CN102959065A

CN102959065A - Fuel efficient engine oil composite

Info

Publication number: CN102959065A
Application number: CN2011800301728A
Authority: CN
Inventors: 吉田悟; 丸山正希
Original assignee: JX Nippon Oil and Energy Corp
Current assignee: Eneos Corp
Priority date: 2010-06-25
Filing date: 2011-02-21
Publication date: 2013-03-06
Also published as: JPWO2011161982A1; JP5767215B2; KR20130100964A; WO2011161982A1

Abstract

Provided is an engine oil that has excellent corrosion and wear protection capabilities and excellent fuel efficiency. The disclosed fuel efficient engine oil composite contains an organic molybdenum (Mo) compound with at least 0.02 mass% molybdenum and an alicyclic epoxy compound in a lubricant base oil and preferably uses molybdenum dithiocarbamate (MoDTC) as the organic molybdenum compound, a compound that that has ester bonds and two epoxidised cycloalkanes as the alicyclic epoxy compound and a compound that has a dynamic viscosity of 4.5 mm2/s or less at 100 C as the lubricant base oil.

Description

Burnup saving type engine oil composition

Technical field

The present invention relates to have excellent erosion resistance and burnup saving type (fuel efficient) machine oil of wear resistant.

Background technology

In recent years, for the Global warming that prevents from approaching, the day by day expectation that becomes improves province's burnup of automobile and reduces CO ₂Discharging.Engine design is important although provide more effectively, and engine interior is reduced friction also can help improved province burnup.Therefore, in slide unit, use low-friction material and use burnup saving type engine oil to become more general.

In order to obtain burnup saving type engine oil, as by SAE (Society of Automotive Engineers, Automotive Engineering Society) lowering viscousity of the oil of the 5W-30 of the viscosity of J300 standard code classification or 0W-30, and comprise reduction friction additive (friction improver; Be abbreviated as " FM "), for example organomolybdenum FM such as molybdenum dithiocarbamate (MoDTC) are known as a kind of effective means.

Yet known sulfuric acid can be produced by the sulphur component that is included in fuel or the machine oil, and some sulfuric acid can pollute machine oil, cause corrosion and the abrasion of engine parts.Therefore, no matter whether comprise MoDTC etc., all tight demand has the machine oil of excellent erosion resistance.

This type of is characterised in that the example of the lubricant composition for internal combustion engine of improved erosion resistance and wear resistant comprises the composition of patent documentation (PLT) 1, described composition comprises Sulfated dithiocarbamic acid oxygen molybdenum, amides, fatty acid partial ester compound and/or fatty acid amine compounds in lubricant base, and benzotriazole derivatives (PLT 1).Yet the anticorrosion effect of said composition and abrasion performance effect are still unsatisfactory.

Patent documentation 2 has proposed a kind of lubricating oil that is characterised in that improved erosion resistance to plumbous and copper, and described lubricating oil comprises specific epoxidised ester compounds (PLT2).PLT 2 has enumerated the multiple epoxidised ester compounds that comprises cycloalkyl, but wherein disclosed unique concrete compound is epoxidation resinous acid 2-ethylhexyl.In addition, although PLT 2 has mentioned the example of organic molybdenum as friction improver perfunctorily, the content of the document and unexposed any relevant its effect especially, does not have the disclosure about the synergistic effect of epoxy compounds and organic molybdenum.

Reference listing

Patent documentation

PLT?1：JP?2008-106199A

PLT?2：JP?2008-518080A

Summary of the invention

The problem that invention will solve

Purpose of the present invention is for providing the machine oil with excellent erosion resistance, wear resistant and saving of fuel (fuel saving property).

For the scheme of dealing with problems

To achieve these goals, the inventor conducts in-depth research multiple lubricant base material and the lubricating oil additive that can be used for machine oil, and find, comprise that the combination of the organic molybdenum of alicyclic epoxide compound and specified quantitative shows excellent province's burnup, erosion resistance and wear resistant as the machine oil of lubricating oil additive.This discovery causes of the present invention finishing.

Therefore, burnup saving type engine oil composition of the present invention that be used for to realize above-mentioned purpose comprises also that except lubricant base concentration take the quality of molybdenum (Mo) is as organic molybdenum and alicyclic epoxide compound more than the 0.02 quality %.

In a preferred embodiment of the invention, described organic molybdenum is molybdenum dithiocarbamate (MoDTC), and described alicyclic epoxide compound has ester bond and two epoxidation naphthenic hydrocarbon parts, and described lubricant base has 4.5mm ²Kinetic viscosity under 100 ℃ below the/s.

The effect of invention

Burnup saving type engine oil composition of the present invention in addition behind life-time service also so that engine parts corrosion and abrasion seldom, and further provide excellent low frictional properties.Therefore the province's burnup in high temperature range is excellent especially for engine oil base oil.

Embodiment

The lubricant base that is used for burnup saving type engine oil composition of the present invention can be mineral oil, synthetic oil or its mixture.Mineral oil preferably has the lubricant base of the high viscosity index (HVI) of the viscosity index more than 120.Lubricant base with the viscosity index more than 120 can pass through hydroisomerized wax or hydrocracking heavy oil, then gained oil product solvent dewaxing or Hydrodewaxing (hydrodewaxing) is obtained.

The hydroisomerization of wax can carry out by the following method: make that to have 300 to 600 ℃ of boiling point and carbon numbers in the scope be 20 to 70 wax material and hydroisomerisation catalysts 300 to 450 ℃ temperature and 0.1 to 2h ^-1LHSV (liquid hourly space velocity) under, contact in the presence of the hydrogen of the dividing potential drop 5 to 14MPa, described wax material such as the slack wax that obtains in the mineral lubricating oils solvent dewaxing technique and wherein appropriate hydrocarbon gas etc. be converted to carbon monoxide and the wax of hydrogen to obtain in the Fischer-Tropsch synthesis method (Fischer-Tropsch synthesis) of synthetic liquid fuel, described hydroisomerisation catalysts for example comprises that the 8th family's metal of load on aluminum oxide or the silica-alumina carriers is (such as nickel, cobalt etc.) and 6A family metal (such as molybdenum, the catalyzer of tungsten etc.) any one or more, zeolite catalyst or contain the catalyzer that comprises platinum etc. of load on the carrier of zeolite.Preferably, in aforesaid method, the transformation efficiency of linear paraffin is more than 80%, and the ratio that is converted into lighting end is below 40%.

Lubricant base with high viscosity index (HVI) also can be obtained by the hydrocracking of heavy oil as described below.Make normal pressure distilled oil, vacuum distillate or bright stock (bright stock) (can carry out hydrogenating desulfurization and hydrodenitrification such as needs) with 300 to 600 ℃ of boiling points in the scope and hydrocracking catalyst 350 to 450 ℃ temperature and 0.1 to 2h ^-1LHSV (liquid hourly space velocity) under, in the presence of the hydrogen of 7 to 14MPa dividing potential drops, contact, described hydrocracking catalyst is such as the catalyzer that comprises any or multiple the 8th family's metal (such as nickel, cobalt etc.) and one or more 6A family metals (such as molybdenum, tungsten etc.) that comprises load on the silica-alumina carriers.In this technique, the rate of cracking (that is, the cut decrement corresponding to the boiling range more than 360 ℃ (distillation ranges) seen in the products therefrom is expressed as quality %) preferred 40 to 90%.

Can by distillation will obtain in the above-mentioned technique hydroisomerizing carburetion product or hydrocrackates product carry out lighting end and remove to produce lubricating oil distillate.Yet itself has high pour point and high viscosity usually this cut, and in addition, its viscosity index is usually not high enough.Therefore, can make the processing that further dewaxes of described cut, thereby except the dewax component and produce lubricant base, this lubricant base has the %C that passes through n-d-M ring analysis mensuration 80 or more _pPour point below ,-10 ℃ and 120 above viscosity indexs.

If carry out above-mentioned dewaxing processing by the solvent dewaxing processing, then preferably by using precise distillation equipment to carry out removing in advance lighting end by distillation, so as will according to the gas-chromatography distillation method measure corresponding at least 371 ℃ but the cut that is lower than 491 ℃ boiling point be adjusted in advance more than the 70 quality %.Like this, can improve the efficient that solvent dewaxing is subsequently processed.Solvent dewaxing is processed can be preferably by for example using methylethylketone/toluene (volume ratio 1/1) to carry out as dewaxing solvent under solvent/oil ratio of 2/1 to 4/1 and under-15 to-40 ℃ the temperature.

On the other hand, if by the processing that dewaxes of Hydrodewaxing method, then preferably only will remove in advance the degree that lighting end proceeds to the Hydrodewaxing processing that can not adversely affect subsequently by distillation, and after Hydrodewaxing finishes, preferably by using precise distillation equipment to distill, so as will according to the gas-chromatography distillation method measure corresponding at least 371 ℃ but the cut that is lower than 491 ℃ boiling point be adjusted into more than the 70 quality %.The Hydrodewaxing step can be preferably by in the presence of the hydrogen of 3 to 15MPa dividing potential drops, 320 to 430 ℃ temperature and 0.2 to 4h ^-1LHSV (liquid hourly space velocity) under make raw material contact to carry out with zeolite catalyst so that the pour point of final lubricant base is below-10 ℃.

Lubricant base with the viscosity index more than 120 can obtain by aforesaid method, if but expectation also can be carried out further solvent treatment or further hydrofinishing.

The example of synthetic oil comprises the oligopolymer of alpha-olefin, the polyol ester that synthesizes by the synthetic diester of diprotic acid (such as hexanodioic acid) and monohydroxy-alcohol, by polyvalent alcohol (such as neopentyl glycol, TriMethylolPropane(TMP) and tetramethylolmethane) and monoprotic acid and composition thereof.

In addition, the blend oil that comprises suitable mineral oil and suitable synthetic oil also can be used as the base oil in the machine oil of the present invention.

No matter be mineral oil, synthetic oil or blend oil, the base oil that is used for burnup saving type engine oil composition of the present invention preferably has the 4.5mm that measures according to JIS K2283 test method ²Kinetic viscosity under 100 ℃ below the/s and 120 above viscosity indexs, in addition, base oil preferably has 1.0mm ²Kinetic viscosity under above 100 ℃ of/s, the %C more than 80 that measures by the n-d-M ring analysis according to AS TM D2140 _pWith the pour point below-10 ℃ according to JIS K2269 determination of test method.

Burnup saving type engine oil composition of the present invention has the above organic molybdenum content in the quality of molybdenum (Mo) of 0.02 quality %, with respect to the total mass of engine oil base oil.If molybdenum content is lower than 0.02 quality %, then will be not enough to keep province's burnup.Preferred 0.03 to the 0.20 quality % of organic molybdenum content is in the quality of molybdenum (Mo).

The specific examples of organic molybdenum comprises molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP) and Mo-amine complex.In these, MoDTC most preferably, and MoDTP is not very preferably, this be since purifying waste gas with the poisoning of three-way catalyst, and described poisoning is caused by phosphorus.

Being used for preferred MoDTC of the present invention can be represented by following general formula (1).

[Chemical formula 1]

In following formula, R ₁To R ₄The expression carbon number is 4 to 18 linearity and/or alkyl and/or the alkenyl of branching, and each X represents Sauerstoffatom or sulphur atom, and wherein Sauerstoffatom and sulphur atom exist with 1/3 to 3/1 ratio.R ₁To R ₄Preferred alkyl, particularly preferably carbon number is the alkyl of 8 to 14 branching, its specific examples comprises butyl, 2-ethylhexyl, isotridecyl and stearyl etc.Be present in four " R " groups, i.e. R in the individual molecule ₁To R ₄, can be same to each other or different to each other.In addition, have different R ₁To R ₄Two or more MoDTC molecules of group can mix use.

The example that can be used for alicyclic epoxide compound of the present invention comprises epoxidation cycloalkanes hydrocarbons and their derivates.Epoxidation naphthenic hydrocarbon preferably has 3 to 12 carbon number.The specific examples of epoxidation naphthenic hydrocarbon comprises epoxidation cyclopropane, epoxidation tetramethylene, epoxidation pentamethylene, epoxidation two pentamethylene, epoxidation hexanaphthene, epoxidation suberane, epoxidation cyclooctane, epoxidation cyclononane, epoxidation cyclodecane, epoxidation cyclododecane and epoxidation norcamphane etc.

The example of the derivative of epoxidation naphthenic hydrocarbon be included in alicyclic moiety have the alkylation of one or more alkyl or alkenyl or alkenylation epoxy cycloalkanes, alicyclic moiety have one or more fatty alkoxyl groups or aryloxy ether compound, have imide and the imide compound of one or more imides and have amide compound of one or more amide group etc. at alicyclic moiety at alicyclic moiety.The ester compound that has one or more carboxyls at alicyclic moiety is preferred example.The compound that also more preferably has two epoxidation naphthenic hydrocarbon part, particularly 3,4-oxirane ring alkyl-3,4-oxirane ring alkyl carboxylic acid ester (wherein the carbon number of each alkyl is 3 to 12), it is most preferred 3 that its specific examples comprises, 4-epoxycyclohexyl methyl-3,4-epoxy cyclohexane manthanoate.These alicyclic epoxide compounds can use separately or two or more are used in combination.

Alicyclic epoxide compound can be included in the composition with any significant quantity, and described significant quantity can be suitably to select in the scope of 0.05 to 2 quality % in the total mass with respect to engine oil base oil.

Burnup saving type engine oil composition of the present invention can further comprise above NM various other additives, in order to realize balanced lubricity.Especially, preferably add metal species washing composition, ashless dispersant and/or abrasion performance agent, disperse (sludge dispersion) and/or wear resistant in order to realize excellent spatter property, sludge.

The metal species washing composition is preferably selected from least a alkaline-earth metal class washing composition in alkaline earth metal sulfonate, alkaline-earth metal phenates and the alkaline-earth metal salicylate.

Alkaline earth metal sulfonate preferably has 300 to 1500 molecular weight, especially the alkaline earth salt of the alkyl aromatic sulfonic acid of 400 to 700 molecular weight (particularly magnesium salts and/or calcium salt, preferred calcium salt).

The alkaline earth salt (particularly magnesium salts and/or calcium salt) of Mannich reaction (Mannich reaction) product of alkaline-earth metal phenates preferred alkyl phenol, alkylphenol sulfide or alkylphenol, wherein alkyl is that carbon number is 4 to 30, preferred carbon number is 6 to 18 linearity or the alkyl of branching.

The salicylic alkaline earth salt of alkaline-earth metal salicylate preferred alkyl (particularly magnesium salts and/or calcium salt), wherein alkyl is that carbon number is 1 to 30, preferred carbon number is 6 to 18 linearity or the alkyl of branching.

The addition of described metal species washing composition can freely change, but preferable alloy class detergent content is counted 0.05 to 0.22 quality %, more preferably 0.1 to 0.2 quality % with the quality of metal, with respect to the total mass of burnup saving type engine oil composition.

The example of ashless dispersant comprises derived from polyolefinic alkenyl succinimide and alkyl succinimide, and derivative.Exemplary succinimide can on average have 4 to 10 nitrogen-atoms by the succinyl oxide with high molecular alkenyl or alkyl substituent and per molecule, more preferably the reaction between the polyalkylene polyamine of 5 to 7 nitrogen-atoms obtains.Especially, preferably will have number-average molecular weight is that 700 to 5000, especially 900 to 3000 polyisobutene is as the polybutylene-based succinimide of high molecular alkenyl or alkyl.

Polybutylene-based succinimide can be obtained by polybutene, and described polybutene can be by obtaining the polymerization of mixtures of high-purity isobutylene or 1-butane and iso-butylene with boron-fluorine class catalyzer or aluminium-chlorine class catalyzer.Usually, 5 to 100mol% polybutylene-based succinimide has vinylidene at the end of polybutene.In order to obtain the excellent inhibition that sludge is formed, the polyalkylene polyamine chain preferably has 2 to 5, more preferably 3 to 4 nitrogen-atoms.

The derivative that is used for polybutylene-based succinimide of the present invention can be so-called modification succinimide, and described modification succinimide can be obtained by the following method by the above-mentioned polybutylene-based succinimide of mentioning: make its and boron compound (such as boric acid) or oxygen-containing organic compound such as alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate and organic acid reaction so that part or all of remaining amino and/or imino-are neutralized or amidation.Boracic alkenyl (or alkyl) succinimide that can be obtained by the reaction with boron compound such as boric acid especially, shows excellent thermostability and oxidative stability.

The addition of described ashless dispersant can freely change, but preferred, ashless dispersant content is 0.5 to 15 quality % with respect to the total mass of burnup saving type engine oil composition.

Burnup saving type engine oil composition of the present invention preferably comprise 0.01 to 0.10 quality %, more preferably 0.05 to 0.08 quality % in the zinc dithiophosphate (ZnDTP) of the quality of phosphorus (P) as the abrasion performance agent, with respect to the total mass of burnup saving type engine oil composition.If the phosphorus atom content that is derived from ZnDTP is lower than 0.01 quality % with respect to the total mass of engine oil base oil, then may not can obtain sufficient abrasion resistance, if and the phosphorus content that is derived from ZnDTP surpasses 0.10 quality %, then the automobile exhaust gas purifying may become remarkable with the poisoning of catalyzer.

It is 1 to 24 linearity or the alkyl of branching that the ZnDTP compound preferably has carbon number, and carbon number is 3 to 24 linearity or alkenyl or the alkyl-cycloalkyl of branching, and perhaps carbon number is 6 to 18 aryl or the alkaryl of linearity or branching.Alkyl and alkenyl can be primary, the second month in a season or uncle's group.

The specific examples of zinc dithiophosphate comprises that dipropyl disulfide is for zinc phosphate, zinc dibutyldithiophosphate, diamyl disulfide is for zinc phosphate, the dihexyl zinc dithiophosphate, the diisoamyl zinc dithiophosphate, the diethylhexyl zinc dithiophosphate, the dioctyl zinc dithiophosphate, the dinonyl zinc dithiophosphate, the didecyl zinc dithiophosphate, two-dodecyl zinc dithiophosphate, dipropyl phenyl zinc dithiophosphate, diamyl phenyl zinc dithiophosphate, dipropyl aminomethyl phenyl zinc dithiophosphate, dinonyl phenyl zinc dithiophosphate, two-dodecylphenyl zinc dithiophosphate and two-dodecylphenyl zinc dithiophosphate etc.

ZnDTP content is in preferred 0.01 to the 0.10 quality % of the quality of phosphorus (P) atom, more preferably 0.03 to 0.08 quality %, with respect to the total mass of engine oil base oil.

Machine oil of the present invention optionally further comprises additive such as ashless antioxidant, viscosity index improver, pour point reducer (pour point-depressant), metal passivator, rust-preventive agent and defoamer.

Embodiment

Below, will the present invention be described in further detail by embodiment.

(kinetic viscosity: 40 ℃ are down 17.7mm to the mineral oil that will obtain by hydrocracking heavy oil and Hydrodewaxing gained oil product ²/ s, 100 ℃ lower is 4.1mm ²/ s; Viscosity index: 134; %C _P: 85; Pour point :-20 ℃) as base oil.

Add following MoDTC as additive, be widely used as and suppress corrosion with benzotriazole derivatives (BTA), epoxy compounds, viscosity index improver (VI) and other additives of lubricating oil additive to described base oil with the ratio shown in the table 1, thus Preparation Example 1 and 2 and the machine oil of comparative example 1 to 6.Other additives comprise the mixture of alkyl zinc dithiophosphate (ZnDTP), calcium sulphonate, alkenyl succinimide, pour point reducer and defoamer, and add to equably in all embodiment and the comparative example with identical amount.Viscosity index improver is added in all embodiment and the comparative example, so that the kinetic viscosity under in each composition 100 ℃ is 9.3 to 9.5mm ²/ s (the SAE viscosity classification corresponding to 30).

MoDTC as used herein is the compound by general formula (1) expression, wherein R ₁To R ₄Be the mixture of 2-ethylhexyl and isotridecyl, the ratio of Sauerstoffatom/sulphur atom is 1/1.

With N, two [(2-ethylhexyl) the aminomethyl]-1H-benzotriazoles of N-(Irgamet 39, made by Ciba Speciality Chemicals) are as benzotriazole derivatives.

As epoxy compounds, use alicyclic epoxide compound 3,4-epoxycyclohexyl methyl-3,4-epoxy cyclohexane manthanoate, and with the non-annularity epoxy compounds: 2-ethylhexyl glycidyl ether (epoxy compounds 1) and neodecanoic acid glycidyl ester (glycidyl neodecanoate ester) (epoxy compounds 2) are used for relatively.

Polymethacrylate compounds is used as viscosity index improver.

[table 1]

Each machine oil of embodiment shown in the his-and-hers watches 1 and comparative example carries out corrosion and oxidation stability test, and after the test, (ICP-AES) carries out ultimate analysis to oil by inductively coupled plasma atomic emission spectrometry.Except test temperature is 135 ℃, test film be copper (Cu), plumbous (Pb) and tin (Sn) in addition, carry out corrosion and oxidation stability test according to JIS K2503.

(test conditions is as follows: load: 400N also to estimate province's burnup of machine oil of above-mentioned test by the SRV rub(bing)test; Amplitude: 1.5mm; Oscillation frequency: 50Hz; And be classified as good (by symbol " zero " expression) or poor (being represented by symbol " * ") temperature: 100 ℃).

The results are shown in table 2.

[table 2]

As shown in table 2, embodiment 1 and 2 engine oil base oil show excellent province's burnup, simultaneously wash-out Cu, Pb and Sn seldom in corrosion and oxidation stability test.Therefore, embodiment 1 and 2 engine oil base oil can provide excellent erosion resistance and wear resistant and high province's burnup.

Do not add comparative example 1 wash-out Cu and Pb seldom in the corrosion oxidation stability test of MoDTC and alicyclic epoxide compound, but its province's burnup is poor.The excellent province's burnup of comparative example 2 demonstrations of having added MoDTC but not added the aliphatic epoxy compound, but it also demonstrates significant Cu corrosion in corrosion and oxidation stability test.

The comparative example 3 and 4 that has added benzotriazole derivatives and MoDTC shows the more Cu of wash-out in the situation of benzotriazole derivatives in a small amount, with the more Pb of demonstration wash-out in the situation of relatively large benzotriazole derivatives, represent excellent province's burnup but poor corrosion and oxidative stability.In addition, the comparative example 5 and 6 that has added MoDTC and non-annularity epoxy compounds shows quite high-caliber Cu wash-out, and erosion resistance extreme difference in the situation of the ester of lipid acid and epoxy particularly.

Utilizability on the industry

The invention provides excellent erosion resistance and wear resistant and economize burnup, therefore can be used as the machine oil of oil engine such as petrol motor, diesel engine and producer gas engine etc.

Claims

1. burnup saving type engine oil composition, it comprises lubricant base, counts the organic molybdenum of the above concentration of 0.02 quality % and alicyclic epoxide compound with respect to described composition total mass with molybdenum (Mo) quality.

2. burnup saving type engine oil composition according to claim 1, wherein said alicyclic epoxide compound comprises ester bond.

3. burnup saving type engine oil composition according to claim 1 and 2, wherein said alicyclic epoxide compound comprises two epoxidation naphthenic hydrocarbon parts.

4. according to claim 1 to 3 each described burnup saving type engine oil compositions, wherein said organic molybdenum is molybdenum dithiocarbamate (MoDTC).

5. according to claim 1 to 4 each described burnup saving type engine oil compositions, wherein said lubricant base has 4.5mm ²Kinetic viscosity under 100 ℃ below the/s.