CN113493718A - Medium-speed cylindrical piston engine lubricating oil composition for ships and preparation method thereof - Google Patents
Medium-speed cylindrical piston engine lubricating oil composition for ships and preparation method thereof Download PDFInfo
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- CN113493718A CN113493718A CN202010189049.1A CN202010189049A CN113493718A CN 113493718 A CN113493718 A CN 113493718A CN 202010189049 A CN202010189049 A CN 202010189049A CN 113493718 A CN113493718 A CN 113493718A
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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
- 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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- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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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
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
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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
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
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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
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
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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
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
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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
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
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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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- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention provides a lubricating oil composition for a medium-speed cylindrical piston engine for a ship and a preparation method thereof. The invention relates to a lubricating oil composition for a medium-speed cylindrical piston engine for a ship, which comprises the following components: (A) a phenolic derivative; (B) polyisobutylene succinimide ashless dispersant; (C) a mixture of magnesium sulfonate and calcium alkyl phenate sulfide; (D) zinc dialkyldithiophosphates; (E) dialkyl dithiocarbamates; (F) a metal deactivator; (G) an ashless friction modifier; (H) a major amount of a lubricant base oil; wherein the structure of the phenolic derivative of the component (A) is shown as a general formula (I):
Description
Technical Field
The invention relates to a lubricating oil composition, in particular to a lubricating oil composition of a medium-speed trunk piston type engine for a ship.
Background
The marine medium speed diesel engine is also called trunk piston diesel engine, and it is characterized by that it uses residual diesel fuel, its sulfur content is 2.5% -3.5%, and some can be up to 5%. The marine medium-speed engine lubricating oil has high requirements on an antioxidant used in the marine medium-speed engine lubricating oil under the working condition that the thermal load is high and the marine medium-speed engine lubricating oil is easy to oxidize and deteriorate. The search for more effective antioxidant additives and the development of lubricating oil compositions for use in marine medium speed trunk piston engines has been a continuing goal of efforts by those skilled in the art.
The lubricating oil for the medium-speed trunk piston engine for the ship needs to have good acid neutralization capacity and has double functions of cylinder oil and system oil. The marine medium-speed cylindrical piston engine is low in rotating speed and high in horsepower, lubricating oil of the engine is thrown out by the large end of the connecting rod and splashed to the cylinder wall to lubricate a piston cylinder part and parts in a crankcase, and a moving part of the engine is difficult to form a lubricating oil film, so that the requirement on the wear resistance of the marine medium-speed engine lubricating oil is high. The medium speed trunk piston engine lubricating oil lubricates the cylinders while lubricating the bearings, so that combustion residues inevitably mix into the crankcase, contaminating the engine lubricating oil, and depositing sludge at the bottom of the crankcase. Meanwhile, the residue fuel contains high content of polycyclic aromatic hydrocarbon and high content of carbon residue, which can promote the generation of more piston deposits and are unfavorable for the work of the engine. The situation is more severe when the engine burns inferior heavy oil. The lubricating oil of the marine medium-speed cylindrical piston engine is recycled for a long time and is in a high-temperature thermal oxidation environment, organic acid, peroxide, colloid and the like are easily generated, the viscosity of the lubricating oil is increased by the products, nonferrous metals are corroded, the cleaning and the lubrication of a piston and the engine are not facilitated, and the service life of an oil product is shortened, so that the lubricating oil is required to have excellent oxidation resistance, cleaning and dispersing performance, corrosion resistance and emulsification and water diversion resistance. Simultaneously, the lubricating oil composition for the medium-speed trunk piston engine meets the performance requirements and puts high requirements on the lubricating oil composition for the medium-speed trunk piston engine.
Hindered phenol antioxidants are widely used because of their excellent antioxidant action. 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, CN1611563A provides 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.
Disclosure of Invention
The invention provides a lubricating oil composition for a medium-speed cylindrical piston engine for a ship and a preparation method thereof.
The invention relates to a lubricating oil composition for a medium-speed cylindrical piston engine for a ship, which comprises the following components:
(A) a phenolic derivative;
(B) polyisobutylene succinimide ashless dispersant;
(C) a mixture of magnesium sulfonate and calcium alkyl phenate sulfide;
(D) zinc dialkyldithiophosphates;
(E) dialkyl dithiocarbamates;
(F) a metal deactivator;
(G) an ashless friction modifier;
(H) a major amount of a lubricant base oil;
wherein the structure of the phenolic derivative of the component (A) is shown as a general formula (I):
in the general formula (I), the R group is selected from a group shown in the general formula (II) or a group shown in the general formula (III); x R in the formula (I)0The radicals and x R in the general formula (III)0The radicals, equal to or different from each other, are 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 formula (II), a group represented by the formula (III), x in the formula (I) and x in the formula (III) which are the same or different from each other, are 0, 1, 2, 3 or 4 (preferably 0, 1 or 2);
in the general formulae (II) and (III), the radical R1' each is independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radicals R in n repeating units2' equal to or different from each other, each independently selected from the group consisting of C having a valence of 2, 3 or 4 optionally substituted by a group of formula (II)1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 2, 3 or 4 optionally substituted by a group of formula (II)1-4Straight or branched chain alkyl); radicals R in n repeating units3' the same or different from each other, each independently selected from a single bond, C having a valence of 2 or 31-20Straight or branched chain alkyl (preferably each independently selected from single bond, 2-valent or 3-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units4' the same or different from each other, each independently selected from a single bond, C having a valence of 2 or 31-20Straight or branched chain alkyl (preferably each independently selected from single bond, 2-valent or 3-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units5' equal to or different from each other, each independently selected from the group consisting of C having a valence of 2, 3 or 4 optionally substituted by a group of formula (II)1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 2, 3 or 4 optionally substituted by a group of formula (II)1-4Straight or branched chain alkyl); radicals R in n repeating units6' 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 single bond, C)1-4Linear or branched alkylene); radical R7' selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); n is an integer of 1 to 10 (preferably an integer of 1 to 3); m in the n repeating units are the same or different from each other and are each independently selected from integers of 0 to 10 (preferably integers of 0 to 5); m' in the n repeating units are the same or different from each other and are each independently selected from integers of 0 to 10 (preferably 0 to 5)An integer); in each repeating unit of the formulae (II), (III), when m is greater than 0, m S atoms are bound to the radical R2'、R5' bonding; when m 'is greater than 0, m' S atoms and the radical R3'、R4' bonding; in each repeating unit of the formulae (II), (III), when the radical R3When 'is a single bond, m' S atoms and the group R2' bonding when the group R4When 'is a single bond, m' S atoms and the group R5' bonding.
In formula (I), preferably, the R group occupies the meta or para position of the phenolic hydroxyl group; x is 1 or 2, one or two R0The groups occupy the ortho position of the phenolic hydroxyl group and are each independently selected from C1-4Straight or branched chain alkyl.
In the general formula (I), further preferably, the R group occupies the meta position of the phenolic hydroxyl group; x is 1 or 2, one or two R0The groups occupy the ortho position of the phenolic hydroxyl group and are each independently selected from C1-4Straight or branched chain alkyl.
In formula (I), more preferably, the R group occupies the meta position to the phenolic hydroxyl group; x is 1, one R0The group occupies ortho position of phenolic hydroxyl group, para position of R group, R0The radicals being selected from C1-4Straight or branched chain alkyl.
The phenolic derivatives of the invention are selected from the following specific compounds or mixtures thereof in any proportion:
the phenolic derivative can be a single compound with a structure shown as a general formula (I) or a mixture with a structure shown as a 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 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 a sulfurization 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 alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radical R in m repeating units2"'s, which may be the same or different from each other, are each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from single bond, C)1-4Linear or branched alkylene); radical R3"' is selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radical 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); radical R in m repeating units5"'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); m is a positive integer (preferably a positive integer between 1 and 10, more preferably a positive integer between 1 and 3).
Phenolic derivatives according to the inventionIn 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 radicals, radicals 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 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).
According to the process for producing a phenol derivative 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 C1-4A linear or branched alkyl group; radical R2”、R4One group in "is selected from the group represented by the general formula (Y), 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 (Y).
According to the process for producing a phenol derivative of the present invention, the phenol compound represented by the general formula (X) is reacted with a sulfurizing agent in the sulfurization reaction. The sulfurization reaction causes the sulfurization agent and carbon-carbon double bond to generate electrophilic addition reaction, when the molecule has 1 carbon-carbon double bond, monosulfuride is generated, and when the molecule has a plurality of carbon-carbon double bonds, monosulfuride and polysullfuride can be generated. The vulcanizing agent is preferably inorganic vulcanizing agent and/or organic vulcanizing agent, and the inorganic vulcanizing agent can be selected from sulfur and Na2S、K2S、ZnS、H2One or more of S and SCl; the organic vulcanizing agentOne or more of di-tert-butyl sulfide (DBPS), dimethyl disulfide (DMDS), dimethyl sulfide (DMS), Ethyl Mercaptan (EM), n-butyl mercaptan (NBM) and tert-nonyl polysulfide (TNPS) can be selected; the vulcanizing agent is more preferably sulfur and Na2S and thiol. The molar ratio of the phenol compound represented by the general formula (X) to the vulcanizing agent is 1: 1 to 6, more preferably 1: 2 to 4. The temperature of the vulcanization reaction is 100-240 ℃, preferably 140-190 ℃; generally, 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 of the conversion of the reaction and the economy of the reaction.
According to the process for producing a phenol derivative of the present invention, a catalyst may or may not be added, preferably a catalyst is added, in the sulfurization reaction. The catalyst is preferably selected from C1～6The organic amine and inorganic base of (b) may be selected from, for example, one or more of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, tripropylamine, butylamine, pentylamine, hexylamine, ammonia, sodium hydroxide, potassium hydroxide, zinc hydroxide, sodium oxide, potassium oxide, zinc oxide, sodium carbonate, potassium carbonate and zinc carbonate. The mass of the catalyst is 0.01-10%, preferably 0.1-5% of the mass of the phenolic ester compound represented by the general formula (X).
According to the method for preparing a phenol derivative of the present invention, after the completion of the sulfurization reaction, the reaction product may be subjected to a purification treatment by one or more methods selected from water washing, distillation, filtration, drying and recrystallization, without particular limitation; when the organic amine and/or inorganic base catalyst is added in the vulcanization reaction, the purification treatment method comprises one or more of acid 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 sulfurization reaction and alkylation reaction, and the product may be collected; can also makeCarrying out sulfuration reaction and alkylation reaction on the phenol compound shown in the general formula (X), and collecting the product. The reaction conditions for the sulfurization reaction of the phenol compound represented by the general formula (X) or the reaction product obtained by the alkylation of the phenol compound with the alkylating agent are the same as those for the sulfurization reaction described above. The alkylation reaction is to react a phenol compound represented by the general formula (X) or a reaction product thereof which is subjected to a sulfurization reaction with a sulfurizing agent with an alkylating agent. The alkylating agent is selected from one or more of halogenated hydrocarbon, aliphatic alcohol and olefin, preferably alkyl halide and/or olefin, for example, one or more of tert-butyl chloride, tert-butyl bromide, isobutene and isopropene can be selected. The molar ratio between the phenol compound represented by the general formula (X) or a reaction product thereof which undergoes a vulcanization reaction with a vulcanizing agent 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 is preferably selected from one or more of inorganic acids, organic acids and lewis acids, more preferably one or more of sulfuric acid, hydrochloric acid, nitric acid, metal chlorides, boron trifluoride and heteropolyacids, and for example, one or more of sulfuric acid, hydrochloric acid, nitric acid, zinc chloride, aluminum chloride, ferric bromide, boron trifluoride, sulfur trioxide and heteropolyacids may be selected. 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 may be subjected to a purification treatment, and the purification treatment may include one or more of water washing, distillation, filtration, drying and recrystallization methods, which are not particularly limited; when a metal chloride catalyst is added to the alkylation 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 C15H(31+x)And x is 0, -2, -4 or-6.
The preparation method of the phenol derivative is simple, convenient to operate, green in raw materials and easy to obtain.
The phenol derivative has excellent antioxidant performance, wear resistance and extreme pressure performance, can be used as a multifunctional additive to effectively reduce the variety and the dosage of the additive in a formula, and can be applied to lubricating oil, lubricating grease, fuel oil and plastic rubber.
According to the invention, the component (A) represents 0.1% to 10%, preferably 0.2% to 6%, of the total mass of the composition.
According to the invention, said component (B) is a polyisobutylene succinimide ashless dispersant, wherein the number average molecular weight of the Polyisobutylene (PIB) moiety is 800-4000, preferably 900-3000, most preferably 1000-2400. The component (B) may be selected from T161 produced by Suzhou specialty oils factory, T161A and T161B produced by additives factory of Jinzhou petrochemical company, LZL 57 produced by Lubrizol additives Co., Ltd, LZ6418 and LZ6420 produced by Lubrizol Corporation, Hitec646 produced by Afton Corporation, and the like. The component (B) accounts for 0.5 to 10 percent of the total mass of the composition, and preferably 1.5 to 8 percent.
According to the invention, the component (C) is selected from a mixture of magnesium sulfonate and calcium alkyl phenate sulfide, preferably a mixture of magnesium overbased sulfonate with a base number of (200-450) mgKOH/g and calcium alkyl phenate sulfide with a base number of (200-450) mgKOH/g, and the preferable mass ratio of the two is between 0.5:1 and 4: 1. The component (C) may be selected from LZL115A and LZL115B manufactured by Lubrizol additive Co., Ltd, LZ6499 and LZ6500 manufactured by Lubrizol Corporation, Hitec7637 manufactured by Afton Corporation, OLOA219 manufactured by Chevron Oronite Company, C9340 manufactured by Infineum Co., Ltd, and the like. The component (C) accounts for 0.2-10 percent of the total mass of the composition, and preferably 0.8-8 percent.
According to the invention, component (D) is a zinc dialkyldithiophosphate, wherein the alkyl group is an alkyl group having 2 to 12 carbon atoms, preferably an alkyl group having 2 to 8 carbon atoms, and may be an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, an isohexyl group, a n-octyl group, a 2-ethylhexyl group, a cyclohexyl group, a methylcyclopentyl group. The component (D) may be selected from T202 and T203 produced by southern Petroleum additives Co., Ltd. without tin, primary alkyl T202, primary alkyl T203, primary secondary alkyl T204 and secondary alkyl T205 produced by additive plant of Kanz petrochemical company, LZ1371 and LZ1375 produced by Lubrizol company, C9417, C9425 and C9426 produced by Infineum company, Hitec7169 and Hitec1656 produced by Afton company, and the like. The component (D) accounts for 0.1 to 5 percent of the total mass of the composition, and the preferred amount is 0.3 to 3 percent.
According to the invention, component (E) is a dialkyldithiocarbamate, wherein the alkyl group is an alkyl group having 2 to 12 carbon atoms, preferably an alkyl group having 2 to 8 carbon atoms, and can be ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, 2-ethylhexyl. The component (E) may be selected from T323 available from the company Limited for petroleum additives, emerging from California, Vanlube7723 available from the company Vanderbilt, and the like. The (E) accounts for 0.02-5% of the total mass of the composition, and the preferred amount is 0.05-2%.
According to the invention, the component (F) is a metal deactivator, preferably one or more metal deactivators selected from the group consisting of triazole derivatives, thiazole derivatives and thiadiazole derivatives, for example, one or more of benzothiazole, tolyltriazole, octyltriazole, 2-mercaptobenzothiazole, 2, 5-dimercapto-1, 3, 4-thiadiazole, 2-mercapto-5-hydrocarbon substituted-1, 3, 4-thiadiazole, 2-dimercapto-5-dithio-1, 3, 4-thiadiazole, N, N-dihexylaminomethylene benzotriazole and 2-mercaptobenzothiadiazole can be used, and common trade designations include T551, T561, T706 and the like. The component (F) accounts for 0.01 to 0.5 percent of the total mass of the composition, and preferably 0.03 to 0.25 percent.
According to the present invention, the component (G) is an ashless friction modifier, preferably selected from one or more of fatty acid polyol esters, aliphatic amines and aliphatic amides, wherein the aliphatic hydrocarbon group is a saturated or unsaturated hydrocarbon group having 6 to 60 carbon atoms, preferably a saturated or unsaturated hydrocarbon group having 10 to 50 carbon atoms. The fatty acid polyol ester comprises fatty acid glyceride, fatty acid pentaerythritol ester, fatty acid glycol ester, fatty acid succinate ester, fatty acid ethanolamine ester, fatty acid diethanolamine ester, fatty acid triethanolamine ester, and monoester, diester or polyester of the compounds, such as oleic acid ethylene glycol monoester, oleic acid monoglyceride, oleic acid diglyceride, stearic acid monopentaerythritol ester, lauric acid ethylene glycol diester, oleic acid diethanolamine monoester, oleic acid triethanolamine monoester, etc.; the aliphatic amines include hydrocarbyl-substituted mono-or polyamines, alkoxylated hydrocarbyl-substituted mono-or polyamines, and alkyl ether amines, etc., such as ethoxylated tallow amine and ethoxylated tallow ether amine; examples of aliphatic amides include oleic acid amide, cocoamide, and the like. The component (G) accounts for 0.02 to 5 percent of the total mass of the composition, and preferably 0.05 to 2 percent.
According to the invention, the component (H) is a major amount of a lubricant base oil and may be selected from mineral oils and/or synthetic lubricating oils. The mineral oils may range in viscosity from light distillate mineral oils to heavy distillate mineral oils, including liquid paraffinic oils and hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types, generally classified as group I, II, III base oils, with common commercial designations including group I150 SN, 600SN, group II 100N, 150N, and the like. The synthetic lubricating oil comprises polymerized hydrocarbon oil, alkylbenzene and derivatives thereof and ester oil. Specific examples of the polymeric hydrocarbon oils include, but are not limited to, polybutene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutene, poly (1-hexene), poly (1-octene), poly (1-decene), common commercial designations including PAO4, PAO6, PAO8, PAO10, and the like; specific examples of said alkylbenzenes and derivatives thereof include, but are not limited to, for example, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene, derivatives of alkylbenzenes including alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologs thereof; the ester-based oil includes an ester or a complex ester formed by condensation reaction of a dicarboxylic acid (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids) with an alcohol (e.g., butanol, hexanol, dodecanol, 2-ethylhexyl alcohol, ethylene glycol, propylene glycol), and specific examples include, but are not limited to, dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, di (eicosyl) sebacate, 2-ethylhexyl diester of linoleic acid dimer. The component (H) constitutes the main component of the lubricating oil composition for medium-speed trunk piston engines for ships.
The preparation method of the lubricating oil composition for the marine medium-speed trunk piston engine comprises the step of mixing the components. The mixing temperature is preferably between 40 ℃ and 90 ℃ and the mixing time is preferably between 1 hour and 6 hours.
The lubricating oil composition for the medium-speed trunk piston engine for the ship has excellent oxidation resistance, high-temperature cleaning performance and abrasion resistance, and can meet the lubricating requirements of the medium-speed trunk piston engine for the ship.
Detailed Description
The present invention is further illustrated but is not to be construed as limited by the following examples.
According to the invention, as said C1-300Straight or branched alkyl, such as C1-20Straight or branched alkyl (preferably C)1-10Straight or branched alkyl, more preferably C1-4Linear or branched alkyl) or polyolefin based. Specific examples of the polyolefin group include polyolefin groups having a number average molecular weight Mn of 300-3000. In this case, the number average molecular weight Mn of the polyolefin group is preferably 500-2000, more preferably 500-1500. According to the invention, the polyolefin radical is (essentially)) Is saturated (exhibits a long-chain alkyl structure), but depending on the kind of the polyolefin as a starting material or the method of producing the polyolefin, the polyolefin group may also contain a small amount of olefinic double bonds in the molecular chain (such as those remaining or introduced during the production of the polyolefin), but this does not affect the achievement of the effect of the present invention, and the present invention does not intend to clarify the amount, and still classify such polyolefin group as an "alkyl group".
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。
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). For example, the 2-valent propyl group may be-CH2-CH2-CH2-*、
The 3-valent propyl group may be
The 4-valent propyl group may be
Wherein represents a binding end in the group that may be bonded to other groups.
According to the invention, in each recurring unit of formula (II), when m is greater than 0, m S atoms are bound to the radical R2'、R5' bonding; when m 'is greater than 0, m' S atoms and the radical R3'、R4' bonding; in each repeating unit of formula (II), when the radical R3When 'is a single bond, m' S atoms and the group R2' bonding when the group R4When 'is a single bond, m' S atoms and the group R5' bonding.
According to the invention, in each recurring unit of formula (II), when m is 0, there is no S atom with the radical R2'、R5' bonding; when m' is 0, there is no S atom with the group R3'、R4' bonding; in each repeating unit of formula (II), when the radical R3'if not singly bound, m' S atoms with radicals R3' bonding when the group R4'if not singly bound, m' S atoms with radicals R4' bonding.
According to the invention, in each recurring unit of formula (II), the radical (S)m、(S)m’、R2'、R3'、R4'、 R5' bond formation rules are met.
According to the invention, m S atoms are bound to the radical R2'、R5' bonding means that the terminal S atom of the m S atoms (or only one S atom present) is bonded to the group R2'、R5' bonded (when m is 1, there is only one S atom, when this S atom is bonded to the group R2'、R5A' bond); m' S atoms and radicals R3'、R4'bonding means that the terminal S atom of the m' S atoms (or only one S atom present) is bonded to the group R3'、R4'bonded (when m' is 1, there is only one S atom, when this S atom is bonded to the radical R3'、R4A 'bond').
According to the invention, in each recurring unit of formula (II), in the radical R2'、R3'、R4'、R5' when bonded to each other, may be via the group R2'、R3'、R4'、R5Either binding end of' forms a covalent bond. In each repeating unit of formula (II), in the group (S)mOr (S)m’And R2'、R3'、R4'、R5' when bonded to each other, may be bonded to the group R2'、R3'、R4'、R5Either binding end of' forms a covalent bond.
According to the invention, in each recurring unit of the formula (II), when the radical R is3'、R4' non-single bond, m ' is greater than 0, m ' S atoms and the group R3'、R4' bonding, R3'、R4' Each is independently selected from the group consisting of 3 valent C1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl); when the group R3'、 R4'non-single bond, m' is 0, there is no S atom and no group R3'、R4' bonding, R3'、R4' Each is independently selected from 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3'、R4' non-single bond, when m is greater than 0, R2'、R5' Each is independently selected from the group consisting of 3 valent C1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl); when the group R3'、R4' non-single bond, when m is 0, R2'、R5' Each is independently selected from 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3' is a single bond, R4' non-single bond, m ' is greater than 0, m ' S atoms and the group R2'、R4' bonding, R4' selected from the group consisting of 3-valent C1-20Straight or branched chain alkyl (preferably each independently)Selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl); when the group R3' is a single bond, R4'non-single bond, m' is 0, there is no S atom and no group R2'、R4' bonding, R4' selected from the group consisting of 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3' is a single bond, R4' non-single bond, when m is greater than 0, R2' selected from the group consisting of C having a valence of 41-20Straight or branched alkyl (preferably selected from C having a valence of 4)1-4Straight or branched alkyl), R5' selected from the group consisting of 3-valent C1-20Straight or branched alkyl (preferably selected from 3-valent C)1-4Straight or branched chain alkyl); when the group R3' is a single bond, R4' non-single bond, when m is 0, R2' selected from the group consisting of 3-valent C1-20Straight or branched alkyl (preferably selected from 3-valent C)1-4Straight or branched alkyl), R5' selected from the group consisting of 2-valent C1-20Straight or branched alkyl (preferably selected from 2-valent C)1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3' non-Single bond, R4' is a single bond, m ' is greater than 0, m ' S atoms and the group R3'、R5' bonding, R3' selected from the group consisting of 3-valent C1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl); when the group R3' non-Single bond, R4When 'is a single bond and m' is 0, there is no S atom or group R3'、R5' bonding, R3' selected from the group consisting of 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3' non-Single bond, R4' is a single bond, when m is greater than 0, R2' selected from the group consisting of 3-valent C1-20Straight or branched alkyl (preferably selected from 3-valent C)1-4Straight or branched alkyl), R5' selected from the group consisting of C having a valence of 41-20Straight chain orBranched alkyl (preferably selected from the group consisting of C having a valence of 41-4Straight or branched chain alkyl); when the group R3' non-Single bond, R4' is a single bond, and when m is 0, R2' selected from the group consisting of 2-valent C1-20Straight or branched alkyl (preferably selected from 2-valent C)1-4Straight or branched alkyl), R5' selected from the group consisting of 3-valent C1-20Straight or branched alkyl (preferably selected from 3-valent C)1-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3'、R4' are all single bonds, m ' is greater than 0, m ' S atoms and the radical R2'、R5' bonding, when m is greater than 0, R2'、R5' Each is independently selected from the group consisting of C having a valence of 41-20Straight or branched chain alkyl (preferably each independently selected from C having a valence of 41-4Straight or branched chain alkyl), when m is 0, R2'、R5' Each is independently selected from the group consisting of 3 valent C1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl).
According to the invention, in each recurring unit of the formula (II), when the radical R is3'、R4When 'are all single bonds, m' is 0, and m is greater than 0, R2'、R5' Each is independently selected from the group consisting of 3 valent C1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 31-4Straight or branched chain alkyl); when the group R3'、R4When 'are all single bonds, m' is 0, and m is 0, R2'、R5' Each is independently selected from 2-valent C1-20Straight or branched chain alkyl (preferably each independently selected from 2 valent C1-4Straight or branched chain alkyl).
According to the present invention, in each repeating unit of formula (II), for example, a structure may be formed including: -CH2-CH2-CH2-CH2-CH2-*、
The raw materials used were as follows:
cardanol, Shanghai Bingshi Binghe chemical science & technology Limited, Industrial products
The cardanol has the structure of
Wherein R is C15H(31-X)And X is 0, 2, 4 or 6.
Zinc chloride, chemical reagents of national drug group, Ltd, analytical purity
Tert-butyl chloride, national pharmaceutical group chemical reagents, Inc., analytical purity
Comparative antioxidant T511, Kyoho, a institute of petrochemical institute, Industrial products
Comparative antioxidant T501, Kyoho, a institute of petrochemical technology, Industrial products
Comparative antioxidant T512, Kyoho, a institute of petrochemical technology, Industrial products
Comparative antiwear agent T405, institute of petrochemical institute, Kyopu, Inc., Industrial products
Sulfur powder, national chemical reagent group, Inc., analytical purity
Absolute ethanol, national pharmaceutical group chemical reagents, Inc., analytical purity
Petroleum ether, national drug group chemical reagent, Inc., analytical purity
Example 16 preparation of tert-butyl Cardanol
30g of cardanol is dissolved in 100ml of acetone, the mixture is placed into a 250ml three-neck reaction flask after being dissolved, 0.9g of zinc chloride catalyst is added, stirring is started, and heating is carried out. While maintaining the reaction temperature at 60 ℃, 9.5g of t-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 by alkali, washing with distilled water to neutrality, distilling under reduced pressure at 1000Pa and 120 ℃ for 1h, removing solvent, water and unreacted raw materials to obtain brownish red transparent viscous liquid, namely 6-tert-butyl cardanol. The product conversion was 85.1%.
EXAMPLE 2 preparation of sulfurized 6-t-butyl Cardanol
70g of 6-t-butyl cardanol (about 0.2mol) prepared in example 1 and 12.8g of sulfur powder (0.4mol) were placed in a 250ml three-necked reaction flask, and stirring and heating were started. The reaction temperature was maintained at 180 ℃ and the reaction was continued for 6 hours. And (3) cooling after the reaction is finished, and filtering to obtain dark brown red viscous liquid, namely the vulcanized 6-tert-butyl cardanol. The product conversion was 92.1%.
EXAMPLE 3 preparation of sulfurized 6-t-butyl Cardanol
70g of 6-t-butyl cardanol (about 0.2mol) prepared in example 1, 19.2g of sulfur powder (0.6mol) and 3.5g of ammonia water were placed in a 250ml three-necked reaction flask, and stirring and heating were started. The reaction temperature was maintained at 150 ℃ and the reaction was continued for 5 hours. And (3) finishing the reaction, cooling and filtering the reactant, washing the reactant with 0.1% hydrochloric acid and deionized water to be neutral, and then performing vacuum dehydration to obtain dark brown red viscous liquid, namely the vulcanized 6-tert-butyl cardanol. The product conversion was 95.8%.
EXAMPLE 4 preparation of sulfurized 6-t-butyl Cardanol
70g of 6-t-butyl cardanol (about 0.2mol) prepared in example 1, 19.2g of sulfur powder (0.6mol) and 0.35g of diethylamine were placed in a 250ml three-necked reaction flask, and stirring and heating were started. The reaction temperature was maintained at 160 ℃ and the reaction was continued for 4 hours. And (3) finishing the reaction, cooling and filtering the reactant, washing the reactant with 0.1% hydrochloric acid and deionized water to be neutral, and then performing vacuum dehydration to obtain dark brown red viscous liquid, namely the vulcanized 6-tert-butyl cardanol. The product conversion was 93.6%.
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. Reducing the pressure to 0.085Mpa and 160 ℃, reacting for 4.2 hours to obtain light yellow liquid, heating to 260 ℃, and distilling under reduced pressure to remove unreacted raw materials to obtain yellow transparent liquid. The reaction conversion was 92.3%.
Example 5
The vulcanized 6-tert-butyl cardanol of examples 2, 3 and 4, the product of comparative example 1 and comparative antioxidants T501, T511 and T512 were dissolved in mineral oil S6 to prepare 0.5% (mass fraction) solutions, and the solutions were tested for their antioxidant performance by a DSC tester of TA company, model No. TA5000, in the United states, under the following test conditions: 190 ℃, oxygen pressure of 0.5MPa and heating speed of 10 ℃/min. The results of the oxidative induction period are shown in Table 1.
TABLE 1
As can be seen from Table 1, the phenolic derivatives of the present invention are capable of significantly increasing the oxidation induction period, and are superior to conventional phenolic antioxidants.
Example 6
Respectively dissolving the sulfurized 6-tert-butyl cardanol and the sulfurized olefin cottonseed oil (T405) of the embodiments 2, 3 and 4 in the mineral oil 150SN to prepare a 1% (mass fraction) solution, and carrying out extreme pressure and wear resistance tests, wherein a test instrument is an SRV vibration friction tester, and the test conditions are as follows: 100N, 200N, 300N, frequency 50Hz, amplitude 1mm, 30 ℃ and 1 h. The test results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the phenol derivative provided by the invention has outstanding anti-wear lubricating performance, the anti-wear and extreme pressure performance of the phenol derivative is far superior to that of a conventional anti-wear agent T405, and the phenol derivative is a multifunctional additive with excellent performance.
Examples 7 to 10 and comparative examples 2 to 5
The formulations of examples 7-10 and comparative examples 2-5 of medium speed trunk piston engine lubricating oil compositions are shown in Table 3. The components are added into a mixing container according to the proportion, heated and stirred for 2 hours at 50 ℃, and then the medium-speed trunk piston engine lubricating oil composition with the viscosity grade of SAE 30 is prepared respectively.
TABLE 3
ASTM D4742 thin layer oxidation test (TFOUT), pressure differential scanning calorimetry test (PDSC test, set temperature 210 ℃ C.) were performed on the compositions of examples 7-10 and comparative examples 2-5, respectively, and the test results are shown in Table 4.
TABLE 4
| Oil sample | TFOUT/min | PDSC/min |
| Example 7 | 127 | 42 |
| Example 8 | 134 | 38 |
| Example 9 | 143 | 49 |
| Example 10 | 148 | 51 |
| Comparative example 2 | 98 | 21 |
| Comparative example 3 | 105 | 25 |
| Comparative example 4 | 118 | 23 |
| Comparative example 5 | 112 | 25 |
As can be seen from Table 4, the oxidation induction periods of the examples are better than those of the comparative examples as shown by the TFOUT test and the PDSC test, which shows that the lubricating oil composition of the invention effectively improves the oxidation induction period of the oil product and has more excellent antioxidant performance.
The compositions of examples 7 to 10 and comparative examples 2 to 5 were each subjected to a high-temperature abrasion resistance test using an HFRR high-frequency reciprocating friction tester under conditions of a load of 10N, a stroke of 1mm and 140 ℃ and the test results are shown in Table 5.
TABLE 5
| Oil sample | HFRR Mill class diameter/mum |
| Example 7 | 274 |
| Example 8 | 265 |
| Example 9 | 259 |
| Example 10 | 253 |
| Comparative example 2 | 317 |
| Comparative example 3 | 341 |
| Comparative example 4 | 367 |
| Comparative example 5 | 348 |
As can be seen from Table 5, the wear-leveling diameters of the inventive examples were smaller than those of the comparative examples, and exhibited better wear resistance.
The compositions of examples 7-10 and comparative examples 2-5 were subjected to engine crankcase coke formation tests simulating piston deposits, respectively. The equipment used in the coke-forming plate test is a 25B-19 type coke-forming plate instrument manufactured by Meitech corporation of Japan, and the test can simulate the working conditions of the lubricating oil circulation of the engine crankcase and the cylinder sleeve piston ring and ensure that the test oil is continuously subjected to thermal oxidation and coked. The test time is 6h, the oil temperature is 150 ℃, and the plate temperature is 320 ℃.
TABLE 6
| Oil sample | Coke weight/mg |
| Example 7 | 59.7 |
| Example 8 | 53.2 |
| Example 9 | 45.8 |
| Example 10 | 41.5 |
| Comparative example 2 | 114.6 |
| Comparative example 3 | 85.3 |
| Comparative example 4 | 74.1 |
| Comparative example 5 | 82.6 |
As can be seen from Table 6, the coke of the examples of the present invention is significantly smaller than that of the comparative examples, and exhibits better high-temperature detergency.
The oil properties of the composition of example 8 are shown in Table 7, and meet the requirements of specification standard JT/T375.0-1998 for medium speed marine oils.
TABLE 7
Claims (11)
1. A lubricating oil composition for a medium-speed trunk piston engine for a ship comprises the following components:
(A) a phenolic derivative;
(B) polyisobutylene succinimide ashless dispersant;
(C) a mixture of magnesium sulfonate and calcium alkyl phenate sulfide;
(D) zinc dialkyldithiophosphates;
(E) dialkyl dithiocarbamates;
(F) a metal deactivator;
(G) an ashless friction modifier;
(H) a major amount of a lubricant base oil;
wherein the structure of the phenolic derivative of the component (A) is shown as a general formula (I):
in the general formula (I), the R group is selected from a group shown in the general formula (II) or a group shown in the general formula (III); x R in the formula (I)0The radicals and x R in the general formula (III)0The radicals, equal to or different from each other, are 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 formula (II), a group represented by the formula (III), x in the formula (I) and x in the formula (III) which are the same or different from each other, are 0, 1, 2, 3 or 4 (preferably 0, 1 or 2);
in the general formulae (II) and (III), the radical R1' each is independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radicals R in n repeating units2' equal to or different from each other, each independently selected from the group consisting of C having a valence of 2, 3 or 4 optionally substituted by a group of formula (II)1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 2, 3 or 4 optionally substituted by a group of formula (II)1-4Straight or branched chain alkyl); radicals R in n repeating units3' the same or different from each other, each independently selected from a single bond, C having a valence of 2 or 31-20Straight or branched chain alkyl (preferably each independently selected from single bond, 2-valent or 3-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units4' the same or different from each other, each independently selected from a single bond, C having a valence of 2 or 31-20Straight or branched chain alkyl (preferably each independently selected from single bond, 2-valent or 3-valent C1-4Straight or branched chain alkyl); radicals R in n repeating units5' equal to or different from each other, each independently selected from the group consisting of C having a valence of 2, 3 or 4 optionally substituted by a group of formula (II)1-20Straight or branched chain alkyl (preferably each independently selected from the group consisting of C having a valence of 2, 3 or 4 optionally substituted by a group of formula (II)1-4Straight or branched chain alkyl); radicals R in n repeating units6' 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 single bond, C)1-4Linear or branched alkylene); radical R7' selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); n is an integer of 1 to 10 (preferably an integer of 1 to 3); m in the n repeating units are the same or different from each other and are each independently selected from integers of 0 to 10 (preferably integers of 0 to 5); m' in the n repeating units are the same or different from each other and are each independently selected from integers of 0 to 10 (preferably integers of 0 to 5); in each repeating unit of the formulae (II), (III), when m is greater than 0, m S atoms are bound to the radical R2'、R5' bonding; when m 'is greater than 0, m' S atoms and the radical R3'、R4' bonding; in each repeating unit of the formulae (II), (III), when the radical R3When 'is a single bond, m' S atoms and the group R2' bonding when the group R4When the' is a single bond, the polymer,m' S atoms and radicals R5' bonding.
2. Composition according to claim 1, characterized in that in formula (I) the R group occupies the meta or para (preferably meta) position of the phenolic hydroxyl group; x is 1 or 2, one or two R0The groups occupy the ortho position of the phenolic hydroxyl group and are each independently selected from C1-4Straight or branched chain alkyl.
3. Composition according to claim 1, characterized in that the phenolic derivative is selected from the following specific compounds or mixtures thereof in any proportion:
4. the composition according to claim 1, wherein the phenol derivative is produced by a process comprising the step of subjecting a phenol compound represented by the general formula (X) to a sulfurization 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 alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radical R in m repeating units2"'s, which may be the same or different from each other, are each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from single bond, C)1-4Linear or branched alkylene); radical R3"' is selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radical 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); radical R in m repeating units5"'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); m is a positive integer (preferably a positive integer between 1 and 10, more preferably a positive integer between 1 and 3).
5. Composition according to claim 4, characterized in that, in the formula (X), the radical R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4Straight-chain or branched alkyl radicals, radicals 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 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).
6. The composition according to claim 4, wherein the vulcanization reaction is a reaction of the phenol compound represented by the general formula (X) with a vulcanizing agent.
7. The composition according to claim 4, wherein the molar ratio of the phenol compound represented by the general formula (X) to the vulcanizing agent is 1: 1-6; the temperature of the vulcanization reaction is 100-240 ℃.
8. The composition according to claim 4, wherein the group R in the phenol compound represented by the formula (X)1”、R3”、R5"when at least one group is hydrogen, the phenol compound represented by the general formula (X) is subjected to sulfurization reaction and alkylation reaction, and the product is collected; or subjecting the phenol compound represented by the general formula (X) to sulfurization reaction and alkylation reaction, and collecting the product.
9. Composition according to any one of claims 1 to 8, characterized in that said component (A) represents from 0.1% to 10% of the total mass of the composition; the component (B) accounts for 0.5 to 10 percent of the total mass of the composition; the component (C) accounts for 0.2 to 10 percent of the total mass of the composition; the component (D) accounts for 0.1 to 5 percent of the total mass of the composition; the (E) accounts for 0.02 to 5 percent of the total mass of the composition; the component (F) accounts for 0.01 to 0.5 percent of the total mass of the composition; the component (G) accounts for 0.02 to 5 percent of the total mass of the composition; the component (H) constitutes the main component of the composition.
10. Composition according to any one of claims 1 to 8, characterized in that component (B) is a polyisobutylene succinimide ashless dispersant, wherein the number average molecular weight of the Polyisobutylene (PIB) moiety is 800-; the component (C) is selected from a mixture of high-base-number magnesium sulfonate with the base number of (200-450) mgKOH/g and high-base-number sulfurized calcium alkyl with the base number of (200-450) mgKOH/g, and the preferable mass ratio of the two is between 0.5:1 and 4: 1; the component (D) is zinc dialkyldithiophosphate, wherein the alkyl group is an alkyl group having 2 to 12 carbon atoms; the component (E) is a dialkyldithiocarbamate, wherein the alkyl group is an alkyl group having 2 to 12 carbon atoms; the component (F) is selected from one or more metal deactivators such as triazole derivatives, thiazole derivatives and thiadiazole derivatives; the component (G) is selected from one or more of fatty acid polyol ester, aliphatic amine and aliphatic amide; the component (H) is selected from mineral oils and/or synthetic lubricating oils.
11. A method of preparing a marine medium speed trunk piston engine lubricating oil composition according to any one of claims 1 to 10, comprising the step of mixing the components therein.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115975704A (en) * | 2021-10-15 | 2023-04-18 | 中国石油化工股份有限公司 | Lubricating oil composition for high-speed diesel engine in railway and preparation method thereof |
| CN115992028A (en) * | 2021-10-19 | 2023-04-21 | 中国石油化工股份有限公司 | Antioxidant composition and preparation method thereof |
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| CN102690710A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Lubricant composition for intermediate-speed trunk piston-type engine of ship |
| CN104520369A (en) * | 2013-07-12 | 2015-04-15 | (株)Mnb绿地公司 | Novel cardanol-based organic vulcanizing agent, production method for same and blended rubber composition for tyres using same |
| CN105219458A (en) * | 2015-09-11 | 2016-01-06 | 中国林业科学研究院林产化学工业研究所 | A kind of epoxy cardanol is as the application of bio-based hindered phenol type antioxidant |
| CN105523899A (en) * | 2015-07-06 | 2016-04-27 | 中国科学院宁波材料技术与工程研究所 | Cleaner production method and use of bisphenol compound anti-oxidant |
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| CN102690710A (en) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | Lubricant composition for intermediate-speed trunk piston-type engine of ship |
| CN104520369A (en) * | 2013-07-12 | 2015-04-15 | (株)Mnb绿地公司 | Novel cardanol-based organic vulcanizing agent, production method for same and blended rubber composition for tyres using same |
| CN105523899A (en) * | 2015-07-06 | 2016-04-27 | 中国科学院宁波材料技术与工程研究所 | Cleaner production method and use of bisphenol compound anti-oxidant |
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| CN115975704A (en) * | 2021-10-15 | 2023-04-18 | 中国石油化工股份有限公司 | Lubricating oil composition for high-speed diesel engine in railway and preparation method thereof |
| CN115992028A (en) * | 2021-10-19 | 2023-04-21 | 中国石油化工股份有限公司 | Antioxidant composition and preparation method thereof |
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