Hsd-type sticky-finger agent, preparation method and application thereof

Abstract

The application provides a new HSD type sticky-finger agent, a preparation method and application. The new lubricating oil viscosity index improver has the following structure: (A x B 4x )C 4xn , A is a double primary amine compound, and only contains C, H and N elements; B is an acrylic ester or a methacrylic ester. A x B 4x are connected through a saturated bond; C is a polymer of styrene, isoprene or butadiene; x is the number of A molecules, and n is the number of primary and secondary amines of A x B 4x , and is an integer of 1-20, but is not limited to the integer. The lubricating oil viscosity index improver has good thickening performance, shear resistance and low-temperature performance. The lubricating oil viscosity index is widely used in gasoline engine oil, diesel engine oil, motorcycle oil and gas engine oil.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of lubricating oil additives, and particularly relates to a HSD type viscosity index agent and a preparation method and application thereof. BACKGROUND

[0002] With the upgrading of emission regulations and the promotion of energy saving and environmental protection, engine oil has also taken a big step towards high quality and high level. In the era of double carbon, the energy consumption structure has been adjusted towards clean and low carbon, especially in the field of transportation.

[0003] From the direction of the development of the lubricating industry, lubricating oil will gradually develop towards high quality and high performance, which is an inevitable trend of the industry development. Viscosity index improver is an indispensable additive for high-grade lubricating oil, especially engine oil. The commonly used viscosity index improver types at present mainly include PMA type (polymethyl acrylate), OCP type (ethylene-propylene copolymer), HSD type (hydrogenated styrene-diene copolymer) and the like. 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 and the like, and is widely used in medium and high-grade engine lubricating oil. At present, the yield and quality stability of HSD type viscosity index improver cannot meet the demand of high-grade lubricating oil viscosity index improver. Developing new HSD type viscosity index improver has become an important task of lubricating oil additive research and development. SUMMARY

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

[0005] A HSD type lubricating oil viscosity index improver has the following structure:

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

[0007] wherein A is a double primary amine containing compound and only contains C, H and N elements;

[0008] B is an acrylate or a methacrylate;

[0009] A x B 4x are connected through a saturated bond;

[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 of 1-20;

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

[0013] Further, (A x B 4x ) C 4xn A is connected with B by Michael addition, ester exchange reaction x B 4x C is connected with B by amino substitution reaction.

[0014] Further, the HSD type lubricating oil viscosity index improver has a number average molecular weight of 80000-800000; preferably 100000-400000.

[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, tetra(4-aminophenyl)methane, 4,4'-tetramethyl-diaminodiphenylmethane, tris(dimethylamino)methane, bis(2,4-diamino-5-methylphenyl)methane, preferably one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, 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, butyl methacrylate, preferably one or more of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate.

[0017] Further, C has a number average molecular weight of 10000-100000, preferably 25000-70000.

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

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

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

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

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

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

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

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

[0026] An HSD type lubricating oil viscosity index improver is generated by Michael addition reaction and ester exchange reaction of compound A and compound B to form an intermediate (A x B 4x ), and then connected with polymer C through amino substitution reaction; wherein, compound A is a double primary amine containing compound, and only contains C, H, N elements; compound B is acrylate or methacrylate; polymer C is a polymerization product of styrene, isoprene, butadiene.

[0027] Specifically, the number average molecular weight of the HSD type lubricating oil viscosity index improver is 80000-800000; preferably 100000-400000.

[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'-tetramethyl-diaminodiphenylmethane, tris(dimethylamino)methane, bis(2,4-diamino-5-methylphenyl)methane; preferably one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, 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, butyl methacrylate; more preferably one or more of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate.

[0030] Specifically, the number average molecular weight of the polymer C is 10000-100000, preferably 25000-70000.

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

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

[0033] Specifically, the HSD type lubricating oil viscosity index improver has a number average molecular weight of 80000-800000, preferably 100000-400000.

[0034] Specifically, the HSD type lubricating oil viscosity index improver has elements of 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 the form of carbonyl (C=O), the molar ratio of the nitrogen element to the oxygen element is (4.0-4.5):1, preferably (2.0-2.5):1, and the nitrogen content is 0.01-10%, preferably 0.02-0.3%.

[0036] The application further provides a preparation method of the HSD type lubricating oil viscosity index improver.

[0037] The compound A and the compound B are reacted to generate an intermediate through Michael addition reaction and ester exchange reaction.

[0038] The styrene and the isoprene and the butadiene are reacted to generate the polymer C.

[0039] The intermediate is connected to the polymer C through amino substitution reaction.

[0040] Specifically, the reaction for generating the intermediate is carried out in the presence of a solvent. Alternatively, the solvent is methanol (solution). After the reaction is completed, the solvent is removed through reduced pressure distillation.

[0041] Specifically, the reaction for generating the intermediate is carried out under nitrogen protection.

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

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

[0044] Specifically, the method for generating the intermediate is: under nitrogen protection and at a temperature of 30-40℃, the compound A, the compound B and the methanol solution are added respectively, and the reaction is carried out for 20-30h; after the reaction is completed, the methanol solution is removed through reduced pressure distillation, and the intermediate is obtained.

[0045] Specifically, the reaction for generating the polymer C includes: first, the butadiene and the isoprene are polymerized, and then the styrene is added to continue the polymerization.

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

[0047] Specifically, the reaction of polymerization of butadiene and isoprene is carried out in the presence of a catalyst. Optionally, the catalyst is selected from one or more of a metallocene catalyst, n-butyllithium, sec-butyllithium, t-butyllithium, α-diimine metal nickel, diethylene glycol monomethyl ether barium, triisobutylaluminum, and tetramethylethylenediamine.

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

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

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

[0051] Specifically, the temperature for continuing polymerization by adding styrene again is 45-65℃.

[0052] Specifically, the time for continuing polymerization by adding styrene again is 2-3h.

[0053] Specifically, after the polymer C is generated by continuing polymerization by adding styrene again, the temperature is lowered to 20-30℃.

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

[0055] Specifically, the reaction for generating the polymer C comprises: under nitrogen protection and at a temperature of 45-65℃, adding butadiene, isoprene, cyclohexane, tetrahydrofuran, and a catalyst (one or more of a metallocene catalyst, n-butyllithium, sec-butyllithium, t-butyllithium, α-diimine metal nickel, diethylene glycol monomethyl ether barium, triisobutylaluminum, and tetramethylethylenediamine), adding styrene, continuing polymerization for 2-3h, and obtaining the polymer C. The temperature is lowered to 20-30℃, and the polymer C is ready for use.

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

[0057] After the polymer C is dispersed in cyclohexane, the polymer C is mixed with the prepared intermediate; at a temperature of 45-65℃, after reaction for 8-24h, 1% isopropyl alcohol is added, and n-hexane is removed by water vapor;

[0058] After hydrogen is introduced into the obtained product, an aluminum-nickel catalyst is added, the temperature is maintained at 50-70℃, the pressure is maintained at 3-5MPa, after reaction for 3-6h, the product is treated by H2O2 / HCl and anhydrous ethanol, and a white solid is obtained, which is the 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 embodiments, the method for preparing 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, and tris(dimethylamino)methane), compound B (including but not limited to one of methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate), and a methanol solution are added respectively, the methanol solution is removed by vacuum distillation after a reaction of 20-30 h, and the product is used after cooling;

[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-butyllithium, sec-butyllithium, tert-butyllithium, α-diimine nickel, diethylene glycol monoethyl ether barium, and triisobutylaluminum) are added, styrene is added, the polymerization reaction is continued for 2-3 h, the temperature is then lowered to 20-30°C, and polymer C is obtained and used after cooling;

[0063] (3) the product of step 2, i.e., polymer C, is dispersed in cyclohexane and then added to step (1), and after a reaction of 8-24 h at 45-65°C, 1% isopropyl alcohol is added, n-hexane is removed by water vapor, and the product is used after cooling;

[0064] (4) the product of step (3) is subjected to hydrogenation, aluminum-nickel catalyst (Al to Ni molar ratio of 1:3-6) is added, the temperature is maintained at 50-70°C, the pressure is maintained at 3-5 MPa, and after 3-6 h, the product is treated with H2O2 / HCl and anhydrous ethanol to obtain a white solid, i.e., the HSD type lubricating oil viscosity index improver.

[0065] The present application includes the HSD type lubricating oil viscosity index improver prepared by the above method.

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

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

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

[0069] The novel lubricating oil viscosity index improver structure has good thickening performance, shear resistance 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 x B 4x )C 4xn , wherein x = 1, n = 3.

[0073] (1) Under nitrogen protection and at a temperature of 40°C, 6g of ethylenediamine and 34.6g of methyl acrylate and 50mL of methanol solution were added into a 250mL flask, respectively, and after 20h of reaction, 66g of ethylenediamine was added, and after 48h of reflux reaction, the methanol solution was removed by vacuum distillation to obtain 105g of viscous liquid as A1B4 product;

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

[0075] (3) 30g of A1B4 liquid was dispersed in 30mL of n-hexane, and then added to step (2), and after 8h of reaction at 50°C, 1% of isopropyl alcohol was added, and then n-hexane was removed by water vapor to obtain 129.5g of viscous liquid, which was ready for use;

[0076] (4) Take 30 g of the sample of step (3) and add it to a 200 mL stainless steel autoclave with a stirring device. Add 80 mL of refined cyclohexane, seal it, and stir in a constant temperature water bath at 60°C. After the glue sample is completely dissolved, add 3 mL of tetrahydrofuran additive under high-purity N2 protection. Continue to stir the autoclave for 30 min. Then add 0.5 g of Al / Ni (molar ratio 5:1), and after 20 min, pass high-purity H2 to pressurize to 4 MPa and keep the pressure constant. Hydrogenation reaction for 3 h. After the reaction is completed, add an appropriate amount of H2O2 / HCl and stir in a 40°C water bath for 3 h. The glue liquid changes from tea brown to white. Agglomerate with anhydrous ethanol. Dry the polymer in a 40°C vacuum oven until the mass is constant. 29.5 g 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 example: N content is 0.029%; GPC: number average molecular weight is 361.2 million, and distribution coefficient is 1.08.

[0078]

[0079]

[0080]

[0081] Example 2

[0082] C is prepared from raw materials styrene, isoprene, and butadiene, and HSD type lubricating oil viscosity index improver (A1B4)C is further prepared from raw materials triethylene diamine (A) and methyl methacrylate (B). x B 4x )C 4xn Wherein, x = 2, n = 3.

[0083] (1) Under nitrogen protection and at a temperature of 40°C, 11.2 g of triethylene diamine and 36.1 g of methyl methacrylate and 50 mL of methanol solution are added to a 500 mL flask, respectively. After 20 h of reaction, 105 g of triethylene diamine is added, and reflux reaction is carried out for 48 h. Then 35.9 g of methyl methacrylate and 50 mL of methanol solution are added, and after 20 h of reaction, 110 g of triethylene diamine is added, and reflux reaction is carried out for 48 h. After removing the methanol solution by vacuum distillation, 385.6 g of viscous liquid is obtained as A2B8 product;

[0084] (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 metering gasification. The flask was placed in a 50°C constant temperature water bath for preheating for 30 min, and then 3 mL of tetramethyl ethylenediamine (TMEDA) and 12.5 mL of n-butyllithium initiator were added, respectively, and the polymerization reaction was carried out for 1.2 h.

[0085] (3) 50 g of A2B8 liquid was dispersed in 30 mL of n-hexane, and then added to step (2). After reaction at 50°C for 12 h, 1% of isopropyl alcohol was added, and then n-hexane and cyclohexane were removed by water vapor to obtain 148.7 g of a viscous liquid, which was used as is;

[0086] (4) 50 g of the sample in step (3) was added to a 220 mL stainless steel high-pressure reaction kettle with a stirring device, and 100 mL of cyclohexane was added. After sealing, stirring was carried out in a 60°C constant temperature water bath. After the glue sample was completely dissolved, 3.2 mL of tetrahydrofuran additive was added under high-purity N2 protection, and the reaction kettle was continuously stirred for 35 min. Then 0.7 g of Al / Ni (molar ratio 5:1) was added, and after 20 min, high-purity H2 was introduced to pressurize to 4 MPa to keep the pressure constant, and the hydrogenation reaction was carried out for 4 h. After the reaction was completed, an appropriate amount of H2O2 / HCl was added, and stirring was carried out in a 40°C water bath for 3 h. The glue liquid changed from tea brown to white, and was coagulated with anhydrous ethanol. The polymer was dried in a 40°C vacuum oven until the mass was constant. 48.6 g of white solid was obtained, which was (A2B8)C. 24 Product (HSD type lubricating oil viscosity index improver).

[0087] The HSD type lubricating oil viscosity index improver of this example: the N content is 0.042%; GPC: the number average molecular weight is 295.2 million, and the distribution coefficient is 1.05.

[0088] Example 3

[0089] C was prepared from raw materials styrene, isoprene and butadiene, and HSD type lubricating oil viscosity index improver (A x B 4x )C 4xn was further prepared from raw materials p-phenylenediamine (A) and ethyl acrylate (B). Wherein, x=1, n=3.

[0090] (1) Under nitrogen protection and at a temperature of 40°C, 11.2 g of tris(dimethylamino)methane and 36.1 g of methyl methacrylate were added to a 250 mL flask, and 50 mL of a methanol solution was added. After reaction for 20 h, 105 g of triethylenediamine was added, and reflux reaction was carried out for 48 h. After removing the methanol solution by reduced pressure distillation, 140.8 g of a viscous liquid was obtained as A1B4 product;

[0091] (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 metering gasification. The flask was preheated in a 50 °C constant temperature water bath for 30 min, and then 3 mL of tetramethyl ethylenediamine (TMEDA) and 12.5 mL of n-butyllithium initiator were added, respectively, and the polymerization reaction was carried out for 1 h.

[0092] (3) 50 g of A1B4 liquid was dispersed in 30 mL of n-hexane, and then added to step (2). After reaction at 50 °C for 12 h, 1% isopropyl alcohol was added, and n-hexane and cyclohexane were removed by water vapor to obtain 148.7 g of viscous liquid, which was used as is;

[0093] (4) 50 g of the sample of step (3) was added to a 220 mL stainless steel high-pressure reaction kettle with a stirring device, and 100 mL of cyclohexane was added. After sealing, stirring was carried out in a 60 °C constant temperature water bath. After the glue sample was completely dissolved, 3.2 mL of tetrahydrofuran additive was added under high-purity N2 protection, and the reaction kettle was continuously stirred for 35 min. Then 0.7 g of Al / Ni (molar ratio 5:1) was added, and after 20 min, high-purity H2 was introduced to pressurize to 4 MPa, and the pressure was kept constant. Hydrogenation reaction was carried out for 4 h. After the reaction was completed, an appropriate amount of H2O2 / HCl was added, and stirring was carried out at 40 °C for 3 h. The glue liquid changed from tea brown to white. Agglomeration was carried out with anhydrous ethanol, and the polymer was dried in a 40 °C vacuum oven until the mass was constant. 48.6 g of white solid was obtained, which was (A1B4)C. 12 Product (HSD type lubricating oil viscosity index improver).

[0094] The HSD type lubricating oil viscosity index improver of this example: the N content is 0.122%; GPC: the number average molecular weight is 114200, and the distribution coefficient is 1.02.

[0095] Experimental Example 1

[0096] The lubricating oil viscosity index improver prepared in Example 1 and the commonly used viscosity index improver (SV 261, Runyon Company) in the current market were respectively used to prepare SN / GF-5 5W-30 gasoline engine oil according to the formulations in Table 1.

[0097] Note: 1, the weight ratio of the composite additives (Ca detergent: dispersant: amine / phenol compound antioxidant, P / Zn / P-containing anti-wear agent and pour point depressant) in functional additive B is 2:3:4:0.8:0.2. 2, the viscosity index improver of Example 1 is dissolved in 90% 100N base oil at a proportion of 10%, and the dry glue content is the same as that of the commercially available SV 261.

[0098] Example 1 and commercially available viscosity modifier were added to the formulation at the dosage, the performance difference between Example 1 and commercially available viscosity modifier was evaluated by the lubricating oil viscosity, low temperature performance, shear resistance and detergency.

[0099] The analysis results of SN / GF-5 5W-30 gasoline engine oil are shown in Table 2 below.

[0100]

[0101] From the analysis data in Table 2, it can be seen that the kinematic viscosity of the SN / GF-5 5W-30 oil prepared by using the viscosity modifier prepared by Example 1 is 10.45 mm 2 / s, and the kinematic viscosity of the commercially available viscosity modifier is 10.09 mm 2 / s. Compared with the commercially available viscosity modifier, the thickening performance of the viscosity modifier prepared by Example 1 is increased by 3.57%. In addition, through the diesel nozzle shear test, the shear stability of the viscosity modifier prepared by Example 1 is better than that of the commercially available viscosity modifier. Therefore, it is proved that the thickening performance and shear resistance of the viscosity modifier prepared by Example 1 are better than those of the commercially available viscosity modifier product. 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 using the viscosity modifier prepared by Example 1 is better than that of the commercially available viscosity modifier. Through the TEOST 33C and TEOST MHT tests, it is proved that the contribution of the viscosity modifier prepared by Example 1 to detergency is better than that of the commercially available viscosity modifier. This may be because the structure of the viscosity modifier prepared by Example 1 is regular and not easy to be oxidized, so that its detergency is better.

[0102] In summary, the polymer prepared by Example 1 is a very excellent viscosity modifier.

[0103] Experimental Example 2

[0104] The lubricating oil dispersant prepared by Example 2 and the commonly used viscosity modifier (LZ 7077, Lubrizol Company) in the market were respectively used to prepare CI-4 15W-40 diesel engine oil according to the formulation in Table 3 below.

[0105]

[0106] Note: 1. The weight ratio of the composite additives (containing Ca detergents: dispersants: amine / phenol compound antioxidants, P / Zn / P anti-wear agents and pour point depressants) in functional additive C is 1.5:3.5:3.2:1.7:0.1. 2. The viscosity modifier prepared by Example 2 is dissolved in 90% 100N base oil at a proportion of 10%, and the dry gel content is the same as that of the commercially available LZ 7077.

[0107] Example 2 and commercially available viscosity modifier were added to the formulation at the dosage, the performance difference between Example 2 and commercially available viscosity modifier was evaluated by the lubricating oil viscosity, low temperature performance, shear resistance and detergency.

[0108] The analysis results of CI-4 15W-40 diesel oil are shown in Table 4 below.

[0109]

[0110] From the analysis data in Table 4, it can be seen that the kinematic viscosity of CI-4 15W-40 oil product prepared by using the tack agent of Example 2 is 14.52 mm 2 / s, while the kinematic viscosity of the commercially available tack agent is 13.90 mm 2 / s. Compared with the commercially available tack agent, the thickening performance of the tack agent of Example 2 is increased by 4.46%. In addition, through the diesel nozzle shear test, the shear stability of the tack agent prepared in Example 2 is better than that of the commercially available tack agent. Therefore, it is shown that the thickening performance and shear resistance of the tack agent prepared in Example 2 are better than those of the commercially available tack agent product. 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 product prepared by using the tack agent of Example 2 is better than that of the commercially available tack agent product. Through the gelling plate test, it is shown that the contribution of the tack agent prepared in Example 2 to detergency is better than that of the commercially available tack agent. This can be because the structure of the tack agent prepared in Example 2 is regular and is not easy to be oxidized, so that the detergency thereof is better.

[0111] In summary, the polymer prepared in Example 2 is a very excellent tack agent.

[0112] Experimental Example 3

[0113] The lubricating oil dispersant prepared in Example 3 and the commonly used tack agent (LZ 7077, Lubrizol Company) in the current market were respectively used to prepare SP 0W-20 gasoline engine oil according to the formulations in Table 5 below.

[0114] Note: 1. Functional additive D composite additive (containing Ca detergent, magnesium detergent, dispersant, amine / phenol compound antioxidant, P / Zn / P containing anti-wear agent and pour point depressant in a weight ratio of 1.5:0.5:3:3:1.9:0.1). 2. The tack agent of Example 3 is dissolved in 90% 100N base oil at a proportion of 10%, and the dry gel content thereof is the same as that of the commercially available LZ 7077.

[0115] The tack agent of Example 3 and the commercially available tack agent were added to the formulations at a dose, and the performance difference between the tack agent of Example 3 and the commercially available tack agent was evaluated through the viscosity, low-temperature performance, shear resistance and detergency of the lubricating oil.

[0116] The analysis results of SP 0W-20 gasoline engine oil are shown in Table 6 below.

[0117]

[0118] From the analysis data of Table 6, it can be seen that the kinematic viscosity of the SP 0W-20 oil product prepared by using the viscous index agent prepared in Example 3 is 8.15 mm 2 / s, while the kinematic viscosity of the commercially available viscous index agent is 7.82 mm 2 / s. Compared with the commercially available viscous index agent, the thickening performance of the viscous index agent prepared in Example 3 is improved by 4.23%. In addition, through the diesel nozzle shear test, the shear stability of the viscous index agent prepared in Example 3 is better than that of the commercially available viscous index agent. Therefore, it is shown that the thickening performance and shear resistance of the viscous index agent prepared in Example 3 are better than those of the commercially available viscous index agent product. Through the analysis of the 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 using the viscous index agent prepared in Example 3 is better than that of the product prepared by using the commercially available viscous index agent. Through the gelling plate test, it is shown that the contribution of the viscous index agent prepared in Example 3 to detergency is better than that of the commercially available viscous index agent. This may be because the viscous index agent prepared in Example 3 has a regular structure and is not easy to be oxidized, so that it has better detergency.

[0119] In summary, the polymer prepared in Example 3 is a very excellent viscous index agent.

[0120] The above describes the preferred embodiments of the present disclosure in combination with the detailed description, but the present disclosure is not limited to the specific details in the above-described embodiments, and various simple modifications can be made to the technical solutions of the present disclosure within the technical concept of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

[0121] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, the present disclosure will not further describe various possible combination manners.

[0122] In addition, various different embodiments of the present disclosure can also be combined in any manner, as long as they do not deviate from the idea of the present disclosure, and they should also be considered as disclosed by the present disclosure.

Claims

1. A HSD type lubricating oil viscosity index improver, having the following structure: Compound A - B - C Compound B - C Compound C wherein, the A is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, 3,3'-dimefhylamino)-1,5 pentanediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4,4',4"-triaminotriphenylmethane, tetra(4-aminophenyl)methane, 4,4'-tetramethyl diaminodiphenylmethane, tris(dimethylamino)methane, bis(2,4-diamino-5-methylphenyl)methane; B is an acrylic ester or a methacrylic ester; C is a polymer of styrene, isoprene, butadiene; n is an integer from 1 to 20; and x is an integer from 1 to 10. (A x B 4x )C 4xn , wherein 3. The HSD type lubricating oil viscosity index improver according to claim 1, wherein, the B is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate; and / or, the number average molecular weight of the C is from 10,000 to 100,000; and / or, n is 1, 2, or 3; and / or, x is 1, 2, or 3. A x B 4x between the atoms; The number average molecular weight of the C is from 25,000 to 70,000. Compound A is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, 3,3'-dimefhylamino)-1,5 pentanediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4,4',4"-triaminotriphenylmethane, tetra(4-aminophenyl)methane, 4,4'-tetramethyl diaminodiphenylmethane, tris(dimethylamino)methane, bis(2,4-diamino-5-methylphenyl)methane; Compound B is an acrylic ester or a methacrylic ester; and Polymer C is a polymer of styrene, isoprene, butadiene. Compound B is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate; and / or, the number average molecular weight of the Polymer C is from 10,000 to 100,000; and / or, the molar ratio of Compound A to Compound B is 1:4; and / or, the molar ratio of the intermediate to Polymer C is 1: (1-800).

2. The HSD type lubricating oil viscosity index improver according to claim 1, characterized by A is connected by a Michael addition and or transesterification reaction x B 4x C is connected by an amino substitution reaction Compound A is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, p-phenylenediamine; and / or, Compound B is selected from one or more of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate; and / or, the number average molecular weight of the Polymer C is from 25,000 to 70,000; and / or, the molar ratio of the intermediate to Polymer C is 1: (1-24). The number average molecular weight of the HSD type lubricating oil viscosity index improver is from 80,000 to 800,000. The number average molecular weight of the HSD type lubricating oil viscosity index improver is from 100,000 to 400,000.

10. The HSD type lubricating oil viscosity index improver according to any one of claims 1-7, wherein the HSD type lubricating oil viscosity index improver comprises C, H, O, and N. ​ 4. The HSD type lubricating oil viscosity index improver according to claim 3, characterized by ​ 5. A HSD type lubricating oil viscosity index improver which is produced by Michael addition reaction and ester exchange reaction of Compound A and Compound B to form an intermediate, and then linking the intermediate to Polymer C through amino substitution reaction; wherein, Compound A is ###0002### Compound B is ###0003### Polymer C is ###0004### and n is an integer of 1 to 1000. ​ 6. The HSD type lubricating oil viscosity index improver according to claim 5, characterized by ​ ​ ​ ​ 7. The HSD type lubricating oil viscosity index improver according to claim 6, characterized by ​ ​ ​ ​ 8. The HSD type lubricating oil viscosity index improver according to any one of claims 1 to 7, characterized by, ​ 9. The HSD type lubricating oil viscosity index improver according to claim 8, characterized by ​ ​ 11. The HSD type lubricating oil viscosity index improver according to claim 10, characterized by In the HSD type lubricating oil viscosity index improver, the carbon element and the oxygen element are linked in a carbonyl manner, the molar ratio of the nitrogen element and the oxygen element is (4.0-4.5):1; and the nitrogen element content is 0.01-10%.

12. The HSD type lubricating oil viscosity index improver according to claim 11, characterized by The molar ratio of the nitrogen element and the oxygen element is (2.0-2.5):1; and the nitrogen element content is 0.02-0.3%.

13. A process for the preparation of the HSD type lubricating oil viscosity index improver according to any one of claims 1 to 12, characterized in that, The method comprises: making compound A and compound B generate an intermediate through Michael addition reaction and ester exchange reaction; making styrene, isoprene and butadiene generate a polymer C; connecting the intermediate to the polymer C through amino substitution reaction.

14. The method of claim 13 wherein the HSD type lubricating oil viscosity index improver is prepared by the process of: The reaction temperature for generating the intermediate is 30-40℃; and / or, The reaction time for generating the intermediate is 20-30h; and / or, The reaction for generating the polymer C comprises: first making butadiene and isoprene polymerize, and then adding styrene to continue polymerization.

15. The preparation method of the HSD type lubricating oil viscosity index improver according to claim 14, characterized in that, The reaction temperature for making butadiene and isoprene polymerize is 45-65℃, and the reaction time is 1-2h.

16. The method of claim 13 wherein the HSD type lubricating oil viscosity index improver is prepared by the process of: The temperature for adding styrene to continue polymerization is 45-65℃, and the polymerization time is 2-3h.

17. A lubricating oil containing the HSD type lubricating oil viscosity index improver according to any one of claims 1-12.

18. The lubricating oil of claim 17, wherein, The content of the HSD type lubricating oil viscosity index improver in gasoline engine oil is 0.2-3%; and the content of the HSD type lubricating oil viscosity index improver in diesel engine oil is 0.3-3%.

19. The lubricating oil of claim 18, wherein, The content of the HSD type lubricating oil viscosity index improver in gasoline engine oil is 0.4-1.5%; and the content of the HSD type lubricating oil viscosity index improver in diesel engine oil is 0.6-2%. The content of the HSD type lubricating oil viscosity index improver in gasoline engine oil is 0.4-1.5%; and the content of the HSD type lubricating oil viscosity index improver in diesel engine oil is 0.6-2%.

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