CN1040124C - Lubricant oil composition and lubricant grease composition - Google Patents
Lubricant oil composition and lubricant grease composition Download PDFInfo
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- CN1040124C CN1040124C CN96105131A CN96105131A CN1040124C CN 1040124 C CN1040124 C CN 1040124C CN 96105131 A CN96105131 A CN 96105131A CN 96105131 A CN96105131 A CN 96105131A CN 1040124 C CN1040124 C CN 1040124C
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Abstract
The present invention discloses a lubricating oil combination and a lubricating grease combination that can greatly improve the thermooxidizing stability and be used under the conditions of the high speed, the high temperature, and the high load capacity. The lubricating oil combination of a mixed antioxidant occupying 0.2 to 8 percent of the total weight of the lubricating oil combination is added into a base oil compounded polyhydric alcohol ester oil and alkylphenyl ether according to the weight ratio of 80:20 to 20:80. The mixed antioxidant is mixed by a dialkyl dithiocarbamate compound (A) and an aromatic amines compound (B) according to the weight ratio of 90:10 to 10:90, the lubricating grease combination occupying 0.2 to 8 percent of the total weight of the lubricating grease combination is added, the lubricating grease combination is used a lithium soap, a lithium complex soap and a diurea compound as a thickening agent.
Description
The present invention relates to the lubricated middle lubricating oil compositions that use such as bearing.
The influence of the lubricating oil that the life-span of rolling bearing is used to a great extent and the lubricity of lubricating grease.In the past, in the lubricating oil that this rolling bearing is used, except mineral oil as base oil, also use diester oil, polyvalent alcohol ester oil, poly-alpha-alkene hydrocarbon ils, polyphenylene oxide wet goods synthetic oil, and then also be used for oxidation inhibitors such as the amine of improveing lubricant parameter, phenol, rust-preventive agent and according to the additives such as extreme pressure lubricating oil additive of purposes.In lubricating grease, except as metallic soap classes such as the lithium soap of thickening material, lithium mixture soaps; Urea compounds such as allophanamide, mineral oil as base oil, also use diester oil, polyvalent alcohol ester oil, poly-alpha-alkene hydrocarbon ils, polyphenylene oxide wet goods synthetic oil, and then, also be used oxidation inhibitor, rust-preventive agent such as amine, phenol into the improvement lubricant parameter, and the additives such as extreme pressure lubricating oil additive that are used according to purposes.Especially oxidation inhibitor is for the necessary additive of the thermostability that improves lubricating oil and lubricating grease, almost all adds in all lubricating oil and lubricating grease.Specifically, use with the amine oxidation inhibitor of phenyl-a-naphthylamine as representative, with 4,4-methylene-bis (2,6-two tertiary butyl phenols) is the phenols oxidation inhibitor of representative etc.The additive effect of oxidation inhibitor and rust-preventive agent except thickening material, outside the kind of base oil, also has very big difference according to conditions such as the type of rolling bearing material, rolling bearing, bearing size, use temperature, environment.
In recent years, along with miniaturization and, the high speed of various rotary machines, lubricating oil and lubricating grease are at high temperature mostly.Use under the rigor condition such as high loading, high speed, and, wish not needing repairing more consumingly, thereby wish to work out better high perofmrnace lubricating oils of thermo-oxidative stability and lubricating grease.
So the environment for use of lubricating oil and lubricating grease is harsh, with former lubricating oil and lubricating grease, thermo-oxidative stability and not needing repairing can not meet the demands aspect these.The in a single day oxidated and deterioration of lubricating grease, then characteristics such as dropping point, shear stability, denseness, the oily characteristic of branch have very big variation, leak grease in bearing, reduce lubricating life widely.And, in case play the base oil oxidative degradation of lubricated main effect, not only oil content reduced, to lose lubricating function along with the generation of greasy filth, viscosity increase etc., and the organic acid that generates owing to oxidative degradation etc. causes the corrosion of bearing owing to steam output increases.The oxidation of lubricating oil deterioration also oxidative degradation with grease base plinth oil is identical.Therefore, in order to seek the long lifetime of lubricating oil and lubricating grease, the oxidative degradation that suppresses lubricating oil and lubricating grease is important.And even oxidative degradation is also softening in lubricating grease, itself does not leak out lubricating grease from bearing, and lubricating grease keeps the flowability of appropriateness in bearing, and it all is important that base oil can fully be supplied with performance such as bearing lubricant housings.Mention the example of lubricating oil, open the spy that to disclose end group in the flat 1-259097 communique be the double urea compound of aromatic series base main body uses the alkyl diphenyl ether oil as thickening material, in base oil lubricating grease.Yet, double urea compound is easily solidified as the lubricated cunning of thickening material, the mobile deterioration of lubricating grease in bearing, it is not enough to cause in bigbore bearing that therefore the lubricating grease that arrives the lubricant housings flows.In order to improve flowing and rust-preventing characteristic of lubricating grease, the spy opens and discloses in the flat 5-98280 communique the alkyl diphenyl ether oil as necessary composition, and 40 ℃ kinematic viscosity is 90～160mm
2The ratio of the base oil of/S and fragrant same clan hydrocarbon end group is the double urea compound formed of 70～95 moles of % as the grease composition of thickening material and to cooperate organic sulfonate, nitrite and HLB as rust-inhibiting additive in this lubricating oil composition be the lubricating grease of 1.5～9 non-ionic surfactant.Open to disclose in the flat 5-140576 communique the spy and a kind ofly produce different sound and rust-preventing characteristic when being used to improve high temperature durability and low temperature initiating, in the mixing oil of poly-alpha-alkene hydrocarbon ils and alkyl diphenyl ether oil, cooperate the lubricating grease of the barium sulfonate of aliphatics double urea compound and rust-inhibiting additive.The spy opens clear 63-162791 communique and special opening discloses Lithium soap grease and improved resistance to oxidation degradation characteristic and the life characteristic under the high temperature in the flat 5-86392 communique.Yet, in the heavy caliber bearing, flow to the mobile not enough and gene basis deficient oil supply of lubricating grease at bearing lubrication position, make the early stage heating of bearing deadlocked, therefore still can not fully accomplish maintenance free.
Even it is also very good to the purpose of this invention is to provide a kind of supply that base oil is infeeded the lubricant housings in bigbore bearing, and the ability that oil film forms is good, and vaporization losses is few, the resistance to oxidation deterioration is good, can reach the lubricating oil composition of the long-term maintenance freeization of bearing
In order to achieve the above object, carried out the research of making great efforts repeatedly, found that, the lubricating oil composition and the grease composition that in base oil, contain specific oxidation inhibitor by specific ratios, its thermo-oxidative stability is good, be suitable for the bearing lubrication used under high speed, high temperature, high loading condition, its lubricating life also prolongs significantly than prior art, thereby has finished the present invention.
Just, the present invention relates to a kind of lubricating oil composition, it is characterized in that, in the lubricating oil composition that contains base oil and additive, contain the mixing oxidation inhibitor that accounts for lubricating oil composition total amount 0.2～8 weight %, this mixing oxidation inhibitor with as oxidation inhibitor (A) dialkyl dithiocarbamate compound and (B) the aromatic amine compounds by 90～10: the cooperation of 10～90 weight ratio forms.
And, relate to a kind of grease composition, it is characterized in that, in containing base oil and lithium soap, lithium-complex soap, double urea compound in the grease composition of any thickening material, contain the mixing oxidation inhibitor that accounts for lubricating grease total amount 0.2～8 weight %, this mixing oxidation inhibitor with as oxidation inhibitor (A) dialkyl dithiocarbamate compound and (B) the aromatic amine compounds by 90～10: the cooperation of 10～90 weight ratio forms.
And, relate to a kind of grease composition, it is characterized in that, base oil is the mixture of polyvalent alcohol ester oil and alkyl phenyl ether oil, in containing lithium soap, lithium-complex soap, double urea compound, contain the mixing oxidation inhibitor that accounts for grease composition total amount 0.2～8 weight % in the lubricating grease of any thickening material, this mixing oxidation inhibitor with as oxidation inhibitor (A) dialkyl dithiocarbamate compound and (B) the aromatic amine compounds by 90-10: 10～90 weight ratio cooperation forms.
Base oil as using in the present invention can use the base oil more than a kind that chooses in mineral oil, diester oil, polyvalent alcohol ester oil, poly-alpha-alkene hydrocarbon ils, the polyphenylene oxide wet goods synthetic oil.Especially, the mixing oil of polyvalent alcohol ester oil and alkyl phenyl ether oil is good aspect thermo-oxidative stability.
Polyol ester (Port リ オ-Le ェ ス テ Le) oil is 5～18 lipid acid synthetic polyvalent alcohol ester oil by the polyvalent alcohol of the carbon skeleton with neopentane and carbon number preferably or be the coordination compound type polyvalent alcohol ester oil that the polyvalent alcohol of the mixing acid of 4～10 aliphatics monocarboxylic acid and aliphatic dicarboxylic acid and trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol is formed by carbon number.As the object lesson of lipid acid, but illustration butyric acid, valeric acid, caproic acid, enanthic acid, sad, 2 ethyl hexanoic acid, isocaprylic acid, n-nonanoic acid, different n-nonanoic acid, capric acid, isodecyl acid, hard ester acid etc.The concrete example of polyvalent alcohol is trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol etc.
The alkyl phenyl ether oil is that substituent carbon number is 10～22, and preferably carbon number is 10～16 alkyl diphenyl base ether oil or alkyl polyphenylene ether oil.The proportioning of polyvalent alcohol ester oil and alkyl phenyl ether oil is 80～20: 20～80 weight ratios, and 70～30: 30～70 weight ratios preferably.
The proportioning of polyvalent alcohol ester oil and alkyl phenyl ether oil can not get good thermo-oxidative stability beyond this scope the time.The content of base oil in the lubricating ester composition does not have special qualification, but in order to obtain the long lifetime, is advisable with 70～95 weight %, preferred 80～90 weight %.The content of base oil when 70 weight % are following, the lubricating grease hardening, then deliquescing when 95% weight % is above either way has a disadvantageous effect to lubricated.
In order to improve the thermo-oxidative stability of lubricating oil and lubricating grease significantly, the mixing oxidation inhibitor of cooperation is (A) dialkyl dithiocarbamate compound of peroxide breakdown form and (B) aromatic amine compounds of radical chain termination type.The ratio of mixture of mixing oxidation inhibitor is 90～10: 10～90 weight ratios, and preferred 80～20: the content of the mixing oxidation inhibitor that 20～80 weight ratios are formed is 0.2～8 weight with respect to the lubricating grease total amount, preferred 0.5～6 weight %.The ratio of mixture of oxidation inhibitor then can not get good thermo-oxidative stability beyond this scope the time.And the effect of addition anti-oxidation deterioration when 0.2 weight % is following of mixing oxidation inhibitor is little, and additive effect reached capacity when 8 weight % were above.
Object lesson as dialkyl dithiocarbamate compound (A), can enumerate: ziram, zinc diethyldithiocarbamate, zinc dibutyl dithiocarbamate, Sodium dimethyldithiocarbamate 40min, Thiocarb, NB sodium dibutyl dithiocarbamate, nickel diethyldithiocarbamate, nickel dibutyl dithiocarbamate, cupric dimethyldithiocarbamate, ferric diethyldithiocarbamate, selenium diethyl dithiocarbamate, tellurium diethyl dithiocarbamate and zinc butyl xanthate etc., especially preferred nickel dibutyl dithiocarbamate.
The concrete example of aromatic amine compounds (B), but illustration: phenyl-a-naphthylamine, alkylation phenyl-alpha-naphthylamine, have alkylated diphenylamine, the N of butyl, octyl group, nonyl etc., N '-two-2-naphthyl-Ursol D, N, N '-phenylbenzene-Ursol D etc.Especially preferred is phenyl-a-naphthylamine, alkylation phenyl-alpha-naphthylamine, alkylated diphenylamine.
The preferably combination of dialkyl dithiocarbamate compound (A) and aromatic amine compounds (B), can enumerate ziram and phenyl-a-naphthylamine, ziram and alkylation phenyl-alpha-naphthylamine, ziram and alkylated diphenylamine, Sodium dimethyldithiocarbamate 40min and phenyl-a-naphthylamine, Sodium dimethyldithiocarbamate 40min and alkylation phenyl-alpha-naphthylamine, Sodium dimethyldithiocarbamate 40min and alkylated diphenylamine, nickel dibutyl dithiocarbamate and phenyl-a-naphthylamine, nickel dibutyl dithiocarbamate and alkylated diphenylamine etc.Especially, preferred combination is nickel dibutyl dithiocarbamate and phenyl-a-naphthylamine, nickel dibutyl dithiocarbamate and alkylation phenyl-alpha-naphthylamine, and nickel dibutyl dithiocarbamate and alkylated diphenylamine.
The dialkyl dithiocarbamate compound has the character that makes copper or Cu alloy material corrosion or variable color according to working conditions.When under the coexistence of this material, using, preferably cooperate some to be used to prevent to corrode additive with variable color as required.As anticorrosive agent, benzotriazole, benzotriazole compound are effective.Its use level is 0.01～2 weight % with respect to the gross weight of lubricating oil composition and grease composition preferably.
The kinematic viscosity of the base oil that uses among the present invention is 20～30mm in the time of 40 ℃
2/ S, preferred 30～200mm
2/ S.As the thickening material that uses in the lubricating grease of the present invention, known lithium soap, lithium-complex soap and double urea compound are arranged.Thickening material and use level thereof can be at random selected according to the working conditions of lubricating grease, and are about NO.2～3 as the larger caliber bearing with 10～20 weight % preferably or by the NLGI denseness.
And, in lubricating oil composition of the present invention or grease composition, also can add rust-preventive agent, oiliness improver, extreme pressure lubricating oil additive and solid lubricant etc. as required.
Lubricating oil composition of the present invention can use separately, also can be used as a kind of composition that constitutes grease composition of the present invention and is used for various uses.Preferably bearing usefulness more preferably is suitable for the heavy caliber bearing and uses.
Lubricating oil composition of the present invention and grease composition cooperate polyvalent alcohol ester oil and alkyl phenyl ether oil to scale in its base oil, good aspect thermotolerance, oxidative stability and oilness.Therefore in this base oil, be combined with the mixing oxidation inhibitor of dialkyl dithiocarbamate compound and aromatic amine compounds, even under coexistences such as copper and Cu alloy material, also can suppress the variation of the vaporization losses, viscosity, total acid value etc. of mixed base oil widely.
Lubricating grease, the oil film thickness that forms on bearing lubrication face is known than thin this of oil lubrication.Its result, lubricated face easily becomes the condition of boundary lubrication of direct contact, also is easy to generate wearing and tearing.Steam output and viscosity that base oil of the present invention can reduce lubricant housings oil change, and therefore present low friction, rise thereby can suppress temperature.Its result is even the long lifetime to lubricating grease also has big contribution in high temperature and high speed.
When the bearing bore is big, with the isolating base oil stalling characteristic of lubricating grease be important.As base oil, be that base oil that vaporization losses, oxidative degradation and viscosity is with low uncertainty is to supply with lubricated face in right amount chronically continuously.Therefore, the retentivity of the thermo-oxidative stability of thickening material, shear stability, base oil is important.Owing to used lithium soap, the lithium-complex soap of these characteristic goods, the mixing oxidation inhibitor of double urea compound and interpolation oxidation inhibitor dialkyl dithiocarbamate compound and Fang Ji family aminated compounds, therefore can improve the resistance to oxidation deterioration of thickening material significantly, lubricated face can be for a long time base oil supplied with, thereby the long lifetime of lubricating grease can be realized.
Below, illustrate in greater detail the present invention according to embodiment and comparative example.The evaluation test method of the lubricating oil of embodiment and comparative example or lubricating grease is as described below.
(the evaluation test method of oxidation inhibitor)
(1) adds thermal degradation when (oxidative degradation) evaluation test method
About lubricating oil and the lubricating grease that is combined with oxidation inhibitor, estimate the effect of adding oxidation inhibitor.The lubricating oil temperature heating in accordance with regulations of oxidation inhibitor will be combined with.The evaluation of the oxidation inhibitor of lubricating grease is after coating lubricating grease 3mm on the confession examination material is thick, heats under the specified temperature condition, with total acid value and the viscosity of measuring lubricating oil behind the petroleum ether extraction.These characteristic variations are few more, and the additive effect of oxidation inhibitor is big more, prevent aspect the oxidation of lubricating oil deterioration good more.
1. steam output measuring method
Get added oxidation inhibitor lubricant 20g in glass beaker, in 150 ℃ thermostatic bath, left standstill 1200 hours, according to the heating before and after the weight change determination steam output.Steam output in this test comprise the lightweight oil content in the lubricating oil and the evaporation of the volatile matter that generates because of oxidative degradation, and oxidative degradation is big more, and the growing amount of volatile matter is many more, so steam output is big more.
2. total acid value measuring method
To the lubricating oil after the heating deterioration test, press JIS K 2501 methods, measure total acid value and obtain the variation of heating the deterioration test front and back.
3. viscosity measurement
To the lubricating oil after the heating deterioration test, press the viscosity measurement of JS K 2283, the kinematic viscosity when measuring 40 ℃ is estimated according to the viscosity ratio before and after the heating.Viscosity ratio is obtained by following formula.
Viscosity before viscosity/heating behind viscosity ratio=the add thermal degradation when
(2) the acceleration lubricating life of rolling bearing test
Filling 5g lubricating grease in round shape rolling bearing (NU314) is by following condition evaluating lubricity.The lubricating life of lubricating grease (h) is defined as bearing temperature by rise run duration 10 ℃ time of test temperature
Rotation number: 8000rpm
Loading: 500kgf
Test temperature: 100 ℃
Embodiment 1～18 and comparative example 1～20
Embodiment is at base oil and the independent respectively mineral oil that uses with alkyl phenyl ether oil and the cooperation of 50: 50 weight ratio of polyol ester oleyl amine shown in the table 1, diester oil, polyvalent alcohol ester oil, the poly-alpha-alkene hydrocarbon ils, in the base oil of polyphenyl ether oil, add the nickel dibutyl dithiocarbamate of oxidation inhibitor (A) dialkyl dithiocarbamate compounds (ノ Network ラ Star Network NBC: the emerging chemistry of imperial palace (strain) system) and (B) lubricating oil formed of the mixing oxidation inhibitor 1 weight % that combines by 50: 50 weight ratios of the phenyl-a-naphthylamine of aromatic amine compounds (ノ Network ラ Star Network PA: the emerging chemistry of imperial palace (strain) is made).Comparative example is the lubricating oil that adds oxidation inhibitor 1 weight % in base oil shown in the table 2.Dipping is as the sheet brass of oxide catalyst, 150 ℃ of heating 1200 hours in each lubricating oil.Mensuration heats steam output, total acid value and the viscosity ratio after the deterioration test, estimates the additive effect of the oxidation inhibitor of relative oil ageing deterioration.Table 3 illustrates embodiment 1～18, and table 4 illustrates the result of comparative example 1～22.
Table 1
| Embodiment | Mixing oil (ratio of mixture 50: 50) | Mix oxidation inhibitor (ratio of mixture 50: 50) | |||
| Polyvalent alcohol ester oil | The alkyl phenyl ether oil | (A) dialkyl dithiocarbamate compounds | (B) aromatic amine compounds | ||
| Alcohol | Lipid acid | ||||
| 1 | TriMethylolPropane(TMP) | Caproic acid (n-C 6) | This phenyl ether of alkyl (モ レ ス コ Ha イ Le-Off LB-100) | This nickel dithiocarbamate of dibutyl [ノ Network ラ Star Network NBC] | Phenyl-a-naphthylamine [ノ Network ラ Star Network PA] |
| 2 | Sad (n-C 8) | ||||
| 3 | Capric acid (n-C 10) | ||||
| 4 | Isocaprylic acid (iso-C 8) | ||||
| 5 | Different three capric acid (iso-C 13) | ||||
| 6 | Mixed fatty acid (mix-C 4) | ||||
| 7 | ″ (mix-C 6) | ||||
| 8 | ″ (mix-C 9-10) | ||||
| 9 | Isocaprylic acid | ||||
| 10 | Tetramethylolmethane | Isodecyl acid | |||
| 11 | Mixed fatty acid (mix-C 4) | ||||
| 12 | ″ (mix-C 5) | ||||
| 13 | ″ (mix-C 9-10) | ||||
| 14 | Two-(2-ethylhexyl) sebates | ||||
| 15 | The trimethylolpropane tris octanoate | ||||
| 16 | Alkyl diphenyl base ether | ||||
| 17 | The poly-alpha-alkene hydrocarbon | ||||
| 18 | Mineral oil (500NT oil) | ||||
Table 2
| Comparative example | Base oil (ratio of mixture 50: 50) | Oxidation inhibitor |
| 1 | Trimethylolpropane tri-heptanoate (Reolube LT2100:C 7) | Nickel dibutyl dithiocarbamate (ノ Network ラ Star Network NBC: the emerging chemistry of imperial palace (strain)) |
| 2 | " decylate (Reolube LT3000:C 10) | |
| 3 | Tetramethylolmethane four Enanthates (Reolube LP2800:C 7) | |
| 4 | Alkyl diphenyl base ether (モ レ ス コ Ha イ Le-Off LB-100) | |
| 5 | Poly-alpha-alkene hydrocarbon (モ-PVC Le oil: Ethylflo 170) | |
| 6 | Mineral oil (500NT oil) | |
| 7 | Trimethylolpropane tri-heptanoate (Reolube LT2100:C 7)/poly-alpha-alkene hydrocarbon | |
| 8 | Alkyl diphenyl base ether (モ レ ス コ Ha イ Le-Off LB-100)/poly-alpha-alkene hydrocarbon (モ-PVC Le oil: Ethylflo 170) | |
| 9 | Mineral oil/poly-alpha-alkene hydrocarbon (50ONT オ イ Le/モ-PVC Le oil: Ethylflo 170) | |
| 10 | Trimethylolpropane tri-heptanoate (Reolube LT2100:C 7) | Phenyl-a-naphthylamine (ノ Network ラ Star Network PA: the emerging chemistry of imperial palace (strain)) |
| 11 | " decylate (Reolube LT3000:C 10) | |
| 12 | Pentaerythritol tetraheptanoate (Reolube LP2800:C 7) | |
| 13 | Alkyl diphenyl base ether (モ レ ス コ Ha イ Le-Off LB-100) | |
| 14 | Poly-alpha-alkene hydrocarbon (モ-PVC Le oil: Ethylflo 170) | |
| 15 | Mineral oil (500NT oil) | |
| 16 | Trimethylolpropane tri-heptanoate (Reolube LT2100:C 7)/poly-alpha-alkene hydrocarbon | |
| 17 | Pentaerythritol tetraheptanoate (Reolube LP2800:C 7)/poly-alpha-alkene hydrocarbon | |
| 16 | Alkyl diphenyl base ether (モ レ ス コ Ha イ Le-Off LB-100)/poly-alpha-alkene hydrocarbon | |
| 19 | Mineral oil/poly-alpha-alkene hydrocarbon (500MT oil/モ-PVC Le oil: Ethylflo 170) | |
| 20 | Trimethylolpropane tri-heptanoate (Reolube (T2100)/poly-alpha-alkene hydrocarbon (モ-PVC Le oil: Ethylflo 170) | Tetramethylolmethane four (3-(3.5-two-tertiary butyl-4-hydroxyphenyl)) propionic ester (イ Le ガ ノ Star Network ス 1010:CIBA GEIGY society) |
| 21 | Alkyl diphenyl base ether (モ レ ス コ Ha イ Le-Off LB-100)/poly-alpha-alkene hydrocarbon (モ-PVC Le oil: Ethylflo 170) | 2,2 '-methylene-bis (4-ethyl-6-tertiary butyl phenol) (ノ Network ラ Star Network NS-5: the emerging chemistry of imperial palace (strain)) |
| 22 | Trimethylolpropane tri-heptanoate (Reolube LT2100)/poly-alpha-alkene hydrocarbon (モ-PVC Le oil: Ethylflo 170) | There is not additive |
Table 3
| Embodiment | The oxidation of lubricating oil deterioration (150 ℃ * 1200h) | |||||
| There is not catalyzer | Brass (JIS H3250) | |||||
| Steam output (wt%) | Total acid value (mgKOH/g) | Viscosity ratio | Steam output (wt%) | Total acid value (mgkOH/g) | Viscosity ratio | |
| 1 | 0.45 | 0.08 | 1.07 | 0.58 | 0.11 | 1.09 |
| 2 | 0.44 | 0.08 | 1.07 | 0.53 | 0.10 | 1.10 |
| 3 | 0.42 | 0.07 | 1.06 | 0.50 | 0.09 | 1.08 |
| 4 | 0.41 | 0.05 | 1.07 | 0.48 | 0.08 | 1.09 |
| 5 | 0.40 | 0.05 | 1.05 | 0.50 | 0.09 | 1.08 |
| 6 | 0.40 | 0.06 | 1.06 | 0.52 | 0.08 | 1.08 |
| 7 | 0.38 | 0.04 | 1.05 | 0.43 | 0.07 | 1.07 |
| 8 | 0.39 | 0.05 | 1.05 | 0.46 | 0.06 | 1.08 |
| 9 | 0.35 | 0.05 | 1.07 | 0.45 | 0.07 | 1.09 |
| 10 | 0.38 | 0.07 | 1.06 | 0.46 | 0.09 | 1.08 |
| 11 | 0.37 | 0.06 | 1.05 | 0.45 | 0.08 | 1.07 |
| 12 | 0.40 | 0.07 | 1.04 | 0.58 | 0.10 | 1.05 |
| 13 | 0.39 | 0.06 | 1.06 | 0.57 | 0.09 | 1.08 |
| 14 | 0.44 | 0.06 | 1.06 | 0.61 | 0.18 | 1.07 |
| 15 | 0.39 | 0.06 | 1.06 | 0.55 | 0.12 | 1.06 |
| 16 | 0.41 | 0.06 | 1.05 | 0.58 | 0.14 | 1.05 |
| 17 | 0.38 | 0.06 | 1.07 | 0.59 | 0.15 | 1.06 |
| 18 | 0.42 | 0.06 | 1.05 | 0.62 | 0.18 | 1.09 |
Table 4
Embodiment 19～36 and comparative example 23-44
| Comparative example | The oxidation of lubricating oil deterioration (150 ℃ * 1200h) | |||||
| There is not catalyzer | Brass (JIS H3250 | |||||
| Steam output (wt%) | Total acid value (mgKOH/g) | Viscosity ratio | Steam output (wt%) | Total acid value (mgKOH/g) | Viscosity ratio | |
| 1 | 0.71 | 0.42 | 1.12 | 0.85 | 0.54 | 1.15 |
| 2 | 0.75 | 0.39 | 1.09 | 0.86 | 0.41 | 1.13 |
| 3 | 0.86 | 0.48 | 1.13 | 0.90 | 0.56 | 1.16 |
| 4 | 0.87 | 0.50 | 1.11 | 0.91 | 0.63 | 1.18 |
| 5 | 0.92 | 0.49 | 1.08 | 1.08 | 0.56 | 1.12 |
| 6 | 0.89 | 0.68 | 1.14 | 1.09 | 0.78 | 1.20 |
| 7 | 0.86 | 0.57 | 1.11 | 1.08 | 0.68 | 1.16 |
| 8 | 0.84 | 0.61 | 1.08 | 1.10 | 0.73 | 1.14 |
| 9 | 0.97 | 0.70 | 1.07 | 1.05 | 0.81 | 1.10 |
| 10 | 1.20 | 0.79 | 1.13 | 1.66 | 0.88 | 1.19 |
| 11 | 1.11 | 0.80 | 1.18 | 1.56 | 0.96 | 1.23 |
| 12 | 1.08 | 0.97 | 1.20 | 1.51 | 1.05 | 1.28 |
| 13 | 1.18 | 0.88 | 1.21 | 1.46 | 0.97 | 1.26 |
| 14 | 1.46 | 0.96 | 1.22 | 1.72 | 1.04 | 1.29 |
| 15 | 1.26 | 0.89 | 1.18 | 1.87 | 1.09 | 1.27 |
| 16 | 1.18 | 0.97 | 1.24 | 1.78 | 1.13 | 1.30 |
| 17 | 1.22 | 1.11 | 1.21 | 1.41 | 1.21 | 1.26 |
| 18 | 1.17 | 1.01 | 1.24 | 1.59 | 1.16 | 1.29 |
| 19 | 1.28 | 0.95 | 1.23 | 1.86 | 1.15 | 1.30 |
| 20 | 1.12 | 1.21 | 1.25 | 1.40 | 1.42 | 1.28 |
| 21 | 1.34 | 1.09 | 1.24 | 1.75 | 1.28 | 1.31 |
| 22 | 5.53 | 4.15 | 1.45 | 5.89 | 5.02 | 1.59 |
Lithium soap grease to the lubricating oil of the oxidation inhibitor shown in the comparative example 1～22 of the embodiment 1～18 that uses interpolation table 1 and table 2 is studied.The manufacturing of Lithium soap grease is carried out as follows.
In being the alkyl diphenyl base ether oil of 410g, total amount adds stearic acid 180g, be heated to consoluet temperature (80～90 ℃) while stirring, under this temperature, add the mixture of lithium hydroxide 28g and hot water 56g, stir in 95～100 ℃ through 1 hour saponification reaction.Then, be heated to about 210 ℃ under stirring and keep adding polynary polyol ester oil 410g after 5 minutes, stir cooling.With it as basic lubricating grease.
Get this basic lubricating grease of 891g, add the 9g oxidation inhibitor, stir be heated to 100 ℃ down after, stirring is cooled to room temperature.Then, mix bright 2-3 time with three roller runner millings, preparation NLGI denseness grade is the Lithium soap grease of NO.2.This Lithium soap grease is coated on sheet glass and the sheet brass, is 150 ℃ through temperature, after 1200 hours the heating deterioration test, measures total acid value, viscosity ratio through the lubricating base oils of extraction, estimates the oxidative degradation of lubricating grease.And, with the acceleration lubricating life test evaluation lubricity of rolling bearing.The result of embodiment shown in the table 5 19～36 and comparative example 23～44.
Embodiment 37～54 and comparative example 45～49
Lithium-complex soap to the lubricating oil of the embodiment 1～18 of use table 1 and the comparative example 45～49 shown in the table 6 is studied.
Table 5
| No. | The oxidative degradation of lubricating grease (150 ℃ * 1200h) | Lubricating life (h) | ||||
| Total acid value (mgKOH/g) | Viscosity ratio | Total acid value (mgKOH/g) | Viscosity ratio | |||
| Embodiment | 19 | 0.10 | 1.08 | 0.14 | 1.10 | 520 |
| 20 | 0.11 | 1.09 | 0.15 | 1.11 | - | |
| 21 | 0.09 | 1.08 | 0.13 | 1.11 | 654 | |
| 22 | 0.08 | 1.09 | 0.13 | 1.12 | - | |
| 23 | 0.07 | 1.09 | 0.15 | 1.12 | 568 | |
| 24 | 0.08 | 1.08 | 0.14 | 1.11 | - | |
| 25 | 0.08 | 1.08 | 0.14 | 1.10 | 657 | |
| 26 | 0.09 | 1.08 | 0.15 | 1.11 | - | |
| 27 | 0.09 | 1.09 | 0.16 | 1.13 | 593 | |
| 28 | 0.11 | 1.10 | 0.18 | 1.15 | - | |
| 29 | 0.12 | 1.11 | 0.19 | 1.16 | 574 | |
| 30 | 0.10 | 1.10 | 0.17 | 1.17 | - | |
| 31 | 0.09 | 1.08 | 0.15 | 1.11 | 568 | |
| 32 | 0.26 | 1.10 | 0.34 | 1.17 | 528 | |
| 33 | 0.21 | 1.09 | 0.27 | 1.16 | 567 | |
| 34 | 0.23 | 1.10 | 0.26 | 1.15 | 570 | |
| 35 | 0.26 | 1.13 | 0.31 | 1.19 | 510 | |
| 36 | 0.27 | 1.12 | 0.36 | 1.18 | 505 | |
| Comparative example | 23 | 0.45 | 1.17 | 0.51 | 1.20 | - |
| 24 | 0.44 | 1.13 | 0.56 | 1.18 | 285 | |
| 25 | 0.51 | 1.16 | 0.66 | 1.19 | - | |
| 26 | 0.54 | 1.17 | 0.62 | 1.22 | 310 | |
| 27 | 0.51 | 1.11 | 0.66 | 1.20 | - | |
| 28 | 0.70 | 1.17 | 0.82 | 1.21 | 295 | |
| 29 | 0.61 | 1.15 | 0.73 | 1.28 | - | |
| 30 | 0.67 | 1.13 | 0.73 | 1.26 | 312 | |
| 31 | 0.76 | 1.13 | 0.82 | 1.26 | - | |
| 32 | 0.82 | 1.18 | 0.95 | 1.25 | 305 | |
| 33 | 0.83 | 1.21 | 0.96 | 1.25 | - | |
| 34 | 1.03 | 1.25 | 1.17 | 1.38 | 229 | |
| 35 | 0.95 | 1.24 | 1.09 | 1.33 | - | |
| 36 | 1.05 | 1.26 | 1.14 | 1.36 | 295 | |
| 37 | 0.93 | 1.24 | 1.18 | 1.40 | - | |
| 38 | 1.01 | 1.30 | 1.17 | 1.42 | 236 | |
| 39 | 1.16 | 1.29 | 1.29 | 1.35 | - | |
| 40 | 1.05 | 1.28 | 1.17 | 1.41 | 240 | |
| 41 | 1.04 | 1.27 | 1.25 | 1.40 | - | |
| 42 | 1.27 | 1.29 | 1.37 | 1.32 | 230 | |
| 43 | 1.14 | 1.28 | 1.30 | 1.51 | - | |
| 44 | 4.25 | 1.76 | 5.39 | 1.88 | 210 | |
Table 6
| Comparative example | Base oil (ratio of mixture 50: 50) | Oxidation inhibitor |
| 45 | Trimethylolpropane tri-heptanoate/poly-alpha-alkene hydrocarbon | Nickel dibutyl dithiocarbamate, (ノ Network ラ Star Network NBC) |
| 46 | Alkyl diphenyl base ether/poly-alpha-alkene hydrocarbon | |
| 47 | Mineral oil/poly-alpha-alkene hydrocarbon | |
| 48 | Trimethylolpropane tri-heptanoate/poly-alpha-alkene hydrocarbon | Alkylation phenyl-alpha-naphthylamine (イ Le ガ ノ Star Network ス LO6) |
| 49 | Alkyl diphenyl base ether/poly-alpha-alkene hydrocarbon | 2,2 '-methylene-bis (4-ethyl-6-tertiary butyl phenol) (ノ Network ラ Star Network NS-5) |
The manufacturing of lithium-complex soap lubricating grease is carried out as follows.
In total amount is the alkyl diphenyl base ether oil of 435g, add 12-oxystearic acid 106.6g and nonane diacid 23.4g, stir under heating for dissolving to 80～90 ℃.Under this temperature, add the mixture of lithium hydroxide 26.1g and hot water 52.2g, stir down in 95～100 ℃ of saponification reactions of carrying out 1 hour.Heat while stirring then until about 210 ℃ of maintenances 5 minutes, add polynary polyol ester oil 435g, stir cooling.With it as basic lubricating grease.
Get this basic lubricating grease 891g, add the 9g oxidation inhibitor, be heated to 100 ℃ while stirring after, stir and be cooled to room temperature.Then, with three roller runner millings mixing 2～3 times.Preparation NLGI denseness is classified as the lithium-complex soap lubricating grease of NO.2.This lithium-complex soap is carried out heating deterioration test similarly to Example 19 and quickens the lubricating life test.It the results are shown in the table 7.
Table 7
Embodiment 55～72 and comparative example 50～54
| No. | The oxidative degradation of lubricating grease (150 ℃ * 1200h) | Lubricating life (h) | ||||
| Catalyst-free | Brass (JIS H3250) | |||||
| Total acid value (mgKOH/g) | Viscosity ratio | Total acid value (mgKOH/g) | Viscosity ratio | |||
| Embodiment | 37 | 0.10 | 1.09 | 0.14 | 1.10 | 545 |
| 38 | 0.09 | 1.08 | 0.15 | 1.10 | - | |
| 39 | 0.10 | 1.08 | 0.14 | 1.11 | 640 | |
| 40 | 0.09 | 1.08 | 0.13 | 1.11 | - | |
| 41 | 0.07 | 1.09 | 0.14 | 1.12 | 672 | |
| 42 | 0.08 | 1.08 | 0.14 | 1.10 | - | |
| 43 | 0.09 | 1.09 | 0.15 | 1.10 | 650 | |
| 44 | 0.09 | 1.08 | 0.15 | 1.12 | - | |
| 45 | 0.10 | 1.08 | 0.15 | 1.11 | 620 | |
| 46 | 0.12 | 1.09 | 0.18 | 1.14 | - | |
| 47 | 0.11 | 1.10 | 0.18 | 1.16 | 615 | |
| 48 | 0.10 | 1.10 | 0.17 | 1.16 | - | |
| 49 | 0.09 | 1.09 | 0.16 | 1.14 | 645 | |
| 50 | 0.26 | 1.13 | 0.31 | 1.17 | 531 | |
| 51 | 0.24 | 1.10 | 0.30 | 1.15 | 570 | |
| 52 | 0.23 | 1.11 | 0.28 | 1.14 | 598 | |
| 53 | 0.26 | 1.11 | 0.30 | 1.15 | 580 | |
| 54 | 0.28 | 1.13 | 0.35 | 1.19 | 568 | |
| Comparative example | 45 | 0.61 | 1.14 | 0.72 | 1.23 | 310 |
| 46 | 0.65 | 1.13 | 0.71 | 1.24 | 325 | |
| 47 | 0.73 | 1.17 | 0.80 | 1.23 | 317 | |
| 48 | 1.01 | 1.28 | 1.11 | 1.42 | 324 | |
| 49 | 1.04 | 1.23 | 1.15 | 1.41 | 308 | |
These examples are to use the allophanamide class lubricating grease with the embodiment 1～18 of table 1 and comparative example 45～49 identical lubricating oil shown in the table 6.
Allophanamide lubricating grease is made as follows.
In 420g alkyl diphenyl base ether oil, add 4,4 '-ditan two cyanate 78.8g, stir down heating for dissolving until 70～75 ℃.Be added on the mixture that is dissolved with octylame 81.2g in the 420g polyvalent alcohol ester oil in 70～75 ℃, stir down in 95～100 ℃ of reactions 1 hour.Heat while stirring until 170 ℃ then.Keep after 30 minutes, stir and be cooled to room temperature.It is defined as basic lubricating grease.
Get this lubricating grease of 891g, add 9g mixings oxidation inhibitor, be heated to 100 ℃ under stirring after, stirring is cooled to room temperature.Then, with three roller runner millings mixing 2～3 times.Preparation NLGI denseness is classified as the allophanamide lubricating grease of No.2.This allophanamide lubricating grease is carried out heating deterioration test similarly to Example 19 and quickens the lubricating life test.It is the results are shown in the table 8.
Embodiment 73～84
With pentaerythritol tetraheptanoate (CIBA-GEIGY society system レ オ Le-Block LP3200) and dialkyl group tetraphenyl ether ((strain) Song Cun research society system: S-3230) cooperate to add in the base oil that forms by 50: 50 weight ratio and make up by the oxidation inhibitor shown in the table 9 (A) dialkyl dithiocarbamate compounds and (B) aromatic amine compounds, both cooperate the mixing oxidation inhibitor 1 weight % that forms by 50: 50 weight ratios, prepare Lithium soap grease by method similarly to Example 19.The thickness of this lubricating grease by 3mm is coated on the sheet brass, when temperature is 150 ℃, carries out 1200 hours heating deterioration test.From add thermal degradation when lubricating grease, measure total acid value and viscosity ratio behind the extraction base oil.It is the results are shown in the table 9.
Table 8
| No. | The oxidative degradation of lubricating grease (150 ℃ * 1200h) | Lubricating life (h) | ||||
| Catalyst-free | Brass (JIS H3250) | |||||
| Total acid value (mgKOH/g) | Viscosity ratio | Total acid value (mgKOH/g) | Viscosity ratio | |||
| Embodiment | 55 | 0.10 | 1.07 | 0.14 | 1.10 | 580 |
| 56 | 0.11 | 1.08 | 0.14 | 1.10 | - | |
| 57 | 0.08 | 1.07 | 0.12 | 1.11 | 540 | |
| 58 | 0.08 | 1.07 | 0.15 | 1.11 | - | |
| 59 | 0.07 | 1.08 | 0.14 | 1.11 | 545 | |
| 60 | 0.08 | 1.08 | 0.13 | 1.10 | - | |
| 61 | 0.08 | 1.09 | 0.13 | 1.10 | 620 | |
| 62 | 0.08 | 1.08 | 0.15 | 1.11 | - | |
| 63 | 0.09 | 1.08 | 0.14 | 1.12 | - | |
| 64 | 0.09 | 1.08 | 0.16 | 1.13 | 581 | |
| 65 | 0.11 | 1.09 | 0.17 | 1.13 | - | |
| 66 | 0.11 | 1.10 | 0.16 | 1.14 | - | |
| 67 | 0.10 | 1.10 | 0.18 | 1.14 | 670 | |
| 68 | 0.26 | 1.12 | 0.30 | 1.16 | 520 | |
| 69 | 0.24 | 1.11 | 0.27 | 1.15 | 540 | |
| 70 | 0.22 | 1.11 | 0.27 | 1.14 | 550 | |
| 71 | 0.23 | 1.12 | 0.26 | 1.13 | 530 | |
| 72 | 0.28 | 1.13 | 0.31 | 1.16 | 215 | |
| Comparative example | 50 | 0.60 | 1.13 | 0.70 | 1.24 | 485 |
| 51 | 0.63 | 1.14 | 0.70 | 1.22 | 350 | |
| 52 | 0.68 | 1.17 | 0.73 | 1.23 | 385 | |
| 53 | 1.01 | 1.21 | 1.00 | 1.31 | 400 | |
| 54 | 1.04 | 1.24 | 1.14 | 1.39 | 335 | |
Table 9
| The oxidative degradation of lubricating grease (150 ℃ * 1200h) | ||||
| Embodiment | Oxidation inhibitor (ratio of mixture 50: 50) | Brass (JIS H3250) | ||
| (A) alkyl dithiocarbamate(s) compound | (B) aromatic amine compounds | Total acid value (mgKOH/g) | Viscosity ratio | |
| 73 | Ziram | Alkylation phenyl-alpha-naphthylamine | 0.09 | 1.07 |
| 74 | " sodium | 0.15 | 1.08 | |
| 75 | " copper | 0.17 | 1.08 | |
| 76 | Zinc diethyldithiocarbamate | 0.07 | 1.07 | |
| 77 | " sodium | 0.10 | 1.08 | |
| 78 | " nickel | 0.11 | 1.08 | |
| 79 | " iron | 0.16 | 1.09 | |
| 80 | " selenium | 0.13 | 1.09 | |
| 81 | " tellurium | 0.13 | 1.09 | |
| 82 | Zinc dibutyl dithiocarbamate | 0.09 | 1.07 | |
| 83 | " sodium | 0.14 | 1.08 | |
| 84 | " nickel | 0.09 | 1.07 | |
Embodiment 85-90
With an alkyl triphenyl ether (society of (strain) Song Cun institute system: S-3102) with trishydroxymethyl glyceryl ester (complex type polyol ester, CIBA-GEIGY society system: レ オ Le-Block LT451) cooperate by 50: 50 weight ratio and add in the base oil that forms by the oxidation inhibitor shown in the table 10 (A) dialkyl dithiocarbamate compounds nickel dibutyl dithiocarbamate (ノ Network ラ Star Network NBC: the emerging chemistry of imperial palace (strain) system and (B) aromatic amine compounds phenyl-a-naphthylamine (ノ Network ラ Star Network PA: the emerging chemistry of imperial palace (strain) system), alkylation phenyl-alpha-naphthylamine (ィ Le ガ ノ Star Network ス L06:CIBA GEIGY society system), octyl diphenylamine (ノ Network ラ Star Network AD-F: the emerging chemistry of imperial palace (strain) system), dinonyldiphenylamine (BANLUBE DND:Vanderbilt society system), alkylated diphenylamine (イ Le ガ ノ Star Network ス L57:CIBA GEIGY society system) and N, the mixing oxidation inhibitor 1 weight % that the combination of N '-phenylbenzene-Ursol D (ノ Network ラ Star Network DP: the emerging chemistry of imperial palace (strain) system) combines by 50: 50 weight ratios prepares lithium-complex soap lubricating grease by the method identical with embodiment 37.This lubricating grease is carried out heating deterioration test similarly to Example 19 and quickens the lubricating life test.It is the results are shown in the table 10.
Table 10
| The oxidative degradation of lubricating grease (150 ℃ * 1200h) | |||||
| Embodiment | Oxidation inhibitor (ratio of mixture 50: 50) | Brass (JIS H3250) | Lubricating life (h) | ||
| (A) alkyl dithiocarbamate(s) compound | (B) aromatic amine compounds | Total acid value (mgKOH/g) | Viscosity ratio | ||
| 85 | Nickel dibutyl dithiocarbamate | Phenyl-a-naphthylamine | 0.08 | 1.08 | 533 |
| 86 | Alkylation phenyl-alpha-naphthylamine | 0.06 | 1.06 | 655 | |
| 87 | Octyl diphenylamine | 0.06 | 1.07 | 635 | |
| 88 | Dinonyldiphenylamine | 0.07 | 1.09 | 630 | |
| 89 | Alkylated diphenylamine | 0.08 | 1.08 | 640 | |
| 90 | N, N '-phenylbenzene-Ursol D | 0.08 | 1.09 | 610 | |
Embodiment 91～111 and comparative example 55～60
With an alkyl tetraphenyl ether ((strain) Song Cun institute: S-3101) with tetramethylolmethane three esters (complex type polyol ester, CIBA-GEIGY society system: レ ォ Le-Block LPE602) in 50: 50 weight ratio cooperate add in the base oil that forms with oxidation inhibitor (A) dialkyl dithiocarbamate compounds and (B) the aromatic amine compounds in the mixing oxidation inhibitor 1 weight % of ratio shown in table 11 and the table 12, by preparing lithium-complex soap lubricating grease with embodiment 37 same procedure.This lubricating grease is carried out the heating deterioration test identical with embodiment 73.The result of embodiment shown in the table 11 91～111, the result of comparative example shown in the table 12 55～60.Embodiment 112 is with tetramethylolmethane four esters (complex type polyol ester; テ カ イ ソ ミ カ Le society system: エ Off コ Le-Block 100Z) and alkyl diphenyl base ether (society of (strain) Song Cun institute system: モ レ ス コ Ha ィ Le-Block LB-100 (cooperates in 50: 50 weight ratios and to add mixing oxidation inhibitor 0.1～8 weight % that combines in the ratio shown in the table 13 in the base oil that forms, by preparing lithium-complex soap lubricating grease with the same method of embodiment 37.This lubricating grease is carried out the heating deterioration test same with embodiment 73.Its result is listed in the table 13.
Table 11
| The oxidative degradation of lubricating grease (150 ℃ * 1200h) | ||||||||
| Embodiment | Oxidation inhibitor (ratio of mixture) | Brass (JIS H3250) | ||||||
| (A) alkyl dithiocarbamate(s) compound | (B) aromatic amine compounds | Total acid value (mgKOH/g) | Viscosity ratio | |||||
| Ziram | Sodium dimethyldithiocarbamate 40min | Nickel dibutyl dithiocarbamate | Phenyl-α-naphthylamines | Alkylation phenyl-alpha-naphthylamine | Alkylated diphenylamine | |||
| 91 | 10 | 90 | 0.10 | 1.06 | ||||
| 92 | 50 | 50 | 0.08 | 1.06 | ||||
| 93 | 90 | 10 | 0.10 | 1.07 | ||||
| 94 | 10 | 90 | 0.08 | 1.07 | ||||
| 95 | 50 | 50 | 0.07 | 1.06 | ||||
| 96 | 90 | 10 | 0.10 | 1.06 | ||||
| 97 | 10 | 90 | 0.10 | 1.07 | ||||
| 98 | 50 | 50 | 0.06 | 1.06 | ||||
| 99 | 90 | 10 | 0.09 | 1.07 | ||||
| 100 | 10 | 90 | 0.09 | 1.07 | ||||
| 101 | 90 | 10 | 0.08 | 1.06 | ||||
| 102 | 10 | 90 | 0.08 | 1.07 | ||||
| 103 | 90 | 10 | 0.09 | 1.08 | ||||
| 104 | 10 | 90 | 0.07 | 1.07 | ||||
| 105 | 90 | 10 | 0.08 | 1.08 | ||||
| 106 | 10 | 90 | 0.09 | 1.08 | ||||
| 107 | 90 | 10 | 0.08 | 1.07 | ||||
| 108 | 10 | 90 | 0.10 | 1.08 | ||||
| 109 | 90 | 10 | 0.09 | 1.07 | ||||
| 110 | 10 | 90 | 0.06 | 1.07 | ||||
| 111 | 90 | 10 | 0.07 | 1.06 | ||||
Table 12
| The oxidative degradation of lubricating grease (150 ℃ * 1200h) | ||||||||
| Comparative Examples | Oxidation inhibitor (ratio of mixture) | Brass (JIS H3250) | ||||||
| (A) alkyl dithiocarbamate(s) compound | (8) aromatic amine compounds | Total acid value (mgKOH/g) | Viscosity ratio | |||||
| Ziram | Sodium dimethyldithiocarbamate 40min | Nickel dibutyl dithiocarbamate | Phenyl-α-naphthylamines | Alkylation phenyl-alpha-naphthylamine | Alkylated diphenylamine | |||
| 55 | 5 | 95 | 0.31 | 1.11 | ||||
| 56 | 95 | 5 | 0.29 | 1.13 | ||||
| 57 | 5 | 95 | 0.29 | 1.13 | ||||
| 58 | 95 | 5 | 0.32 | 1.12 | ||||
| 59 | 5 | 95 | 0.35 | 1.13 | ||||
| 60 | 95 | 5 | 0.28 | 1.15 | ||||
Table 13
| The oxidative degradation of lubricating grease (150 ℃ * 1200h) | ||||||||||||||
| Embodiment 112 oxidation inhibitors (ratio of mixture wt%) | Total acid value (mgKOH/g) | Viscosity ratio | ||||||||||||
| 0.1 | 0.2 | 0.5 | 2.0 | 5.0 | 6.0 | 8.0 | 0.1 | 0.2 | 0.5 | 2.0 | 5.0 | 6.0 | 8.0 | |
| Ziram (10) phenyl-a-naphthylamine (90) | 0.29 | 0.15 | 0.08 | 0.07 | 0.07 | 0.06 | 0.06 | 1.23 | 1.15 | 1.07 | 1.06 | 1.05 | 1.05 | 1.05 |
| Ziram (10) alkylation phenyl-alpha-naphthylamine (90) | 0.31 | 0.16 | 0.09 | 0.07 | 0.07 | 0.07 | 0.07 | 1.25 | 1.16 | 1.08 | 1.07 | 1.06 | 1.06 | 1.06 |
| Nickel dibutyl dithiocarbamate (10) alkylated diphenylamine (90) | 0.35 | 0.17 | 0.08 | 0.07 | 0.06 | 0.06 | 0.06 | 1.26 | 1.17 | 1.09 | 1.08 | 1.07 | 1.06 | 1.06 |
Embodiment 113-124
Use is at the trimethylolpropane tris monooctyl ester shown in the table 14 (Reolub LT3000), pentaerythritol tetraheptanoate (Reolubu LP2800) and tetramethylolmethane four esters (complex type polyvalent alcohol ester oil;
テ カ
The ィ Application
ェ Network コ Le-Block 100Z) and alkyl diphenyl base ether (society of (strain) Song Cun institute system: add in base oil モ レ ス コ Ha ィ Le-Block LB-100) that aromatic amine alkylation phenyl-(alpha-naphthylamine (ィ Le ガ ノ Star ケ ス L06) is the lubricating oil of 1 weight %, prepares Lithium soap grease by method similarly to Example 19 by mixing oxidation inhibitor (A) the dialkyl dithiocarbamate compounds nickel dibutyl dithiocarbamate (ノ Network ッ Network NBC) of 50: 50 weight ratios with (B) ミ カ Le society system:.This lubricating grease is carried out the heating deterioration test same with embodiment 73.Its result is listed in the table 14.
Table 14
| The oxidative degradation of lubricating grease (150 ℃ * 1200h) | ||||||
| Embodiment | Oxidation inhibitor (ratio of mixture) | Brass (JIS H3250) | ||||
| The trimethylolpropane tris monooctyl ester | Tetramethylolmethane four Enanthates | Tetramethylolmethane four esters (コ Application Off レ Star Network ス type) | Alkyl diphenyl base ether (モ レ ス コ Ha イ Le-Off LB-100) | Total acid value (mgKOH/g) | Viscosity ratio | |
| 113 | 10 | 90 | 0.10 | 1.13 | ||
| 114 | 20 | 80 | 0.07 | 1.07 | ||
| 115 | 90 | 10 | 0.11 | 1.14 | ||
| 116 | 80 | 20 | 0.07 | 1.08 | ||
| 117 | 10 | 90 | 0.10 | 1.13 | ||
| 118 | 20 | 80 | 0.07 | 1.07 | ||
| 119 | 90 | 10 | 0.12 | 1.13 | ||
| 120 | 80 | 20 | 0.07 | 1.07 | ||
| 121 | 10 | 90 | 0.10 | 1.13 | ||
| 122 | 20 | 80 | 0.07 | 1.08 | ||
| 123 | 90 | 10 | 0.12 | 1.13 | ||
| 124 | 80 | 20 | 0.08 | 1.07 | ||
Can be clear that from embodiment, with mineral oil, diester oil, polyvalent alcohol ester oil, contain in the base oil that alkyl phenyl ether oil and polyvalent alcohol ester oil and alkyl phenyl ether oil combine (A) alkyl dithiocarbamate(s) compound and (B) lubricating oil of the mixing oxidation inhibitor that combines of aromatic amine compounds, and the lithium soap that will use above-mentioned lubricating oil, lithium-complex soap and double urea compound are used for the lubricating grease of thickening material, compare with the lubricating oil and the lubricating grease of comparative example, even its steam output under hot conditions, the variation of total acid value and viscosity ratio also seldom, thermo-oxidative stability, lubricating life is good, and the maintenance freeization of bearing is had very big contribution.
The present invention's lubricating oil composition and grease composition even its thermostability and oxidative stability are also very good under the former hot conditions that lubricating grease not can do with, can be made huge contribution to the maintenance freeization of the prolongation of bearing life and whirler etc.
Claims (2)
1. lubricating oil composition, it is characterized in that, in the lubricating oil composition that contains the base oil more than a kind from the synthetic oil of mineral oil, diester oil, polyvalent alcohol ester oil, poly-alpha-alkene hydrocarbon ils, polyphenyl ether oil, selected and additive, contain and account for the mixing oxidation inhibitor that the lubricating oil composition gross weight is 0.2～8 weight %, this mixing oxidation inhibitor with as oxidation inhibitor (A) dialkyl dithiocarbamate compound and (B) the aromatic amine compounds by 90～10: 10～90 weight ratio cooperation forms.
2. the lubricating oil composition of claim 1, it is characterized in that, as above-mentioned oxidation inhibitor, (A) the dialkyl dithiocarbamate compound is a nickel dibutyl dithiocarbamate, and (B) the aromatic amine compounds is more than one the compound that is selected from phenyl-a-naphthylamine, alkylation phenyl-alpha-naphthylamine, the alkylated diphenylamine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP96506/95 | 1995-04-21 | ||
| JP9650695 | 1995-04-21 | ||
| JP245756/95 | 1995-09-25 | ||
| JP24575695A JP3370829B2 (en) | 1995-04-21 | 1995-09-25 | Lubricating grease composition |
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| CN98105678A Division CN1070910C (en) | 1995-04-21 | 1998-03-23 | Lubricating grease composition |
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| CN1040124C true CN1040124C (en) | 1998-10-07 |
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| CN96105131A Expired - Lifetime CN1040124C (en) | 1995-04-21 | 1996-04-19 | Lubricant oil composition and lubricant grease composition |
| CN98105678A Expired - Lifetime CN1070910C (en) | 1995-04-21 | 1998-03-23 | Lubricating grease composition |
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| JP3284821B2 (en) * | 1995-04-21 | 2002-05-20 | 株式会社日立製作所 | Electric rotating machine |
| JP2001187891A (en) * | 1995-04-21 | 2001-07-10 | Hitachi Ltd | Lubricating oil composition and lubricating grease composition |
| KR100296478B1 (en) * | 1997-03-26 | 2001-10-25 | 포만 제프리 엘 | Improved Spindle Motor |
| JP2006071104A (en) * | 1997-07-02 | 2006-03-16 | Nsk Ltd | Rolling bearing |
| JP4809543B2 (en) * | 2001-05-16 | 2011-11-09 | 古河電気工業株式会社 | Anticorrosion heat resistant transmission line |
| JP4310286B2 (en) | 2004-03-31 | 2009-08-05 | 三菱重工業株式会社 | Lubricating oil composition |
| US7879778B2 (en) | 2006-06-27 | 2011-02-01 | Exxonmobil Research And Engineering Company | Synthetic phenolic ether lubricant base stocks and lubricating oils comprising such base stocks mixed with co-base stocks and/or additives |
| JP5496087B2 (en) * | 2007-06-20 | 2014-05-21 | クリューバー リュブリケーション ミュンヘン ソシエタス ヨーロピア ウント コンパニー コマンディートゲゼルシャフト | Grease composition |
| JP2009040954A (en) * | 2007-08-10 | 2009-02-26 | Daido Chem Ind Co Ltd | Lubricant composition for warm working of magnesium and magnesium alloy |
| JP4790688B2 (en) * | 2007-10-15 | 2011-10-12 | 出光興産株式会社 | High temperature lubricating oil composition |
| WO2009134656A1 (en) * | 2008-04-28 | 2009-11-05 | Dow Global Technologies Inc. | Polyalkylene glycol-based wind turbine lubricant compositions |
| WO2009153317A1 (en) * | 2008-06-19 | 2009-12-23 | Shell Internationale Research Maatschappij B.V. | Lubricating grease compositions |
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| JP2011021194A (en) * | 2010-09-08 | 2011-02-03 | Nsk Ltd | Grease composition and one-way clutch built-in type rotation transmission |
| JP5729590B2 (en) | 2010-12-29 | 2015-06-03 | Ntn株式会社 | Grease composition, grease-filled bearing, universal joint and linear motion device |
| WO2013183676A1 (en) | 2012-06-05 | 2013-12-12 | Ｊｘ日鉱日石エネルギー株式会社 | Grease composition |
| JP6480323B2 (en) * | 2015-12-28 | 2019-03-06 | Ｊｘｔｇエネルギー株式会社 | Lubricating oil composition |
| JP6845633B2 (en) * | 2016-08-04 | 2021-03-17 | 協同油脂株式会社 | Grease composition |
| CN110546244A (en) * | 2017-03-20 | 2019-12-06 | 陶氏环球技术有限责任公司 | Synthetic lubricant compositions with improved oxidation stability |
| CN107325868A (en) * | 2017-06-28 | 2017-11-07 | 广西大学 | A kind of composition of whirlpool spray-rocket/punching press composite engine lubricant |
| CN109504354B (en) * | 2019-01-14 | 2021-03-09 | 中海石油(中国)有限公司上海分公司 | Lubricant, drilling fluid and application thereof |
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| EP0417972A1 (en) * | 1989-09-07 | 1991-03-20 | Exxon Research And Engineering Company | Lubricating oil composition |
| CN1079500A (en) * | 1992-09-29 | 1993-12-15 | 宋立贵 | Hydraulic lubricating oil for food processing machinery |
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| EP0083123A1 (en) * | 1981-12-29 | 1983-07-06 | The Procter & Gamble Company | Alphaphoshato amide compounds and lubricant and hydrocarbon fuel compositions containing them |
| GB2241707A (en) * | 1990-03-07 | 1991-09-11 | Exxon Research Engineering Co | Lubricating grease composition |
| US5256321A (en) * | 1992-07-10 | 1993-10-26 | The Lubrizol Corporation | Grease compositions |
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- 1996-04-19 KR KR1019960011855A patent/KR100191904B1/en not_active IP Right Cessation
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- 1998-03-23 CN CN98105678A patent/CN1070910C/en not_active Expired - Lifetime
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|---|---|---|---|---|
| US486983A (en) * | 1892-11-29 | Samuel morris lillie | ||
| US4965005A (en) * | 1987-09-17 | 1990-10-23 | Ciba-Geigy Corporation | Aminomethyl derivatives of monothiocarbamates and dithiocarbamates as additives for lubricants |
| EP0417972A1 (en) * | 1989-09-07 | 1991-03-20 | Exxon Research And Engineering Company | Lubricating oil composition |
| CN1079500A (en) * | 1992-09-29 | 1993-12-15 | 宋立贵 | Hydraulic lubricating oil for food processing machinery |
| CN1091464A (en) * | 1993-04-02 | 1994-08-31 | 李书林 | Cold-drawing antirust lubricating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH093468A (en) | 1997-01-07 |
| CN1070910C (en) | 2001-09-12 |
| CN1203260A (en) | 1998-12-30 |
| KR100191904B1 (en) | 1999-06-15 |
| JP3370829B2 (en) | 2003-01-27 |
| CN1136074A (en) | 1996-11-20 |
| KR960037806A (en) | 1996-11-19 |
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