CN1272415C - Alkyl succinite hydrazide additive for lubricant - Google Patents
Alkyl succinite hydrazide additive for lubricant Download PDFInfo
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- CN1272415C CN1272415C CNB028257952A CN02825795A CN1272415C CN 1272415 C CN1272415 C CN 1272415C CN B028257952 A CNB028257952 A CN B028257952A CN 02825795 A CN02825795 A CN 02825795A CN 1272415 C CN1272415 C CN 1272415C
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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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/40—Six-membered ring containing nitrogen and carbon only
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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
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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
- 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
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
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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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- 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
- 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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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/12—Gas-turbines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Abstract
The present invention discloses a composition which comprises lubricant (A) and at least one kind of alkyl amber hydrazide compound with a general formula (I), wherein R1 is selected from a group of linear chain or branched chain alkyl, alkenyl, alkaryl, alkyl ether, alkyl ester and alkylene ester. R2 is selected from a group of hydrogen, linear chain or branched chain alkyl, alkenyl, alkyl ether and alkyl ester. R3 and R4 are independently selected from hydrogen, linear chain or branched chain alkyl and alkenyl, aryl and alkaryl.
Description
Background of invention
1. invention field
The present invention relates to lubricant, lubricating oil particularly, and to relate more specifically to derived from the alkyl succinhydrazide be 4-alkyl-1,2-dihydrogen dazin-3, a class of 6-diketone is ashless and the extreme-pressure additive of wear-resisting, the antifatigue of phosphorated not.
2. description of Related Art
In the process of exploitation lubricating oil, many trials have been done, to be provided as the additive that it gives antifatigue, wear-resisting and extreme pressure property.As anti-wear additive, zinc dialkyl dithiophosphate (ZDDP) was used more than 50 year in formulated oil.But zinc dialkyl dithiophosphate can produce ash content, and this produces particulate matter in motor vehicle exhaust, and the discharging of way minimizing zinc in environment sought by administration.In addition, phosphorus also is a kind of component of ZDDP, is used for automobile to reduce the service life of the catalytic converter that pollutes according to suspecting that it has shortened.It is very important being limited in the particulate matter that forms in the engine application process because of toxicity and environment reason and polluting, and also is very important but keep the wear resistance of lubricating oil not descend.
Because the known aforesaid drawbacks that contains the additive of zinc and phosphorus has made great efforts to provide the lubricating oil additive that does not contain zinc and phosphorus, perhaps the content of these materials obviously reduces at least.
Not containing zinc example promptly ashless, not phosphorated lubricating oil additive is US 5,512, in 190 disclosed 2,5-dimercapto-1,3,4-thiadiazoles and unsaturated list-, two-and the reaction product of Three-glycerol ester and US 5,514,189 in disclosed dialkyl dithio amino formate deutero-organic ether.
US 5,512, disclose a kind of additive that antiwear characteristic is provided for lubricating oil in 190.This additive is 2,5-dimercapto-1,3,4-thiadiazoles and unsaturated list-, two-and the reaction product of mixture with triglycerides thing.The lubricating oil additive of producing by the following method with antiwear characteristic is wherein also disclosed: make unsaturated list-, two-and the mixture of Witepsol W-S 55 and diethanolamine reaction with the generation intermediate reaction product, and make this intermediate reaction product and 2,5-dimercapto-1,3, the reaction of 4 thiadiazoles.
US 5,514, and 189 disclose and have been found that dialkyl dithio amino formate deutero-organic ether is effectively wear-resisting/anti-oxidant additives to lubricant and fuel.
US 3,284, and 234 disclose a kind of stable fibrous material, and it comprises uses the fibrous material of the fibrous material dipping of the hydrazides of 0.1wt% at least, and described hydrazides is selected from following compound and its mixture:
(I)RCONHNH
2
(II)RCONHNHCOR
(III)R′(CONHNH
2)
2
Wherein each R is independently selected from hydrogen and the alkyl that contains 1-2 carbon atom, and R ' is selected from (CH
2-)
nWherein, wherein n is the integer of 0-5, and 1-2 the atom that the alkylidene group of 2-6 carbon atom is selected from oxygen and sulphur interrupts.
US 5,084,195 and US 5,300,243 the appointment anti-wear additive of N-acyl-thiocarbamates thiocarbamide as lubricant or hydraulic fluid disclosed.
German patent DE 1,260,137 disclose a kind of ethidene polymer that allegedly shows low film block, and this polymkeric substance prepares by add the fatty acid hydrazide with six above carbon atoms in common internal lubricant.Lauroyl hydrazides, palmityl hydrazides and stearyl hydrazides are concrete the application.
Day disclosure application No.03140346 discloses a kind of inflexible vinyl chloride resin composition, it is said that said composition has improved processing characteristics, and it comprises 100 parts of vinyl chloride resins and 3-20 part is selected from following compound: (R
1CONH)
2(CH
2)
n(R wherein
1C for the OH-replacement
1-C
23Alkyl and n are 1-10), (R
2CONH)
2(CH
2)
n(R wherein
2C for the OH-replacement
4-C
23Alkyl and n are 1-10), R
3CONHNH
2(R wherein
3C for the OH-replacement
4-C
23Alkyl), R
4NHCONHR
5(R wherein
4The alkyl that replaces for OH-) and (R
6NHCONH)
2R
7(R wherein
6C for the OH-replacement
7-C
23Alkyl, and R
7Be C
1-C
10Alkylidene group, phenylene or crystalline 1,2-phenylene derivatives).Stearic acid hydrazide and capric acid hydrazide are mentioned especially.
The US patent application No.09/871 of application on May 31 calendar year 2001,120 disclose a kind of composition, and said composition comprises:
(A) lubricant and
(B) at least a alkyl hydrazide compound with following general formula:
R wherein
1Be hydrocarbon with 1-30 carbon atom or functionalized hydrocarbon, R
2And R
3Be independently selected from hydrocarbon with 1-30 carbon atom or functionalized hydrocarbon and hydrogen.
The disclosure of aforementioned reference here quotes in full as a reference.
Summary of the invention
The present invention relates to the compound of following general formula:
Wherein
R
1Be alkyl, alkenyl, alkaryl, alkyl oxide or the alkyl group of straight or branched, preferably have 1-30 carbon atom;
R
2Be alkyl, alkenyl, alkyl oxide or the alkyl group of hydrogen, straight or branched, preferably have 1-30 carbon atom and
R
3And R
4Can be the same or different, can be alkyl, aryl, alkenyl or the alkaryl of hydrogen or straight or branched, preferably have 1-30 carbon atom.
Alkyl succinhydrazide compound of the present invention uses as antifatigue ashless, not phosphorous, not sulfur-bearing, wear-resisting, extreme pressure, rut preventives in lubricating oil.
The invention still further relates to a kind of lubricating oil composition, said composition comprises the alkyl succinhydrazide compound of at least a above-mentioned general formula of lubricating oil and sense improvement in performance amount.More specifically, the present invention instructs a kind of composition, and said composition comprises:
(A) lubricant and
(B) at least a alkyl succinhydrazide compound with following general formula
Wherein
R
1Be selected from alkyl, alkenyl, alkaryl, alkyl oxide, alkyl ester and the alkylene ester group of straight or branched;
R
2Be selected from alkyl, alkenyl, alkyl oxide and the alkyl group of hydrogen, straight or branched; With
R
3And R
4Be independently selected from alkyl and alkenyl, aryl and the alkaryl of hydrogen, straight or branched.
The alkyl succinhydrazide preferably exists to the concentration of about 10wt% with about 0.01wt% in composition of the present invention.
The description of preferred embodiment
Alkyl succinhydrazide compound of the present invention is the compound with following general formula:
Wherein
R
1Be selected from alkyl, alkenyl, alkaryl, alkyl oxide and the alkyl group of straight or branched;
R
2Be selected from alkyl, alkenyl, alkyl oxide and the alkyl group of hydrogen, straight or branched; With
R
3And R
4Be independently selected from alkyl and alkenyl, aryl and the alkaryl of hydrogen, straight or branched.
In the said structure general formula, R
1, R
2, R
3And/or R
4Comprise alkyl or alkenyl part, this part can be the hydrocarbon chain of straight or branched, this hydrocarbon chain is saturated fully or part is undersaturated, preferably have 1-30 carbon atom, 1-22 carbon atom more preferably, most preferably be 1-18 carbon atom, methyl for example, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, oil base, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, triacontyl, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, the nonene base, the decene base, undecenyl, dodecenyl succinic, the tridecylene base, the tetradecene base, 15 carbene bases, the cetene base, the heptadecene base, the vaccenic acid base, 19 carbene bases, the eicosylene base, the heneicosene base, two dodecenyl succinic, the tricosene base, the tetracosa carbon thiazolinyl, the ppentacosene base, triacontylene base and analogue, and their isomer and mixture.In addition, as described above, R
1And R
2Can ester or oxygen ether group can be arranged for straight chain or side chain, the saturated or undersaturated hydrocarbon chain of part in hydrocarbon chain, and R
3And/or R
4Can be alkaryl group, for example nonyl phenyl, dodecylphenyl, and analogue.
Use alkyl succinhydrazide compound of the present invention and can improve the antifatigue of lubricant, wear-resisting and extreme pressure property.
Additive of the present invention synthetic substantially
The common preparation method of alkyl succinhydrazide of the present invention comprises adding alkyl succinic acid acid anhydrides and solvent in reaction vessel, and described solvent boiling is taking place more than 80 ℃ and can fall the water by product by azeotropic distillation.This solvent also should not react with all reactant and products.The example of this solvent has hydrocarbon such as heptane, decane and dodecane; With aromatic solvent such as toluene, tetralin and dimethylbenzene.Under initial reaction temperature is room temperature or about 20 ℃, slowly in reaction vessel, add the hydrazides hydrate.According to the amount of existing solvent and applied hydrazides, add hydrazides after, the reaction medium temperature can heat release about 20 ℃ to 30 ℃.The temperature of reaction medium is increased to reflux temperature to finish reaction and to remove the water by product then.Removing solvent under the condition of step-down or under vacuum then, to obtain final product.If desired, this product can polishedly filter.When preparing product based on monoalkyl or asymmetric hydrazides such as methyl and phenyl hydrazides, a small amount of possible by product also can be for having the hydrazides succinimide of following structure:
R wherein
1, R
2And R
3As top description.It is believed that this material that exists as a small amount of component also can show antiwear characteristic in lubricant fluid in product.
Use with other additive
Alkyl succinhydrazide additive of the present invention can partly or entirely substitute the zinc dialkyl dithiophosphate of using at present and use.They also can be used with other other additive combination of using in lubricating oil usually, and, anti-wear additive ashless with other used.These alkyl succinhydrazide also demonstrate the synergy with other this quasi-representative additive, to improve the performance characteristic in lubricating oil.Usually the additive of using in lubricating oil for example has dispersion agent, sanitising agent, sanitas/rust-preventive agent, antioxidant, anti-wear agent, antifoams, friction modifier, sealed expander, demulsifying agent, VI improving agent, pour point depressor and analogue.For example with reference to US 5,498,809, wherein described useful lubricating oil composition additive, its disclosure here quotes in full as a reference.The example of dispersion agent comprises polyisobutenyl succinimide, polyisobutenyl succinic ester, Mannich Base ashless dispersants, and analogue.The example of sanitising agent comprises alkylphenol metal-salt, sulfurized alkylphenol metal-salt, alkylsulphonic acid metal-salt, alkylated salicylamide acid metal salt and analogue.Examples of antioxidants comprises alkylating diphenylamine, the alkylating phenylenediamine of N-, the phenols that is obstructed, alkylating Resorcinol, hydroxylated sulfo-diphenyl ether, alkylidene bisphenols, oil-soluble copper and molybdenum compound, and analogue.The example of the anti-wear additive that can use with additive combination of the present invention comprises organic borate, organic phosphite, sulfur-containing organic compound, zinc dialkyl dithiophosphate, diaryl zinc dithiophosphate, phosphorus sulfurized hydrocarbon, and analogue.Be the example of these additives below, they can be commercially available by Lubrizol Corporation: Lubrizol 677A, Lubrizol 1095, Lubrizol 1097, Lubrizol1360, Lubrizol 1395, Lubrizol 5139 and Lubrizol 5604 or the like.The example of friction modifier comprise fatty acid ester and acid amides, organic sulfide with unvulcanized molybdenum compound, dialkyl thiocarbamic acid molybdenum (molybdenum monomer, dipolymer and trimer), molybdenum dialkyl-dithiophosphate, and analogue.The example of antifoams is polysiloxane and analogue.The example of rust-preventive agent is the pure and mild analogue in poly (oxyalkylene) Quito.The example of VI improving agent comprises olefin copolymer and dispersant olefin copolymers, and analogue.The example of pour point depressor is polymethacrylate and analogue.
The example of the conventional anti-wear agent of adaptable representativeness has zinc dialkyl dithiophosphate and diaryl zinc dithiophosphate.
Suitable phosphoric acid ester comprises dialkyl phosphorodithioate, and wherein alkyl on average contains at least 3 carbon atoms.Useful especially is the metal-salt of at least a dialkyl phosphorodithioic acid, and wherein alkyl on average contains at least 3 carbon atoms.The acid of dialkyl phosphorodithioate of can deriving can be described by the acid of following general formula:
R wherein
5And R
6Identical or different, and be the basic alkyl derivative of the replacement of alkyl, cycloalkyl, aralkyl, alkaryl or above-mentioned any group, and in acid each R
5And R
6Group on average has at least 3 carbon atoms." basic alkyl " refers to contain substituent group (partly containing 1-4 substituting group as each group) as ether, ester, nitro or halogen, and wherein said substituting group can not influence the hydrocarbon characteristic of group in itself.
Suitable R
5And R
6The object lesson of group comprises sec.-propyl, isobutyl-, normal-butyl, sec-butyl, n-hexyl, heptyl, the 2-ethylhexyl, diisobutyl, iso-octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, butyl phenyl, o, p-de amyl group phenyl, octyl phenyl, the phenyl that polyisobutene (molecular weight is 350) replaces, the phenyl that four propylidene replace, β-octyl group butyl naphthyl, cyclopentyl, cyclohexyl, phenyl, chlorophenyl, o-dichloro-phenyl, the bromo phenyl, naphthylmethylidyne, the 2-methylcyclohexyl, benzyl, the chloro benzyl, the chloro amyl group, the dichloro-phenyl, nitrophenyl, dichloro-decyl and xenyl.It is preferred having about 3 alkyl and about 6 aryl to about 30 carbon atoms to about 30 carbon atoms.Particularly preferred R
5And R
6Group is the alkyl with 4-18 carbon atom.
Phosphorodithioic acid can and easily obtain by thiophosphoric anhydride and alcohol or phenol reaction.It is under about 20 ℃-200 ℃ that this reaction is included in temperature, mixes 4 mol of alcohol or phenol and 1 mole of thiophosphoric anhydride.When carrying out, reaction discharges hydrogen sulfide.Can use alcohol, phenol or the two, for example C
3-C
30Alcohol, C
6-C
30Fragrant and mellow mixture etc.
Be used to prepare phosphatic metal and comprise I family metal, II family metal, aluminium, lead, tin, molybdenum, manganese, cobalt and nickel.Zinc is preferred metal.Can comprise Lithium Oxide 98min with the example of the metallic compound of acid-respons, lithium hydroxide, Quilonum Retard, the amylalcohol lithium, sodium oxide, sodium hydroxide, yellow soda ash, sodium methylate, sodium propylate, sodium phenylate, potassium oxide, potassium hydroxide, salt of wormwood, potassium methylate, silver suboxide, silver carbonate, magnesium oxide, magnesium hydroxide, magnesiumcarbonate, magnesium ethylate, magnesium propylate, phenol magnesium, calcium oxide, calcium hydroxide, lime carbonate, calcium methylate, calcium propylate, amylalcohol calcium, zinc oxide, zinc hydroxide, zinc carbonate, propyl alcohol zinc, strontium oxide, strontium hydroxide, Cadmium oxide, cadmium hydroxide, cadmium carbonate, the ethanol cadmium, barium oxide, hydrated barta, the barium hydrate, barium carbonate, barium ethylate, amylalcohol barium, aluminum oxide, Tripropoxyaluminum, plumbous oxide, lead hydroxide, lead carbonate, stannic oxide, butanols tin, cobalt oxide, cobaltous hydroxide, cobaltous carbonate, the amylalcohol cobalt, nickel oxide, nickel hydroxide and nickelous carbonate.
In some example, add some components, particularly carboxylic acid or metal carboxylate, as little metal acetate or acetate, use with metal reactant, will help reaction and form improved product.For example the zinc acetate with the zinc oxide applied in any combination about at the most 5% of requirement will help forming zinc dithiophosphate.
The preparation of phosphorodithioic acid metal-salt is known in the art, and is described in many patents of having authorized, comprises US 3,293,181, US 3,397, and 145, US 3,396,109 and US 3,442,804, its disclosure is here quoted as a reference.As the useful sulfonamide derivatives that also has phosphorothioate compound of anti-wear additive, as US 3,637, described in 499, its disclosure is here quoted as a reference.
Gross weight with lubricating oil composition is a benchmark, as anti-wear additive the amount of zinc salt in lubricating oil of normal application be 0.1-10wt%, be preferably 0.2-2wt%.They can be prepared according to known technology, promptly at first by alcohol or phenol and P
2S
5React and the formation phosphorodithioic acid, use in the suitable zn cpds then and phosphorodithioic acid.
Can use the mixture of alcohol, comprise the mixture of primary and secondary alcohol, secondary alcohol provides improved antiwear characteristic usually, and primary alconol provides thermostability.The two mixture is useful especially.Briefly say, can use any alkalescence or neutral zn cpds, but oxide compound, oxyhydroxide and carbonate are the most normal application.Owing in neutralization reaction, used excessive basic zinc compound, cause to be purchased additive and to contain excessive zinc usually.
Dialkyl zinc dithiophosphate (ZDDP) is the oil soluble salt of the dialkyl ester of phosphorodithioic acid, and it can be represented by following general formula:
R wherein
5And R
6With describe in the aforementioned formula identical.
The particularly preferred additive of Ying Yonging comprises alkylating pentanoic, the alkylating phenol that is obstructed, the alkylation phenolic ester and the molybdenum dithiocarbamate that are obstructed in the embodiment of this invention.
Lubricant compositions
When composition contained these additives, they were sneaked in the base oil with a certain amount of usually, thereby additive wherein can effectively provide their normal service functions.The representative significant quantity of these additives is described in table 1.
| Table 1 | ||
| Additive | Preferred wt% | Preferred wt% |
| V.I. improving agent | 1-12 | 1-4 |
| Sanitas | 0.01-3 | 0.01-1.5 |
| Antioxidant | 0.01-5 | 0.01-1.5 |
| Dispersion agent | 0.01-10 | 0.01-5 |
| The lubricating oil improving agent that flows | 0.01-2 | 0.01-1.5 |
| Sanitising agent/rust-preventive agent | 0.01-6 | 0.01-3 |
| Pour point depressor | 0.01-1.5 | 0.01-0.5 |
| Antifoams | 0.001-0.1 | 0.001-0.01 |
| Anti-wear agent | 0.001-5 | 0.001-1.5 |
| Sealed expander | 0.1-8 | 0.1-4 |
| The friction conditioning agent | 0.01-3 | 0.01-1.5 |
| Lubricating base oil | Surplus | Surplus |
When using other additive, though not necessarily, but the enriched material of additive that may it is desirable to prepare the concentrated solution that contains theme additive of the present invention or dispersion liquid and one or more described other additives is (when being made up of additive agent mixture, described enriched material is called as additive-package here), thereby several additives can be added simultaneously, in base oil to form lubricating oil composition.Utilize solvent and/or mixing and, multifunctional additive for lubricating oils more easily is dissolved in the lubricating oil, but this not very crucial with mild heat.When the combination of the base lubricant of additive-package and predetermined amount, prepare enriched material or additive-package usually, containing the additive of appropriate amount, thereby in final formulation, provide the concentration of hope.Therefore, can in a small amount of base oil or other compatible solvent, add theme additive of the present invention with other ideal additive, the additive-package that contains active ingredient with formation, the total amount of its active ingredient is about 2.5 to about 90wt% by proper ratio usually, be preferably about 15 to about 75wt%, and more preferably about 25 to about 60wt%, and remaining is base oil.Final formulation can be used the additive-package of about 1-20wt% usually, and remaining is base oil.
Here represented all wt per-cent (particularly point out except) all active ingredient (AI) content with additive is benchmark, and/or be benchmark with the gross weight of any additive-package or formulation, and described gross weight oils for the AI weight of each additive adds or the gross weight of thinner.
Put it briefly, it is about additive of 0.05 to about 30wt% that lubricant compositions of the present invention contains concentration.Gross weight with oil compositions is a benchmark, and the concentration range of additive is about 0.1 to about 10wt% to be preferred.Preferred concentration range is about 0.2 to about 5wt%.The oil concentrate of additive can contain 1 to about 75wt% the additive reaction product of having an appointment in the carrier of lubricating oil viscosity or thinning oil.
Put it briefly, additive of the present invention all can be used in multiple lube base stock.Lube base stock can be any natural or synthetic lube base stock cut, and it has about kinematic viscosity of 2 to about 200cSt at 100 ℃, and more preferably about 3 to about 150cSt, and most preferably is about 3 to about 100cSt.Lube base stock can derive from natural lubricating oil, ucon oil or its mixture.Proper lubrication oil base material package is drawn together the base-material that obtains by synthetic wax and wax isomerization, and the hydrocracking base-material that produces of aromatics or polar compound by hydrocracking (rather than solvent extraction) crude oil.Natural lubricating oil comprises animal oil such as lard, vegetables oil (for example Tower rape oil, Viscotrol C, Trisun Oil R 80), oil, mineral oil and derives from coal or the oil of shale.
Synthetic oil comprises the hydrocarbon ils that hydrocarbon ils and halogen replace, for example alkene of polymerization and copolymerization, alkylbenzene, polyphenyl, alkylating diphenyl ether, alkylating diphenylsulfide, and their derivative, analogue, homologue etc.Ucon oil also comprises alkylene oxide polymers, interpolymer, multipolymer and derivative thereof, and wherein terminal hydroxyl groups is by modifications such as esterification, etherificates.
Another kind of suitable ucon oil comprises the ester of dicarboxylic acid and multiple alcohol.Useful ester comprises that also those are by C as synthetic oil
5To C
12The material that monocarboxylic acid and many alcohol and many alcohol ethers make.
Silicon-based oil (as poly-alkyl-, poly-aryl-, poly-alkoxyl group-or poly-aryloxy-silicone oil and silicic acid ester oil) be another kind of useful ucon oil.Other ucon oil comprises liquid ester, polymeric tetrahydrofuran (THF), the poly-alpha olefins of phosphoric acid, and analogue.
Lubricating oil can be derived from unrefined, purified, purified oil, or its mixture again.Unrefined oil is directly obtained without being further purified or handling by natural source or synthetic source (for example coal, shale or tar and pitch).The example of unrefined oil comprises the shale oil that directly obtained by distillation procedure, the oil that is directly obtained by rectifying or the ester oil that is directly obtained by esterification process, then these materials each all directly use without further processing.Refining oil is with refining oil is not similar, and just refining oil is handled in one or more purification steps, thereby has improved one or more characteristics.Suitable purification technique comprises rectifying, hydrotreatment, dewaxing, solvent extraction, acid or alkaline extraction, filtration, diafiltration and similar operations, and all these all are known concerning those skilled in the art.Application class is similar to the method that obtains refining oil, can obtain refining oil again by handling refining oil.These again refining oil be also referred to as refiltered oil or handling oil again, their are often used the technology that removes useless additive and oil decomposition product and carry out additional processing.
Also can use the lube base stock that obtains by the hydroisomerization of wax, perhaps use separately, perhaps with aforesaid natural and/or synthetic base-material applied in any combination.Under the effect of hydroisomerisation catalysts, carry out the isomerized oil that hydroisomerization can produce this wax by natural or synthetic wax or its mixture.Natural wax is generally that mineral oil carries out solvent dewaxing and the soft wax that reclaims; Synthetic wax is generally the wax that is produced by Fischer-Tropsch process.The isomerization product of gained carries out solvent dewaxing and rectifying usually, thereby reclaims the various cuts with particular viscosity.The feature of wax isomer is that also it has very high viscosity index, and its VI is generally at least 130, is preferably at least 135 or higher, and through after the dewaxing, its pour point is-20 ℃ or lower approximately.
Additive of the present invention is useful especially as component in many different lubricating oil compositions.This additive can be included in many oil with lubricant viscosity, and the oil of described lubricant viscosity comprises natural and synthetic lubricating oil and composition thereof.This additive can be included in the crankcase lubricating oil of oil engine of Mars igniting and ignition.Described composition also can be used in internal combustion engine lubricant, turbine lubricant, automatic transmission fluid, gear lubricant, compressor lubricant, metal working lubricant, hydraulic fluid and other lubricating oil and grease composition.This additive also can be used in motor fuel composite.
By following embodiment, it is more obvious that advantage of the present invention and key character will become.
Embodiment
Embodiment 1
The preparation of the cetene base hydrazides of side chain
In the 250mL three neck round-bottomed flasks of a thermopair that is equipped with mechanical stirrer, Dean-Stark water vessel, feed hopper, temperature regulator, heating jacket and nitrogen protection gas, add 75mL toluene and 31.8 gram (0.1 mole) cetene base succinyl oxides.In feed hopper, add 5.0 gram (0.1 mole) hydrazides monohydrates.At room temperature in 5 minutes the timed interval, in the reaction medium that stirs, dropwise slowly add hydrazides.Reaction medium is with about 20 ℃ of heat release.Elevated temperature removes the Dean-Stark water vessel with backflow toluene then.The back flow reaction medium is up to having removed 3.7mL water, and the infrared analysis of product sample shows that all acid anhydrides have all changed into succinhydrazide.Next cool off reaction medium to room temperature and put into the Roto-vaporizer to remove toluene solvant.Next by Celite strainer auxiliary agent bed filtration reaction product, restrain clarifying yellow liquid thereby obtain 33.
Embodiment 2
The preparation of the N-methyl vaccenic acid base succinhydrazide of side chain
In the 250mL three neck round-bottomed flasks of a thermopair that is equipped with mechanical stirrer, Dean-Stark water vessel, feed hopper, temperature regulator, heating jacket and nitrogen protection gas, add 75mL toluene and 17.1 gram (0.05 mole) vaccenic acid base succinyl oxides.In feed hopper, add 2.3 gram (0.05 mole) methylhydrazides.At room temperature in 5 minutes the timed interval, in the reaction medium that stirs, dropwise slowly add hydrazides.A spot of heat release appears in reaction medium.Elevated temperature removes the Dean-Stark water vessel with backflow toluene then.The back flow reaction medium removes up to no longer including water, and the infrared analysis of product sample shows that all acid anhydrides have all changed into succinhydrazide.Next cool off reaction medium to room temperature and put into the Roto-vaporizer to remove toluene solvant.Next by Celite strainer auxiliary agent bed filtration reaction product, restrain clarifying yellow liquid thereby obtain 18.4.
Embodiment 3-6
The vaccenic acid base succinhydrazide of dodecenyl succinic succinhydrazide, N-phenyl dodecyl succinhydrazide and side chain for preparing dodecenyl succinic succinhydrazide, the side chain of straight chain by said process.
Embodiment 7
Four ball wear tests
According to the experiment condition of ASTMD4172, wipe to determine with concentration to be the antiwear characteristic that 1.0wt% is present in the alkyl succinhydrazide of the present invention in the SAE 5W-20 GF-3 engine lubrication oil formulation of preparing fully in the experiment at four ball millings.The lubricating oil of being tested of preparation fully also contains the cumene hydroperoxide of 1wt% to help the in-engine environment of dry run.Described additive is tested its validity (description in the reference table 2) in the engine lubrication oil formulation, and compares with the identical formulations that contains or do not contain any zinc dialkyl dithiophosphate.In table 3, (average wear scar diameter, mm) increase with its validity reduces the numerical value of test-results.
| Table 2 SAE 5W-20 prototype engine lubricating oil formulation | |
| Component | Formulation A (wt%) |
| Neutral solvent 100 | 22.8 |
| Neutral solvent 150 | 60 |
| Succinimide dispersants | 7.5 |
| Peralkaline calcium phenylate sanitising agent | 2.0 |
| Neutral calcium sulphonate sanitising agent | 0.5 |
| Rust-preventive agent | 0.1 |
| Antioxidant | 0.5 |
| Pour point depressor | 0.1 |
| OPC VI improving agent | 5.5 |
| Anti-wear additive 1 | 1.0 |
1When no anti-wear additive exists in table 2, neutral solvent 100 is set to 1.0wt%
| Table 3 four ball millings are wiped the result | ||
| Compound | Formulation | Wear scar diameter, mm |
| No anti-wear additive | A | 0.73(0.74) * |
| The zinc dialkyl dithiophosphate of 1.0wt% | A | 0.50(0.51) |
| The zinc dialkyl dithiophosphate of 0.5wt% | A | 0.70(0.67) |
| The dodecenyl succinic succinhydrazide of straight chain | A | 0.39(0.39) |
| The dodecenyl succinic succinhydrazide of side chain | A | 0.39 |
| N-phenyl dodecenyl succinic succinhydrazide | A | 0.66(0.41) |
| N-methyl dodecenyl succinic succinhydrazide | A | 0.38(0.39) |
| The cetene base succinhydrazide of side chain | A | 0.40(0.39) |
| The vaccenic acid base succinhydrazide of side chain | A | 0.40(0.61) |
*The result of the numeral revision test in the bracket.
Embodiment 8
The wear test of Cameron-Plint TE77 high frequency friction machine
Be used for determining that another test of these product antiwear characteristics is based on the Cameron-Plint wear test that dish is gone up sliding ball.(hardness is 800 ± 20kg/mm to the flushing instance element
2, diameter is that the sclerosis of 60/0.4 micron of AISI 52100 steel balls of 6mm and RC grinds NSOH B01 normality dish), use the hexane sonication 15 minutes of technical grade then.Repeat this process with Virahol.Sample is with nitrogen drying and put into TE77.In oil bath, add the 10mL sample.Test moves under the amplitude of 30 hertz frequency, 100 newton's load, 2.35mm.At room temperature begin test with sample and oil.In 15 minutes, temperature rises to 50 ℃ rapidly then, stops 15 minutes in this temperature.In 15 minutes, make temperature rise to 100 ℃ then, stopped 45 minutes in this temperature.In 15 minutes, make temperature rise to 150 ℃ for the third time, and stopped 15 minutes at 150 ℃ at last.The total length of test is 2 hours.When off-test, use the wear scar diameter on LeicaStereoZoom6 Stereomicroscope and the Mitutoyo 164 serial Digimatic Head measurement 6mm balls.In the following embodiments, the lubricating oil of being tested of preparation fully contains the cumene hydroperoxide of 1wt% to help the in-engine environment of dry run.The additive of test is sneaked in the SAE 5W-20 PrototypeGF-4 engine lubrication oil formulation of preparing fully with 1.0wt% and is mixed, and described engine lubrication oil formulation does not contain ZDDP.Test the validity (referring to the description in the table 4) of additive in this engine lubrication oil formulation pilot scale, and with the identical formulations that contains or do not contain any zinc dialkyl dithiophosphate relatively.In table 4, the numerical value of test-results (ball milling scar diameter, dish scar width and the dish scar degree of depth) reduces with the increase of its validity.
| The table 4 Cameron-Plint test that rubs | |||
| The additive of 1.0wt% | Ball milling scar (mm) | Dish scar width (mm) | The dish scar degree of depth (μ m) |
| Dodecenyl succinic-the succinhydrazide of side chain | 0.59(0.54) | 0.43(0.56) | 10.59(10.07) |
| No anti-wear additive 1 | 0.66 | 0.74 | 15.05 |
| Zinc dialkyl dithiophosphate (1.0wt%) | 0.39 | 0.72 | 1.83 |
| Zinc dialkyl dithiophosphate (0.5wt%) | 0.62 | 0.76 | 14.77 |
1When no anti-wear additive exists in the table 4, neutral solvent 100 is set to 1.0wt%.
Under the situation that does not depart from ultimate principle of the present invention, can make many changes and improvements, therefore should be with reference to claims, to understand protection scope of the present invention.
Claims (10)
1. composition comprises:
(A) lubricant and
(B) at least a alkyl succinhydrazide compound with following general formula:
Wherein:
R
1Be selected from alkyl, alkenyl, alkaryl, alkyl oxide, alkyl ester and the alkylene ester group of straight or branched;
R
2Be selected from alkyl, alkenyl, alkyl oxide and the alkyl group of hydrogen, straight or branched; With
R
3And R
4Be independently selected from alkyl and alkenyl, aryl and the alkaryl of hydrogen, straight or branched;
The concentration that exists of wherein said alkyl succinhydrazide is about 0.01wt% to about 10wt%.
2. the described composition of claim 1, wherein said lubricant is a lubricating oil.
3. the described composition of claim 1, wherein R
1Be straight chain hydrocarbon, branched-chain hydrocarbon, complete saturated hydrocarbon chain or the undersaturated hydrocarbon chain of part.
4. the described composition of claim 1, wherein R
1For having the hydrocarbon chain of 1 to 30 carbon atom.
5. the described composition of claim 1, wherein R
1Cetene chain for straight or branched.
6. the described composition of claim 1, wherein R
2, R
3And R
4Be independently selected from hydrogen, aryl, alkyl, alkaryl and alkenyl.
7. the described composition of claim 1, wherein R
2, R
3And R
4Identical.
8. the described composition of claim 7, wherein R
2, R
3And R
4Be hydrogen.
9. the described composition of claim 1 further comprises at least a following additive that is selected from: dispersion agent, sanitising agent, sanitas/rust-preventive agent, zinc dialkyl dithiophosphate, VI improving agent, pour point depressor, antioxidant and friction modifier.
10. the described composition of claim 1 further comprises at least a following material that is selected from: zinc dialkyl dithiophosphate, diaryl zinc dithiophosphate and their mixture.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2002/030963 WO2004029183A1 (en) | 2002-09-26 | 2002-09-26 | Alkyl-succinhydrazide additives for lubricants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1606611A CN1606611A (en) | 2005-04-13 |
| CN1272415C true CN1272415C (en) | 2006-08-30 |
Family
ID=32041254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028257952A Expired - Fee Related CN1272415C (en) | 2002-09-26 | 2002-09-26 | Alkyl succinite hydrazide additive for lubricant |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1543096B1 (en) |
| JP (1) | JP4027934B2 (en) |
| CN (1) | CN1272415C (en) |
| AT (1) | ATE393807T1 (en) |
| AU (1) | AU2002334726A1 (en) |
| DE (1) | DE60226350T2 (en) |
| WO (1) | WO2004029183A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106609167A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Wear-resistant additive for low-sulfur diesel oil as well as preparing method thereof and diesel oil combination |
| CN107794097A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of low acid type diesel oil multi-efficient additive and Dresel fuel compositions |
| CN107794096A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | Diesel oil multi-efficient additive and Dresel fuel compositions |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE524537T1 (en) | 2006-08-04 | 2011-09-15 | Infineum Int Ltd | METHOD AND APPLICATION FOR PREVENTING DEPOSITS IN A FUEL INJECTOR |
| CN103215107B (en) | 2007-06-11 | 2015-03-11 | 出光兴产株式会社 | Detergent dispersant, additive composition for lubricating oil, and lubricating oil composition |
| JP5379361B2 (en) * | 2007-08-08 | 2013-12-25 | 出光興産株式会社 | Antiwear agent, additive composition for lubricant and lubricating oil composition |
| CN107353965B (en) * | 2016-12-26 | 2020-08-25 | 中国林业科学研究院林产化学工业研究所 | Preparation method of castor oil-based extreme pressure water-based lubricating additive |
| CN109370739B (en) * | 2018-12-05 | 2021-08-03 | 武汉轻工大学 | Non-classical tribology isostere with hydrazide group as phosphate group |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2640005A (en) * | 1950-10-28 | 1953-05-26 | Ethyl Corp | Succinhydrazides |
| DE1050485B (en) * | 1955-08-19 | 1959-02-12 | Esso Research and Engineering Company Elizabeth NJ (V St A) | Lubricating and heating oil additives |
| GB2327944B (en) * | 1997-08-06 | 2001-10-10 | Ciba Sc Holding Ag | Hetercyclic thioethers as additives for lubricants |
-
2002
- 2002-09-26 WO PCT/US2002/030963 patent/WO2004029183A1/en active Application Filing
- 2002-09-26 DE DE60226350T patent/DE60226350T2/en not_active Expired - Lifetime
- 2002-09-26 CN CNB028257952A patent/CN1272415C/en not_active Expired - Fee Related
- 2002-09-26 EP EP02807876A patent/EP1543096B1/en not_active Expired - Lifetime
- 2002-09-26 JP JP2004539751A patent/JP4027934B2/en not_active Expired - Fee Related
- 2002-09-26 AU AU2002334726A patent/AU2002334726A1/en not_active Abandoned
- 2002-09-26 AT AT02807876T patent/ATE393807T1/en not_active IP Right Cessation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106609167A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Wear-resistant additive for low-sulfur diesel oil as well as preparing method thereof and diesel oil combination |
| CN106609167B (en) * | 2015-10-22 | 2019-03-08 | 中国石油化工股份有限公司 | A kind of low-sulfur diesel-oil antiwear additive, preparation method and Dresel fuel compositions |
| CN107794097A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of low acid type diesel oil multi-efficient additive and Dresel fuel compositions |
| CN107794096A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | Diesel oil multi-efficient additive and Dresel fuel compositions |
| CN107794097B (en) * | 2016-08-31 | 2020-08-18 | 中国石油化工股份有限公司 | Low-acid type diesel oil multi-effect additive and diesel oil composition |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2002334726A1 (en) | 2004-04-19 |
| JP4027934B2 (en) | 2007-12-26 |
| JP2005524762A (en) | 2005-08-18 |
| CN1606611A (en) | 2005-04-13 |
| EP1543096A1 (en) | 2005-06-22 |
| DE60226350D1 (en) | 2008-06-12 |
| ATE393807T1 (en) | 2008-05-15 |
| WO2004029183A1 (en) | 2004-04-08 |
| DE60226350T2 (en) | 2009-06-10 |
| EP1543096B1 (en) | 2008-04-30 |
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