Engine protective agent as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of automobiles, and particularly relates to an engine protective agent and a preparation method and application thereof. The invention provides an engine protective agent, which comprises the following components by mass: 4-6% of a viscosity index improver; 5%-20% of a detergent; 5%-20% of a dispersant; 1%-3% of an antioxidant; 10%-50% of a friction reducing agent; the balance of saturated polyol ester base oil; the detergent comprises magnesium alkyl salicylate and calcium sulfonate; the antifriction agent comprises liquid organic molybdenum and nano rare earth lanthanum boride. The engine protective agent provided by the invention has excellent antifriction and noise reduction performance, also has good cleaning and dispersing performance, and can greatly improve the fuel economy of vehicles and reduce the formation of oil sludge and carbon deposition.

Description

Technical Field

[0001] The invention belongs to the technical field of automobile technology, and specifically relates to an engine protective agent and a preparation method and application thereof. Background Art

[0002] In recent years, new energy vehicles have developed explosively around the world, especially in China. With the rapid growth of new energy vehicles, many automakers around the world have announced that they will stop researching and redeveloping fuel engines, which has affected major additive companies to slow down the in-depth redevelopment of fuel engine oil additives. However, the current market for fuel engine vehicles is huge. With the increase in the age of fuel vehicles and the new fuel economy requirements, stricter requirements are put forward for engine friction and noise reduction. However, the engine protective agents currently on the market have many problems such as uneven quality, imperfect formulation system, poor friction and noise reduction performance, etc., which cannot meet the requirements. Summary of the invention

[0003] In order to solve the problems existing in the prior art, the present invention provides an engine protective agent and a preparation method and application thereof. The engine protective agent provided by the present invention has excellent friction reduction and noise reduction performance, and at the same time, the engine protective agent provided by the present invention also has good cleaning and dispersing performance, and can greatly improve the fuel economy of the vehicle and reduce the formation of sludge and carbon deposits.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides an engine protective agent, which comprises the following components in terms of mass percentage:

[0006]

[0007] The balance is saturated polyol ester base oil;

[0008] The detergent includes magnesium alkyl salicylate and calcium sulfonate;

[0009] The friction reducer comprises liquid organic molybdenum and nanometer boride rare earth lanthanum.

[0010] Preferably, the viscosity index improver is polymethacrylate; the polymethacrylate is a polymethacrylate with a star-shaped block structure.

[0011] Preferably, the mass ratio of magnesium alkyl salicylate to calcium sulfonate in the detergent is (2.0-3.0):1.

[0012] Preferably, the dispersant is boronated polyisobutylene succinimide.

[0013] Preferably, the antioxidant is an ester-type hindered phenol.

[0014] Preferably, the mass ratio of liquid organic molybdenum to nano-boride rare earth lanthanum in the friction reducer is (2.0-3.5):1.

[0015] Preferably, the saturated polyol ester base oil is trimethylolpropane ester.

[0016] The present invention also provides a method for preparing the engine protective agent described in the above technical solution, comprising the following steps:

[0017] The viscosity index improver, the detergent, the dispersant and the saturated polyol ester base oil are first mixed to obtain a base fluid;

[0018] The base fluid is sequentially mixed with an antioxidant and a friction reducer to obtain the engine protective agent.

[0019] Preferably, the first mixing method is stirring and mixing; the stirring and mixing temperature is 55 to 65° C.; the stirring and mixing time is 20 to 30 minutes;

[0020] The second mixing method is stirring and mixing; the stirring and mixing temperature is 60-70° C.; and the stirring and mixing time is 30 minutes.

[0021] The present invention also provides the use of the engine protective agent described in the above technical solution or the engine protective agent prepared by the preparation method in automobile engines.

[0022] The present invention provides an engine protective agent, which comprises the following components in mass percentage: 4% to 6% viscosity index improver; 5% to 20% detergent; 5% to 20% dispersant; 1% to 3% antioxidant; 10% to 50% friction reducer; the balance is saturated polyol ester base oil; the detergent comprises magnesium alkyl salicylate and calcium sulfonate; the friction reducer comprises liquid organic molybdenum and nano-boronated rare earth lanthanum. In the present invention, the detergent adopts a calcium-magnesium compound system, which can effectively reduce the occurrence of low-speed pre-ignition (LSPI). In the present invention, the friction reducer is a compound of liquid organic molybdenum and nano-boronated rare earth lanthanum friction reducer, which can form an effective and lasting protective film on the surface of the friction pair, and can obtain a long-term low friction force and friction coefficient, thereby achieving long-term protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a test result diagram of the liquid phase corrosion test of the steel rod in the engine protective agent of Example 1;

[0024] Figure 2 This is a test result diagram of the liquid phase corrosion test of the steel rod in the engine protective agent of Example 2;

[0025] Figure 3This is a test result diagram of the liquid phase corrosion test of the steel rod in the engine protective agent of Example 3;

[0026] Figure 4 This is a graph showing the corrosion test results of a copper sheet in the engine protective agent of Example 1;

[0027] Figure 5 This is a graph showing the corrosion test results of a copper sheet in the engine protective agent of Example 2;

[0028] Figure 6 This is a graph showing the corrosion test results of a copper sheet in the engine protective agent of Example 3;

[0029] Figure 7 This is a graph showing the test result of the crankcase high temperature gelling tendency of the aluminum plate in the engine protective agent of Example 1;

[0030] Figure 8 This is a graph showing the test result of the crankcase high temperature gelling tendency of the aluminum plate in the engine protective agent of Example 2;

[0031] Fig. 9 This is a graph showing the test result of the crankcase high temperature gelling tendency of the aluminum plate in the engine protective agent of Example 3;

[0032] Fig.10 The friction coefficient test diagram of the sample in Huizhou 150N and the sample in Huizhou 150N with the engine protective agents of Examples 1 to 3 added respectively;

[0033] Fig.11 The friction force test diagrams of the sample in Huizhou 150N and the sample in Huizhou 150N with the engine protective agents of Examples 1 to 3 added respectively;

[0034] Fig.12 is the average wear spot diameter of the sample after the anti-wear test in Huizhou 150N;

[0035] Fig.13 is the average wear spot diameter of the sample after the anti-wear test in Huizhou 150N with the engine protective agent of Example 1 added;

[0036] Fig.14 is the average wear spot diameter of the sample after the anti-wear test in Huizhou 150N with the engine protective agent of Example 2 added;

[0037] Fig.15 is the average wear spot diameter of the sample after the anti-wear test in Huizhou 150N with the engine protective agent of Example 3 added;

[0038] Fig.16 This is a comparison chart of the average wear spot diameters of Huizhou 150N and samples added with Examples 1 to 3. DETAILED DESCRIPTION

[0039] The present invention provides an engine protective agent, which comprises the following components in terms of mass percentage:

[0040]

[0041] The balance is saturated polyol ester base oil;

[0042] The detergent includes magnesium alkyl salicylate and calcium sulfonate;

[0043] The friction reducer comprises liquid organic molybdenum and nanometer boride rare earth lanthanum.

[0044] In the present invention, the engine protective agent includes 4% to 6% of viscosity index improver by mass percentage, preferably 5%. In the present invention, the viscosity index improver is preferably polymethacrylate; the polymethacrylate is preferably a star-shaped block structure polymethacrylate, specifically preferably TK-chem V6601 provided by Dalian Xinyi Industry New Materials Development Co., Ltd., which can be obtained by controlled free radical polymerization technology.

[0045] In the present invention, the engine protective agent includes 5% to 20% detergent in mass percentage, more preferably 10% to 15%. In the present invention, the detergent includes magnesium alkyl salicylate and calcium sulfonate; in the present invention, the magnesium alkyl salicylate is preferably high base number magnesium alkyl salicylate RHY 109 produced by Lanzhou Lubricant Research and Development Center; the calcium sulfonate is preferably medium base number synthetic calcium sulfonate RF 1105 produced by Ruifeng New Materials. In the present invention, the mass ratio of magnesium alkyl salicylate to calcium sulfonate is preferably (2.0 to 3.0):1, more preferably 2.5:1. In the present invention, the detergent is selected from magnesium alkyl salicylate and calcium sulfonate, which can effectively control low-speed pre-ignition.

[0046] In the present invention, the engine protective agent includes 5% to 20% dispersant, preferably 10% to 15%, by mass percentage. In the present invention, the dispersant is preferably boronized polyisobutylene succinimide. In the present invention, the boronized polyisobutylene succinimide is specifically preferably KT 1961B produced by Jinzhou Kangtai Co., Ltd. In the present invention, the boronized polyisobutylene succinimide is an ashless dispersant obtained by boronization process.

[0047] In the present invention, the engine protective agent includes 1% to 3% antioxidant by mass percentage, preferably 2%. In the present invention, the antioxidant is preferably ester-type hindered phenol, and the ester-type hindered phenol is specifically preferably Vanlube BHC produced by Vanderbilt.

[0048] In the present invention, the antioxidant is preferably an ashless additive, which has significant antioxidant properties, does not crystallize at low temperatures and is not easily volatile, and has good compatibility with additives such as molybdenum compounds.

[0049] In the present invention, the engine protective agent includes 10% to 50% of friction reducer, preferably 20% to 40% by mass. In the present invention, the friction reducer includes liquid organic molybdenum and nano-boronized rare earth lanthanum; the liquid organic molybdenum is preferably dialkyl dithiophosphate molybdenum, specifically preferably dialkyl dithiophosphate molybdenum produced by Pacific Union (Beijing) Petrochemical Co., Ltd., code-named POUPCC 1001. In the present invention, the nano-boronized rare earth lanthanum is preferably SK3115 produced by Qingdao Suofurun. In the present invention, the mass ratio of the liquid organic molybdenum to the nano-boronized rare earth lanthanum is preferably (2.0 to 3.5):1, more preferably 3:1.

[0050] In the present invention, the nano rare earth lanthanum easily forms a high melting point compound with the oxygen element in the organic molybdenum, promotes the diffusion and enrichment of the oxygen element to the friction interface, and improves the forming ability, compactness and continuity of the lubricating film. At the same time, the liquid organic molybdenum molecule contains some polar atoms, such as S, P, O. These highly active components are affected by the metal surface energy and can have affinity with the metal surface and firmly adsorb on the metal surface, thereby quickly forming a layer of semi-chemical and semi-physical adsorption film on the metal surface. However, as the load pressure and temperature of the friction pair surface gradually increase, when the adsorption oil film on its surface cannot meet the requirements, the polar molecules will rapidly undergo a series of complex chemical reactions under the specific environment of friction (i.e., under the effects of high temperature, high pressure and catalysis), forming a chemical adsorption film composed of substances such as MoS2, FePO2, FeS, and FeO (engine pistons and cylinder sleeves will have Fe elements, and the elements such as Mo, S, P, and O in the protective agent at high temperatures will form compounds with the Fe element, thereby forming a protective film on its surface), thereby avoiding friction on the metal surface. In addition, in the liquid organic molybdenum molecules, the organic groups and the molecules of the base oil will produce a synergistic effect during the friction reaction process, which can enhance the oxidation stability of the base oil and extend the service life of the oil.

[0051] In the present invention, the engine protective agent, by mass percentage, comprises a balance of saturated polyol ester base oil, the saturated polyol ester base oil is preferably trimethylolpropane ester, specifically preferably a saturated polyol ester produced by Yingkou Xinghuo Chemical Co., Ltd., code-named TMP108A.

[0052] In the present invention, the trimethylolpropane ester is a high-quality saturated polyol ester with good high and low temperature performance, good solubility for additives, outstanding wear resistance and low high temperature coking amount.

[0053] The present invention also provides a method for preparing the engine protective agent described in the above technical solution, comprising the following steps:

[0054] first mixing a viscosity index improver, a detergent, a dispersant and a saturated polyol ester base oil to obtain a base fluid;

[0055] The base fluid is sequentially mixed with an antioxidant and a friction reducer to obtain the engine protective agent.

[0056] In the present invention, the first mixing method is preferably stirring and mixing; the stirring and mixing temperature is preferably 55 to 65° C., more preferably 60° C.; the stirring and mixing time is preferably 20 to 30 min, more preferably 25 min.

[0057] In the present invention, the second mixing method is preferably stirring and mixing; the stirring and mixing temperature is preferably 60-70° C., more preferably 65° C.; the stirring and mixing time is preferably 30 minutes.

[0058] The present invention also provides the use of the engine protective agent described in the above technical solution or the engine protective agent prepared by the above preparation method in automobile engines.

[0059] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0060] The sources and physicochemical properties of the raw materials involved in Examples 1 to 3 are as follows:

[0061] Viscosity index improver: Dalian Xinyi Industry TK-chem V6601, which is a star-block structured polymethacrylate (PMA), colorless and transparent or light yellow viscous liquid, with a kinematic viscosity of 100℃ / (mm 2 / s): 1354, density (20℃) kg / m 3 : 920, open cup flash point / ℃: 180, shear stability SSI (KRL 20h): 30.9%, which has a more significantly improved viscosity index and better shear stability.

[0062] The detergent includes calcium sulfonate and magnesium alkyl salicylate: calcium sulfonate adopts medium base synthetic calcium sulfonate RF 1105 produced by Ruifeng New Materials, with a density (20℃) kg / m 3 :1.03, 100℃ kinematic viscosity / (mm 2 / s): 39.3, open flash point / ℃: 198, TBN / (mgKOH / g): 165.

[0063] The alkyl magnesium salicylate adopts the high base value alkyl magnesium salicylate RHY109 produced by Lanzhou Lubricant Research and Development Center, with an open flash point / ℃: 202, TBN / (mgKOH / g): 310.

[0064] The dispersant is boronized polyisobutylene succinimide, which is an ashless dispersant. KT 1961B produced by Jinzhou Kangtai Co., Ltd. is used, and the density (20°C) is kg / m 3 :0.92,100℃ kinematic viscosity / (mm 2 / s): 335, open flash point / ℃: 192, N / %: 1.73, boron / %: 0.51, alkali value / (mgKOH / g): 15.

[0065] The antioxidant is Vanlube BHC produced by Vanderbilt, density (20℃) kg / m 3 :0.97,100℃ kinematic viscosity / (mm 2 / s): 6.2, open flash point / ℃: 152.

[0066] The friction reducer includes dialkyl dithiophosphate molybdenum and nano boronized rare earth lanthanum. The dialkyl dithiophosphate molybdenum is produced by Pacific Union (Beijing) Petrochemical Co., Ltd., code name POUPCC 1001, density (20℃) kg / m 3 :1.002,100℃ kinematic viscosity / (mm 2 / s): 325, open flash point / ℃: 162, molybdenum content / %: 9.3, sulfur content / %: 12.3, phosphorus content / %: 3.5.

[0067] The nano-boride rare earth lanthanum is SK3115 produced by Qingdao Suofurun, with a density (20℃) kg / m 3 :0.95, 100℃ kinematic viscosity / (mm 2 / s): 15, open flash point / ℃: 196, pour point / ℃: -15, lanthanum content / %: 2.5, boron content / %: 3.3.

[0068] The trimethylolpropane ester base oil is a saturated polyol ester produced by Yingkou Xinghuo Chemical Co., Ltd., code-named TMP108A, with a kinematic viscosity of 40°C / (mm 2 / s): 20.0, 100℃ kinematic viscosity / (mm 2 / s): 4.4, viscosity index (VI): 140, pour point / ℃: -53, open flash point / ℃: 250, acid value (mgKOH / g): 0.05, with good high and low temperature performance.

[0069] Examples 1 to 3

[0070] Table 1 Model and dosage of each component in Examples 1 to 3

[0071]

[0072]

[0073] The mass ratio of POUPCC 1001 and SK 3115 in the friction reducer is 3:1;

[0074] The mass ratio of RHY 109 to RF 1105 in the detergent is 2.5:1.

[0075] Preparation method: TK-chemV6601, RF 1105, RHY 109 and KT 1961B were added to the base oil according to the mass ratio, stirred and heated to 60°C, and stirred at this temperature for 25 minutes to obtain the base liquid;

[0076] Then add Vanlube BHC, POUPCC 1001 and SK 3115 into the base liquid in turn, and continue stirring at 65°C for 30 minutes to allow various additives to be fully dissolved in the base oil. After being fully dissolved, the engine protective agent is obtained.

[0077] test

[0078] (1) The physical and chemical indicators of the engine protective agents prepared in Examples 1 to 3 were tested. The test results are shown in Table 2.

[0079] Table 2 Physical and chemical indicators of the engine protective agent of Examples 1 to 3

[0080]

[0081] It can be seen from Table 2 that the physical and chemical indicators of the energy-saving engine protective agent tested in Examples 1 to 3 are all within the design value range, and the viscosity index (VI) of Example 3 is the highest. The viscosity index is a reflection of the viscosity-temperature performance. The higher the value, the smaller the change of oil viscosity with temperature, the more stable the oil film between the friction pairs, and the more prominent the friction reduction property.

[0082] (2) The engine protection agents in Examples 1 to 3 were subjected to corrosion tests in a liquid phase corrosion test machine according to the liquid phase corrosion test method of GB 11143-2008. The test results are shown in Table 3 and Figures 1 to 3 As shown:

[0083] Table 3 Engine protection agent liquid phase corrosion test results of Examples 1 to 3

[0084] Test items Design value Example 1 Example 2 Example 3 Liquid phase corrosion (distilled water method) Rust-free Rust-free Rust-free Rust-free

[0085] From Table 3 and Figures 1 to 3It can be seen that there is no liquid phase corrosion in the three embodiments, which is within the design requirements. Figures 1 to 3 In terms of gloss, Example 2 and Example 3 are significantly better than Example 1.

[0086] (3) Copper sheet corrosion test

[0087] The engine protection agents in Examples 1 to 3 were subjected to a copper sheet corrosion test. According to GB 5096-2017, a test method for copper corrosion of petroleum products was performed at 100°C for 3 hours. The test results are shown in Table 4 and Figures 4 to 6 shown.

[0088] Table 4 Engine protection agent copper sheet corrosion test results of Examples 1 to 3

[0089] Test items Design value Example 1 Example 2 Example 3 Copper corrosion / level (100℃, 3h) ≤2 1b 1a 1a

[0090] From Table 4 and Figures 4-5 It can be seen that the copper sheet corrosion test results in the three embodiments are no greater than level 1, which are all within the design requirements. Figures 4 to 6 In terms of the degree of corrosion, Example 1 is significantly more serious than Example 2 and Example 3.

[0091] (4) Crankcase high temperature gelling tendency test

[0092] The engine protective agents in Examples 1 to 3 were tested for their tendency to form a gel at high temperatures in crankcases according to the crankcase simulation method of SH / T0300-1992. Experimental temperature: plate temperature: 320°C, oil temperature: 150°C, laboratory time: continuous sputtering for 360 minutes. The experimental results are shown in Table 5 and Figures 7 to 9 .

[0093] Table 5 Engine protection agent crankcase simulation test results of Examples 1 to 3

[0094] Test items Design value Example 1 Example 2 Example 3 Test Method High temperature gelation tendency ≤5 2 1 1 SH / T0300

[0095] From Table 5 and Figures 7 to 9 It can be seen that the high temperature gelation tendency test results of the three embodiments are all within the design requirements. Figures 7 to 9 In terms of the degree of coking, Example 2 and Example 3 are obviously better than Example 3.

[0096] (5) Friction reduction performance test

[0097] The engine protective agents in Examples 1 to 3 were tested for friction reduction performance according to the test method for determining the anti-wear performance of lubricating oils in SH / T 0189-2017. Test conditions: 392N, 1200r / min, 75°C, 3600s.

[0098] In order to obtain more accurate friction reduction performance data of the embodiments, in the later stage of the experiment, embodiments 1 to 3 were added to Huizhou 150N (CNOOC Huizhou Petrochemical Co., Ltd.) at a ratio of 1% (mass fraction) for testing. The Huizhou 150N index test is shown in Table 6.

[0099] Table 6 Huizhou 150N index test

[0100]

[0101]

[0102] The samples of Examples 1 to 3 were added to Huizhou 150N (CNOOC Huizhou Petrochemical Co., Ltd.) at a ratio of 1% (mass fraction), heated to 60°C and stirred for 20 minutes, and then the samples were subjected to anti-wear tests. Fig.10 and Fig.11 , wear spot performance test see Figures 12 to 16 .

[0103] Depend on Figures 10 to 16 It can be seen that Examples 1 to 3 have excellent friction reduction performance in the base oil Huizhou 150N. Among the three examples, Example 3 has the most outstanding performance in friction force, friction coefficient and average wear spot diameter, which is significantly better than Example 1 and Example 2.

[0104] Comprehensively testing various physical and chemical indicators, Examples 1 to 3 can all meet the design indicator requirements of an engine protective agent, but among the three examples, Example 3 is significantly better than Example 1 and Example 2 in terms of comprehensive performance indicators.

[0105] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. An engine protective agent, It is characterized in that In terms of mass percentage, it includes the following components: The balance is saturated polyol ester base oil; The detergent includes magnesium alkyl salicylate and calcium sulfonate; The friction reducer comprises liquid organic molybdenum and nanometer boride rare earth lanthanum.

2. The engine protective agent according to claim 1, It is characterized in that The viscosity index improver is polymethacrylate; the polymethacrylate is a polymethacrylate with a star-shaped block structure.

3. The engine protective agent according to claim 1, It is characterized in that The mass ratio of magnesium alkyl salicylate to calcium sulfonate in the detergent is (2.0-3.0):

1.

4. The engine protective agent according to claim 1, It is characterized in that The dispersant is boronated polyisobutylene succinimide.

5. The engine protective agent according to claim 1, It is characterized in that The antioxidant is an ester type hindered phenol.

6. The engine protective agent according to claim 1, It is characterized in that The mass ratio of liquid organic molybdenum to nano-boride rare earth lanthanum in the friction reducer is (2.0-3.5):

1.

7. The engine protective agent according to claim 1, It is characterized in that The saturated polyol ester base oil is trimethylolpropane ester.

8. A method for preparing the engine protective agent according to any one of claims 1 to 7, The following steps are involved: first mixing a viscosity index improver, a detergent, a dispersant and a saturated polyol ester base oil to obtain a base fluid; The base fluid is sequentially mixed with an antioxidant and a friction reducer to obtain the engine protective agent.

9. The preparation method according to claim 8, It is characterized in that The first mixing method is stirring and mixing; the stirring and mixing temperature is 55 to 65° C.; the stirring and mixing time is 20 to 30 minutes; The second mixing method is stirring and mixing; the stirring and mixing temperature is 60-70° C.; and the stirring and mixing time is 30 minutes.

10. Use of the engine protective agent according to any one of claims 1 to 7 or the engine protective agent prepared by the preparation method according to claim 8 or 9 in automobile engines.

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