CN113388431B - Diesel engine oil composition and preparation method thereof - Google Patents
Diesel engine oil composition and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/16—Ethers
- C10M129/18—Epoxides
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/042—Epoxides
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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Abstract
The invention provides a diesel engine oil composition, which comprises a phenol derivative, an amine antioxidant, a sulfurized alkylphenol salt, sulfonate, ZDDP, an ashless dispersant, a viscosity index improver, a pour point depressant, an anti-foaming agent and a main amount of lubricating oil base oil; the structure of the phenolic derivative is shown as the general formula (I):
Description
Technical Field
The invention relates to lubricating oil, in particular to a diesel engine oil composition and a preparation method thereof.
Background
Modern engines usually work under different fuel oil engines and different environmental conditions, so that the engine oil has the advantages of easy starting, proper viscosity maintenance under high temperature conditions, wear resistance and friction reduction, and maintenance of the detergency of moving parts and prevention of corrosion and rusting. Heavy duty diesel engines, especially high power density diesel engines, require higher high temperature oxidation resistance, coking resistance, and wear resistance of the oil due to their high combustion temperature and high average explosion pressure.
CN 102618364 discloses a high power density diesel engine lubricating oil composition which can reduce engine wear and has good detergency, oil sludge dispersibility and high temperature oxidation resistance. CA 2341066C discloses a diesel oil composition containing less than 0.1 wt% phosphorus and comprising an ashless dispersant, a neutral calcium containing phenate, an overbased calcium or magnesium sulfonate, a dialkyl dithiophosphate and a phenolic or amine antioxidant. CN 10554292 discloses an energy-saving diesel engine oil with long oil change mileage and a preparation method thereof, and the diesel engine oil has good wear resistance and friction reduction, oxidation stability and thermal stability and can effectively prolong the oil change period. EP 1420060B discloses a low phosphorus content heavy duty diesel oil composition which meets API CI-4 specification requirements while being compatible with oxidation and reduction catalysts in engine after-treatment devices. US 20190153351a discloses a diesel oil composition comprising a base oil, at least one amine-type and/or one phenolic antioxidant and a group v base oil capable of passing the wolvo T-13 engine oil oxidation test.
At present, hindered phenol antioxidants widely used in the fields of lubricating oil, fuel oil and the like are symmetrical hindered phenol antioxidants, and related patents are numerous, for example, CN 1611563a discloses a symmetrical hindered phenol antioxidant which has the characteristics of low condensation point and strong oxidation resistance, but has the defect of strong steric hindrance effect in a molecular structure commonly existing in the symmetrical hindered phenol antioxidants.
The ortho positions of the asymmetric hindered phenolic hydroxyl are two different substituent groups, so that the steric hindrance effect of the phenolic hydroxyl is weakened, the activity of the phenolic hydroxyl is improved by reducing the steric hindrance effect, and the improvement of the antioxidant performance of the phenolic hydroxyl is facilitated. The cardanol is a main component of cashew nut shell liquid, is a natural phenolic compound, is an important agricultural and sideline product for cashew nut production, and is wide in source and huge in storage amount. Therefore, the asymmetric hindered phenol antioxidant is synthesized by adopting the abundant and low-cost natural compounds as raw materials, and meets the definition of green chemistry and the requirements of national sustainable development strategy.
Disclosure of Invention
The invention provides a diesel engine oil composition and a preparation method thereof.
The diesel engine oil composition comprises a phenol derivative, an amine antioxidant, a sulfurized alkylphenol salt, sulfonate, ZDDP, an ashless dispersant, a viscosity index improver, a pour point depressant, an anti-foaming agent and a main amount of lubricating oil base oil; the structure of the phenolic derivative is shown as the general formula (I):
in the general formula (I), the radicals R1、R2、R3、R4、R5Are the same or different from each other and are each independently selected from hydrogen and C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group of the formula (II), with the proviso that each group R1、R2、R3、R4、R5At least one group of (a) is a group represented by the general formula (II);
in the general formula (II), the group R1' is selected from a single bond, C1-20Straight or branched alkylene (preferably selected from the group consisting of single bond and C)1-4Linear or branched alkylene); radicals R in n repeating units2' the same or different from each other, each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from the group consisting of a single bond, C1-4Straight or branched chain alkylene); radicals R in n repeating units3' the same or different from each other, each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from the group consisting of a single bond, C1-4Linear or branched alkylene); radical R4' is selected from hydrogen, C1-20Straight or branched chainAlkanyl radical (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radicals R in n repeating units5' same or different from each other, each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); radicals R in n repeating units6' same or different from each other, each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); n is a positive integer (preferably a positive integer between 1 and 3).
In the context of the present invention, the straight-chain or branched-chain alkyl group may be a straight-chain or branched-chain alkyl group, may also be a straight-chain or branched-chain alkenyl group containing one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 to 2) carbon-carbon double bonds, may also be a straight-chain or branched-chain alkynyl group containing one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 to 2) carbon-carbon triple bonds, and may also be a straight-chain or branched-chain alkyl group containing one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 to 2) carbon-carbon double bonds and carbon-carbon triple bonds.
In the formula (I), preferably the radical R1、R3、R5Are the same or different from each other and are each independently selected from hydrogen and C1-4Straight-chain or branched alkyl radicals, radicals R1、R3、R5At least one group selected from C1-4A linear or branched alkyl group; radical R2、R4Are the same or different from each other and are each independently selected from hydrogen and C1-300Straight or branched chain alkyl (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group represented by the general formula (II), wherein at least one group is selected from the group represented by the general formula (II).
In the formula (I), further preferably, the group R1、R5One group in (1) is selected from C1-4A linear or branched alkyl, the other group being selected from hydrogen; radical R3Selected from hydrogen, C1-4A linear or branched alkyl group; radical R2、R4One group is selected from the group represented by the general formula (II) and the other group is selected from hydrogen.
In the formula (I), more preferably, the radical R1Is selected from C1-4Straight or branched alkyl, R5Selected from hydrogen; radical R3Selected from hydrogen, C1-4A linear or branched alkyl group; radical R2Selected from hydrogen, R4Selected from the group represented by the general formula (II).
The phenolic derivative can be a single compound with a structure shown in a general formula (I) or a mixture with a structure shown in the general formula (I); when the phenolic derivative is a mixture of the structures shown in the general formula (I), the value of n in each group of each compound can be the same or different, and the sum of n in each compound can be the same or different.
The phenolic derivatives of the invention are selected from the following specific compounds or mixtures thereof in any proportion:
the process for producing a phenol derivative of the present invention comprises a step of subjecting a phenol compound represented by the general formula (X) to epoxidation reaction,
in the general formula (X), each group R1”、R2”、R3”、R4”、R5"equal to or different from each other, each independently selected from hydrogen, C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y);
wherein the radical R1"' is selected from a single bond, C1-20Straight or branched chainAlkylene (preferably selected from the group consisting of single bond and C)1-4Linear or branched alkylene); radicals R in m repeating units2"' same or different from each other, each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from the group consisting of a single bond, C1-4Straight or branched chain alkylene); radical R3"' is selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radicals R in m repeating units4"'s, equal to or different from each other, are each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); radicals R in m repeating units5"' equal to or different from each other, each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); m is a positive integer (preferably a positive integer between 1 and 10, more preferably a positive integer between 1 and 3).
According to the process for the preparation of the phenolic derivatives of the present invention, in the general formula (X), preferably, the group R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4Straight-chain or branched alkyl, radical R1”、R3”、R5At least one group in' is selected from C1-4A linear or branched alkyl group; radical R2”、R4"equal to or different from each other, each independently selected from hydrogen, C1-300Straight or branched alkyl (preferably C)1-30Linear or branched alkyl or polyolefin with a number average molecular weight Mn of 300-3000), wherein at least one group is selected from C1-300Straight or branched alkyl (preferably C)1-30Linear or branched alkyl or polyolefin with a number average molecular weight Mn of 300-3000).
According to the process for the preparation of phenolic derivatives of the present invention, in the general formula (X), it is further preferred that the group R1”、R5One group in' is selected from C1-4A linear or branched alkyl group, the other group being selected from hydrogen; radical R3"is selected from hydrogen and C1-4Straight or branched chain alkyl(ii) a Radical R2”、R4One group in' is selected from the group represented by the general formula (II), and the other group is selected from hydrogen.
According to the process for the preparation of the phenolic derivatives of the present invention, in the general formula (X), more preferably, the group R1Is selected from C1-4Straight or branched alkyl, R5"is selected from hydrogen; radical R3"is selected from hydrogen and C1-4A linear or branched alkyl group; radical R2"is selected from hydrogen, R4"is selected from the group represented by the general formula (II).
According to the process for producing a phenol derivative of the present invention, the epoxidation reaction is a reaction of a phenol compound represented by the general formula (X) with an epoxidizing agent. The epoxidizing agent is preferably peroxide, and for example, one or more of hydrogen peroxide, formic acid peroxide, peracetic acid, peroxosulfonic acid, m-chloroperoxybenzoic acid, tert-butyl hydroperoxide, tert-butyl peroxyacetate, methyl ethyl ketone peroxide, dibenzoyl peroxide and cyclohexanone peroxide can be selected. The molar ratio of the phenol compound represented by the general formula (X) to the epoxidizing agent is preferably 1: 1 to 10, more preferably 1: 2 to 5. The temperature of the epoxidation reaction is 0-100 ℃, preferably 10-80 ℃; generally speaking, the longer the reaction time, the higher the conversion, and the reaction time is generally 0.5 to 10 hours, preferably 3 to 5 hours, in combination with the conversion of the reaction and the economy of the reaction.
According to the method for producing a phenol derivative of the present invention, a catalyst may or may not be added, preferably, a catalyst may be added, in the epoxidation reaction. The catalyst is preferably an inorganic acid, and for example, one or more of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, heteropolyacid and solid acid can be used. The mass of the catalyst is 0.01 to 3%, preferably 0.2 to 0.6% of the mass of the phenol compound represented by the general formula (X).
According to the method for preparing a phenol derivative of the present invention, after the epoxidation reaction is completed, the reaction product may be subjected to a purification treatment, the purification treatment including one or more of washing, distillation, filtration, drying and recrystallization methods, without any particular limitation; when the inorganic acid catalyst is added in the epoxidation reaction, the purification treatment may be carried out by one or more of alkali washing, water washing, distillation, filtration, drying and recrystallization.
According to the process for producing a phenol derivative of the present invention, it is preferable that when the group R in the phenol compound represented by the general formula (X)1”、R3”、R5"when at least one group is hydrogen, the phenol compound represented by the general formula (X) may be subjected to epoxidation reaction and alkylation reaction (preferably, t-butylation reaction), and the product may be collected. The reaction conditions for subjecting the phenol compound represented by the general formula (X) to epoxidation reaction are the same as those described above. The alkylation reaction (preferably, t-butylation reaction) is a reaction of a phenol compound represented by the general formula (X) with an alkylating agent (t-butylation agent) to produce an epoxidation reaction. The alkylating agent is selected from halogenated hydrocarbons, fatty alcohols and olefins, preferably from C1-4Alkyl halide and C2-4For example, one or more of tert-butyl chloride, tert-butyl bromide, isopropene and isobutene can be used (the tert-butyl alkylating agent is preferably one or more of tert-butyl chloride, tert-butyl bromide and isobutene). The molar ratio between the reaction product of the epoxidation reaction of the phenol compound represented by the general formula (X) and the alkylating agent is preferably 1: 1 to 5, more preferably 1: 1 to 2.5; the reaction temperature is preferably 20 to 100 ℃, more preferably 40 to 80 ℃; generally, the longer the reaction time, the higher the conversion, and the time for the reaction is preferably 0.5 to 10 hours, more preferably 3 to 5 hours, in view of the conversion of the reaction and the economy of the reaction. The catalyst can be added or not added in the alkylation reaction, and the catalyst is preferably added; the catalyst comprises one or more of metal chloride, inorganic acid, organic acid and Lewis acid, preferably metal chloride and inorganic acid, for example, one or more of zinc chloride, aluminum chloride, stannic chloride, concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, boron trifluoride and heteropoly acid. The mass of the catalyst is preferably 0.1 to 10%, more preferably 1 to 6% of the mass of the phenol compound represented by the general formula (X). After the alkylation reaction is finished, the reaction product can be purified by washing, distilling, filtering,One or more of drying and recrystallization methods, which are not particularly limited; when a metal chloride catalyst is added to the epoxidation reaction, the purification treatment may be carried out by one or more of alkali washing, water washing, distillation, filtration, drying and recrystallization.
The phenol compound represented by the general formula (X) of the present invention is preferably derived from a natural plant cashew nut, contains a large amount of cashew nut shell oil in the cashew nut shell, contains meta-phenol as a main component, is generally called cardanol, and has the following structure:
wherein R is C15H31+xAnd x is 0, -2, -4 or-6.
The preparation method of the phenol derivative is simple and green, and has high product yield and high purity. The phenol derivative has excellent antioxidant performance, can be used as an antioxidant, and can be applied to lubricating oil, lubricating grease, fuel oil and plastic rubber.
According to the invention, the amine antioxidant is preferably selected from alkylated diphenylamines and/or alkylated naphthylamines, for example one or more of octylbutyldiphenylamine, dinonyldiphenylamine, styryloctyldiphenylamine, octylpentyldiphenylamine, p-diisooctyldiphenylamine, alkylated phenyl-alpha-naphthylamine may be used, common commercial designations including T534, T558, Irganox L57, Hitec 4793, Irganox L06.
According to the invention, the sulphurised alkylphenol salts are preferably chosen from medium-base sulphurised-alkylphenates and/or high-base sulphurised-alkylphenates, the common commercial designations including T121, T122, OLOA 219, infinium 9394, S206, T115.
According to the invention, the sulfonate is preferably selected from one or more of low base number calcium sulfonate, medium base number calcium sulfonate, high base number calcium sulfonate, medium base number magnesium sulfonate and high base number magnesium sulfonate, common commercial designations including T105, T106B, LZ 6477, LZ 6478, T107, Hitec 7637 and the like.
According to the invention, the alkyl group in the zinc dialkyldithiophosphate (ZDDP) is an alkyl group or an aryl group containing 2 to 12 carbon atoms, preferably an alkyl group containing 2 to 8 carbon atoms, and may be ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, 2-ethylhexyl, cyclohexyl, methylcyclopentyl, and common trade designations include T203, T204, T205, T206, ADX 308L, and the like. According to the present invention, the ashless dispersant is preferably selected from one or more of polyisobutylene succinimide, polyisobutylene succinate ester and high molecular weight succinimide, for example one or more of monobutyldiimide, bissuccinimide, polyisobutylene succinate ester and high molecular weight succinimide may be used, common trade designations including T151, T152, LZ 6406, T154, LZ6414, T161, LZ6418 and the like.
According to the invention, the viscosity index improver is preferably selected from one or more of polyisobutylene, polymethacrylate, ethylene-propylene copolymer and styrene diene copolymer, for example, one or more of polymethacrylate, ethylene-propylene copolymer and styrene isoprene copolymer can be selected, and common trade marks include Viscoplex 2-540, Viscoplex 2-700, LZ 7060, LZ 7067, T613, Infineum SV206, Infineum SV260, etc.
According to the invention, the pour point depressant is preferably selected from one or more of alkylbenzene, polyester and polyolefin pour point depressants, for example, one or more of alkylbenzene, polymethacrylate and poly alpha-olefin can be selected, and common trade marks comprise Hitec 623, Viscoplex 1-300, T803B and the like.
According to the invention, the anti-foaming agent is preferably selected from one or more of silicon type anti-foaming agent, non-silicon type anti-foaming agent and composite anti-foaming agent, for example, one or more of simethicone, acrylate copolymer and methacrylate copolymer can be selected, and common trade marks include T901, T911, T922 and the like.
According to the present invention, the lubricant base oil is preferably selected from mineral base oils and/or synthetic base oils, for example, one or more of group I mineral oils, group II mineral oils, group III hydrogenated mineral oils, ester oils, polyalphaolefins and alkylnaphthalenes may be selected, for example, one or more of group III hydrogenated mineral oils, ester oils and polyalphaolefins may be selected, and common trade designations include 150N, pentaerythritol ester, PAO8 and PAO10, and the like.
According to the invention, the phenolic derivative accounts for 0.1-3% of the total mass of the composition, preferably 0.2-2%; the amine antioxidant accounts for 0.1-3% of the total mass of the composition, preferably 0.2-2%; the sulfurized alkylphenate constitutes 0.2% to 3%, preferably 0.5% to 1.5%, of the total mass of the composition; the sulfonate accounts for 0.5-4%, preferably 1-3% of the total mass of the composition; the ZDDP accounts for 0.3-3% of the total mass of the composition, preferably 0.5-2%; the ashless dispersant accounts for 1-8%, preferably 3-6% of the total mass of the composition; the viscosity index improver accounts for 0.1-15% of the total mass of the composition, preferably 0.2-12%; the pour point depressant accounts for 0.05 to 1 percent of the total mass of the composition, preferably 0.1 to 0.6 percent; the antifoaming agent accounts for 0.001-0.05%, preferably 0.01-0.03% of the total mass of the composition; the major amount of lubricant base oil constitutes the major component of the composition.
According to the invention, the preparation method of the diesel engine oil composition comprises the step of mixing the components. The mixing temperature is preferably 40-80 ℃, and the mixing time is preferably 1-2 h.
The diesel engine oil composition improves the oxidation resistance of diesel engine oil, can effectively inhibit the viscosity increase of oil products caused by oxidation in the using process, and prolongs the oil change period of products; the oil product still has excellent dispersion performance under the condition that the soot content is up to 6 percent, and simultaneously has good piston cleaning performance, can effectively inhibit coking and carbon deposition of piston ring grooves and ring lands and the discoloration problem of skirt linings, and can meet the specification requirements of API CH-4 and CI-4.
Detailed Description
The present invention is further illustrated, but is not to be construed as being limited, by the following examples.
The raw materials used were as follows:
cardanol, Shanghai Bingshi chemical science and technology Co., Ltd, Industrial products
The cardanol has the structure of
Wherein R is C15H31-XAnd X is 0, 2, 4 or 6.
Concentrated sulfuric acid, national chemical group chemical reagent, Inc., analytical grade
Hydrogen peroxide (30%), national chemical group chemical reagent limited, analytically pure
Zinc chloride, national chemical group chemical reagent Limited, analytical pure
Sodium bicarbonate, national chemical group chemical reagent Limited, analytical pure
Potassium hydroxide, national chemical group chemical reagent Limited, analytical pure
Formic acid, national chemical group chemical reagents Limited, analytical pure
Tert-butyl chloride, national pharmaceutical group chemical reagents, Inc., analytical purity
Isobutene, a product of the Yanshan division of petrochemical China
2-Octyldodecanol, chemical reagents of carbofuran, chemical purity
(3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid methyl ester, Shinpu, institute of petrochemical institute, Ltd, Industrial products
Comparative antioxidant T501, Shinpu, institute of petrochemical institute, Ltd., Industrial products
Comparative antioxidant T511, Kyoho, a institute of petrochemical institute, Industrial products
Comparative antioxidant T512, Kyopu, a institute of petrochemical institute, Ltd
Acetone, chemical reagents of national drug group, Ltd, analytical purity
Absolute ethanol, national chemical group chemical reagent Limited, analytical pure
Petroleum ether, national drug group chemical reagent, Inc., analytical purity
Example 1 preparation of epoxidized cardanol
100g of cardanol, 8g of formic acid, 0.3g of sulfuric acid and 200g of hydrogen peroxide are added into a three-neck flask with mechanical stirring, a reflux condenser and temperature control, and stirring and heating are started. The reaction temperature was maintained at 70 ℃ and the reaction was carried out for 3 hours. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Filtering the reaction product, washing with 5% KOH solution with alkali, washing with distilled water to neutrality, distilling the organic phase at 100Pa and 150 ℃ under reduced pressure for 1H, removing water and unreacted raw materials to obtain an orange-red transparent liquid, which is marked as H-1. The conversion rate of the product is 96.2%, and the purity of the epoxidized cardanol is more than 98%.
Example 2 preparation of epoxidized cardanol
100g of cardanol is added into a three-neck flask with mechanical stirring, a reflux condenser and temperature control, and stirring and heating are started. The reaction temperature was maintained at 12 ℃ and 150g of m-chloroperoxybenzoic acid was slowly added and allowed to react for 5 hours. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Filtering the reaction product, washing with 5% KOH solution with alkali, washing with distilled water to neutrality, distilling the organic phase at 100Pa and 150 ℃ under reduced pressure for 1H, removing water and unreacted raw materials to obtain an orange-red transparent liquid, which is marked as H-2. The conversion rate of the product is 97.6%, and the purity of the epoxidized cardanol is more than 98%.
EXAMPLE 32 preparation of tert-butyl-4-epoxypentadecylphenol
35g of the epoxidized cardanol prepared in example 1 was dissolved in 100ml of acetone, and after dissolving, the mixture was placed in a 250ml three-neck reaction flask, 0.9g of zinc chloride catalyst was added, and stirring and heating were started while maintaining the reaction temperature at 60 ℃. 9.5g of tert-butyl chloride was slowly added dropwise to the reaction flask, and the reaction was continued for 3 hours after the completion of the dropwise addition. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Filtering the reaction product, washing with 5% KOH solution, washing with distilled water to neutrality, distilling at 1000Pa and 120 deg.C under reduced pressure for 1h, and removing solvent, water and unreacted raw materials to obtain dark brown red viscous liquid, which is marked as F-1. The product conversion was 81.6%.
EXAMPLE 42 preparation of tert-butyl-4-epoxypentadecylphenol
35g of the epoxidized cardanol prepared in example 2 was dissolved in 100ml of acetone, and after dissolving, the mixture was placed in a 250ml three-neck reaction flask, 0.4g of concentrated sulfuric acid catalyst was added, and stirring and heating were started while maintaining the reaction temperature at 50 ℃. 12g of tert-butyl chloride was slowly added dropwise to the reaction flask, and the reaction was continued for 4 hours after the dropwise addition was completed. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Filtering the reaction product, washing with 5% sodium bicarbonate solution with alkali, washing with distilled water to neutrality, distilling at 1000Pa and 120 deg.C under reduced pressure for 1h, and removing solvent, water and unreacted raw materials to obtain dark brown red viscous liquid, which is marked as F-2. The product conversion was 82.1%.
EXAMPLE 52 preparation of tert-butyl-4-epoxypentadecylphenol
35g of the epoxidized cardanol prepared in example 1 was dissolved in 100ml of acetone, and after dissolving, the mixture was placed in a 250ml three-neck reaction flask, and 2g of a concentrated sulfuric acid catalyst was added thereto, and the mixture was stirred and heated while maintaining the reaction temperature at 70 ℃. 14g of isobutene were slowly passed into the reaction flask and the reaction was continued for 5 hours after the completion of the passage. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Filtering the reaction product, washing with 5% KOH solution, washing with distilled water to neutrality, distilling at 1000Pa and 120 deg.C under reduced pressure for 1h, and removing solvent, water and unreacted raw materials to obtain dark brown red viscous liquid, which is marked as F-3. The product conversion was 90.5%.
Comparative example 1
0.5mol (149g) of 2-octyldodecanol and 0.5mol (143g) of methyl (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate were put into a500 ml three-necked reaction flask, and 1.25g of a LiOH catalyst was added thereto, stirred and heated. The reaction was carried out under reduced pressure of 0.085MPa at 160 ℃ for 4.2 hours. The obtained product is light yellow liquid, the temperature is increased to 260 ℃, and unreacted raw materials are removed by reduced pressure distillation to obtain yellow transparent liquid. The reaction conversion was 92.3%.
Example 6
2-tert-butyl-4-epoxypentadecylphenol of examples 3, 4 and 5, respectively, and the product of comparative example 1 and a comparative antioxidant were dissolved in mineral oil S6 to prepare 0.5% (by mass) of a composition, and the compositions were subjected to oxidation resistance tests, respectively, using a DSC tester manufactured by TA of the American company under the test conditions of TA 5000: 190 ℃, oxygen pressure of 0.5MPa and heating speed of 10 ℃/min. The results of the oxidative induction period measured are shown in Table 1.
TABLE 1
As can be seen from Table 1, the phenolic derivative provided by the invention can significantly improve the oxidation induction period, and is superior to the conventional phenolic antioxidant.
Example 7
The product prepared in example 3 was analyzed by ir spectroscopy, the results of which are shown in table 2.
Table 2 infrared analysis results of the product of example 3
Examples 8 to 10 and comparative examples 2 to 4 of Diesel Engine oil composition
The formulations of examples 8 to 10 and comparative examples 2 to 4 of the diesel engine oil composition are shown in Table 3. The components are added into a blending container according to the proportion, heated and stirred for 2 hours at 55 ℃, and then the embodiments 8-10 and the comparative examples 2-4 of the diesel engine oil composition are respectively prepared.
The main additives used therein include:
t534 Diphenylamine antioxidant, Beijing Xinpu Fine chemical engineering technology development Co., Ltd
T512, phenolic ester antioxidant, limited development of Beijing Xingpo fine chemical engineering technology
Irganox L57, dialkyldiphenylamine antioxidants, BASF
Irganox L135, high molecular weight phenolic antioxidant, BASF
T161, polymeric succinimide ashless dispersant, tin-free southern additive plant
T151, ashless dispersant monobutyldiimide, tin-free southern additive plant
T152, ashless dispersant bis-succinimide, tin-free southern additive plant
T106, high base number calcium sulfonate, tin-free south additive plant
T121, medium-basicity sulfurized calcium alkyl phenate, stanneless southern additive plant
T203, zinc dioctyldithiophosphate, tin-free south additive plant
LZ 7067 viscosity index improver of OCP type
Viscoplex 1-300, PMA pour point depressant
150N, group III base oil, Korea Shuanglong
T922, antifoam, Shanghai Shenpu Fine plant
The pressure differential thermal scan measurements (PDSC), the thin layer oxidation test (TFOUT), and the crankcase simulation test (also known as the coke oven test) were performed on examples 8 to 10 and comparative examples 2 to 4 of the diesel oil composition, respectively, and the test methods are shown in the following, and the test results are shown in Table 4.
1. Differential heating scanning calorimetry (PDSC)
A Du Pont 2100 differential thermal scanning thermal analyzer was used, equipped with a high pressure cell. The temperature rise range of the test is 140 ℃ to 360 ℃, the temperature rise speed is 10 ℃/min, and the oxygen flow is 150 ml/min.
2. Thin layer Oxidation test (TFOUT, ASTM D7098)
The sample, water and catalyst were placed in a glass cartridge and then in an oxygen bomb with a pressure gauge. And (3) filling oxygen with the pressure of 620Kpa into the oxygen bomb at room temperature, putting the oxygen bomb into an oil bath at the temperature of 160 ℃, enabling the oxygen bomb to form an angle of 30 degrees with the horizontal, axially rotating at the speed of 100r/min, stopping the experiment when a certain pressure drop is achieved, and recording the experiment time.
3. Crankcase simulation test (also known as coke oven test)
The oil was evaluated for antioxidant and detergent properties by testing the area and total amount of coke deposits on the surface of the aluminum plate resulting from thermal oxidation of the oil samples. The test conditions are that the temperature of the plate is 330 ℃, the temperature of the oil is 110 ℃, the time of an oil splashing switch is 20s and 40s respectively, and the running test is 3 h.
TABLE 3 formulation compositions of examples 8-10 and comparative examples 2-4
The lubricant base oils used in Table 3 above comprised 98.5% of a 150N group III base oil, 1% of LZ 7067, and 0.5% of Viscoplex 1-300.
TABLE 4
Claims (3)
1. A diesel engine oil composition comprising a phenolic derivative, an amine antioxidant, a sulfurized alkylphenate, a sulfonate, ZDDP, an ashless dispersant, a viscosity index improver, a pour point depressant, an anti-foaming agent, and a major amount of a lubricating oil base oil; the phenolic derivative is 2-tert-butyl-4-epoxy pentadecyl phenol; the amine antioxidant is selected from alkylated diphenylamine and/or alkylated naphthylamine; the sulfurized alkylphenate is selected from medium-base sulfurized alkylphenates and/or high-base sulfurized alkylphenates; the sulfonate is selected from one or more of low-base-number calcium sulfonate, medium-base-number calcium sulfonate, high-base-number calcium sulfonate, medium-base-number magnesium sulfonate and high-base-number magnesium sulfonate; the alkyl group in the ZDDP is an alkyl group containing 2 to 12 carbon atoms; the ashless dispersant is selected from one or more of polyisobutylene succinimide, polyisobutylene succinate ester and high molecular weight succinimide; the viscosity index improver is selected from one or more of polyisobutylene, polymethacrylate, ethylene-propylene copolymer and styrene diene copolymer; the pour point depressant is selected from one or more of alkylbenzene, polyester and polyolefin pour point depressants; the anti-foaming agent is selected from one or more of silicon type anti-foaming agent, non-silicon type anti-foaming agent and composite anti-foaming agent; the lubricating oil base oil is selected from mineral base oil and/or synthetic base oil; the phenolic derivative accounts for 0.1% -3% of the total mass of the composition; the amine antioxidant accounts for 0.1-3% of the total mass of the composition; the sulfurized alkylphenol salt accounts for 0.2% -3% of the total mass of the composition; the sulfonate accounts for 0.5% -4% of the total mass of the composition; the ZDDP accounts for 0.3% -3% of the total mass of the composition; the ashless dispersant accounts for 1-8% of the total mass of the composition; the viscosity index improver accounts for 0.1-15% of the total mass of the composition; the pour point depressant accounts for 0.05-1% of the total mass of the composition; the antifoaming agent accounts for 0.001% -0.05% of the total mass of the composition; the lubricant base oil constitutes the main component of the composition.
2. The composition according to claim 1, wherein the phenolic derivative is prepared by a process comprising: so that the cardanol undergoes epoxidation reaction and then tert-butylation reaction, and the product is collected.
3. A method of making a diesel engine oil composition comprising the step of mixing the components of the composition of any one of claims 1 to 2.
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