Ashless rust inhibitor and preparation method therefor

Abstract

The present invention provides an ashless rust inhibitor and a preparation method therefor. The preparation method comprises the following steps: in a non-polar solvent, mixing dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid to obtain mixed acid A; mixing polyene polyamine and the mixed acid A according to a molar ratio of (0.5-2.0):1, and adding deionized water and methanol for reaction until the pH value of the solution is neutral; and adding methylmethacrylate and base oil into the reacted system, carrying out heating distillation, and then carrying out reduced pressure distillation until no obvious distillate is generated, so as to obtain the ashless rust inhibitor. The present invention further provides an ashless rust inhibitor prepared by the method. The ashless rust inhibitor of the present invention integrates the advantages of a dinonylnaphthalenesulfonic acid group and a dodecenylsuccinic acid group at the molecular level, and has a better rust inhibition effect; in addition, the ashless rust inhibitor has a good synergistic effect with an extreme pressure antiwear agent.

Description

Ashless rust inhibitor and preparation method thereof

[0001] Cross-reference information

[0002] This application claims priority to the Chinese patent application filed with the China Patent Office on July 3, 2023, with application number 202310805380.5 and invention name “A kind of ashless rust inhibitor and its preparation method”, the entire contents of which are incorporated by reference into this application. Technical Field

[0003] The invention relates to an ashless rust preventive and a preparation method thereof, belonging to the technical field of rust preventive preparation. Background Art

[0004] To meet the demands of demanding operating conditions, industrial oils are typically supplemented with extreme pressure anti-wear agents containing active sulfur. The introduction of active sulfur can corrode copper and steel components in the system. Furthermore, because water inevitably enters the oil during operation, it can exacerbate corrosion of steel components. Therefore, to better protect mechanical components, a certain amount of rust inhibitor must be added to the oil.

[0005] Furthermore, as the precision of components increases, the requirements for oil filterability are also becoming increasingly stringent. Ash-containing additives containing metal ions can affect oil filterability, thus necessitating the addition of 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.

[0006] It is well known that compounds containing both carboxylic acid and hydroxyl functional groups can be used as ashless rust inhibitors. For example, US Patent No. 4,409,411 discloses the preparation of an alkyl succinate polyol ester ashless rust inhibitor for rust prevention of fuel oil and lubricating oil; US Patent No. 5,055,230 discloses an ashless rust inhibitor containing hydroxyl, ester and carboxylic acid groups, which can be used in water-based or oil-based products.

[0007] US Patent No. 4165292 discloses the preparation of an ashless rust inhibitor of alkyl succinic acid amine, which is used for rust prevention of lubricating oils. US Patent No. 5275749 discloses an ashless rust inhibitor of an acylated aspartic acid derivative. US Patent No. 5254277 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.

[0008] 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 combination 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.

[0009] Summary of the Invention

[0010] 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.

[0011] To achieve the above object, the present invention first provides a method for preparing an ashless rust inhibitor, which comprises the following steps:

[0012] In a non-polar solvent, dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid are mixed to obtain a mixed acid A;

[0013] Mix polyene polyamine and mixed acid A in a molar ratio of 0.5-2.0:1, add deionized water and methanol to react until the pH value of the solution is neutral;

[0014] Methyl methacrylate and base oil are added to the system after the reaction, and the temperature is increased for distillation, and then the reduced pressure distillation is performed until no obvious distillate is generated, thereby obtaining the ashless rust inhibitor.

[0015] In the above preparation method, preferably, the molar ratio of the dinonylnaphthalenesulfonic acid to dodecenylsuccinic acid is 1:4-4:1.

[0016] 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.

[0017] 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.

[0018] In the above preparation method, preferably, the polyene polyamine includes one or a combination of two or more of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

[0019] In the above preparation method, preferably, the molar ratio of the deionized water to the polyene polyamine is 0.5-1.5:1.

[0020] 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 achieved.

[0021] In the above preparation method, preferably, the reaction after adding deionized water and methanol is carried out at a temperature of 70±5°C.

[0022] In the above preparation method, preferably, the molar ratio of methyl methacrylate to polyene polyamine is 0.05-0.15:1.

[0023] 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.

[0024] 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.

[0025] In the above preparation method, preferably, the temperature of the temperature-raising distillation is 145±5°C.

[0026] 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.

[0027] In the above preparation method, preferably, the pressure of the reduced pressure distillation is 2±1 kPa.

[0028] 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 and the mixed acid A are mixed 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, the temperature is raised to 145±5°C, and distillation is carried out until most of the solvent and its azeotrope with water are replaced by the base oil; then, reduced pressure distillation is carried out at 2±1kPa until no obvious distillate is produced, thereby obtaining the ashless rust inhibitor according to the present invention.

[0029] The present invention also provides an ashless rust inhibitor, which is prepared by the above preparation method.

[0030] 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.

[0031] The prior art does not involve an ashless rust inhibitor of a mixed acid amine of dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid.

[0032] The ashless rust inhibitor of the present invention is a single agent. Its anionic portion is a mixed acid of dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid, and its cationic portion is a polyene polyamine. This ashless rust inhibitor combines the advantages of dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid groups at the molecular level, resulting in improved rust prevention. Furthermore, this ashless rust inhibitor exhibits excellent synergistic effects with extreme pressure and anti-wear agents. The present invention is characterized by mild reaction conditions, a gel-free amination reaction, and the complete participation of the polyene polyamine in the reaction, eliminating the need for post-treatment and achieving 100% utilization. DETAILED DESCRIPTION

[0033] In order to have a clearer understanding of the technical features, objectives 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 understood as limiting the scope of implementation of the present invention.

[0034] Example 1

[0035] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0036] 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;

[0037] 14.6 g of triethylenetetramine was slowly added dropwise to the flask and the addition was completed within 10 minutes;

[0038] Then 3.2 g of methanol and 2.7 g of deionized water were added to the flask;

[0039] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0040] 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;

[0041] Finally, distill under reduced pressure at 2±1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-1 is obtained.

[0042] Example 2

[0043] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0044] 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.

[0045] 9.5 g of tetraethylenepentamine was slowly added dropwise to the flask and the addition was completed within 10 minutes;

[0046] Then 1.6 g of methanol and 1.4 g of deionized water were added to the flask;

[0047] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0048] 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;

[0049] Finally, distill under reduced pressure at 2±1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-1 is obtained.

[0050] Example 3

[0051] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0052] Add 58 g of dioxane to a 250 ml three-necked flask equipped with a reflux condenser, then add 23 g of dinonylnaphthalenesulfonic acid and 14 g of dodecenylsuccinic acid to the flask and start stirring.

[0053] 21 g of diethylenetriamine was slowly added dropwise to the flask and the addition was completed within 10 minutes;

[0054] Then, 6.4 g of methanol and 5.4 g of deionized water were added to the flask;

[0055] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0056] 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;

[0057] Finally, distill under reduced pressure at 2±1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-3 is obtained.

[0058] Example 4

[0059] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0060] 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;

[0061] A mixture of 16.7 g of triethylenetetramine and tetraethylenepentamine was slowly added dropwise to the flask. The addition was completed within 10 minutes.

[0062] Then 3.2 g of methanol and 2.7 g of deionized water were added to the flask;

[0063] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0064] 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;

[0065] Finally, distill under reduced pressure at 2±1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-4 is obtained.

[0066] Example 5

[0067] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0068] To a 250 ml three-necked flask equipped with a reflux condenser, add 48 g of dioxane, 18.4 g of dinonylnaphthalenesulfonic acid, and 17.0 g of dodecenylsuccinic acid, and start stirring.

[0069] A mixture of 12.5 g of triethylenetetramine and diethylenetriamine was slowly added dropwise to the flask. The addition was completed within 10 minutes.

[0070] Then 3.2 g of methanol and 2.7 g of deionized water were added to the flask;

[0071] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0072] 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;

[0073] Finally, distill under reduced pressure at 2±1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-5 is obtained.

[0074] Example 6

[0075] This embodiment provides a method for preparing an ashless rust inhibitor, which specifically comprises the following steps:

[0076] 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.

[0077] A mixture of 14.6 g of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine was slowly added dropwise to the flask. The addition was completed within 10 minutes.

[0078] Then 3.2 g of methanol and 2.7 g of deionized water were added to the flask;

[0079] Slowly raise the temperature to 70±5℃ and react for 1-2 hours until the pH value of the solution is neutral;

[0080] 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;

[0081] Finally, distill under reduced pressure at 2±1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-6 is obtained.

[0082] Comparative Example 1

[0083] 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. The obtained ashless rust inhibitor is AAR-a.

[0084] Comparative Example 2

[0085] 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. The obtained ashless rust inhibitor is AAR-b.

[0086] Test example:

[0087] 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.

[0088] Table 1 Performance evaluation of ashless rust inhibitor

[0089] Among them: the manufacturer of extreme pressure anti-wear agent IR353 is BASF;

[0090] Liquid phase corrosion (B method) is carried out in accordance with ASTM D665B;

[0091] The wear scar diameter was tested according to ASTM D4172.

[0092] As can be seen in Table 1, AAR-1 exhibits excellent rust prevention performance, achieving acceptable liquid phase corrosion resistance at only a 0.02% dosage. It also exhibits a very good synergistic effect with the EPAA, enabling the EPAA to exhibit excellent EPAA performance at very low dosages. In contrast, a commercially available product (BASF's IRGACOR L844) requires a 0.03% dosage to achieve acceptable liquid phase corrosion resistance, negatively impacting EPAA performance. Therefore, 0.03% EPAA is required to achieve the same performance level as AAR-1.

[0093] Using stearic acid or oleic acid instead of dodecenylsuccinic acid and dinonylnaphthalenesulfonic acid for compounding cannot obtain qualified anti-rust performance.

[0094] Similar results were obtained when the ashless rust inhibitors of Examples 2 to 6 were evaluated using the same evaluation protocol, indicating that the ashless rust inhibitor of the present invention has superior rust prevention performance and excellent synergy with the extreme pressure anti-wear agent, significantly reducing the dosage of the extreme pressure anti-wear agent.

[0095] The above are typical embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the principles of the present invention should be within the scope of protection 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, 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 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.

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

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

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

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

16. An ashless rust inhibitor prepared by the preparation method according to any one of claims 1 to 15.

17. 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 16.

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