CN111040840A

CN111040840A - Diesel engine oil composition and preparation method thereof

Info

Publication number: CN111040840A
Application number: CN201811195310.8A
Authority: CN
Inventors: 刘依农; 段庆华; 苏朔; 徐冰
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Beijing General Fine Chemical Technology Development Co ltd; Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2018-10-15
Filing date: 2018-10-15
Publication date: 2020-04-21

Abstract

本发明提出了一种柴油机油组合物及其制备方法。本发明的柴油机油组合物包括黏度指数改进剂、清净剂、分散剂、抗氧剂、抗磨剂、降凝剂和主要量的润滑基础油；所述黏度指数改进剂的结构如通式(I)或(II)所示：

其中各基团的定义见说明书。本发明的柴油机油组合物具有优异的高温清净性、烟炱分散性、抗氧化性、抗磨性、金属腐蚀抑制性能和低温性能，可以满足API CI‑4规格的要求，同时本发明的柴油机油组合物具有降低的磷含量，能够满足环保排放的要求。The invention provides a diesel engine oil composition and a preparation method thereof. The diesel engine oil composition of the present invention comprises a viscosity index improver, a detergent, a dispersant, an antioxidant, an antiwear agent, a pour point depressant and a major amount of lubricating base oil; the structure of the viscosity index improver is as shown in the general formula ( I) or (II) shown:

The definition of each group is shown in the specification. The diesel engine oil composition of the present invention has excellent high-temperature detergency, soot dispersibility, oxidation resistance, anti-wear property, metal corrosion inhibition performance and low temperature performance, and can meet the requirements of API CI-4 specifications. The engine oil composition has a reduced phosphorus content and is able to meet environmental emission requirements.

Description

Diesel engine oil composition and preparation method thereof

Technical Field

The invention relates to a lubricating oil composition for an internal combustion engine, in particular to a diesel engine oil composition.

Background

At present, the diesel engine adopts the technologies of direct injection, fuel delayed injection, high top ring piston and tail gas circulation to meet the requirements of high power and low emission, thus causing high working temperature of oil products, large soot content and higher requirements on oil product formulas. For example, in a diesel engine, the working temperature of a piston top bank can reach more than 300 ℃ at most, and the temperature can aggravate oil oxidation to generate a large amount of polar substances such as coking precursors, organic acids, inorganic acids and the like; the existence of soot also brings the problems of oil filter blockage and cylinder sleeve piston ring and valve group abrasion. Thus, the soot dispersion requirements for engine oils are also stringent, e.g., 4.8% soot in CI-4 oils when passing the T-8 bench test. Therefore, the cleaning, dispersing, antioxidant and antiwear abilities of common oil products can not meet the above requirements.

In solving the problem of high-temperature detergency of diesel engine oils, various detergent combinations are often used, for example, a combination of a high base number sulfonate and a high base number sulfurized alkylphenate. In order to solve the problem of soot dispersibility, an ashless dispersant with better dispersibility or a viscosity index improver with dispersibility is required to meet the requirement, but the currently adopted ashless dispersant cannot completely meet the requirement of soot dispersibility, and the dosage needs to be increased, so that the cost of the composition is increased. If the dispersion type tackifier is adopted, the addition amount of the ashless agent can be reduced on the premise of ensuring the dispersion and the wear resistance of oil products to be unchanged, and the cost is reduced, so the dispersant type tackifier is a current research hotspot and has a plurality of related research reports.

CN1523090A discloses an engine lubricating oil composition, in particular to a lubricating oil composition for a heavy-duty diesel engine, which is characterized in that the lubricating oil composition contains a large amount of hydrogenated base oil, a proper amount of high-base-number salicylate, low-base-number salicylate, sulfurized alkylphenol salt, boronized bissuccinimide ashless dispersant, high-molecular ashless dispersant, zinc dialkyl dithiophosphate and phenol type and amine type auxiliary antioxidant. The lubricating oil composition can meet the specification requirements of SAE J300 and API CF-4 diesel engine oils.

CN101935574A introduces an engine lubricating oil composition, in particular to a lubricating oil composition for a heavy-duty diesel engine, which is characterized in that the lubricating oil composition contains a large amount of hydrogenated base oil, a proper amount of alkyl salicylate, sulfurized alkyl phenate, sulfonate, a high-molecular ashless dispersant, a polyisobutylene bis (succinimide) ashless dispersant, zinc dialkyl dithiophosphate, a phenol antioxidant, an amine antioxidant and a sulfur-containing antioxidant antiwear agent. The lubricating oil composition can meet the specification requirements of CF-4 diesel engine oil specified in GB 11122-2006.

CN1782049A relates to a lubricating oil additive composition, which comprises a high molecular weight polyisobutylene succinimide ashless dispersant, a boronized polyisobutylene succinimide dispersant, a polyisobutylene succinimide dispersant coupled with phenol, a metal detergent and an oxidation and corrosion inhibitor by taking the total weight of the composition as a reference. The composition has excellent soot dispersing performance and endows oil products with good oxidation resistance and corrosion resistance. The high-grade diesel engine oil with CF-4 grade or above can be prepared by adding the high-grade diesel engine oil into I-type and II-type base oil or synthetic base oil with high viscosity index.

US5719107 uses borated high molecular weight polyisobutylene succinimide to prepare heavy-duty diesel engine oil, and the oil product can reach the requirements of API CF-4 and CG-4.

It is seen from the above patent documents that in order to meet the severe high temperature detergency requirements of diesel engine oils, more metallic detergents are required in lubricating oil compositions, while the soot dispersion problem requires ashless dispersants with better performance. The performance requirements of high-grade diesel engine oils are not fully met by the existing detergents and ashless dispersants, and therefore further improvements are needed in the art.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a diesel engine oil composition and a preparation method thereof.

The diesel engine oil composition comprises a viscosity index improver, a detergent, a dispersant, an antioxidant, an antiwear agent, a pour point depressant and a main amount of lubricating base oil; the structure of the viscosity index improver is shown as a general formula (I) or (II):

in the general formula (I), m repeating units are the same or different from each other, and L is C having a valence of m₁～C₂₀Hydrocarbyl (preferably C)₁～C₂₀Alkyl groups); m is a positive integer (preferably an integer of 1 to 10, more preferably an integer of 1 to 5); in the general formula (I) and the general formula (II), x sub-repeating units of the n repeating units are the same as or different from each other, and y sub-repeating units of the n repeating units are the same as or different from each other; each R₀Are the same or different from each other and are each independently selected from H, C₁～C₄Alkyl (preferably H and methyl) and C₂～C₄An alkenyl group; r in x sub-repeating units₁Are the same or different from each other and are each independently selected from H and C₁～C₄Alkyl (preferably H and methyl), R in x sub-repeat units₂Are the same or different from each other and are each independently selected from the group consisting of a single bond and C₁～C₆Alkylene (preferably selected from single bond and C)₁～C₄Alkylene) groups A in x sub-repeating units, which are identical or different from each other, are each independently selected from H、C₁～C₄Alkyl groups (preferably H and methyl), groups of formula (III-a) and groups of formula (III-b); r in y sub-repeat units₃Are the same or different from each other and are each independently selected from H and C₁～C₄Alkyl (preferably H and methyl), R in y sub-repeat units₄Are the same or different from each other and are each independently selected from the group consisting of a single bond and C₁～C₆Alkylene (preferably selected from single bond and C)₁～C₄Alkylene) groups, the A' groups in y sub-repeat units being the same or different from each other, each being independently selected from H, C₁～C₄Alkyl (preferably H and methyl) and a group of formula (IV); r of n repeating units₅Are the same or different from each other and are each independently selected from the group consisting of a single bond and C₁～C₆Alkylene (preferably selected from single bond and C)₁～C₄Alkylene groups);

wherein R' is selected from the group consisting of C having a valence of 3₂～C₆Hydrocarbyl (preferably C)₂～C₄Alkyl or alkenyl); r' is selected from H, C₁～C₄Alkyl, phenyl, C₇～C₁₀Alkylphenyl (preferably H, methyl and phenyl); x' is an integer between 1 and 5 (preferably 2 or 3); y' is an integer of 0 to 5 (preferably an integer of 1 to 4); z' is an integer between 1 and 5 (preferably 1, 2 or 3); the z 'R' groups are the same or different from each other and are independently selected from OH and C₁～C₄Alkyl (preferably H, hydroxy and methyl) wherein at least one R' "is selected from OH (preferably located ortho or para to the nitrogen atom attached to the phenyl ring, most preferably para);

x in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 10000 (preferably an integer of 10 to 5000), and y in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 3000 (preferably an integer of 10 to 1000); n is an integer of 1 to 3000 (preferably an integer of 10 to 1000);

at least one sub-repeat unit in which x is greater than 0 is present in one repeat unit of the n repeat units and at least one A group is selected from the group consisting of a group of formula (III-a) and a group of formula (III-b);

at least one sub-repeat unit with y greater than 0 is present in at least one repeat unit of the n repeat units, and at least one of the A' groups is selected from the group represented by formula (IV).

According to the invention, the weight average molecular weight of the viscosity index improver is 10000-600000, preferably 50000-500000, and more preferably 80000-300000.

According to the invention, the viscosity index improver is a polymer, the main chain of which is preferably a polyolefin, and the polyolefin can be a single C_2～20Polymers of olefins, which may also be C_2～20Copolymers of two or more (e.g., 3, 4, or 5) of the olefins. The polyolefin is preferably C_2～20Copolymers of two of the olefins, most preferably ethylene propylene (preferably, ethylene content of 20% to 80% (more preferably 30% to 70%), propylene content of 20% to 80% (more preferably 40% to 70%).

The preparation method of the viscosity index improver comprises the following steps: a first step of reacting a compound represented by the general formula (I ') or (II ') with a halogenating agent, a second step A of reacting with a compound represented by the formula (IV '), and a second step B of reacting with a compound represented by the formula (III ' -a '), (III ' -B ') and/or (III ' -c ');

in the formula (I'), m repeating units are the same or different from each other, and L is C having a valence of m₁～C₂₀Hydrocarbyl (preferably C)₁～C₂₀Alkyl groups); m is a positive integer (preferably an integer of 1 to 10, more preferably an integer of 1 to 5); in the general formulae (I ') and (II'), x sub-repeating units of n repeating units are the same as or different from each other, and y sub-repeating units of n repeating units are the same as or different from each other; each R₀Are the same or different from each other, and are each independentlySelected from H, C₁～C₄Alkyl (preferably H and methyl) and C₂～C₄An alkenyl group; r in x sub-repeating units₁Are the same or different from each other and are each independently selected from H and C₁～C₄Alkyl (preferably H and methyl), R in x sub-repeat units₂Are the same or different from each other and are each independently selected from the group consisting of a single bond and C₁～C₆Alkylene (preferably selected from single bond and C)₁～C₄Alkylene) groups A in x sub-repeat units, which are the same or different from each other, are each independently selected from H, C₁～C₄Alkyl (preferably H and methyl); r in y sub-repeat units₃Are the same or different from each other and are each independently selected from H and C₁～C₄Alkyl (preferably H and methyl), R in y sub-repeat units₄Are the same or different from each other and are each independently selected from the group consisting of a single bond and C₁～C₆Alkylene (preferably selected from single bond and C)₁～C₄Alkylene) groups, the A' groups in y sub-repeat units being the same or different from each other, each being independently selected from H, C₁～C₄Alkyl (preferably H and methyl); r of n repeating units₅Are the same or different from each other and are each independently selected from the group consisting of a single bond and C₁～C₆Alkylene (preferably selected from single bond and C)₁～C₄Alkylene groups);

wherein R' is selected from the group consisting of C having a valence of 3₂～C₆Alkyl (preferably C)₂～C₄Alkyl groups); r' is selected from H, C₁～C₄Alkyl (preferably H and methyl); x' is an integer between 1 and 5 (preferably 2 or 3); y' is an integer of 0 to 5 (preferably an integer of 1 to 4); z' is an integer between 1 and 5 (preferably 1, 2 or 3); the z 'R' groups are the same or different from each other and are independently selected from OH and C₁～C₄Alkyl (preferably H and methyl) wherein at least one R' "is selected from OH (preferably located ortho or para to the nitrogen atom to which the phenyl ring is attached, most preferably para); x in n repeating units are identical to each other orDifferent from each other, each independently selected from an integer of 0 to 10000 (preferably an integer of 10 to 5000), and y in the n repeating units are the same or different from each other, and each independently selected from an integer of 0 to 3000 (preferably an integer of 10 to 1000); n is an integer of 1 to 3000 (preferably an integer of 10 to 1000); at least one sub-repeat unit in which x is greater than 0 is present in one repeat unit of the n repeat units and wherein at least one A group is selected from H;

at least one sub-repeat unit, wherein y is greater than 0, is present in at least one repeat unit of the n repeat units, and wherein at least one A' group is selected from H.

According to the method for preparing the viscosity index improver, the compound shown in the general formula (I ') or (II') is preferably selected from polyolefin, and the polyolefin can be single C_2～20Polymers of olefins, which may also be C_2～20Copolymers of two or more (e.g., 3, 4, or 5) of the olefins. The polyolefin is preferably C_2～20Copolymers of two of the olefins, most preferably ethylene propylene (preferably, ethylene content of 20% to 80% (more preferably 30% to 70%), propylene content of 20% to 80% (more preferably 40% to 70%).

According to the preparation method of the viscosity index improver, the weight average molecular weight of the compound shown in the general formula (I ') or (II') is 10000-600000, preferably 50000-500000, and more preferably 80000-300000.

According to the method for preparing the viscosity index improver of the present invention, the compound represented by the general formula (III '-a') may be C_4～8Alkyl or alkenyl anhydrides, preferably C_4～6The alkyl or alkenyl anhydride may be one or more selected from maleic anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride and octanoic anhydride.

According to the preparation method of the viscosity index improver, the compound shown in the general formula (III '-b') can be selected from C_2～30Polyene polyamines, preferably C_2～10The polyene polyamine can be one or more selected from hexamethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine.

According to the method for preparing the viscosity index improver of the present invention, the compound represented by the general formula (IV') may be selected from C_2～30Hydroxyaniline, C_2～30Hydroxy diphenylamine, preferably C_2～10The hydroxyaniline is one or more selected from p-hydroxyaniline, o-hydroxyaniline and m-hydroxyaniline.

According to the method for preparing the viscosity index improver, the halogenating agent is preferably selected from halogenated succinimide, halogen and C_1～10The alkyl halide of (3) is preferably selected from halogenated succinimide and halogen, and specifically, one or more of N-chlorosuccinimide, N-bromosuccinimide, chlorine, bromine water and iodine can be selected. Preferably, the halogenating agent is dissolved in a chlorinated hydrocarbon, preferably C_1～4The chlorinated hydrocarbon(s) can be selected, for example, from one or more of methyl chloride, methylene chloride, chloroform, carbon tetrachloride and 1, 1-dichloroethane, in an amount of from 50% to 500%, preferably from 100% to 300%, by mass of the halogenating agent.

According to the method for producing a viscosity index improver of the present invention, in the method for producing a viscosity index improver, the second step a is performed after the first step is finished. When the second a-step is carried out after the end of the first step, the reaction product of the first step has been separated from the reaction mixture of the first step as described previously. Alternatively, the reaction product of the first step may be used directly in the form of the reaction mixture of the first step for carrying out the second a step without such isolation. Alternatively, the second B step may be performed after the second a step is finished. When the second B step is performed after the end of the second a step, the reaction product of the second a step has been separated from the reaction mixture of the second a step as described herein. Alternatively, the reaction product of the second a step may be used directly in the form of the reaction mixture of the second a step for carrying out the second B step without such isolation.

According to the method for preparing the viscosity index improver of the present invention, in the second step B, the reaction with the compound represented by the formula (III '-a'), (III '-B') and/or the compound represented by the formula (III '-c') is a reaction with the compound represented by the formula (III '-a'), (III '-B'), a reaction with the compound represented by the formula (III '-c'), or a reaction with a mixture of the compounds represented by the formula (III '-a'), (III '-B'), (III '-c'). The reaction with the compounds represented by the formulae (III '-a') and (III '-b') means that the reaction with the compound represented by the formula (III '-a') may be carried out first and then with the compound represented by the formula (III '-b').

According to the preparation method of the viscosity index improver, the molar ratio between the compound shown in the general formula (I ') or (II') and the halogenating agent is 1: 10-200, preferably 1: 50-150 parts of; the molar ratio between the compound represented by the general formula (I ') or (II ') and the compound represented by the formula (IV ') is 1: 10-200, preferably 1: 50 to 150. The molar ratio of the compound shown in the general formula (I ') or (II') to the compound shown in the formula (III '-a') and the compound shown in the formula (III '-b') is 1: 100-500: 100-500, preferably 1: 150-350: 150 to 350 parts by weight; the molar ratio between the compound of formula (I ') or (II') and the compound of formula (III '-c') is 1: 100-500, preferably 1: 150 to 350.

According to the method for producing a viscosity index improver of the present invention, the compound represented by the general formula (I ') or (II') is preferably dissolved in the lubricating base oil. The lubricating base oil can be one or more of API group I, II, III and IV lubricating base oils, preferably API group I oil and/or API group II oil. The I-type oil is distillate oil (preferably distillate oil obtained by clay refining and solvent refining), the viscosity index of the I-type oil is between 80 and 100, and the kinematic viscosity of the I-type oil at 100 ℃ is between 2 and 10mm²Between/s; the II-type oil is distillate oil (preferably obtained by hydrogenation treatment), the viscosity index of the II-type oil is between 100 and 120, and the kinematic viscosity of the II-type oil at 100 ℃ is 2 to 10mm²Between/s; the III-class oil is distillate oil (preferably obtained by hydrogenation and isomerization), the viscosity index of the III-class oil is more than 120, and the kinematic viscosity of the III-class oil at 100 ℃ is 2-10 mm²Between/s; the IV oil is preferablySelecting α -olefin polymerized synthetic oil, wherein the viscosity index is between 120 and 150, and the kinematic viscosity at 100 ℃ is between 2 and 10mm²Is between/s.

According to the preparation method of the viscosity index improver, the compound represented by the general formula (I ') or (II') is preferably dissolved in the lubricating base oil at 80-250 ℃ (preferably 120-200 ℃), wherein the dissolving time is preferably 1-20 hours (more preferably 2-10 hours); preferably, an inert gas (preferably nitrogen) is introduced during the dissolution.

According to the preparation method of the viscosity index improver, the compound shown in the general formula (I ') or (II') and the halogenating agent are preferably reacted at the temperature of 50-150 ℃ (preferably 70-90 ℃) for 1-10 hours (preferably 1-5 hours).

According to the method for producing a viscosity index improver of the present invention, it is preferable to add an initiator in the reaction (first step) of the compound represented by the general formula (I ') or (II') with a halogenating agent. The initiator is preferably an azo compound and/or a peroxide, and for example, one or more of azobisbutyronitrile, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisisobutyrocarboxamide, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyvalerate and methyl ethyl ketone peroxide (preferably one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, di-t-butyl peroxide and dicumyl peroxide) may be used. The addition amount of the initiator is preferably 1 to 50 percent, and preferably 5 to 25 percent of the mass of the compound shown in the general formula (I ') or (II').

According to the method for preparing the viscosity index improver, a product (a reaction product of the first step) obtained by reacting the compound represented by the general formula (I ') or (II') with the halogenating agent is a halide of the compound represented by the general formula (I ') or (II').

According to the method for preparing the viscosity index improver of the present invention, preferably, in the second step a of reacting the halide of the compound represented by the general formula (I ') or (II') with the compound represented by the formula (IV ') and then with the compounds represented by the formulae (III' -a '), (III' -b '), the halide of the compound represented by the general formula (I') or (II ') is reacted with the compound represented by the formula (IV') first, then with the compound represented by the formula (III '-a'), and then with the compound represented by the formula (III '-b'). The halide of the compound represented by the general formula (I ') or (II ') and the compound represented by the formula (IV ') are reacted at a temperature of 50 to 200 ℃ (preferably 70 to 120 ℃), and the reaction time is 10 to 200 minutes (preferably 10 to 60 minutes). And (D) carrying out a second A step reaction on the halide of the compound shown in the general formula (I ') or (II ') and the compound shown in the formula (IV ') to obtain a product in the second A step. The reaction temperature of the product of the second step A and the compound shown in the formula (III '-a') is 100-200 ℃ (preferably 140-180 ℃), and the reaction time is 1-5 hours (preferably 2-4 hours). The reaction temperature of the reaction product of the halide of the compound represented by the general formula (I ') or (II ') and the compound represented by the formula (IV ') or (III ' -a ') (i.e., the reaction product of the second step A and the compound represented by the formula (III ' -a ')) and the compound represented by the formula (III ' -b ') is 50 to 200 ℃ (preferably 80 to 120 ℃), and the reaction time is 1 to 5 hours (preferably 2 to 4 hours).

According to the preparation method of the viscosity index improver, the temperature for reacting with the compound of formula (IV') in the second step A is preferably 50-200 ℃ (preferably 70-120 ℃), and the reaction time is 10-200 minutes (preferably 10-60 minutes).

According to the method for preparing the viscosity index improver of the present invention, it is preferable that the initiator is added in the second B step. The initiator is preferably an azo compound and/or a peroxide, and for example, one or more of azobisbutyronitrile, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisisobutyrocarboxamide, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyvalerate and methyl ethyl ketone peroxide (preferably one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, di-t-butyl peroxide and dicumyl peroxide) may be used. The addition amount of the initiator is preferably 1 to 50 percent, and preferably 5 to 25 percent of the mass of the compound shown in the general formula (I ') or (II').

According to the preparation method of the viscosity index improver, preferably, in the second step B, the reaction temperature with the compound represented by the formula (III '-a') is 100-200 ℃ (preferably 140-180 ℃), the reaction time is 1-5 hours (preferably 2-4 hours), the reaction temperature with the compound represented by the formula (III '-B') is 50-200 ℃ (preferably 80-120 ℃), and the reaction time is 1-5 hours (preferably 2-4 hours).

According to the method for preparing the viscosity index improver, inert gas (preferably nitrogen gas) is preferably introduced during the reaction.

According to the preparation method of the viscosity index improver of the present invention, preferably, after the reaction is completed, the reaction product may be subjected to a purification treatment including one or more of filtration, centrifugation, water washing, distillation, drying and recrystallization methods, without being particularly limited.

According to the diesel engine oil composition, the detergent is selected from one or more of sulfonate, sulfurized alkylphenol salt and alkyl salicylate, and preferably a mixture of sulfonate and sulfurized alkylphenol salt, wherein the mass ratio of sulfonate to sulfurized alkylphenol salt is 3-1: 1 to 2. The sulfonate is preferably calcium sulfonate, more preferably a mixture of high-base-number calcium sulfonate and low-base-number calcium sulfonate, and the mass ratio of the high-base-number calcium sulfonate to the low-base-number calcium sulfonate is 4-1: 1. the high base number calcium sulfonate is preferably calcium sulfonate with a base number of 200mgKOH/g or more. The low-base-number calcium sulfonate is preferably calcium sulfonate with a base number of 20-50 mgKOH/g. The sulfurized alkylphenate is preferably an overbased sulfurized alkylphenate having a base number of 200mgKOH/g or more, and may be a sulfurized calcium alkylphenate, sulfurized magnesium alkylphenate, or a sulfurized calcium magnesium alkylphenate complex salt, and more preferably an overbased sulfurized calcium magnesium alkylphenate complex salt having a base number of 200mgKOH/g or more and/or an overbased sulfurized calcium alkylphenate.

According to the diesel engine oil composition, the dispersant is preferably an ashless polyisobutylene succinimide dispersant, more preferably a mixture of polyisobutylene mono-succinimide and polyisobutylene bis-succinimide, and the mass ratio of the polyisobutylene mono-succinimide to the polyisobutylene bis-succinimide is 1: 1-1: 6.

According to the diesel engine oil composition, the antioxidant is preferably dialkyl zinc dithiophosphate and an ashless antioxidant, more preferably a mixture of the dialkyl zinc dithiophosphate and the ashless antioxidant, the mass ratio of the dialkyl zinc dithiophosphate to the ashless antioxidant is 1: 0.1-10, the ashless antioxidant is preferably one or more of an aromatic amine antioxidant, a phenolic ester antioxidant and a shielding phenol antioxidant, the aromatic amine antioxidant can be dialkyl diphenylamine, the phenolic ester antioxidant can be β - (3, 5-di-tert-butyl-4-hydroxyphenyl) octyl propionate, and the shielding phenol antioxidant can be 2, 6-di-tert-butyl-p-cresol.

According to the diesel engine oil composition of the invention, the antiwear agent is preferably one or more of thiocarbamate, phosphate and phosphite, for example dialkyl dithiocarbamate, tricresyl phosphate and alkyl phosphite, and common trade marks include T323, T304 and T306.

According to the diesel engine oil composition of the present invention, the pour point depressant is preferably one or more of poly α -olefin, polyfumarate and polymethacrylate, more preferably poly α -olefin pour point depressant, common commercial designations include T803, T803B.

According to the diesel engine oil composition, the lubricating base oil is preferably one or more selected from API I, II, III, IV and V base oils, and the viscosity at 100 ℃ is more preferably 1-40 mm²(more preferably 4 to 35 mm)²S) lubricating base oil.

According to the diesel engine oil composition, the viscosity index improver accounts for 1-15%, preferably 2-10% of the total mass of the composition; the detergent accounts for 1-12% of the total mass of the composition, and preferably 2-10%; the dispersant accounts for 1 to 15 percent of the total mass of the composition, preferably 2 to 10 percent; the antioxidant accounts for 0.05-6%, preferably 1-3% of the total mass of the composition; the antiwear agent accounts for 0.05-3%, preferably 0.1-1% of the total mass of the composition; the pour point depressant accounts for 0.05 to 3 percent of the total mass of the composition, preferably 0.1 to 1 percent; the lubricating base oil constitutes the main component of the composition.

The method of preparing the diesel engine oil composition of the present invention includes the step of mixing various additives and a lubricating base oil.

The diesel engine oil composition has excellent high-temperature detergency, soot dispersibility, oxidation resistance, abrasion resistance, metal corrosion inhibition performance and low-temperature performance, can meet the requirement of API CI-4 specification, and has reduced phosphorus content and can meet the requirement of environmental emission.

Detailed Description

The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.

All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.

When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, steps, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently used, but would become known in the art to be suitable for a similar purpose.

In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.

In the context of the present invention, the expression "halo" refers to fluoro, chloro, bromo or iodo.

In the context of the present invention, the term "hydrocarbyl" has the meaning conventionally known in the art and includes straight or branched chain alkyl, straight or branched chain alkenyl, straight or branched chain alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, or combinations thereof, wherein straight or branched chain alkyl, straight or branched chain alkenyl, cycloalkyl, cycloalkenyl, aryl, or combinations thereof are preferred. Specific examples of the hydrocarbon group include C_1-50A hydrocarbon radical comprising C_1-50Straight or branched alkyl, C_2-50Straight-chain or branched alkenyl, C_2-50Straight-chain or branched alkynyl, C_3-50Cycloalkyl radical, C_3-50Cycloalkenyl radical, C_3-50Cycloalkynyl group, C_6-50Aryl or a combination thereof, wherein C is preferred_1-50Straight or branched alkyl, C_2-50Straight-chain or branched alkenyl, C_3-50Cycloalkyl radical, C_3-50Cycloalkenyl radical, C_6-50Aryl or a combination thereof. The combined group includes a group obtained by bonding or substitution of one or more groups selected from a linear or branched alkyl group, a linear or branched alkenyl group, a linear or branched alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, and an aryl group. By bonded is meant that one group forms a chemical bond (preferably a covalent bond) with one or more other groups. The substitution refers to one group as a substituent to replace a hydrogen atom in another group. As said combination group, for example, there may be mentioned one or more C_1-50Straight or branched chain alkyl (preferably one or more C)_1-20Straight or branched alkyl) with one or more C_6-50Radicals obtained by bonding or substitution of aryl radicals, preferably one or more phenyl or naphthyl radicals, one or more C_1-50Straight or branched alkenyl (preferably one or more C)_1-20Straight or branched alkenyl) with one or more C_6-50Radicals obtained by bonding or substitution of aryl radicals, preferably one or more phenyl or naphthyl radicals, one or more C_1-50Straight or branched chain alkyl (preferably)Selecting one or more C_1-20Straight or branched alkyl) with one or more C_3-50A group obtained by bonding or substitution of a cycloalkyl group (preferably one or more cyclobutyl, cyclopentyl or cyclohexyl groups), one or more C_1-50Straight or branched alkenyl (preferably one or more C)_1-20Straight or branched alkenyl) with one or more C_3-50A group obtained by bonding or substitution of a cycloalkyl group (preferably one or more cyclobutyl, cyclopentyl or cyclohexyl groups), one or more C_1-50Straight or branched chain alkyl (preferably one or more C)_1-20Straight or branched alkyl) with one or more C_3-50A group obtained by bonding or substitution of cycloalkenyl (preferably one or more cyclobutenyl, cyclobutadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl or cyclohexadienyl), one or more C_1-50Straight or branched alkenyl (preferably one or more C)_1-20Straight or branched alkenyl) with one or more C_3-50Cycloalkenyl (preferably one or more cyclobutenyl, cyclobutadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl or cyclohexadienyl) groups obtained by bonding or substitution. As the above-mentioned combination group, there may be mentioned, for example, one or more C_1-50Straight or branched alkylphenyl, mono-or polyphenyl C_1-50Straight or branched chain alkyl or mono-or poly-C_1-50C bonded by straight-chain or branched alkylphenyl radicals_1-50Straight or branched chain alkyl, etc., of which C is more preferable_1-50Straight or branched alkylphenyl radicals, e.g. tert-butylphenyl, phenyl C_1-50Straight or branched alkyl (e.g. benzyl) or C_1-50C bonded by straight-chain or branched alkylphenyl radicals_1-50Straight or branched chain alkyl (such as t-butylbenzyl).

In the context of the present invention, by "heterohydrocarbyl" is meant one or more (such as 1 to 4, 1 to 3, 1 to 2 or 1) -CH within the hydrocarbyl molecular structure (excluding the end of the backbone or any side chain in the hydrocarbyl molecular structure)₂The radicals-being selected from-O-, -S-, -N ═ N-and-NR '- (R' is H or C_1-4Straight-chain or branched alkyl) group obtained by direct substitution with a substituent group, or a hydrocarbon-based molecular structureOne or more (such as 1 to 4, 1 to 3, 1 to 2, or 1) -CH(s) internal to the structure (excluding the end of the main chain or any side chain in the hydrocarbyl molecular structure)<Radical substituted by radical-N<A group obtained by direct substitution. Obviously, from the viewpoint of structural stability, when a plurality of substituent groups are present, the substituent groups are not directly bonded to each other; and only when a plurality of-S-S-S are present, these-S-S may be directly bonded to each other. As said substituent, it is preferably-O-or-S-. The number of carbon atoms of the hydrocarbon group is represented by the group-CH₂-or a group-CH<Substituted with a corresponding decrease, but for the sake of simplicity, the number of carbon atoms of the hydrocarbon group before the substitution is still used to refer to the number of carbon atoms of the heterohydrocarbon group. By "heteroalkyl" is meant a straight or branched heteroalkyl, straight or branched heteroalkenyl, straight or branched heteroalkynyl, straight or branched heterocyclyl, straight or branched heterocyclenyl, straight or branched heterocycloalkynyl, straight or branched heteroaryl, or combinations thereof, with straight or branched heteroalkyl, straight or branched heteroalkenyl, straight or branched heterocyclyl, straight or branched heterocycloalkenyl, straight or branched heteroaryl, or combinations thereof being preferred. As the heterohydrocarbon group, a linear or branched heteroalkyl group is exemplified, C₄Straight chain alkyl radicals such as

(the group indicated by the arrow in the formula is not located within the molecular structure but at the end of the main chain) by direct substitution with a substituent-O-to give a substituted compound

Or

Is called C₄A linear heteroalkyl group. Or, C₄Branched alkyl radicals such as

(the groups indicated by the arrows are not located within the molecular structure but at the ends of the main and side chains) by a substituent-N<Direct substitution will obtainTo obtain

Is called C₄A branched heteroalkyl group. According to the invention, as the heterohydrocarbyl group, there may be mentioned, for example, C_3-50Heterohydrocarbyl, of which C is preferred_3-20Straight or branched heteroalkyl radicals or C_3-6Linear or branched heteroalkyl.

In the context of the present specification, the expression "number + valence + group" or the like refers to a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring, a combination thereof, or the like) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure. For example, "3-valent straight or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight or branched alkane (i.e., the base chain to which the straight or branched alkyl corresponds), and "2-valent straight or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom).

In the context of the present specification, a hydrocarbyl or heterohydrocarbyl group or the like substituted with a substituent group refers to a hydrocarbyl or heterohydrocarbyl group that is obtained by substituting a hydrogen atom in the hydrocarbyl or heterohydrocarbyl group with the substituent group. The substituent group is preferably selected from C_1-20Alkoxy, hydroxy, amino and mercapto.

In the context of the present specification, a hydrocarbyl or heterohydrocarbyl group or the like substituted with one or more substituent groups refers to a hydrocarbyl or heterohydrocarbyl group that is obtained by substituting a hydrogen atom in the hydrocarbyl or heterohydrocarbyl group with one or more substituent groups.

In the context of the present specification, a hydrocarbyl or heterohydrocarbyl group or the like optionally substituted with one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) substituent groups refers to a hydrocarbyl or heterohydrocarbyl group optionally substituted with one or more substituent groups for the hydrogen atoms in the hydrocarbyl or heterohydrocarbyl group, and may also optionally be substituted with unsubstituted groups.

In the present specification, the term "single bond" is sometimes used in the definition of a group. By "single bond", it is meant that the group is absent. For example, assume the formula-CH₂-A-CH₃Wherein the group a is defined as being selected from the group consisting of a single bond and a methyl group. In this respect, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly simplified to-CH₂-CH₃。

Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.

The method for measuring the weight average molecular weight adopted by the invention is gel permeation chromatography, and the model of a Gel Permeation Chromatograph (GPC) is Waters1515, United states Waters company; testing parameters: 7725 hand sample injector, 1515 isocratic pump, 2414 refractive index detector; the Waters STYRAGEL chromatographic columns are connected in series by 4 types: HR0.5+ HR1+ HR 2; mobile phase: tetrahydrofuran; flow time: 1 mL/min; and (3) testing temperature: at 40 ℃. The method for evaluating the performance of the composition according to the embodiment is as follows:

varnish formation and char formation test: paint formation and coke-forming panel experiments were performed on an L-1 type panel coke former. The conditions for the char formation test were: the plate temperature/oil temperature is 320 ℃/100 ℃, the time is 2 hours, and the stop/start time is 45 seconds/15 seconds. The conditions of the paint formation test were: the temperature of the plate/oil is 300 ℃/150 ℃ and the time is 2 hours, and the oil is continuously supplied.

High-temperature detergency: the test was conducted on an L-A type detergency tester to examine the high-temperature detergency thereof. The test conditions were: the plate temperature/oil temperature is 300 ℃/100 ℃, the time is 1 hour, the stop/start time is 40 seconds/20 seconds, and the oil drop speed is 1.0 ml/min.

Antioxidant stability: the thermal oxidation stability of the oil product is examined by a PDSC pressure differential scanning calorimetry method. The test conditions were: the flow rate of oxygen is 50mL/min, the oil sample is 1-2 mg, the temperature rise speed is 50 ℃/min, and the constant temperature is 180 ℃.

Dispersibility test: the carbon black is used as a dispersing matrix, and the dispersing capacity of the oil sample to foreign pollutants under low temperature conditions is examined. Mixing 19.5g of the test oil with 0.5g of carbon black ointment, and stirring at high speed for 10 min; then oscillating for 5min by using ultrasonic waves under the condition of constant current of 14A, and standing the sample in a 50 ℃ oven for 18 h; taking out the solution and dropwise adding the solution on industrial filter paper, controlling the quality of the solution drop to be between 0.020 and 0.025g, standing the solution in a 50 ℃ oven for 2 hours, and measuring the diameter (D) of the diffusion ring and the diameter (D) of the oil ring. The ratio γ is D/Dx100 as a measure of the dispersibility.

Oil film breaking load: evaluating the antifriction and antiwear performances of the GB/T3142-82 lubricant;

the diameter of the abrasion marks: SH/T0189 lubricating oil abrasion resistance measurement method (four-ball method);

metal corrosion test: astm d5968(CBT) metal corrosion evaluation test.

The main raw materials used are as follows:

high base number calcium sulfonate T106: the base number is 311mgKOH/g, the calcium content is 10.2 percent, the sulfur content is 1.8 percent, and the Liaoning Tianhe fine chemical industry Co., Ltd;

low base number calcium sulfonate T104: base number 28mgKOH/g, calcium content 1.5%, sulfur content 2%, available from southern additive company without tin;

high base number sulfurized calcium alkyl phenate T122 with base number of 260mgKOH/g, calcium content of 10.9%, sulfur content of 3.0%, available from southern additive company without tin;

monomeric polyisobutylene succinimide (T151) with a nitrogen content of 2.1% and a base number of 50mgKOH/g, produced by southern additive company without tin; diisobutylene succinimide (T152), nitrogen content 1.25%, base number 55mgKOH/g, produced by southern additive company without tin;

zinc dialkyl dithiophosphate (T203) with 10.2 percent of zinc, 14.0 percent of sulfur and 7.7 percent of phosphorus, which is produced by Liaoning Nintendo Fine chemical Co., Ltd;

dialkyl diphenylamine (T534) with nitrogen content of 4.6 percent and base number of 179mgKOH/g, produced by Liaoning Tianhe Fine chemical Co., Ltd;

t512 phenolic ester type antioxidant, flash point (open), 224 ℃, density (20 ℃), 0.9628g/cm³Manufactured by Beijing Xinpu fine chemical Co., Ltd;

tricresyl phosphate, acid value less than or equal to 0.10mgKOH/g, specific gravity less than or equal to 1.185, Zibo Huihua chemical Co., Ltd;

dialkyl dithio-amino formate, flash point is greater than 170 ℃, Liaoning Tianhe fine chemical Co., Ltd;

phosphite ester, phosphorus content of 14.5% -16.0%, acid value less than or equal to 15mgKOH/g, Zibohuihua chemical Co.

T803B pour point depressant, polyolefin pour point depressant, luobo additives ltd;

foreign dispersed tackifier DOCP, nitrogen content: 0.25% and a weight average molecular weight Mw of 182500, manufactured by Exxon.

EXAMPLE 1 preparation of ethylene-propylene copolymer viscosity index improver OCP

100 g of ethylene-propylene copolymer (Mw: 182000, ethylene content 55%, available from Jilin petrochemical company, China) was placed in a 2000 ml three-neck flask with temperature control, water cooling, and stirring, and cut into 0.5cm pieces³Introducing nitrogen to protect the small blocks, adding 900 g of 150SN (produced by China petrochemical high-bridge oil company), heating to 135 ℃, controlling the stirring to 300 r/min, keeping the temperature for 5 hours to obtain 1000 g of viscosity index improver, analyzing the weight average molecular weight Mw of the viscosity index improver to be 116310, and determining the ethylene content to be 55%.

Example 2 preparation of a Dispersion-type ethylene-propylene copolymer viscosity index improver DOCP1

100 g (0.000086mol) of the OCP viscosity index improver prepared in example 1 is taken and put into a 250 ml three-neck flask with temperature control, water cooling and stirring, nitrogen is used for protection, the temperature is raised to 85 ℃, then 1.0 g of benzoyl peroxide as an initiator is added, 1.4 g (0.0088mol dissolved in 6 g of carbon tetrachloride) of N-bromosuccinimide is added, the reaction temperature is controlled to be 75 ℃, the reaction is carried out for 5 hours, then 1.0 g (0.009mol) of p-hydroxy aniline is added, the reaction temperature is controlled to be 75 ℃, the reaction is carried out for 50 minutes, and then solid residues are filtered and removed.

To the brominated tackifier obtained above, 1.5 g of azobisisobutyronitrile and 2.4 g (0.024mol) of maleic anhydride were added, and a graft reaction was carried out at 150 ℃ for 2 hours. After the reaction, unreacted maleic anhydride was removed by purging with nitrogen at 150 ℃ for 2 hours. Then 2.48 g (0.024mol) of diethylenetriamine is added dropwise within 15 minutes at the controlled temperature of 100 ℃, and the mixture reacts for 2 hours at the controlled temperature, nitrogen is introduced into the mixture after the reaction to purge the mixture to obtain a product DOCP1, and the weight average molecular weight Mw of the product is 138200, and the nitrogen content is 0.24%.

Example 3 preparation of a Dispersion-type ethylene-propylene copolymer viscosity index improver DOCP2

100 g (0.000086mol) of the viscosity index improver obtained in the reaction of the example 1 is taken, added into a 250 ml three-neck flask with temperature control, water cooling and stirring, protected by nitrogen, heated to 85 ℃, then 1.2 g of azodiisobutyronitrile serving as an initiator is added, 0.8 g (0.01mol) of bromine water is added, the reaction temperature is controlled to be 80 ℃, the reaction is carried out for 4 hours, then 1.0 g (0.009mol) of m-hydroxyaniline is added, the reaction is carried out for 30 minutes, and then solid slag is removed by filtration.

To the brominated tackifier, 1.2 g of benzoyl peroxide and 2.8 g of maleic anhydride (0.0286mol) were added, and a graft reaction was carried out at 150 ℃ for 2 hours. After the reaction, unreacted maleic anhydride was removed by purging with nitrogen at 150 ℃ for 2 hours. Then, 3.6 g (0.025mol) of triethylene tetramine was added dropwise at 110 ℃ over 15 minutes, the mixture was reacted at this temperature for 3 hours, nitrogen was introduced into the mixture after the reaction, and then DOCP2 was obtained as a product, and the weight average molecular weight Mw of the product was 143200, and the nitrogen content was 0.23%.

Example 4 preparation of a Dispersion-type ethylene-propylene copolymer viscosity index improver DOCP3

100 g (0.000086mol) of the OCP viscosity index improver prepared in example 1 is taken and put into a 250 ml three-necked bottle with temperature control, water cooling and stirring, nitrogen is used for protection, the temperature is raised to 85 ℃, 1.2 g of azodiisobutyronitrile serving as an initiator is added, 1.0 g of N-chlorosuccinimide (0.0075mol dissolved in 3 g of carbon tetrachloride) is added, the reaction temperature is controlled to 85 ℃, the reaction is carried out for 3 hours, 1.0 g of p-hydroxy diphenylamine is added, the reaction is carried out for 50 minutes, and then solid residues are removed by filtration.

To the above chlorinated tackifier were added azobisisobutyronitrile (1.3 g) and maleic anhydride (2.2 g, 0.022mol), and graft reaction was carried out at 150 ℃ for 2.5 hours. After the reaction, unreacted maleic anhydride was removed by purging with nitrogen at 150 ℃ for 2 hours. Then 2.48 g (0.024mol) of diethylenetriamine is added dropwise within 15 minutes at the controlled temperature of 115 ℃ to react for 2 hours at the controlled temperature, nitrogen is introduced into the reaction product to purge the reaction product to obtain a product DOCP3, and the weight average molecular weight Mw of the product is 140500, and the nitrogen content is 0.24%.

EXAMPLE 5 preparation of sulfurized calcium magnesium alkyl phenate Complex salt

Adding 70 g of dodecylphenol and 75 g of 150SN neutral oil into a 500ml three-neck flask which is provided with a temperature control system and is electrically stirred, stirring for 15 minutes, adding 18 g of sulfur, 4 g of calcium oxide and 4 g of magnesium oxide, heating to 90 ℃ to react for 50 minutes, gradually deepening the color of the reaction material, discharging hydrogen sulfide gas, and introducing the reaction tail gas into a 10% sodium hydroxide solution absorption device. Then the temperature was gradually raised to 150 ℃, then 8g of decaol, 4 g of calcium oxide, 4 g of magnesium oxide and 35 g of ethylene glycol were added dropwise over a period of 1 hour. The reaction temperature was controlled at 150 ℃ and the high alkalization reaction was carried out by feeding carbon dioxide, a second addition of 4 g of calcium oxide and 4 g of magnesium oxide was carried out when the carbon dioxide absorption reached 5.85 g (93% of the theoretical 6.29 g), carbon dioxide was fed in, a third addition of 4 g of calcium oxide and 4 g of magnesium oxide was carried out when the carbon dioxide absorption reached 5.97 g (95% of the theoretical 6.29 g), and finally carbon dioxide was fed in until 6.16 g (98% of the theoretical 6.29 g) was reached. Then cooling to 120 ℃, adding 100 g of No. 120 gasoline and 20 g of diatomite filter aid for filtration, carrying out reduced pressure distillation on the high-base number calcium alkylphenol sulfide containing gasoline, controlling the temperature at the bottom of the kettle to 170 ℃, and the vacuum degree to be more than 0.09MPa, distilling out the solvent and ethylene glycol to obtain the high-base number calcium alkylphenol sulfide composite salt, wherein the base number of the high-base number calcium alkylphenol sulfide composite salt is 275mgKOH/g, the sulfur content is 2.3%, the calcium content is 4.9%, the magnesium content is 5.2%, and the kinematic viscosity at 100 ℃ is 157mm²/s。

Examples 6 to 9 and comparative examples 1 to 4 of Diesel Engine oil composition

And (3) the 150SN, the 500SN and the 150BS are in accordance with the following 75: 25: 5 to prepare the lubricating base oil, and the performance of the lubricating base oil can meet the requirement of 15W/40 base oil.

Examples 6 to 9 and comparative examples 1 to 3 of diesel engine oil compositions were prepared according to the formulation composition of Table 1, and comparative example 4 was a commercially available 15W/40CI-4 diesel engine oil. The compositions were subjected to evaluation tests for detergency, oxidation resistance, dispersibility, abrasion resistance and metal corrosion, respectively, and the test results are shown in Table 2.

TABLE 1 examples 6 to 9 and comparative examples 1 to 3 of diesel engine oil compositions of the present invention

TABLE 2 evaluation results

As can be seen from the data in Table 2, the diesel engine oil composition of the invention has excellent high-temperature detergency, soot dispersibility, oxidation resistance, low-temperature performance and abrasion resistance, and can meet the technical requirements of API 15W/40 CI-4.

Claims

1. A diesel engine oil composition comprising a viscosity index improver, a detergent, a dispersant, an antioxidant, an antiwear agent, a pour point depressant and a major amount of lubricating base oil; the viscosity index improver is structured as shown in the following formula: Formula (I) or (II) is shown:

In the general formula (I), m repeating units are the same or different from each other, L is an m-valent C ₁ -C ₂₀ hydrocarbon group (preferably a C ₁ -C ₂₀ alkyl group); m is a positive integer (preferably between 1 and 10) In the general formula (I) and general formula (II), the x sub-repeat units of the n repeating units are the same or different from each other, and the y sub-repeat units of the n repeat units The units are the same or different from each other; each R ₀ is the same or different from each other, and each is independently selected from H, C ₁ -C ₄ alkyl (preferably H and methyl) and C ₂ -C ₄ alkenyl; in the x sub-repeating units R ₁ are the same or different from each other, each independently selected from H and C ₁ -C ₄ alkyl (preferably H and methyl), and R ₂ in the x sub-repeating units are the same or different from each other, each independently selected from single bonds and C ₁ -C ₆ alkylene (preferably selected from single bond and C ₁ -C ₄ alkylene), the A groups in the x sub-repeating units are the same or different from each other, each independently selected from H, C ₁ -C ₄ alkyl groups (preferably H and methyl), groups represented by formula (III-a) and groups represented by formula (III-b); _R in y sub-repeat units are the same or different from each other, each independently are independently selected from H and C ₁ -C ₄ alkyl groups (preferably H and methyl), and R ₄ in the y sub-repeating units are the same or different from each other, each independently selected from single bonds and C ₁ -C ₆ alkylene groups ( Preferably selected from single bonds and C ₁ -C ₄ alkylene), the A' groups in the y sub-repeating units are the same or different from each other, each independently selected from H, C ₁ -C ₄ alkyl (preferably H and methyl group) and the group represented by formula (IV); R ₅ in n repeating units are the same or different from each other, each independently selected from single bond and C ₁ -C ₆ alkylene (preferably selected from single bond and C ₁ to C ₄ alkylene);

wherein R' is selected from trivalent C ₂ -C ₆ hydrocarbon groups (preferably C ₂ -C ₄ alkyl or alkenyl); R" is selected from H, C ₁ -C ₄ alkyl, phenyl, C ₇ -C ₁₀ Alkylphenyl (preferably H, methyl and phenyl); x' is an integer between 1 and 5 (preferably 2 or 3); y' is an integer between 0 and 5 (preferably an integer between 1 and 4) Integer); z' is an integer between 1 and 5 (preferably 1, 2 or 3); z'R"' groups are the same or different from each other, each independently selected from OH, C ₁ -C ₄ alkyl ( H, hydroxyl and methyl are preferred), wherein at least one R"' is selected from OH (preferably in the ortho or para position to the nitrogen atom attached to the benzene ring, most preferably in the para position);

In the n repeating units, x is the same or different from each other, and each is independently selected from an integer of 0 to 10,000 (preferably an integer of 10 to 5,000), and y in the n repeating units is the same or different from each other and is independently selected from 0 to an integer of 3000 (preferably an integer of 10-1000); n is selected from an integer of 1-3000 (preferably an integer of 10-1000);

In at least one repeating unit of n repeating units, there is a sub repeating unit whose x is greater than 0, and at least one A group is selected from the group represented by formula (III-a) and the group represented by formula (III-b) the group shown;

In at least one repeating unit of n repeating units, there is a sub repeating unit whose y is greater than 0, and at least one A' group therein is selected from the group represented by formula (IV).

2 . The diesel engine oil composition according to claim 1 , wherein the weight average molecular weight of the viscosity index improver is 10,000-600,000 (preferably 50,000-500,000, more preferably 80,000-300,000). 3 .

3. The diesel engine oil composition according to claim 1, wherein the preparation method of the viscosity index improver comprises: reacting the compound represented by the general formula (I') or (II') with a halogenating agent The first step, the second A step of reacting with the compound shown in formula (IV'), and then with the compound shown in formula (III'-a'), (III'-b') and/or ( The second B step in which the compound shown in III'-c') reacts;

In the general formula (I'), m repeating units are the same or different from each other, L is an m-valent C ₁ -C ₂₀ hydrocarbon group (preferably a C ₁ -C ₂₀ alkyl group); m is a positive integer (preferably one of 1-10) In the general formula (I') and the general formula (II'), the x sub-repeating units of the n repeating units are the same or different from each other, and the n repeating units are the same or different from each other. The y sub-repeat units are the same or different from each other; each R ₀ is the same or different from each other, and each is independently selected from H, C ₁ -C ₄ alkyl (preferably H and methyl) and C ₂ -C ₄ alkenyl; x sub-repeat The R ₁ in the units are the same or different from each other, each independently selected from H and C ₁ -C ₄ alkyl (preferably H and methyl), and the R ₂ in the x sub-repeating units are the same or different from each other, each independently selected from A single bond and a C ₁ -C ₆ alkylene group (preferably selected from a single bond and a C ₁ -C ₄ alkylene group), the A groups in the x sub-repeating units are the same or different from each other, each independently selected from H, C ₁ - _C4 alkyl (preferably H and methyl); R ₃ in y sub-repeating units are the same or different from each other, each independently selected from H and _C1 - _C4 alkyl (preferably H and methyl), y The R ₄ in the sub-repeating units are the same or different from each other, each independently selected from a single bond and a C ₁ -C ₆ alkylene group (preferably selected from a single bond and a C ₁ -C ₄ alkylene group), in y sub-repeating units The A' groups are the same or different from each other, and each is independently selected from H, C ₁ -C ₄ alkyl (preferably H and methyl); R ₅ in the n repeating units are the same or different from each other, and each is independently selected from single bond and C ₁ -C ₆ alkylene (preferably selected from single bond and C ₁ -C ₄ alkylene);

wherein R' is selected from trivalent C ₂ -C ₆ alkyl (preferably C ₂ -C ₄ alkyl); R" is selected from H, C ₁ -C ₄ alkyl (preferably H and methyl); x' is An integer between 1 and 5 (preferably 2 or 3); y' is an integer between 0 and 5 (preferably an integer between 1 and 4); z' is an integer between 1 and 5 (preferably 1, 2 or 3); z'R"' groups are the same or different from each other, each independently selected from OH, C ₁ -C ₄ alkyl (preferably H and methyl), wherein at least one R"' is selected from OH (preferably It is located in the ortho or para position of the nitrogen atom connected to the benzene ring, most preferably the para position); the x in the n repeating units are the same or different from each other, and each is independently selected from an integer of 0-10000 (preferably an integer of 10-5000). ), y in the n repeating units are the same or different from each other, each independently selected from an integer of 0-3000 (preferably an integer of 10-1000); n is selected from an integer of 1-3000 (preferably an integer of 10-1000);

In at least one repeating unit of n repeating units, there is a sub repeating unit whose x is greater than 0, and at least one A group is selected from H;

In at least one repeating unit of the n repeating units, there is a sub-repeating unit whose y is greater than 0, and at least one of the A' groups is selected from H.

4. The diesel engine oil composition according to claim 3, wherein the compound represented by the general formula (I') or (II') is selected from polyolefins (the polyolefins are a single C2 _～ A polymer of ₂₀ olefin or a copolymer of two or more of _C2-20 olefins (eg, 3, 4 or 5) olefins).

5. The diesel engine oil composition according to claim 3, wherein the compound represented by the general formula (I') or (II') has a weight-average molecular weight of 10,000 to 6,000,000 (preferably 50,000 to 500,000, more Preferably it is 80000～300000).

6. The diesel engine oil composition according to claim 3, wherein the compound represented by the general formula (III'-a') is a C _4-8 alkyl group or an alkenyl acid anhydride (preferably a C _4-6 alkyl group) Or alkenyl anhydride, specifically can select one or more in maleic anhydride, valeric anhydride, caproic anhydride, heptanoic anhydride and octanoic anhydride); the compound shown in general formula (III'-b') is C _2～30 Polyene polyamine (preferably C _2-10 polyene polyamine, specifically one or more of diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine can be selected); The compound shown in general formula (IV') is the hydroxyaniline of C _2～30 , the hydroxydiphenylamine of C _2～30 (preferably the hydroxyaniline of C _2～10 , specifically can select p-hydroxyaniline, o-hydroxyaniline and m-hydroxyl). One or more of aniline); the halogenating agent is halogenated succinimide, halogen and C _1～10 halogenated alkane (preferably selected from halogenated succinimide and halogen, specifically can be selected from N-chlorosuccinimide One or more of succinimide, N-bromosuccinimide, chlorine, bromine water and iodine).

7. The diesel engine oil composition according to claim 3, wherein the molar ratio between the compound represented by the general formula (I') or (II') and the halogenating agent is 1:10-200 ( Preferably, 1:50-150); the molar ratio between the compound represented by the general formula (I') or (II') and the compound represented by the formula (IV') is 1:10-200 (preferably 1:50) ~150); the molar ratio between the compound represented by the general formula (I') or (II'), the compound represented by the formula (III'-a'), and the compound represented by the formula (III'-b') is 1: 100-500: 100-500 (preferably 1: 150-350: 150-350); the compound represented by the general formula (I') or (II') and the compound represented by the formula (III'-c') The molar ratio between the indicated compounds is 1:100-500 (preferably 1:150-350).

8 . The diesel engine oil composition according to claim 3 , wherein the temperature at which the compound represented by the general formula (I′) or (II′) reacts with the halogenating agent is 50-150° C. (preferably 70-90° C. 9 . ℃), the reaction time is 1 to 10 hours (preferably 1 to 5 hours); in the reaction of the compound represented by the general formula (I') or (II') and the halogenating agent, an initiator (the initiator is preferably Azo compounds and/or peroxides, such as azobisisobutyronitrile, azobisisobutyronitrile, azobisisoheptanenitrile, dimethylazobisisobutyrate, azobisisobutyramidine Hydrochloride, Azoisobutylcyanoformamide, Benzoyl Peroxide, Di-tert-Butyl Peroxide, Dicumyl Peroxide, Tert-Butyl Peroxybenzoate, Tert-Butyl Peroxy-tert-Valerate one or more of esters and methyl ethyl ketone peroxide).

9. The diesel engine oil composition according to claim 3, wherein the halide of the compound represented by general formula (I') or (II') is combined with formula (III'-a'), (III'-b) When the compound represented by ') is reacted, the halide of the compound represented by the general formula (I') or (II') reacts with the compound represented by the formula (IV'), and then reacts with the compound represented by the formula (III'-a') , and then react with the compound represented by the formula (III'-b'); the halide of the compound represented by the general formula (I') or (II') reacts with the compound represented by the formula (IV') The temperature is 50 ℃～ 200°C (preferably 70°C to 120°C), the reaction time is 10 to 200 minutes (preferably 10 to 60 minutes); the halide of the compound represented by general formula (I') or (II') and formula (IV') The temperature of the reaction of the product of the compound shown with the compound shown in (III'-a') is 100°C to 200°C (preferably 140°C to 180°C), and the reaction time is 1 to 5 hours (preferably 2 to 4 hours); The reaction product of the halide of the compound represented by the general formula (I') or (II') and the compound represented by the formula (IV') and (III'-a') occurs with the compound represented by the formula (III'-b') The reaction temperature is 50°C to 200°C (preferably 80°C to 120°C), and the reaction time is 1 to 5 hours (preferably 2 to 4 hours).

10. The diesel engine oil composition according to claim 3, wherein in the second step A, the temperature of the reaction is 50°C to 200°C (preferably 70°C to 120°C), and the reaction time is 10 to 200° C. minutes (preferably 10-60 minutes); in the second step B, add an initiator (the initiator is preferably an azo compound and/or a peroxide, for example, azobisbutyronitrile, azobisisobutyronitrile can be selected , azobisisoheptanenitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azoisobutylcyanoformamide, benzoyl peroxide, di-tert-butyl peroxide , one or more of dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy valerate and methyl ethyl ketone peroxide); In the second B step, with (III'- The reaction temperature of the compound shown in a') is 100°C to 200°C (preferably 140°C to 180°C), and the reaction time is 1 to 5 hours (preferably 2 to 4 hours); The temperature at which the compound reacts is 50°C to 200°C (preferably 80°C to 120°C), and the reaction time is 1 to 5 hours (preferably 2 to 4 hours).

11. The diesel engine oil composition according to any one of claims 1 to 10, wherein the detergent is selected from one or more of sulfonates, sulfurized alkylphenates and alkylsalicylates (preferably a mixture of sulfonate and sulfurized alkyl phenolate, the mass ratio between the two is 3-1:1-2); the dispersant is a polyisobutylene succinimide ashless dispersant (preferably a polyisobutylene succinimide). A mixture of isobutylene monosuccinimide and polyisobutylene bissuccinimide, the mass ratio between the two is between 1:1 and 1:6); the antioxidant is dialkyldithio Zinc phosphonate and ashless antioxidant (preferably a mixture of zinc dialkyldithiophosphonate and ashless antioxidant, the mass ratio between the two is 1:0.1-10); the antiwear agent is One or more of thiocarbamate, phosphate and phosphite; the pour point depressant is one or more of polyalpha-olefin, polyfumarate and polymethacrylate (preferably polyα-olefin pour point depressant); the lubricating base oil is selected from one or more of API I, II, III, IV and V base oils (preferably, the viscosity at 100°C is 1-40 mm ² /s (more preferably 4 to 35 mm ² /s) of lubricating base oil).

12. The diesel engine oil composition according to claim 11, wherein the sulfonate is calcium sulfonate (preferably a mixture of high base number calcium sulfonate and low base number calcium sulfonate, the The mass ratio is 4 to 1:1); the sulfurized alkyl phenate is an overbased sulfurized alkyl phenate with a base value of more than 200 mgKOH/g (preferably an overbased sulfurized alkyl group with a base value of more than 200 mgKOH/g). Calcium and magnesium phenate complex salts and/or overbased sulfurized alkyl phenates).

13. The diesel engine oil composition according to one of claims 1 to 10, characterized in that, based on the total mass of the diesel engine oil composition, the viscosity index improver accounts for 1% to 15% ( Preferably, 2% to 10%); the detergent accounts for 1% to 12% (preferably 2% to 10%) of the total mass of the composition; the dispersant accounts for 1% to 15% of the total mass of the composition (preferably 2% to 15%). %-10%); the antioxidant accounts for 0.05%-6% (preferably 1%-3%) of the total mass of the composition; the anti-wear agent accounts for 0.05%-3% (preferably 0.1%-3%) of the total mass of the composition % to 1%); the pour point depressant accounts for 0.05% to 3% (preferably 0.1% to 1%) of the total mass of the composition; the lubricating base oil constitutes the main component of the composition.

14. The preparation method of the diesel engine oil composition according to any one of claims 1 to 13, comprising the step of mixing various additives and lubricating base oil.