A non-ash rust inhibitor and its preparation method

Abstract

The present invention provides an ashless rust inhibitor and a preparation method thereof. The preparation method comprises the following steps: in a non-polar solvent, dinonylnaphthalene sulfonic acid and dodecenyl succinic acid are mixed to obtain a mixed acid A; polyalkenepolyamine and the mixed acid A are mixed in a molar ratio of 0.5-2.0:1, deionized water and methanol are added for reaction until the pH value of the solution is neutral; methyl methacrylate and base oil are added to the reaction system, the temperature is raised for distillation, and then vacuum distillation is carried out until no obvious distillate is produced, thus obtaining the ashless rust inhibitor. The present invention also provides an ashless rust inhibitor prepared by the above method. The ashless rust inhibitor of the present invention integrates the advantages of dinonylnaphthalene sulfonic acid groups and dodecenyl succinic acid groups at the molecular level, has better rust prevention performance, and moreover, the ashless rust inhibitor has a good synergistic effect with extreme pressure and anti-wear agents.

Description

Technical Field

[0001] The present invention relates to a non - ash rust inhibitor and its preparation method, belonging to the technical field of rust inhibitor preparation. Background Art

[0002] To meet the requirements of harsh working conditions, extreme pressure and anti - wear agents containing active sulfur components are generally added to industrial oils. The introduction of active sulfur elements will corrode copper and steel components in the system. Moreover, since water will inevitably enter the oil during the working process, it will exacerbate the rusting of steel components. Therefore, in order to better protect mechanical components, a certain amount of rust inhibitor needs to be added to the oil.

[0003] In addition, as the precision of components is getting higher and higher, the requirement for the filterability of oils is also getting higher and higher. And ash - forming additives containing metal ions will affect the filterability of oils. Therefore, a non - ash rust inhibitor needs to be added to the oil. Currently, commonly used oil - soluble non - ash rust inhibitors include organic carboxylic acids / esters, organic amines and nitrogen - containing compounds, and heterocyclic compounds.

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

[0005] Patent US4165292 discloses the preparation of an alkyl succinic acid amide non - ash rust inhibitor for rust prevention of lubricating oils. Patent US5275749 discloses an acylated aspartic acid derivative non - ash rust inhibitor. Patent US5254277 discloses a non - ash rust inhibitor of bis(hydroxyethyl) animal fat amine and its carboxylic acid ester for rust prevention of polyol esters.

[0006] In addition, due to competitive adsorption among them, many rust inhibitors will have an adverse effect on the performance of extreme pressure and anti - wear agents. Therefore, special attention needs to be paid to the compounding of rust inhibitors and extreme pressure and anti - wear agents. However, there is currently a lack of rust inhibitors that can achieve good cooperation with extreme pressure and anti - wear agents. Summary of the Invention

[0007] To solve the above - mentioned technical problems, the purpose of the present invention is to provide a non - ash rust inhibitor and its preparation method. This non - ash rust inhibitor not only has excellent rust - proof performance but also has good synergistic effects with extreme pressure and anti - wear agents.

[0008] To achieve the above - mentioned purpose, the present invention first provides a preparation method of a non - ash rust inhibitor, which includes the following steps:

[0009] In a non-polar solvent, dinonylnaphthalene sulfonic acid and dodecenyl succinic acid are mixed to obtain mixed acid A;

[0010] Polyethylenepolyamine and mixed acid A are mixed at a molar ratio of 0.5 - 2.0:1, and deionized water and methanol are added for reaction until the pH value of the solution is neutral;

[0011] Methyl methacrylate and base oil are added to the reacted system, heated for distillation, and then vacuum distilled until no obvious distillate is produced, thus obtaining the ashless rust inhibitor.

[0012] In the above preparation method, preferably, the molar ratio of dinonylnaphthalene sulfonic acid to dodecenyl succinic acid is 1:4 - 4:1.

[0013] In the above preparation method, when calculating the molar ratio of polyethylenepolyamine to mixed acid A, the molar amount of mixed acid A is based on the sum of the molar amounts of dinonylnaphthalene sulfonic acid and dodecenyl succinic 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 polyethylenepolyamine 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 deionized water to polyethylenepolyamine is 0.5 - 1.5:1.

[0017] In the above preparation method, preferably, the molar ratio of methanol to polyethylenepolyamine is 1.0 - 2.0:1. In the present invention, attempts to replace methanol with absolute ethanol or n-butanol cannot achieve the effects required by the present invention.

[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 polyethylenepolyamine is 0.05 - 0.15:1.

[0020] In the above preparation method, preferably, the addition amount of the base oil is such that the ratio of the total mass of mixed acid A and polyethylenepolyamine 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 distillate distills out. At this time, 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 vacuum distillation is 2 ± 1 kPa.

[0025] According to a specific embodiment of the present invention, preferably, the above 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, polyenepolyamine and 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 reaction is carried out 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; then, vacuum distillation is carried out at 2 ± 1 kPa until no obvious distillate is produced, and the ashless rust inhibitor of the present invention is obtained.

[0026] The present 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 0.02 wt% of the ashless rust inhibitor and 0.01 - 0.03% of an extreme pressure and anti-wear agent; the ashless rust inhibitor is the above ashless rust inhibitor provided by the present invention.

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

[0029] The ashless rust inhibitor of the present invention is a single agent, the anionic part of which is a mixed acid of dinonylnaphthalenesulfonic acid and dodecenylsuccinic acid, and the cationic part is polyenepolyamine. The ashless rust inhibitor of the present invention integrates the advantages of dinonylnaphthalenesulfonic acid groups and dodecenylsuccinic acid groups at the molecular level, has better rust prevention performance, and moreover, the ashless rust inhibitor has a good synergistic effect with the extreme pressure and anti-wear agent. The characteristics of the present invention are that the reaction conditions are mild, there is no gel in the amination reaction, polyenepolyamine can participate in the reaction completely, and no post-treatment is required, thereby achieving a 100% yield. Specific Embodiments

[0030] In order to have a clearer understanding of the technical features, objectives, and beneficial effects of the present invention, the technical solutions of the present invention are described in detail below, but it should not be construed as a limitation on the implementable scope of the present invention.

[0031] Example 1

[0032] This embodiment provides a preparation method of an ashless rust inhibitor, which specifically includes the following steps:

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

[0034] Slowly drop 14.6 g of triethylenetetramine into the flask, and complete the feeding within 10 minutes;

[0035] Subsequently, add 3.2 g of methanol and 2.7 g of deionized water to the flask;

[0036] Slowly heat up to 70 ± 5 °C and react for 1 - 2 hours until the pH value of the solution is neutral;

[0037] Subsequently, add 1.0 g of methyl methacrylate and 57 g of mineral base oil 150SN to the system, and slowly heat up to 145 ± 5 °C for distillation until most of the solvent and its azeotrope with water are replaced by the base oil;

[0038] Finally, carry out vacuum distillation at 2 ± 1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-1 is obtained.

[0039] Example 2

[0040] This embodiment provides a preparation method of an ashless rust inhibitor, which specifically includes the following steps:

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

[0042] Slowly drop 9.5 g of tetraethylenepentamine into the flask, and complete the feeding within 10 minutes;

[0043] Subsequently, add 1.6 g of methanol and 1.4 g of deionized water to the flask;

[0044] Slowly heat up to 70 ± 5 °C and react for 1 - 2 hours until the pH value of the solution is neutral;

[0045] Subsequently, add 0.5 g of methyl methacrylate and 28 g of Liaohe No. 10 base oil to the system, and slowly heat up to 145 ± 5 °C for distillation until most of the solvent and its azeotrope with water are replaced by the base oil;

[0046] Finally, carry out vacuum distillation at 2 ± 1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-1 is obtained.

[0047] Example 3

[0048] This embodiment provides a preparation method of an ashless rust inhibitor, which specifically includes the following steps:

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

[0050] Slowly drop 21 g of diethylenetriamine into the flask, and complete the feeding within 10 minutes;

[0051] Subsequently, add 6.4 g of methanol and 5.4 g of deionized water into the flask;

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

[0053] Subsequently, add 2 g of methyl methacrylate and 86 g of hydrogenated base oil 150N into the system, and slowly raise the temperature to 145 ± 5 °C for distillation until most of the solvent and its azeotrope with water are replaced by the base oil;

[0054] Finally, carry out vacuum distillation at 2 ± 1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-3 is obtained.

[0055] Example 4

[0056] This embodiment provides a preparation method of an ashless rust inhibitor, which specifically includes the following steps:

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

[0058] Slowly drop a mixture of 16.7 g of triethylenetetramine and tetraethylenepentamine into the flask, and complete the feeding within 10 minutes;

[0059] Subsequently, add 3.2 g of methanol and 2.7 g of deionized water into the flask;

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

[0061] Subsequently, add 1 g of methyl methacrylate and 56 g of hydrogenated base oil Yubase 4 into the system, and slowly raise the temperature to 145 ± 5 °C for distillation until most of the solvent and its azeotrope with water are replaced by the base oil;

[0062] Finally, carry out vacuum distillation at 2 ± 1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-4 is obtained.

[0063] Example 5

[0064] This example provides a preparation method of an ashless rust inhibitor, which specifically includes the following steps:

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

[0066] Slowly add a mixture of 12.5 g of triethylenetetramine and diethylenetriamine to the flask, and complete the feeding within 10 minutes;

[0067] Subsequently, add 3.2 g of methanol and 2.7 g of deionized water to the flask;

[0068] Slowly heat up to 70 ± 5 °C and react for 1 - 2 hours until the pH value of the solution is neutral;

[0069] Subsequently, add 1 g of methyl methacrylate and 21 g of industrial white oil W1-100 to the system, and slowly heat up to 145 ± 5 °C for distillation until most of the solvent and its azeotrope with water are replaced by the base oil;

[0070] Finally, perform vacuum distillation at 2 ± 1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-5 is obtained.

[0071] Example 6

[0072] This example provides a preparation method of an ashless rust inhibitor, which specifically includes the following steps:

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

[0074] Slowly add a mixture of 14.6 g of diethylenetriamine, triethylenetetramine and tetraethylenepentamine to the flask, and complete the feeding within 10 minutes;

[0075] Subsequently, add 3.2 g of methanol and 2.7 g of deionized water to the flask;

[0076] Slowly heat up to 70 ± 5 °C and react for 1 - 2 hours until the pH value of the solution is neutral;

[0077] Subsequently, add 1 g of methyl methacrylate and 35 g of Hengli No. 10 base oil to the system, and slowly heat up to 145 ± 5 °C for distillation until most of the solvent and its azeotrope with water are replaced by the base oil;

[0078] Finally, perform vacuum distillation at 2 ± 1 kPa until no obvious distillate is produced, and the ashless rust inhibitor AAR-6 is obtained.

[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 products were blended according to the blending scheme in Table 1, and the liquid-phase rust inhibition performance of the ashless rust inhibitor AAR-1 and its influence on extreme pressure and anti-wear properties were tested. The results are shown in Table 1.

[0085] Table 1 Performance Evaluation of Ashless Rust Inhibitors

[0086]

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

[0088] The liquid-phase rust test (Method B) was carried out in accordance with the provisions of ASTM D665B;

[0089] The wear scar diameter was tested in accordance with the provisions of ASTM D4172.

[0090] It can be seen from Table 1 that AAR-1 has excellent rust inhibition performance. Only a dosage of 0.02% can achieve qualified liquid-phase rust inhibition, and it has a very good synergistic effect with the extreme pressure and anti-wear agent, enabling the extreme pressure and anti-wear agent to exhibit excellent extreme pressure and anti-wear properties at a very low dosage. For the commercially available product (IRGACOR L844 from BASF), a dosage of 0.03% is required for the liquid-phase rust inhibition to be qualified, and it will have a negative impact on the extreme pressure and anti-wear properties. A dosage of 0.03% of the extreme pressure and anti-wear agent needs to be added to reach the performance level of AAR-1.

[0091] Using stearic acid and oleic acid to replace dodecenyl succinic acid and dinonylnaphthalene sulfonic acid for compounding also cannot obtain qualified rust inhibition performance.

[0092] Using the same evaluation scheme to evaluate the ashless rust inhibitors in Examples 2 - 6, similar results can be obtained. It shows that the ashless rust inhibitor of the present invention has excellent rust inhibition performance and very good synergism with the extreme pressure and anti-wear agent, and can significantly reduce the dosage of the extreme pressure and anti-wear agent.

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

Claims

1. A preparation method of an ashless rust inhibitor, which comprises the following steps: In a non-polar solvent, dinonylnaphthalene sulfonic acid and dodecenyl succinic acid are mixed to obtain a mixed acid A; Polyalkylene polyamine and mixed acid A are mixed in a molar ratio of 0.5 - 2.0:1, and deionized water and methanol are added for reaction until the pH value of the solution is neutral; Methyl methacrylate and base oil are added to the reaction system, heated for distillation, and then vacuum distilled until no obvious distillate is produced, thus obtaining the ashless rust inhibitor.

2. The preparation method according to claim 1, wherein, The molar ratio of the dinonylnaphthalene sulfonic acid to the dodecenyl succinic 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 of n-heptane and toluene.

4. The preparation method according to claim 1, wherein, The polyalkylene 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 polyalkylene polyamine is 0.5 - 1.5:

1.

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

1.

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

8. The preparation method according to claim 1, wherein, The molar ratio of the methyl methacrylate to the polyalkylene 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 polyalkylene 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 mineral oil, hydrogenated oil, and PAO base oil.

11. The preparation method according to claim 10, wherein, The mineral oil includes industrial white oil.

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

13. The preparation method according to claim 1 or 12, wherein, The heating distillation is carried out until no obvious fraction is distilled out.

14. The preparation method according to claim 1, wherein, The pressure of the vacuum distillation is 2 ± 1 kPa.

15. An ashless rust inhibitor, which is prepared by the preparation method according to any one of claims 1 - 14.

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

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