Ash-free dispersing type antirust agent and preparation method thereof

Abstract

The preparation method mainly comprises the following steps: preparing an imidazoline derivative-free intermediate by taking polyene polyamine and oleic acid as raw materials, dropwise adding the imidazoline derivative intermediate into alkyl-substituted succinic anhydride and xylene as raw materials, and reacting to obtain the ashless dispersing type antirust agent. After the reaction is completed, removing xylene through reduced pressure distillation to obtain the ashless dispersing type antirust agent. The invention further discloses application of the ashless dispersing type antirust agent as an antirust agent in industrial oil products. The ash-free dispersing type antirust agent disclosed by the invention not only keeps excellent antirust performance through modification, but also enhances oil solubility, has oil sludge dispersing performance, and can be widely applied to the fields of lubricating grease, emulsified oil, industrial oil, internal combustion engine oil and the like as a multipurpose additive.

Description

Technical Field

[0001] The invention belongs to the technical field of lubricating oil additives, and in particular relates to an ashless dispersible rust inhibitor. The invention also relates to a preparation method of the ashless dispersible rust inhibitor. Background Art

[0002] Imidazoline and its derivatives are widely used in lubricating grease, emulsified oil, industrial oil and other fields due to their good anti-rust effect. Although imidazoline and its derivatives can be used alone as rust inhibitors, their oil solubility is poor, so they need to be modified by organic carboxylic acids to enhance their oil solubility.

[0003] The Chinese patent "A Rust Inhibitor Composition" (publication number: CN111575088A, application date: 20190219, publication date: 20200825) discloses a rust inhibitor prepared with imidazoline derivatives and organic carboxylic acids as raw materials. Although the rust inhibitor has excellent anti-rust performance, the oil solubility of the rust inhibitor has not been improved because it has not been modified for oil solubility and is simply physically mixed.

[0004] Another effect of chemically modifying imidazoline derivatives is to achieve the versatility of additives. In recent years, a multi-purpose rust inhibitor has appeared on the market, which can meet the protection and use needs of metal products under various conditions. In addition to having good rust prevention performance, this rust inhibitor also has lubrication and other functions. The lubricating and rust-preventing dual-purpose agents that have been developed have been widely used in internal combustion engines and military industries, and the market demand for such rust inhibitors is increasing. Studies have shown that the primary amine in the structure of imidazoline derivatives prepared with polyene polyamines is easy to react with long-chain organic carboxylic acids or anhydrides, and the product structure is similar to polyisobutylene succinimide, and polyisobutylene succinimide-type ashless dispersant is currently the most widely used and most used lubricating oil ashless dispersant. This makes the modified imidazoline derivatives maintain rust prevention performance, improve oil solubility, and also give sludge dispersibility, making it a multi-purpose rust inhibitor. Therefore, it is of great significance to provide an ashless dispersible rust inhibitor with good oil solubility so that it can be widely used as a rust inhibitor in industrial oil products. Summary of the invention

[0005] The object of the present invention is to provide an ashless dispersible rust inhibitor, which has excellent rust prevention performance, good oil solubility and excellent sludge dispersibility.

[0006] Another object of the present invention is to provide a method for preparing an ashless dispersed rust inhibitor.

[0007] The technical solution adopted by the present invention is an ashless dispersible rust inhibitor, the general structural formula of which is shown in formula (2):

[0008]

[0009] In the formula, R1 is Wherein n is 0 to 2; R2 is a C11 to C17 aliphatic hydrocarbon group; and R3 is one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer, and poly-alpha-olefin.

[0010] Another technical solution adopted by the present invention is a method for preparing an ashless dispersible rust inhibitor, which specifically comprises the following steps:

[0011] Step 1, add polyene polyamine into the reactor, start stirring and heat to 110°C to 110°C, add oily acid dropwise for reaction for 1h to 3h, continue to heat to 200°C to 210°C for reaction for 1h to 8h, and obtain the imidazoline derivative intermediate after the reaction is completed;

[0012] Step 2: Add hydrocarbon-substituted succinic anhydride and xylene to another reactor, raise the temperature to 90°C to 110°C, then drop the imidazoline derivative intermediate prepared in step 1 into the reactor under the condition of keeping the temperature at 80°C, the dropping time is 30min to 10min, after the dropping is completed, raise the temperature to 130°C to 110°C and react for 2h to 1h, after the reaction is completed, distill off the xylene to obtain an ash-free dispersed rust inhibitor.

[0013] The present invention is also characterized in that

[0014] In step 1, the molar ratio of oleic acid to polyene polyamine is 0.8-1.05:1.

[0015] In step 2, the mass ratio of xylene to the hydrocarbon-substituted succinic anhydride is 0.9 to 1.25:1.

[0016] In step 2, the ratio of the amount of the hydrocarbon-substituted succinic anhydride to the amount of the imidazoline derivative intermediate is (0.8-1.2):1.

[0017] The polyene polyamine is one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

[0018] The structure of the imidazoline derivative intermediate in step 1 is shown in formula (1):

[0019]

[0020] In the formula, R1 is Wherein n is 0 to 2; R2 is an aliphatic hydrocarbon group of C11 to C17.

[0021] The hydrocarbon group in the hydrocarbon-substituted succinic anhydride is one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer and poly-alpha-olefin.

[0022] The general structural formula of the ashless dispersible rust inhibitor is shown in formula (2):

[0023]

[0024] In the formula, R1 is Wherein n is 0 to 2; R2 is a C11 to C17 aliphatic hydrocarbon group; and R3 is one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer, and poly-alpha-olefin.

[0025] The beneficial effect of the present invention is that, through modification, the ashless dispersible rust inhibitor not only maintains excellent rust prevention performance, but also enhances oil solubility and has sludge dispersibility. As a multi-purpose additive, it can be widely used in the fields of grease, emulsified oil, industrial oil, internal combustion engine oil, etc. DETAILED DESCRIPTION

[0026] The present invention is described in detail below in conjunction with specific implementation modes.

[0027] The present invention discloses an ashless dispersible rust inhibitor, the general structural formula of which is shown in formula (2):

[0028]

[0029] In the formula, R1 is Wherein n is 0 to 2; R2 is a C11 to C17 aliphatic hydrocarbon group; and R3 is one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer, and poly-alpha-olefin.

[0030] The preparation method of the above-mentioned ashless dispersible rust inhibitor comprises the following specific steps:

[0031] Step 1, add polyene polyamine into the reactor, start stirring and heat to 110°C to 110°C, add oil acid dropwise for reaction for 1h to 3h, continue to heat to 200°C to 210°C for reaction for 1h to 8h, and the reaction is completed to obtain an imidazoline derivative intermediate, whose structural formula is shown in formula (1):

[0032]

[0033] In the formula, R1 is Wherein n is 0 to 2; R2 is an aliphatic hydrocarbon group of C11 to C17.

[0034] The molar ratio of oleic acid to polyene polyamine is 0.8-1.05:1, and the polyene polyamine is one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

[0035] Step 2: Add alkyl-substituted succinic anhydride and xylene to another reactor, raise the temperature to 90°C to 110°C, then drop the imidazoline derivative intermediate prepared in step 1 into the reactor under the condition of keeping the temperature at 80°C for 30 to 10 minutes. After the dropwise addition is completed, raise the temperature to 130°C to 110°C and react for 2h to 1h. After the reaction is completed, distill off the xylene to obtain an ashless dispersed rust inhibitor, the structural formula of which is shown in formula (2):

[0036]

[0038] In the formula, R1 is Wherein n is 0 to 2; R2 is a C11 to C17 aliphatic hydrocarbon group; and R3 is one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer, and poly-alpha-olefin.

[0039] The mass ratio of xylene to hydrocarbon-substituted succinic anhydride is 0.9-1.25:1, the amount ratio of hydrocarbon-substituted succinic anhydride to imidazoline derivative intermediate is 0.8-1.2:1, and the hydrocarbon group in the hydrocarbon-substituted succinic anhydride is one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer, and poly-alpha-olefin.

[0040] Preferably, the hydrocarbon group is a polyisobutylene group.

[0041] Preferably, the number average molecular weight of the polyisobutylene group is 900-5000.

[0042] In the above preparation process, the ash-free dispersible rust inhibitor is modified to not only maintain excellent rust prevention performance, but also enhance oil solubility and sludge dispersion performance. As a multi-purpose additive, it can be widely used in grease, emulsified oil, industrial oil, internal combustion engine oil and other fields.

[0043] Example 1

[0044] The preparation method of the ashless dispersible rust inhibitor of the present embodiment specifically comprises the following steps:

[0045] Step 1: Add 111 g of triethylenetetramine into a four-necked jacketed reaction bottle equipped with a mechanical stirrer and a thermometer, start the mechanical stirrer, raise the temperature to 110° C., and dropwise add 282 g of oleic acid to react for 3 h, then continue to raise the temperature to 220° C. to react for 1 h. After the reaction is completed, an imidazoline derivative intermediate can be obtained.

[0046] Step 2: Add 800g of polyisobutylene succinic anhydride with a number average molecular weight of 1000 and 1000g of xylene into another reactor, raise the temperature to 90°C, and then drop the imidazoline derivative intermediate prepared in step 1 into the reactor under the condition of keeping the temperature at 80°C for 30 minutes. After the dropwise addition is completed, raise the temperature to 130°C and react for 1 hour. After the reaction is completed, distill off the xylene to obtain an ashless dispersed rust inhibitor.

[0047] Example 2

[0048] The preparation method of the ashless dispersible rust inhibitor of the present embodiment specifically comprises the following steps:

[0049] Step 1: Add 103 g of diethylenetriamine into a four-necked jacketed reaction bottle equipped with a mechanical stirrer and a thermometer, turn on the mechanical stirrer, heat to 110° C., and dropwise add 282 g of oleic acid to react for 3 h, continue to heat to 220° C. to react for 1 h, and the reaction is completed to obtain an imidazoline derivative intermediate.

[0050] Step 2: Add 1080g of polyisobutylene succinic anhydride with a number average molecular weight of 900 and 1220g of xylene to another reactor, raise the temperature to 100°C, and then drop the imidazoline derivative intermediate prepared in step 1 into the reactor under the condition of keeping the temperature at 80°C for 10 minutes. After the dropwise addition is completed, raise the temperature to 110°C and react for 2 hours. After the reaction is completed, distill off the xylene to obtain an ashless dispersed rust inhibitor.

[0051] Example 3

[0052] The preparation method of the ashless dispersible rust inhibitor of the present embodiment specifically comprises the following steps:

[0053] Step 1: Add 18.9 g of tetraethylenepentamine into a four-necked jacketed reaction bottle equipped with a mechanical stirrer and a thermometer, turn on the mechanical stirrer, raise the temperature to 110° C., and dropwise add 28.2 g of oleic acid to react for 3 h, continue to raise the temperature to 220° C. to react for 1 h, and the reaction is completed to obtain an imidazoline derivative intermediate.

[0054] Step 2: Add 900g of polyisobutylene succinic anhydride with a number average molecular weight of 5000 and 358g of xylene to another reactor, heat it to 110°C, and then drip the imidazoline derivative intermediate prepared in step 1 into the reactor under the condition of keeping the temperature at 80°C for 10 minutes. After the dripping is completed, heat it to 135°C and react for 3 hours. After the reaction is completed, distill off the xylene to obtain an ashless dispersed rust inhibitor.

[0055] Comparative Example 1

[0056] The imidazoline type rust inhibitor was synthesized by the method disclosed in the Chinese patent "A Rust Inhibitor Composition" (publication number: CN201910122398.9, application date: 20190219, publication date: 20200825) and compared with the ashless dispersed rust inhibitor of the present invention.

[0057] In order to further verify the oil solubility and rust prevention performance of the ashless dispersible rust inhibitor of the present invention, the present invention adopts the method of the prior art, that is, the method of Comparative Example 1 to prepare an imidazoline type rust prevention composition, and the performance of the ashless dispersible rust inhibitor prepared in Examples 1 to 3 is tested and compared, as follows:

[0058] The rust inhibitors prepared in Comparative Example 1 and Examples 1 to 3 were added to Class I base oil HVI150, Class II base oil HVIP8, Class III base oil VHVI10 and synthetic ester base oil Kunlun KE3018 at 1% (mass fraction) to examine their solubility, and the results are shown in Table 1. As can be seen from the table, the rust inhibitors prepared in Examples 1 to 3 have good oil solubility in various base oils, while the rust inhibitor prepared in Comparative Example 1 has good solubility in Class I base oil, but poor solubility in hydrogenated base oil and synthetic ester base oil.

[0059] Table 1 Dissolution performance of rust inhibitor

[0060] Base oil Comparative Example 1 Example 1 Example 2 Example 3 HVI150 transparent transparent transparent transparent HVIP8 turbid transparent transparent transparent VHVI10 turbid transparent transparent transparent KE3018 turbid transparent transparent transparent

[0061] T151 and T111 are two succinimide-type ashless dispersants. In order to verify the sludge dispersibility of the ashless dispersible rust inhibitor of the present invention, the low-temperature sludge dispersibility of the rust inhibitors prepared by T151, T111, Comparative Example 1 and Examples 1 to 3 was evaluated.

[0062] Antirust performance: 0.07% (mass fraction) of the rust inhibitors prepared by T151, T111, Comparative Example 1 and Examples 1 to 3 were added to HVI150 base oil, and the antirust performance was examined by liquid phase corrosion (GB / T 11113 (B method)).

[0063] Evaluation of low temperature sludge dispersion performance: 1g of the above additives, 10g of base oil and 9g of sludge were added to a 100mL beaker, heated and stirred at 150℃ for 1.5 hours, and a drop of the above test oil was dropped on the filter paper while hot, and placed in an oven at 80℃ for 2 hours to measure the ratio of the diffusion circle to the oil circle to obtain the spot test data. The higher the spot dispersion value, the better the dispersibility of the low temperature sludge.

[0064] Table 2 Antirust performance and sludge dispersion performance

[0065]

[0066] As can be seen from Table 2, T151 and T111 have poor antirust performance, and Comparative Example 1 has poor sludge dispersibility. The ashless dispersible rust inhibitor of the present invention has the same antirust performance as Comparative Example 1, and low-temperature sludge dispersibility comparable to that of commercially available T151 and T111, and combines the performance characteristics of the rust inhibitor and the ashless dispersant. This shows that the ashless dispersible rust inhibitor still maintains excellent antirust performance after being modified with long-chain succinic anhydride, while improving oil solubility so that it can be dissolved in hydrogenated base oil. At the same time, it gives the product excellent sludge dispersibility.

Claims

1. Ashless dispersible rust inhibitor, characterized in that: Its general structural formula is shown in formula (2): In the formula, R1 is Wherein n is 0 to 2; R2 is a C11 to C17 aliphatic hydrocarbon group; and R3 is one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer, and poly-alpha-olefin.

2. A method for preparing an ashless dispersible rust inhibitor, characterized in that: Specifically include the following steps: Step 1, add polyene polyamine into the reactor, start stirring and heat to 110°C to 110°C, add oily acid dropwise for reaction for 1h to 3h, continue to heat to 200°C to 210°C for reaction for 1h to 8h, and obtain the imidazoline derivative intermediate after the reaction is completed; Step 2: Add hydrocarbon-substituted succinic anhydride and xylene to another reactor, raise the temperature to 90°C to 110°C, then drop the imidazoline derivative intermediate prepared in step 1 into the reactor under the condition of keeping the temperature at 80°C, the dropping time is 30min to 10min, after the dropping is completed, raise the temperature to 130°C to 110°C and react for 2h to 1h, after the reaction is completed, distill and remove xylene to obtain an ash-free dispersed rust inhibitor.

3. The method for preparing the ashless dispersible rust inhibitor according to claim 2, characterized in that: The molar ratio of oleic acid to polyene polyamine in step 1 is 0.8-1.05:

1.

4. The method for preparing the ashless dispersible rust inhibitor according to claim 2, characterized in that: In step 2, the mass ratio of xylene to the hydrocarbyl-substituted succinic anhydride is 0.9 to 1.25:1; The amount ratio of the hydrocarbon-substituted succinic anhydride to the imidazoline derivative intermediate substance is 0.8-1.2:

1.

5. The method for preparing the ashless dispersible rust inhibitor according to claim 2, characterized in that: The polyene polyamine is one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

6. The method for preparing the ashless dispersible rust inhibitor according to claim 2, characterized in that: The structure of the imidazoline derivative intermediate described in step 1 is shown in formula (1): In the formula, R1 is Wherein n is 0 to 2; R2 is an aliphatic hydrocarbon group of C11 to C17.

7. The method for preparing the ashless dispersible rust inhibitor according to claim 2, characterized in that: The hydrocarbon group of the hydrocarbon-substituted succinic anhydride in step 2 is one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer, and poly-alpha-olefin.

8. The method for preparing the ashless dispersible rust inhibitor according to claim 2, characterized in that: The structural formula of the ashless dispersible rust inhibitor is shown in formula (2): In the formula, R1 is Wherein n is 0 to 2; R2 is a C11 to C17 aliphatic hydrocarbon group; and R3 is one of polypropylene, polyethylene, polystyrene, polyisobutylene, ethylene-propylene copolymer, and poly-alpha-olefin.

Images