Novel HSD viscosity index agent as well as preparation method and application thereof

Abstract

The invention provides a novel HSD viscosity index agent as well as a preparation method and application thereof. The structure of the novel lubricating oil viscosity index improver is shown in the following formula: (AxB4x) C4xn, A is a compound containing double primary amine and only contains C, H and N elements; and B is acrylate or methacrylate. AxB4x is connected through a saturated bond; c is a polymer of styrene, isoprene and butadiene; x is the number of molecules of A, and n is the number of primary and secondary amines of AxB4x, including but not limited to an integer from 1 to 20. The lubricating oil viscosity index improver structure has good thickening performance, anti-shearing performance and low-temperature performance. 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 specifically relates to a novel HSD-type viscosity modifier and a preparation method and application thereof. Background Art

[0003] From the perspective of the development of the lubrication industry, lubricants will gradually develop in the direction of 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. Currently, 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, and good oil solubility. It is widely used in medium and high-end engine lubricants. At present, the output and quality stability of HSD type viscosity index improver cannot meet the demand for high-end lubricant viscosity index improver. The development of new HSD type viscosity index improver has become an important task in the research and development of lubricant additives. Summary of the invention

[0004] The present invention provides a novel HSD type lubricating oil viscosity index improver, which has good thickening performance, shear resistance and low temperature performance.

[0005] An HSD type lubricating oil viscosity index improver, the structure of which is shown in the following formula:

[0006] (A x B 4x )C 4xn ,

[0007] Wherein, A is a compound containing diprimary amines and contains only C, H, and N elements;

[0008] B is acrylate or methacrylate;

[0009] A x B 4x They are connected by saturated bonds;

[0010] C is a polymer of styrene, isoprene and butadiene;

[0011] n is the number of secondary amines of A, and n is an integer from 1 to 20;

[0012] x is the number of A molecules, an integer from 1 to 10.

[0013] Furthermore, (A x B 4x )C 4xn Connect A via Michael addition and transesterificationx B 4x , connecting C via amino substitution reaction.

[0014] Furthermore, the number average molecular weight of the HSD type lubricating oil viscosity index improver is 80,000-800,000; preferably 100,000-400,000.

[0015] Further, A is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, 3,3'-bis(dimethylamino)-1,5-pentanediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4,4',4"-triaminotriphenylmethane, tetrakis(4-aminophenyl)methane, 4,4'-tetramethyldiaminodiphenylmethane, tris(dimethylamino)methane, and bis(2,4-diamino-5-methylphenyl)methane, preferably one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, and p-phenylenediamine.

[0016] Further, B is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, preferably one or more of methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.

[0017] Furthermore, the number average molecular weight of C is 10,000-100,000, preferably 25,000-70,000.

[0018] Furthermore, (A x B 4x )C 4xn The elements are C, H, O, and N. The carbon element and the oxygen element are linked in a carbonyl (C=O) manner. The molar ratio of nitrogen element to oxygen element is 4.0-4.5:1, preferably 2.0-2.5:1. The nitrogen content is 0.01-10%, preferably 0.02-0.3%.

[0019] Furthermore, n is any integer from 1 to 20.

[0020] Furthermore, x is any integer from 1 to 10.

[0021] Furthermore, n is 1, 2 or 3.

[0022] Furthermore, x is 1, 2 or 3.

[0023] Specifically, A is ethylenediamine, B is methyl acrylate, C is a polymer of styrene, isoprene and butadiene, x=1, and n=3.

[0024] Specifically, A is triethylenediamine, B is methyl methacrylate, C is a polymer of styrene, isoprene and butadiene, x=2, and n=3.

[0025] Specifically, A is p-phenylenediamine, B is ethyl acrylate, C is a polymer of styrene, isoprene and butadiene, x=1, and n=3.

[0026] A HSD type lubricating oil viscosity index improver, which is prepared by reacting compound A and compound B through Michael addition reaction and transesterification reaction to generate an intermediate (A x B 4x ), and then connected with polymer C through amino substitution reaction; wherein compound A is a diprimary amine-containing compound and contains only C, H, and N elements; compound B is acrylate or methacrylate; polymer C is a polymerization product of styrene, isoprene, and butadiene.

[0027] Specifically, the number average molecular weight of the HSD type lubricating oil viscosity index improver is 80,000-800,000; preferably 100,000-400,000.

[0028] Specifically, the compound A is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, 3,3'-bis(dimethylamino)-1,5-pentanediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4,4',4"-triaminotriphenylmethane, tetrakis(4-aminophenyl)methane, 4,4'-tetramethyldiaminodiphenylmethane, tris(dimethylamino)methane, and bis(2,4-diamino-5-methylphenyl)methane; preferably one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, and p-phenylenediamine.

[0029] Specifically, the compound B is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate; more preferably, it is one or more of methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.

[0030] Specifically, the number average molecular weight of the polymer C is 10,000-100,000, preferably 25,000-70,000.

[0031] Specifically, the molar ratio of compound A to compound B is 1:4.

[0032] Specifically, the intermediate (A x B 4x ) to polymer C is 1:(1-800), preferably 1:(1-24).

[0033] Specifically, the number average molecular weight of the HSD type lubricating oil viscosity index improver is 80,000-800,000; preferably 100,000-400,000.

[0034] Specifically, the elements of the HSD type lubricating oil viscosity index improver are C, H, O, and N.

[0035] Specifically, in the HSD type lubricating oil viscosity index improver, the carbon element and the oxygen element are linked in a carbonyl (C=O) manner, the molar ratio of the nitrogen element to the oxygen element is (4.0-4.5):1, preferably (2.0-2.5):1; the nitrogen content is 0.01-10%, preferably 0.02-0.3%.

[0036] The present invention also provides a method for preparing the above-mentioned HSD type lubricating oil viscosity index improver, comprising:

[0037] Allowing compound A and compound B to undergo Michael addition reaction and transesterification reaction to generate an intermediate;

[0038] Make styrene, isoprene and butadiene generate polymer C;

[0039] The intermediate is linked to polymer C via an amino substitution reaction.

[0040] Specifically, the reaction to generate the intermediate is carried out in the presence of a solvent. Optionally, the solvent is methanol (solution). After the reaction is completed, the solvent is removed by vacuum distillation.

[0041] Specifically, the reaction to generate the intermediate is carried out under nitrogen protection.

[0042] Specifically, the reaction temperature for generating the intermediate is 30-40°C.

[0043] Specifically, the reaction time for generating the intermediate is 20-30h.

[0044] Specifically, the method for generating the intermediate is as follows: under nitrogen protection and at a temperature of 30-40° C., compound A, compound B and a methanol solution are added respectively, and the reaction is carried out for 20-30 hours; after the reaction is completed, the methanol solution is removed by a reduced pressure distillation method to obtain an intermediate.

[0045] Specifically, the reaction for generating polymer C includes: firstly polymerizing butadiene and isoprene, and then adding styrene to continue the polymerization.

[0046] Specifically, the polymerization reaction of butadiene and isoprene is carried out in the presence of a solvent. Optionally, the solvent is cyclohexane and tetrahydrofuran.

[0047] Specifically, the polymerization reaction of butadiene and isoprene is carried out in the presence of a catalyst. Optionally, the catalyst is selected from one or more of metallocene catalysts, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, α-diimine metal nickel, diethylene glycol monoethyl ether barium, triisobutyl aluminum, and tetramethylethylenediamine.

[0048] Specifically, the polymerization reaction of butadiene and isoprene is carried out under nitrogen protection.

[0049] Specifically, the reaction temperature for the polymerization of butadiene and isoprene is 45-65°C.

[0050] Specifically, the reaction time of the polymerization of butadiene and isoprene is 1-2 hours.

[0051] Specifically, the temperature for adding styrene to continue the polymerization is 45-65°C.

[0052] Specifically, styrene is added to continue the polymerization for 2-3 hours.

[0053] Specifically, after styrene is added to continue polymerization to generate polymer C, the temperature is lowered to 20-30°C.

[0054] Specifically, the molar ratio of styrene, isoprene and butadiene is 1:(1-1.5):(1-1.5).

[0055] Specifically, the reaction for generating polymer C includes: adding butadiene, isoprene, cyclohexane, tetrahydrofuran and a catalyst (one or more of metallocene catalyst, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, α-diimine metal nickel, diethylene glycol monoethyl ether barium, triisobutyl aluminum, tetramethylethylenediamine) under nitrogen protection and at a temperature of 45-65° C., adding styrene, continuing the polymerization reaction for 2-3 hours, and then cooling the polymer C to 20-30° C. for standby use.

[0056] Specifically, the preparation method of the HSD type lubricating oil viscosity index improver comprises:

[0057] Dispersing polymer C in cyclohexane and then mixing it with the prepared intermediate; reacting at 45-65°C for 8-24 hours, adding 1% isopropanol, and removing n-hexane with water vapor;

[0058] After hydrogen is introduced into the obtained product, an aluminum-nickel catalyst is added, and the pressure is maintained at 3-5 MPa at 50-70°C. After reacting for 3-6 hours, the product is treated with H2O2 / HCl and anhydrous ethanol to obtain a white solid, which is an HSD type lubricating oil viscosity index improver.

[0059] Specifically, the aluminum-nickel catalyst has a molar ratio of Al to Ni of 1:(3-6).

[0060] In some specific embodiments, the preparation method of the HSD type lubricating oil viscosity index improver comprises:

[0061] (1) under nitrogen protection and at a temperature of 30-40° C., compound A (including but not limited to one of ethylenediamine, diethylenetriamine, triethylenetetramine, tris(dimethylamino)methane), compound B (including but not limited to one of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate) and a methanol solution are added respectively, reacted for 20-30 hours, and the methanol solution is removed by a reduced pressure distillation method, and then set aside;

[0062] (2) under nitrogen protection and at a temperature of 45-65° C., butadiene, isoprene, cyclohexane, tetrahydrofuran and a catalyst (one or more of a metallocene catalyst, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, α-diimine metal nickel, diethylene glycol monoethyl ether barium, triisobutyl aluminum, and tetramethylethylenediamine) are added, and styrene is added. After continuing the polymerization reaction for 2-3 hours, the temperature is lowered to 20-30° C. to obtain a polymer C for standby use;

[0063] (3) dispersing the product of step 2, i.e., polymer C, in cyclohexane, and then adding it to step (1), reacting at 45-65° C. for 8-24 hours, adding 1% isopropanol, and removing the n-hexane with water vapor for standby use;

[0064] (4) After hydrogen is introduced into the product of step (3), aluminum and nickel catalysts (molar ratio of Al to Ni is 1:3-6) are added respectively, and the pressure is maintained at 3-5 MPa at 50-70° C. After 3-6 hours, the product is treated with H2O2 / HCl and anhydrous ethanol to obtain a white solid, which is an HSD type lubricating oil viscosity index improver.

[0065] The present invention comprises an HSD type lubricating oil viscosity index improver prepared by the above method.

[0066] The present invention also provides lubricating oil containing the HSD type lubricating oil viscosity index improver.

[0067] Specifically, the content of the HSD type lubricating oil viscosity index improver in the gasoline engine oil is 0.2-3wt%, preferably 0.4-1.5wt%.

[0068] Specifically, the content of the HSD type lubricating oil viscosity index improver in the diesel engine oil is 0.3-3wt%, preferably 0.6-2wt%.

[0069] The novel lubricating oil viscosity index improver structure of the present invention has good thickening performance, anti-shear performance and low temperature performance. The novel lubricating oil viscosity index improver is widely used in gasoline engine oil, diesel engine oil, motorcycle oil and gas engine oil. DETAILED DESCRIPTION

[0070] The specific embodiments of the present disclosure are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure, and are not used to limit the present disclosure.

[0071] Example 1

[0072] C is prepared from raw materials styrene, isoprene and butadiene, and HSD type lubricating oil viscosity index improver (A) is further prepared from raw materials ethylenediamine (A) and methyl acrylate (B). x B 4x )C 4xn , where x=1, n=3.

[0073] (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 hours, 66 g of ethylenediamine was added. After reflux reaction for 48 hours, the methanol solution was removed by vacuum distillation to obtain 105 g of viscous liquid as the A1B4 product;

[0074] (2) In an absolutely dry 250 mL flask, 150 mL of cyclohexane and 28 g of styrene were added respectively, and then 36 g of butadiene and 36 g of isoprene were introduced into the flask by vaporization according to the metered amount. The flask was placed in a 50°C constant temperature water bath for preheating for 30 min, and then 3 mL of tetramethylethylenediamine (TMEDA) and 12.5 mL of n-butyllithium initiator were added respectively, and the polymerization reaction was carried out for 3 h.

[0075] (3) Dispersing 30 g of A1B4 liquid in 30 mL of n-hexane, adding it to step (2), reacting at 50° C. for 8 h, adding 1% isopropanol, and removing the n-hexane with water vapor to obtain 129.5 g of viscous liquid for standby use;

[0076] (4) 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°C. 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 0.5g Al / Ni (molar ratio 5:1). After 20min, introduce high-purity H2 and pressurize it to 4MPa to keep the pressure constant. The hydrogenation reaction is carried out for 3h. After the reaction is completed, add an appropriate amount of H2O2 / HCl and stir it in a 40°C water bath for 3h. 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. 29.5g of white solid is obtained, which is (A1B4)C 12 Product (HSD type lubricating oil viscosity index improver).

[0077] The HSD type lubricating oil viscosity index improver of this embodiment has an N content of 0.029%; GPC has a number average molecular weight of 361,200 and a distribution coefficient of 1.08.

[0078] A:

[0079] B:

[0080] C:

[0081]

[0082] C: Example 2

[0083] C is prepared from raw materials styrene, isoprene and butadiene, and HSD type lubricating oil viscosity index improver (A) is further prepared from raw materials triethylenediamine (A) and methyl methacrylate (B). x B 4x )C 4xn , where x=2, n=3.

[0084] (1) Under nitrogen protection and at a temperature of 40°C, 11.2 g of triethyleneethylenediamine, 36.1 g of methyl methacrylate and 50 mL of methanol solution were added to a 500 mL flask, and after reacting for 20 hours, 105 g of triethyleneethylenediamine was added, and the mixture was refluxed for 48 hours. 35.9 g of methyl methacrylate and 50 mL of methanol solution were added, and after reacting for 20 hours, 110 g of triethyleneethylenediamine was added, and the mixture was refluxed for 48 hours. After removing the methanol solution by vacuum distillation, 385.6 g of viscous liquid was obtained as the A2B8 product;

[0085] (2) In an absolutely dry 250 mL flask, 150 mL of cyclohexane and 28 g of styrene were added respectively, and then 36 g of butadiene and 36 g of isoprene were introduced into the flask by vaporization according to the metered amount. The flask was placed in a 50°C constant temperature water bath for preheating for 30 min, and then 3 mL of tetramethylethylenediamine (TMEDA) and 12.5 mL of n-butyllithium initiator were added respectively, and the polymerization reaction was carried out for 1.2 h.

[0086] (3) Dispersing 50 g of A2B8 liquid in 30 mL of n-hexane, adding it to step (2), reacting at 50° C. for 12 h, adding 1% isopropanol, and removing n-hexane and cyclohexane with water vapor to obtain 148.7 g of viscous liquid for standby use;

[0087] (4) Take 50g of the sample from step (3) 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 35min. Then add 0.7g Al / Ni (molar ratio 5:1). After 20min, introduce high-purity H2 and pressurize it to 4MPa to keep the pressure constant. The hydrogenation reaction is carried out for 4h. After the reaction is completed, add an appropriate amount of H2O2 / HCl and stir it in a 40°C water bath for 3h. 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 24 Product (HSD type lubricating oil viscosity index improver).

[0088] 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 295,200 and a distribution coefficient of 1.05.

[0089] Example 3

[0090] C is prepared from raw materials styrene, isoprene and butadiene, and HSD type lubricating oil viscosity index improver (A) is further prepared from raw materials p-phenylenediamine (A) and ethyl acrylate (B). x B 4x )C 4xn . Wherein, x=1, n=3.

[0091] (1) Under nitrogen protection and at a temperature of 40°C, 11.2 g of tris(dimethylamino)methane, 36.1 g of methyl methacrylate and 50 mL of methanol solution were added to a 250 mL flask, respectively, and reacted for 20 h. Then, 105 g of triethylenediamine was added, and refluxed for 48 h. The methanol solution was removed by vacuum distillation to obtain 140.8 g of viscous liquid as the A1B4 product;

[0092] (2) In an absolutely dry 250 mL flask, 150 mL of cyclohexane and 28 g of styrene were added respectively, and then 36 g of butadiene and 36 g of isoprene were introduced into the flask by vaporization according to the metered amount. The flask was placed in a 50°C constant temperature water bath for preheating for 30 min, and then 3 mL of tetramethylethylenediamine (TMEDA) and 12.5 mL of n-butyllithium initiator were added respectively, and the polymerization reaction was carried out for 1 h.

[0093] (3) Disperse 50 g of A1B4 liquid in 30 mL of n-hexane, add it to step (2), 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;

[0094] (4) Take 50g of the sample from step (3) 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 (A1B4)C 12 Product (HSD type lubricating oil viscosity index improver).

[0095] 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 114,200 and a distribution coefficient of 1.02.

[0096] Experimental Example 1

[0097] The lubricating oil viscosity modifier prepared in Example 1 and a common viscosity modifier (SV 261, Infineum) currently on the market were used to prepare SN / GF-5 5W-30 gasoline engine oil according to the formula shown in Table 1 below.

[0098] Table 1 SN / GF-5 5W-30 gasoline engine oil

[0099]

[0100] Note: 1. The weight ratio of the composite additive (Ca detergent: dispersant: amine / phenol composite antioxidant, P / Zn / P antiwear agent and pour point depressant) in functional additive B is 2:3:4:0.8:0.2. 2. The viscosity modifier of Example 1 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 261.

[0101] 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.

[0102] The analysis results of SN / GF-5 5W-30 gasoline engine oil are shown in Table 2 below.

[0103] Table 2 Analysis results of SN / GF-5 5W-30 gasoline engine oil

[0104]

[0105] 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 10.45 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 3.57%. 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 better than that of the commercial viscosity index agent prepared products. Through the TEOST 33C and TEOST MHT tests, it is shown that the contribution of the viscosity index agent prepared in Example 1 to detergency is better than that of 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 it have better detergency.

[0106] In summary, the polymer prepared in Example 1 is a very excellent viscosity modifier.

[0107] Experimental Example 2

[0108] 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.

[0109] Table 3CI-4 15W-40 diesel engine oil

[0110]

[0111] Note: 1. The weight ratio of the composite additive in functional additive C (containing Ca detergent: dispersant: amine / phenol composite antioxidant, P / Zn / P anti-wear agent and 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.

[0112] Example 2 and a commercial viscosity modifier were added to the formulation at different dosages, and the performance differences between Example 2 and the commercial viscosity modifier were evaluated by measuring the viscosity, low temperature performance, shear resistance and detergency of the lubricating oil. The analysis results of CI-4 15W-40 diesel engine oil are shown in Table 4 below.

[0113] Table 4 Analysis results of CI-4 15W-40 diesel engine oil

[0114]

[0115] From the analysis data in Table 4, it can be seen that the kinematic viscosity of the CI-415W-40 oil prepared with the viscosity modifier prepared in Example 2 is 14.52 mm 2 / s, while the kinematic viscosity of the commercially available viscosity modifier is 13.90 mm 2 / s. Compared with the commercially available viscosity index agent, the thickening performance of the viscosity index agent in Example 2 is improved by 4.46%. 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 the commercially available viscosity index agent. This shows that the thickening performance and shear resistance of the viscosity index agent prepared in Example 2 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 CI-415W-40 oil prepared by the viscosity index agent prepared in Example 2 is better than that of the 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 the commercially available viscosity index agent. 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.

[0116] In summary, the polymer prepared in Example 2 is a very excellent viscosity agent.

[0117] Experimental Example 3

[0118] The lubricating oil dispersant prepared in Example 3 and a common viscosity index agent (LZ 7077, Lubrizol Corporation) in the current market were respectively used to prepare SP 0W-20 gasoline engine oil according to the formula in Table 5 below.

[0119] Table 5SP 0W-20 gasoline engine oil

[0120]

[0121] Note: 1. Functional additive D composite additive (containing Ca detergent, magnesium detergent: dispersant: amine / phenol compound antioxidant, containing P / Zn / P anti-wear agent and pour point depressant in a weight ratio of 1.5:0.5:3:3:1.9:0.1). 2. Example 3 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 commercially available LZ 7077.

[0122] 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.

[0123] The analysis results of SP 0W-20 gasoline engine oil are shown in Table 6 below.

[0124] Table 6 Analysis results of SP 0W-20 gasoline engine oil

[0125]

[0126] 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 commercial 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 commercial 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 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 SP 0W-20 oil product prepared by the viscosity index agent prepared in Example 3 is better than that of the commercial viscosity index agent prepared product. Through the gel board test, it is shown that the contribution of the viscosity index agent prepared in Example 3 to detergency is better than that of the commercial viscosity index agent. This may be because the viscosity index agent prepared in Example 3 has a regular structure and is not easily oxidized, thus making it have better detergency.

[0127] In summary, the polymer prepared in Example 3 is a very excellent viscosity modifier.

[0128] The preferred embodiments of the present disclosure are described in detail above, but the present disclosure is not limited to the specific details in the above embodiments. Within the technical concept of the present disclosure, a variety of simple modifications can be made to the technical solution of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

[0129] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0130] In addition, various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A HSD type lubricating oil viscosity index improver, the structure of which is shown in the following formula: (A x B 4x )C 4xn , in, A is a diprimary amine compound and contains only C, H, and N elements; B is acrylate or methacrylate; A x B 4x They are connected by saturated bonds; C is a polymer of styrene, isoprene and butadiene; n is an integer from 1 to 20; x is an integer from 1 to 10.

2. The HSD type lubricating oil viscosity index improver according to claim 1, characterized in that: A is attached via Michael addition and / or transesterification x B 4x , connecting C via amino substitution reaction.

3. The HSD type lubricating oil viscosity index improver according to claim 1 or 2, characterized in that: A is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, 3,3'-bis(dimethylamino)-1,5-pentanediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4,4',4"-triaminotriphenylmethane, tetrakis(4-aminophenyl)methane, 4,4'-tetramethyldiaminodiphenylmethane, tris(dimethylamino)methane, and bis(2,4-diamino-5-methylphenyl)methane; and / or, The B is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate; and / or, The number average molecular weight of C is 10000-100000, preferably 25000-70000; and / or, n is 1, 2 or 3; and / or, x is 1, 2, or 3.

4. A HSD type lubricating oil viscosity index improver, which is formed by reacting compound A and compound B through Michael addition reaction and transesterification reaction to generate an intermediate, and then connected with polymer C through amino substitution reaction; wherein, Compound A is a diprimary amine-containing compound and contains only C, H and N elements; compound B is acrylate or methacrylate; polymer C is a polymer of styrene, isoprene and butadiene.

5. The HSD type lubricating oil viscosity index improver according to claim 4, characterized in that: The compound A is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, 3,3'-bis(dimethylamino)-1,5-pentanediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4,4',4"-triaminotriphenylmethane, tetrakis(4-aminophenyl)methane, 4,4'-tetramethyldiaminodiphenylmethane, tris(dimethylamino)methane, and bis(2,4-diamino-5-methylphenyl)methane; preferably one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, and p-phenylenediamine; and / or, The compound B is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate; more preferably, one or more of methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate; and / or, The number average molecular weight of the polymer C is 10,000-100,000, preferably 25,000-70,000; and / or, The molar ratio of compound A to compound B is 1:4; and / or, The molar ratio of the intermediate to the polymer C is 1:(1-800), preferably 1:(1-24).

6. The HSD type lubricating oil viscosity index improver according to any one of claims 1 to 5, characterized in that: The number average molecular weight of the HSD type lubricating oil viscosity index improver is 80,000-800,000, preferably 100,000-400,000.

7. The HSD type lubricating oil viscosity index improver according to any one of claims 1 to 6, characterized in that 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 nitrogen content is 0.01-10%, preferably 0.02-0.3%.

8. The method for preparing the HSD type lubricating oil viscosity index improver according to any one of claims 1 to 7, characterized in that: include: Allowing compound A and compound B to undergo Michael addition reaction and transesterification reaction to generate an intermediate; Make styrene, isoprene and butadiene generate polymer C; The intermediate is linked to polymer C via an amino substitution reaction.

9. The method for preparing the HSD type lubricating oil viscosity index improver according to claim 8, characterized in that: The reaction temperature for generating the intermediate is 30-40°C; and / or, The reaction time for generating the intermediate is 20-30h; and / or, The reaction for generating polymer C includes: first polymerizing butadiene and isoprene, and then adding styrene to continue the polymerization; optionally, the reaction temperature of butadiene and isoprene polymerization is 45-65°C, and the reaction time is 1-2h; optionally, the temperature of adding styrene to continue the polymerization is 45-65°C, and the polymerization time is 2-3h.

10. A lubricating oil containing the HSD type lubricating oil viscosity index improver according to any one of claims 1 to 7; Preferably, the content of the HSD type lubricating oil viscosity index improver in gasoline engine oil is 0.2-3%, preferably 0.4-1.5%; the content of the HSD type lubricating oil viscosity index improver in diesel engine oil is 0.3-3%, preferably 0.6-2%.

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