[0081] Comparative Example 2

[0082] This comparative example provides a method for preparing an ashless rust inhibitor. The specific steps are the same as those in Example 1, except that oleic acid is used, and the obtained ashless rust inhibitor is AAR-b.

[0083] Test example:

[0084] The test oil was blended according to the blending scheme in Table 1, and the liquid phase corrosion performance of the ashless rust inhibitor AAR-1 and its effect on extreme pressure and anti-wear properties were tested. The results are shown in Table 1.

[0085] Table 1 Performance evaluation of ashless rust inhibitor

[0086]

[0087] Among them: the manufacturer of extreme pressure anti-wear agent IR353 is BASF;

[0088] Liquid phase corrosion (B method) is carried out in accordance with ASTM D665B;

[0089] The wear scar diameter was tested according to ASTM D4172.

[0090] As can be seen from Table 1, AAR-1 has excellent anti-rust performance, and only 0.02% of the dosage is required to achieve qualified liquid phase corrosion, and it has a very good synergistic effect with the extreme pressure anti-wear agent, so that the extreme pressure anti-wear agent exhibits excellent extreme pressure anti-wear performance at a very low dosage. For the commercially available product (IRGACOR L844 of BASF), 0.03% of the dosage is required to meet the liquid phase corrosion requirements, and it will have a negative impact on the extreme pressure anti-wear performance. It is necessary to add 0.03% of the extreme pressure anti-wear agent to achieve the performance level of AAR-1.

[0091] Using stearic acid or oleic acid instead of dodecenylsuccinic acid and dinonylnaphthalenesulfonic acid for compounding cannot obtain qualified antirust performance.

[0092] The ashless rust inhibitors of Examples 2 to 6 were evaluated using the same evaluation scheme, and similar results were obtained, indicating that the ashless rust inhibitor of the present invention has excellent antirust performance, has very good synergy with the extreme pressure antiwear agent, and can significantly reduce the dosage of the extreme pressure antiwear agent.

[0093] The above are typical embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the principles of the present invention should be within the protection scope of the present invention.

Claims

1. A method for preparing an ashless rust inhibitor, comprising the following steps: In a nonpolar solvent, dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid are mixed to obtain a mixed acid A; The polyene polyamine and the mixed acid A are mixed in a molar ratio of 0.5-2.0:1, and deionized water and methanol are added to react until the pH value of the solution is neutral; Methyl methacrylate and base oil are added to the system after the reaction, and the temperature is raised for distillation, and then the reduced pressure distillation is performed until no obvious distillate is produced, thereby obtaining the ashless rust inhibitor.

2. The preparation method according to claim 1, wherein The molar ratio of the dinonylnaphthalenesulfonic acid to dodecenylsuccinic acid is 1:4-4:

1.

3. The preparation method according to claim 1, wherein The non-polar solvent includes one or a combination of two or more of n-heptane, dioxane and toluene.

4. The preparation method according to claim 1, wherein The polyene polyamine includes one or a combination of two or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

5. The preparation method according to claim 1, wherein The molar ratio of the deionized water to the polyene polyamine is 0.5-1.5:

1.

6. The preparation method according to claim 1, wherein The molar ratio of the methanol to the polyene polyamine is 1.0-2.0:

1.

7. The preparation method according to claim 1, wherein The reaction after adding deionized water and methanol was carried out at a temperature of 70±5°C.

8. The preparation method according to claim 1, wherein The molar ratio of methyl methacrylate to polyene polyamine is 0.05-0.15:

1.

9. The preparation method according to claim 1, wherein The addition amount of the base oil is: the ratio of the total mass of the mixed acid and the polyene polyamine to the mass of the base oil is 40:60-70:

30.

10. The preparation method according to claim 1 or 9, wherein: The base oil includes one or a combination of two or more of industrial white oil, mineral oil, hydrogenated oil, and PAO base oil.

11. The preparation method according to claim 1, wherein: The temperature of the distillation is 145±5°C.

12. The preparation method according to claim 1 or 11, wherein: The temperature-raising distillation is carried out until no obvious fraction is distilled out.

13. The preparation method according to claim 1, wherein: The pressure of the reduced pressure distillation is 2±1 kPa.

14. An ashless rust inhibitor prepared by the preparation method according to any one of claims 1 to 13.

15. An oil product, wherein: The oil product contains more than 0.02wt% of ashless rust inhibitor and 0.01-0.03% of extreme pressure anti-wear agent; The ashless rust inhibitor is the ashless rust inhibitor according to claim 14.

Images