HSD type viscosity index agent for engine lubricating oil, preparation method of HSD type viscosity index agent and lubricating oil

Abstract

The invention belongs to the field of lubricating oil additives, and particularly relates to an HSD type viscosity index improver for engine lubricating oil, a preparation method of the HSD type viscosity index improver and the lubricating oil. The HSD type viscosity index agent for the engine lubricating oil is of a star-shaped structure composed of a core and a plurality of arms, the core is a dendrimer with the tail end being an aldehyde group or a double bond, the arms are olefin copolymers comprising two or more than three of ethylene, propylene, styrene, isoprene and butadiene, and the core is connected with the arms through saturated bonds. The lubricating oil HSD type viscosity index improver provided by the invention has excellent thickening performance, shear resistance, low-temperature performance and the like. The viscosity index of the lubricating oil is widely applied to gasoline engine oil, diesel engine oil, motorcycle oil and gas engine oil.

Description

Technical Field

[0001] The invention belongs to the field of lubricating oil additives, and in particular relates to an HSD type viscosity modifier for engine lubricating oil, a preparation method and the lubricating oil. Background Art

[0002] With the upgrading of emission regulations and the promotion of energy conservation and environmental protection, engine oil has also made great strides towards high quality and high level. Entering the "dual carbon" era, the energy consumption structure has been adjusted towards clean and low carbon, especially in the field of transportation. From the perspective of the development of the lubrication industry, lubricants will gradually develop towards high quality and high performance, which is also an inevitable trend in the development of the industry. Viscosity index improver is an indispensable additive for high-end lubricants, especially engine oils. At present, the commonly used types of viscosity index improvers are mainly PMA type (polymethacrylate), OCP type (ethylene-propylene copolymer), HSD type (hydrogenated styrene-diene copolymer), etc. Compared with PMA type and OCP type, HSD type viscosity index improver has the characteristics of good thermal stability, excellent shear performance, good oil solubility, etc., and is widely used in medium and high-end engine lubricants.

[0003] Currently, industrial HSD viscosity index improvers are prepared using styrene and diene copolymers, and their thickening performance, shear resistance, and cleaning performance still need to be improved. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an HSD type viscosity index improver for engine lubricating oil, a preparation method and lubricating oil. The HSD type viscosity index improver for engine lubricating oil provided by the present invention is different from the existing HSD type viscosity index improver in terms of raw materials and preparation, products and performance. The thickening performance, shear resistance, low temperature and cleaning performance of the HSD type viscosity index improver are significantly improved, and the HSD type viscosity index improver is a viscosity index improver with great application value.

[0005] Specifically, the HSD viscosity index improver for engine lubricating oil provided in the first aspect of the present invention is a star-shaped structure composed of a core and multiple arms, wherein the core is a dendritic macromolecule with an aldehyde group or a double bond at the end, and the arm is an olefin copolymer including two or more of ethylene, propylene, styrene, isoprene, and butadiene, and the core and the arm are connected by a saturated bond. The novel HSD viscosity index improver for engine lubricating oil provided in the present invention has excellent thickening performance, shear resistance, low temperature and cleaning performance. Its outstanding thickening performance, shear resistance, low temperature and cleaning performance, by adopting the viscosity index improver, can make the engine lubricating oil maintain viscosity under extreme working conditions, reduce machine wear and friction, and extend the service life of the engine; at the same time, its excellent cleaning performance also makes the engine interior better kept clean, improves combustion efficiency, and reduces exhaust emissions, and has significant application value.

[0006] Preferably, the number of arms is related to the generation number n of the dendrimer; the number of arms of the 0th generation dendrimer is not less than 6.

[0007] More preferably, the number of arms is 4 to 16384, preferably 6 to 128, and more preferably 6 to 64.

[0008] More preferably, the arm is an ethylene-propylene copolymer, or a styrene-isoprene-butadiene copolymer, or an isoprene-butadiene copolymer.

[0009] Preferably, the method for preparing the core comprises: subjecting an amine compound to a Michael addition reaction and an ester exchange reaction with methyl acrylate or methyl methacrylate to obtain a 0th generation dendrimer; repeating the steps to obtain 1st to 10th generation dendrimers; subjecting the 0th to 10th generation dendrimers to a Schiff base reaction with an aldehyde compound to obtain dendrimers of different generations with an aldehyde group or a double bond at the end.

[0010] Preferably, the amine compound is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3,5-triaminobenzene, p-phenylenediamine, m-phenylenediamine, and o-phenylenediamine; and / or, the aldehyde compound is selected from one or more of dialdehyde compounds, acrolein, crotonaldehyde, and 3-pentenal; the dialdehyde compound is preferably glyoxal, malondialdehyde, succinaldehyde, or glutaraldehyde.

[0011] Preferably, the number average molecular weight of the arm is 10,000 to 100,000, preferably 10,000 to 50,000.

[0012] Preferably, the number average molecular weight of the HSD type lubricating oil viscosity index improver is 4 to 54 million, preferably 4 to 32 million, and more preferably 11 to 640,000.

[0013] Further preferably, the elements of the HSD type lubricating oil viscosity index improver are C, H, O, and N; optionally, in the HSD type lubricating oil viscosity index improver, the carbon element and the oxygen element are linked in a carbonyl manner, and the molar ratio of the nitrogen element to the oxygen element is (4.0~4.5):1, preferably (2.0~2.5):1; the content of the nitrogen element is 0.01%~10%, preferably 0.02%~0.3%.

[0014] In the present invention, by optimizing the raw materials used for the novel HSD type viscosity modifier, the molecular structure can be made more reasonable, and by further optimizing the core and arm length, the star-shaped structure of the HSD type viscosity modifier is made more regular, thereby improving the thickening performance and anti-shear performance of the viscosity modifier.

[0015] The second aspect of the present invention provides a method for preparing the HSD type viscosity index improver for engine lubricating oil, comprising subjecting the core to an addition reaction with the arm to obtain an HSD type lubricating oil viscosity index improver.

[0016] Preferably, the reaction for generating the core comprises: reacting the dendrimer with one or more of glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, acrolein, and acryloyl chloride through a Schiff base reaction or an acylation reaction; the reaction temperature is preferably 20-40° C., and the reaction time is 0.1-30 h.

[0017] More preferably, the reaction temperature of the dendrimer with one or more of glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde and acrolein is 30-40°C, and the reaction time is 20-30h; the reaction temperature of the dendrimer with acryloyl chloride is 20-40°C, and the reaction time is 0.1-8h.

[0018] Preferably, the reaction for generating the arms comprises: polymerizing butadiene and isoprene, and then adding styrene for polymerization; the reaction temperature for the polymerization of butadiene and isoprene is preferably 45-65°C, and the reaction time is 1-2h; the reaction temperature for the polymerization of adding styrene is preferably 45-65°C, and the reaction time is 2-3h.

[0019] Preferably, the reaction for generating the arms comprises: polymerizing ethylene and propylene, the reaction temperature is preferably 45-65° C., and the reaction time is 1-2 h.

[0020] Preferably, the reaction for generating the arms comprises: polymerizing butadiene and isoprene, the reaction temperature is preferably 45-65° C., and the reaction time is 1-2 h.

[0021] In the present invention, by adopting optimized core and arm generation methods, raw materials and process parameters, the synthesis steps can be reduced, the preparation time of each step can be reduced, and the preparation efficiency of the HSD type viscosity modifier can be improved. In particular, the process steps can be further optimized under optimal conditions, which is more suitable for industrial production.

[0022] A third aspect of the present invention provides an engine lubricating oil, comprising the HSD type viscosity modifier for engine lubricating oil or the HSD type viscosity modifier for engine lubricating oil obtained by the preparation method of the HSD type viscosity modifier for engine lubricating oil.

[0023] Preferably, the engine lubricant is a gasoline engine lubricant, a diesel engine lubricant, a motorcycle oil and / or a gas engine oil, preferably a gasoline engine lubricant or a diesel engine lubricant; more preferably, in the gasoline engine lubricant, the content of the HSD type viscosity modifier for engine lubricant is 0.2% to 3%, preferably 0.4% to 1.5%; in the diesel engine lubricant, the content of the HSD type viscosity modifier for engine lubricant is 0.3% to 3%, preferably 0.6% to 2%.

[0024] The beneficial effect of the present invention is at least that the lubricating oil viscosity index improver structure provided by the present invention has good thickening performance, shear resistance and low temperature performance, etc. The lubricating oil viscosity index is widely used in gasoline engine oil, diesel engine oil, motorcycle oil, and gas engine oil. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] If no specific technology or conditions are specified in the embodiments of the present invention, the technology or conditions described in the literature in this field or the product instructions are used. If the manufacturer of the devices, instruments, reagents, etc. is not specified, they are all conventional products that can be purchased through regular channels. The raw materials used in the present invention can be easily purchased in the domestic product market.

[0027] Example 1

[0028] The present embodiment provides an HSD type viscosity index improver for engine lubricating oil and a preparation method thereof, wherein raw materials styrene, isoprene and butadiene are used as arms (C), and raw materials ethylenediamine (A), methyl acrylate (B) and glyoxal are further used as cores to prepare an HSD type lubricating oil viscosity index improver (A x B 4x )C 4xy , where x=1, y=2. The specific steps are as follows.

[0029] (1) Under nitrogen protection and at a temperature of 40°C, 6 g of ethylenediamine, 34.6 g of methyl acrylate and 50 mL of methanol solution were added to a 250 mL flask respectively. After reacting for 20 h, 66 g of ethylenediamine was added. After reflux reaction for 48 h, the methanol solution was removed by vacuum distillation to obtain 105 g of viscous liquid as the A1B4 product (0-generation ethylenediamine is a core dendrimer molecule) for standby use.

[0030] (2) Under nitrogen protection and at 40°C, 50g of A1B4 product (0-generation ethylenediamine as the core dendrimer), 100mL of toluene, 200g of glyoxal, and 0.5mL of triethylamine were added to a 250mL flask. After reacting for 4 hours, the toluene solution was removed by vacuum distillation and then purified with methanol solution to obtain 145g of viscous liquid. This is the A1B4 product derivative (0-generation ethylenediamine as the core dendrimer derivative) with an aldehyde group at the end, which is ready for use.

[0031] (3) In an absolutely dry 250 mL flask, add 150 mL of cyclohexane and 28 g of styrene, then introduce 36 g of butadiene and 36 g of isoprene into the flask by vaporization according to the metered amount. Place the flask in a 50 °C constant temperature water bath and preheat for 30 min. Then, add 3 mL of tetramethylethylenediamine (TMEDA) and 12.5 mL of n-butyllithium initiator, respectively, and allow the polymerization reaction to proceed for 3 h.

[0032] (4) Disperse 30 g of A1B4 liquid in 30 mL of n-hexane and add it to step (2). After reacting at 50 °C for 8 h, add 1% isopropanol and remove the n-hexane with water vapor to obtain 129.5 g of viscous liquid for standby use.

[0033] (5) Take 30g of the sample from step (3) and add it to a 200mL stainless steel autoclave with a stirring device, add 80mL of refined cyclohexane, seal it and stir it in a constant temperature water bath at 60℃. After the gel sample is completely dissolved, add 3mL of tetrahydrofuran additive under the protection of high-purity N2, and continue to stir the reactor for 30min. Then add 0.5gAl / Ni (molar ratio 5:1). After 20min, introduce high-purity H2 and pressurize to 4MPa to keep the pressure constant. Hydrogenate for 3h. After the reaction is completed, add an appropriate amount of H2O2 / HCl and stir in a 40℃ water bath for 3h. The gel solution changes from brown to white. Use anhydrous ethanol to condense. The polymer is dried in a vacuum oven at 40℃ until the mass is constant. 29.5g of white solid is obtained, which is the (A1B4)C8 product (HSD type lubricating oil viscosity index improver).

[0034] The HSD type lubricating oil viscosity index improver of this embodiment has an N content of 0.029% and a gel permeation chromatography (GPC): a number average molecular weight of 426,200, an arm number of 6.23, and a distribution coefficient of 1.08.

[0035] Example 2

[0036] The present embodiment provides an HSD type viscosity index improver for engine lubricating oil and a preparation method thereof, wherein the raw materials are isoprene and butadiene as arms (C), and the raw materials are 1,4-butanediamine (A), methyl methacrylate (B), and acrolein as cores to prepare an HSD type lubricating oil viscosity index improver (A x B 4x )C 4xn , where x = 2 and n = 3. The specific steps are as follows.

[0037] (1) Under nitrogen protection and at a temperature of 40°C, add 8.8 g of 1,4-butanediamine, 36.1 g of methyl methacrylate and 50 mL of methanol solution to a 500 mL flask, react for 20 hours, then add 121 g of ethylenediamine and reflux for 48 hours. Then add 35.9 g of methyl methacrylate and 50 mL of methanol solution, react for 20 hours, then add 242 g of ethylenediamine and reflux for 48 hours. After removing the methanol solution by vacuum distillation, 255.6 g of viscous liquid is obtained as the A2B8 product (2nd generation 1,4-butanediamine is a core dendrimer) for standby use.

[0038] (2) Under nitrogen protection and at 40°C, 50 g of A2B8 product (2-generation ethylenediamine as the core dendrimer), 100 mL of toluene, 318 g of acrolein, and 0.5 mL of triethylamine were added to a 250 mL flask. After reacting for 4 hours, the toluene solution was removed by vacuum distillation and then purified with methanol solution to obtain 267 g of viscous liquid. This is the A2B8 derivative (2-generation 1,4-butanediamine as the core dendrimer derivative) with an aldehyde group at the end, which is ready for use.

[0039] (3) In an absolutely dry 250 mL flask, add 150 mL of cyclohexane and 36 g of butadiene, then introduce 36 g of isoprene into the flask by vaporization according to the metered amount. Place the flask in a 50 °C constant temperature water bath and preheat for 30 min. Then, add 3 mL of tetramethylethylenediamine (TMEDA) and 12.5 mL of n-butyllithium initiator, and allow the polymerization reaction to proceed for 1.2 h.

[0040] (4) Disperse 50 g of the A2B8 derivative liquid in 30 mL of n-hexane and add it to step (3). After reacting at 50 °C for 12 h, add 1% isopropanol and remove n-hexane and cyclohexane with water vapor to obtain 148.7 g of a viscous liquid for standby use.

[0041] (5) Take 50g of the sample from step (4) and add it to a 220mL stainless steel autoclave with a stirring device. Add 100mL of cyclohexane, seal it and stir it in a constant temperature water bath at 60°C. After the gel sample is completely dissolved, add 3.2mL of tetrahydrofuran additive under the protection of high-purity N2, and continue to stir the reactor for 35 minutes. Then add 0.7g Al / Ni (molar ratio 5:1). After 20 minutes, introduce high-purity H2 and pressurize it to 4MPa to keep the pressure constant. The hydrogenation reaction is carried out for 4 hours. After the reaction is completed, add an appropriate amount of H2O2 / HCl and stir it in a 40°C water bath for 3 hours. The gel solution changes from dark brown to white. It is condensed with anhydrous ethanol and the polymer is dried in a vacuum oven at 40°C until the mass is constant. 48.6g of white solid is obtained, which is (A2B8)C. 16 Product (HSD type lubricating oil viscosity index improver).

[0042] The HSD type lubricating oil viscosity index improver of this embodiment has an N content of 0.042%; GPC has a number average molecular weight of 637,800, an arm number of 16.42, and a distribution coefficient of 1.05.

[0043] Example 3

[0044] The present embodiment provides an HSD type viscosity index improver for engine lubricating oil and a preparation method thereof, wherein raw materials styrene, isoprene and butadiene are used as arms (C), and raw materials 1,3,5-triaminobenzene (A), ethyl acrylate (B) and acryloyl chloride are used as cores to prepare an HSD type lubricating oil viscosity index improver (A x B 6x )C 6xn . Where x=1, n=2. The specific steps are as follows.

[0045] (1) Under nitrogen protection and at a temperature of 40°C, 12.3 g of 1,3,5-triaminobenzene, 36.1 g of methyl methacrylate and 50 mL of methanol solution were added to a 250 mL flask respectively. After reacting for 20 h, 105 g of ethylenediamine was added. After reflux reaction for 48 h, the methanol solution was removed by vacuum distillation to obtain 140.8 g of viscous liquid as the A1B6 product (0-generation 1,3,5-triaminobenzene as a core dendrimer molecule) for standby use.

[0046] (2) Under nitrogen protection and at 40°C, 50g of A1B6 product (0-generation 1,3,5-triaminobenzene as the core dendrimer), 100mL of toluene, 224g of acryloyl chloride, and 0.5mL of triethylamine were added to a 250mL flask. After reacting for 2h, the toluene solution was removed by vacuum distillation and then purified with methanol solution to obtain 158g of viscous liquid. This is the A1B6 derivative (0-generation 1,3,5-triaminobenzene as the core dendrimer derivative) with an aldehyde group at the end, which is ready for use.

[0047] (3) In an absolutely dry 250 mL flask, add 150 mL of cyclohexane, then vaporize 28 g of ethylene and 42 g of propylene into the flask according to the metered amount. Preheat the flask in a 50 °C constant temperature water bath for 30 min, then add 3 mL of tetramethylethylenediamine (TMEDA) and 12.5 mL of n-butyllithium initiator, and allow the polymerization reaction to proceed for 1 h.

[0048] (4) Disperse 50 g of the A1B6 derivative liquid in 30 mL of n-hexane, add it to step (3), react at 50 °C for 12 h, add 1% isopropanol, remove n-hexane and cyclohexane with water vapor, and obtain 148.7 g of viscous liquid for standby use.

[0049] (5) Take 50g of the sample from step (4) and add it to a 220mL stainless steel autoclave with a stirring device. Add 100mL of cyclohexane, seal it and stir it in a constant temperature water bath at 60°C. After the gel sample is completely dissolved, add 3.2mL of tetrahydrofuran additive under the protection of high-purity N2, and continue to stir the reactor for 35 minutes. Then add 0.7gAl / Ni (molar ratio 5:1). After 20 minutes, introduce high-purity H2 and pressurize it to 4MPa to keep the pressure constant. The hydrogenation reaction is carried out for 4 hours. After the reaction is completed, add an appropriate amount of H2O2 / HCl and stir it in a 40°C water bath for 3 hours. The gel solution changes from dark brown to white. It is condensed with anhydrous ethanol and the polymer is dried in a vacuum oven at 40°C until the mass is constant. 48.6g of white solid is obtained, which is (A1B6)C 12 Product (HSD type lubricating oil viscosity index improver).

[0050] The HSD type lubricating oil viscosity index improver of this embodiment has an N content of 0.122%; GPC has a number average molecular weight of 118,900, an arm number of 11.86, and a distribution coefficient of 1.02.

[0051] Experimental Example 1

[0052] The lubricating oil viscosity modifier prepared in Example 1 and a common viscosity modifier currently on the market (SV265, Infineum) were used to prepare SN / GF-5 5W-30 gasoline engine oil according to the formula in Table 1 below.

[0053] Table 1 SN / GF-5 5W-30 gasoline engine oil

[0054] Note: 1. The weight ratio of the composite additive in functional additive B (Ca detergent: dispersant: amine / phenol composite antioxidant: P / Zn / P antiwear agent: pour point depressant) is 2:3:4:0.8:0.2. 2. Example 1 The viscosity modifier is dissolved in 90% 100N base oil at a ratio of 10%, and its dry rubber content is the same as that of the commercially available SV 265.

[0055] Example 1 and a commercially available viscosity modifier were added to the formulation in different dosages, and the performance difference between Example 1 and the commercially available viscosity modifier was evaluated by measuring the viscosity, low temperature performance, shear resistance and detergency of the lubricating oil.

[0056] The analysis results of SN / GF-5 5W-30 gasoline engine oil are shown in Table 2 below.

[0057] Table 2 Analysis results of SN / GF-5 5W-30 gasoline engine oil

[0058] From the analysis data in Table 2, it can be seen that the kinematic viscosity of the SN / GF-5 5W-30 oil prepared with the viscosity modifier prepared in Example 1 is 11.05 mm 2 / s, while the kinematic viscosity of the commercially available viscosity modifier is 10.09 mm 2 / s. Compared with the commercial viscosity index agent, the thickening performance of the viscosity index agent in Example 1 is improved by 9.51%. In addition, through the diesel nozzle shear test, the shear stability of the viscosity index agent prepared in Example 1 is better than that of the commercial viscosity index agent. This shows that the thickening performance and shear resistance of the viscosity index agent prepared in Example 1 are better than those of the commercial viscosity index agent products. Through the analysis of low-temperature dynamic viscosity and low-temperature pumping viscosity, it can be seen that the low-temperature performance of the SN / GF-5 5W-30 oil prepared by the viscosity index agent prepared in Example 1 is equivalent to that of the commercial viscosity index agent prepared products. Through the TEOST 33C and TEOST MHT tests, it is shown that the viscosity index agent prepared in Example 1 contributes better to detergency than the commercial viscosity index agent. This may be because the viscosity index agent prepared in Example 1 has a regular structure and is not easily oxidized, which makes its detergency performance better. In summary, the polymer prepared in Example 1 is an excellent viscosity index agent.

[0059] Experimental Example 2

[0060] CI-4 15W-40 diesel engine oil was prepared according to the formula in Table 3 using the lubricating oil dispersant prepared in Example 2 and a common viscosity index agent (LZ 7077, Lubrizol) currently on the market.

[0061] Table 3 CI-4 15W-40 diesel engine oil

[0062] Note: 1. The weight ratio of the composite additive in functional additive C (containing Ca detergent: dispersant: amine / phenol composite antioxidant, containing P / Zn / P antiwear agent: pour point depressant) is 1.5:3.5:3.2:1.7:0.1. 2. Example 2 The viscosity modifier is dissolved in 90% 100N base oil at a ratio of 10%, and its dry rubber content is the same as that of the commercially available LZ 7077.

[0063] Example 2 and a commercially available viscosity modifier were added to the formulation at different dosages, and the performance differences between Example 2 and the commercially available viscosity modifier were evaluated by measuring the viscosity, low temperature performance, shear resistance and detergency of the lubricating oil.

[0064] The analysis results of CI-4 15W-40 diesel engine oil are shown in Table 4 below.

[0065] Table 4 Analysis results of CI-4 15W-40 diesel engine oil

[0066] From the analysis data in Table 4, it can be seen that the kinematic viscosity of the CI-4 15W-40 oil prepared with the viscosity modifier prepared in Example 2 is 15.82 mm 2 / s, while the kinematic viscosity of the commercially available viscosity modifier is 13.90 mm 2 / s. Compared with commercially available viscosity index agents, the thickening performance of the viscosity index agent in Example 2 is improved by 13.81%. In addition, through the diesel nozzle shear test, the shear stability of the viscosity index agent prepared in Example 2 is better than that of commercially available viscosity index agents. This shows that the thickening performance and shear resistance of the viscosity index agent prepared in Example 2 are better than those of commercially available viscosity index agent products. Through the analysis of low-temperature dynamic viscosity and low-temperature pumping viscosity, it can be seen that the low-temperature performance of the CI-4 15W-40 oil prepared by the viscosity index agent prepared in Example 2 is equivalent to that of commercially available viscosity index agent prepared products. Through the gel board test, it is shown that the viscosity index agent prepared in Example 2 contributes better to detergency than commercially available viscosity index agents. This may be because the viscosity index agent prepared in Example 2 has a regular structure and is not easily oxidized, which makes it have better detergency. In summary, the polymer prepared in Example 2 is an excellent viscosity index agent.

[0067] Experimental Example 3

[0068] The lubricating oil dispersant prepared in Example 3 and a common viscosity index agent (SV 261L, Infineum) in the current market were used to prepare SP 0W-20 gasoline engine oil according to the formula in Table 5 below.

[0069] Table 5 SP 0W-20 gasoline engine oil

[0070] Note: 1. Functional additive D composite additive (containing Ca detergent: magnesium detergent: dispersant: amine / phenol composite antioxidant: containing P / Zn / P anti-wear agent: pour point depressant in a weight ratio of 1.5:0.5:3:3:1.9:0.1). 2. Example 3 The viscosity modifier is dissolved in 90% 100N base oil at a ratio of 10%, and its dry rubber content is the same as that of the commercially available SV261L.

[0071] Example 3 and a commercially available viscosity modifier were added to the formulation at different dosages, and the performance difference of the commercially available viscosity modifier of Example 3 was evaluated by measuring the viscosity, low temperature performance, shear resistance and detergency of the lubricating oil.

[0072] The analysis results of SP 0W-20 gasoline engine oil are shown in Table 6 below.

[0073] Table 6 Analysis results of SP 0W-20 gasoline engine oil

[0074] From the analysis data in Table 6, it can be seen that the kinematic viscosity of the SP 0W-20 oil prepared with the viscosity modifier prepared in Example 3 is 8.15 mm 2 / s, while the kinematic viscosity of the commercially available viscosity modifier is 7.82 mm 2 / s. Compared with the commercially available viscosity index agent, the thickening performance of the viscosity index agent in Example 3 is improved by 4.23%. In addition, through the diesel nozzle shear test, the shear stability of the viscosity index agent prepared in Example 3 is better than that of the commercially available viscosity index agent. This shows that the thickening performance and anti-shear performance of the viscosity index agent prepared in Example 3 are better than those of the commercially available viscosity index agent products. Through the analysis of low-temperature dynamic viscosity and low-temperature pumping viscosity, it can be seen that the low-temperature performance of the SP 0W-20 oil product prepared by the viscosity index agent prepared in Example 3 is better than that of the commercially available viscosity index agent prepared product. Through the gel board test, it is shown that the viscosity index agent prepared in Example 3 contributes better to detergency than the commercially available viscosity index agent. This may be because the viscosity index agent prepared in Example 3 has a regular structure and is not easily oxidized, thereby making its detergency better. In summary, the polymer prepared in Example 3 is an excellent viscosity index agent.

[0075] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A HSD type viscosity modifier for engine lubricating oil, characterized in that: The HSD viscosity modifier for engine lubricating oil is a star-shaped structure consisting of a core and multiple arms, wherein the core is a dendritic macromolecule with an aldehyde group or a double bond at the end, and the arm is an olefin copolymer including two or more than three of ethylene, propylene, styrene, isoprene, and butadiene, and the core is connected to the arm via a saturated bond.

2. The HSD type viscosity modifier for engine lubricating oil according to claim 1, characterized in that: The number of arms is related to the generation number n of the dendrimer; the number of arms of the 0th generation dendrimer is not less than 6.

3. The HSD type viscosity modifier for engine lubricating oil according to claim 2, characterized in that: The number of arms is 6 to 16384, preferably 6 to 128, and more preferably 6 to 64.

4. The HSD viscosity modifier for engine lubricating oil according to any one of claims 1 to 3, characterized in that: The arm is an ethylene-propylene copolymer, or a styrene-isoprene-butadiene copolymer, or an isoprene-butadiene copolymer.

5. The HSD viscosity modifier for engine lubricating oil according to any one of claims 1 to 4, characterized in that: The core preparation method comprises: subjecting an amine compound to a Michael addition reaction and an ester exchange reaction with methyl acrylate or methyl methacrylate to obtain a 0th generation dendrimer; repeating the steps to obtain 1st to 10th generation dendrimers; subjecting the 0th to 10th generation dendrimers to a Schiff base reaction with an aldehyde compound to obtain dendrimers of different generations with an aldehyde group or a double bond at the end; Preferably, the amine compound is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3,5-triaminobenzene, p-phenylenediamine, m-phenylenediamine, and o-phenylenediamine; and / or, the aldehyde compound is selected from one or more of dialdehyde compounds, acrolein, crotonaldehyde, and 3-pentenal; the dialdehyde compound is preferably glyoxal, malondialdehyde, succinaldehyde, or glutaraldehyde.

6. The HSD viscosity modifier for engine lubricating oil according to any one of claims 1 to 5, characterized in that: The number average molecular weight of the arm is 10,000 to 100,000, preferably 10,000 to 50,000.

7. The HSD viscosity modifier for engine lubricating oil according to any one of claims 1 to 6, characterized in that: The number average molecular weight of the HSD type lubricating oil viscosity index improver is 4 to 54 million, preferably 4 to 32 million, and more preferably 11 to 640,000.

8. The HSD viscosity index improver for engine lubricating oil according to any one of claims 1 to 7, characterized in that the elements of the HSD lubricating oil viscosity index improver are C, H, O, and N; optionally, in the HSD lubricating oil viscosity index improver, the carbon element and the oxygen element are linked in a carbonyl manner, and the molar ratio of the nitrogen element to the oxygen element is (4.0-4.5):1, preferably (2.0-2.5):1; the content of the nitrogen element is 0.01%-10%, preferably 0.02%-0.3%.

9. A method for preparing an HSD type viscosity modifier for engine lubricating oil, characterized in that: The method comprises subjecting the core and the arm to an addition reaction to obtain an HSD type lubricating oil viscosity index improver; Preferably, the reaction for generating the core comprises: reacting the dendrimer with one or more of glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, acrolein, and acryloyl chloride through a Schiff base reaction or an acylation reaction; the reaction temperature is preferably 20-40° C., and the reaction time is 0.1-30 h; preferably, the reaction temperature of the dendrimer with one or more of glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, and acrolein is 30-40° C., and the reaction time is 20-30 h; the reaction temperature of the dendrimer with acryloyl chloride is 20-40° C., and the reaction time is 0.1-8 h; And / or, the reaction for generating the arms comprises: polymerizing butadiene and isoprene, and then adding styrene for polymerization; the reaction temperature for the polymerization of butadiene and isoprene is preferably 45-65° C., and the reaction time is 1-2 hours; the reaction temperature for the polymerization of styrene is preferably 45-65° C., and the reaction time is 2-3 hours; Alternatively, the reaction for generating the arms comprises: polymerizing ethylene and propylene, the reaction temperature is preferably 45-65° C., and the reaction time is 1-2 h; Alternatively, the reaction for generating the arms comprises: polymerizing butadiene and isoprene, the reaction temperature is preferably 45-65° C., and the reaction time is 1-2 h.

10. An engine lubricating oil, characterized in that: An HSD type viscosity modifier for engine lubricating oil comprising the HSD type viscosity modifier for engine lubricating oil according to any one of claims 1 to 8 or the HSD type viscosity modifier for engine lubricating oil obtained by the preparation method of the HSD type viscosity modifier for engine lubricating oil according to claim 9; Preferably, the engine lubricant is a gasoline engine lubricant, a diesel engine lubricant, a motorcycle oil and / or a gas engine oil; more preferably, in the gasoline engine lubricant, the content of the HSD type viscosity modifier for engine lubricant is 0.2% to 3%, preferably 0.4% to 1.5%; in the diesel engine lubricant, the content of the HSD type viscosity modifier for engine lubricant is 0.3% to 3%, preferably 0.6% to 2%.

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